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This application is a 371 of PCT/US94/08868 filed Aug. 8, 1994 which is a CIP of application Ser. No. 08/106,468 filed Aug. 13, 1993.
BACKGROUND OF THE INVENTION
This invention relates to substituted ketone derivatives of Formula I useful in the treatment of inflammation in lung, central nervous system, kidney, joints, endocardium, pericardium, eyes, ears, skin, gastro-intestinal tract and urogenital system. More particularly, this invention relates to substituted ketone derivatives that are useful inhibitors of interleukin-1β converting enzyme (ICE). Interleukin-1β converting enzyme (ICE) has been identified as the enzyme responsible for converting precursor interleukin-1β (IL-1β) to biologically active IL-1β. ##STR2##
Mammalian interleukin-1 (IL-1) is an immunoregulatory protein secreted by cell types as part of the inflammatory response. The primary cell type responsible for IL-1 production is the peripheral blood mono-cyte. Other cell types have also been described as releasing or containing IL-I or IL-I like molecules. These include epithelial cells (Luger, et al., J. Immunol. 127: 1493-1498 (1981), Le et al., J. Immunol. 138: 2520-2526 (1987) and Lovett and Larsen, J. Clin. Invest. 82: 115-122 (1988), connective tissue cells (Ollivierre et al., Biochem. Biophys. Res. Comm. 141: 904-911 (1986), Le et al, J. Immunol. 138: 2520-2526 (1987), cells of neuronal origin (Giulian et al., J. Esp. Med. 164: 594-604 (1986) and leukocytes (Pistoia et al., J. Immunol. 136: 1688-1692 (1986), Acres et al., Mol. Immuno. 24: 479-485 (1987), Acres et al., J. Immunol. 138: 2132-2136 (1987) and Lindenmann et al., J. Immunol 140: 837-839 (1988).
Biologically active IL-I exists in two distinct forms, IL-1α with an isoelectric point of about pI 5.2 and IL-162 with an isoelectric point of about 7.0 with both forms having a molecular mass of about 17.5 kDa (Bayne et al., J. Exp. Med. 163: 1267-1280 (1986) and Schmidt, J. Exp. Med. 160: 772 (1984). The polypeptides appear evolutionarily conserved, showing about 27-33% homology at the amino acid level (Clark et al., Nucleic Acids Res. 14: 7897-7914 (1986).
Mammalian IL-1β is synthesized as a cell associated precursor polypeptide with a molecular mass of about 31 kDa (Limjuco et al., Proc. Natl. Acad. Sci USA 83: 3972-3976 (1986). Precursor IL-1β is unable to bind to IL-1 receptors and is biologically inactive (Mosley et al., J. Biol. Chem. 262: 2941-2944 (1987). Biological activity appears dependent upon some form of proteolytic processing which results in the conversion of the precursor 31 kDa form to the mature 17.5 kDa form. Evidence is growing that by inhibiting the conversion of precursor IL-1β to mature IL-1β, one can effectively inhibit the activity of interleukin-1.
Mammalian cells capable of producing IL-1β include, but are not limited to, keratinocytes, endothelial cells, mesangial cells, thymic epithelial cells, dermal fibroblasts, chondrocytes, astrocytes, glioma cells, mono-nuclear phagocytes, granulocytes, T and B lymphocytes and natural killer cells.
As discussed by J. J. Oppenheim, et al., Immunology Today, vol. 7(2):45-56 (1986), the activities of interleukin-1 are many. It has been observed that catabolin, a factor that promotes degradation of cartilage matrix, also exhibited the thymocyte co-mitogenic activities of IL-1 and stimulates chondrocytes to release matrix metalloproteinases and plasminogen activator. In addition, a plasma factor termed `proteolysis inducing factor` stimulates muscle cells to produce prostaglandins which in turn leads to proteolysis, the release of amino acids and, in the long run, muscle wasting, and appears to represent a fragment of IL-1 with fever-inducing, acute phase response and thymocyte co-mitogenic activities.
IL-1 has multiple effects on cells involved in inflammation and wound healing. Subcutaneous injection of IL-1 leads to margination of neutrophils and maximal extravascular infiltration of the polymorphonuclear leukocytes (PMN). In vitro studies reveal IL-1 to be a chemotactic attractant for PMN, to activate PMN to metabolize glucose more rapidly, to reduce nitroblue tetrazolium, and to release PMN lysozomal enzymes. Endothelial cells are stimulated to proliferate by IL-1 to produce thromboxane, to become more adhesive, and to release procoagulating activities. IL-1 also enhances collagen type IV production by epidermal cells, induces osteoblast proliferation and alkaline phosphatase production, and stimulates osteoclasts to resorb bone. Even macrophages have been reported to be chemotactically attracted to IL-1 to produce prostaglandins in response to IL-1 and to exhibit a more prolonged and active tumoricidal state.
IL-1 is also a potent bone resorptive agent which upon infusion into mice causes hypercalcemia and increases in bone resorptive surface as revealed by histomorphometry (Sabatini, M. et al., PNAS 85:5235-5239, 1988).
Accordingly, disease states in which the ICE inhibitors of Formula I may be useful as therapeutic agents include, but are not limited to, infectious diseases where active infection exists at any body site, such as meningitis and salpingitis; complications of infections including septic shock, disseminated intravascular coagulation, and/or adult respiratory distress syndrome; acute or chronic inflammation due to antigen, antibody, and/or complement deposition; inflammatory conditions including arthritis, cholangitis, colitis, encephalitis, endocarditis, glomerulonephritis, interstitial nephritis, hepatitis, myocarditis, pancreatitis, pericarditis, reperfusion injury and vasculitis. Immune-based diseases which may be responsive to ICE inhibitors of Formula I include but are not limited to conditions involving T-cells and/or macrophages such as acute and delayed hypersensitivity, graft rejection, and graft-versus-host-disease; auto-immune diseases including Type I diabetes mellitus and multiple sclerosis. ICE inhibitors of Formula I may also be useful in the treatment of bone and cartilage resorption as well as diseases resulting in excessive deposition of extracellular matrix. Such diseases include periodontal diseases, interstitial pulmonary fibrosis, cirrhosis, systemic sclerosis, and keloid formation. ICE inhibitors of Formula I may also be useful in treatment of certain tumors which produce IL-1 as an autocrine growth factor and in preventing the cachexia associated with certain tumors.
SUMMARY OF THE INVENTION
Novel ketone derivatives of Formula I are found to be potent inhibitors of interleukin-1β converting enzyme (ICE). Compounds of Formula I are useful in the treatment of deseases including inflammation in lung, central nervous system, kidney, joints, endocardium, pericardium, eyes, ears, skin, gastrointestinal tract and urogenital system.
DETAILED DESCRIPTION OF THE INVENTION
The invention encompasses compounds of Formula I. ##STR3## or a pharmaceutically acceptable salt thereof thereof: wherein:
R 1 is
(a) substituted C 1-6 alkyl or substituted C 1-6 alkoxy, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) halo which is defined to include F, Br, Cl, and I,
(4) C 1-3 alkyloxy,
(5) C 1-3 alkylthio,
(6) phenyl C 1-3 alkyloxy, and
(7) phenyl C 1-3 alkylthio;
(b) substituted C 2-6 alkenyl or substituted C 2-6 alkenyloxy, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) halo,
(4) C 1-3 alkyloxy,
(5) C 1-3 alkylthio,
(6) phenyl C 1-3 alkyloxy, and
(7) phenyl C 1-3 alkylthio;
(c) aryl, aryl C 1-6 alkyl, and aryl C 2-6 alkyloxy wherein the C 1-6 alkyl is optionally substituted with C 1-3 alkylcarbonylamino, and the aryl group is selected from the group consisting of:
(1) phenyl,
(2) naphthyl,
(3) pyridyl,
(4) furyl,
(5) pyrryl,
(6) thienyl,
(7) isothiazolyl,
(8) imidazolyl,
(9) benzimidazolyl,
(10) tetrazolyl,
(11) pyrazinyl,
(12) pyrimidyl,
(13) quinolyl,
(14) isoquinolyl,
(15) benzofuryl,
(16) isobenzofuryl,
(17) benzothienyl,
(18) pyrazolyl,
(19) indolyl,
(20) isoindolyl,
(21) purinyl,
(22) carbazolyl,
(23) isoxazolyl,
(24) thiazolyl,
(25) oxazolyl,
(26) benzthiazolyl, and
(27) benzoxazolyl,
and mono- and di-substituted aryl as defined above in items (1) to (27) wherein the substitutents on the aryl are independently selected from C 1-6 alkyl, C 1-6 alkyloxy, halo, hydroxy, amino, C 1-6 alkylamino, amino C 1-6 alkyl, carboxyl, carboxyl C 1-6 alkyl, and C 1-6 alkylcarbonyl;
R 2 is
(a) phenyl,
(b) 1-naphthyl,
(c) substituted 2-naphthyl wherein the substituents are individually selected from the group consisting of
(1) hydrogen,
(2) halo,
(3) C 1-6 alkyl,
(4) perfluoro C 1-3 alkyl,
(5) nitro,
(6) cyano,
(7) C 1-6 alkylcarbonyl,
(8) phenylcarbonyl,
(9) carboxy,
(10) aminocarbonyl,
(11) mono- and di-C 1-6 alkylaminocarbonyl,
(12) phenylaminocarbonyl,
(13) formyl,
(14) aminosulfonyl,
(15) C 1-6 alkyl sulfonyl,
(16) phenyl sulfonyl,
(17) formamido,
(18) C 1-6 alkylcarbonylamino,
(19) phenylcarbonylamino,
(20) C 1-6 alkoxycarbonyl,
(21) C 1-6 alkylsulfonamido carbonyl,
(22) phenylsulfonamido carbonyl,
(23) C 1-6 alkyl carbonylamino sulfonyl,
(24) phenylcarbonylamino sulfonyl,
(25) C 1-6 alkyl amino,
(26) C 1-3 dialkyl amino,
(27) amino,
(28) hydroxy,
(29) C 1-6 alkyloxy, and
(30) aryl, aryl C 1-6 alkyl, and aryl C 1-6 alkoxy wherein the aryl group is selected from the group consisting of:
(a) phenyl,
(b) naphthyl,
(c) pyridyl,
(d) furyl,
(e) pyrryl,
(f) thienyl,
(g) isothiazolyl,
(h) imidazolyl,
(i) benzimidazolyl,
(j) tetrazolyl,
(k) pyrazinyl,
(l) pyrimidyl,
(m) quinolyl,
(n) isoquinolyl,
(o) benzofuryl,
(p) isobenzofuryl,
(q) benzothienyl,
(r) pyrazolyl,
(s) indolyl,
(t) isoindolyl,
(u) purinyl,
(v) carbazolyl,
(w) isoxazolyl,
(x) thiazolyl,
(y) oxazolyl,
(z) benzthiazolyl, and
(a1) benzoxazolyl, and mono- and di-substituted aryl or heteroaryl as defined above in items (a) to (a1) wherein the substitutents are independently selected from C 1-6 alkyl, C 1-6 alkyloxy, halo, hydroxy, amino, C 1-6 alkylamino, amino C 1-6 alkyl, carboxyl, carboxyl C 1-6 alkyl, and C 1-6 alkylcarbonyl;
R 3 is
(a) hydrogen,
(b) C 1-6 alkyl,
(c) phenyl and phenyl C 1-6 alkyl, and mono- and di-substituted phenyl wherein the substitutents are independently selected from C 1-6 alkyl, C 1-6 alkyloxy, halo, hydroxy, amino, C 1-6 alkylamino, amino C 1-6 alkyl, carboxyl, carboxyl C 1-6 alkyl, and C 1-6 alkylcarbonyl;
X 1 is selected from the group consisting of
(a) a single bond, and
(b) an amino acid of Formula II ##STR4## X 2 is selected from the group consisting of (a) a single bond, and
(b) an amino acid of Formula III ##STR5## X 3 is selected from the group consisting of (a) a single bond, and
(b) an amino acid of Formula II ##STR6## wherein R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently selected from the group consisting of:
(a) hydrogen,
(b) substituted C 1-6 alkyl, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) halo,
(4) C 1-3 alkylthio,
(5) thiol,
(6) C 1-6 alkylcarbonyl,
(7) carboxy,
(8) aminocarbonyl,
(9) amino carbonyl amino,
(10) amino,
(11) C 1-3 alkylamino, wherein the alkyl moiety is substituted with hydrogen or hydroxy, and
(12) guanidino;
(c) aryl and aryl C 1-6 alkyl wherein the aryl group is selected from the group consisting of:
(1) phenyl,
(2) naphthyl,
(3) pyridyl,
(4) furyl,
(5) pyrryl,
(6) thienyl,
(7) isothiazolyl,
(8) imidazolyl,
(9) benzimidazolyl,
(10) tetrazolyl,
(11) pyrazinyl,
(12) pyrimidyl,
(13) quinolyl,
(14) isoquinolyl,
(15) benzofuryl,
(16) isobenzofuryl,
(17) benzothienyl,
(18) pyrazolyl,
(19) indolyl,
(20) isoindolyl,
(21) purinyl,
(22) carbazolyl,
(23) isoxazolyl,
(24) thiazolyl,
(25) oxazolyl,
(26) benzthiazolyl, and
(27) benzoxazolyl,
and mono- and di-substituted aryl or heteroaryl as defined above in items (1) to (27) wherein the substitutents are independently selected from C 1-6 alkyl, C 1-6 alkyloxy, halo, hydroxy, amino, C 1-6 alkylamino, amino C 1-6 alkyl, carboxyl, carboxyl C 1-6 alkyl, and C 1-6 alkylcarbonyl;
(d) R 4 and R 5 , R 6 and R 7 , and R 8 and R 9 may be joined, such that together with the nitrogen atom to which R 4 (or R 6 or R 8 ) is attached there is formed a mono-cyclic saturated ring of 5 to 8 atoms, said ring having exactly one hetero atom which is nitrogen, said ring optionally having an oxo group, said ring including, ##STR7## Y is O, S, or NH.
One class of this genus is the compounds wherein:
R 1 is
(a) substituted C 1-6 alkyl or substituted C 1-6 alkoxy, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) chloro or fluoro,
(4) C 1-3 alkyloxy, and
(5) phenyl C 1-3 alkyloxy,
(b) aryl C 1-6 alkyl wherein the aryl group is selected from the group consisting of
(1) phenyl,
(2) naphthyl,
(3) pyridyl,
(4) furyl,
(5) thienyl,
(6) thiazolyl,
(7) isothiazolyl,
(8) benzofuryl,
(9) benzothienyl,
(10) indolyl,
(11) isooxazolyl, and
(12) oxazolyl,
and mono- and di-substituted aryl as defined above in items (1) to (12) wherein the substitutents are independently C 1-4 alkyl, halo, and hydroxy;
R 4 is hydrogen and R 5 is selected from the group consisting of
(a) hydrogen,
(b) substituted C 1-6 alkyl, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) halo,
(4) C 1-4 alkyl thio
(5) thiol
(6) C 1-6 alkylcarbonyl,
(7) carboxy,
(8) aminocarbonyl,
(9) C 1-4 alkylamino, and C 1-4 alkylamino wherein the alkyl moiety is substituted with an hydroxy, and
(10) guanidino,
(11) C 1-4 alkyloxy,
(12) phenyl C 1-4 alkyloxy,
(13) phenyl C 1-4 alkylthio, and
(c) aryl C 1-6 alkyl, wherein the aryl group is elected from the group consisting of
(1) phenyl,
(2) naphthyl,
(3) pyridyl,
(4) furyl,
(5) thienyl,
(6) thiazolyl,
(7) isothiazolyl,
(8) benzofuryl,
(9) benzothienyl,
(10) indolyl,
(11) isooxazolyl, and
(12) oxazolyl,
and wherein the aryl may be mono- and di-substituted, the substituents being each independently C 1-6 alkyl, halo, hydroxy, C 1-6 alkyl amino, C 1-6 alkoxy, C 1-6 alkylthio, and C 1-6 alkylcarbonyl;
R 6 , R 7 , R 8 and R 9 are each independently selected from the group consisting of
(a) hydrogen,
(b) C 1-6 alkyl, wherein the substituent is selected from
(1) hydrogen,
(2) hydroxy,
(3) halo,
(4) --S--C 1-4 alkyl,
(5) --SH,
(6) C 1-6 alkylcarbonyl,
(7) carboxy,
(8) aminocarbonyl,
(9) C 1-4 alkylamino, and C 1-4 alkyl amino wherein the alkyl moiety is substituted with an hydroxy, and
(10) guanidino, and
(c) aryl C 1-6 alkyl, wherein aryl is defined as immediately above, and wherein the aryl may be mono- and di-substituted, the substituents being each independently C 1-6 alkyl, halo, hydroxy, C 1-6 alkyl amino, C 1-6 alkoxy, C 1-6 alkylthio, and C 1-6 alkylcarbonyl.
Within this class are the compounds wherein X 1 , X 2 and X 3 , are each independently selected from the group consisting of the L- and D- forms of the amino acids including glycine, alanine, valine, leucine, isoleucine, serine, threonine, aspartic acid, asparagine, glutamic acid, glutamine, lysine, hydroxy-lysine, histidine, arginine, phenyl-alanine, tyrosine, tryptophan, cysteine, methionine, omithine, β-alanine, homoserine, homotyrosine, homophenylalanine and citrulline.
Alternatively, within this class are the subclass of compounds wherein
R 1 is C 1-3 alkyl, C 1-3 alkenyl, C 1-3 alkoxy or C 1-3 alkenyloxy; R 6 , R 7 , R 8 and R 9 are each individually
(a) hydrogen,
(b) C 1-6 alkyl,
(c) mercapto C 1-6 alkyl,
(d) hydroxy C 1-6 alkyl,
(e) carboxy C 1-6 alkyl,
(g) aminocarbonyl C 1-6 alkyl,
(h) mono---or di-C 1-6 alkyl amino C 1-6 alkyl,
(i) guanidino C 1-6 alkyl,
(j) amino-C 1-6 alkyl or N-substituted amino-C 1-6 alkyl wherein the substituent is carbobenzoxy,
(k) carbamyl C 1-6 alkyl, or
(l) aryl C 1-6 alkyl, wherein the aryl group is selected from phenyl and indolyl, and the aryl group may be substituted with hydroxy, C 1-3 alkyl.
Exemplifying the invention are the following compounds:
a) N-Allyloxycarbonyl-3-amino-4-oxo-5-phenoxy-pentanoic acid.
b) N-Allyloxycarbonyl-3-amino-5-(l -naphthyloxy)-4-oxopentanoic acid.
c) N-Allyloxycarbonyl-3-amino-5-(2-naphthyloxy)-4-oxopentanoic acid.
d) N-Allyloxycarbonyl-3-amino-5-(3-aminocarbonyl-2-naphthyloxy)-4-oxopentanoic acid.
e) N-Allyloxycarbonyl-3-amino-5-(3-(N-phenyl)amino-carbonyl-2-naphthyloxy)-4-oxopentanoic acid.
f) N-Allyloxycarbonyl-3-amino-5-(3-cyano-2-naphthyloxy)-4-oxopentanoic acid.
g) N-Allyloxycarbonyl-3-amino-5-(3-hydroxymethyl-2-naphthyloxy)-4-oxopentanoic acid.
h) N-Allyloxycarbonyl-3-amino-5-(3-methoxycarbonyl-2-naphthyloxy)-4-oxopentanoic acid.
i) N-Allyloxycarbonyl-3-amino-5-(3-imidazolyl -2-naphthyloxy)-4-oxopentanoic acid.
j) N-(N-Acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alaninyl)-3-amino-5-phenoxy-4-oxopentanoic acid.
k) N-(N-Carbobenzyloxy-(L)-valinyl-(L)-alaninyl)-3-amino-5-(3-aminocarbonyl-naphthyl-2-oxy)-4-oxo-pentanoic acid, triethylamine salt.
l) N-(N-Carbobenzyloxy-(L)-valinyl-(L)-prolinyl)-3-amino-5-(3-aminocarbonyl-naphthyl-2-oxy)-4-oxo-pentanoic acid.
m) N-(2-indoloyl)-3-amino-5-(3-aminocarbonyl-naphthyl-2-oxy)-4-oxo-pentanoicacid.
This invention also concerns to pharmaceutical composition and methods of treatment of interleukin-1 and interleukin-1β mediated or implicated disorders or diseases (as described above) in a patient (including man and/or mammalian animals raised in the dairy, meat, or fur industries or as pets) in need of such treatment comprising administration of interleukin-1β inhibitors of Formula (I) as the active constituents.
Illustrative of these aspects, this invention concerns pharmaceutical compositions and methods of treatment of diseases selected from septic shock, allograft rejection, inflammatory bowel disease and rheumatoid arthritis in a patient in need of such treatment comprising:
administration of an interleukin-1β converting enzyme inhibitor of Formula (I) as the active constituent.
Compounds of the instant invention have are particularly useful in the treatment of ICE mediated diseases advantageously treated with agents that are selective inhibitors of ICE. For example, structurally related compounds such as those disclosed in U.S. Pat. No. 5,055,451, issued to Krantz et. al., Oct. 8, 1991 by design inhibit cathepsin B. Compounds of the instant invention are selective inhibitors of ICE over Catiepsin B. For purposes of this specification a compound is to be considered selective for ICE over Cathepsin B if the ratios of the IC 50 for ICE to the IC 50 for Cathepsin B is 0.01 or smaller.
Compounds of the instant invention are conveniently prepared using the procedures described generally below and more explicitly described in the Example section thereafter. ##STR8##
An appropriately N-protected aspartic acid ester A is first treated with an alkyl chloroformate to form the mixed anhydride in situ which is subsequently reacted with excess diazomethane to form the diazomethyl ketone B. Subsequent reaction of B with hydrobromic acid in acetic acid forms the bromomethyl ketone C. Reaction of C with a metal salt of a desired aryloxy compound affects displacement of the bromide to form the aryloxymethyl ketone D. Removal of the t-butyl ester with strong acid (trifluoroacetic acid or hydrochloric acid) will give the desired final product E. In situ removal of the `Alloc` protecting group with a palladium catalyst and alkyltin hydride in the presence of a carboxylic acid or N-protected amino acid or peptide and a suitable condensing agent(s) will provide other examples.
The compounds of the instant invention of the Formula (I), as represented in the Examples hereinunder shown to exhibit in vitro inhibitory activities with respect to interleukin-1β. In particular, these compounds have been shown to inhibit interleukin-1β converting enzyme from cleaving precusor interleukin-1β as to form active interleukin-1β.
Compounds of the instant invention of Formula (I) are evaluated in vivo by inhibiting LPS-induced fever in rats and by reducing inflammation in carrageenan-induced paw edema in rats by methodology described by R. Heng, T. Payne, L. Revesz, B. Weidmann in PCT W093/09135 (published 13 May 1993).
This invention also relates to a method of treatment for patients (including man and/or mammalian animals raised in the dairy, meat, or fur industries or as pets) suffering from disorders or diseases which can be attributed to IL-1/ICE as previously described, and more specifically, a method of treatment involving the administration of the IL-1/ICE inhibitors of Formula (I) as the active constituents.
Accordingly, disease states in which the ICE inhibitors of Formula I may be useful as therapeutic agents include, but are not limited to, infectious diseases where active infection exists at any body site, such as meningitis and salpingitis; complications of infections including septic shock, disseminated intravascular coagulation, and/or adult respiratory distress syndrome; acute or chronic inflammation due to antigen, antibody, and/or complement deposition; inflammatory conditions including arthritis, cholangitis, colitis, encephalitis, endocarditis, glomerulonephritis, hepatitis, myocarditis, pancreatitis, pericarditis, reperfusion injury and vasculitis. Immune-based diseases which may be responsive to ICE inhibitors of Formula I include but are not limited to conditions involving T-cells and/or macrophages such as acute and delayed hypersensitivity, graft rejection, and graft-versus-host-disease; auto-immune diseases including Type I diabetes mellitus and multiple sclerosis. ICE inhibitors of Formula I may also be useful in the treatment of bone and cartilage resorption as well as diseases resulting in excessive deposition of extracellular matrix such as interstitial pulmonary fibrosis, cirrhosis, systemic sclerosis, and keloid formation. ICE inhibitors of
Formula I may also be useful in treatment of certain tumors which produce IL 1 as an autocrine growth factor and in preventing the cachexia associated with certain tumors.
For the treatment the above mentioned diseases, the compounds of Formula (I) may be administered orally, topically, parenterally, by inhalation spray or rectally in dosage unit formulations containing conventional non-toxic pharmaceutically acceptable carriers, adjuvants and vehicles. The term parenteral as used herein includes subcutaneous injections, intravenous, intramuscular, intracistemal injection or infusion techniques. In addition to the treatment of warm-blooded animals such as mice, rats, horses, cattle, sheep, dogs, cats, etc., the compounds of the invention are effective in the treatment of humans.
The pharmaceutical compositions containing the active ingredient may be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsions, hard or soft capsules, or syrups or elixirs. Compositions intended for oral use may be prepared according to any method known to the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of sweetening agents, flavoring agents, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets contain the active ingredient in admixture with non-toxic pharmaceutically acceptable excipients which are suitable for the manufacture of tablets. These excipients may be for example, inert diluents, such as calcium carbonate, sodium carbonate, lactose, calcium phosphate or sodium phosphate; granulating and disintegrating agents, for example, corn starch, or alginic acid; binding agents, for example starch, gelatin or acacia, and lubricating agents, for example magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl mono-stearate or glyceryl distearate may be employed. They may also be coated by the techniques described in the U.S. Pat. Nos. 4,256,108; 4,166,452; and 4,265,874 to form osmotic therapeutic tablets for control release.
Formulations for oral use may also be presented as hard gelatin capsules wherein the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin, or as soft gelatin capsules wherein the active ingredient is mixed with water or an oil medium, for example peanut oil, liquid paraffin, or olive oil.
Aqueous suspensions contain the active materials in admixture with excipients suitable for the manufacture of aqueous suspensions. Such excipients are suspending agents, for example sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethyl-cellulose, sodium alginate, polyvinylpyrrolidone, gum tragacanth and gum acacia; dispersing or wetting agents may be a naturally-occurring phosphatide, for example lecithin, or condensation products of an alkylene oxide with fatty acids, for example polyoxyethylene stearate, or condensation products of ethylene oxide with long chain aliphatic alcohols, for example heptadecaethyl-eneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol mono-oleate, or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides, for example polyethylene sorbitan mono-oleate. The aqueous suspensions may also contain one or more preservatives, for example ethyl, or n-propyl, p-hydroxybenzoate, one or more coloring agents, one or more flavoring agents, and one or more sweetening agents, such as sucrose or saccharin.
Oily suspensions may be formulated by suspending the active ingredient in a vegetable oil, for example arachis oil, olive oil, sesame oil or coconut oil, or in a mineral oil such as liquid paraffin. The oily suspensions may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. Sweetening agents such as those set forth above, and flavoring agents may be added to provide a palatable oral preparation. These compositions may be preserved by the addition of an anti-oxidant such as ascorbic acid.
Dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water provide the active ingredient in admixture with a dispersing or wetting agent, suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients, for example sweetening, flavoring and coloring agents, may also be present.
The pharmaceutical compositions of the invention may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil, for example olive oil or arachis oil, or a mineral oil, for example liquid paraffin or mixtures of these. Suitable emulsifying agents may be naturally-occurring gums, for example gum acacia or gum tragacanth, naturally-occurring phosphatides, for example soy bean, lecithin, and esters or partial esters derived from fatty acids and hexitol anhydrides, for example sorbitan mono-oleate, and condensation products of the said partial esters with ethylene oxide, for example polyoxyethylene sorbitan mono-oleate. The emulsions may also contain sweetening and flavoring agents.
Syrups and elixirs may be formulated with sweetening agents, for example glycerol, propylene glycol, sorbitol or sucrose. Such formulations may also contain a demulcent, a preservative and flavoring and coloring agents. The pharmaceutical compositions may be in the form of a sterile injectable aqueous or oleagenous suspension. This suspension may be formulated according to the known art using those suitable dispersing or wetting agents and suspending agents which have been mentioned above. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example as a solution in 1,3-butane diol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or diglycerides. In addition, fatty acids such as oleic acid find use in the preparation of injectables.
The compounds of Formula (I) may also be administered in the form of suppositories for rectal administration of the drug. These compositions can be prepared by mixing the drug with a suitable non-irritating excipient which is solid at ordinary temperatures but liquid at the rectal temperature and will therefore melt in the rectum to release the drug. Such materials are cocoa butter and polyethylene glycols.
For topical use, creams, ointments, jellies, solutions or suspensions, etc., containing the compounds of Formula (I) are employed. (For purposes of this application, topical application shall include mouth washes and gargles.)
Dosage levels of the order of from about 0.05 mg to about 140 mg per kilogram of body weight per day are useful in the treatment of the above-indicated conditions (about 2.5 mg to about 7 gms. per patient per day). For example, inflammation may be effectively treated by the administration of from about 0.01 to 50 mg of the compound per kilogram of body weight per day (about 0.5 mg to about 3.5 gms per patient per day).
The amount of active ingredient that may be combined with the carrier materials to produce a single dosage form will vary depending upon the host treated and the particular mode of administration. For example, a formulation intended for the oral administration of humans may contain from 0.5 mg to 5 gm of active agent compounded with an appropriate and convenient amount of carrier material which may vary from about 5 to about 95 percent of the total composition. Dosage unit forms will generally contain between from about 1 mg to about 500 mg of an active ingredient.
It will be understood, however, that the specific dose level for any particular patient will depend upon a variety of factors including the activity of the specific compound employed, the age, body weight, general health, sex, diet, time of administration, route of administration, rate of excretion, drug combination and the severity of the particular disease undergoing therapy.
The following Examples are intended to illustrate the preparation of compounds of Formula I, and as such are not intended to limit the invention as set forth in the claims appended, thereto.
Additional methods of making compounds of this invention are known in the art such as U.S. Pat. No. 5,055,451, issued to Krantz et al., Oct. 8, 1991 which is hereby incorporated by reference.
EXAMPLE 1
N-Allyloxycarbonyl-3-amino-4-oxo-5-phenoxy-pentanoic acid ##STR9## Step A: N-Allyloxycarbonyl-3-amino-5-diazo-4-oxopentanoic acid, t-butyl ester ##STR10##
To a solution of N-allyloxycarbonyl-(L)-aspartic acid, β-t-butyl ester (6.23 g, 22.8 mmol) and 4-methyl morpholine (2.63 mL, 23.94 mmol) in 50 mL of freshly distilled dichloromethane at -10° C. was added freshly distilled isobutyl chloroformate (3.04 mL, 23.48 mmol). After 15 min, the solution was filtered and excess ethereal diazomethane was added. The mixture was stirred at 0° C. for 1 h and concentrated. The mixture was purified by medium pressure liquid chromatography (MPLC) on silica-gel (35×350 mm column, eluting with 25% ethyl acetate in hexane) to give the title compound as a pale yellow oil: 1 H NMR (400 MHz, CDCl 3 ) δ5.91 (1H, m), 5.62 (1H, br s), 5.31 (1H, d), 5.24 (1H, d), 4.61 (2H, br d), 4.50 (1H, m), 2.92 (1H, dd), 2.60 (1H, dd), 1.43 (9H, s).
Step B: N-Allyloxycarbonyl-3-amino-5-bromo-4-oxopentanoic acid, t-butyl ester ##STR11##
To a solution of N-allyloxycarbonyl-3-amino-5-diazo-4-oxopentanoic acid, β-t-butyl ester in ether was added approximately one equivalent of hydrobromic acid (30% in acetic acid). After 30 min, the solution was diluted with ether and washed three times with water. The combined organic layers were dried over magnesium sulphate, filtered, and concentrated in vacuo. The product was purified by MPLC on silica gel eluted with 20% ethyl acetate in hexane to afford the title compound as a colorless solid:
1 H NMR (400 MHz, CD 3 OD) δ5.93 (1H, m), 5.31 (1H, d), 5.19 (1H, d), 4.69 (1H, t), 4.58 (2H, br d), 4.29 (2H, ABX), 2.82 (1H, dd), 2.63 (1H, 20 dd), 1.43 (9H, s).
Step C: N-Allyloxycarbonyl-3-amino-4-oxo-5-phenoxy-pentanoic acids t-butyl ester ##STR12##
To a solution of phenol (59 mg, 0.628 mmol) in dimethyl-formamide (5 ml) was added potassium carbonate (87 mg, 0.628 mmol). The mixture was stirred for 5 min, followed by addition of N-allyloxy-3-amino-5-bromo-4-oxo-pentanoic acid, β-t-butyl ester (200 mg, 0.571 mmol). The mixture was stirred for 16 hours at room temperature, then diluted with ethyl acetate and washed with saturated sodium bicarbonate solution. The organic layer was dried over anhydrous sodium sulfate and filtered. The solvent was removed in vacuo and the product purified by flash column chromatography on silica gel eluted with 20% t-butyl methyl ether in hexane to provide the title compound. 1 H NMR (CD 3 OD) δ7.25 (2H, m), 6.92 (3H, m), 5.9 (1H, m), 5.22 (2H, m), 4.9 (2H, ABX), 4.7 (1H,t), 4.55 (2H, dd), 2.85 (1H, dd), 2.7 (1H, dd) 1.45 (9H, s).
Step D: N-Allyloxycarbonyl-3-amino-4-oxo-5-phenoxy-pentanoic acid ##STR13##
N-allyloxycarbonyl-3-amino4-oxo-5-phenoxy-pentanoic acid, t-butyl ester from Step C (170 mg, 0.467 mmol) was dissolved in dichloromethane (8 ml) and trifloroacetic acid (8 ml) under nitrogen. The resulting mixture was stirred for 15 minutes. The solvent was reduced in vacuo to provide the target compound. 1 H NMR (CDCl 3 ) δ7.3 (2H, m), 6.92 (3H, m), 5.45 (1H, br.s), 5.2 (2H, m), 4.6 (1H, bs), 4.52 (2H, d), 4.2 (2H, br.s), 2.95 (2H, dbr.); mass spectrum: mile 308(M+1) + , 263.9, 213.7, 106.7, 154.7, 119.0.
By following the procedures described in Example 1, Examples 2-9 may be prepared:
EXAMPLE 2
N-Allyloxycarbonyl-3-amino-5-(1-naphthyloxy)-4-oxopentanoic acid ##STR14## 1 H NMR(CDCl 13 ) δ7.8(1H, m), 7.49(3H, m), 7.31(1H, m), 7.25 (1H, m), 7.15 (1H, m), 5.89 (1H, m), 5.25 (2H, m), 5.0 (2H, ABX), 4.68 (1H, m), 4.55 (2H, m), 3.2 (1H, dd), 3.0 (1H, ddd); mass spectrum: m/e 380 (M+Na) + , 358.1 (M+1) + , 338.8, 196.7, 176.7, 143.9, 119.1.
EXAMPLE 3
N-Allyloxycarbonyl-3-amino-5-(2-naphthyloxy)-4-oxopentanoic acid ##STR15## 1 H NMR(CDCl 3 ) δ7.72 (3H, m), 7.42 (1H, m), 7.35 (1H, m), 7.15 (2H, m), 5.85 (1H, m), 5.25 (2H, m), 5.0 (1H,m), 4.82 (2H, br.s), 4.59 (2H, m), 3.2-2.6 (2H, m); mass spectrum: m/e 380(M+Na) + , 358.1 (M+1) + , 338.8, 196.7, 176.7, 143.9, 119.1.
EXAMPLE 4
N-Allyloxycarbonyl-3 -amino-5 -(3 -aminocarbonyl-2-naphthyloxy)-4-oxopentanoic acid ##STR16## 1 H NMR (CD 3 OD) δ7.52 (2H, m), 7.35 (2H, m), 5.9 (1H, m), 5.85 (2H, q), 5.2 (2H, m), 4.72-4.15 (5H,br, m), 2.9 (2H, m); mass spectrum: m/e 423.0 (M+Na) + , 401.8 (M+1) + . 383.8, 365.9, 325.9, 187.7, 170.7, 134.9.
EXAMPLE 5
N-Allyloxycarbonyl-3-amino-5-(3-(N-phenyl)aminocarbonyl-2-naphthyloxy)-4-oxopentanoic acid ##STR17## 1 H NMR (CDCl 3 ) δ7.8 (1H, m), 7.69 (1H, m), 7.45 (2H, m), 7.25 (4H, br m), 7.06 (1H, m), 6.05 (1H, m), 5.9 (1H, m), 5.62 (1H, NH), 5.2 (2H, m), 5.0 (1H, m), 4.7-4.38 (4H, m), 3.1-2.8 (2H, m); mass spectrum: m/e 499.7 (M+Na) + , 477.6 (M+1) + , 459.4, 366.1, 264.0, 182.7, 170.7, 141.9, 115.2.
EXAMPLE 6
N-Allyloxycarbonyl-3-amino-5-(3-cyano-2-naphthyloxy)-4-oxopentanoic acid ##STR18## 1 H NMR (400 MHz, CDCl 3 ) δ8.10 (1H, s), 7.75 (2H, m), 7.58 (2H, m), 7.42 (2H, m), 5.88 (1H, m), 5.15-5.38 (2H, m), 4.85 (2H, s), 4.58 (2H, m), 4.40(1H, m); mass spectrum: m/e M+1(383.1), 365.1, 169.1, 112.1.
EXAMPLE 7
N-Allyloxycarbonyl-3 -amino-5-(3-hydroxymethyl-2-naphthyloxy)-4-oxopentanoic acid ##STR19## 1 H NMR (400MHz, CDCl 3 ) δ7.50 (3H, m), 7.42 (2H, m), 7.05 (1H, s), 5.83 (1H, m), 5.20 (2H, m), 4.70-4.92 (2H, m), 4.20-4.61 (5H, brm), 2.60-3.01 (2H, m); mass spectrum: m/e M+K + (426.0), M+Na + (410.0), M + (387.0) 369.9, 352.0, 269.0, 239.0.
EXAMPLE 8
N-Allyloxycarbonyl-3-amino-5-(3-methoxycarbonyl-2-naphthyloxy)-4-oxopentanoic acid ##STR20## 1 H NMR (400MHz, CDCl 3 ) δ8.39 (1H, s), 7.82 (1H, d), 7.72 (1H, d), 7.55 (1H, t), 7.42 (2H, m), 7.23(1H, s), 5.85 (1H, m), 5.50 (1H, s), 5.10-5.40 (1H, m), 4.42-4.70 (4H, m), 4.25 (1H, m), 3.95 (3H, s), 2.75-2.98 (2H, m); mass spectrum: m/e M+Na + (438), M+1 (416), 384, 326, 214, 202, 171, 170.
EXAMPLE 9
N-Allyloxycarbonyl-3-amino-5-(3-(2-hydroxyethyl-1 -aminocarbonyl)-2-naphthyloxy)-4-oxopentanoic acid ##STR21## 1 H NMR (200 MHz, CD 3 OD) δ8.49 (1H, s), 7.75-7.93 (2H, m), 7.31-7.57 (4H, m), 5.90 (1H, m), 5.00-5.38 (2H, m), 4.18-4.79 (5H, m), 3.82 (2H, t), 3.65 (2H, t), 2.90 (2H, m); mass spectrum: m/e M+1 (444.9), 394.1, 278.9, 218.9, 202.9.
EXAMPLE 10
N-Allyloxycarbonyl-3-amino-5 -(3 -imidazolyl -2-naphthyloxy)-4-oxopentanoic acid ##STR22## Step A: 3-Benzyloxy-naphthalene-2-carboxylic acid, benzyl ester ##STR23##
To a solution of 3-hydroxy-naphthalene-2-carboxylic acid (3.76 g, 20 mmol) in dimethylformamide, at 0° C., was added sodium hydride (1.01 g, 42 mmol) 15 minutes later, freshly distilled benzyl bromide (4.98 ml, 42 mmol) was added. After stirring at room temperature under nitrogen for 16 hours, the solution was diluted with ethyl acetate and washed twice with 2N aqueous hydrochloric acid. The organic layer was then dried over anhydrous sodium sulfate and concentrated in vacuo to provide the title compound (7.12 g).
Step B: (3-Benzyloxy-2-naphthyl)methyl alcohol ##STR24##
To a solution of 3-benzyloxy-naphthalene-2-carboxylic acid, benzyl ester (7.12 g, 19.34 mmol) in dry dichloromethane at -78° C. was dropwise added diisobutylaluminum hydride (DIBAL-H) (27 ml of 1.5M solution in toluene, 40.6 mmol). The reaction was warmed to room temperature after one hour. Sixteen hours later, the reaction was cooled to 0° C. and was quenched carefully with water. The mixture was diluted with ethyl acetate and washed twice with 2N hydrochloric acid. The organic layer was dried over anhydrous sodium sulfate, filtered and then concentrated in vacuo. The residue was eluted through silica gel with dichloromethane to give the title compound (3.2 g).
Step C: 3-Benzyloxy-naphthalene-2-carboxaldehyde ##STR25##
To a solution of (3-benzyloxy-2-naphthyl)methyl alcohol (3.2 g, 12.12 mmol) in dichloromethane was added 4A molecular sieves (6.06 g) and 4-methylmorpholine N-oxide (2.13 g, 18.18 mmol). After 5 minutes, tetrapropylammonium perruthenate (TPAP) (606 mg) was added and the mixture was stirred at room temperature for 3 hours. The mixture was filtered through silica gel eluted with dichloromethane. The eluate was concentrated in vacuo to give the title compound (2.45 g).
Step D: 2-Benzyloxy-3-(2-imidazolyl)naphthalene ##STR26##
3-Benzyloxy-naphthalene-2-carboxaldehyde (90 mg, 0.34 mmol) and trimeric glyoxal dihydrate (210 mg, 1.02 mmol) were dissolved in 10 ml methanol. The solution was vigorously stirred as concentrated ammonium hydroxide (2 ml) was then slowly added. After 16 hours, the solution was concentrated in vacuo. The residue was eluted with 10% ethyl acetate in hexane through a pad of silica gel to give the title compound (62 mgs).
Step E: 2-Benzyloxy-3-(1-(2-trimethylsilylethoxymethyl)-2-imidazolyl)-naphthalene ##STR27##
To the solution of 2-benzyloxy-3-(2-imidazolyl)naphthalene (62 mgs, 0.206 mmol) in dry dimethylfonmamide was slowly added sodium hydride (5.2 mg, 0.216 mmol). After 1 hour, 2-(trimethylsilyl)ethoxymethyl chloride (SEM-Cl) (40 ul, 0.227 mmol) was added and the mixture was stirred under nitrogen for 3 hours. The solution was diluted with ethyl acetate and washed 3 times with water. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The yellow solid was eluted with 20% ethyl acetate in hexane through a pad of silica gel to give the the title compound (40 mgs).
Step F: 3 -(1 -(2-trimethylsilylethoxymethyl)-2-imidazolyl)-2-naphthol ##STR28##
2-Benzyloxy-3-(1-(2-trimethylsilylethoxymethyl)-2-imidazolyl)naphthalene (40 mg) and Pd/C (50 mg) was dissolved in 10 ml methanol. The mixture was stirred vigorously under one atmosphere of hydrogen for 2 hours. The mixture was filtered through celite filter aid, the pad washed with fresh methanol, and the combined eluents concentrated in vacuo. The residue was purified by column chromatography on silica gel eluted with 5% acetone in hexane to afford the title compound (24 mgs).
Step G: N-Allyloxycarbonyl-3-amino-5-(3-imidazolyl-2-naphthyloxy)-4-oxopentanoic acid, t-butyl ester ##STR29##
Potassium carbonate (10 mg, 0.071 mmol) and 3-(1-(2-trimethylsilylethoxymethyl)-2-imidazolyl)-2-naphthol (24 mg, 0.071 mmol) were stirred in dimethylformamide (5 ml) under nitrogen for 5 minutes. N-Allyloxycarbonyl-3-amino-5-bromo-4-oxopentanoic acid, t-butyl ester (25 mg, 0.071 mmol) was then added and the mixture was stirred for 16 hours at room temperature under nitrogen atmosphere. The mixture was diluted with ethyl acetate and was successively washed three times with saturated aqueous sodium carbonate solution. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The yellow oil was purified by column chromatography on silica gel eluted with 20% t-butyl methyl ether in hexane to give the title compound (22 mgs).
Step H: N-Allyloxycarbonyl-3-amino-5-(3-imidazolyl-2-naphthyloxy)-4-oxopentanoic acid ##STR30##
N-Allyloxycarbonyl-3-amino-5-(3 -imidazolyl-2-naphthyloxy)-4-oxopentanoic acid, t-butyl ester (22 mg, 0.0360 mmol) was dissolved in dichloromethane (8 ml) and trifluoroacetic acid (8 ml) under nitrogen. After 15 minutes, the solution was concentrated in vacuo to afford the title compound (15 mg): 1 H NMR (400 MHz, CD 3 OD) δ8.45 (1H, s), 7.85 (1H, d), 7.78 (1H, d), 7.50 (2H, m), 7.41 (3H, m), 5.50 (1H, m), 5.15-5.38 (4H, m), 4.71(1H, m), 4.60 (2H, m); mass spectrum: m/e M+1 (424.3), 394.5, 172.1, 119.1, 98.1, 86.1.
EXAMPLE 11
N-(N-Acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alaninyl)-3-amino-5-phenoxy-4-oxopentanoic acid ##STR31## Step A: N-(N-Acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alaninyl)-3-amino-4-oxo-5-phenoxy-pentanoic acid, t-butyl ester ##STR32##
To a solution of N-allyloxycarbonyl-3-amino-4-oxo-5-phenoxy-pentanoic acid, t-butyl ester (from Step C, Example 1) (86 mg, 0.24 mmol) in a 1:1 mixture of dichloromethane:dimethylformamide (6 ml) was added N-acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alanine (87 mg, 0.26 mmol), N-hydroxybenztriazole (38 mg, 0.28 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (50 mg, 0.26 mmol) and bis(triphenylphosphine) palladium(II) chloride (10 mg). To the stirred mixture, tributyltin hydride (76 ul, 0.28 mmol) was added dropwise. After 16 hours, the mixture was diluted with ethyl acetate and successively washed with 2N hydrochloric acid and saturated sodium bicarbonate solution. The solution was dried over anhydrous sodium sulfate and the solvent was reduced in vacuo. The product was purified by flash column chromatography on silica gel eluted with 5% methanol in dichloromethane to give the title compound. 1 H NMR (CD 3 OD) δ7.25 (2H, t), 7.05 (2H, m), 6.95 (3H, m), 6.66 (2H, m), 5.0 (2H, m), 4.75 (1H, tt), 4.55 (1H, m), 4.32 (1H, m), 4.15 (1H, m), 3.1-2.6 (4H, complex), 2.05 (1H, m), 1.98 (3H, ss), 1.42 (9H, s), 1,37 (3H, m), 0.95 (9H, m).
Step B: N-(N-Acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alaninyl)-3-amino-4-oxo-5-phenoxy-pentanoic acid ##STR33##
N-(N-Acetyl-(L)-tyrosinyl-(L)-valinyl-(L)-alaninyl)-3-amino-4-oxo-5-phenoxy-pentanoic acid, t-butyl ester (56 mg, 0.086 mmol) was dissolved in a 1:1 mixture of dichloromethane and trifloroacetic acid (20 ml). The mixture was stirred for 15 minutes and then the solvent was reduced in vacuo to afford the title compound. 1 H NMR (CD 3 OD), δ7.25 (2H, m), 7.05 (2H, m), 6.95 (3H, m), 6.7 (2H, m), 5.0 (2H, m), 4.72 (1H, tt) 4.58 (1H, m), 4.3 (1H, m), 4.15 (1H, m), 3.1-2.7 (4H, complex), 2.03 (1H, m), 1.89 (3H, m), 1.37 (3H, m), 0.97 (9H, m); mass spectrum: m/e 636.9 (M+K) + , 599.4 (M+1) + , 545.5, 393.8, 375.9, 304.9, 294.9, 205.7, 177.7.
By following the procedures described in Example 11, Examples 12-14 may be prepared:
EXAMPLE 12
N-(N-Carbobenzyloxy-(L)-valinyl-(L)-alaninyl)-3 -amino-5 -(3 -amino-carbonyl-naphthyl-2-oxy)-4-oxo-pentanoic acid, triethylamine salt ##STR34## 1 H NMR (CD 3 OD) δ7.84 (2H, m), 7.6-7.2 (8H, m), 5.50-5.15 (2H, m), 5.08 (2H, br s), 4.74 (1H, m), 4.40 (1H, m), 3.90 (1H, m), 2.98 (6H, q), 2.90-2.65 (2H, m), 2.08 (1H, br m), 1.41 (3H, d), 1.20 (9H, t), 0.93 (6H, m).
EXAMPLE 13
N-(N-Carbobenzyloxy-(L)-valinyl-(L)-prolinyl)-3-amino-5-(3-amino-carbonyl-naphthyl-2-oxy)-4-oxo-petanoic acid ##STR35## 1 H NMR (CD 3 OD) δ7.87 (2H, m), 7.66 (2H, m), 7.55 (2H, m), 7.49-7.25 (5H, m), 5.40, 5.20 (2H, ABq), 5.08 (2H, br s), 4.63, 4.45 (1H, t), 4.30, 4.11 (1H, m), 3.90, 3.70 (1H, br m), 3.11-2.80 (2H, m), 2.26 (1H, br m), 2.17-1.80 (2H, br m), 1.08-0.84 (6H, m), 0.80 (2H, d), 0.68 (2H, d).
EXAMPLE 14
N-(2-indoloyl)-3-amino-5-(3-aminocarbonyl-naphthyl-2-oxy)-4-oxo-pentanoic acid ##STR36## 1 H NMR (CD 3 OD) δ7.85-7.0 (1 1H, m), 5.33 (2H, ABq), 5.15 (1H, t), 3.18, 2.95 (2H, dd).
EXAMPLE 15
Inhibition of Interleukin-1β Converting Enzyme (ICE).
A fluorometric assay used to evaluate the inhibition of interleukin-1β converting enzyme (ICE) hydrolysis of a peptide substrate (Ac-Tyr-Val-Ala-Asp-AMC) by the compounds described in Examples 1-15 has been described in detail (N. A. Thornberry et al., Nature 1992, 356, 768-774). Briefly, liberation of AMC (aminomethylcoumarin) from the substrate was monitored continuously in a spectrofluorometer using an excitation wavelength of 380 nm and an emission wavelength of 460 nm. Details for determining kinetic constants for reversible and irreversible inhibition are described (N. A. Thomberry et al., Biochemistry 1994, 33, 3934-3940).
Inhibition of Interleukin-1β Converting Enzyme (ICE) by Examples 1-14
______________________________________Example Ki k.sub.onNo. (μM) (± S.E.) (M.sup.-1 s.sup.-1) (± S.E.)______________________________________1 3.5 (0.6)2 9.5 (2.)3 5.0 (1.)4 0.3 (0.1)5 0.5 (0.1)6 0.62 (0.1) 4500 (900)7 1.2 (0.2)8 2.6 (0.5)9 0.52 (0.1) 1000 (200)10 0.09 (0.02) 12,000 (2,400)11 0.003 (0.0005)12 430,000 (86,000)13 340,000 (68,000)14 390 (78)______________________________________ | This invention relates to substituted ketone derivatives of formula (I) useful in the treatment of inflammation in lung, central nervous system, kidney, joints, endocardium, pericardium, eyes, ears, skin, gastrointestinal tract and urogenital system. More particularly, this invention relates to substituted ketone drivatives that are useful inhibitors of interleukin-1β converting enzyme (ICE). Interleukin-1β converting enzyme (ICE) has been identified as the enzyme responsible for converting precursor interleukin-1β (IL-1β) to biologically active IL-1β. | 2 |
[0001] This application is a continuation of and claims priority from U.S. Provisional Application No. 62/167,864 filed on May 28, 2015, entitled ‘Power Compaction Method’(JAF001/PRO), which are all incorporated herein by reference.
FIELD OF TECHNOLOGY
[0002] This disclosure relates generally to a method of Direct Power Compaction (DPC). In one example embodiment to methods, apparatus, and systems to compact loose ground by vibration and compaction of H piles driven by vibrators (vibro-hammer or pile driver). The DPC method is an efficient and highly economical technique for densifying loose soils. In the procedure piles, with an innovative H pattern structure, are driven in the ground using a combination of downward and vibratory force to move particles of the looses oil closer together and reduce the voids between them. Subsequent backfilling and vibration at the H-pile sites achieves the highest density possible and provides for an improved ground soil structure and load bearing capacity.
BACKGROUND
[0003] Because of the shortage of usable land in industrial areas, especially along waterfront sites, there has been a recent trend towards building large industrial complexes, such as power plants, steel mills, and shipyards on landfill sites or other sites with a loose top soil or soil layer. Additionally, there are several projects presently being planned for construction of large intercontinental airports on landfill sites along the coasts of the United States and the Great Lakes, as well as other sites along other lakes, oceans and rivers around the world.
[0004] In conventional landfill construction projects, the fill is generally provided by depositing relatively solid dry materials along the ocean or water bed, or in the case of swamp land, depositing clean dry fill along the swamp until a firm foundation had been established. Due to the enormous expense of trucking or transporting in fill, and the time and material necessary, the costs involved for conventional land filling have become almost prohibitive when compared to the actual costs of the buildings and facilities constructed on the filled areas, alternative locations and the projected revenue from building in new locations. Thus, there is a need for an invention that converts location specific sub-par land fill or loose soil areas into usable land.
[0005] Recently, new techniques of land filling have been developed involving the hydraulic sand filling of swampy or underwater sites. Generally, this method uses slurry of earth and water from a nearby ocean or lakebed that is hydraulically pumped through a large pipe to the fill site. The slurry is deposited on the fill site and the water drains away, depositing the solid material. With this method it is possible to simultaneously dredge the adjacent river or ocean bed while using the fill area as a depository for the dredged material, of which is a markedly efficient process.
[0006] When hydraulic landfill is used, the material, which is generally granular in nature, must first be compacted prior to commencing any construction thereon. This fill can be compacted by allowing the sand or loose soil to naturally settle over a sufficiently long period of time, usually a matter of months or years, depending on the degree of compaction needed, which in turn is dependent upon the type of material and the weight of any contemplated construction. Alternatively, mechanical means can be used to force the water out of the sand thereby achieving compaction. Generally, this involves large rolling drums, which are rolled back and forth over the material, compacting it as it is deposited of which the rolling drums method, among other prior art methods, takes time, and as mentioned below, are sometimes unfeasible due to environmental circumstances, cost limitations or space limitations.
[0007] When hydraulic landfill is used, continual mechanical compaction is sometimes impossible because of the high fluid consistency of the fill immediately after it is deposited. Even when sufficient drainage has occurred, rolling is time consuming and generally ineffective for sufficient compaction at substantial depths. Natural settlement is unsatisfactory because of the amount of time necessary during which no construction can take place.
[0008] Because hydraulic landfill projects will often require use of up to 20 or 30 feet of fill to form a sufficient base for a foundation, it is necessary that the compaction be uniformly achieved to substantial depths. This becomes especially important in situations where large facilities are to be subsequently constructed. Pounding or rolling the surface to effect compaction will not provide a sufficient degree of compaction more than a few feet below the surface and it becomes necessary to have some sort of soil penetrating device to compact the soil lower down.
[0009] Prior soil compaction systems applicable to hydraulically filled areas and which provide sufficiently deep penetration have employed one of the varying types of penetrating torpedo-type devices which are solid in nature and are lowered down through the soil to some depth. Once lowered, the particular device is set into vibration by a rotating eccentric or other appropriate means, thereby compacting the soil. These prior devices have proven unsatisfactory for certain applications in that they require a separate means for forcing them to a lowered position in the ground, and the hole through which the device is lowered and raised must be back- filled with uncompact fill, once the device is with- drawn.
[0010] It is therefore an object of this invention to provide a device for vibration-compacting a loose ground capable of reducing construction cost by simultaneously improving the ground in a wide range by rod compaction method. Another object of the invention is to provide a method of compacting soil or other granular materials that will provide a relatively high degree of compaction. Another object of the invention is to provide a method of compacting soil or other granular material that will provide a high degree of compaction to relatively large depths. Another object of the invention is to provide a method of compacting soil or other granular material that will not require additional material to backfill holes through which the compacting device is lowered into the soil. Another object of the invention is to provide a method of compacting soil or other granular material, which can be operated, with a minimum expenditure of time and manpower as the invention will provide for an ability to compact soil over a larger footprint than prior art. Another object of the invention is to provide an apparatus for the compaction of soil or other granular materials.
SUMMARY
[0011] Disclosed are methods, apparatus, and systems to provide a device for vibration-compacting a loose soil ground via Direct Power Compaction (DPC). As disclosed herein, a device for vibration-compacting a loose soil ground may be formed by multiple parts. A crane or other structure ay provide a fixed point or a main cable of which the present invention may be attached to. A shock absorber or damper may be fixed to the main cable, of which a vibrator device such as a vibro-hammer or pile driver may be secured under. A rod mounting plate of which may transmit vibration and force to a multitude of rods or piles, may be attached to the bottom output of the vibrator device. A plurality of rods may be vertically fixed to the lower surface of the plate using adapters at specified intervals, such as in a preferred embodiment, four rods may be attached in an H pattern. The vibrator device may be connected to the main wire rope of a crawler crane as to be vertically moved integrally with the rod mounting beam and the rod. The device may also enlist a holding plate position at the bottom section of the rods, wherein the holding plate comprises of a box metal holding body with loosely fitting holes, allowing the vertical movement of the rods through the holes or recesses in the holding plate and maintaining the interval between the rods constant. Each rod may be loosely fitted through the loose insertion hole of each rod formed on the holding body. The holding body may be connected to the auxiliary wire rope of the crawler crane for stability and strength. The compaction strength control also may be possible on an as-needed basis by controlling driving pitch, force and the cycle of compaction, and so forth.
[0012] In this aspect, the method may comprise using the above described H-piles or rods. Vibratory energy may be delivered directly into the ground. The typical configuration may be a quadruple axial DPC rig with a vibro-hammer at the top of each pile wherein the quadruple rods may be position in an H pattern. The extent of the treatment required for optimal densification or compaction may depend on the ground or soil content, grain size/geometry and other factors such as materials, of the soil being compacted. The best results may be realized in sandy soils with low fines content. For loose sands/granular soils, the DPC method yields may result equivalent to those of other densifications/compaction methods, but the simplicity and speed of the DPC method may make it the most efficient and economical solution for improvement of sandy soils.
[0013] Another aspect of the disclosure may include a system in which H shaped piles may first be driven into the ground through a combination of the structure such as the crane lowering the present invention such that the rods may penetrate into the ground along with the effects of the vibrating device, of which enables penetration into the ground, but also vibration of the surrounding soil, helping to minimize the void between the soil materials and compact the soil.. When the rods reach the required depth, they may then be pulled up by a distance and inserted again by a distance. The ground may be compacted by the vibration of the vibro-hammer transmitting through the rods while the repetition of driving and withdrawing the rods is repeated. As the area under the rods becomes more compacted, the rods may withdraw more, and drive to a lesser depth every cycle, thus retreating the rods over cycles as the ground becomes compacted, until the rods are retreated to ground level and the entirety of the ground site is compacted. The above process may be executed while backfilling supply sand or another material, such as gravel at the ground surface hence the ground surface would not be lowered by the compaction effect. The lengths of pulling up distance and of the driving in distance may be calculated from the void ratio on the original ground of n value and the design ratio of n value, while the lengths may determine the driving pitch.
[0014] Yet another aspect of the disclosure may include an apparatus for the compaction of granular material comprising an elongated hollow member that is set into vibration by a constant vibrating hammer, the member and hammer being suspended from a crane-like apparatus. While in constant vibration, the member may be lowered into the ground in a substantially vertical position to a predetermined depth, maintained in the lowered position for a period of time, and then withdrawn. The same procedure may be repeated at a plurality of locations.
[0015] In this aspect, such apparatus, and systems may comprise methods to implement the methods described heretofore.
[0016] The methods and systems disclosed herein may be implemented in any means for achieving various aspects. Other features will be apparent from the accompanying drawings and from the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Example embodiments are illustrated by way of example and are not limited to the figures of the accompanying drawings, in which, like references indicate similar elements.
[0018] FIG. 1A-1F are component and detailed representations of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0019] FIG. 2 is an upward facing vertical schematic view of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0020] FIG. 3 is component side view of the present invention direct power compacting rig with vibration and driving device mounted on a crane, according to one or more embodiments.
[0021] FIG. 4 shows a step-by-step illustration of the compacting method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0022] FIG. 5 is a detailed side view of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0023] FIG. 6 shows a detailed side view of a construction method of the direct power compacting rig with vibration and driving device, according to one or more embodiments..
[0024] FIG. 7 shows a detailed side view of a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0025] FIG. 8 shows a detailed side view a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0026] FIG. 9 shows a detailed side view a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0027] FIG. 10 shows a graphical representation of a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0028] FIG. 11 shows a graphical representation of a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments.
[0029] Other features of the present embodiments will be apparent from the accompanying drawings and from the detailed description that follows.
DETAILED DESCRIPTION
[0030] Disclosed are methods, apparatus, and systems to compact loose ground soil by vibration and compaction of H rods or piles driven by a vibration and driving device such as a vibro-hammer or other apparatus such as a pile driver. Although the present embodiments have been described with reference to specific example embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader spirit and scope of the various embodiments. In addition, the components shown in the figures, their connections, couples, and relationships, and their functions, are meant to be exemplary only, and are not meant to limit the embodiments described herein.
[0031] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a direct power compacting rig.
[0032] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a direct power compacting rig with one or more rods to be driven into the ground for compaction or solidification purposes.
[0033] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a direct power compacting rig with one or more rods to be driven into the ground for compaction or solidification purposes and a vibration and driving device such as a vibro-hammer connected to the rods, such that the vibro hammer may vibrate and transmit vibration and force into the ground soil as the rods move to a specific depth.
[0034] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a direct power compacting rig with one or more rods to be driven into the ground for compaction or solidification purposes and attached to the main cable of a crane. It is noted that the crane maybe substituted for any other structure or machine such as a building, scaffolding structure, etc. The crane or structure may be moveable or mobile, and may be mounted or placed on the ground, or also may be water borne such as on a boat or barge, or moveable by any other method. As well as this it may be noted that the crane or other structure may move the present invention rig in any x, y or z direction in respect to the ground plane so that the point where work is done may be changed by the operator.
[0035] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibration and driving device such a s vibro-hammer attached or connected to the main wire cable of a crane or other structure of which in a preferred embodiment, the majority of the rig weight may be placed on the main cable. It is noted that in other embodiments, for other structures, multiple cables or ropes may be used, and in some embodiments, solid mounting points may be preferable, such as a solid mount to an articulating crane structure etc. The structure or crane may be water based such as on a floating barge or ship or land based such as a crawler crane or overhead crane. The structure or crane may be stationery, moving, rotating or of any type, either through the movement of the crane or structure mechanism, such as a tilting or rotating crane structure, or by moving the structure or crane itself to position the present invention over the intended compaction sites.
[0036] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibration and driving device such a s vibro-hammer attached or connected to the main wire cable of a crane or other structure of which in a preferred embodiment, the majority of the rig weight may be placed on the main cable and of which the main cable, or cables may lower the rig, and driving rods into the ground, such that either through the weight of the rig, the weight of the rig and the effects of the vibration and driving device, or through the use of other aides in addition, the rods may penetrate into the ground soil to a specific depth. It is noted that the vibration and forces of the rods may be transmitted into the ground, as is known in the art, the loose ground soil, or ground soil may compact, as the force and vibration reduced the voids between the particles of the soil, and thus the soil becomes improved. It is also noted that the force may radiate out from the rods, such that the rods may effect an immediate and proximate area of which may be compacted. Some of these methods may be termed as Direct Power Compaction Method (DPC), but may be among others enabled by the device.
[0037] The crane or structure of which the present invention vibration and driving rig is mounted on may raise and lower the rig through any method, such as on a typical crane, wherein the main cable is retracted via pulleys and motors. Other methods may include raising and lowering the boom of the crane and in turn raising and lowering the rig, a hydraulic ram raising and lower the rig, as well as any other methods
[0038] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibration and driving device attached or connected to a structure or crane of which in between the aforementioned connection between the vibration and driving device and the main wire or mount to the crane or structure, is a shock absorber or vibration reduction device such as a damper shock or shock system. The shock absorber may be connected to the main wire cable or other structure by a hook and loop method, or through any other method. The shock absorbing device may be mounted to the vibration and driving device through any mounting method such as solid mount between the shock absorber and vibration and driving device. In some other embodiments, the connection between the shock absorber and the vibration and driving device may be a movable or pivotable structure such as a hook and eye. The shock absorber or dampening device may be a commonly found industrial damper or shock absorber such as a hydraulic shock absorber. In other embodiments, the damper may be coil spring based, or any other type of absorber or dampener. The shock absorber or dampener may be an active element, including sensor and servos or other pieces, such as using sensors and magnetorheological dampers or other shocks of which can control the amount of vibration travelling from the vibro-hammer and associated rods to the crane or main cable. Additionally, the dampener may provide for active dampening such as a sway control device such as a tuned mass damper or active mass dampener to reduce sway of the device. Also, the shock absorber may also provide for a fundamental absorbing ability for when the entire H-beam structure, vibration and driving device and structure are lowered and raised to reduce shock to the structure, crane and associated devices and structures.
[0039] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibrating device such as a vibro-hammer or pile driver of which is connected to the shock absorber through any method, and of which in turn is connected to the crane main cable through any method.
[0040] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibrating device such as a vibro-hammeror pile driver of which relates to rod compaction equipment. The vibrating or driving device such as the vibro-hammer or pile driver may solidify loose soil such as sandy soil as the rods or piles are impacted and inserted into the ground at the compaction site.
[0041] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibrating or driving device such as a vibro-hammeror pile driver and of which may use magnetic, hydraulic, electrical, steam, diesel or any other lifting or vibrating mechanism. The vibro-hammer may provide for a weight that raises and then is dropped or actively lowered in addition to the force of gravity, such that the hammer pushes a pile, rod or other mechanism or structure into the ground, transferring force into the soil or ground, and thus impacting and compressing the ground to solidify, compact or strengthen the soil or ground. This may be done at any frequency such as 1 time per a second (1 Hz), many times per a second (>1 Hz), or 1 time over many seconds (<1 Hz).
[0042] In another embodiment, the present invention may include an apparatus for the compaction of granular material comprising an elongated hollow member that is set into vibration by a constant vibrating hammer, the member and hammer being suspended from a crane-like apparatus. While in constant vibration, the member may be lowered into the ground in a substantially vertical position to a predetermined depth, maintained in the lowered position for a period of time, and then withdrawn. The same procedure may be repeated at a plurality of locations.
[0043] The mechanism for the vibratory hammer may be a vertical travel lead system, hydraulic hammer, hydraulic press in, vibratory like driver/ extractor, or piling rig. The preferred embodiment may use a vibratory pile driver/ extractor of which contains a system of counter-rotating weights, powered by hydraulic or electric motors, and designed in such a way that horizontal vibrations cancel out, while vertical vibrations are transmitted into the pile. Vibratory hammers can either drive in or extract a pile. Additionally, any type of hammers may be used with several different vibration rates, such as 1200 vibrations per minute to 2400 vibrations per minute, or over any range. The vibration rate may be chosen based on soil conditions at the site and other factors such as power requirements and purchase price of the equipment and needs of the operator.
[0044] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibro-hammer, of which is connected to a vibration dampener or shock absorber, of which is connected to or hangs from a crane main cable. The vibro-hammer may then pressure, drive or vibrate, such as driving a force into a piles or rods of which then may transfer force into the ground. The present invention may provide the ability to drive multiple rods into the ground through the use of an adapter plate and adapters. The adapter plate may connect through any means to the output of the vibro-hammer and transfer force to connected rods or piles. In a preferred embodiment, this may be four or more rods.
[0045] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may describe a vibration and driving device of which is connected to a vibration dampener or shock absorber, of which is connected to or hangs from a crane main cable. The vibration and driving device may then pressure, drive or vibrate into a connecting plate, of which provides a provision to mount at least one, and preferably four rods, pile or H beams. The plate may be directly connected to the vibration and driving device, through a direct connection such as with a friction fit or interlocking structures with bolts, welds or by any other method such that a force travels from the vibration and driving device uniformly into the plate and uniformly distributes to the rods or piles. The plate may then transfer the force uniformly through the plate and into the rods, of which may typically be a hollow cylindrical steel pipe. Depending on the particular vibration and driving device and coupling arrangement used, the vibro-hammer can be attached to plate and to the pipe at any position that will enable it to set the pipes or rods into vibration such that they may impact and compact the ground soil. The plate may be of any design, and may be structured as a square plate with a length and width dimension, such that the rods may be mounted at a particular distance from each other, and a height dimension such the plate is strong enough to withstand the impact forces of the vibration and driving device and ground soil. The plate may be made of any material, wherein the material suits the demands of the system for strength, cost and weight and may be of any method such as steel or a honeycomb structure, wherein the structure may be made of any material that can transfer the forces to the rods or piles.
[0046] In one or more embodiments, which may be in addition to the above and below embodiments, the plate, as aforementioned, may be connected to up to four rods, piles or beams of which may transfer force into the ground and compact the loose soil such that the loose soil may be solidified or compacted for a purpose.
[0047] In one or more embodiments, which may be in addition to the above and below embodiments, the rods or beams may be made of any material such as steel, iron, aluminum or any other metal, alloy, composite, or mixture of materials. The beams or rods may be a single piece design, or multi piece design, wherein they may be made of different elements, welded or connected together with each section built to a purpose, such as the bottom driving end made of a stronger or harder material with a wider base such that the surface area of the soil contacting the driver is increased and the strength of the material reduces wear. The middle rod portion may be may be made of a relatively weaker material compared to the impact end, wherein the material still tolerates the forces of the impact, but in the interest of cost, weight and other reasons, does not need to have the strength the bottom impact portion has to withstand contact with the ground or soil. The driving end of each rod may be of any design, such as a wider flat base, or in some circumstances, a cone shape to drive through hard soil layers. These ends may be interchangeable or replaceable to reduce downtime and cost for wear or changing conditions or needs.
[0048] In one or more embodiments, which may be in addition to the above and below embodiments, the rod or pile may be shaped in a fashion wherein the rod, pile or driver fits within a particular dimension or is designed for a purpose such as for shipping or transporting.
[0049] In one or more embodiments, which may be in addition to the above and below embodiments, the rod is shaped in a fashion wherein the rod, pile or driver is structured in particular dimensions to provide for a strength, weight and cost restraint.
[0050] In one or more embodiments, which may be in addition to the above and below embodiments wherein the rods, piles or driver are positioned on the plate in a patterned fashion, and wherein the preferred embodiment may have four rods in a square or H pattern, and wherein each rod is positioned by a set distance from one another.
[0051] In one or more embodiments, which may be in addition to the above and below embodiments, wherein above the ground and surrounding a portion of the lower section of the rods or driver, a holding plate or catch fork is designed and structured, wherein the rods travel through recesses or loosely fitting holes in the holding plate or catch fork such that the rods do not push down or transmit force into or on the holding plate or catch fork, but that the catch fork provides lateral stability to the rods, so that the rods are driven straight into the ground. The catch fork or holding plate may be made of any material, and may provide for friction reduction sleeves where the rods go through the holding plate or catch fork. The catch fork may be connected or otherwise structured or connected to the crane or structure on which the rig is mounted so that the catch fork is stationary in terms of the crane and ground plane. The holding plate or catch fork may also be hung or otherwise supported via auxiliary wires, cables or rope to the boom of the crane or other places on the crane. In one or more embodiments, which may be in addition to the above and below embodiments, the catch fork may be formed in a substantially box-type or any other shape or configuration wherein a rod mounting beam that may be fixed vertically at regular interval or, a plurality of rods may be vertically fixed to the lower surface of the device at specified intervals. Additionally the catch fork or rod mounting beam may be connected to the vibration and driving device and mounting plate. The device also may comprise of a box metal holding body allowing the vertical movement of the rod by maintaining the interval between the rods constant. Each rod may be loosely fitted through an insertion hole or recess in the holding body or catch fork. The holding body may be connected to the auxiliary wire rope of the crane.
[0052] In one or more embodiments, which may be in addition to the above and below embodiments, there also may be a transducer or damper of which may help position, limit or reduce unwanted force transmitted from the catch fork to the crane or structure. The transducer may be of any type such as foam, rubber, coil spring, or any other type of dampening such as a hydraulic damper. The transducer may also move the catch folk to direct the entire rig along with the crane boom or reposition the impact site.
[0053] In one or more embodiments, which may be in addition to the above and below embodiments, the present invention may provide a method to impact the ground soil in any pattern. The pattern may be determined on the needs or purpose of the project and the soil. An embodiment may have a pattern that is based on the soil shape or soil survey wherein specific areas were found to need compaction. The pattern may be to specific distances and depths as set by the operator, and the crane and catch fork may move or position the rods or piles to the specific impact site or sites.
[0054] In some embodiments, which may be in addition to the above and below embodiments, the present invention may provide a method to impact the ground soil with rods or piles. The piles or rods may be inserted to a specific depth in a down stroke by the force provided by the driver or vibration and driving device and the weight of the rig, among other possible sources, which in turn compacts the soil as the rods are driven into the soil. The rods are then retracted to a specific depth in an upstroke. The rods, then may be again inserted or forced down to another specific depth in a down stroke, and in turn compacting or solidifying the soil directly under the rods or piles, as well as the soil surrounding the rods and impact areas. The rods or piles may then be retracted to another specific depth in another upstroke, and then reinserted to another depth in another down stroke. This pattern may be repeated, such that the ground soil may be solidified and compacted to fit the needs of the operator.
[0055] It is noted that in the above cycle, the rods may be inserted first to the lowest depth in a down stroke, and the subsequent upstroke may be to any depth above the lowest depth. The then, subsequent re insertion down stroke, may be higher than the initial lowest depth, as the soil compacts and solidifies below the rod or pile. The subsequent retraction upstrokes and insertion down strokes, may provide for less and less depth, as over the cycles, the soil becomes compacted at less and less depth, and as such the rod or pile compacts soil at a less and less depth. As such, the rod or pile compacts the soil along the entire distance or depth of the initial insertion, until all the soil is compacted from the initial depth, and surrounding area, to the ground level and surrounding area. It is noted that the depths of the upstroke and down stroke, while above described in be in a preferred embodiment, may also provide for changing down stroke depths, of which may be larger than earlier down strokes. As well as this, the upstrokes may or may not retreat the rods out of the soil or ground completely.
[0056] In some embodiments, in addition to the above and below embodiments a material, such as additional soil, or other material, such as solidification material, or other types of soil with desired properties, maybe introduced to the impact site and bores. The material may be introduced as backfill as the rod, driver or pile forces or compacts the existing soil, or may provide for additional material to be compacted, either to provide for more area, or provide or alter the soil with additional or desired characteristics, such as to reduce moisture content for a specific compacted area, or finer or larger grain soil depending on the application. The additional material may be provided through any method, such as a backhoe or tractor, or may be piped or fed through a pressurized line such as in the introduction of concrete. In a preferred embodiment the material is simply pushed into the impact site and bore by a tractor as the piles or rods are retracted, such that the material may provide for backfill as the soil is compacted in a subsequent down stroke, and as such keep the ground plane at the initial height or provide for additional material for compaction.
[0057] An auxiliary note is made that the present invention vibration and driving rig may be power by any means, such as a diesel generator, hydraulic system, or electric system as examples. Also, control of the device may be through any means, whether hydraulic, electric and electronic, or lever based, at the rig site, remotely, over a network, on the crane or from and by any means. The present invention may also include sensors, servos, or other devices in which measurements, effects and surveys may be completed, prior, during or after the process and of which allows the device to manually or automatically be adjusted in any manner. This includes printed readouts, display screens, notification monitors, or any user interface, or computer interface system, of which may automatically or manually require input and adjustment depending on the application.
[0058] FIG. 1A-1F are component and detailed representations of the present invention vibration rig, according to one or more embodiments.
[0059] FIG. 1A is a front view of the present invention direct power compacting rig with a vibration and driving device such as a vibro-hammer. The rig in a preferred embodiment may be connected or hanging from the main cable of a crane over the intended impaction point. A shock absorber or damper 105 may be suspended from the main crane cable wherein, the rig may be suspended below. Attached to the shock absorber or damper 105 , through any means, may be the vibro-hammer 104 of which may be of any design or structure as aforementioned. The hammer may connect directly to the distribution plate 103 , of which may transfer force to the four adapters 102 a , 102 b , 102 c and 102 d , of which 102 a and 102 b are visible in FIG. 1A . These adapters may transmit force into the rods 101 a , 101 b , 101 c , and 101 d , of which 101 a and 101 b are visible in FIG. 1A . These rods may vibrate or move and impact the ground at a specific force and Hz provided by the vibro-hammer, of which may provide for compaction, vibration and ground improvement.
[0060] FIG. 1B provides a rear view of the present invention, which is the same structure of that in front view FIG. 1A . FIG. 1B provides for a view of the adapters 102 c and 102 b and rods 101 c and 101 d of which were not visible in FIG. 1A .
[0061] FIG. 1C provides for a component representation of the present invention direct power compacting rig with vibro-hammer 101 , wherein the plate 103 is visible and connects to the adapters 102 a , 102 b , 102 c , and 102 d of which taper to connect to the rods 101 a , 101 b , 101 c and 101 d.
[0062] FIG. 1D provides for a detail front view of the direct power compacting rig with vibro-hammer 101 of which is the same view as FIG. 1A , but with details of which are missing in the component view.
[0063] FIG. 1E provides the same rear view of the present invention direct power compacting rig with vibro-hammer 101 as FIG. 1B , but further provides details of which are missing in the component view.
[0064] FIG. 1F provides the same bottom view as FIG. 1C but provides further details missing in the component view.
[0065] FIG. 2 is a downward facing vertical schematic view of the present invention direct power compacting rig impact sites, according to one or more embodiments. FIG. 2 provides a preferred embodiment of a pattern of four group impact points, each with four individual impact sites performed by one rig. Site 205 a provides for distance between the four individual impact sites in the y-axis as 282 a and the x-axis as 282 b . The individual impact sites pacing corresponds to the distance the rods are presented and patterned on the rig. The distance may be of any measurement that is suitable to the conditions and needs and may be designed as such. FIG. 2 also presents three other group impact sites of which each have four individual impact sites. The spacing between the group impact sites is dictated the rig's movement, and the grouped impact sites may be measured by distances in the y axis by a distance 281 a , as exampled by between sites 205 a and 205 c and in the x axis by 281 b , as exampled between impact sites 205 c and 205 d . Each group of four individual impact sites may be performed at once by a rig with four rods or drivers. It is also noted that other patterns and schematics may be used wherein there is a different amount of rods or drivers or necessitated by the terrain or soil.
[0066] FIG. 3 is component side view of the present invention direct power compacting rig with vibration and driving device such as a vibro-hammer mounted on a crane, according to one or more embodiments. FIG. 3 presents a crane 315 of which the DPC rig 301 is mounted on. The crane 315 may have a main cable 320 of which may be made of steel braided cable, or any other material. The cable 320 may connect to a shock absorber 305 , of which may connect to the vibration and driving device or vibro-hammer 304 . The hammer may then connect to the adapting plate 303 , of which is connected to the adapters 302 , of which the adapters are connected to the drivers or rods, of which 301 a and 302 b are in view. The rods may run in a square H-pattern formation down to the impact site 301 e . The rods upon impact may be forced or pushed by the impact from the ground, and may pivot or otherwise undesirably move in the x or z axis. Thus, a holding body or plate 306 may extend from the crane, or other structure, and of which may also be further supported by guy wires or other auxiliary cables 321 a , 321 b , and 321 c , of which may connect by any fashion to the crane or another structure and the holding plate 306 . The holding plate 306 may then provide for a recess or loose fitting hole for each respective rod to pass through, and of which the plate may limit the amount of travel the rods may be forced into at any given direction. A transducer or shock absorber 316 may limit the shock impacted into the holding plate and transferred to the crane or structure. The transducer or shock absorber 316 may also aid in the positioning of the rods or drivers and provide further strength.
[0067] FIG. 4 shows the construction method and steps of the present invention direct power compacting rig with vibro-hammer, according to one or more embodiments. FIG. 4 displays an example embodiment with simplified single rod and vibration rig in different steps 481 , 482 , 483 , 484 , 485 , 486 and 487 , of which each step is in various position of compaction. Rod and vibration rig 481 displays the first position, wherein the rod is resting on the ground prior to any work being done. Rod 482 shows the second step being completed, wherein the rod is inserted or penetrated into the ground to a specific depth in a down stroke. A sand, or other material supply may be provided, at point 471 , wherein, the sand may either be stacked around the impact site by a tractor or backhoe, such that when the rod is then later retracted in an upstroke and reinserted or driven down in a down stroke, the material may fall into the bore. It is noted that the rod in upstrokes may be retreated to a point below the ground plane, or may be retracted out of the ground completely, depending on the embodiment and needs of compaction. The introduced material, introduced by a tractor or backhoe piled around the insertion site, then may be used as a backfill to fill the ground as it is compacted so that the ground plane stays level, or may be used as compaction material by falling in the bore and under the rod completely or incompletely and subsequently compacted with the soil material. The material may also be provided through other means, such as through hoses or pipes, wherein the material may be pressured, or introduced at a specific depth. Rod 483 shows the third step completed, wherein the rod is pulled up in an upstroke by a specific distance 491 . Rod 484 shows the fourth step completed wherein the rod is inserted again in a down stroke, by a distance 492 , and wherein the rod compacts the soil with either just the existing ground soil already in the bore or with additional sand or material provided 471 . Rod 485 shows the fifth step completed wherein the rod is pulled up in an upstroke by a depth 493 . Rod 486 shows the sixth step wherein the rod is inserted again in a down stroke, wherein the rod compacts the soil either already in the bore, or with additional material 471 provided. As seen in the seventh step, the vibro-hammer and rod 487 may then be pulled up out of the ground, wherein then the ground is then fully compacted, and wherein the rig may be repositioned to another site. Waves 491 show the compaction of the rod or driver transmitted through the soil, such that the soil becomes compacted. These compaction effects may radiate as shown, but also may radiate to the sides of the rods as both the downward force of the rods is applied, as well as the vibration. The soil, being loose, may have large gaps or distance between individual particles, and the compaction may reduce these gaps, making a tighter, harder and more compact soil. The force and vibration transmitted by the vibration and driving device, and subsequently the rods, may perform the aforementioned compaction. It is noted that there may be intermediary steps between each of the aforementioned steps and the numbering is purely for example purposed. Also, it is noted that the steps may be any order and that the depths may vary due to the needs of the operator. The steps may also be repeated in any plurality and patterned, including additional steps, such as additional compaction cycles after the example sixth step and before the example seventh step.
[0068] FIG. 5 is a detailed side view of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments. FIG. 5 presents a crane 515 of which provides a main cable 506 which connects to the present invention direct power compacting rig with vibro-hammer 504 of which is connected to the adapter plate and adapters 503 , of which connects to rods 501 a and 501 b , of which impact and penetrate the ground. There may be a holding plate 506 of which may limit the movement of the rods, and of which may be connected directly or through a transducer or shock absorber to the crane 515 and further supported by guy wires 507 .
[0069] FIG. 6 shows a detailed side view of a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments. FIG. 6 shows the example step one wherein the vibration rig 601 is positioned over an impact site 691 , wherein a tractor or backhoe 670 provides sand or other material 671 to the impact site and the rods are retracted above the ground plane.
[0070] FIG. 7 shows a detailed side view of a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments. FIG. 7 shows the example step two wherein the direct power compacting rig with vibro-hammer 701 is positioned over an impact site 791 , and the rods 702 are inserted or penetrated into the ground at their full depth, or the depth necessary for the current function. A backhoe or tractor 770 may provide sand or another material 771 , of which may flow or fall into the bores, simultaneously or after the rods are inserted.
[0071] FIG. 8 shows a detailed side view a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments. FIG. 8 shows the example step three wherein the vibration rig 801 is positioned over an impact site 891 , and the rods 802 are retreated or moved to a specific higher depth than the depth in example step 2 . This may provide or create a cavity or bore 895 of which sand or another material 871 , provided by a machine 870 , may have fallen into or placed in by the operators, or of which the cavity may be filled of existing loose ground soil caved in or fallen from the walls of the cavity.
[0072] FIG. 9 shows a detailed side view a construction method of the present invention direct power compacting rig with vibration and driving device, according to one or more embodiments. FIG. 9 shows the example step four wherein the vibration rig 901 is positioned over an impact site 991 , and the rods 902 are inserted or penetrated again to a depth, of which compacts the existing ground soil and possibly the material 971 that has been introduced by a machine 970 . The re-insertion of the rods may compact the soil and material such that the soil becomes compacted and stronger. Area 995 may be represented as a compaction zone wherein the ground soil solely has become compacted, or the ground soil mixed with the material 971 may be compacted. The compaction area also may radiate out from the impact points, creating a larger area wherein the machine may have influenced and provided strength and compaction as the forces and vibration are transmitted throughout the ground. Also, the vibro-hammer at a specific Hz, may further provide positive effects in compaction that radiates throughout the ground soil and material.
[0073] FIG. 10 shows a graphical representation of a construction method of the present invention vibration and driving device, according to one or more embodiments. FIG. 10 graph the depth of the rods changing over time with example depths from a study. For instance in area 1010 , it is seen that for a given time, the rod depth increases from 0 m to 10 m. Then it is seen in area 1020 , the depth increases in an alternating fashion, providing a driving and vibrating motion of up and down strokes, which provides for compaction. For instance, arrow 1021 shows the depth change in a down stroke, while arrow 1022 provides the distance of an upstroke. With an alternating up stroke and down stroke, as the rod is retracted, the ground becomes compacted, as for each upstroke, the rod is retracted and existing or new soil or other material may fill the hole below the driver. On the subsequent down stroke, which is less than the preceding upstroke, the material may be compacted in the area below the rod or driver. The process then repeats, alternating upstrokes and down strokes, such that along the depth of the rod, the ground becomes compacted until the rod fully retreats and the entire depth has been compacted. [ 73 ] FIG. 11 shows a graphical representation of a construction method of the present invention vibration and driving rig, according to one or more embodiments. FIG. 11 provides for a study improvement of a typical use of the present invention. On the graph the x-axis provides for the SPT N-value which is a standard penetration test and good meter of ground strength and penetration resistance, wherein a higher value is considered to be stronger. The y-axis provides for an indicator of depth and soil type. The results of the study provides the black line with diamond indicators representing the penetration values for the existing unmodified soil such as gravel or sand at the respective depths marked and the grey line with square indicators representing the penetration value for the modified soil. In this example, it may be seen that the gray line with square indicators, which represents the ground soil after being modified by the present invention, may be of a higher value than that of the original soil as the SPT N-value for each specific depth and gravel type after modification was improved over the original values.
[0074] A number of embodiments have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the claimed invention. In addition, the methods depicted in the figures do not require the particular order shown, or sequential order, to achieve desirable results. In addition, other steps may be provided, or steps may be eliminated, from the described flows, and other components may be added to, or removed from, the described systems. Accordingly, other embodiments are within the scope of the following claims.
[0075] It may be appreciated that the various systems, methods, and apparatus disclosed herein may be performed in any order. The structures in the figures may be shown as distinct and communicating with only a few specific structures and not others. The structures may be merged with each other, may perform overlapping functions, and may communicate with other structures not shown to be connected in the figures. Accordingly, the specification and/or drawings may be regarded in an illustrative rather than a restrictive sense.
[0076] The structures and modules in the figures may be shown as distinct and communicating with only a few specific structures and not others. The structures may be merged with each other, may perform overlapping functions, and may communicate with other structures not shown to be connected in the figures. Accordingly, the specification and/or drawings may be regarded in an illustrative rather than a restrictive sense. | The system, method and apparatus described relates generally to a method of Direct Power Compaction (DPC). In one example embodiment to methods, apparatus, and systems to compact loose ground by vibration and compaction of H piles driven by vibrators or drivers (vibro-hammer). The DPC method is an efficient and highly economical technique for densifying loose soils. In the procedure piles, with an innovative H pattern structure, are driven in the ground using a combination of downward and vibratory force to move particles of the loose or sandy soil closer together and reduce the voids between them. Subsequent backfilling and vibration at the H-pile sites achieves the highest density possible and provides for an improvement ground soil structure and load bearing capacity. | 4 |
FIELD OF THE INVENTION
[0001] The present invention is directed towards pitch based graphite fabric or felts made from stretch broken pitch precursor yarns for use in fuel cell gas diffusion layer substrates and high thermal conductivity reinforced composites and the like.
BACKGROUND OF THE INVENTION
[0002] The use of carbonaceous material in conjunction with electron collection is well known. The function of the carbon or graphite has primarily been that of an electrical current (a currency) collector. A number of carbonaceous fiber based substrates have been proposed for fabricating gas diffusion layers (“GDLs”) in fuel cell and forming specialized reinforced plastic composites. In a first application, the carbon or graphite fibers are used to create a porous substrate exhibiting a good electrical conductivity. In a second application the fiber is used to provide high mechanical properties and if desired raise the thermal conductivity of the reinforced plastic. High in-plane and through-the-thickness thermal conductivity reinforced plastic mounting plates are desirable, for example, in electronic applications where a large amount of heat needs to be rapidly dissipated away from electronic components mounted on the plates.
[0003] Fuel cell GDLs have been fabricated from papers, felts and fabrics using a number of polyacrylonitrile (“PAN”) derived fibers. Fuel cells and other electrochemical devices are typically built from an assembly of bipolar plates, a GDL, a catalyst layer and a membrane. Such a device is shown in FIG. 1. The gas diffusion layer is also referred as membrane electrode or electrode substrate.
[0004] The fibrous GDL substrate is generally coated on one side or both sides with a carbonaceous mixture, the mixture containing fine graphite powders and various conductive fillers. A catalyst may be deposited within the porosity or at the surface of the coating.
[0005] While the GDL substrate is frequently fabricated with a PAN based paper, PAN based woven fabric or needled felt can be used. It is believed that the latter forms provide better handling ability as they have higher tensile strength than a paper media. These characteristics are essential in carrying the fibrous support during the coating operations. Several references refer to the use of PAN fiber to fabricate the GDL media. In particular, PCT Publication No.: WO 01/04980 describes the use of a low cost PAN to fabricate various forms of GDL media. In applications involving fuel cells, it is desirable that the gas diffusion layer so formed be as thin as possible. Accordingly, the fabric used in such application should be thin and have a smooth surface.
[0006] Typically, in fuel cell design, the base fabric is created by spinning yams from staple PAN filament that typically ranges in length from one to two inches. These yams are then woven into a plain weave fabric. The woven fabric is then carbonized by a heat treatment process in a nitrogen atmosphere. The now carbonized fabric is subject to a further heat treatment (at a higher temperature) to graphitize it, also in a nitrogen atmosphere. The fabric is subsequently coated with a carbonaceous mixture on which a platinum based catalyst may be deposited. Some fuel cell stack fabricators elect to apply the catalyst on the membrane.
[0007] PAN based fibers are the lowest cost carbon or graphite fibers available on the market. However, PAN fibers exhibit fairly poor electrical and thermal properties when compared with pitch based carbon or graphite fibers. Pitch derived carbon or graphite fibers exhibit electrical conductivity four to six times greater than PAN derived fibers and are a better choice than PAN fibers in a fuel cell application where superior electro-conductivity is needed to enhance overall fuel cell performance. An object of the present invention is to overcome the drawbacks of the existing forms and high cost of pitch fibers. Pitch fibers are available in costly large tow yams or in the form of chopped fibers. None of these forms are suitable for fabricating a thin flat fabric or needle felt. The smallest denier commercially available in pitch is a tow of 3850 denier, which would generate a heavy thick GDL layer. Another limitation of typical commercial pitch fiber is their high moduli which limits their forming ability. For example, it is impossible to needle punch a highly carbonized or graphitized pitch fiber. One approach to yield a suitable size yarn for weaving or a suitable web for needling a felt is to subject tows of pitch fiber in a thermoset state to a stretch breaking process.
[0008] Reinforced plastics used for heat dissipation can also benefit from the invention. In such applications, mounting plates supporting electronic components play a structural role and act as conduits to dissipate heat away from electronic components. Pitch fibers, in the form of unidirectional fiber lay-up, sheet molding compound, paper and fabrics, are already used in these applications. The textile forms derived from the invention will help provide the electronics industry with lower cost thin fabric or needled punch felt that exhibits high through-the-thickness thermal conductivity. Following graphitization of the thermoset pitch textile, plates or other geometries may be readily fabricated into a rigid component through densification with thermoset or thermoplastic polymers.
SUMMARY OF THE INVENTION
[0009] It is therefore a principal object of the invention to provide for the use of pitch precursor graphite fibers in unique forms in increased applications, including fuel cells and in high thermal conductivity reinforced composites.
[0010] It is a further object of the invention to provide for the use of pitch precursor graphite fibers in unique forms, which may be woven into relatively thin fabrics or needle punched in thin mats.
[0011] It is a yet further object of the invention to provide for such fiber forms which are relatively inexpensive.
[0012] A further object of the invention is to provide for a fabric or a mat made from pitch precursor graphite fiber in unique forms having superior thermal and electrical conductivity.
[0013] A further object of the invention is to provide for a fabric or a mat made from a blend of pitch precursor graphite fiber in unique forms and PAN based graphite fiber.
[0014] These and other objects and advantages are provided by the present invention. In this regard the present invention takes pitch precursor yarn at the thermoset stage, which is prior to carbonization or graphitization. This yam is relatively thick, i.e. 3850 denier or more. The yam is then stretch broken by stretch breaking. Stretch breaking involves a process that starts with higher denier yams and reduces them to lower denier yams whereby the multiple filaments within the yam bundle, are randomly broken and then drawn to a lower denier. These are then recombined in a durable yam or in the form of a web also called a ribbon. The yarn is then woven or otherwise formed into a thin fabric, which is subject to heat treatments to convert the yarns into highly graphite yams. Alternatively, the web can be stacked to a given thickness and at the desirable fiber orientation and needle punched. These yams have the same relative properties that are obtained by the more expensive process of heat treating yams and then forming a fabric therefrom. The fabric or the mat can be used in a fuel cell by impregnating or coating it with an appropriate carbonaceous mixture or used to fabricate high thermal conductivity reinforced plastic composites.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Thus by the present invention its objects and advantages will be realized the description of which should be taken in conjunction with the drawings, wherein:
[0016] [0016]FIG. 1 shows a fuel cell featuring a gas diffusion layer;
[0017] [0017]FIG. 2 shows a representative stretch breaking apparatus;
[0018] [0018]FIG. 3 shows a cross section of the yam prior to stretch breaking;
[0019] [0019]FIG. 4 shows a cross section of the yarn after stretch breaking; and
[0020] [0020]FIG. 5 shows a stretch broken web or ribbon.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0021] In this regard, the present invention is directed toward taking higher denier pitch precursor fiber tows and stretch breaking them into smaller denier yarn form or a ribbon form. The fiber retains the desired characteristics but is easier to process into thin fabrics for use in applications such as fuel cells where thin fabric or thin mat reinforcements are desirable.
[0022] Accordingly, there exists many methods and apparatus for achieving stretch breaking of yams or filaments. An example of such an apparatus is that set forth in U.S. Pat. No. 5,045,388, the disclosure of which is incorporated herein by reference. While the particular apparatus used is not part of the present invention, a brief description of a typical apparatus is in order. In this regard, FIG. 2 is a schematic representation of the apparatus disclosed in the immediate aforementioned patent.
[0023] The apparatus of FIG. 2 generally includes a creel 10 holding a rotatable bobbin 12 of a tow 14 of continuous filament fibers, a stretch breaking machine 16 with an integral hot air treater 18 and a windup 20 for winding a package 22 . The stretch breaking machine 16 includes two breaker block units 22 , 24 . Unit 22 consists of driven roll 22 a engaging and forming successive nips with ceramic coated metal rolls 22 b and 22 c which are water cooled. Roll 22 a is covered with elastomer. In a similar arrangement, driven elastomer covered roll 24 a engages and forms nips with ceramic coated metal rolls 24 b and 24 c. Roll 24 a is covered with elastomer.
[0024] In operation the continuous filament fiber tow 14 is drawn from package 12 on creel 10 through guide 15 by means of driven roll 22 a and associated nip rolls 22 b and 22 c. Roll 22 a is driven at a higher speed (about 10 percent faster) than roll 24 a to tension the tow. The conversion of the tow 14 into stretch broken aligned fiber tow 14 ′ occurs between rolls 22 a and 24 a. The tow 14 passes between the nips formed between rolls 24 a, 24 b and 24 c, which grip the tow. Since in this application the tow is reinforced with resin, the tow is then pulled through heater 18 , which softens the resin by raising its temperature to about its melting point. Since the speed of roll 22 a is faster than roll 24 a, a tension is created in the tow between the rolls which is sufficient to break each of the continuous filaments in the tow between rolls 22 a and 24 a. Because the resin is soft the filaments do not transfer the shear load through the resin to adjacent filaments and because no shear load is transferred, the continuous filaments break randomly instead of all in one location. This random break distribution allows the tow 14 ′ to remain continuous without separating. The resin cools rapidly after leaving heater 18 and is rapidly cooled when moved over water cooled rolls 22 b and 22 c which are at a temperature of about 50° F. The stretch broken tow is then wound into package 22 on winder 20 for further processing.
[0025] Other examples of stretch breaking includes that set forth in U.S. Pat. No. 4,080,778 and that described in U.S. Pat. No. 4,837,117. It should be noted that some stretch breaking equipment runs dry, without a resin.
[0026] Turning now more particularly to that to which the present invention is directed, as aforesaid, for fuel cells and similar applications, graphite materials in the form of either wovens or non-wovens are used as a substrate onto which catalyst containing coatings are applied. There are numerous attributes that the ideal graphite material will possess. Amongst these are in-plane and thru-thickness electrical and thermal conductivity. Fabrics are preferred over paper by many users because the fabrics are more durable and easier to handle through the coating processes that are required. Papers are smoother than “standard” fabrics and hold promise for lower production costs. Fabrics or mats should, however, be as thin as possible and have smooth surfaces.
[0027] The baseline fabric that is used by many in this field is manufactured by way of a multi-step process. The weaving yarns are spun from staple polyacrylonitrile (PAN) filaments that typically range in length from one to two inches. These yarns are woven into a plain weave fabric. The fabric is then subjected to a carbonization heat treatment process that is conducted in a nitrogen atmosphere. The resulting “carbon” fabric is then subjected to a graphitization process, which heat treats the material to yet a higher temperature. This is also conducted in a nitrogen atmosphere. The resulting properties of the graphite fabric are less than ideal but acceptable performance can be achieved with proper fuel cell design.
[0028] For thermal management applications, graphite fiber is combined with thermoset and/or thermoplastic polymers to yield high thermal conductivity composites.
[0029] Graphite fibers using a petroleum pitch precursor instead of a PAN precursor is preferred, since pitch precursor graphite fibers have superior mechanical, thermal and electrical performance compared to PAN based graphite fibers. However, the cost of such fibers precludes their use in many applications. In addition, the smallest pitch precursor yams currently available are approximately 3850 denier and therefore only relatively thick fabrics can be woven from them. The present approach is to obtain pitch precursor yarn 30 at an intermediate stage in its processing, i.e. at the thermoset stage, prior to carbonization or graphitization. The yarn 30 is then stretch broken by any means suitable for the purpose. (Stretch breaking, as aforesaid, is a process that starts with high denier yarns and reduces them to low denier yarns 32 by a process whereby the multiple filaments within the yarn bundle are randomly broken and drawn to a lower denier.) Following stretch breaking, the resulting intermediate product, which is in the form of a ribbon 34 , can be processed in a number of ways, including being held by a serving yarn after being stretch broken and spun to yield various textile products.
[0030] The ribbon 34 can be further reduced and is formed in a small yarn of an equivalent filaments count between 200 and 500. For example, the original tow may be reduced to approximately 500 denier, a reduction of approximately 8:1. This low denier yarn is then woven into a thin, smooth surface fabric and then subjected to two consecutive heat treatment processes. Alternatively, the yarn can be knitted or braided. The heat treatments convert the pitch precursor (thermoset stage yarn) into highly graphitic yarns with the same relative properties that are derived by the more expensive process of heat treating yarns and then weaving fabric from them.
[0031] Furthermore, the ribbon 34 can be directly formed into a stitch bonded multiaxial fabric. In addition, several layers of ribbons 34 can be mechanically secured by needle punching to fabricate a felt.
[0032] The resulting textile products offer electrical and thermal performance approximately six times greater than the standard PAN based fabrics. It can also be made thinner and be less costly thereby allowing a wider range of applications. The following table summarizes the desired and expected performance of the various options discussed.
PITCH PAN PRE- PRE- CURSOR CURSOR DESIRED (PRIOR (BASE- PITCH PRE FEATURE ATTRIBUTE ART) LINE) CURSOR Filaments Either Continuous Dis- Dis- continuous or continuous continuous discontinuous Yarn Denier Low High High Low Fabric Thin Thick Medium Thin Thickness Conductivity High High Low High Price Low High Low Low Durability High High High High
[0033] Alternatively a blend of thermoset pitch and PAN fibers to create a hybrid yarn may be fed to the stretch breaking apparatus. An intimate mixture of both fiber types may be accomplished within the equipment. The resulting yarn or web has a higher electrical and thermal conductivity than the prior art using only PAN fiber.
[0034] The same textile products could be included in a thermoplastic or thermoset resin system to fabricate high thermal conductivity composites.
[0035] Thus by the present invention, its objects and advantages have been realized, and although preferred embodiments have been disclosed and described herein, its scope should not be limited thereby; rather its scope should be determined by that of the appended claims. | A pitch precursor yarn, which is stretch broken and formed into a fabric or felt which is heat treated into graphitic fiber media for fuel cell gas diffusion layer substrates and high thermal conductivity reinforced composites. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus and method for removing fluids from a well. More particularly, the present invention relates to a mobile apparatus capable of lifting fluids, particularly oil, out of a well using a swab mounted on the free end of a cable which is run down the well and then retrieved, bringing the fluid up with it, and collecting and storing the fluid as it is removed from the well.
The present invention relates particularly to the production of oil from shallow oil wells, on the order of approximately 1,000 to 1,500 feet deep. These wells are typically located in soft formations, such as sand, which make them difficult to produce. When used on such wells, conventional production methods such as pumping, chamber lifts or jetting have several disadvantages. For instance, because of the high sand content of the oil in those wells, the pumps which are used are subject to clogging. Further, because of the low production of such wells, it is not economical to jet high-pressure air into the well to force the oil up out of the well because an electric motor is required to operate an air compressor, and large amounts of energy are consumed to produce a relatively small amount of oil from the well.
Many different devices and methods have been tried for the production of oil from these stripper wells (wells which produce less than about 10 barrels of oil a day). However, so far as is known, all the equipment and methods developed must be removed from the well from time to time so that the well may be sand pumped or swabbed to clean the well bore and perforations. Sand pumping and swabbing with conventional rental units is a relatively expensive procedure, and is prohibitively expensive on many stripper wells due to their low production. Although swabbing the wells is one of the best and most reliable methods, it is also the most expensive, requiring a two or three man crew and perhaps as much as half a day, depending upon the depth of the well, to perform.
There is, therefore, a need for a method and apparatus capable of producing oil from those wells economically. There is also a need for an apparatus and method capable of producing oil from those types of wells in an economical and reliable fashion.
SUMMARY OF THE INVENTION
The present invention provides an apparatus capable of cleaning and producing shallow wells in economical fashion comprising a mobile support means, a power winch mounted on the mobile support means and having a cable attached thereto, and means operably connected to the power winch to maintain a relatively constant tension on the cable while the cable is being wound off of the power winch into the oil well. A swab is mounted on the free end of the cable and is operable to lift oil out of the oil well when the cable is wound back onto the power winch. Also provided is a means in fluid connection with the oil well which is operable to receive the oil lifted out of the well by the swab.
An object of the present invention is to provide an economical and reliable apparatus and method for cleaning the well while simultaneously producing fluid from the well.
Another object of the present invention is to provide a mobile apparatus for producing fluids from a shallow well.
Another object of the present invention is to provide a method and apparatus capable of being operated by a single operator and which can be moved from one well to another, collecting fluid from each well and temporarily storing it until it is convenient to deposit the fluid in a more permanent location or until the storage tank on the apparatus is full.
Another object of the present invention is to provide a device for maintaining relatively constant tension on a cable when that cable is being used to lower a swab into a well.
Another object of the present invention is to provide a swab which can be used to remove fluid from a well.
Still another object of the present invention is to provide a swab which, if it becomes lodged or stuck in the well, can be freed without damaging or ruining the well.
Another object of the present invention is to provide a power winch to lower a swab into a well which is automatically braked to a stop in the event of a power failure or loss of hydraulic fluid.
Another object of the present invention is to provide an apparatus capable of effecting a relatively tight seal with a well to help insure efficient production of the fluid in the well.
Another object of the present invention is to provide an apparatus which, when the seal is broken, will prevent the flow of fluid back into the well.
Another object of the present invention is to provide an apparatus which will not be damaged, and which will not damage the well, when the seal with the well is broken and the apparatus is removed therefrom.
Another object of the present invention is to provide an apparatus in which the hydraulic fluid used to transmit power is cooled by the fluid produced from the well.
Other objects of the present invention will be apparent to those skilled in the art who have the benefit of this disclosure from the following detailed description of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a presently preferred embodiment of the present invention mounted on a truck.
FIG. 2a is an enlarged, perspective view of the power winch of the embodiment shown in FIG. 1.
FIG. 2b is an enlarged, perspective view of the other side of the power winch shown in FIG. 2a, showing the hydraulic motor and hydraulic fluid reservoir of the embodiment of FIG. 1.
FIG. 3 is an enlarged, perspective view of the standpipe and boom assembly of the embodiment shown in FIG. 1.
FIG. 3a is an enlarged, perspective view of the standpipe assembly shown in FIG. 3, with the boom raised to show the swab mounted on the bottom thereof.
FIG. 3b is a perspective view of the bottom of the standpipe assembly and swab as it would appear if the swab were hung up on the side of the well head when the apparatus of the present invention is moved away from the well.
FIG. 4 is a longitudinal section through the swab shown in FIGS. 3a and 3b.
FIG. 4a is a longitudinal section through a portion of an alternative construction of a swab which may be constructed in accordance with the present invention.
FIG. 5a is a schematic view of the constant tension maintaining unit mounted within the cab of the truck shown in FIG. 1.
FIG. 5b is a view of the constant tension maintaining unit of FIG. 5a from the opposite side shown in FIG. 5a.
FIG. 6 is a schematic hydraulic diagram of the apparatus of FIG. 1.
FIG. 7 is a schematic, side view of the constant tension unit of the embodiment shown in FIG. 1.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, there is shown a presently preferred embodiment of the invention, indicated generally by the reference numeral 10. One of the main advantages of the present invention is that it is mobile, and may be mounted on a mobile support means such as a truck 12. The apparatus of the present invention consists of several parts mounted on the truck 12, including the standpipe and boom assembly 14, the constant tension maintaining unit 16, the power winch, indicated generally at reference numeral 18, and the oil receiving unit, indicated generally at 20.
Referring to FIGS. 2a and 2b, the power which 18 is comprised of a reel 22 mounted on axle 24 which is journaled in ears 26. The ears 26 are attached to frame 30 by bolts 28. The frame 30 is comprised of uprights 32, cross members 34 and braces 36.
Reel 22 is provided with brake drum 38 and a brake band 40 encircling the brake drum 38. Tension rod 42 is attached to brake band 40 by welding at one end and to lever 44 on pivot 46 at the other end. Lever 44 is mounted on axle 48 which is journaled in lugs 50. The lugs 50 are attached by bolts 52 to platform 54. Platform 54 is mounted to the upright 32 of frame 30 by means of support member 56, which is welded to the bar 58, which is, in turn, welded to upright 32, and by the brace 60, which is also welded to the upright 32. Lever 44 is pivotally mounted to the extension member 62 of hydraulic cylinder 64 on pin 66 which is journaled on both sides of the U-shaped member 68. Lever 44 is also provided with a weight 70 hung on the end of a cable 72.
The reel 22 of power winch 18 is powered by hydraulic motor 74, which drives the chain 76 and sprocket 78. The sprocket 78 is mounted on the same axle 24 as, and is integral with, the reel 22. Hydraulic motor 74 is mounted to plate 80, which is mounted to cross member 34 of frame 30 by means of brace 82 and I-beam 84. Cable 86 is attached at one end to the reel 22 and is wound thereon.
Referring to FIG. 3, the standpipe and boom assembly 14 is supported on the front of truck 12 by means of frame 88, to which columns 90 are welded. Additional support for columns 90 is provided by the braces 92 and 94. Hydraulic cylinder 96 is mounted on collar 98, which is supported by the uprights 100 which are welded to the frame 88. The ram 102 of hydraulic cylinder 96 is pivotally mounted to yoke 104 which is integral with the extension members 106 which telescope up out of the columns 90. Boom members 108 are integral with the extension members 106, and are braced by triangle braces 110. Standpipe retention members 112 are welded to the ends of boom members 108, and braced by slats 114 and braces 116. Additional reinforcement for the standpipe and boom assembly 14 is provided by angle braces 120. The standpipe housing 122 is integral with the standpipe retention members 112, and oil saver 124 is mounted to the top of housing 122. Cable 86 enters housing 122 through the oil saver 124, the function of which will be described below.
The bottom of the housing 122 is provided with a back-up plate assembly 126, comprised of an upper plate 128 and a lower plate 130, hinged together by hinges 132 and held in closely approximated position by a frangible sheer pin 134. Lower plate 130 is provided with a back-up plate seal 136 made of neoprene, neofab or other resilient material, which seals against the top of wellhead 138 (see FIG. 3b) when standpipe housing 122 is lowered by action of hydraulic cylinder 96. Cable 86 extends down through standpipe housing 122 and swab 140 is suspended from the end of the cable 86 (see FIG. 3a). Check valve 142 is in fluid connection with the interior of the hollow housing 122, and is connected to hose 144, which is connected to funnel 146. Check valve 142 is a one-way valve which prevents fluid from flowing back out of hose 144 and tank 150. Funnel 146 is in fluid communication with the overhead pipe 148, which connects to the storage tank 150. Vent 151 is provided in storage tank 150 to facilitate the filling and emptying of storage tank 150. Fittings and hoses (not shown) are provided as is known in the art by which the fluid collected in storage tank 150 may be transferred out of the tank 150 into another, stationary storage tank (not shown). A pump (not shown) driven by hydraulic fluid, by power take-off from truck 12 or directly off of motor 242 may be provided to facilitate the unloading of fluid from storage tank 150.
Referring to FIG. 4, swab 140 is shown in more detail. Cable 86 is attached to swab 140 by means of rope socket 152, which is integral with the casing 176 of swab bar 154. A collar 156 formed in the lower end of the casing of swab bar 154 is threaded to receive mandrel 158. Casing 176 is filled with lead to provide the weight needed to cause swab 140 to move downwardly through the fluid in the well as will be explained. Swab cups 160 are placed on mandrel 158, and retained thereon by the flange 162. Three swab cups 160 are shown, spaced along the length of mandrel 158 for purposes of clarity, but as few as one and as many as will fit on the length of mandrel 156 may be used, depending on the amount of fluid to be removed from the well as will be described. The bottom of mandrel 158 is provided with threads 164 to receive a threaded insert 166 having an orifice 168 therein. The orifice 168 is sealed by a check valve comprising a ball 170 and valve seat 172. Lumen 174 of mandrel 158 communicates with the space 178 in collar 156, which is provided with discharge ports 180 for passage of fluid therethrough.
An alternative construction of swab 140 is shown in FIG. 4a, in which corresponding parts are given the same numbers as in FIG. 4. Mandrel 158' is threaded onto swab bar 154' and swab cup 160' is mounted on mandrel 158' in the same manner as shown in FIG. 4. However, swab cup(s) 160' is retained on mandrel 158' by shear sleeve 159', which is a cylindrical ring retained on the end of mandrel 158' by frangible shear pins 161. The operation of shear sleeve 159 and shear pins 161 is discussed below.
Referring now to FIGS. 3, 5a, 5b, and 7, the constant tension maintaining unit 16 is shown in more detail. Constant tension maintaining unit 16 is comprised of a pulley 182 which rides on cable 86 and is journaled in reciprocating rod 184. Control cable 186 is secured to the bottom of reciprocating rod 184, and travels downwardly over pulleys 188 and 190, which are mounted on axles 192 which are welded to slats 114 and uprights 100, respectively, of the standpipe and boom assembly 14. Control cable 186 then enters the cab 194 of truck 12 through opening 196 (see FIG. 3). Once inside the cab 194, control cable 186 passes under pulley 198 and upwardly around pulley 200, back down and around pulley 202, back out of the opening 196, over the pulley 204, and is attached to the weight 206. The mounting brackets upon which the pulleys 198, 200, 202 and 238 (see FIG. 5b) in the schematic diagrams are mounted are not shown for purposes of clarity. Pulley 204 is mounted to uprights 100. As shown in FIGS. 5a and 5b, as control cable 186 travels between pulleys 198 and 200, it passes in close proximity to spool valve 208. The spool valve 208 has a handle in the form of a pair of vise-grip pliers 210, the jaws of which are provided with rubber blocks 212 which can be releasably clamped onto control cable 186 between pulleys 198 and 200. Spool valve 208 is a sandwich valve which is a part of the hydraulic compression control unit 214.
Also located within the interior of the cab 194 of truck 12 is a remote control valve unit, indicated generally at reference numeral 216. Lever 218 is attached, by way of bracket 220, to the dashboard 222 of the cab 194. Pulley 224 is journaled on the end of strap 226, which is integral with lever 218 and will pivot with lever 218 on bracket 220. A remote control cable 228 is anchored at one end to the floor of the cab 194 by eyelet 230, passes up and over the pulley 224, back down towards the floor and under pulley 232, which is journaled in L bracket 234 also attached to floor of cab 194. Remote control cable 228 passes upwardly towards the hydraulic compression control unit 214, and over pulley 236 which is mounted concentrically with pulley 198. Remote control cable 228 then continues upwardly over pulley 238 and back down to the spool valve 208, where it is anchored on the vise-grip pliers 210. The remote control cable 228 is kept constantly under tension by means of the spring 240 which is suspended from the top of the truck cab 194 and attaches to the end of strap 226.
Referring to FIGS. 1 and 6, the hydraulic system of the presently preferred embodiment of the invention will be described. The hydraulic system is powered by a motor 242 mounted to the truck 12 (see FIG. 1). Motor 242 powers the hydraulic pump 244. A master shutoff valve 246 is provided to bypass the system, thereby shutting down all hydraulic pressure to the system. The hydraulic fluid is pumped through storage tank 150 in input line 208 i through loop 250' to the spool valve 208. Cylinder line 248 branches off of input line 208 i to power the hydraulic cylinder 64 in the upward direction only. Hydraulic fluid passes out of the spool valve 208 into the input lines 74 i , to the hydraulic motor 74, and returns to spool valve 208 i through the output line 74 o . Hydraulic fluid is also routed from the spool valve 208 to the raising cylinder 96 through input line 96 i and returns through output line 96 o . Operator-controlled valves 258 and 260 are provided in lines 96 i and 96 o , respectively for raising and lowering ram 102. Valves 258 and 260 are shown schematically on control unit 214 in FIG. 5b, as are hydraulic pressures gauges 262, a gauge 262 being supplied for each of the different circuits shown in FIG. 6. The circuit is completed by output line 208 o , which passes the hydraulic fluid through several loops 250' located in the storage tank 150 and then into the hydraulic oil reservoir input line 252 i , to the hydraulic oil reservoir 252, and on out of the hydraulic oil reservoir 252 to the pump 244 through output line 252 o and water trap 266. Oil saver line 254 runs from input line 96 i to the oil saver 124, powering the oil saver 124 in one direction only under control of valve 264.
Operation of the apparatus of the present invention is as follows. The operator drives the truck 12 to the well head 138, and engages valve 264 on the hydraulic compression unit 214 to lower the standpipe and boom assembly 14 down over the well head 138 until the seal 136 engages and seals the top of the well head 138. The operator then pushes the vise-grip pliers 210 which form the handle of spool valve 208 downwardly and closes the vise-grips to grasp the remote control cable 228. In the downward position, the spool valve 208 causes power to be applied to the power winch 18, resulting in the winding of the cable 86 off of the reel 22, thereby lowering the swab 140 down into the well. The cable 86 may be provided with markers or flags (not shown) at 100 foot intervals or with a cable line counter to determine the depth to which swab 140 is lowered. When the swab 140 hits the fluid in the well, there will be a momentary slack in the tension on cable 86 as the buoyancy of swab 140 and the limited amount of fluid which can pass through orifice 168 as described below causes the swab 140 to float in the fluid. This slack in cable 86 will result in the downward movement of the control cable 186 in the vicinity of pulley 182 due to the weight 206 at the end of the control cable 186. The movement caused by the weight 206 will be transmitted to the control cable 186 in the upward direction between pulleys 198 and 200, causing the spool valve 208, by virtue of the blocks 212 which are clamped around control cable 186, to be moved upwardly into the neutral position. When in the neutral position, the flow of hydraulic fluid to the hydraulic motor 74 and the brake cylinder 64 is shut off, causing the brake band 40 to be applied to the brake drum 38 by virtue of the downward force applied to the lever arm 44 by weight 70, resulting in the stopping of the reel 22 so that no more cable is wound off of the reel 22. A mirror 153 is provided so that the operator can monitor the various operations of the apparatus of the present invention from inside the cab 194 of truck 12.
Swab 140 is provided with the swab bar 154, which is comprised of a casing 176 filled with lead or other material of sufficiently heavy weight (i.e., over 140 pounds) to continue to cause the swab 140 to drift downwardly through the fluid in the well. In a presently preferred embodiment, a swab bar 154 of approximately 145 pounds is being used. The continued downward movement of the swab 140 through the fluid in the well will cause the slack in cable 86 in the vicinity of pulley 182 to be taken up such that the spool valve 208 will be opened partially by being pulled downwardly by control cable 186 as the slack is removed from cable 86. This downward pull will cause the speed at which cable 86 unwinds from the reel 22 to be adjusted to correspond to the speed of the downward movement of the swab 140 through the fluid in the well by applying and releasing the brake band 40 to drum 38 and powering hydraulic motor 74. This construction, in addition to adjusting the rate at which cable 86 is wound off of reel 22 to correspond to the rate at which swab 140 sinks down through the fluid in the well, has the advantage of stopping the power winch 18 if damage occurs (i.e., a broken chain drive or loss of hydraulic pressure) because of the slack which will be caused in cable 86 by the damage.
By monitoring the length of cable 186 which is reeled off of reel 22, the operator can determine that swab 140 has sunk down through a sufficient amount of fluid. When swab 140 reaches that desired depth, the operator pushes the lever 218 forward, causing the spool valve 208 to be moved to the upward position, resulting in the reversal of the direction of rotation of the reel 22 so that the cable 86 will be wound back onto the reel 22, retracting the swab 140 from the well.
The swab cups 160 on mandrel 158 of swab 140 will each support approximately 100 feet of oil in a well of 41/2 to 51/2 inches in diameter. Consequently, if three of the cups 160 are placed on mandrel 158, a column of approximately 300 feet of oil can be lifted from the well. Wells of larger diameter require swabs of larger diameter. Once the direction of reel 22 has been reversed, the swab cups 160 will catch and hold the oil, lifting it up out of the well, where it will be funneled into the standpipe housing 122, through check valve 142 and hose 144, into funnel 146 and up over the cab 194 of truck 12 through the overhead pipe 148 and into the storage tank 150. Fluid receiving unit 20 routes the fluid removed from the well overhead through pipe 148 to reduce the back pressure against the fluid as it comes out of the well.
To keep the oil from being lifted up out of the well and out of the top of the standpipe housing 122, the operator engages the oil saver 124, which has a rubber doughnut therein. When hydraulic pressure is applied to that doughnut, it is forced against the cable 86 so that as oil is drawn upwardly, it cannot escape out the opening through which cable 86 passes. Once the swab 140 has been retrieved all the way up to the top of the well and into the standpipe housing 122, there will still be a column of oil in the standpipe housing 122 above swab 140. To avoid spilling this column of oil, the standpipe housing is provided with a short loop of hose 256 which is placed such that one end is above the swab 140 when the swab is retracted all the way into standpipe housing 122, and one end is below the swab 140 so that the oil in the column above swab 140 when retracted will drain back down into the well. If the well contains more than, for instance, the 300 feet of oil, the operator can then reverse the direction of rotation of the reel 22 and reenter the well to retrieve the additional oil.
Swab 140 is provided with a threaded insert 166 having an orifice 168 therein (see FIGS. 4 and 4a). Depending upon the type of fluid to be raised out of the well with the present apparatus, and the viscosity of that fluid, this threaded insert 166 may be replaced with an insert with an orifice 168 of different size. The ability to switch threaded inserts 166, thereby changing the size of the orifice 168, is particularly important due to the high viscosity of the oil which is often found in stripper wells. Even though some oil will pass between the edges of swab cup(s) 160 and the walls of the well as swab 140 sinks, most of the oil passes through orifice 168, consequently the size of orifice 168 will have considerable effect on the rate at which swab 140 sinks, which, in turn, affects constant tension maintaining unit 16, which controls spool valve 208. The size of orifice 168 is also important because, if it is too large, swab 140 will not float momentarily on the oil when lowered into the well so that the operator will not be able to tell how deep into the fluid swab 140 has been lowered. As swab 140 sinks through the oil in the well, the oil passes through the orifice 168, past the ball 170, and up into the lumen 174 in the mandrel 158 of swab bar 140. The oil passes next into the space 178 and out the discharge ports 180 of collar 156 as the swab 140 sinks down through the fluid in the well. When power winch 18 is reversed to retract swab 140 from the well, ball 170, which is constructed of rubber covered nylon or similar resilient material, will be seated in valve 172 by the back pressure of the fluid which has passed through orifice 168, thereby preventing flow back through orifice 168. Both the swab 140 shown in FIGS. 4 and 4a operate similarly in this regard.
The mandrel 158 shown in FIG. 4 is preferably constructed of aluminum so that, should swab 140 become stuck in the well, a concentrated mineral acid such as hydrochloric acid can be poured down into the well so that it will move downwardly through the oil until it reaches mandrel 158, where it will dissolve the aluminum such that swab cups 160 will be left in the well and swab bar 154 will be freed from the well. In this manner, the well will not be ruined should the swab 140 be hung up downhole. Alternatively, the mandrel 158' (see FIG. 4a) may be provided with the shear sleeve 159' and shear pins 161'. Should swab 140' be hung up or lodged in the well, an additional upward force is applied by way of cable 86, shearing the frangible shear pins 161', allowing the swab bar (not shown in FIG. 4a), and everything mounted on it except the shear sleeve 159', swab cup(s) 160' and broken shear pins 161' to be removed from the well.
Once the operator has retrieved all the available fluid from the well, the standpipe and boom assembly 14 is raised up off the well head 138 and the operator can proceed to the next well to repeat the process until the storage tank 150 is filled. In order to avoid possible damage to swab 140 if the operator does not raise the standpipe and boom assembly 14 all the way such that, as the truck backs away, swab 140 hangs up on the inside edges of the well head 138, the back-up plate assembly 126 is provided with an upper 128 and lower plate 130 hinged together at 132, and a sheer pin 134 to hold the plates in close approximation. When the swab 140 catches the well head 138, shear pin 134 will break, allowing lower plate 130 to break away from upper plate 128, thereby preventing damage to the apparatus (see Fig. 3b).
Although the invention has been described in terms of the foregoing preferred embodiment, this preferred embodiment is described by example only, and the scope of the invention is not restricted to this preferred embodiment. Rather, the scope of the present invention is limited only by the following claims. | Apparatus and method for removing fluid from a well. The apparatus is mobile, and includes a power winch mounted on a mobile support means with a cable attached to the winch. A constant tension maintaining unit is connected to the winch to maintain relatively constant tension on the cable while the cable is wound off the power winch into the well, and a swab is mounted on the free end of the cable. The swab is operable to lift the fluid out of the well when the cable is wound back onto the power winch. Also included is a means in fluid connection with the well operable to receive the fluid lifted out of the well by the swab. Also provided is a swab bar for use in removing fluid from a well and a device for effecting a seal with the well head. | 4 |
This application is a continuation of application Ser. No. 595,334, filed Mar. 30, 1984, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates generally to mechanical cotton pickers. More particularly, the present invention relates to rotary doffer assemblies of improved advantageous construction for removal of cotton from rotating picking spindles in conventional machines for cotton picking.
Typical cotton picker units include rotating heads disposed on a vertical axis and carrying a series of radially extending rotating spindles which pick exposed cotton from open cotton bolls as a consequence of the rotation of the spindles on their own axes and by reason of slight barbing or roughening of the spindle surfaces. In turn, the cotton-bearing spindles pass rotating doffer discs having radially extending and vertically projected annular teeth or lugs which function to wipe or doff the gathered cotton from the spindles as the doffers and spindles rotate in cooperating relationship. The operation of conventional picking units and the arrangement of doffers and spindles are described and depicted in Deere and Company publication No. A-29-84-1 "Cotton Pickers and Strippers" which is incorporated herein by reference.
In operation, the picker spindles of cotton machines not only are subjected to varying accumulations of cotton thereon depending upon increases or decreases in the harvested yield per acre, relative moisture content of the bolls, variations in speed at which the field is traversed, and the like, but likewise, encounter varying accumulations of associated matter such as rocks, dirt, plant stock, weeds, etc. Accordingly, the lugs or teeth of the doffer assemblies as well as the associated hub and disc to which the doffer lugs are attached are subjected to varying load stresses, shock forces and elevated temperatures during normal operation which tend to cause splitting and breakage of the doffer elements or otherwise sufficient wear and deterioration to require the expensive replacement of individual doffer elements and, depending upon the degree of difficulty encountered in picker-doffer alignment, may necessitate the replacement of the entire doffer assembly.
Heretofore, various doffer designs have been suggested to provide doffers which are sufficiently flexible to accomodate the abrasion, shock, and friction load forces and temperatures to which the doffer assemblies are subjected while at the same time attempting to maintain sufficient structural rigidity to promote adequate wear life for such doffer assemblies. For example, doffer elements, including the annular lugs thereon, made of an elastomeric material such as sponge rubber are disclosed in U.S. Pat. No. 2,738,636. U.S. Pat. No. 2,693,071 discloses doffer discs in which the disc body is derived from thermosetting or thermoplastic materials and the doffing fingers or lugs are produced from tire tread stock. It has been found through field experience that such doffer elements derived from elastomeric rubbers, while providing the desired resiliency, do not maintain sufficient durability levels and are further disadvantageous from the standpoint that such normally black materials when subjected to the load stresses and temperatures encountered during operation tend to result in black specks in the raw cotton which often objectionably appear in the final cotton fabrics.
Another approach is that of U.S. Pat. No. 2,847,815 describing doffer lugs or pads which are integrally connected to a center disc made of rubber or synthetic rubber material having a Durometer hardness of 60 and in which the disc is strengthened by the inclusion of fabric rings, e.g., cotton, artificial fibers such as nylon, rayon or dacron bonded to both sides of the disc.
More recently, U.S. Pat. No. 3,971,197 describes doffer elements comprising an integrally molded doffer with a disc shaped reinforcement, preferably perforated, embedded in the doffer along a rim or annular portion of the disc. The doffer body is of molded elastomeric material such as natural or synthetic rubbers and blends thereof or may be derived from liquid cast materials such as polyurethane. The polyurethane material is described only as being capable of liquid casting or molding and having a Durometer range of 70-90 on the shore A hardness scale. The doffer assembly described may also be constructed with layers of polyurethane so that the first layer may comprise 10 to 30% of the doffer thickness and have a Durometer of 55-75 on the shore D hardness scale while a second layer is 70 to 90% of the thickness having a hardness range of 65 to 95 on the shore A hardness scale. The foregoing doffer allows for both circumferential and axial deflection.
However, it has been found in practice that the doffers derived from such castable polyurethanes, while achieving a degree of flexibility are, nevertheless, subject to deterioration through breakage of the doffer lugs or large portions thereof when subjected to shock and striking forces such as those resulting from the doffer elements being struck by accumulated debris between the spindles and the doffer elements or by striking of the lugs by the rotating spindles if minor misalignments should occur.
SUMMARY OF THE INVENTION
It is, therefore, a primary object of the present invention to provide doffer elements, and particularly, doffer lugs or teeth which do not suffer from the disadvantages experienced with heretofore proposed doffers.
Another object of the present invention is to provide improved disc units for doffer assemblies which are abrasion, shock, and temperature resistant while at the same time being flexible, structurally stable and long wearing.
In accordance with the foregoing, a doffer unit for cotton picking machines is provided comprising a central hub portion, a ring or flange portion concentric thereto and a plurality of radially extending lugs carried by the ring and wherein such lugs are advantageously constructed from millable polyurethane elastomers.
THE DRAWINGS
These and other objects features and advantages of the present invention will be apparent to those skilled in the art upon reference to the following specification and the accompanying drawings wherein:
FIG. 1 is a plan-view depicting the lug side of a doffer of the invention;
FIG. 2 is a cross-sectional view taken along line 2--2 of FIG. 1.
FIG. 3 is an edge view taken in the direction of line 3--3 in FIG. 1.
FIG. 4 is a graph showing the results of comparative flex testing.
DETAILED DESCRIPTION OF THE INVENTION
Consistent with the objects, features and advantages of the present invention, a disc-shaped doffer 10 for cotton is provided. More specifically, the doffer 10 includes a hub portion in the form of a plate 11 which may be comprised of metal or other suitable rigid or semi-rigid material derived from, for example, a thermosetting or thermoplastic material, including phenol-formaldehyde condensation products, polyvinylchloride, resin or fiber reinforced rubber elastomers, polycarbonate resin, etc. The hub plate 11 may, optionally, be further provided with a keyway (not shown) to register with corresponding keyways in the doffer carrier or driveshaft (not shown). Concentric with the hub plate 11 is an annular flange or ring 12 which may be of integral one-piece construction or may comprise a separately formed piece which is fastened or molded thereon. The ring includes a plurality of circumferentially spaced doffer lugs 14 which extend radially and are raised relative to a surface 15 of the ring.
The doffer lugs of improved construction in accordance with the present invention are comprised of millable polyurethane elastomers which have now been surprisingly found to be superior in physical-mechanical properties compared to materials heretofore employed in the construction of doffers, including previously proposed liquid cast polyurethanes.
Accordingly, an important feature of the present invention is in the provision of cotton doffer lugs derived from certain polyurethanes broadly classified as millable polyurethane elastomers. As the result of extensive comparative testing of various polyurethane elastomer formulations and variations in the components thereof, including reinforcing and pigmenting fillers and curing agents as well as the rate and temperature of curing or vulcanization conditions, the applicant herein has accomplished the provision of a polyurethane material having the requisite properties for particular application in the construction of superior long wearing cotton doffers.
The preferred polyurethane elastomers for use in the improved doffers of the present invention comprise millable polyurethanes to which conventional techniques of mill compounding and vulcanization are applicable. Stable hydroxy-terminated polymers are prepared by the reaction of linear polyesters [e.g., poly(ethyleneadipate)] or polyethers [e.g., poly(oxytetramethylene) glycol] with selected diisocyanates. Presently preferred are polyester based urethanes due to their resistance to high temperature failure.
Vulcanization of the foregoing polyurethanes may be effected by several different types of reagents, most commonly including, isocyanates, sulfur systems and peroxides. Suitable curing agents of the isocyanate types include, the dimer of tolylene-2,4-diisocyanate utilized at a curing temperature of about 150° C. causing the dissociation of the dimer into free isocyanates thereby effecting cure. Sulfur and peroxide cured polyurethane elastomers usually incorporate urea and amide groups as suitable crosslinking sites. The extent of crosslinking affects the properties in the resultant elastomer. Typical sulfur curing systems include sulfur, accelerators and an activator. The preferred accelerators for use herein are selected from, for example, mercapto-benzothiazoles and 2-mercaptobenzothiazyl disulfide.
The activators deemed suitable for use herein comprise, for instance, organo zinc oxide complexes, zinc chloride-benzothiazyl complexes (e.g., CAYTUR-4®), etc. The preferred peroxide curing agent is dicumyl peroxide, although other suitable peroxides may be utilized.
As millable polyurethane elastomers preferred herein for the construction of doffers having the desired properties, there may be mentioned Urepan-600, Adiprene C, Genthane S and Millathane 76 (Technical Sales Engineering, St. Petersburg, Fla.). The millable polyurethanes of the invention are linear or slightly branched chain polymers having a molecular weight between about 10,000 to 50,000 and a Mooney viscosity of about 20 to 65. Suitable polyurethane base formulations for the preparation of finished shaped doffers as depicted in FIG. 1 are set forth below:
EXAMPLE 1
Sulfur Cured
______________________________________Polyurethane (millathane 76 ®) 100Hi-Sil 243 (hydrated amorphous silica).sup.1 35MBTS.sup.2 4MBT.sup.3 2Thanecure.sup.4 1Sulfur 1.5AC Poly 617 ®.sup.5 2Cadmium Stearate 0.5Batch Weight 146.sup.6Cure Doffer Pads 45 min, 290° F.; 15 min, 310° F.______________________________________ .sup.1 Cabot Corporation .sup.2 2mercaptobenzothiazyl disulfide (accelerator) .sup.3 mercapto benzothiazole (accelerator) .sup.4 ZnCl.sub.2 + MBTS (activator) (Technical Sales Engineering) .sup.5 Allied Chemical, polyethylene lubricant .sup.6 parts per hundred weight of raw polymer (PHR)
EXAMPLE 2
Peroxide Cured
______________________________________Polyurethane (millathane 76 ®) 100Hi-Sil 243 30Stearic Acid 0.5Di cup 40C.sup.1 2Batch Weight 132.5Cure Duffer Pads 20 min, 310° F., 10 min, 320° F.______________________________________ .sup.1 dicumyl peroxide, Hercules.
EXAMPLE 3
(Sulfur Cured)
______________________________________Polyurethane (millathane 76 ®) 100Carbon Black.sup.1 32MBTS 4MBT 2Thanecure 1Sulfur 1.5Cadmium Stearate 0.5Batch Weight 141Cure Doffer Pads 45 min, 290° F.______________________________________ .sup.1 N220, Phillips Petroleum
It will be appreciated that the polyester urethanes are subject to hydrolytic degradation and thus, where appropriate, the above formulations may contain, for example, a polycarbodiimide (1-4 phr) as a stabilizer.
As will be appreciated by those skilled in the art, the temperature and duration of curing, as well as the type of curing agent employed, affects the mechanical properties observed in the resultant cured polyurethane elastomers. It has been found with respect to sulfur cured systems that compression molding temperatures of 310° F. for 15 minutes or at 290° F. for 30 minutes result in ideally suitable doffer lugs having the desired properties of being resiliently deflectable as well as sufficiently tough to withstand the repeated abrasion, shock and temperature stresses thereon. Suitable curing conditions when utilizing a peroxide curing agent have been found to be within the range of about 295° F. to 335° F. for about 1.5 to 30 minutes.
The physical-mechanical properties characterizing the millable polyurethane elastomers utilized in accordance with the practices of the present invention as well as certain of the comparative properties for previously suggested castable polyurethanes are set forth below in Table I:
TABLE I__________________________________________________________________________ Polyol/isocyanatePhysical CastableProperties Polyurethane.sup.1 Example 1 Example 2 Example 3__________________________________________________________________________Specific Gravity 1.27 1.37 1.37 1.36Volume Change, Percent 2.1 3.7 3.0 4.448 hrs./158° F./JDN 305 SpindleGreaseTear Strenqth (ASTM-D624C, 375 335 185 240Die C, Ambient, PI (%)At 212° F., PI 215(57) 275(81) 75(40) 230(95)At 300° F., PI 95(25) 170(51) 45(24) 125(52)Tested at Ambient:Tensile, PSI 7115 3930 3540 4475Modulus at 100 E, PSI 575 310 345 655Modulus at 200 E, PSI 705 640 715 1630Modulus at 300 E, PSI 905 1110 1340 2750Ultimate E 700 605 475 495Hardness, Shore A 80 72 73 76Tested at 212° F.:Tensile, PSI (%) No rupture* 1730(44) 730(21) 2035(45)Modulus at 100 E, PSI 320(56) 175(56) 215(63) 405(62)Modulus at 200 E, PSI 375(53) 410(64) 490(69) 1050(64)Modulus at 300 E, PSI 425(47) 605(54) ** 1475(54)Modulus at 900 E, PSI 2665 ** ** **Ultimate E, Softens* 650(107) 290(61) 415(83)Tested at 300° F.:Tensile, PSI (%) No rupture* 650(17) 445(13) 1155(25)Modulus at 100 E, PSI 140(24) 140(46) 205(59) 285(44)Modulus at 200 E, PSI 155(22) 365(57) ** 760(47)Modulus at 300 E, PSI 175(19) 515(47) ** 1105(40)Modulus at 900 E, PSI 490 * * *Ultimate E, Softens* 410(68) 150(32) 305(61)Elongation Set (%) 30%-212° F. 10%-212° F. 10%-212° F. 80%-300° F. 15%-300° F. 15%-300° F.Crack Growth, Demattia TestCycles (32nds of an inch)(ASTM D430-B)After 800 cycles Failed 4 16 -- 2,000 6 29 -- 5,000 12 failed 2510,000 16 " 2915,000 19 " Failed20,000 22 "25,000 23 "30,000 25 failed35,000 30__________________________________________________________________________ .sup.1 Polymeric Technology, Inc., Oakland, CA. *Tensile failure beyond limits of test machine **not measurable
It will be appreciated from the foregoing that castable polyurethanes do not possess mechanical properties which are in anyway favorably comparable to those of the millable polyurethane elastomers utilized in the improved doffers of the present invention.
It should be especially noted that one of the advantages of the present invention is that the polyurethane molding compositions, following vulcanization, are machinable. Accordingly, the molded doffers may be tool cut, shaped or otherwise worked to obtain completely uniform lug alignment thereby permitting narrow spindle/doffer tolerances. Castable polyurethanes, of course, lack the abrasion and high temperature resistance of the millable polyurethanes and, thus, are not readily machinable.
It will also be appreciated by reference to FIG. 1 that the doffer lug portions 14 can be integrally heat bonded to the center doffer disc 12 according to conventional assembly methods. Alternatively, of course, the outer doffer lug portion can be prepared separately in suitable curing presses having the desired configuration and optionally provided with an inner annular portion of sufficient dimensions to overlappingly engage the center doffer disc 12 to accomplish joining same by conventional fastening means such as rivets, pins, bolts, screws, etc. Likewise, in an alternative embodiment, the entire doffer assembly can be formed as an integral unit by conventional injection molding and curing methods. For example, such injection molding techniques may be carried out by placing the disc plate mold in the preconfigured mold apparatus and injecting the polyurethane molding composition in the closed mold. It should be noted that to ensure proper bonding between the disc plate and the doffer lugs, the disc plate material should be thoroughly degreased, sand blasted and cleaned before applying bonding adhesives and carrying out the molding operation.
While the invention has been described and illustrated with reference to certain preferred embodiments thereof, those skilled in the art will appreciate that various changes, modifications, and substitutions can be made therein without departing from the spirit of the invention. It is intended, therefore, that the invention be limited only by the scope of the claims which follow. | A doffer unit for cotton picking machines is provided comprising a central hub portion, a ring or flange portion concentric thereto and a plurality of radially extending lugs carried by the ring and wherein such lugs are advantageously constructed from millable polyurethane elastomers. | 0 |
FIELD OF THE INVENTION
The present invention relates generally to mechanisms for protecting mechanical drive components from overloads, and more particularly relates to a shear device coupled between components of an agricultural disc mower that protects the various components of the mower in the event a cutterhead strikes an object and creates an overload condition.
BACKGROUND OF THE INVENTION
Typical disc cutterbars used in agriculture include an elongated housing containing a train of meshed idler and drive spur gears, or a main power shaft coupled by respective bevel gear sets, for delivering power to respective drive shafts for cutterheads spaced along the length of the cutterbar. The cutterheads each comprise a cutting disc including diametrically opposed cutting blades (though configurations with three or more blades are known) and having a hub coupled to an upper end of a drive shaft, the lower end of the drive shaft carrying a spur gear in the case where a train of meshed spur gears is used for delivering power, and carrying a bevel gear of a given one of the bevel gear sets in the case where a main power shaft is used. In either case, bearings are used to support the various shafts. The cutterheads are rotated at a relatively fast speed making the drive components, such as gears, bearings and shafts, vulnerable to damage in the event that the unit strikes a foreign object. For background information on the structure and operation of some typical disc cutterbars, reference is made to U.S. Pat. No. 4,815,262, issued to E. E. Koch and F. F. Voler, the descriptive portions thereof being incorporated herein in full by reference.
In order to minimize the extent of such possible damage to the drive components, it is known to incorporate a shear device somewhere in the drive of each unit that will “fail” upon a predetermined overload being imposed on the device. As used herein with reference to shear devices, the terms “fail” or “failing” are intended to cover the actual function of such devices, i.e., shearing, fracturing, breaking and the like. Several different such shear devices and arrangements are shown in U.S. Pat. Nos. 4,999,981, 4,497,161 and 5,715,662.
The '981 patent shows a shear mechanism that comprises a shaft with a weakened portion created by a cut groove, or break zone 41 (seen, for example, in FIG. 3 thereof) in driven shaft 20 . Upon overload, the shaft breaks at zone 41 that is located outside the support bearing such that there is a clean and complete break in the shaft. This structure is intended to eliminate the input of kinetic energy to the cutterhead after failure of the shear mechanism, thereby eliminating damage to the drive system and gearing. While this structure may in fact eliminate the input of further kinetic energy, it does not stop rotation of the cutterhead or prevent the damage that continued rotation would generate.
A somewhat different shear mechanism is disclosed in FIGS. 2 and 3 of the '161 patent. Cutting disc 3 is connected by a series of shear bolts 26 to the vertical shaft 8 . Upon impact of the cutterhead with an obstruction, the shear bolts fail, stopping the input of rotational force to the cutterhead. FIG. 4 shows a slightly different embodiment where a resilient cover plate 28 depresses balls 30 arranged in holes of the disc 3 and fitting into recesses 31 of the disc 27 . An overload impact is intended to cause balls 30 to snap out of the recesses 31 so that the direct rotary joint between shaft 8 and cutting disc 3 is interrupted. It is stated that the connection can be reestablished by continuing to rotate disc 3 with respect to the disc 27 so that the balls 30 again snap into the recesses 31 . The embodiments set forth in this patent exhibit the same shortcomings as seen in the '981 patent, i.e., standard shear mechanisms do not stop rotation of the cutterhead, and thus do not prevent additional damage thereby encountered.
The shear mechanisms shown in the '662 patent each employ shearable splines. In a first embodiment the shear device is in the form of either a collar or clamping member having internal splines received on a splined upper end of the drive shaft and having shearable cylindrical drive lugs engaged with complementary shaped openings provided in an upper surface of a disk hub. Referring more specifically to FIG. 2 thereof, the upper end of drive shaft 26 has a splined section 86 . Shear collar 88 establishes a drive connection between shaft 26 and hub 80 . The collar 88 includes internal splines 90 engaged with the splined section 86 of shaft 26 just above hub 80 . Shearable cylindrical drive lugs 92 project downwardly from the bottom of collar 88 and are received in complementary holes 94 in hub 80 . An overload situation causes the lugs 92 to shear and the continuing transfer of rotational power to cease. FIGS. 4 through 6 show another embodiment where shaft 34 has a splined upper end section 110 . Instead of a shear collar, a shear device in the form of a cap-like clamping member 114 is used for transferring torque from shaft 34 to hub 80 . Clamping member 114 has an annular lower portion 116 provided with interior splines 118 engaged with the splined section 110 of shaft 34 . A plurality of shearable lugs 120 extend downwardly from lower portion 116 and are received in complementary shaped cylindrical openings 94 in hub 80 , whereby torque is transferred from shaft 34 to hub 80 . Again, when an overload occurs, lugs 120 shear, and torque is no longer transmitted. The final embodiment shown in the '662 patent is shown in FIGS. 7 through 9. Instead of a disk hub 80 , a disk hub 127 is used which has a central splined opening 128 disposed in spaced concentric relationship t the splined upper end section 110 of shaft 34 . A ring-like shear insert 130 is received on the upper end of the drive shaft 34 and has inner splines 132 engaged with the splined upper end section of the shaft and has outer splines 134 engaged with the splined opening 128 of hub 126 . Splines 132 are designed to shear upon overload.
Similar to the devices discussed above, the embodiments of the '662 patent do not stop the cutterhead from rotating, even after power is cut off by a shear device. The third embodiment shown in this patent exhibits an additional shortcoming in that upon failure of the shearable splines, the broken pieces tend to become temporarily “jammed” in among the other parts and components, resulting in even further, though short lived, torque to be transferred, and the resultant additional damage to the cutterheads.
Particularly in its preferred embodiment, the instant invention overcomes the drawbacks and shortcomings of the prior art. A two-piece hub design, with a spring mounted ball and detent as a shear mechanism therebetween will fail with substantially no residual transfer of torque. The use of this unique shear mechanism results in no broken pieces to become “jammed” in among the other parts and components, and can be easily repaired by simply realigning the top and bottom hubs so that the spring-loaded ball in the top disc hub fits into the detent in the lower disc hub. Upon failure, the two-piece hub, one of which is driven directly by the drive shaft, separates and the upper disc hub is driven up a specially threaded retaining bolt and separates from the lower hub and drive shaft. This upward movement separates the upper disc hub from the drive train and removes the affected cutting implement from the path of the other cutterheads on the cutterbar. The upper disc hub continues to rotate upward until it reaches a threadless portion of the retaining bolt. There, the upper disc hub is permitted to rotate freely until the absence of drive train inertia causes it to stop.
Clearly, the concept of a shear mechanism is not new, however the use of a spring-mounted ball and detent instead of a pin, lug, or bolt, as well as the utilization of a specially threaded retaining bolt, provides advantages in overcoming the problems and shortcomings of the prior art as discussed above. In order to limit the damage to a cutterbar in an overload situation, two characteristics are pursued—a quick, clean disengagement of the driven elements, and the prevention of damage to adjacent discs on the cutterbar by rapid removal of the affected disc from the cutting plane. For non-traditional shear mechanisms, attention is directed to U.S. Pat. No. 2,056,785 (rubber), U.S. Pat. No. 3,064,454 (solder, glass, and other fracturable and fusible materials), and U.S. Pat. No. 3,521,464 (plastic).
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide a specially threaded retaining bolt, operating in conjunction with a shear mechanism, in a mechanical drive train for an agricultural cutterbar that will not only stop the transfer of power along the drive train in the event of overload, but also remove the affected disc hub from the path of other cutterheads on the cutterbar.
It is another object of the present invention is to provide a novel shear device between hub components of a cutterhead.
It is a further object of the present invention is to provide a disc cutterbar with multiple cutterheads, each comprising a drive shaft connected to an inner hub which is connected to an outer hub via a shear mechanism. Upon failure of the shear mechanism, the upper hub and blades are rotated to a position above the cutting plane and out of the path of other cutterheads on the cutterbar.
It is yet a further object of this invention to provide an improved disc cutterbar that is relatively durable in construction, inexpensive of manufacture, carefree of maintenance, easy to assemble, simple and effective in use, and less likely than prior art cutterbars to sustain costly damage upon contact with a fixed object.
These and other objects, features and advantages are accomplished according to the instant invention by providing a disc cutterbar having a two-piece mounting hub, one piece rotatably driven and the other supporting a knife for severing standing crop material, with spring-mounted ball and detent devices holding the two pieces members together and forming a shear device therebetween. A specially threaded retaining bolt is associated with the knife-supporting piece whereby, upon failure of said shear device, the knife-supporting piece is rotated out of the cutting plane and away from the operational cutterheads.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages of this invention will be apparent upon consideration of the following detailed disclosure of the invention, especially when taken in conjunction with the accompanying drawings wherein:
FIG. 1 is a top plan view of a disc mower mounted on the three-point hitch of a tractor, the disc mower having a modular disc cutterbar incorporating the principles of the instant invention, the rotational path of the individual disc members being shown in phantom, the disc mower being one of the configurations in which the improved disc cutterbar of the instant invention can be utilized;
FIG. 2 is a cross-sectional view of the cutterhead module taken along line 2 — 2 of FIG. 1;
FIG. 3 is an enlarged view of a portion of FIG. 2;
FIG. 4 is a top plan view of the lower locking block taken along line 3 — 3 of FIG. 3;
FIG. 5 is a view similar to FIG. 3, showing a cross-sectional view of the cutterhead module taken along line 2 — 2 of FIG. 1 after the shear mechanism has failed and the upper disc hub 42 and lower disc hub 43 have separated.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings and particularly to FIG. 1, a modular disc cutterbar incorporating the principles of the instant invention can best be seen in a configuration in which the disc cutterbar is conventionally utilized. For a more detailed description of a conventional modular disc cutterbar and various configurations thereof reference is made to U.S. Pat. No. 5,996,323. The disclosure in that patent is hereby incorporated herein in its entirety by reference.
Cutterbar 30 is mounted in a disc mower 10 having a support frame 11 connected to the three-point hitch mechanism 3 of a tractor T on which the mower 10 is carried in a conventional manner. The disc mower 10 receives operative power from the conventional tractor power take-off shaft 5 . The mower drive mechanism 15 receives the rotational power from shaft 5 and transfers the rotational power to a gearbox 17 , which in turn transfers the rotational power to the cutterbar drive mechanism.
An alternative configuration for the disc cutterbar would be to incorporate the cutterbar in a disc mower-conditioner. This well-known configuration is shown in more detail in U.S. Pat. No. 5,761,890, which is also hereby incorporated herein in its entirety by reference. One skilled in the art and knowledgeable about commercial applications of disc cutterbars will readily recognize that there are other specific configurations of cutterbars to which the invention to be disclosed herein will be applicable. Such skilled individual will also readily recognize that the cutterbar need not necessarily be modular in construction.
Modular cutterbar 30 is formed from alternating cutterhead modules 40 and spacer modules 32 . Each cutterhead module 40 , as best seen in FIGS. 1 and 2, includes a hollow cast housing 41 (FIG. 2) having a shape to retain a low profile and to establish an oil reservoir 89 therewithin. As will be discussed in more detail below, the cutterheads 40 are gear driven and assembled in such a manner as to establish a specific timing relationship between adjacent units. More particularly, the cutterheads are arranged such that the knives 82 on adjacent units have overlapping cutting paths, but do not come into contact with each other. Failure to maintain this timed relationship during operation will result in one unit hitting the adjacent unit(s), damaging the cutterheads (and possibly initiating a chain reaction that damages all cutterheads), the drive train of the cutterbar and/or tractor T. In such case, the damage is usually significant.
Referring particularly to FIG. 2, it can be seen that each cutterhead module 40 is provided with a forwardly positioned rock guard 65 and a skid shoe 70 that passes beneath cutterhead module 40 for engagement with the surface of the ground. The rock guard 65 has a conventional semi-circular configuration and is mounted to opposing forward mounting arms of the spacer modules 32 in known manner adjacent to the corresponding cutterhead module 40 .
One skid shoe 70 is mounted beneath each cutterhead module 40 to protect the cutterhead module from wear due to engagement with the surface of the ground. Each skid shoe is formed as a generally planar body portion 71 with a mounting tab 73 affixed thereto and projecting upwardly. The body portion 71 is also formed with a forward end that is bent upwardly to engage the corresponding rock guard 65 .
Modular drive mechanism 75 , best seen in FIG. 2, is fully disclosed in the '323 patent and reference is made thereto for a more complete description.
Broadly, within each cutterhead unit there is a two-piece hub, one upper disc hub and one lower disc hub, normally held together by a shear mechanism. The lower hub is connected to a drive shaft, and the upper hub is connected to a rotatable knife support member and positioned on a specially threaded retaining bolt. At the top of the retaining bolt is an area that remains threadless. When a knife engages a solid or fixed object and a shear force generated adequate to cause the shear mechanism to fail, the upper disc hub rotates upward along the threads of the retaining bolt to the threadless area of the bolt where it is permitted to rotate freely. By thus preventing the knives from rotating further, damage is prevented to the drive train of the cutterbar and between adjacent cutterhead units.
Attention is now directed to FIGS. 3-5. In the preferred embodiment, upper disc hub 42 is affixed to lower disc hub 43 by means of multiple spring-mounted balls and detents 50 (only one shown in FIGS. 3 and 5 ). Bore hole 51 through upper disc hub 42 contains a spring 52 and ball 53 . Detent 54 in lower disc hub 43 is aligned with the spring-mounted ball 53 to affix the two hubs. By controlling the compression force of spring 51 on ball 52 (and that of any others used), a specific shear point or force can be calculated so that failure will occur at the desired point and upon a specific impact. After failure of the shear device 50 , upper disc hub 42 is free to rotate upward on threads 61 about specially threaded retaining bolt 60 until it reaches the threadless point of the bolt 62 . At threadless point 62 , the upper disc hub 42 ends its upward rotation, rotates freely, and eventually comes to a stop on its own.
Retaining bolt 60 has a nut at the tope end thereof, a threaded portion 63 at the opposing end thereof for tightening in a centrally threaded bore in driven shaft 86 . Driven shaft 86 is splined at 82 and thus affixed to lower disc hub 43 . The intermediate portion of retaining bolt 60 is reverse threaded at 61 and to upper disc hub 42 . Bolts 81 hold cover 84 and cover, or “turtle”, 80 in place on upper disc hub 42 , but do not extend into lower hub 43 .
A useful characteristic of the shear mechanism of the instant invention is that the ball and detent design allows for shear pin failure without any byproducts that could affect the other operations of the cutterbar. Devices such as that shown in the '662 patent listed above would, upon failure of the shear device, present metallic debris that would likely interfere with, and “jam” up the brake disclosed herein.
As can be seen in FIGS. 2 and 3, upper disc hub 42 is detachably splined onto driven shaft 86 . Upper disc hub 42 is affixed to lower disc hub 43 by multiple spring-mounted ball and detent devices that, as described above, serve as a shear device. Turtle 80 , and thus knives 82 , rotates with lower hub 43 . The driven shaft 86 is rotatably supported by a bearing block detachably mounted to the cutterhead module housing 41 by bolts. The bearing block seals an opening in the top of the housing 41 through which the drive gears can be extracted from the oil reservoir 89 .
As most clearly seen in FIG. 5, when the cutterhead engages a fixed object of sufficient mass or rigidity to generate a shearing force on the spring-mounted balls and detents 50 adequate to cause failure thereof, the upper and lower disc hubs 42 , 43 will separate and upper disc hub 42 will rotate upwardly via threads 36 .
As taught in the incorporated patents, the drive mechanism 75 in each cutterhead module 40 is coupled to the other cutterhead module drive assemblies by a transfer shaft that passes through a spacer module. A transfer shaft is splined at each opposing end thereof to be finally received within either of the hubs to transfer rotational power thereto.
Referring again to the configurations of utilization of the cutterbar 30 as depicted in FIG. 1, it can be seen that the drive mechanism 75 in a disc mower 10 receives rotational power from a gearbox 17 that is supported adjacent the inboardmost cutterhead module 40 . Accordingly, the drive assembly is connected directly to the output shaft (not shown) of the gearbox 17 . The transfer of rotational power to the remaining cutterhead modules 40 proceeds as described above.
As seen in FIG. 4, four shear devices, i.e., balls and detents, are used in the preferred embodiment. Any reasonable number can be used, so long as together the shear forces can be adjusted within useful limits. The shear force may be adjusted or established by the selection of springs, the sizes of the balls, the depth of the detents, and the number and location of shear devices used. The balls and detents are space equally around the rotational axis of the hubs, but this is not necessarily done in all possible embodiments. Additionally, it is possible to use balls and detents of different sizes to establish the required shear force.
It will be understood that changes in the details, materials, steps and arrangements of parts which have been described and illustrated to explain the nature of the invention will occur to and may be made by those skilled in the art upon a reading of this disclosure within the principles and scope of the invention. The foregoing description illustrates the preferred embodiment of the invention; however, concepts, as based upon the description, may be employed in other embodiments without departing from the scope of the invention. Accordingly, the following claims are intended to protect the invention broadly as well as in the specific form shown. | A disc cutterbar having a two-piece mounting hub, one piece rotatably driven and the other supporting a knife for severing standing crop material, with spring-mounted ball and detent devices holding the two pieces members together and forming a shear device therebetween is disclosed. A specially threaded retaining bolt is associated with the knife-supporting piece whereby, upon failure of the shear device, the knife-supporting piece is rotated out of the cutting plane and away from the operational cutterheads. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a hydraulic control system for an automatic transmission.
2. Description of the Prior Art
Generally, an automatic transmission for an automotive vehicle is provided with a torque converter and a shift gear mechanism of which a plurality of frictional elements, such as a clutch, brake are selectively actuated to switch a power transmitting path to thereby establish a desired shift stage automatically.
The automatic transmission includes a hydraulic control unit for controlling a hydraulic fluid to and from an actuator of the frictional element. The hydraulic control unit is provided with a regulator valve for adjusting a hydraulic pressure from an oil pump to a line pressure, a manual valve for manually switching a shift range, a plurality of shift valves for selectively actuating the frictional elements, and auxiliary valves actuated in connection with various operations. In recent years, the shift valve has been controlled through a solenoid so as to accomplish a sophisticated shift control in response to a vehicle operating condition.
In such kind of the automatic transmission, as disclosed in Japanese Patent public disclosure (JP A2) No. 63-186055, a low reverse hydraulic circuit for supplying a hydraulic pressure to a low reverse brake is provided independently from a 3-4 clutch hydraulic circuit for supplying a hydraulic pressure to a 3-4 clutch and operates independently from each other so as to prevent a double lock situation in which both the low reverse brake and the 3-4 clutch are engaged concurrently.
However, In such an automatic transmission as aforementioned, it is impossible to engage the 3-4 clutch when a L(low)-range or 1-range is selected in the manual valve that a higher shift stage, for example a third stage cannot be established in the L-range.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a hydraulic control system for an automatic transmission which can establish a higher shift stage in a low range selected.
It is another object of the present invention to prevent a double lock of a frictional element for a lower shift stage such as the low reverse brake and another frictional element for a higher shift stage such as the 3-4 clutch.
The above and other object of the present invention can be accomplished by a hydraulic control system for an automatic transmission comprising a shift gear mechanism for providing a plurality of shift stages of different speed ratios, a plurality of frictional elements to be selectively actuated for switching a power transmitting path to establish a desired shift stage, a manual valve for manually selecting a shift range among a plurality of shift ranges providing predetermined shift stages, a 1-2 shift valve for making a shift operation between a first stage and a second stage, a 2-3 shift valve for making a shift operation between the second stage and a third stage, a low stage frictional element for establishing a lower shift stage, a low stage hydraulic circuit for controlling the low stage frictional element by introducing a hydraulic pressure through the manual valve and the 1-2 shift valve, a high stage frictional element for establishing a higher shift stage, a high stage hydraulic circuit for controlling the high stage frictional element by introducing a hydraulic pressure through the manual valve, the 1-2 shift valve and the 2-3 shift valve, the 1-2 shift valve interrupting the introduction of the hydraulic pressure for the low stage hydraulic circuit when the hydraulic pressure is introduced into the high stage hydraulic circuit and introducing the hydraulic pressure to the low stage hydraulic circuit when the introduction of the hydraulic pressure to the high stage hydraulic circuit is interrupted.
According to the above feature of the invention, when the 1-2 shift valve is switched to introduce the hydraulic pressure into the low stage hydraulic circuit in the case where the manual valve is operated to select L-range or 1-range, the low stage frictional element such as a low reverse brake is engaged to establish a lower shift stage such as a first stage in the 1-range. When the hydraulic pressure is introduced into the high stage hydraulic circuit by virtue of the switching action of the 1-2 shift valve, the high stage frictional element such as a 3-4 clutch is engage to establish a higher shift stage such as a third stage in the 1-range. This enables the engine to prevent an overrun in the low-range. In this case, the switching action of the hydraulic pressure between the introduction and interruption for the low stage hydraulic circuit corresponds to that between the interruption and introduction for the high stage hydraulic circuit as the shift valve is switched. Therefore, a reliable prevention can be accomplished against the double lock of the high and low stage frictional elements.
Further objects, features and advantages of the present invention will become apparent from the Detailed Description of Preferred Embodiments which follows when read in light of the accompanying Figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of an automatic transmission to which a control system in accordance with the present invention can be applied;
FIG. 2A, 2B, and 2C show a hydraulic control circuit incorporated into the automatic transmission of FIG. 1 for controlling a lock-up clutch;
FIG. 3 shows a part of hydraulic control circuit of FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, an automatic transmission 10 according to the present invention includes a torque converter 20, a shift gear mechanism 30 driven by an output of the torque converter 20, a plurality of frictional elements 46 and one-way clutches 51 and 52 for switching a power transmitting path of the shift gear mechanism 30 to establish one of D, 2, L, R-range when running. In the D-range, 1-4th shift stages are provided. 1-3rd shift stages are provided in the 2-range. 1-3rd shift stages are provided in the L-range.
The torque converter 20 includes a pump 22 provided in a case 21 connected with an engine output shaft 1, a turbine 23 facing the pump 22 to be driven by the pump 22 through a hydraulic fluid, a stator 25 disposed between the pump 22 and the turbine 23 and supported by a transmission case 11 through a one-way clutch 24 and a lock-up clutch 26 disposed between the case 21 and the turbine 23 for directly connecting the engaging output shaft 1 with the turbine 23. The rotation of the turbine 23 is transmitted to the shift gear mechanism 30 through the turbine shaft 27. The engine output shaft 1 is connected with a pump shaft 12 passing through the turbine shaft 27. The pump shaft 12 drives an oil pump 13 provided at a rear end portion of the automatic transmission 10.
The shift gear mechanism 30 of a Ravigneaux-type planetary gear mechanism includes a small sun gear 31 movably mounted on the turbine shaft 27, a large sun gear 32 movably mounted on the turbine shaft 27 rearward of the small sun gear 31, a plurality of short pinion gears 33 meshed with the small sun gear 31, a long pinion gear 34 meshed with the short pinion gear 33 at a front portion and with the large sun gear 32, a carrier 35 for rotatably carrying the long pinion gear 34 and the short pinion gear 33, and a ring gear 36 meshed with a front portion of the long pinion gear 34.
Between the turbine shaft 27 and the small sun gear 31 are disposed a forward clutch 41 and a first one-way clutch 51 in series and a coast clutch 42 in a juxtaposed relationship with the clutches 41 and 51. A 3-4 clutch 43 is disposed between the turbine shaft 27 and the carrier 35. A reverse clutch 44 is disposed between the turbine shaft 27 and the large sun gear 32. Between the large sun gear and the reverse clutch 44 is disposed a 2-4 brake 45 as a band brake fixing the large sun gear 32. Between the carrier 35 and the transmission case 11 are disposed a second one-way clutch 52 for supporting the carrier 35 against a reactive force acting thereto and a low reverse brake 46 for fixing the carrier 35 in a juxtaposed arrangement. The ring gear 36 is connected with the output gear 14 through which a rotation is transmitted to right and left wheels (not shown) through a differential mechanism.
A relationship between operations of the frictional elements and the shift stages obtained has been known so that a detailed explanation is omitted by showing the relationship in Table 1. In the table 1, (0) means that the corresponding element is engaged to transmit the torque. (*) means that the corresponding element races when coasting.
TABLE 1__________________________________________________________________________ ONE-WAYCLUTCH BRAKE CLUTCHFORWARD COAST 3-4 REVERSE 2-4 LOW REVERSE 1st 2ndRANGE(41) (42) (43) (44) (45) (46) (51) (52)__________________________________________________________________________R ◯ ◯ND 1st◯ ◯* ◯* 2nd◯ ◯ ◯* 3rd◯ ◯ ◯ ◯* 4th◯ ◯ ◯2 1st◯ ◯* 2nd◯ ◯ ◯ ◯* 3rd◯ ◯ ◯ ◯*1 1st◯ ◯ ◯ ◯* ◯* 2nd◯ ◯ ◯ ◯* 3rd◯ ◯ ◯ ◯*__________________________________________________________________________
Hereinafter, a hydraulic control circuit 60 is explained taking reference with FIG. 3.
An actuator 45' of the 2-4 brake 45 includes a servo piston having an apply port 45a' and a release port 45b'. When the hydraulic pressure is introduced only into the apply port 45a', the 2-4 brake 45 is engaged. When the hydraulic pressure is supplied to both the port 45a' and the port 45b' or when no hydraulic pressure is supplied to both of them, the 2-4 brake 45 is disengaged. Actuators of the other frictional elements 41-44, and 46 include usual hydraulic pistons so that they are engaged when the hydraulic pressure is introduced into the actuators.
The hydraulic control circuit 60 is provided with a regulator valve 61 for adjusting a hydraulic pressure from the oil pump 13 to a main line 110 to a line pressure, a manual valve 62 for selecting a range in the D, 2, L and R through manual operation and 1-2,2-3 and 3-4 shift valves 63, 64 and 65 which control the hydraulic pressure for the actuators of the frictional elements 41-46.
The manual valve 62 is provided with an input port e and a first through fourth output ports a-d. When a spool 62a is moved, the input port e is communicated with the first and second output ports a, b in the D-range and 2-range, with the first and third ports a, c in the L-range and with the fourth port d in the R-range. With the output ports a-d are connected lines 111-114 respectively.
In the 1-2, 2-3, 3-4 shift valves 63, 64 and 65, spools 63a, 64a and 65a are urged rightwardly as illustrated. At right end of the spools 63a, 64a and 65a are provided pilot ports 63b, 64b and 65b respectively. With the pilot port 63b of the 1-2 shift valve 63 is connected a pilot line 115 separated from the main line 110 through a line 118. With the pilot port 64b of the 2-3 shift valve 64 is connected a pilot line 116 separated from the first output line 111. With the pilot port 65b is connected a pilot line 117 communicated with the main line 110. On the pilot lines 115, 116 and 117 are provided 1-2, 2-3 and 3-4 solenoid valves 66, 67 and 68. When the solenoid valve 66-68 are energized or ON, the pilot lines 115, 116 and 117 are drained so that the pilot pressure of the ports 63b-65b are discharged. Thus, the spools 63a-65a are placed at the right position. When the solenoid valves 66-67 are deenergized or OFF, the hydraulic pressure is introduced into the pilot ports 63b-65b through the pilot lines 115, 116 and 117 to place the spools 63a-65a at a left position.
The solenoid valves 66-68 are controlled between ON and OFF based on a map defined by the vehicle speed and throttle communicated with the frictional elements 41-46 through the shift of the spool 63a-65a of the shift valves 63-65. Thus, the frictional element 41-46 are selectively engaged as shown in Table 1 to establish a specific shift stage. In this case, a relationship between the ON and OFF of the solenoid valves 66-68 and the shift stages is shown in Table 2.
TABLE 2__________________________________________________________________________ D 2 1 1 2 2←3 3 4 1 2 3 1 2__________________________________________________________________________1-2 SOLENOID VALVE (66) OFF ON ON ON ON OFF ON ON OFF ON2-3 SOLENOID VALVE (67) ON ON ON OFF OFF ON ON OFF ON ON3-4 SOLENOID VALVE (68) ON ON OFF OFF ON ON OFF OFF OFF OFF__________________________________________________________________________
When a down shift is made from the third to second stages, an intermediate stage is established.
A forward clutch line 119 is separated from the first output line 111 connected with the main line 110. The line 119 is connected with a forward clutch 41 through a one-way orifice Thus, in the D, 2 and L-range, the forward clutch 41 is engaged. A N-D accumulator 72 is connected with the forward clutch line 119 through a line 120 for providing a damping effect during the engagement of the forward clutch 41. A numeral 73 designates a one-way orifice.
The first output line 111 is connected with the 1-2 shift valve 63. When the 1-2 solenoid valve 66 is turned 0N to move the spool 63a of the 1-2 shift valve 63 rightwardly, the line 111 is communicated with a servo apply line 121 so that the hydraulic pressure is introduced to the apply port 45a' of the servo piston 45' through a one-way orifice 74. Thus, when the 1-2 solenoid valve 66 is ON in D, 2 and L-range, in other words, when the second, third or fourth stages is established in the D-range, when the second or third stages is established in the 2-range and when the second stage is established in the L-range, the hydraulic pressure is introduced into the apply port 45a' as a servo apply pressure. In this case, when the hydraulic pressure is not introduced into the release port 45b' wherein the second or fourth stage in the D-range, the second stage in the 2-range or the second stage in the L-range is established, the 2-4 brake is engaged. A 1-2 accumulator 75 for damping in engaging the 2-4 brake 45 is connected with the apply port 45a' through a line 122.
The first output line 111 is communicated with the 3-4 shift valve 65 and with a line 123 when the 3-4 solenoid valve 68 is OFF and the spool 65a is in the left position. The line 123 is communicated with the 2-3 shift valve 64 and with a coast clutch line 124 when the 2-3 solenoid valve 67 is ON and spool 64a is in the right position. The coast clutch line 124 is communicated with the coast clutch 42 through a one-way orifice 76 and a ball valve 77 for switching the hydraulic passage. Thus, when the 2-3 solenoid valve 67 is ON and the 3-4 solenoid valve 68 is OFF, in other words when the second stage in the 2-range and the first or second stages in the L-range are established, the coast clutch 42 is engaged.
The second output line 112 communicated with the main 110 in the D, 2 and L-ranges is communicated with the 1-2 shift valve 63. When the 1-2 solenoid valve 66 is ON so that the spool 63a is in the right position, the second output line 112 is communicated with a line 147. The line 147 is communicated with the 2-3 shift valve 64 and with a 3-4 clutch line 125 when the 2-3 solenoid valve 67 is OFF so that a spool 64a of the 2-3 shift valve 63 is in the left position. The line 125 is connected with the 3-4 clutch 43 through a one-way orifice 78. Thus, when the 1-2 solenoid valve 66 is ON and the 2-3 solenoid valve 67 is OFF in the D, 2 and 1-range, in other words, when the third or fourth stage in the D-range, the third stage in the 2-range or the third stage in the L-range is established, the 3-4 clutch 43 is engaged. In the illustrated embodiment, the second output line 112 of the manual valve 62, the line 147, the 3-4 clutch line 125 forms a 3-4 clutch circuit as a high stage hydraulic circuit A (see FIG. 3) for introducing a hydraulic pressure into the 3-4 clutch 43 as a high stage frictional element. An accumulator 79 for damping in engaging the 3-4 clutch 43 is connected with the clutch line 125. A numeral 80 is a one-way orifice.
A line 126 separated from the 3-4 clutch line 123 is communicated with the 3-4 shift valve 65 and communicated with a line 127 when the 3-4 solenoid valve 68 is OFF in which the spool 65a is in the left position, and with a servo release line 128 through a 2-3 timing 102. The servo release line 128 is communicated with the release port 45b' of the servo piston 45' through a one-way orifice 81. Thus, when the 1-2 solenoid valve 66 is on and both the 2-3 and 3-4 solenoid valves 67 and 68 are OFF in the D, 2 or L-range, in other words, when the third stage in the D, 2 or L-range, the servo release pressure is introduced into the release port 45b' of the servo piston 45' to release the 2-4 brake 45.
A line 129 separated from the servo release line 128 is communicated with a coast clutch line 124 and with the coast clutch 42 through a coast control valve 82 and the ball valve 77. Thus, when the third stage is established in the D-range, 2-range and L-range in which the hydraulic pressure is introduced into the servo release line 128, the coast clutch 42 is engaged.
The third output line 113 communicated with the main line 110 through the manual valve 62 is communicated with the 1-2 shift valve 63 through a ball valve 83 as a switching valve. The line 113 is communicated with a low reverse brake line 130 when the 1-2 solenoid valve 66 is OFF to place the spool 63a at the left position and communicated with the low reverse brake 46 through a one-way orifice 84 for the accumulator. The low reverse brake 46 is engaged when the 1-2 solenoid valve 66 is OFF in the L-range or when the first stage is established in the L-range. In the illustrated embodiment, the third output line 113 and the low reverse brake line 130 forms a low reverse hydraulic circuit B (see FIG. 3) as a lower range circuit for introducing the hydraulic pressure into the low reverse brake 46 as a low stage frictional element.
A bypass passage 131 is provided on the low reverse brake line 130. The bypass passage 131 includes a first bypass passage 131a separated from an upstream portion of the line 130 and communicated with the 3-4 shift valve 65, and a second bypass passage 131b extended from the 3-4 shift valve 65 to a downstream portion of the one-way orifice 84. When the 3-4 solenoid valve 68 is OFF to place the spool 65a at the left position, the first and second bypass passage 131a and 131b are communicated with each other.
The low reverse brake line 130 is connected with a N-R accumulator 85 for damping the low reverse brake 46 when the brake 46 is engaged.
The fourth output line 114 communicated with the main line 110 when the manual valve 62 is in the R-range is communicated with the ball valve 83 through a line 132 separated from the line 114. Further, the fourth output line 114 is communicated with the reverse clutch through a reverse clutch line 133. Thus, in the R-range, only when the 1-2 solenoid 66 is OFF, the low reverse brake 46 is engaged. The reverse clutch 44 is kept engaged in the R-range.
The hydraulic control unit 60 is also provided with a lock-up shift valve 86 for actuating the lock-up clutch 26 of the torque converter 20 shown in FIG. 1 and a lock-up control valve 87 for adjusting the hydraulic pressure introduced into the torque converter 20. Numerals 88 and 89 designate a duty solenoid valve and a lock-up solenoid valve respectively.
The lock-up shift valve 86 is connected with the regulator valve 61 through a torque converter line 134. A first and second pilot ports 86b and 86c provided at opposite ends of the valve 86 are communicated with lines 136 and 137 separated from a pilot line 135 which is separated from the main line 110 and provided with a reducing valve 90. The lock-up solenoid valve 89 is provided on the line 136. When the lock-up solenoid valve 89 is ON to place the spool 86a of the lock-up shift valve 86 at the right position, the torque converter line 134 is communicated with a torque converter line 138 and with the inside of the torque converter 20 so that the hydraulic pressure in the torque converter 20 is increased to engage the lock-up clutch 26. When the lock-up solenoid valve 89 is OFF to move the spool 86a of the valve 86 leftward, the converter line 134 is communicated with a lock-up release line 139 so that a lock-up release pressure is introduced into the torque converter 20 to release the lock-up clutch 26. Numeral 94 designates a converter release valve.
In addition, the hydraulic control circuit 60 is provided with a bypass valve 101 and a 3-2 timing valve 103 in addition to the coast timing valve 82 and the 2-3 timing valve 102.
The coast timing valve 82 is disposed on a line 129 separated from the line 128 and communicated the coast clutch line 124 through the ball valve 77. The servo apply pressure is introduced to one end of the spool 82a through a line 140 separated from the servo apply line 121. When the servo release pressure introduced into the other end of the spool 82a through the line 129 added to a spring force is increased beyond the servo apply pressure, the line 129 is opened. Therefore, when a shift up operation from the second to the third stages (a 2-3 shift-up operation ) is made in the D or 2 range, the coast clutch 42 is engaged after the servo release pressure is increased enough to release the 2-4 brake 45. As a result, a double lock condition can be avoided that both the 2-4 brake 45 and the coast clutch 42 are engaged concurrently. In this case, the servo apply pressure is introduced into one end of the spool 82a of the coast timing valve 82 so that the communication timing of the line 129 is changed in accordance with the servo apply pressure. As a result, a relationship between the communication timing and the pressure level of the servo release can be maintained appropriately.
The one-way valve 101 is provided on a bypass line 141 which bypasses the one-way orifice 78 provided on the 3-4 clutch line 125. A spool 101a of the valve 101 is subjected to a 3-4 clutch pressure produced at downstream of the oneway orifice 78 at one end, and subjected to a throttle modulator pressure adjusted by a regulator valve 91 to a pressure corresponding to the engine load at the other end through a line 142. When the 3-4 clutch pressure is increased beyond a predetermined value to move the spool 101a to the left position, the bypass line 141 is interrupted. At the beginning, the 3-4 clutch pressure is increased quickly by the hydraulic pressure introduced through the bypass line 141. Thereafter, the 3-4 clutch pressure is increased gradually by means of the one-way orifice 78. As a result, the engaging timing of the 3-4 clutch 43 can be controlled in the 2-3 shift up operation. Numerals 92 and 93 designates a duty solenoid valve and an accumulator.
The 2-3 timing valve 102 is provided between the servo release line 128 and a line 127 communicated with the 3-4 shift valve 65. A spool 102a of the valve 102 is subjected to the 3-4 clutch pressure at one end and to the servo release pressure at the other end. The valve 102 communicates the servo release line 128 with the line 127 and drains the line 128 in accordance with the servo release pressure so that the servo pressure is controlled in response to the 3-4 clutch pressure.
The 3-2 timing valve 103 is provided between a first bypass line 143 bypassing the one-way orifice 74 on the servo apply line 121 and a second bypass line 144 bypassing the one-way orifice 71 on the forward clutch line 119. The valve 103 is communicated with a pilot line 145 separated from a line 118 communicated with the main line 110 at one end portion of a spool 103a, communicated with a drain line 146 separated from the servo release line 128 at an intermediate portion of the spool 103a. The pilot line 145 is provided with a 3-2 solenoid valve 95. The timing valve 103 opens and closes the first and second bypass lines 143 and 144 in accordance with the 3-2 solenoid valve 95 in a 1-2 shift up operation (shift up operation from the first stage to the second stage), the 3-2 shift down operation and a 4-2 shift down operation (shift down operation from the fourth stage to the second stage) so as to control hydraulic supply timing. In detail, the valve 103 is operated to communicate the first bypass line 143 so as to provide the apply port 45a' with the servo apply pressure increasing rapidly in an initial stage of the 1-2 shift up operation. After a certain time period from the start of the shift operation, the first bypass line 143 is interrupted so that the servo apply pressure increasing gradually is introduced into the apply port 45a' of the servo piston 45' through the one-way orifice 74. In the 3-2 shift down operation, the valve 103 communicates the drain line 146 with a drain port and thereafter interrupts the drain line 146. As a result, the servo release pressure is decreased quickly at initial stage of the shift operation through the drain line 146 and decreased gradually at final stage of the shift operation through the one-way orifice 81 which reduces a flow area of the servo release line 128. In the 4-2 shift down operation, the valve 103 opens the second bypass line 144 at initial stage so that the forward clutch pressure increasing rapidly is introduced into the forward clutch 41. At final stage of the shift operation, the second bypass line 144 is closed so that the forward clutch pressure increasing gradually by virtue of the one-way orifice is introduced into the forward clutch 41. The main line 110 is communicated with a back pressure ports 72a, 75a, 79a and 85a of the accumulators 72, 75, 79 and 85 to provide them with the hydraulic pressure. The main line 110 is provided with the regulator valve 91 connected with the reducing valve 90 and the duty solenoid valve 92. The duty solenoid valve 92 which is controlled by a ON-OFF signal is actuated to drain the main line 110 when it is ON so that the back pressure acting on the accumulators 72, 75, 79 and 85 is reduced. Thus, the back pressure provided by the main line 110 is controlled by a duty ratio (ratio of a valve opening time in one cycle) of the duty solenoid valve 92.
the low reverse hydraulic circuit A and the 3-4 clutch hydraulic circuit B in the hydraulic circuit 60 controls the engagement of the low reverse brake 46 and the 3-4 clutch 43 by means of the switching action of the shift valve 63 and 2-4 shift valve 64. Through this control, the third stage can be established in the L-range. It should be however noted that the low reverse hydraulic circuit A is opened to engage the low reverse brake 46 when the 3-4 clutch hydraulic circuit B is closed to disengage the 3-4 clutch 43 and vice versa in response to the switching action of the 1-2 shift valve 63. Therefore, the double lock can be avoided that the low reverse brake 46 and the 3-4 clutch 43 are engaged concurrently.
Although the present invention has been explained with reference to a specific, preferred embodiment, one of ordinary skill in the art will recognize that modifications and improvements can be made while remaining within the scope and spirit of the present invention. The scope of the present invention is determined solely by the appended claims. | A hydraulic control system for an automatic transmission including a shift gear mechanism having a plurality of frictional elements to be selectively actuated for switching a power transmitting path to establish a desired shift stage, a manual valve for manually selecting a shift range among a plurality of shift ranges providing predetermined shift stages, a 1-2 shift valve for making a shift operation between a first stage and a second stage, a 2-3 shift valve for making a shift operation between the second stage and a third stage, a low stage frictional element for establishing a lower shift stage, a low stage hydraulic circuit for controlling the low stage frictional element by introducing a hydraulic pressure through the manual valve and the 1-2 shift valve, a high stage frictional element for establishing a higher shift stage, a high stage hydraulic circuit for controlling the high stage frictional element by introducing a hydraulic pressure through the manual valve, the 1-2 shift valve and the 2-3 shift valve, the 1-2 shift valve interrupting the introduction of the hydraulic pressure for the low stage hydraulic circuit when the hydraulic pressure is introduced into the high stage hydraulic circuit and introducing the hydraulic pressure to the low stage hydraulic circuit when the introduction of the hydraulic pressure to the high stage hydraulic circuit is interrupted. This enables the engine to prevent an overrun in the low-range. A reliable prevention can be accomplished against the double lock of the high and low stage frictional elements. | 5 |
BACKGROUND OF THE INVENTION
This invention relates to wheelbarrows, and in particular, to a semi-enclosed chute attachment for a wheelbarrow.
There is a need both in home and commercial applications for a wheeled tool which allows one to transport bulky or heavy loads. The most commonly used tool to accomplish this purpose is called a wheelbarrow. A wheelbarrow is generally comprised of a forward wheel, a frame joined to and extending back from the wheel and terminating at the back of the wheelbarrow in handles which the user lifts to roll the wheelbarrow, two support legs joined to the frame at the back of the wheelbarrow in front of the handles, and a container resting on the frame. The container, also referred to as a tray or a tub, typically is roughly rectangular in shape. The front of the wheelbarrow container may be somewhat rounded. A wheelbarrow is usually unloaded by tipping vertically over the front wheel.
Most wheelbarrows are designed to have the widest possible utility in transporting a variety of materials within the wheelbarrow. As such, the wheelbarrow is an effective and highly useful tool. However, some of the applications for which a wheelbarrow is effective require an accurate pouring of the contents being emptied from the wheelbarrow. The front shape of the normal wheelbarrow container provides a broader pouring front than is always desirable. The prior art contains various patents for devices with the purpose of expanding the capacity of a wheelbarrow tray. However, none of these devices specifically address the need to accurately channel the materials being emptied from the wheelbarrow. There is, therefore, a need for a pouring, chute-like attachment for a conventional wheelbarrow.
SUMMARY OF THE INVENTION
The present invention provides a semi-enclosed pouring chute attachment for a wheelbarrow. The primary function of the invention attachment is to serve as an accuracy enhancing channeling device for materials being emptied from the wheelbarrow. The material could be solids, semi-solids, or liquids. The attachment sits on the front of the wheelbarrow and is secured by upper side channels and either rope of shock/bungee cords from the sides of the attachment to the handles of the wheelbarrow. In an alternate embodiment, the wheelbarrow container may have a funnel end as an integral part thereof or as an insert.
These together with other objects of the invention, along with various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed hereto 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 is illustrated a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a right side elevational view of a conventional wheelbarrow.
FIG. 2 is a left side elevational view of a conventional wheelbarrow.
FIG. 3 is a rear perspective view of a conventional wheelbarrow.
FIG. 4 is a top view of a conventional wheelbarrow.
FIG. 5 is a side perspective view of a wheelbarrow with a chute attachment.
FIG. 6 is a front view a wheelbarrow with a chute attachment.
FIG. 7 is a top view a wheelbarrow with a chute attachment.
FIG. 8 is a top view of the chute attachment.
FIG. 9 is a section view along the lines 9 — 9 of FIG. 8 .
FIG. 10 is a front perspective view of an alternate embodiment of the invention.
FIG. 11 is a top view of the embodiment illustrated in FIG. 10 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings in detail wherein like elements are indicated by like numerals, especially FIGS. 1–4 , reference numeral 10 generally represents a wheelbarrow having a front with a single forward wheel 11 , two side frame pieces 12 , 13 running in a rearwardly diverging manner from the front wheel 11 , from which two handles 14 , 15 are respectively extended and form a wheelbarrow rear, two rearward support legs 16 , 17 each joined to a side frame piece 12 , 13 , respectively, at the back of the wheelbarrow in front of the handles 14 , 15 , and a container body 20 resting on the two side frame pieces 12 , 13 behind the forward wheel 11 and in front of the handles 14 , 15 , said container body 20 having an open top 21 , generally planar bottom 22 attached to said side frame pieces 12 , 13 , upwardly and outwardly inclined opposing sides 23 , 24 , an upwardly and outwardly inclined front end 25 and opposing rear end 26 . The container body front end 25 , rear end 26 and sides 23 , 24 have a continuous rim 27 formed along the top 21 . On the forward end of the side frame pieces 12 , 13 are respectively two bearings 18 in which a wheel shaft 19 is journaled.
Referring more particularly to FIGS. 5–9 , the chute attachment embodying the features of the present invention is indicated generally at 30 and may be attached to the container body front end 25 and sides 23 , 24 . The chute attachment 30 has a front spout 31 with two opposite side walls 32 curving downward and toward each other, thereby merging and forming a curved spout bottom 33 . The spout 31 has a forward end 34 and a rearward end 35 , said forward end 34 shaped generally like an open, half-cylinder. The chute attachment 30 has two sides 40 beginning at the spout rearward end 35 and extending from each spout side wall 32 rearwardly and divergently outward a predetermined distance. The predetermined distance for each side chute attachment side 40 is approximately equal to one-half the distance between the wheelbarrow container body sides 23 , 24 .
At the predetermined distance each chute attachment side 40 diverges and extends rearwardly a desired distance in parallel relationship with the opposite side 40 . Each attachment side 40 has a top 41 , a bottom 42 , an interior surface 43 , an exterior surface 44 , and a rear end 45 , said interior surface 43 being defined as the surface facing the opposite side. The top 41 of each attachment side 40 is rolled inwardly forming a longitudinal interior surface channel 46 with an open bottom 47 . The attachment side rear end 45 has a plurality of holes 48 formed therein. The holes 48 are adapted to receive hooks 51 attached to bungee cords 50 or the like.
The chute attachment 30 is adapted to fit over the wheelbarrow container body front end 25 and sides 23 , 24 , wherein the chute attachment side channels 46 are fitted over the container body rim 27 , channel open ends 47 first. A bungee cord 50 with two ends and a hook 51 attached to each end is looped over each wheelbarrow handle 14 , 15 and the bungee cord hooks 51 placed into engagement with the respective chute attachment side holes 48 . Alternatively, a hole 28 could be drilled in each wheelbarrow container body side 23 , 24 . The bungee cords 50 could then be replaced with a small mechanical fastener, e.g., bolt and wing nut, attached through a chute attachment side hole 48 and the wheelbarrow container body side hole 28 .
Referring more particularly to FIGS. 10–11 , in an alternate embodiment of the invention, the wheelbarrow container body front end 25 is be shaped in the form of a spout 31 . The container body sides 23 , 24 would merge into and form the spout side walls 32 .
It is understood that the above-described embodiment is merely illustrative of the application. Other embodiments may be readily devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof. | A semi-enclosed pouring chute attachment for a wheelbarrow. The attachment sits on the front of the wheelbarrow and is secured by upper side channels and either rope of shock/bungee cords from the sides of the attachment to the handles of the wheelbarrow. In an alternate embodiment, the wheelbarrow container may have a funnel end as an integral part thereof. | 1 |
FIELD OF THE INVENTION
[0001] The subject of the present invention relates to a sidestep assembly for a vehicle for enabling a user to easily access a toolbox in the bed of a pick-up truck. The invention also relates to a sidestep for accessing a roof rack on a SUV, minivan, or sport wagon, or even bikes, etc., that are mounted on the top of the vehicle.
BACKGROUND AND SUMMARY OF THE INVENTION
[0002] It is common to provide running boards on pick-up trucks, sport utility vehicles, and other types of vehicles where it is desirable to provide the user with ease of entry into the cabin of the vehicle. It is also advantageous to provide a sidestep near the rear of the running board that assists in easy access to a toolbox that may be located in the bed of the pick-up truck. Traditionally, running boards are located inward towards the side of the vehicle. The problem though is that they do not provide a solid surface for the user to stand on while accessing the toolbox.
[0003] It is also common to provide roof racks on minivans, SUVs and sport wagons and to secure bicycles, skis, kayaks, canoes, boats, or even sport boxes to the roof of these vehicles. A recurring problem though is accessing these items once they are secured to the vehicle. Traditional running boards however, don't provide easy access to the roof or anything secured thereto.
[0004] It is known to provide steps to provide access to a tailgate area of a pick-up truck. However, currently there are no retractable step products that are simple in design yet provide ease of access to the toolbox that is located in the bed of a truck. Rear access via the tailgate is often awkward and more time consuming if quick and simple access is required to the side of a box for replacement of tools. Further, toolboxes are generally located in the front area of the truck bed and, because typical running boards do not extend rearward enough, they do not provide ease of access to the forward part of a truck bed. Thus, it would be desirable to provide a sidestep located near the front end of the truck bed, or where the toolbox is located. It would also be desirable to provide an after market sidestep that can be connected to an existing running board. It would also be desirable to provide a sidestep as an OEM product for use in connection with an existing running board. It would also be desirable to provide an extended tube style board with a rotatable wider rear section that when rotated out, provides a wider step surface that is positioned further outward than the typical tube style running board. It is also desirable to provide a sidestep that provides ample foot contact area as well as step height so as to meet typical OEM requirements for ergonomics.
[0005] It is also desirable to provide a sidestep that provides easy access to a toolbox that is simple in design, easy to operate, and has minimal working components, and is economic and ergonomic. Accordingly, it is an object of the present invention to provide an improved retractable sidestep which overcomes the above referenced disadvantages.
[0006] It is another object of the present invention to provide an improved sidestep that can rotate out from a stowed position to a deployed position thus allowing the user to have an improved standing surface when accessing the top of the roof or a toolbox that is located in the bed of a truck.
[0007] According to one aspect of the present invention, there is provided a sidestep assembly comprised of a step positioned adjacent to the running board. A latch mechanism is provided that is located within the step and said mechanism is operable to lock the step in a stowed position or to be released to allow the step to be repositioned to a deployed position. The latch mechanism includes a release button, a push rod, a latch plate, a latch spring and a set of guide pins. The sidestep assembly further includes a spring deployment mechanism having an elongated tube with a spring positioned therein. The spring acts to rotate the step once the latch mechanism has been released, thus allowing the step to rotate out into a useable position for the user to stand on and to access a toolbox. A support tube assembly is part of the running board of the vehicle and includes a mounting bracket that secures the elongated tube in place relative to the running board. This allows the step mechanism to pivot relative to the elongated tube, between a stowed position and a deployed position.
[0008] The step assembly can be easily deployed by depressing the release button, thus allowing the step to rotate outward automatically to a deployed position where a mechanism stop locks it in place. After the user is done using the step, the step can be rotated via hand or foot means to rotate the step to the stowed position, where it automatically locks in place.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Further areas of applicability of the present invention will become apparent from a detailed description hereafter. It will be understood that the detailed description and specific examples come out while indicating preferred embodiments of the invention, are intended for purposes of illustration only, since the 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.
[0010] FIG. 1 is a perspective view of a vehicle illustrating the sidestep assembly;
[0011] FIG. 2 is a perspective view of the sidestep assembly shown in a stowed position, with the step shown in phantom;
[0012] FIG. 3 is a plan view of the FIG. 2 sidestep assembly, illustrating the sidestep assembly relative to the running board of a vehicle;
[0013] FIG. 4 is a perspective view of the sidestep assembly shown in the deployed position, with the sidestep extrusion shown in phantom;
[0014] FIG. 5 is a side view section of 5 - 5 taken from FIG. 1 showing the sidestep assembly in the stowed position, further illustrating the support tube relative to the extruded step;
[0015] FIG. 6 is a perspective view of the sidestep assembly shown in the deployed position, relative to the running board of the vehicle;
[0016] FIG. 7 is a section cut taken from the direction of arrow 7 - 7 from FIG. 6 , showing the step assembly in its deployed position relative to the running board; and
[0017] FIG. 8 is a perspective view of the step assembly shown in the stowed position, illustrating the spring located within the support tube, which is located within the extruded step.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0018] Referring to the figures, where like numerals indicate like or corresponding parts throughout the various figures, a side step assembly 10 is shown adjacent to a running board 12 that is in turn affixed to a vehicle 14 . A toolbox 16 is shown located in the forward edge of a truck bed. The purpose of the present invention is to provide ease of access by a user to the toolbox 16 via the use of a novel sidestep assembly 10 . Alternatively, the step assembly 10 can provide ease of access to a roof rack where sporting equipment can be secured. The vehicle 14 can be a truck, minivan, SUV, sport wagon or any vehicle where it is desirable to access something elevated on the vehicle 14 . For illustrative purposes only, the following description will relate to accessing a toolbox in a pick-up truck.
[0019] The sidestep assembly 10 is stream lined with the running board 12 to provide an aesthetically pleasing design. With reference to FIG. 2 , the sidestep assembly 10 is shown in the stowed position and is comprised of a sidestep extrusion 18 , a latch system 20 , a spring deploy system 22 , and a support tube assembly 24 . These components work in unison to provide a rotatable step 19 that can rotate between a stowed position 26 or a deployed position 28 ( FIG. 4 ). Once in the deployed position 28 , the user has an extended surface that protrudes away from the side panel of the truck bed, thus providing an improved solid surface to stand on when accessing the toolbox 16 .
[0020] With reference to FIG. 3 , the latch system 20 is comprised of a latch release button 30 , a seal spring 32 , a button seal 34 , a latch push rod 36 , a latch plate 38 , a set of latch guide pins 40 , a latch spring 42 , and a spring retainer 44 . The purpose of the latch system 20 is to maintain the sidestep 19 in the closed position during transport, but to be disengaged when the operator needs to access a toolbox.
[0021] The latch release button 30 extends through a hole 46 that is located in the end cap 102 of the sidestep extrusion 18 . The seal spring 32 biases the button seal 34 closed to keep debris out of the interior of the extrusion. One end 48 of the push rod 36 engages a “U” shaped slot 50 located in the latch plate 38 . They are affixed via conventional means. The latch plate 38 further includes a pair of diagonally spaced slots 52 that are operable to receive latch guide pins 40 in spaced apart locations. The latch spring 42 engages the other end of the latch plate 38 causing the latch plate to be biased inward towards a slot running the axial length of the support tube. One end of the latch spring 42 is cradled within the spring retainer 44 so as to maintain position of the spring. The retainer 44 is secured to the end cap.
[0022] With continued reference to FIGS. 2, 3 , and 8 , the spring deployment system 22 is comprised of a deploy spring 54 that is positioned within the support tube. The deploy spring has an end 56 that engages a notch 58 that is located within a cylindrically shaped profile 86 of the extrusion 18 . The opposite end 59 of the deploy spring 54 is secured to a spring anchor pin 60 thus allowing the torsion spring 54 to impart rotation to the step 19 once the latch system 20 is released via latch release button 30 .
[0023] With reference to FIGS. 2, 3 , and 7 , the support tube assembly 24 is comprised of a mounting bracket 62 , which is secured via weld nuts 64 to a conventional running board 12 , which in turn is affixed to the vehicle 14 via conventional methods. The support tube assembly 24 further includes a support tube 66 that is an integral part of the mounting bracket 62 . The mounting bracket 62 further having an inner extruded wall 68 that is operable to engage the outer extruded wall 70 of the running board 12 . Thus, the mounting bracket 62 fits within the running board 12 and forms an integral part located within the running board 12 that is not viewable to the user. It will be appreciated that the mounting bracket 62 could be connected to a minivan, SUV, or sport wagon by various means so as to provide a side step assembly that offers access to the top of each type of vehicle.
[0024] The support tube 66 extends the entire length of the mounting bracket 62 , and through a substantial portion of the sidestep extrusion 18 . The portion 72 of this support tube that extends within the step extrusion 18 , acts as a pivot point for the step 19 to rotate there about, between the stowed position (shown in FIG. 2 ) and the deployed position (shown in FIG. 4 ). This allows the step assembly 10 to rotate approximately 180 degrees whereby the step is ergonomically aligned with the running board 12 when in the stowed position, yet can be rotated outwardly away from the body of the vehicle, to the deployed position. The support tube is preferably made of steel as are the components of the mounting bracket 62 , each of which having sufficient strength to support a user.
[0025] With reference to FIGS. 5, 7 , and 8 , the support tube 66 has an axially extending slot 74 extending the majority of the tube 66 for receiving an edge 108 of the latch plate 38 . This construction creates a mechanical stop for the sidestep 19 to be maintained in the stowed position while the vehicle is traveling down the road.
[0026] With reference now to FIGS. 5, 7 , and 8 , the components of the sidestep extrusion 18 will now be discussed. The sidestep extrusion 18 is comprised of a curved outer wall 76 that acts as the top surface when the step in the stowed position. A lower wall 78 has a textured grip surface 80 for user to stand on once in the deployed position. The interior of the step extrusion 18 has an interior cavity 82 with support channels 84 extending throughout. The support channels 84 provide rigidity to the structure, which is preferably an extruded aluminum design. It will be appreciated that the step extrusion 18 can be made of other methods and other materials.
[0027] The interior cavity 82 of the step extrusion 18 further includes a cylindrically shaped profile 86 that runs the entire length of the step, that is operable to receive the support tube 66 . There is sufficient clearance between the support tube 66 and the extruded portion 86 , so as to allow for a rotatable fit there between. The cavity 82 further includes a circular profile 88 adjacent to and connected with the cylindrically shaped profile 86 . The circular profile 88 extends essentially the entire length of the sidestep, and has a horizontally slotted portion or groove 90 that is operable to receive the latch plate 38 . There is sufficient clearance 92 within the groove 90 to allow the latch plate to traverse therein relative to the support tube 66 . This allows the latch plate 38 to engage (as shown in FIG. 5 ) the support tube 66 , or to disengage and pull away from the support tube 66 (as shown in FIG. 7 ). The circular profile 88 further includes a vertically spaced opening 94 that is operable to receive and secure in place the latch guide pins 40 . The latch guide pins 40 extend through the latch plate 30 and allow the plate to traverse outward and away from the support tube 66 , when the latch release button 30 is pressed.
[0028] With reference to FIG. 7 , a deploy stop key 96 is positioned within a groove 98 of the support tube 66 . The key 96 engages a deploy stop 100 integral with the cylindrical portion 86 when the sidestep rotates to a deployed position as shown in FIG. 7 . This mechanical arrangement provides a stop for the step to be firmly located in place. It will be appreciated, that others stop designs can be provided, and are contemplated to be well within the scope of the present invention.
[0029] In addition to the step extrusion 18 , the step 19 further includes an outer end cap 102 and an inner end cap 104 . The caps serve to close off the interior space of the cavity 82 , keeping the interior components thereof free of material. The end caps are preferably made of the same material as the step 18 . The caps are secured to the step extrusion 18 by conventional means.
[0030] It will further be appreciated that the latch system 20 be comprised of sufficiently rigid materials to provide structural integrity for this particular application. Likewise, the spring deployment system 22 is comprised of a sufficiently strong torsional spring 54 as to allow proper rotational movement of the step 19 .
[0031] A discussion of the operation of the step assembly 10 will now be presented. With reference to FIGS. 2, 5 , and 7 , the assembly 10 is shown in the stowed position ( FIG. 2 ) which is its normal operating condition when the vehicle is traveling down the road. Once the vehicle stops, the operator can deploy the sidestep by depressing the latch release button 30 . Pressing the latch release button 30 inward causes the push rod 36 to move inward thus causing the latch plate 38 to traverse outward in the direction of arrow 106 . This action induces edge 108 of the latch plate to disengage from the slot 74 located in the outer perimeter of the support tube 66 . Once the latch plate 38 fully disengages the slot 74 , the spring deployment system 22 then imparts rotation in a counter clockwise direction thus allowing the step 19 to advance towards a deployed position as shown in FIGS. 4 and 7 . The step 19 continues to rotate in a counter clockwise manner until the deploy stop key 96 engages deploy stop 100 . This provides a firm mechanical stop and a rigid connection between the running board 12 and the sidestep 19 so as to provide a firm stepping area.
[0032] When it is desirable to then return the step 19 to a stowed position, the operator merely rotates the step in a clockwise direction thus loading the spring and further allowing the edge 108 of the latch plate 38 to reengage the slot 74 located in the support tube 66 . The step is now in a secure stowed position which can be re-deployed later.
[0033] It will be appreciated that other variations of the sidestep assembly 10 can be utilized. For example, the step assembly 10 could be secured to a structure other than a running board, while providing easy access to the roof of a vehicle. The same rotatable feature would be employed, thus providing stowed and deployed positions. Such variations are not to be regarded as a departure from the spirit and scope of the invention. | A manually retractable side step assembly for a vehicle includes a rotatable step having a latch mechanism and a spring system that work in concert to rotate the step from a stowed position to a deployed position. In a stowed position, the step is in line with the running board of the vehicle. However, depressing a release button automatically rotates the step 180°, thus exposing an enlarged step area for providing ease of access to a roof rack on a minivan, SUV, or sport wagon, or if used with a pick-up truck, ease of access to a toolbox that is located in the rear of the truck. | 1 |
This application claims the benefit of U.S. Provisional Application No. 60/296,407, filed on Jun. 6, 2001.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates generally to a method of providing a unique cell culture medium. More particularly, this invention relates to a method of extracting fluid from a cell culture apparatus that includes a uniformly distributed extracellular matrix adhered to a substrate.
2. Background of Related Technology
The network of fibrous and globular proteins lying between cells is called the extra-cellular matrix (ECM). ECM is a vital component of the cellular environment. Various ECM components are secreted by cells to form an interstitial matrix and basement membrane, the framework to which cells are anchored in vivo. These structures provide spatial orientation and the stability required for the organization and development of tissue-specific histology. However, the ECM is not merely an inert scaffolding, but an essential player in the regulation of the cell growth and differentiation. The ECM provides a milieu which plays a pivotal role in regulating cellular functions during normal pathological remodeling processes such as embryonic development, tissue repair, inflammation, tumor invasion, and metastasis. For example, ECM is known to function in the induction, sequestration, storage and presentation of growth factors.
In recognition of the fact that ECM is a vital component of the cellular micro environment, more and more researchers are incorporating extracellular matrix into their cell culture systems. In vitro use of ECM provides cells with conditions which more closely approximate their in vivo physiologic environments. ECM provides cells with mechanical support and influences their behavior by providing biochemical cues that affect cells via cell surface receptors.
The basement membrane is a specific type of extracellular matrix and is composed primarily of laminin and type IV collagen. A well-known Basement Membrane Matrix extracted from the Engelbreth-Holm-Swarm mouse tumor, is sold under the brand name MATRIGEL®. The terms MATRIGEL®, MATRIGEL® Matrix, and the like, as used herein refer to BD MATRIGEL® Basement Membrane Matrix (Becton, Dickinson and Co.), a mixture of basement membrane proteins derived from the Engelbreth-Holm-Swarm mouse tumor. This mouse tumor is rich in basement membrane proteins. The major matrix components are laminin, collagen IV, entactin and heparan sulfate proteoglycan and also contains growth factors, matrix metalloproteinases (MMPs [collagenases]), and other proteinases (plasminogen activators), as well as several undefined compounds, but it does not contain any detectable levels of tissue inhibitors of metalloproteinases (TIMPs). At room temperature, MATRIGEL® Matrix gels to form reconstituted basement membrane and is similar in its structure, composition, physical property and ability to retain functional characteristics typical of basement membranes in vivo.
A number of methods have been developed using MATRIGEL® Matrix to investigate the invasion of the basement membrane matrix by tumor cells, in vitro. Typically these methods involve the coating of MATRIGEL® Matrix onto the microporous membranes of cell culture inserts. Conventional techniques to prepare an ECM containing cell culture system include, first, warming a cold, neutralized solution of soluble collagen to induce polymerization and precipitation of native fibrils. Incubating the MATRIGEL® Matrix at a raised temperature of over 4° C. polymerizes the matrix.
Whereas amorphous, chemically cross-linked and alkali denatured collagen films for use in cell cultures are often dried to improve shelf life and to eliminate the need to prepare the cell culture substrate prior to each use, cell culture substrates containing native fibrillar collagen are prepared and used only in the form of firm, adherent gels of native fibrils. These gels are most often produced, as mentioned above, by warming a cold, neutralized solution of soluble collagen to induce polymerization and precipitation of native fibrils. However, they are not dried for storage because previous attempts to collapse and dry the native fibrillar collagen gels have resulted in the loss of native structure, suboptimal fiber formation and poor permeability characteristics. Native fibrillar collagen cell culture substrates must, therefore, be made just prior to use. This increases the labor and inconvenience associated with studies involving cell cultures with native fibrillar collagen. Thus, there exists a need for a cell culture substrate that contains a native fibrillar collagen, such as those found in MATRIGEL® Matrix, that can be prepared from a manufacture well before their intended use.
Conventional methods of preparing a cell culture apparatus containing native fibrillar collagen desirably remove fluid residing in the matrix just prior to use and after the gel is polymerized. Conventional methods to remove the fluid from an ECM include air drying and drying at elevated temperatures. Common elevated drying conditions include rapid drying at elevated temperatures with a drying airflow which promote large salt crystals and more pronounced patterning of the MATRIGEL® Matrix. Rapid drying of the MATRIGEL® Matrix results in poor distribution of the invading cells.
Conventional fluid removing techniques also include placing the underside of the porous surface on an absorbent material for a period of 3 minutes to overnight and/or applying a gentle vacuum to the underside of the porous surface. Fluid removed by slow drying under conditions of slowly decreasing temperature and without airflow resulted in the most even coating and, thus, the most even distribution of invading cells. For example, Swiderek, et al (U.S. Pat. No. 5,731,417) discloses methods of making dried films of native fibrillar collagen for cell culture which includes air drying the substrates.
Conventional drying methods degrade the functionality of the cell culture apparatus. For example, conventional coating and drying methods often result in an uneven or disrupted coating which gives rise to uneven cell invasion manifested by the formation of the various patterns such as intense central dots or rings of invading cells. As a result, the accurate counting of invading cells under the microscope is greatly complicated. Additionally, the ability to discriminate between invasive and non-invasive cells is significantly diminished. Invasive cells include HT-1080 cells and non-invasive cells include NIH 3T3 cells. Therefore, a distributed fibrillar collagen substrate, such as a MATRIGEL® matrix, is desirably uniform and consistent.
SUMMARY OF INVENTION
This invention relates to a cell culture apparatus and method that includes a dried extracellular matrix and has been developed for the in vitro growth of cells. In particular, this invention contemplates a method of providing a substrate with a ready-to-use uniformly distributed extracellular matrix including a) applying extracellular matrix components to a substrate area; b) incubating the extracellular matrix components to allow polymerization thereof; c) freezing the polymerized extracellular matrix on the substrate area; d) lyophilizing the frozen extracellular matrix on the substrate area; e) allowing the lyophilized extracellular matrix to warm to room temperature.
Another aspect of this invention provides a cell culture apparatus including a surface intended for cell growth, said surface having attached thereto a dried uniformly distributed extracellular matrix, said matrix formed by the steps including a) applying extracellular matrix components to a substrate area; b) incubating the extracellular matrix components to allow polymerization thereof; c) freezing the polymerized extracellular matrix on the substrate area; d) lyophilizing the frozen extracellular matrix on the substrate area; e) allowing the lyophilized extracellular matrix to warm to room temperature.
The invention also provides a cell culture apparatus including a surface adapted to grow cells thereon; and an extracellular matrix coating on the surface, the matrix coating comprising the polymerization product of a solution of bioactive proteins, wherein fluid residing within the matrix is substantially removed through lyophilization.
The present invention attempts to solve the deficiencies of the prior art by describing a method that provides a cell culture apparatus which contains an extracellular matrix that has a uniform distribution, is effective over a wider range of ECM concentrations, gives a highly uniform tumor cell migration over the entire cell culture surface, facilitates counting of cells, differentiates between invasive tumor cells and supposedly non-invasive control cells. Additionally, the present invention also includes cell culture apparatus that includes an extracellular matrix prepared well in advance of its intended use.
DETAILED DESCRIPTION OF INVENTION
The present invention provides a highly uniform extracellular matrix coating from edge to edge of a substrate and is effective over a significantly wider range of extracellular matrix concentrations than those prepared by conventional liquid drying processes. The uniformity of the coating gives a highly uniform tumor cell migration over the entire extracellular matrix surface as opposed to the conventional process where cell migration takes place in a very uneven manner at the center of the membrane. The uniform migration facilitates counting of the cells by either manual methods or by image analysis. The lyophilized coating also has a great ability to differentiate between invasive tumor cells and supposedly non-invasive control cells.
A cell culture apparatus having dried native fibrillar collagen may be substituted for conventional collagen cell culture substrates in any of the cell culture protocols and methods known in the art. The native fibrillar collagen cell culture substrate on the porous surface is placed in the well of a tissue culture plate with the underside of the porous surface in contact with an appropriate culture medium. This allows the culture medium to flow through the porous surface into contact with the cell culture substrate. The culture medium and other materials which may be present in it diffuse through the cell culture substrate into contact with cells seeded on its surface. For ease of handling, the cell culture substrate may be prepared on the microporous membrane of a cell culture insert.
Upon application of a cold extracellular matrix to a porous surface, the temperature of the cold, neutralized collagen solution is allowed to increase to about 15° C. to about 40° C. to initiate native collagen fibril and fiber formation. For the incubation step of the present invention, temperatures desirably are elevated, preferably about 37° C., with about 5% carbon dioxide in a humidified chamber. As the temperature of the collagen solution increases, native fibrils begin to polymerize and gel on the porous surface, coating the upper side thereof. The gel comprises large, organized fibers of collagen with the striations characteristic of native collagen as well as entrapped fluid from the collagen solution (interfibril fluid). Desirably, the incubation step would be an amount of time sufficient for the extracellular matrix to form a gel. The incubation step may be conducted in the presence of carbon dioxide. In general, about 0.5 to about 3 hours at about 37° C. is sufficient to obtain complete polymerization on a porous surface such as the membrane of a cell culture insert.
After the collagen of the extracellular matrix is polymerized, the interfibril fluid of the polymerized collagen is desirably drawn out of the gel. The method of the present invention directs the gel coated inserts to be frozen at a temperature no warmer than −30° C. prior to initiating the lyophilization process. Coated inserts may be frozen in a lyophilizer and then lyophilized overnight during which time the lyophilizer is allowed to warm to room temperature. This process collapses the gel onto the porous surface and forms a thin membrane of native collagen fibers and fibrils. Desirably a uniform cake is obtained which adheres to the insert membrane.
The native fibrillar collagen cell culture substrates of this invention may be produced as dried films on porous surfaces. They desirably retain the native fibrillar collagen structure in dried form and therefore have the improved permeability characteristics of cast collagen gels and the storage stability of amorphous or cross-linked collagen films. The dried membrane may be removed from the porous surface for cell culture if desired, but it is generally preferable to use the native fibrillar collagen cell culture substrate on its porous surface for added structural support and ease of handling. Cells on the upper surface of the cell culture substrate may be exposed to media, growth factors, and other materials by diffusion thereof through the underside of the porous surface and the cell culture substrate, as the cell culture films of the invention exhibit excellent diffusion properties.
Salt concentrations which are at about physiologic concentrations or higher, preferably about 0.15 Molar to about 1 Molar, may be used to promote formation of large native collagen fibers. At salt concentrations below physiologic concentrations there is little, if any, collagen fiber formation. However, as salt is increased to approximately physiologic concentrations, fiber formation becomes essentially complete, with little amorphous collagen being present. Additionally, as salt is increased above physiologic concentrations, larger and larger fibers are formed. However, when the salt concentration reaches about 1.1 Molar, fiber formation is again essentially completely absent. When the solubilized collagen is in acidic solution, the pH may be raised to approximately 6-8, preferably about 7.0-7.4, concurrently with adjustment of the salt concentration by addition of cold NaOH in a buffer such as phosphate buffered saline (PBS) to give a final salt concentration of about 0.15 Molar-1 Molar, preferably at least about 0.6 Molar (about 4 times physiologic salt). The collagen is maintained in solution by storage in the cold (usually about 4° C.) until polymerization of collagen fibrils and fibers is desired. The collagen concentration is not critical for formation of the native collagen fibers, but is preferably about 10 to about 500 μg/cm 2 of porous surface when intended for use as a cell culture substrate, more preferably about 65 to about 85 μg/cm 2 .
A variety of polymerization conditions, including non-physiological conditions, may be used to produce the cell culture films without concern for negative effects of non-collagenous residuals such as salts or organic materials on the cell environment. Collapsing the gel onto the porous surface and drying, in accordance with the method of this invention, to form the fibrillar collagen film provides a uniform surface for even distribution of cells and if desired, a concentration of collagen (about 5-10 mg/ml). The native fibrillar collagen structure provides the in vivo spatial orientation for binding of cell receptors not found in amorphous collagen cell culture substrates. The fibrillar collagen network also provides a textured surface which results in a higher collagen surface area on each film than is found on the essentially two-dimensional surfaces of other collagen cell culture substrates. The native fibrillar collagen cell culture substrates bind cells more avidly and uniformly to their surfaces than do the collagen substrates of the prior art. That is, many diverse cell types applied to the surface bind to it rapidly and completely (e.g., epithelial cells, endothelial cells and fibroblasts).
Organizational entropy drives the polymerization reaction of the invention. As the physical mechanism is the same for other proteins which undergo a similar type of self-assembly, any protein or proteins which spontaneously form organized polymeric structures in vitro will produce native constructs when substituted for collagen in the foregoing production process. These include proteins which form homopolymers (e.g., fibronectin or laminin) and heteropolymers (e.g., laminin with collagen IV or laminin with proteoglycans). Extracellular matrix components which comprise proteins which undergo self assembly, such as those found in MATRIGEL® (Collaborative Biomedical Products, a company of Becton, Dickinson and Co.), may be polymerized and dried according to the methods of the invention to produce native constructs. Although all such proteins may not produce gels which collapse and form a film in the same manner as collagen gels when the interfibril fluid is removed, withdrawal of the interfibril fluid from the polymerized substrate and drying should still allow retention of the native construct in the final product.
Any membrane material may be used as the substrate with the method of the invention, however, there may be positive or negative effects of the selected membrane in certain biological applications. Whereas, etched membranes may be preferred for transport studies, cast membranes may also be used if the permeability coefficient of the material being tested does not exceed the permeability coefficient of the membrane (i.e., the permeability coefficient of the membrane is not a limiting factor). For convenience in cell culture applications, culture plate inserts which incorporate porous membranes may be preferred. For example, suitable substrates include BIOCOAT control cell culture inserts, which are porous polyethylene terephthalate membranes available from Collaborative Biomedical Products. Other suitable substrates included TRANSWELL cell culture inserts, which are porous polycarbonate membranes available from Costar. Further suitable substrates are MILLICELL Culture Plate Inserts, which are porous polytetrafluoroethylene membranes, porous cellulose membranes, or porous polycarbonate membranes available from Millipore Corporation. Polyethylene terephthalate (PET) membranes may be preferred over materials such as high density polycarbonate for applications involving microscopy due to their higher transparency. For these reasons, different membranes may therefore be preferred for different applications and can be routinely selected by one skilled in the art.
Suitable porous surfaces to be used as the substrate of the present invention include natural or synthetic polymers such as cellulose membranes, porous polycarbonate, porous polytetrafluoroethylene (e.g., TEFLON mesh membranes such as Millipore CM), nylon membranes and meshes, glass filters, porous polyethyleneterephthalate, polymethylpentane, polyproplyene, polyethylene and various types of filters (e.g., ANOPORE aluminum crystal filters). The porous surface should have a pore size which is small enough to prevent the collagen solution from flowing though prior to polymerization but large enough to allow passage of fluids such as media and the interfibril fluid. In general, membranes having pore sizes of about 0.5 to about 30 microns provide the desired properties. A surface comprising a membrane with pores approximately 8 microns is preferred for most general cell culture applications such as material transport studies.
After drying, the cell culture apparatus of the present invention may be sterilized, for example by irradiation (e.g., ultraviolet light, electron beam or gamma irradiation) or exposure to ethylene oxide gas. The native fibrillar collagen films of the invention, in contrast to the collagen cell culture substrates of the prior art, retain their native fibrillar structure when dried and therefore more closely resemble an in vivo collagen substrate.
A wide variety of materials, including bioactive proteins, may be co-polymerized with the extracellular matrix of the present invention or incorporated into the film by adsorption to the collagen, as desired for a particular cell culture system. These include, but are not limited to, cells, antibodies, enzymes, receptors, growth factors, additional components of the extracellular matrix, cytokines, hormones and drugs. These materials may be added to the cold collagen solution at the appropriate concentration for the selected cell culture application. Polymerization of the native collagen fibrils as described above binds the material to or copolymerizes the material with the collagen fibers. Due to the open fiber structure of the cell culture substrate, biologically active added materials are readily available to the cultured cells to moderate or regulate their properties or behavior.
The cells to be cultured may be seeded at subconfluence or confluence on the upper surface of the substrate and placed under environmental conditions appropriate for cell growth. For example, when the cell culture substrate is prepared on the surface of the membrane of an insert for the well of a culture dish, a small amount of growth medium is placed in the well. The insert is placed in the well so that the culture medium contacts the underside of the porous membrane and diffuses through the cell culture substrate into contact with cells seeded on the substrate surface.
Any cell culture medium appropriate for growth and differentiation of epithelial cells may be used in cell cultures employing the present collagen cell culture substrates. These include, but are not limited to Dulbecco's Modified Eagle Medium (DMEM), MEM, M-199 and RPMI. Supplements, as are known in the art, may be added to the culture medium and include serum (e.g., fetal bovine serum (FBS) or calf serum), serum-containing supplements (NU-SERUM), and serum-free supplements (MITO+). A preferred cell culture medium for intestinal epithelial cells is DMEM supplemented with MITO+ Serum Extender (Collaborative Biomedical Products, Bedford, Mass.) to provide a fully defined, serum-free cell culture environment.
The following examples are given to illustrate certain embodiments of the invention and are not to be construed as limiting the invention as defined by the appended claims and equivalents thereof.
EXAMPLE 1
Preparation of a Cell Culture Apparatus Having a Dried Uniformly Distributed Extracellular Matrix
The following experimental example describes the preparation of dried uniformly distributed native fibrillar collagen cell culture substrates on 1 μm polyethyleneterephthalate (PET) membranes in PET cell culture inserts. In this example, about 200 μm of MATRIGEL® Matrix is added to the membrane.
A cold acid solution of MATRIGEL® Matrix is adjusted to 674 μm/ml by addition of 10 times Dulbecco's phosphate buffered saline (DPBS)/NaOH to obtain a final concentration of about 4 times DPBS, pH 7.4, and the mixture is kept on ice until use. Insert holders are placed in tissue culture dishes. The cell culture inserts are placed in the insert holders with sterile forceps and lids are placed on the dishes until use. The MATRIGEL® collagen coating gel (0.10 ml) is dispensed onto each membrane, the culture dish lid is replaced and the dish is rocked gently to evenly distribute the coating solution on the membrane. The coated membranes are incubated at 37° C. to allow the collagen to polymerize (about 2.0 hrs.), keeping the membranes in a humid environment to prevent premature drying.
After the collagen is polymerized, the coated inserts are placed in a pre-chilled lyophilizer and frozen (at a temperature no warmer than −30° C.) prior to initiating the lyophilization process. Inserts are lyophilized overnight during which time the lyophilizer is allowed to warm to room temperature. A uniform cake is obtained which adheres to the insert membrane.
The native collagen cell culture substrates are then sterilized in the tissue culture dishes by exposure to 0.05-0.06 Joules of ultraviolet light and are stored at 4 degree C. in sealed bags until use.
EXAMPLE 2
Invasion Assay
NIH 3T3 (non-invasive) and HT-1080 (invasive) cells were grown to near confluence in DMEM containing 10% fetal bovine or newborn calf serum. The cells were harvested by trypsinization and washed in DMEM without adding serum or proteinase inhibitor. The cells were suspended in DMEM at 1×10 5 /ml. Prior to preparing the cell suspension, the dried layer of MATRIGEL® Matrix was rehydrated with DMEM for 2 hours at room temperature. The rehydration solution was carefully removed, 0.75 ml DMEM containing 5% fetal bovine serum was added to each plate well as a chemoattractant, and 0.5 ml (5×10 4 cells) of cell suspension was added to each insert. The plate inserts were incubated for 22 hours at 37° C., 5% CO 2 atmosphere. Non-coated membrane inserts were also seeded to serve as controls.
Fixation and Staining of Coated Inserts
Following incubation, the upper surface of the membrane in each insert was gently scrubbed with a cotton swab to remove all of the non-invading cells and the MATRIGEL® Matrix. The invading cells on the undersurface of the membrane were fixed and stained by sequentially transferring them through the three solutions of the Diff-Quik (Dade) staining kit. The excess stain was removed by dipping each insert into distilled water. The upper surface of the membrane was swabbed a second time to remove any residual water, cells or MATRIGEL® Matrix. The inserts were transferred to another 24-well plate and allowed to air dry. The number of cells which had invaded through the MATRIGEL® Matrix on the membrane was quantitated on the lower side of the membrane by direct counting in a microscope after the cells had been stained with Diff-Quik.
The cells were enumerated by taking photomicrographs at 40 or 200× magnification depending on the number and distribution of the cells. Photographs were taken without removing the membrane from the insert housing. The cells in multiple fields (usually 5) of each photograph were counted with the aid of a ruled grid. Data was expressed as % invasion, i.e., the ratio of cells invading through the MATRIGEL® Matrix coated inserts relative to the uncoated control insert.
Protein Staining of Coated Inserts
In order to assess the evenness of the distribution of the coat, coated inserts were stained with Coomassie Blue for a profile on the protein content across the insert surface. Coated inserts were rehydrated with buffered saline for 2 hours at room temperature. The rehydration solution was carefully removed and replaced with Coomassie staining solution (1 mg per ml Coomassie Brilliant Blue R-250 in 10% acetic acid, 40% methanol). After 30 minutes, the stain was carefully removed, the inserts were rinsed twice with distilled water and allowed to air dry. The quality of the MATRIGEL® Matrix deposition was assessed at 100× magnification.
EXAMPLE 3
Results of Invasion Assay Employing Inventive Cell Culture Apparatuses
This example demonstrates that cell culture inserts which were prepared in accordance with the methods of the invention performed according to desired performance specifications; these specifications are shown in Table 1 below where NIH 3T3 (3T3) cells are representative of non-invasive tumor cells and HT-1080 cells are representative of metastatic tumor cells.
TABLE 1
Desired Performance Specifications
Coat Surface
NIH 3T3 Invasion
HT-1080 Invasion
Patterning
Distribution
10% or less
25% or greater
None
Even
Inventive cell culture inserts were tested for the ability of NIH 3T3 cells and HT-1080 cells to invade a basement membrane matrix. Fixed and stained inserts were examined as described above to assess the degree of invasion and patterning. The results of these assessments are detailed below.
The inventive cell culture apparatuses showed essentially no invasion of the control NIH 3T3 cells, i.e. the non-invasive cells. There was, however, a high degree of invasion of the HT 1080 tumor cells. Invading HT-1080 cells were evenly distributed across the surface of each insert, providing a highly uniform tumor cell migration over the entire cell culture surface. The inventive cell culture apparatuses were devoid of patterning such as intense central dots or rings of invading cells. The results of the present example were demonstrated with both individual 24 well inserts, as well as the 24 multi well inserts. The thin, even coat of MATRIGEL® Matrix, uniformly spread across the membrane surface by this method, may permit shorter times for completion of tumor invasion assays. | Method of providing a substrate with a ready-to-use uniformly distributed extracellular matrix is disclosed. This method includes applying extracellular matrix components to a substrate area; incubating the extracellular matrix components to allow polymerization thereof; freezing the polymerized extracellular matrix on the substrate area; lyophilizing the frozen extracellular matrix on the substrate area; and allowing the lyophilized extracellular matrix to warm to room temperature. Also contemplated is a cell culture apparatus having a dried uniformly distributed extracellular matrix formed by the above-mentioned method. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to flame monitoring of boilers with tangential firing, and particularly to a scanner system for monitoring the flames of the individual burners in the tangentially fired boiler.
Tangentially fired boilers are characterized by a combustion chamber which is generally square in horizontal cross-section. The combustion chamber is enclosed by four walls lined with collant-carrying tubes, and the boiler is provided with burners at each corner which fire into a large central fireball. Generally, several different levels or tiers of burners are provided and different fuels are often burned on each level. A liquid heat transfer medium, often water, is circulated through the tubes to remove heat from the furnace. As a secondary effect the medium-carrying tubes sheild the boiler casing to prevent heat damage.
It is desirable to observe the flame of each burner in the boiler to assure that each burner is operating as intended. In the past there have been attempts to employ a flame scanner which sights through the burner wind box at each corner where a small narrow angle opening into the boiler is provided. A scanner mounting system of this type limits the ability of the scanner to see the burner flame. Scanners used in the past employ extended sensing tubes which position the sensor at the furnace end of the burner support and tilting structure (bucket), and employ a flexible mounting assembly in order to allow the sensing tube to tilt with the burner. These sensors required extreme methods of cooling (air or water) in order to maintain the tube temperature below 400° F. The position of the sensor with regard to the burner tip and within the space provisions of the "bucket" caused the sensor to detect flame through the unburned fuel skirt of the burner and could cause the sensor to respond to the radiation from the fireball rather than solely from the associated burner. As a consequence, unignited fuel can be introduced into the furnace resulting in explosions within the furnace under light-off cold furnace conditions.
It has been suggested that scanners be mounted above the burner pods in order to look down on the fireball. However, such a system would not be able to detect a flame-out condition in a tiered, multiple burner boiler, since the scanner would lock onto the fireball and fail to detect a problem with an individual burner within the boiler.
SUMMARY OF THE INVENTION
In order to overcome the foregoing problems and to permit the scanning of each burner in a tangentially fired boiler, a plurality of scanners are positioned at ports located on the side walls adjacent the corner mounted burners. Each scanner is oriented to intersect a diagonal in the horizontal plane of the burner and thus to sight the flame of the associated burner. Closely-spaced coolant-carrying tubes forming the boiler walls are oriented with at least one tube in a serpentine pattern and with two or three tubes displayed laterally and outwardly of the flame zone thereby providing an opening approximately the width of one or two tubes. The spacing and orientation of the tubes minimizes heat load on the scanner port and adjacent boiler casing wall and provides a sufficient viewing angle to permit detection of flame conditions at each burner. Each scanner is capable of repositioning up or down in order to track the movement of the corresponding burner tip. Each scanner is capable of positioning at varying lateral displacements from the burner tip to correspond to the flame front positions associated with different types of fuels. The serpentine tube bend pattern readily accomodates the needed lateral displacement of the scanner.
One object of the present invention is to provide a scanner mounting system for viewing the flame zone of individual burners in order to detect a flame-out condition at any burner.
A further object of the invention is to provide a scanner system which is capable of tracking vertically displacement of individual flames within a boiler assembly.
A still further object of the invention is to provide a suitable scanner port in the side of a tube-walled boiler which provides sufficient cooling of the scanner ports.
Further objects and advantages of this invention will be apparent upon reference to the following detailed description taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of the furnace illustrating one tier or level of burner assemblies with scanners for viewing individual flame zones.
FIG. 2 is a horizontal cross-sectional view of one corner of FIG. 1.
FIG. 3 is a side sectional view along 3--3 of FIG. 2.
FIG. 4 is a side elevational view along 4--4 of FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, the invention is described in conjunction with a tangentially fired boiler 10 having a square furnace 12 in the plan view. The furnace area is defined by four walls 14 with an array of vertically disposed, closely spaced tubes 16 shielding the walls 14.
Referring also to FIG. 2, at each corner 18, the tubes 16 are flared slightly outward to admit the outlet of a burner assembly 20. According to the invention, a scanner system 22 is mounted laterally of each corner 18 and provided with a viewing field 24 transverse of the flame path 26 emanating from the respective burner assembly 20.
The burner assembly 20 may include at each level a windbox 28 and one or more burners 30 together with an extendable igniter 31 at each level or tier. Although the exact details of the burner assembly 20 are not pertinent to this invention, it is useful to recognize that the burner assembly 20 may include a fuel nozzle 32 adapted for angular displacement to provide vertical flame travel. In a typical boiler 10, there may be several burner levels each having a similar configuration. For example, one burner level may be adapted to fire oil whereas the adjacent lower or upper burner levels may be adapted to fire coal or gas or the like. Since the firing characteristics and flame length of the various fuels may differ at adjacent levels or tiers, the location of a scanner assembly 22 according to the invention along the side wall 14 at each level may be horizontally displaced from the scanner systems at adjacent levels.
In FIG. 2, the tubes 16 are seen to be so closely spaced as to abut one another. Insulation 34, such as refractory material, is provided directly behind the tubes 16 and on both sides of a boiler casing 36.
Referring particularly to the scanner system 22, a sensor is mounted to a pivotal bracket 40 behind the boiler casing 36. A variety of sensor types are available and may be used in the particular application. In particular, infrared, ultraviolet and other wavelength sensitive sensors or commercially available. An infrared sensor may be used to detect gas or oil flames. Exemplary infrared sensors are sold under the mark Fireye by the Electronics Corporation of America, Cambridge, Massachusetts and are also manufactured by Minneapolis-Honeywell, Minneapolis, Minnesota as Model C7 015A. Ultraviolet sensors may also be used to detect gas or oil flames. Minneapolis-Honeywell and the Electronics Corporation of America also manufacture such ultraviolet sensors. Wavelength sensitive sensors tuned to the near infrared spectrum may be used to detect coal or oil flames. The Electronics Corporation of American and Minneapolis-Honeywell manufacture suitable devices.
Referring again to the structure of FIG. 2, a port 42 may be provided in the side of the casing 36 spaced from the burner assembly 20, and a shaped plate 44 may be seal-selded into the port 42. The plate 44 may comprise two panels 46 and 48 joined at a margin 50 and disposed at approximately right angles along a vertical axis. The first panel 46 may be seal-selded along its side margin to the casing 36 disposed furthest from the burner assembly 20, and the second panel 48 may be selded to the edge of casing 36 nearest the burner assembly 22 so that panel 46 is approximately parallel to the flame path 26 whereas panel 48 is transverse to the flame path 26 and extends outwardly of the boiler casing 36. Panel 46 is provided with a viewing window 54 flexibly coupled with sensor 38. The flexible coupling may be centered on an axis through bracket 40, which may be mounted to panel 46. The relative lengths of panel 46 and 48 establish the horizontal viewing angle of the scanner assembly. Therefore, to change the horizontal angle, the relative lengths need only be adjusted.
For convenience in explaining the displacement of the tubes 16, each is numbered sequentially from the burner assembly 20. Selected tubes are shown in phantom to indicate the location and numbering of the tubes 16 in an unmodified wall section and are shown in solid lines to indicate the location and numbering of tubes in the modified wall section with the desired opening. FIG. 2 will be best understood in conjunction with a reference to FIG. 4. According to the invention, the tubes 15 are displaced in a pattern adopted to produce an opening for the scanner system 22 while minimizing the heat load on the scanner port and casing 36 at the opening. For this purpose, as shown in FIGS. 2 and 4, tube 5 is displaced outwardly from the center of the furnace toward and abutting the boiler casing 36 adjacent the port 42. Refractory material 35 may be packed over tube 5 along the viewing path 24 to provide protective insulation.
Alternatively, tube 5 may be displaced to a location directly behind ahd abutting tube 4. In this dispostion of tubes, tube 4 and tube 5 act as a heat-sink for the casing and port 42.
Tube 8 may also be displaced to the boiler casing 36. For the same vertical length, tube 7 is displaced laterally to the former location of tube 8. At that location, tube 7 abuts tube 9 on one side. Tube 8 is directly behind. Refractory material 35 is packed around tube 8 and along the viewing path 24 as with tube 5.
Tube 6 is also displaced from its normal position. However, tube 6 is displaced in a predetermined serpentine pattern at vertical locations corresponding to the locations of the scanner system 22 at each of the firing levels. For example, at the level shown in FIG. 2, tube 6 is displaced laterally away from the corner 18 to abut tube 7. As shown in FIG. 4, tube 6 is longitudinally extended along the adjacent tube 7 above and below the level of the scanner system 22. At the scanner and burner levels above and below the level of FIG. 2, tube 6 is bent in an opposite sense so that a segment runs adjacent and abutting tube 4.
The tube displacement described above provides a sufficient horizontal width for a field of view of approximately two tube diameters. The location of the scanner system 22 is relatively close to the casing 36 so that a suitably broad field of view of a selected portion of the flame zone is provided.
The field of view, angle of view, and displacement of the scanner 22 from the burner assembly 30 is, however, sufficiently narrow so that no portion of the flame of the adjacent burner assembly at the adjacent corner is in the view of the scanner 22. In other words, only one flame path 26 is in the view field 24 of any single scanner 22.
Tube 6, as it crosses between tube 4 and tube 7, overlies and partially protects a refractory plug 56 between scanner levels. The transverse angle of tube 6 between tubes 7 and 4 may be approximately 45°. The actual minimum angle is not critical for the purposes of this invention. A sharper angle may be employed if sufficient tube length is available and if the level of radiation to which plugs 56 are exposed under segments of tube 6 is sufficiently low. As a practical matter, however, the angle may be somewhat less than 45° since the system of the present invention is typically built into an existing boiler where extreme-angled tube bending may be impractical or inconvenient.
Referring now to FIG. 3, there is shown in side elevational view the multilevel arrangements of the scanners 22. The plug 56 of refractory material is seen to be built between the sites of the scanners 22 at each tier and also between each scanner 22 and the array of tubes 16. At each tier, the refractory wall is provided with a vertically wide-angled cut-away viewing area 57 which is adapted to allow the scanner 22 clearance for pivoting in the vertical plane. The insulation 35 is packed along the boiler casing 36 and the tubes 16 adjacent the aperture 54.
The system according to the invention operates as follows. With water or other heat transfer medium flowing through the tubes 16, and a fireball generated within the furnace 12, the scanner 22 at each burner assembly 20 is oriented to view a portion of the flame emanating from the burner assembly 20 at its level across flame axis 26. By remote means (not shown) the scanner 22 may be made to track the flame, should it move vertically within the furnace 12. The fluid flowing through the boiler tubes 16 serves to cool the boiler casing 36 as the heat sink for the scanner ports 42. Tube 6 especially acts as a heat sink for the refractory plugs 56 between levels.
In addition, since the center of the scanner port 42 at each tier is alternately nearer and further displaced from the corner 18 because of the serpentine pattern of tube 6, the scanner 22 for the alternative fuels, generally coal and oil, may be mounted at a characteristic distance from the mouth of the burner assembly 20 to provide each of the scanners 22 with a viewing angle of the desired zone within the flame body to which the scanner is optimally sensitive. For example, since fuel such as gas and oil tend to burn more closely to the nozzle than does a coal fuel, scanners 22 for such fuels are generally located closer to the burner assembly 20 than are the scanners 22 for coal firing nozzles. In this manner, sufficient heat dissipation is provided at the optimal location to cool the scanner ports 42 and the scanners are mounted at the optimal location for viewing a desired flame zone of a variety of burner fuels. Where the optimal combustion zone of alternative fuels at alternating levels differs widely, some latitude in the choice of scanners 22 may be used to compensate for the disparity in available viewing angle. For example, sensors 38 may be chosen which are optimally sensitive to the flame spectrum within the available viewing angle.
The invention has now been explained with reference to specific embodiments. Still other embodiments will be apparent from this description to those of ordinary skill in the art. It is therefore not intended that the invention be limited except as indicated by the appended claims. | A flame-sensing system for a tangentially fired broiler in which a plurality of scanners are positioned on the side walls of the combustion chamber adjacent respective burners, and oriented to sight the flame from the respective burners, rather than the central fireball. Closely spaced coolant-carrying tubes lining the boiler walls are oriented with at least one tube in a serpentine pattern and with two or three tubes displaced laterally and rearwardly of the flame zone to provide space for a viewing port approximately the width of two tubes. The displacement pattern tends to dissipate the heat load on the scanner port to prevent scanner or boiler case overheating. | 5 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention pertains to weighing devices specifically designed to weigh discrete pieces carried on a continuous delivery system such as a belt. As an example, it might be desired to have the aggregate weight of a series of packages or pieces of meat or other products carried by a belt.
There have been attempts to arrive at such aggregate weights by separating the belt-load into separate batches and weighing each batch. Generally that type of system requires at least one attendant to be sure that spacing of an entire batch, and no more is on the scale at any one time. Thus, it is required that the flow of packages onto the scale be at least momentarily stopped so that no piece will be partially on or partially off the scale when the weight is recorded. The attendant is necessary to space the margins of the scale platform with each weight cycle.
By the present invention, a weighing device is provided at which no attendant is required for spacing of packages on the scale. Weights are taken so that if one partial component of weight is measured on the first pass over the scale, the rest of the weight will be recorded on the next pass. Thus, the need for a constant presence of an attendant is eliminated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of the weighing system for larger discrete articles,
FIG. 2 is a view similar to FIG. 1 of the system adapted for a use with smaller particulate matter,
FIG. 3 is a perspective view of one member of the system apart from the system,
FIG. 4 is an elevational view of the operating motor from line 4--4 of FIG. 3,
FIG. 5 is an end elevational view of the motor of FIG. 4
FIG. 6 is a view from line 6--6 of FIG. 4, and
FIG. 7 is a view similar to FIG. 6 of an alternative type of encoder plate.
DESCRIPTION
Briefly this invention pertains to weighing devices for weighing a substantial number of discrete articles of similar nature. The system is designed to be placed in a conveyor belt route delivering cuts of meat or similar discrete packages where any package may be of slightly different weight from the other, but where the overall weight of all is the desired result of the weighing.
More specifically, and referring to the drawings, the system includes a series of the units to be inserted into the continuing path of a conveyor system. Each unit consists of a base 10 upon which is mounted a simple frame 11 supporting a separate belt unit comprising a belt 12 engaged on a pair of rollers including one driven roller 13 and one idler 14. Each belt 12 must end close enough to the start of the next belt so that the flow of packages is continuous particularly where those packages are of different sizes. That same condition must exist at the entrance and exit from the system.
Equally, the rate of lineal speed of the belts 12 must be synchronized so that the flow across the three parts of the system is even and without blockage of the flow.
The need for this synchronization can best be understood by realizing the function of the system. If the contents of the delivery system (belt) is envisioned as a continuous although not necessarily uniform stream of packages, then a division of those packages into a continuous series of units which can be weighed individually leads to a total weight as those individual units are totalled. However, in order for that total to be accurate, each individual unit must be accurately divided and weighed. Thus, if a unit of flow includes a partial package at its ending, then the remainder of the package must be weighed at the beginning of the next unit in the flow. Thus a precise beginning and end of each unit of flow must be measured.
This is done in the present invention by accurately controlling the speed of the belts and the time interval between recording the weights of each unit. The means by which this desideratum is accomplished will then be described always with the idea in mind of obtaining accurate measurements of weight for each accurately delineated unit of flow in the packages over the belt conveyors.
In practice the entrance and exit conveyor belts 12a and 12c are principally regulating devices adapted to keep the flow over the central or weighing belt 12b uniform. The frame 11 of the two outer belts are simply set on the bases 10 in those locations. However the central weighing belt 12b and its rollers 13 and 14 are mounted on a similar frame 11a which is set on a customary electronic weighing device 15. Such devices are well known in the art and can be electrically actuated to provide an instantaneous reading of the weight at the time of the actuation.
Accuracy, then, depends on the accuracy of the division of the units on the belts. If each particle on the belt is weighed once and only once, then accuracy has been achieved. Two variables determine that division. The first is the speed or at least the traverse of one and only one belt length in the interval between successful actuation of the weighing trigger. The second is the smooth transition onto and off of the belt 12b. All of the design and structure is conceived and designed to that end.
Therefore, as the packages are picked up by the first belt 12a, they are transported at a uniform rate resulting in a smooth transition to the second belt 12b. At that transition, the space between the belts must be small enough so as not to trap a package. In the usual installation that gap should be less than one and one half inches, preferably much less than that. Tests have shown for the usual installation a gap of three-quarters of an inch works very well. To maintain that limit, the line rollers 13 and the idler rollers 14 must be of a diameter of not more than 33/4 inches.
Because of the uniform speed of the belts 12a and 12b, there should be no other interference with the smooth transition onto the belt 12b. Also, because of similar limitations at the exit from that belt to the continuing carrier 12c and from there to the outlet belt (not shown). So long as the entrance and exit from the weighing belt 12b are untrammeled, the weighing process will be accurate.
The alternative arrangement shown in FIG. 2 shows how the scale device can be used for particulate matter of a finer division than most packages. Again, the separation provided by the triple belt arrangement provides added accuracy. The use of a falling product for the first belt 12a to the weighing belt 12b may cause a very slight inaccuracy because of the impact of the falling product onto that belt. However, the need for accuracy is somewhat less with most particulate matter so that such small inaccuracies may be accommodated. The mechanism to guarantee the inclusion on belt 12b of only unweighed material is best shown and illustrated in FIGS. 3-7. The frame 11a is shown diagrammatically and may take a somewhat more sophisticated form although that form does not form any part of the invention.
As noted, each conveyor belt 12 is driven by a motor 16 through a belt 17 or chain. In FIG. 3 this driving device is shown enclosed in a guard 18. The power belt 17 drives a driving roller 14 and the belt which carries the packages as indicated above.
It has been discovered that most motors, even those operating on a 60 Hertz power source are not accurate enough to accomplish the spacing desired for the proper weighing of the product going over the scale. Therefore, a special system is provided on the motor to ensure that the transport across the belt 12b is always the same. This system and a modification are shown in FIGS. 4-7.
The motor drive 20 is designed to be mounted on the frame 11 by means of a base 21. Each motor 20 drives a shaft 22 which causes a sprocket or pulley or the like to transmit motion to each of the belts 20a, 20b, and 20c in the customary way. Opposite the shaft a cooling fan may be provided in a housing 23 as is customary.
Beyond the housing 23, applicant provides a system by which the rotations of the shaft may be counted. In FIGS. 4,5 and 6, applicant has illustrated one possible system. That system includes a unit 25 supported by a bracket 26 from the shell 23 of the motor. The unit 25 may include both a source of light and a receptor spaced apart so as to allow the receptor to receive reflected impulses of light from the source. In order to provide the impulses of reflected light, a plate 28 fixed to an extension 29 of the shaft 22 is rotated by that shaft. A plurality of vanes 30 is formed on the plate 28. Each vane 30 is adapted to reflect a beam of light as the vane 30 passes the source. Thus the rotation of the motor and therefore of the plate 28 creates impulses of light which can be counted by the receptor part of the unit 25.
By calibrating the passage of the belt once across the top of the frame against the total number of impulses, a valid measure of a single passage can be obtained. Thus, because it is desired to make a record of each single passage of the belt 12b, and that such passage must be accurately measured, it is obvious that a system--electronic preferably--can be used to trigger a weight record from the weighing device 15 each time the number of impulses reaches the calibrated number. In that way accurate total weight can be accumulated while the packages are being carried by the belt.
It will be obvious that there are other impulse generating systems which can be used instead of the plate 28 with fingers 30. As an example still using an optical system, a plate 32 perforated by holes 33 (FIG. 7) could be used to generate the impulses to trigger the weighing impulse. In this type of system, a U shaped support would bracket the plate 32 so that a light source or one side of the plate would be aimed at a receptor on the opposite side. Thus the holes 33 would provide the impulses.
It is apparent that by this system, an accurate total weight of a batch of packages or a series of batches of packages can be arrived at. The system may be particularly useful in weighing cuts of meat either of a single type (hams, loins or the like) or of a variety of types of cut--say from a single animal to determine the yield of useful meat compared to live weight. However, the system is not limited to such types of packages and may be used with a variety of other industries when a total weight of a series of packages is of interest. | A scale system for the continuous weighing of a series of packages on a conveyor. The packages are run over a series of synchronized belts on tables, one of which records the weight on a section of the conveyor at intervals timed to assure that no single package will be weighed more than once. | 6 |
This application is a Continuation of U.S. application Ser. No. 10/433,877, filed on Jun. 3, 2003, now U.S. Pat. No. 7,256,683, which is the national phase under 35 USC 371 of PCT International Application PCT/AU01/01566, filed on Dec. 3, 2001; which claims priority to Australian Patent Application No. PR1878, filed on Dec. 4, 2000. All publications, patents, patent applications, databases and other references cited in this application, all related applications referenced herein, and all references cited therein, are expressly incorporated herein by reference in their entirety as if restated here in full and as if each individual publication, patent, patent application, database or other reference were specifically and individually indicated to be incorporated by reference.
FIELD OF THE INVENTION
The present invention relates generally to monitoring systems and, in particular, concerns a device, method and system for monitoring the status of a circuit. The device is especially useful in security management systems, fire systems and building management systems, and it will therefore be convenient to describe the invention in relation to those example applications. It should be understood however that the invention is intended for broader application and use.
BACKGROUND
Security management systems are typically employed in correctional facilities, such as prisons, as well as buildings intended for other purposes where restricted access is required. Some examples of such systems include those sold under the names Pagasus, Card key and Access. In general, these systems are proprietary, and components from one system will not work with components from another system. Additionally, any modifications to the hardware or software must generally be made by the originally manufacturer.
In a typical prior art security management system (SMS) a number of field devices, perhaps several hundred or even thousands, are wired back via various circuits to a centralised SMS control unit. Typical field devices include infra-red motion detectors, read switches on doors and windows, glass breakage tapes on windows, smoke or heat detectors and tamper switches. Each of these field devices includes a switchable element which is triggered when an abnormal or specified condition occurs, for example a read switch detects that a door is opened, an infra-red motion detector senses movement or a smoke detector senses smoke in the air. The switchable element may be a normally open contact (ie., it closes when triggered) or it may be a normally closed contact (ie., it opens when triggered).
In general, a first resistive component is connected in series with the switchable element and a second resistive component, referred to herein as a field resistor, is connected in parallel with the switchable element. The field resistor is typically connected across the terminal block of the field device at the time of installation. If more than one field device is connected within a particular circuit, the switchable element of each of those devices is connected in parallel with the field resistor. In this configuration, the field resistor is usually connected across the switchable element of the last field device on a line extending from the SMS control unit.
FIG. 1 shows a typical example of a single line circuit connected to a switchable element SW 1 of a single field device. The circuit includes a first resistive component R 1 in series with the switchable element SW 1 and a second resistive component R 2 (field resistor) in parallel with the switchable element SW 1 . Several field devices may be connected to this circuit and, in that event, the switchable elements of those field devices would be connected in parallel with the field resistor R 2 . In practice, the field resistor R 2 would be connected to the field device farthest from the input terminals 1 , 2 of the SMS control unit.
On considering the circuit shown in FIG. 1 , it will be appreciated that the line resistance measurable at input terminals 1 , 2 of the SMS control unit will change when the switch SW 1 closes. With the switch SW 1 in the open position the line resistance will be R 1 plus R 2 . With the switch SW 1 in the closed position the line resistance will be R 1 alone. The SMS control unit determines the status of the switch SW 1 (opened or closed) by continuously measuring the circuit resistance of the line connected to its input terminals 1 , 2 .
Each manufacturer of SMS equipment specifies a particular value of field resistor to be connected across the last field device in a line. Typical values may be 2 k.OMEGA., 4.7 k.OMEGA.or 10 k.OMEGA. The resistance of the cable itself is in general insignificant in comparison to the values of the resistive components R 1 and R 2 involved in the circuit. In many applications, the series resistor R 1 is the same value as the field resistor R 2 . In any particular installation, wherein all lines are connected to a single SMS control unit, the field resistor R 2 for each line of the system in the same value.
The various field devices in a particular installation are often supplied by other manufacturers and those devices can generally be used with any SMS control unit. This is because the field devices merely contain a switching element and the field resistor is connected during installation of the system. In some cases however, the supplier of the SMS control unit may also supply field devices and, in those cases, the field resistor may be hard wired within the device, rather than being externally wired across the terminal block at the time of installation. In that event, the field devices can only be used with the same brand of SMS control unit.
These factors cause a few problems when the owner of an SMS system needs to upgrade or modify its system. Because each line connected to the system includes a field resistor of a particular value, the owner is forced to return to the original supplier of the SMS in order to provide an upgrade. Alternatively, the system owner must rewire each of the lines connected to the system and replace the field resistor with a different value, as specified by the supplier of the new SMS control unit. Where the resistor is built into the field device it cannot be changed and the system owner is forced to also replace each of the devices if it wants to change to a different brand of SMS control unit.
Typical SMS systems include an operator interface providing a graphical representation of the system being monitored and controlled. The software employed in the interface is proprietary and cannot be changed by the user. Any modification to the operator interface thus needs to be made by the original supplier and this makes the owner vulnerable to excessive ongoing maintenance costs by the supplier.
In an attempt to remove this dependency on the original supplier, the present inventor has in the past developed a universal replacement for a proprietary SMS system using a standard programmable logic controller (PLC) and analog input cards. This provided a flexible solution which could be programmed to cater for a wide variety of field resistor values. Any PLC could be used to replace the proprietary system without having to change the field resistors, thus saving considerable installation time. The programming of the PLC is more time-consuming, because all processing is done within the central processor of the PLC and this needs to be programmed using conventional ladder logic, but overall installation time is reduced. The main problem with this approach in a commercial installation, however, is the high cost of analog input cards for commercially available PLCs. The cost of these cards makes this form of PLC-based SMS prohibitively expensive for large installations.
There therefore remains a need for a flexible system which can reproduce the function of a security management system, or similar systems, or which can be used in conjunction with standard and commonly available hardware and software to provide the necessary functionality.
SUMMARY OF THE INVENTION
The present invention accordingly provides a device for monitoring the status of a circuit based on a measurable parameter of the circuit, the device including:
measurement means for measuring the parameter of the circuit; comparison means for comparing the measured parameter to at least one threshold value and for assigning a status based on the result of the comparison; and output means for presenting an indication of the assigned status.
This device may be used to measure the electrical resistance of a circuit and, based on that measurement, provide the functionality of a traditional security management system.
In one embodiment, the circuit is an electrical circuit containing at least one switchable element. This switchable element may be incorporated within a field device of the type described above. The circuit includes a first resistive component in series with the switchable element and a second resistive component in parallel with the switchable element such that the status of the switchable element is reflected in the circuit resistance.
In one embodiment the threshold value is adjustable by a user. In this way, the device is able to cater for a wide variety of values of the first and second resistive components. This enables the device to be retrofitted to existing SMS systems, wherein the resistors may have been installed many years earlier and may not be readily accessible for replacement.
Preferably, the comparison means includes a plurality of threshold values for assigning a corresponding plurality of status conditions. In one embodiment, the plurality of status conditions includes the following:
short circuit, alarm 2 , normal, alarm 1 , and open circuit.
The device preferably also includes communication means for communicating the status to a monitoring system. The communication means preferably employs an open communication standard such as the DeviceNet.™ open network standard developed by the Open DeviceNet Vendor Association Inc. DeviceNet.™ is a low cost communications link used to connect industrial devices (such as limit switches, photo electric sensors, process sensors, panel displays and operator interfaces) to a network and eliminate expensive hard wiring. The direct connectivity provides improved communication between devices as well as important device-level diagnostics not easily accessible or available through hard wired I/O interfaces. DeviceNet.™ is a simple, networking solution that reduces the cost and time to wire and install industrial automation devices, while providing interchangeability of “like” components from multiple vendors. A description of the DeviceNet.™ standard can be found in the July 2000 DeviceNet.™. Product Catalogue by Open Vendor Association, Inc. This Produce Catalog is incorporated herein by cross-reference.
Another aspect of the present invention provides a security management system incorporating a circuit monitoring device of the type described above. Such a system may utilise standard programmable logic controller hardware together with standard operator interface software to provide a fully functional security management system. The circuit monitoring device may be in the form of a separate module which is connected to the PLC using a communications module based on the DeviceNet.™ standard, or other suitable open communication standard. Alternatively, the circuit monitoring device may be configured as a plug-in card which connects directly to the back plane of the PLC. In this form, different versions of the circuit monitoring device would need to be made to plug in to different brands of PLC. A separate DeviceNet.™ module thus has the advantage that it can be used with any brand of PLC.
A major advantage of the present invention is that it allows the retrofit of existing security management systems, fire systems and building management systems, while utilising the existing circuit wiring regardless of existing resistance values. Retrofits and new installations may use various PLCs and operator interfaces, and a variety of hardware and software, instead of being locked into proprietary hardware and software.
As a further alternative, the circuit monitoring device may be built into a card which is adapted to plug directly into a personal computer or similar device.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention will now be described with reference to the accompanying drawings. In the drawings:
FIG. 1 shows a circuit in a prior art security management system;
FIG. 2 shows a monitoring system-incorporating three embodiments of the circuit monitoring device of the present invention;
FIG. 3 shows a circuit block diagram for one input of the circuit monitoring device of the present invention;
FIG. 4 shows a diagrammatic representation of comparisons made to determine status conditions according to the present invention;
FIG. 5 shows a circuit diagram for an end of line resistance module.
FIG. 6 shows a circuit diagram for a closed loop module; and
FIG. 7 shows a circuit diagram for a prototype circuit monitoring device in accordance with one embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 2 of the drawings shows an example application of the circuit monitoring device of the present invention. In this application a number of circuit monitoring devices are used in a security management system (SMS) to monitor the status of various circuits containing field devices such as motion detectors, read switches on doors and windows, smoke detectors, etc. In particular, a centralised SMS control unit 5 communicates with three monitoring devices 10 , 20 and 30 to monitor three individual electrical circuits labelled generally as A, B and C in FIG. 2 respectively.
The SMS control unit 5 includes a conventional programmable logic controller (PLC) such as an Allen Bradley model SLC 505 produced by Rockwell Automation, or any other suitable model produced by another manufacturer such as Siemens, Omron, Mitsubishi, etc. The PLC includes a microprocessor card 6 and may include various input and output cards or communications cards.
Circuit A includes a switchable element SWA associated with a field device (eg. an infra-red motion detector), a first resistive component R 1 in series with the switchable element SWA and a second resistive component R 2 in parallel with the switchable element SWA. The second resistive component R 2 is typically wired across the terminal block of the field device at the time of installation and is often referred to as a field resistor.
In this application, the circuit monitoring device 10 may be called an “end-of-line resistance module (EOL module) because it measures the end-of-line resistance of circuit A. It is thus convenient to hereinafter refer to the device 10 in this way.
Similar to the conventional circuit shown in FIG. 1 , the end-of-line resistance of circuit A will change when the switchable element SWA closes or opens. The measured resistance may thus be used by EOL module 10 to determine whether the switch SWA is open or closed. Further, the EOL module 10 can determine the existence of a fault condition such as an open circuit (infinite resistance) or short circuit (very low resistance).
The EOL module 10 is configured electrically and mechanically to be plugged directly into the back plane of the PLC. This module may thus be produced as a form of plug-in card, similar to conventional digital and analog input and output cards. Communication between the microprocessor 6 of the PLC and the EOL module 10 is via the back plane of the PLC.
FIG. 2 also shows two remote EOL modules 20 and 30 . A scanner module, being a communications card, is provided to enable communication with remote EOL modules 20 and 30 .
EOL module 20 monitors the resistance of circuit B whilst EOL module 30 monitors the resistance of circuit C. Circuit B is identical to circuit A but the EOL module 20 is remote from the PLC. EOL module 20 employs the DeviceNet.™ standard to communicate with the PLC via a communications link 8 and DeviceNet communications card 7 which is plugged into the back plane of the PLC.
EOL module 30 is a closed loop form of resistance module which measures the resistance of circuit C via inputs 1 and 2 and inputs 3 and 4 . This circuit provides an extra level of security in the event that a section of the circuit fails due to an open or short circuit. The EOL module 30 also operates according to the DeviceNet.™ standard and communicates with the communications card 7 of the PLC via communications links 8 and 9 .
FIG. 3 shows an example input circuit as may be used within any one of the EOL modules 10 , 20 or 30 . The input circuit includes an operational amplifier (OPAMP) 40 , an analog to digital converter 41 (A/D converter), a microprocessor 42 and a communication module 43 . A field circuit, for example circuit A, B or C of FIG. 2 , is connected to the input of the OPAMP 40 . An analog output of the OPAMP 40 is converted by the A/D converter 41 to a count value representing its analog input. This count value is then a numerical representation of the end-of-line resistance of the field circuit. The microprocessor 42 compares the value of the measured resistance with various thresholds to determine the status of the field circuit, and of any switchable element within the field circuit. The result of this comparison is communicated to a centralised monitoring system such as the SMS control unit 5 shown in FIG. 2 .
In the EOL module 10 ( FIG. 2 ) the communication module 43 is adapted for communication across the back plane of the PLC to the microprocessor 6 . In EOL modules 20 and 30 ( FIG. 2 ) the communication module 43 is a DeviceNet.™ communication module implementing the DeviceNet.™ communication standard.
For the sake of simplicity, FIG. 3 shows a single field circuit connected to a single A/D converter, microprocessor and communications module. However, in practice, an EOL module would include multiple inputs, for example, 8 or 16. In the case of a 16 input EOL module, sixteen OPAMP may be used and these may be connected respectively to 16 A/D converters. However, the outputs from the sixteen OPAMPS may alternatively be multiplexed to a single A/D converter. A single microprocessor may be used to read each of the digital resistance values to determine a status condition for each of the field circuits.
FIG. 7 shows a circuit diagram for a prototype circuit monitoring device. The device provides for eight input circuits connected to an eight channel analog to digital converter. This is connected via an I/O bus to a central processing unit (CPU) which is in turn connected to a DeviceNet.™ communication module.
FIG. 4 shows a diagrammatic representation of the comparisons made by the microprocessor 42 ( FIG. 3 ) for a field circuit. This example assumes that the EOL module uses a 16 bit A/D converter. Such a converter produces a count value ranging from 0 to 32,767. This count represents the measured end-of-line resistance of the field circuit. The count is compared to various thresholds, as shown, to determine a status condition for the field circuit. If the count is below 8,000, an Open Circuit condition is assigned. If the count is above 30,000, a Short Circuit condition is assigned. A value between 15,000 and 16,000 is considered to be the normal operational range for the circuit, and a Normal condition is assigned. Values between 8,000 and 15,000 are assigned an Alarm 1 condition whilst values between 16,000 and 30,000 are assigned a Alarm 2 condition.
Referring now to circuit A in FIG. 2 , and assuming that switch SWA is a normally open switch, one would expect the normal end-of-line resistance of the circuit to be equal to the values of R 1 plus R 2 . This resistance value would produce a count between 15,000 and 16,000 in FIG. 4 . A range of count values are specified in order to allow for variations in the circuit resistance resulting from cable resistance and connections. Some variation would clearly occur depending on the length of the cable extending to the field devices and the cross-sectional area of those cables. When the switch SWA closes, the end-of-line resistance would drop to the value of R 1 alone. In FIG. 4 , this would produce a Alarm 2 condition. Alternatively, if the switch SWA was instead a normally closed, that condition would be considered “normal” and opening the switch SWA would result in an increase in the end-of-line resistance to the value of R 1 plus R 2 . This would produce an Alarm 1 condition in FIG. 4 . Thus, what is considered “normal” depends on the type of switchable element used in the field circuit. It will also be appreciated that the definition of High and Low in FIG. 4 could be reversed compared to the scenario just described.
The EOL module 10 can also detect the presence of a fault condition, such as an open circuit or a short circuit. In the case of a short circuit, the end-of-line resistance drops to a very low value, depending upon the resistance of the cable and the location along the cable of the short circuit. In the case of an open circuit, the resistance increases to a very high value, dependent upon the resistance of the insulation of the cable. A range of values is thus used to allow for such variations.
It is considered that appropriate software for the microprocessor 42 shown in FIG. 3 may be written by any skilled computer programmer and, accordingly, need not be described herein in detail. The language used may be a high level language or a low level machine language appropriate to the particular microprocessor used in the EOL module.
The various threshold values shown in FIG. 4 at 8,000, 15,000, 16,000 and 30,000 are preferably configured as variables which may be set as parameters of the EOL module. In this way, the EOL module may be configured to operate with a wide range of field resistors, thus enabling the EOL module to be retrofitted to a wide range of field circuits wherein the series and field resistors (R 1 , R 2 respectively) already exist and cannot readily be changed.
After comparing the measured resistance to each of the threshold values the microprocessor 41 ( FIG. 3 ) produces, as an output, an indication of the status of the field circuit, eg. circuit A, B or C in FIG. 2 . This output may be in the form of individual flags or bits which are set when a particular status condition is assigned and thus has only two possible values from each comparison. For example, five output bits may represent five possible status conditions, namely Short Circuit, Alarm 2 , Normal, Alarm 1 and Open Circuit.
Thus, in accordance with an embodiment of the invention, the EOL module measures the end-of-line resistance of the field circuit, compares the measured resistance to a number of threshold values and assigns a status based on the result of the comparison. This status is then presented as an output in the form of five digital bits which then can be read by or transmitted to a centralised monitoring system. This centralised system does not need to concern itself with the actual value of the end-of-line resistance for the circuit but merely with the determined status of the circuit. This is significant because merely a few bits of information needs to be transferred, rather than a whole word representing the analog value. In FIG. 2 , the microprocessor 6 of the PLC merely needs to read 5 flags or bits from EOL module 20 , via the communications module 7 . The microprocessor 6 is not concerned with, and is not even aware of, the actual end-of-line resistance of the circuit B which is connected to the EOL module 20 . The communications module 7 , being a conventional scanner module produced by the manufacturer of the PLC equipment, scans the EOL module 20 using conventional DeviceNet.™ standards.
To configure a particular EOL module, such as a module 20 in FIG. 2 , the threshold values are controlled by software at the module level. For example, using software called RS Networks (Rockwell Software Networks) produced by Rockwell Automation, it is possible to access any particular module connected to the PLC network. The RS Networks software displays the parameters of each of those modules and the parameters can then be changed. In the present application, the threshold values (shown in FIG. 4 ) may be changed as parameters of the DeviceNet.™. EOL module 20 . Once the parameters are set, they are stored within the module 20 , not the PLC, and are retained within non-volatile memory of that module.
In one form, the parameters may be set individually for each input of a multi-input module. However, more likely, the parameters would be identical for each input of the module and each, at least initially, would be set using the same parameters. Individual changes could be made after setting the default parameter for the whole module.
The EOL modules may also be programmed with default threshold values at the time of manufacture. For example, the threshold value may be set at levels appropriate for field circuits employing field resistors having a value of 4.7 k.OMEGA. In this way, the EOL module may be used in a PLC-based retrofit, for a conventional security management system which normally uses field resistors having a value of 4.7 k.OMEGA., without needing to program the EOL modules at all. If the system being replaced uses field resistors having a different value, then the EOL modules can be reprogrammed for that value.
FIGS. 5 and 6 show extended versions of circuits B and C in FIG. 2 respectively. In each of FIGS. 5 and 6 a number of field devices are connected within the circuit. Like reference numerals are used in FIGS. 5 and 6 to represent like component in FIG. 2 . The field devices may be smoke detectors, read switches or other forms of detector.
A PLC based security management system would preferably be provided with an operator interface in the form of a visual display unit and an input device, such as a computer keyboard. A visual representation of the system being monitored would be presented on the visual display. A number of standard Supervisory Control And Data Acquisition (SCADA) software packages are available which can be run on standard personal computer (PC) hardware. Some examples include FIX by intellution, Citec by CI Technologies. Alternatively, a customised user interface may be developed using graphical programing tools such as Active X, Visual Basic or Visual C++. The personal computer may be networked to one or more PLCs to provide an integrated security management system.
Similar PC and PLC hardware and software may be employed to create a fully functional fire system or building management system.
Such PC/PLC-based systems using EOL modules according to the present invention may be readily retrofitted to existing systems, while utilizing the existing circuit wiring regardless of existing resistance values. A system built in this way, either as an original installation or as a retrofit, provides a flexible and relatively inexpensive option which eliminates dependency on proprietary hardware and software.
A system employing the present invention provides various options including:
End-of-line resistance (as shown in FIG. 5 );
Closed loop resistance (as shown in FIG. 6 );
Dual redundancy,-end-of-line or closed loop (see below);
Intrinsically safe (see below).
Dual redundancy may be provided at various levels. For example, two communication lines may be provided between a communications scanner module in the PLC and a remote EOL module. If one of the lines fails, the other keeps going. Alternatively, or in addition, two scanner modules may be provided in the PLC. Further, two microprocessors may be provided within the PLC in critical application. Such dual redundant systems are typically required in specialized fire systems.
Intrinsically safe systems are often required in hazardous locations. This may be achieved by using an intrinsically safe barrier or module, which are commonly available, or by making the EOL module itself intrinsically safe. This saves on added wiring and additional hardware costs but would make the cost of the module itself somewhat greater.
Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the amended claims. For example, the DeviceNet.™ standard has been referred to herein for providing the communication link between a remote EOL module and a PLC communication scanner module. There are, however, various communication networks which may be just as efficient. Such variations to the described system are considered to fall well within the scope of the appended claims. | The circuit monitoring device is disclosed. The device is for monitoring circuit resistance. At configurable thresholds digital flags are triggered, the device can be used as a Security/Building management system. The device uses open technology is fully scaleable and allows programmable logic controllers to be used as security management systems. Using a soft logic option a PC could take the place of the PLC. | 6 |
This application is a continuation-in-part of Ser. No. 08/005,331 filed Jan. 15, 1993, now U.S. Pat. No. 5,345,659, which is a continuation-in-part of Ser. No. 787,424 filed Nov. 12, 1991, now U.S. Pat. No. 5,179,767, which is a continuation-in-part of Ser. No. 553,258 filed Jul. 16, 1990, now U.S. Pat. No. 5,088,162, and all of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The referenced application Ser. No. 553,258 relates generally to an elongated, strap-like connector, with generally C-shaped cross sections configured to nest ridges of an opposing strap end. Also, random sections of the strap-like connector were provided that may be affixed to objects so as to allow their connection. Teeth might be added to control lateral movement of the nested ridges in the C-shaped openings. Means to confirm interlock was also disclosed and claimed.
Certain improvements to the invention were claimed in referenced application Ser. No. 787,424. One major improvement was the combining of the larger and smaller ridges, so that the connector consisted of one cross section configuration, instead of two. If used on a small strap, each side of the strap could be looped and connected to the same side or the opposite side. The flexing of the ridges allowed the simultaneous nesting of a series of ridges, even though their outer, cross section widths were greater than the openings they would be inserted into.
Additional improvements to the invention were claimed in referenced application Ser. No. 08/005,331 filed Jan. 15, 1993. One such improvement was a flexible, hook-like, tapered ridge suitable for vertical removal from a mold, due to its ability to straighten. The tapered, flexible design allowed for a more complicated connector. Virtually an unlimited number of rows or clusters of ridges could be positioned, both laterally and longitudinally. Previously, only one or two rows of ridges, using an injection mold, were practical, without using a relatively expensive and complicated mold. The improved, flexible, hook-type ridge disclosed herein gains its shear strength in number of connections, and may be used as an alternative to hook-and-loop type connectors.
The herein disclosed injection mold design can be modified to make a flexible connector with improved hooks, for hook-and-loop type connectors. Provost, in U.S. Pat. No. 4,984,339, discloses a hook, for hook-and-loop fasteners, which has a base intimately engaging a substantially planar base member and in which the hook tapers smoothly and continuously from the base member to the free end. That hook design, when manufactured in accordance with U.S. Pat. No. 4,872,243 to Fisher, can result in a continuous strip or roller-molded connector with hooks thereon. The planar base member can be approximately 0.010 inches thick, which provides for good flexibility. This thin base may not be commercially achievable using a conventional injection mold process.
It would be desirable to use a conventional injection mold to manufacture a connector with improved hooks, for hook and loop connectors, wherein the connector is flexible, yet with a base thick enough to allow the hot liquid plastic to flow in the mold during forming. Typically, the connector claimed by Fisher may be sold to manufacturers who re-manufacture it into desired shapes to fit their needs. It would be desirable to many manufacturers to be able to purchase a connector with improved hooks, for hook-and-loop connections, where the connector was flexible and formed exactly to their specifications through conventional injection molding.
With certain types of connectors, such as shoe connectors, it is desirable to have individual ridges with a great deal of shear strength. Individual, flexible, and tapered ridges lack a great deal of shear strength. Also, it would be desirable if a shoe strap or other strap could be joined with little or no pressure. In addition, a shoe strap would be easier to use, if the ridges were recessed within the strap. Many of the ridge designs previously disclosed flexed during connection, which, for certain applications, required greater mechanical pressure than desirable.
Loosely fitted, generally inflexible or flexible ridge-to-ridge type connectors, hereinafter disclosed, can have ease of connection and disconnection, while having far greater shear strength than the previously disclosed tapered, flexible, ridge-type connectors, and enable more versatile designs than previously possible, when produced by means of the improved injection mold design hereinafter disclosed.
There is also need for improved, easy to connect, ridge-to-ridge and hook-to-loop type connectors that lend themselves to the injection mold process.
SUMMARY OF THE INVENTION
The present invention includes provision for a plurality of improved ridges configured and spaced to nest inverted ridge means, incorporated into a strap-like shoe connector. Other connectors are disclosed which also are of an improved design suitable for the improved injection mold design herein disclosed.
The disclosures in herein applicant's U.S. patent applications, Ser. No. 787,464, and Ser. No. 553,258, provided for C-shaped cross sections formed by the side walls of ridges of a strap-like shoe connector. The ridges had a strap-like base, typically a narrow, flexible midsection, and an outermost portion with hook-like cross sections. In the present invention, the base or center of the C-shaped cross section is missing.
It is an object of this invention to enable up to 40 or more rows of ridges, per inch, to be incorporated onto a product's surface, so that such surface appears relatively flat, yet has small, lateral, and longitudinal perforations partially or fully through the surface.
It is yet another object of this invention that the ridges may have variable cross sections, depending upon the intended use, which may be generally flexible or inflexible, rounded, oblong, hooked, tapered, angular, parallel, sloping, pointed, or chisel-like on one or both sides or ends of a ridge. The variable cross sections may be used to assist ridge nesting based on the intended use of the product to be connected. A connector may have differently configured ridges.
It is a further object of this invention that loosely nesting ridges, configured for ease of connection/disconnection of objects, may incorporate a means to control their lateral engagement, such as staggered groupings of ridges or rows of ridges with individual ridges laterally not aligned.
It is another object of this invention that grooves and/or ridges running perpendicular to the ridges may be used to control lateral engagement of ridges.
It is an additional object of this invention that certain ridges need not nest or contact the side walls of a plurality of other ridges to achieve interlock of the connector means, but that the connector means still has means to achieve complete interlock.
It is an object of this invention that a connector strap, such as for a shoe, may have ridges substantially recessed between two outer, strap-like members suitable to receive raised ridges into the openings between the recessed ridges.
It is an object of this invention that a connector may have ridges placed between two more outer, strap-like connector members, with said ridges partially or fully recessed, and with single or multiple hook-like projections on said ridges.
It is an object of this invention that a partially inflated bladder be added to a shoe; and that a connector be positioned on the shoe so that, when tightened, pressure is applied to the surface of the bladder, which in turn increases the internal pressure of the bladder, which in turn tightens the shoe fit.
Yet another object is the provision of a connector means connectible to inverted ridge means and comprising:
a) a plurality of parallel ridges spaced apart and configured so that the inverted ridge means may be nested between and gripped by certain of the parallel ridges,
b) and including means associated with the connector means to confirm completed, adjusted interlock of the inverted ridge means with the parallel ridges in response to the nesting,
c) and including an object to which the connector means is connected.
It is an added object of this invention that a connector means may have ridges with single or multiple hook-like cross sections, with hooks having chisel-like cross sections, the space between two ridges located, to allow the insertion of a similar configured ridge, substantially without mechanically spreading the two ridges further apart, so that connection of connector parts occurs with minimal mechanical resistance.
It is yet another object of this invention to employ relatively simple, injection-type molds for forming strong, flexible or relatively inflexible ridges with the undercut outer, terminus portion of a ridge being formed by a protrusion from one mold part, while the nonundercut portion of said ridge being formed by a cavity of the other mold part.
It is an object of this invention that the improved ridge configuration may be incorporated into previous disclosures of the patents and applications of which this application is a continuation-in-part.
It is yet another object of this invention that the term shoe and shoe connector, as used herein, means and is applicable to baby shoes and boots, canvas, leather, and synthetic foot apparel, including sports and recreational shoes, high-top shoes, boots, and the like.
It is an additional object of this invention that one specification for ridges with hook-like termini provides for an average cross section width as small as approximately 0.008 inches, to achieve desired flexibility.
It is an object of this invention that a strap-like connector may have ratchet-like ridges, the connector configured to provide ratchet-like tightening when pulled across another connector part and wherein the strap-like connector's ratchet connection is to be confirmed by a C-shaped connector means.
It is an object of this invention that the improved ridge design, suitable for manufacture in the improved, disclosed injection mold plate forming cavities, may be substantially modified by employing a thinner mold plate with scribe-forming cavities, which would substantially shorten laterally the ridges, so as to form instead a hook suitable to engage a loop, such as for hook and loop connector. It is understood that said hooks would require several additional modifications, such as spacing, alignment, and thickness, for desired strength, etc. It is an object of this invention that the mold design (in a form for manufacture of ridge connectors or for hook connectors) have at least two mold parts, which at least join at the terminus of the hook, so as to allow air to vent, so that a well-defined, pointed hook terminus can be achieved.
U.S. Pat. No. 5,179,767 claimed an improved buckle which allowed ratchet-like tightening of a tongue that flexibly fit into said buckle; the buckle and tongue would in turn be connected to a strap. It is another object of this invention to provide for an improved, double-ended tongue, connectible to a pair of buckles to provide an improved, adjustable connection.
These and other objects and advantages of the invention, as well as the details of an illustrative embodiment, will be more fully understood from the following specification and drawings, in which:
DRAWING DESCRIPTION
FIG. 1 is a plan view of one form of connector apparatus;
FIG. 2 is a perspective view of another form of the connector to be used as one of a pair, as at FIG. 5, 51 and 54;
FIG. 3 is an enlarged schematic view showing meshing of ratchet-like ridges;
FIG. 4 is an enlarged section showing retention of a strap by a C-shaped connector;
FIG. 5 is a perspective view of a boot, with connectors thereon;
FIG. 6 is a view like that of FIG. 2 showing an alternative configuration;
FIG. 7 is a view like FIG. 3 showing an alternative meshing of ridges and slots;
FIG. 8 is a perspective view of a strap-like connector with ridges spanning between two strap-like members;
FIG. 9 is a section taken at 9--9 in FIG. 8 showing connection to a second strap-like connector;
FIG. 10 is a section taken through two mold parts;
FIG. 11 is a view like FIG. 10 showing modified mold parts;
FIGS. 12(a)-12(d) are sections showing various ridge configurations;
FIGS. 13 and 14 are perspective views of modified connector elements with ratchet teeth;
FIG. 15 is a perspective view of a modified connector;
FIGS. 16-18 show objects mounting or carrying connectors, as referred to;
FIG. 19 is a perspective view of connector means with hooks for hook and loop-type connectors;
FIG. 20 is a view of a prior art hook;
FIGS. 21(a) and (b) are profile views of two improved hooks, as for hook and loop-type connectors;
FIG. 22 is a plan view of the FIG. 19 connector;
FIG. 23 is an enlarged section taken through a connector of FIG. 22;
FIG. 24 is a view like FIG. 10 showing mold parts separated and hook formation;
FIG. 25 is a section taken on lines B--B of FIG. 24 showing the mold parts closed together;
FIG. 26 is a perspective view of an improved double-ended, tongue-like ridge, with double buckles and ratchet-tightening design; and
FIG. 26a is a perspective view of a connector.
DETAILED DESCRIPTION
FIG. 1 shows a specialized connector used on a shoe, to replace laces. Note opposite alternate straps 10 at shoelace eyelet locations, with angled slots 11 through the straps (like slots 21 at FIG. 2, 21 at FIG. 3, and 65 at FIG. 7), which receive raised ridges 12 (like raised ridges 22 at FIG. 2, 22 at FIG. 3, and 72 and 73 at FIG. 7). The straps 10 extend laterally, while the connector members 13, holding the ridges 12, extend longitudinally in FIG. 1. There are holes 16 through the connector members 13. Ridges 12, holes and connector members 13 together form a web. Each connector member also carries straps 10, as shown. Each strap may be held in place or alignment with a C-shaped connector 14 (an example is shown in greater detail at 24 in FIGS. 2, 3 and 4) or with a hook-like ridge at 72 in FIG. 7. The ridges 12 may generally resemble the ridges 22 of FIGS. 2 and 3, or 72 and 73 of FIG. 7. Alternately, ridges 15 may occupy most of the connector members, as at 13. Ridges 15 may be of similar design, as ridge 141 of FIG. 14, while straps 10 carry downwardly projecting, raised ridges, as at 136 of FIG. 13. Strap 10 may, for example, be like straps at FIGS. 2, 6, 7, and 8.
FIG. 2 shows a connector of this invention which may be used for a shoe or boot, in the manner as indicated at 51 in FIG. 5; the strap 20 on base 23 has slanted slots or holes 21 which nest ridges 22 on another base 23, like that of FIG. 2, but rotated 180°. Slots 21 are formed by ridges 25 and connector members 26, which together form a web. Strap 20 on one base is partially held in place in C-shaped connector 24, on the other base or connector member 23, whereby a very secure dual connection is made, using two laterally oppositely extending straps 20, offset longitudinally.
FIG. 3 shows a cross-section view of strap 20 (like strap 11 of FIG. 1, or strap 20 of FIG. 4) having slots 21 defined by ridges 25 and connector member 26 engaged by ridges 22 (like ridges 12 of FIG. 1 or ridges 22 of FIG. 2), and in the process of being nested in C-shaped cross section 24, formed by lobes like 24 of FIG. 4, and 24 of FIG. 2. Ridges 22 and 25 are angled to allow ratchet-like tightening of straps.
FIG. 4 shows a cross section of C-shaped connector 24 (like 14 of FIG. 1, 24 of FIG. 2, and FIG. 3) with strap 20 (like strap 11 of FIG. 1) nested therein between lobes 24.
Accordingly, the flexible connector apparatus may be considered to comprise:
a) a plurality of parallel ridges spaced apart and configured to grip certain parallel ridges,
b) a connector member supporting the ridges.
And, as shown, the first base has a first elongated and flexible tongue portion carrying downwardly projecting ridges, as at 25 of FIG. 3; and the second base has a second elongated and flexible tongue portion carrying similarly downwardly projecting ridges 25. Also, when used in the shoe of FIG. 5, the downwardly projecting ridges 25 of one connector engage the upwardly projecting ridges, as at 22 of FIGS. 2 and 3. Slots, as defined, may be formed by ridges.
Further, a C-shaped connector is provided on one base and guidedly nesting the straps of the other base to retain it in alignment relative to meshed ridges and slots.
FIG. 5 shows how forms of the connector may be used with a boot or shoe 50. For clarity, the boot 50 is shown partially assembled. The connector 51 may be either of the type shown at FIG. 2 or at FIG. 6. Alternately, instead of connectors with two connector straps 54, multiple strap connectors may be used, as at FIG. 1. Straps 54 of the connector 51 would be simultaneously pulled, as one would pull shoe laces to tighten the shoe. The upper connector straps 52 would operate simultaneously, and may be of designs, as shown at FIGS. 7, 8, 9, 13, 14, and 15 herein; straps 52 may be extended continuously around the shoe/boot or only partially. Ridges 56 may resemble raised, generally inflexible, ridges 72 or 73 of FIG. 7, or generally flexible ridges 151 of FIG. 15. Straps 57 can be used with downwardly projecting ridges, like 131 of FIG. 13 or 151 of FIG. 15. Straps 57 may have single or multiple rows of ridges. The connector 53, when tightened, creates pressure on the sealed bladder 55, which causes it to expand to make the shoe/boot a tighter fit. To this end, one or more straps may be used.
FIG. 6 shows an alternate design to the connector shown at FIG. 2. The strap 60 has slots 65 (as at 65 in FIG. 7) which engage ridges on another connector, like ridges 62 and 63 on connector member 64 (like 72 and 73 of FIG. 7), the arrangement being like that of FIG. 1, without the need for the C-shaped connector 14.
FIG. 7 is a cross section view of strap 60, with recessed ridges 74 and 81 engaging raised ridges 72 and 73, with connector member 64 extending beyond (like 13 of FIG. 1). Slots 65 are formed between ridges 74 and 81. Ridges 73 are used primarily for shear and ratchet-like connector adjustment. Accidental vertical disconnection is primarily controlled by nesting of ridges 74 and 81 with ridges 72. Note hook undercuts 77 and 79 of ridges. The spaces or slots 65 between ridges 74 and 81 are open. Also, the spaces 65 and 66 between ridges 74 and 81, and between ridges 72 and 73, are open, which creates greater flexibility of the strap 64. Spaces 65 and 66 allow the mold protrusion (111 of FIG. 11) to form the undercut portions 77, 78, and 79 of ridges 72, 73, 74, and 81, which create the overhangs.
As can be seen, ridges 72 and 73 are spaced apart so that very little, if any, mechanical spreading is required to nest ridges 74 and 81. Improved interlock of ridges is accomplished through the use of an improved overhang in the form of a chisel-like, sharp-edged, hook terminus 83. Ridge 80 is vertically held in place between ridges 73, because it is connected to strap 60 (beyond), which in turn is connected to ridge 81, which, when fully nested, locks ridge 80 under the overhang 82 of ridge 78. It is understood that ridges 72 or 73 may be used on a connector, a strap or other article, and may connect to other raised ridges, as at 72, or recessed ridges, as at 74 and 81.
FIG. 8 is a perspective view of a portion of a general utility strap 86, which may be used as at 52 and 53 of FIG. 5. Ridges 80 are double ended 81 and have hook termini 82 and 83 facing in opposite directions. A plurality of such ridges 80 extend longitudinally and are endwise connected at 84 to connector members 85. It is understood additional connector members 85 and ridges 80 may be added laterally. A third connector member may divide ridges 80 with hook termini 82 from ridges with hook termini 83.
FIG. 9 is a cross sectional view taken at 9--9 in FIG. 8 of connector 86, and showing a partial view of the FIG. 8 connector, connected to a similar connector 92. Note hook elements 82, 83, 95, and 96. When upper connector 86 is connected to lower connector 92, a hook element 96 of a connector 86 engages a hook element 82' of connector 92, in hooking relation. Although the ridges 80 are loosely nested, the hook elements 95 and 96 of connector 86 cooperate and are spaced for a tight fit during nesting, with similar hook elements 82' and 83' of connector 92, to prevent accidental disconnection of connectors 86 and 92 when nested. Desired disconnection is accomplished by peeling connectors 86 and 92 apart.
A random cut section of this type connector, with recessed ridges 80, may be press fitted to connect to a similar section of connector, either top or bottom, and have equal shear strength in two directions. At FIG. 8 the ends 81 of ridges 80 lock between connector members 85 and provide lateral shear strength. Where one way shear strength on one side of a strap is only needed, such as shoe connector 52 at FIG. 5, it should be understood hook termini 82 and 83 may face only in one direction; and ridges 80 may only be single ended.
FIG. 10 is a cross section view of two mold parts 100 and 101 in the process of separating, so that a gap 102 is exposed between the mold parts above the newly-formed or molded ridges 103. With injection molds, it is highly desirable that, when the mold part 103 is formed, the mold parts 100 and 101 may be perpendicularly separated in direction 97 without the part 103 being locked into either of the mold parts 100 and 101, due to overhangs, such as hooks 104. If hook 104 was formed by mold 100 at 105, ridge 103 could not be readily separated from mold 100. Because mold parts 100 and 101 come together side-by-side at 104 and 105, to form the chisel edge, there is a slight gap (between the two side-by-side molds), which allows air to escape and the hot molten plastic to be formed into a sharp chisel edge 104. The protrusions 106 and cavities 107 of mold part 100 cooperate with the protrusions 108 and cavities 109 of mold part 101, to mold double-ended ridge 103. Note plastic injection port 99, platen 99', and actuator 98 for mold part 100.
FIG. 11 is a cross section view of two modified mold parts 110 and 111 in the process of separating, so that a gap 116 is exposed above the tops of newly-formed ridges 114 and 115. The cavities 113 of mold part 110 cooperate with the protrusions 112 of mold part 111 to form the ridges 114 and 115. The protrusions 112 of mold part 111 will typically taper slightly, providing draft, so that the ridges can be vertically extracted. Likewise, the cavities 113 also taper or slope, so that there is little friction when separating the ridges 114 and 115. Molds of the type of FIG. 11 are suitable for strong, generally inflexible, ridges of FIGS. 1-4, 6, 7, 13, and 14; or generally flexible ridges of FIGS. 12 and 15. Note plastic injector 300, platen 301 and actuator 302 to open and close part 110.
FIGS 12(a)-12(e) are cross section views of examples of five ridge designs 120, 121, 122, 123, and 124, which can be molded by operation of mold parts 110 and 112 of FIG. 11. Ridges 120, 121, 122, and 123 are designed to flex during disengagement from nesting ridges at 120, 125, 126, 125', and 126'. Ridges 121 and 122 are configured to flex initially at 125' and 126', then flex and release at 125 and 126. Ridges are not connected to a base in the preferred embodiment, but only connected at the lateral ends 158 to connector members 157 and 157' which, together with the ridges 151 and 151', form a web 150, indicated for example at FIG. 15. Ridge 124, like ridge 141, FIG. 14, has minimal flex at the tip of chisel-like terminus 127.
FIG. 13 is a perspective view of a connector part 130 with ratchet-like, laterally extending teeth 132, spaced between longitudinally extending ridges 131, which are configured and spaced to nest with ridges 141 of connector part 140 of FIG. 14. A preferred embodiment would use ridge 124 instead of ridges 131 and 141, so that connector part 130 would have the same configuration as connector part 140. Ratchet-angled teeth 132 are configured for ratchet-like advancement relative to ratchet-like teeth 142 of FIG. 14, to resist relative movement of said bases in substantially parallel planes, and in direction parallel to length direction of the ridges. In both FIGS. 13 and 14, there are holes 133, 134, 143, and 144 which improve the flexibility of the connector parts 130 and 140, while allowing the forming of undercut portions 135 and 145 of the ratchet-like teeth 132 and 142, and the forming of the undercut portions 136 and 146 of ridges 131 and 141. Said holes 133, 134, 143, and 144, and undercuts 135, 136, 145, and 146 may be formed by protrusions, such as 112, of a mold part 111 of FIG. 11. Ridges 131 are supported by connector member 137 at their longitudinal ends 138.
FIG. 14, as explained under FIG. 13, is a part 140, configured to nest with part 130 of FIG. 13.
FIG. 15 is a perspective view of a portion of a connector part or web 150 having ridges 151 and 151', such as at FIG. 12(a), with hooks facing in one direction. The terminus hook portions 152 of these ridges 151 and 151' are configured to flexibly engage inverted nesting ridges 153, which are turned 180° relative to ridges 151 and 151', and then meet only slight resistance at 154 to achieve nesting at 155. See the broken lines indicating stages of relative movement. Ridges 151 and 151' are free-floating except where connected to connector members 157 and 157' at 158. The lateral space between ridges 151 and 151' generally equals the lateral width of the connector member 157' and is narrower than the lateral widths of ridges 151 and 151.' Ridges 151 and 151', together with connector member 157 and 157', form a web 150 Ridges 151 align laterally with the space 159 between ridges 151', to provide restricted lateral movement of nested ridges 155. In some preferred embodiments, ridges will be aligned laterally, as at 56 in FIG. 5. It is understood that connectors using a large multiple of connector members 157 and 157' with a large multiple of ridges 151 and 151' may be used instead of hook and loop-type connectors.
FIG. 16 shows a child's building block 160 and 160', which has multiple lateral and longitudinal elongated ridges 161 and 162 on the upper and lower portions of the body 160 and 160'. The ridges 161 and 162 are spaced to nest similarly spaced ridges on a similar block when ridges are aligned and press-fitted into spaces between ridges 168 and 168'.
Posts 163 of block portion 160' and interior side walls 164 are sized to connect to Leggo®-type toy blocks. Likewise, body 160 has three similarly configured posts 163' (one shown) and interior side walls (not shown). Peg 165 is sized to compression fit into holes 166 and 166' of posts 163 and 163', which are irregularly shaped, as at 167, so as to join body parts 160 and 160'.
Generally, rectangular ridges at FIGS. 16, 17, and 18 use generally inflexible plastic. A tight fit or slightly looser fit with protrusions 187 may be used for connection. In FIG. 17, the block forms a hole to receive the object with ridges thereon to be rotatable in the hole, the ridges rotating with the insert relative to the block. At FIG. 16, one peg may be used so as to rotate body part 160 relative body part 160'. At FIG. 18, outer edges 186 of ridges 161 may be slightly rounded to assist nesting.
FIG. 19 is a perspective view of a connector means 190 to engage loops, as in hook-and-loop connectors. Improved hooks 191 and 191' face in opposite directions and are free-floating except where laterally connected to connector members 192 and 193. Hooks 191 and 191' are width-wise very narrow at dimension W2, compared to the width of ridges of width dimension W1 of FIG. 15, so as to be able to engage loops. These hooks 191 and 191' are too narrow at W2 to effectively engage similar configured hooks. The spaces between hooks 191 and 191' are approximately equal to the lateral widths W3 of longitudinal connector members 193, at their point of connection with said connector members at 197. In the preferred embodiment, hooks 191 will taper from the narrowest widthwise dimension W2 to their connection with connector members 193 at 197.
FIG. 20 shows in profile view the hook 200 disclosed by Provost. Note the inner surface of hook 200 has a generally concave face 201 and outer, generally convex face 203, with a widened base 204 engaging a substantially planar carrier base member 205. The hook 206 tapers smoothly and continuously in width from the base member 204 to the rounded free end 207.
FIG. 21(a) and (b) show profile views of two improved hooks 210 and 210' of this invention. Hook 210 has a chisel-like, sharp-edged terminus at 211 configured to engage a larger percentage of loops than the rounded free end 206 of hook 200 of FIG. 20. The outer portion 207 of the free end 206 of hook 200 may allow a loop 208 to slip off and not engage. The sharp edged areas 211 and 211' of hooks 210 and 210' require less displacement and snap back of a loop 213 and 213' than loop 208. The upper and lower surfaces 212 and 212' of hooks 210 and 210' are generally parallel and do not need to taper for removal from the mold of this invention (see FIG. 24). Hook 210, as can be seen, does not continuously taper from its outer, sharp edged, free end 211 to its opposite terminus 214. There is no planar base member 205 or base member 204, as provided at FIG. 20. The hooks 210 and 210' are free floating to improve the flexibility of the web, which is made up of hooks 191 and 191' and connector member 193. As at FIG. 19, undercut surfaces 215 and 215' are slightly inwardly sloping to vertical, unlike at 201 of hook 200 of FIG. 20, to allow for clean, vertical separation of hook 244 from mold part 243, as at FIG. 24.
FIG. 22 is a plan view of the connector at FIG. 19. Note section A--A at FIG. 19 and in FIG. 22. The undercut portions 195 and 196 correspond to the mold portion 243 of FIG. 24, which is configured to form one undercut portion of ridge; while portion 243' is configured to form undercut portion 194.
FIG. 23 is a cross section view of a connector 220 also corresponding to section AA of FIG. 19, showing connector members 193 and 193' and hooks 191 and 191'. Note hooks 190 and 191, and connector member 193 and 193', has a slight taper which improves removal from mold cavities, as at FIG. 11, which also allows for greater flexibility of the hooks at W2, and a stronger, lower portion of ridge 191 and 191' at 197.
FIG. 24 is a cross section view of an upper mold part 241 partially separated 242 from lower mold part 248. A recently formed hook 191' is also shown. Proximate section B--B, the hook has a sharp, chisel-like, outer terminus 245. When the mold parts 241 and 248 come together at 246, a slight amount of air can vent at clearance 246 allowing the hot, molten plastic to form clean, sharp, chisel-like end 245. In the preferred embodiment, upper mold part 241 and cavity 247 has been etched by a wire EDM machine in a metal plate 241, while protrusions 249 of lower mold part cooperate to form ridge 244.
FIG. 25 is a cross section end view at section B--B of FIG. 24; however, mold parts 241 and 248 are shown together without gap at 246. Recently formed hooks 191 and 191' are shown. Cross section AA of FIG. 23 corresponds to hooks 191 and 191' and connector members 193.
Upper mold part 256 is made up of a series of metal plates 241, 257 and 259 which are locked together. Certain plates 257 are configured to form the top side of connector member 193. Other plates 259 are scribe to mirror image the upward facing portion of hooks 191. The mold part 241 of FIG. 24 will flair out, as at 260, where ridge is less than full height. The metal plate 261 viewed at 90° appears like mold part 248. Said flair of metal plates provides draft needed for meshing of upper 241 and lower 248 mold parts.
FIG. 26 shows an improved, tongue-like ridge 265 configured to adjustably nest in two buckles 266 and 266'. Holes 267 in 265 provide means for ratchet-like tightening of the connector when tongue 265 is pushed further into buckle 266 and 266'. Modified C-shaped connectors 268 (as seen in FIG. 26a) nest in each buckle-like housing 266 and 266'. The open ends 275 of said C-shaped connectors 268 align with the buckle end openings 269 and 269'; said C-shaped connectors 268 nest said tongue-like ridge 265; said C-shaped connector 268 is slightly bowed at 270, so that when its opposite side walls 271 and 271' are manually pinched, the bowed center 270 will flex upwardly for retracting ratchet tooth 272 upwardly, said ratchet tooth is shown in cross section at 272'. Multiple teeth 272 and 272' may be used or alternate ratchet means. Buckles 266 and 266' have side openings 273 and 273' to provide access to C-shaped connector 268 side walls 271 and 271'. Buckles 266 and 266' have slots 274 and 274' for a connecting strap, not shown. Tooth 272 ratchets in holes 267. Buckle 266' is like 266 and functions in the same way, but endwise oppositely. | A connector means including shoe connector means comprising a plurality of improved ridges configured using an improved injection mold design so that inverted ridge means may be nested between and gripped by certain of the ridges. The connector means also includes means to confirm complete, adjusted interlock of the nested ridges. Additionally disclosed are products that would incorporate such connector means. Also disclosed is improved, chisel-like, ridge hook design suitable for strong connectors with little or no mechanical resistance to connection. Improved, generally rectangular, rigid, ridge design for toy building blocks is also disclosed. Also disclosed is improved hook for hook and loop fasteners with connector members suitable for injection molding. An injector mold design suitable for manufacturing ridge-type connectors or hook-type connectors for hook and loop connectors is disclosed. Also disclosed is an improved, adjustable tongue and double-buckle connector for straps. | 8 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of copending International Application No. PCT/DE03/00507 filed Feb. 18, 2003 which designates the United States, and claims priority to German application no. 102 06 908.5 filed Feb. 19, 2002.
TECHNICAL FIELD OF THE INVENTION
[0002] The invention relates to an injector, in particular for an accumulator injection device with an improved connection geometry.
DESCRIPTION OF THE RELATED ART
[0003] There are various known forms of injectors for accumulator injection devices. Injectors of this type have a high-pressure connection for feeding in fuel under high pressure, an electrical connection plus a leakage connection for removing any leakage out of the injector. Here, the connection points are located at different positions on the injector, in particular on the injector head and on the main body of the injector.
[0004] DE 199 40 387 C1, for example, discloses a leakage connection for a fuel injector for which a connection stub is formed in one piece with an injector body. In this case, a stepped bore is provided in the connection stub so that it can be joined to a connection nipple, which engages with an insert in the stepped bore. Here, an elastic clip is used to make a joint between the connection nipple and the connection stub. In addition, a separate electrical connection is provided, and a separate high-pressure inlet connection for the fuel.
[0005] In addition, WO 01/18382 A1 discloses a common rail injector on which an electrical connection and a leakage return connection are located on the head end of the injector. For this purpose, a connection stub for the leakage connection is formed on the injector, this being surrounded by a cap-like sleeve. This cap-like sleeve also provides protection for the electrical connection terminals. In addition, the leakage connection is formed by a connector shell which is plugged together removably, by means of locking devices, over the connection stub and the sleeve body of the electrical terminal. As a result, this known solution comprises numerous individual parts, in order to provide the connection geometry required for the electrical connection and the leakage connection.
SUMMARY OF THE INVENTION
[0006] Starting from this point, it is the object of the present invention to provide a leakage connection or injector with a leakage connection, as applicable, which is simply constructed and can be supplied at low cost.
[0007] This object is achieved by an injector, in particular for an accumulator injection device, comprising an inlet connection, a leakage connection and an electrical connection, wherein the leakage connection and the electrical connection are formed as a one-piece molded component, which is molded directly onto the injector.
[0008] The molded component can be manufactured from plastic. The leakage connection can be arranged with an offset of 180° to the electrical connection. The one-piece molded component can be arranged on the head of the injector. The inlet connection can be arranged on the end face of the head of the injector. The one-piece molded component can be arranged around the inlet connection. A leakage return bore can be formed in the injector as a simple cylindrical borehole. A recess can be formed, running around the outer perimeter of the leakage connection, in order to attach a locking device. The leakage connection and the electrical connection can be each arranged at an angle of approximately 45° to a center line of the injector. The one-piece molded component may completely cover the end face of the head of the injector, like a cap.
[0009] The object can also be achieved by a leakage connection for attaching a leakage line to an injector, wherein the leakage connection and an electrical connection for the injector are formed as a one-piece molded component, where the one-piece molded component is molded directly onto the injector.
[0010] The leakage connection can be formed in the one-piece molded component in a direction which is offset by 180° to that of the electrical connection. The leakage connection and the electrical connection can be each arranged at an angle of approximately 45° to a center line of the injector. The leakage connection and the electrical connection can be completely manufactured in a single work step by means of injection molding of a plastic.
[0011] In the case of the solution in accordance with the invention, a leakage connection for the injector is integrated into a molded surround for the electrical connection. Hence, in accordance with the invention a one-piece component is provided, which is molded onto the injector, and incorporates the leakage connection and the electrical connection. This involves the one-part component being molded directly onto the injector, so that the number of components is kept to a minimum. Here, the injector is molded on in one operation, in which the electrical connection and the leakage connection are manufactured at the same time. As the one-part component is molded directly onto the injector, it is then impossible to remove it from the injector without damaging it. Thus, the leakage connection in accordance with the invention and the electrical connection can be manufactured particularly cost-effectively.
[0012] Since, according to the invention, the leakage connection is formed in one piece with the electrical connection, it is preferable that only one further leakage borehole, in the form of a simple cylindrical bore, is provided in the injector for feeding in the leakage. This makes it possible, in particular, to eliminate the expensive manufacture of a stepped borehole, used in the prior art, with its subsequent rework steps, such as deburring and hardening, required because the wall thickness gets progressively thinner towards the outside. In addition, there is also no need for additional connection stubs for the leakage borehole. Furthermore, a leakage nipple attachment will preferably be integrated into the one-part molded surround.
[0013] For this reason it is particularly preferable if the one-piece molded component is made of plastic.
[0014] Preferably, the leakage connection in the one-piece molded component will be arranged with an offset of 180° relative to the electrical connection. The axes of the electrical connection and of the leakage connection will then lie in a plane passing through a central axis of the injector, resulting in a relatively simple construction for the molding die.
[0015] In order to provide a particularly compact construction, the one-piece molded component with the two connections will preferably be arranged on the head of the injector. Here, the term ‘head of the injector’ is to be understood as that end of the injector which is furthest from the end from which fuel is sprayed into a combustion space in a combustion engine.
[0016] In accordance with a further preferred form of embodiment of the present invention, the inlet connection (high-pressure connection) of the injector is arranged on the end face of the head of the injector. The one-piece molded component will then preferably be molded around the inlet connection. The one-piece molded component will then have a type of capping function, with only a single through passage for the inlet connection, on the face of the end area.
[0017] Running round the outer perimeter of the molded-on leakage connection there will preferably be a recess, in particular a groove with a U-shaped cross-section. A locking device can engage in this groove, providing an interlock with a return line.
[0018] In accordance with a particularly preferred form of the present invention, the leakage connection and the electrical connection will be arranged at an angle of approximately 45° to a center line of the injector. This will enable the connection to be kept particularly compact.
[0019] According to a further preferred form of the present invention, the one-piece molded component will preferably enclose the entire head end of the injector, so as to maintain a complete covering over the injector head.
[0020] In addition, according to the invention a leakage connection is provided for attaching a leakage line to an injector, whereby the leakage connection and an electrical connection for the injector are formed in a one-piece component. This one-piece component is molded directly onto the injector. Hence, in accordance with the invention, the leakage connection is integrated into the molded surround of the electrical connection, so that it is simple and cheap to manufacture and has a minimum number of component parts. Doing so enables the connection lines to the leakage connection, which are necessary in the injector, to be particularly simply constructed and again provided very cheaply.
[0021] The present invention will be used in particular with fuel accumulator injection systems such as, for example, common-rail systems. The integration of the leakage connection and the electrical connection into one molded component, in accordance with the invention, enables a particularly compact construction to be provided which, especially in cramped engine compartments, gives installation space advantages.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The invention is described below by reference to a preferred form of embodiment together with the drawing. The drawing shows:
[0023] [0023]FIG. 1 a schematic perspective view of an injector in accordance with an exemplary embodiment of the present invention,
[0024] [0024]FIG. 2 a side view of the injector shown in FIG. 1, and
[0025] [0025]FIG. 3 a partially sectioned side view of the injector shown in FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] An injector 1 in accordance with an exemplary embodiment is described below by reference to FIGS. 1 to 3 . As shown in FIG. 1, a one-piece component 2 is affixed to the head 10 of the injector 1 by means of injection molding. The one-piece component 2 incorporates a leakage connection 3 plus an electrical connection 7 . As can be seen from FIGS. 1 and 2 in particular, the molded component 2 is molded onto the head 10 of the injector 1 in the form of a cover. Here, the molded component 2 is molded around a fuel inlet connection 8 arranged on the end face of the head 10 , so as to form a ring-shaped main body 6 of the molded component 2 , from which the leakage connection 3 and the electrical connection 7 branch off.
[0027] As can be seen in particular from FIGS. 2 and 3, the leakage connection 3 and the electrical connection 7 are arranged at an angle a of about 45° to a center line X-X of the injector. Furthermore, the leakage connection 3 is arranged with respect to the electrical connection 7 in such a way that their two center lines lie in the same plane. In other words, the leakage connection 3 is arranged to be offset by 180° relative to the electrical connection 7 (cf. FIG. 1).
[0028] Because, with the exemplary embodiment illustrated, the inlet connection 8 , the electrical connection 7 and the leakage connection 3 are all arranged on the head 10 of the injector, a particularly compact and slim injector 1 is obtained. This means in particular that, because all the connections are arranged at its head end, the injector 1 can be built into various engines from different manufacturers, which offer different installation space. The injector in accordance with the invention is therefore universally usable, and it is not necessary to have available a special injector for each engine manufacturer.
[0029] Because the one-piece molded part 2 is molded directly onto the injector, it can then only be removed from the injector by destroying it. However, this direct molding-on does also prevent any unintended removal, for example due to vibrations or such causes.
[0030] As shown in FIG. 3, in particular, a leakage line 9 arranged in the injector 1 takes the form of a simple cylindrical bore, with a chamber at its end. Because, in accordance with the invention, the leakage connection is formed completely in the molded component, the prior art stepped bore in the injector head, which must be expensively manufactured and reworked, is superfluous. As the one-piece component 2 is a molded component it is possible, in particular, to form the inner recess 5 of the leakage connection 3 in a simple manner, e.g. even as a step-shape.
[0031] As shown in FIGS. 2 and 3, a groove 4 is formed running round the outer perimeter of the leakage connection 3 , which is used to accept a locking element, by which a return line can be fixed.
[0032] Since the leakage connection 3 and the electrical connection 7 on the ring-shaped main body 6 are essentially arranged to lie opposite each other, this results in a particularly simple construction for the molding die. Thus, the two connections 3 and 7 can be formed in a single work step. In doing this, the electrical connection 7 can be formed in the familiar way as a plug connection, so that the subsequent assembly into the engine can also be carried out quickly and simply.
[0033] Thus the present invention concerns an injector, in particular for an accumulator injection device, with an inlet connection 8 , a leakage connection 3 and an electrical connection 7 . The leakage connection 3 and the electrical connection 7 are formed as a one-piece molded component 2 , which is molded directly onto the injector 1 .
[0034] The present invention is not restricted to the exemplary embodiment illustrated. Various derivatives and changes can be applied without going beyond the boundaries of the invention. | An injector, especially for an accumulator injection device, comprises an inlet connection ( 8 ), a leakage connection ( 3 ) and an electric connection ( 7 ). The leakage connection ( 3 ) and the electric connection ( 7 ) are embodied as a single-piece injection component ( 2 ), wherein the component is directly injection-moulded onto the injector ( 1 ). | 5 |
OTHER APPLICATIONS
This application is a divisional application based on copending application Ser. No. 455,475 filed Jan. 4, 1983, now U.S. Pat. No. 4,596,093 issue June 24, 1986.
FIELD OF INVENTION
This invention relates to improvements in solar greenhouses and the like and more particularly to improved structural members suitable for providing guidance for shading and like types of members which are to be displaced in guided direction to form a shield against solar radiation, wind, rain and snow or the like.
BACKGROUND
Solar greenhouses may be elegantly designed and proportioned to complement the beauty of a dwelling. They provide a versatile form of additional living space that can capture and store solar energy. Provision is thus made for a practical addition which confines a place in the sun for gardening, dining, lounging and so forth. In fact, such additional spaces have been used for accommodating hot tubs and spa accoutrements and the like.
Commercial systems are available for providing selective shading for solar greenhouses and the like. In one known arrangement, a shade is transferred from one motor driven towards a second motor driven roller by straps which are fastened to the leading edge of a shade, these straps being attached to one of the rollers and being wound upon the same to draw the shade from the other roller upon which the shade is coiled and normally stored. In addition, the leading edge of the shade is provided in the form of a rigid member, the edges of which are guided in a channel provided in a guiding member which has no structural function and is intended solely for the purpose of being a shade guide.
An inspection of the available system reveals that the leading rigid element of the aforegoing system extends laterally beyond the lateral edges of the shade so that the lateral edges of the shade are spaced from the guide and thus provide means for an inadvertent passage of solar radiation or the like between the guides and the shade edges. It is also to be noted that the guides have no structural function to be performed as has been noted hereinabove, and that the guides are generally mounted inwardly of the solar greenhouse structure in such a manner as to be readily receptive of inadvertent damaging forces or the like. Moreover, it will be noted that the shade is inconveniently positioned with its lateral edges subject to damage and deterioration.
Also commercially available are shades having lateral edges into which are incorporated wires or cables or the like which give to these lateral edges a conformation which is bulbous in nature. These bulbous lateral edges are accommodated in guiding tracks which heretofore have been exclusively rectilinear and solely vertically disposed. These shades have not been incorporated into solar greenhouses or other such complex structures for purposes of providing selective shielding or shading.
Also commercially available are rollers within which are provided internal motors of generally cylindrical conformation. These motors are utilized for selectively driving the rollers for taking up straps attached to shades or for rewinding shades and the like. Insofar as I am aware, these motor driven rollers have not been utilized in conjunction with the structural members of solar greenhouses or the like in the manner which will be described in greater detail hereinbelow.
SUMMARY OF INVENTION
It is a general object of the invention to provide improved systems and structural members to enable the selective shading and shielding of solar greenhouses and the like inclusive of, but not limited to, the selective erection of shielding walls relative to swimming pools and other such accommodations.
It is a further object of the invention to provide improved structural elements suitable for use in solar greenhouses and the like in order to provide for ready installation of shading systems and so forth.
Yet another object of the invention is to provide for improved insulating and shading systems for solarium type greenhouses and the like utilizing integral built-in tracks to carry shading fabric so that the fabric may be readily held taut between two such tracks without sag.
Still another object of the invention is to provide an insulating and shading system for solar greenhouses including curved eave portions in which the insulating shade fabric travels from, for example, a top ridge around the curved eave-section to a bottom sill without the intervention of guide rollers adjacent the curved-eave section.
Yet another object of the invention is to provide an insulating and shading system wherein integral built-in track channels are made accessible at the top and bottom of the tracking system by improved designing of the structural members into which the integral tracks are incorporated.
Still another object of the invention is to provide bottom sill and top ridge structures with improvements such as to provide for ready access to a built-in track system.
It is yet another object of the invention to provide a shading system which is sealed on these sides and which is readily adaptable to being sealed on the fourth side thereof.
It is a further object of the invention to incorporate into a solar greenhouse or the like, a bottom sill construction confining a concealed chamber into which a continous roller or a segmented series of rollers are installed for purposes of rolling up insulating and shading fabric or cables associated therewith for purposes for providing for selective shading.
In accordance with the invention, there is provided a system in which shading fabric may be rolled up, stored and concealed in a chamber provided in a specially improved bottom sill construction.
It is yet a further object of the invention to provide for a multiplicity of shade panels which may be activated simultaneously or selectively in correspondence with panels incorporated into a solar greenhouse construction.
It is moreover an object of the invention to provide for a shading system wherein the operation of the associated shade mechanism may be manual or motorized or associated with a spring loaded roller or the like.
Still another object of the invention is to provide an insulating and shading system designed to provide a maximum insulation and sun shading as well as such privacy as may be desirable in a glass structure and to accomplish these results with the least obtrusive amount of visible parts.
It is yet another object of the invention to provide an improved fabric tracking system which may be utilized with fabric such as clear plastic, radiation impermeable fabric and the like to serve as a swimming pool enclosure or the like. In such an arrangement, as will be described in greater detail hereinbelow, the fabric source may be incorporated in a bottom sill for transferral in an upward direction to provide a wall to shield the enclosed area from winds, cold, snow and the like while permitting the control of the degree of shielding.
Still another object of the invention is to provide an improved insulating and shading system which may be added to a host structure readily at any time after the host structure has been completed.
It is an additional object of the invention to provide an improved tracking system which fixes the spacing between an associated glazing arrangement and shading system to minimize the possibility of damage to the glazing.
It is still a further object of the invention to provide for the incorporation of improved track channels into a structural member to provide in turn for ready displacement for a shade or shielding fabric or the like through a curved-eave portion in such a manner as to eliminate the need for associated guide rollers or other surplus structure, thereby simplifying the construction of shading and insulating systems and minimizing the cost thereof.
In achieving the above and other objects of the invention, there is provided a structural member constituted of an elongated hollow bar provided with at least one longitudinally extending track channel having a relatively narrow longitudinally extending slot-type mouth. Adventageously, the bar is provided with a second track channel and mouth, arranged in mirror image relationship to the aforesaid channel and mouth and opening in opposite direction with respect to the same.
In accordance with a preferred embodiment of the invention, the channels are substantially circular in cross-section and the mouths define reentrant angles therewith. Preferably, the mouths also have widths which are no more than about 50% of the diameters of the channels.
In a specific embodiment of the invention, the bar is generally quadrilateral in shape and includes two pairs of parallel sides, said mouths being located in the sides of one pair. The sides of the other pair are provided with screw grooves.
In accordance with a further aspect of the invention, one of the sides of the aforesaid other pair are provided with at least one channel adapted for receiving a sealing member. A sealing member may be arranged in the latter said channel and a glazing member may be provided to rest against the sealing member. The glazing member will be held against the structural member by a mutin or the like arranged to rest against the glazing member, there being provided a fastening device extending through the muntin into the corresponding screw groove.
In accordance with a specific feature of the aforesaid structural member, each of the channels which are provided for tracking is at least partly defined by two interior walls. One of these interior walls has two opposed surfaces conforming to the shape of the corresponding channel, and the other of the interior walls has two opposed surfaces, one of which conforms to the shape of the corresponding channel and the other of which is flat.
The aforesaid structural member may be incorporated into, for example, a solar greenhouse construction. This solar greenhouse construction may, in accordance with the invention, comprise a glazing support means to support said glazing in a conformation to define a at least partly enclosed space, said glazing being permeable to solar radiation to allow the radiation to pass into the space, there being provided a shade means in the space adapted for being positioned adjacent at least part of the glazing to intercept at least part of the radiation passing through the glazing. The support means includes at least one of the aforesaid structural members and is provided with at least one track channel in which the shade means in engaged and by which the shade means is guided along the glazing. Thus, the invention distinguishes from what has been previously available in that it provides for incorporating a track channel into a structural member with the shade means being directly engaged by and incorporated into the structural members of the greenhouse.
According to various aspects of the invention, the shade means may include a roller and a shade coupled to the same and being adapted for being rolled onto and unrolled from the roller. The invention also incorporates the commercially available arrangement whereby a motor is provided within the roller to drive the same. In accordance with one embodiment of the invention, the shade means may include rollers spaced vertically along the glazing with a shade being coupled to each of the rollers and adapted for being drawn from one of the rollers towards the other of the rollers. As has been implied hereinabove, the glazing preferably includes a curved-eave portion along which extends the above noted support means and the aforesaid channel or channels.
The invention in one form provides for a support means which includes at least two spaced and parallel glazing bars supporting and spanned by at least part of the glazing. Each of these glazing bars is provided, in the form noted above, with at least one of the above-described track channels. The track channels in the bars are aligned in parallel with the shade extending between the two channels and being held taut thereby. The shade means or shade may include parallel bulbous peripheries engaged in respective of the channels, and, in this arrangement, the channels are provided with relatively narrow slot-type mouths opening from the bars whereby to admit the entry of the shade means and to entrap the bulbous peripheries in these channels. As a possible alternative, or included in the arrangement generally described hereinabove, the shade means may include cables extending through and beyond these bulbous peripheries, the cables extending as well through the channels in a manner which is peculiarly distinguishable from the arrangement which is known from the prior art.
In accordance with yet another aspect of the invention there is provided a horizontal sill below and supporting the aforesaid support means with the roller arranged at the bottom of the support means being contained within the sill and coupled to the shade means. The shade means may include a plurality of parallel shades with the support means including a plurality spaced parallel glazing bars each provided with two of the afore-described track channels, said channels being arranged in cooperating pairs between which extend respective of the shades.
Advantageously the invention provides for a fixed spacing between the glazing and the associated shades. This advantage is developed from the fact that the structural member includes both the tracking channels and the means for supporting the glazing. Preferably, this spacing is a minimum of about 11/2 inches thereby providing for a most suitable accommodation of the glazing and minimizing possibilities of damage to the same.
The horizontal base sill which will be described in detail below is a feature of the invention. It includes a sloped upper wall and a vertical wall extending along and upwardly from the sloped wall to define a moisture drain therewith. The support means which has been referred to hereinabove will include vertical bars supporting the glazing and including angled lower extremities accommodated in the drain formed by the sloped upper wall and vertical wall, said lower extremities and drain having matching profiles.
In further accordance with this aspect of the invention, the sill further includes a base and inner and outer walls extending upwardly from said base and defining, with said upper wall, an internal chamber. Said upper wall extends from said outer wall and terminates short of the inner wall to define a slot therewith through which at least part of the shade means can pass into the internal chamber.
In accordance with further features of the invention there is provided an arrangement of generally horizontal cap members covering the aforesaid drain and extending between the aforesaid bars, said cap members including break away sections covering the slots at least in part. The bars extend downwardly past the cap members and include lateral walls, each provided with one of the aforesaid track channels opening into the aforesaid internal chamber. As has been noted above, the aforesaid bars may be hollow members, each including two of the aforesaid lateral walls and inner and outer walls extending between the lateral walls and forming inner and outer corners therewith. The bars may include internal thickened portions constituted by interior walls located at the inner corners and defining in part, the aforesaid track channels. The above-noted inner walls may each be provided with a vertical slot between the aforesaid channels, said vertical slot being bounded by serrated or screw threaded walls whereby to facilitate engagement of an attachment or fastening member or the like. The base sill of the invention may be provided with at least one internal horizontal groove constituting a drainage channel.
In accordance with yet another aspect of the invention, the base sill structure thereof may include a second outer wall spaced from the first said outer wall and constituting a facing. A thermal-break member connects the outer walls together and the glazing may preferably be accommodated between the aforesaid vertical wall and the second outer wall with a resilient gasket member being provided between the glazing and the second outer wall. Moreover, the outer walls may include respective protrusions extending towards each other and defining facing grooves into which the thermal break member extends, said protrusions having upper surfaces cooperatively constituting a platform for supporting the glazing. In this case a padding strip may be provided on a platform with the glazing resting thereon.
In this arrangement the facing grooves will have reentrant angles in the outer walls and the thermal break member will have a cross-section preferably in the shape of a Maltese cross having horizontal arms accommodated in respective of the facing grooves.
A further feature of the invention finds the outer walls and protrusions mentioned above cooperatively defining a downwardly opening chamber, said construction further comprising a flashing member partly accommodated in the latter said chamber and extending outwardly therefrom.
In the aforesaid arrangement, and as will be described in greater detail hereinafter, a plurality of coaxially aligned rollers may be provided in the internal chamber of the sill. The rollers being respectively located between respective pairs of the vertical bars and the shade means being a plurality of shades respectively coupled to these rollers. By way of variation, a single roller may be employed in the internal chamber of the sill, this single roller extending past a plurality of the aforesaid vertical bars with the shade means including shades all coupled to the same roller.
As will become apparent upon an inspection of the detailed description, which follows hereinafter, storage means may be provided for the shades such that the shades may be drawn downwardly therefrom or such that the shades may be drawn upwardly therefrom. These shades may be adapted for motorized operation or for manual operation.
The ridge structure to be described in greater detail hereinbelow constitutes another feature of the invention. This ridge structure is provided for engaging the support means at the upper end of the same. The ridge structure has preferably a vent provided therein with a blower arranged in the ridge structure and adapted for displacing air from between the shade means and the glazing and expelling the air outwardly through the vent.
The support means includes glazing bars of the type which have been generally described above and the glazing bars may include ends cut at an angle to define a spaced with the ridge structure to permit the appropriate positioning of a guide roll which will be located at least partly in the space defined with the ridge structure to guide the shade such that the lateral edges thereof are received in and guided by the track channels of the glazing bars. The above and other objects, features and advantages of the invention will be found in the detailed description which follows hereinbelow as illustrated in the accompanying drawing.
BRIEF DESCRIPTION OF DRAWING
In the Drawing:
FIG. 1 is an interior perspective view of a portion of a lean-two type solar greenhouse provided with a shading arrangement in accordance with a preferred embodiment of the invention;
FIG. 2 is a partly diagrammatic and perspective view of a broken-away portion of the bottom sill construction embodied in the structure of FIG. 1 in correspondence with line A--A in FIG. 1;
FIG. 3 is a view of the ridge structure of FIG. 1 in correspondence with line B--B therein, the view being on a large scale and being partially diagrammatic in nature;
FIG. 4 is a partially diagrammatic view corresponding section line B--B of FIG. 1; and
FIG. 5 is a sectional view corresponding to line C--C in FIG. 1 but further illustrating a glazing and muntin connected thereto.
DETAILED DESCRIPTION
In FIG. 1 is illustrated a portion of a lean-two type solar greenhouse of the kind generally in the 1982 Theme Catalog entitled Four Seasons Passive Solar Greenhouse and Sun Space published and distributed by Fours Seasons Solar Corp. of Farmingdale, N.Y. The illustrated portion of the Solar Greenhouse in FIG. 1 includes a gable end 10 and a front portion 12 having a curved-eave portion 14 and an upper sloped portion 16. Further illustrated are base sills 18 and 20 which may, for example, be mounted on a base wall or flat slab or deck (not shown) with appropriate fasteners. The method of mounting the base sill on the supporting ground is not a feature of the present invention and requires no further description in this text. The gable end 10 includes a plurality of parallel vertical glazing bars such as indicated at 22, 24, and 26. The bar 26 is in abutting relationship against the side of a dwelling or some other such similar construction. The front portion 12 includes a plurality of vertical glazing bars 28, 30, 32, 34 and 36. The glazing bar 36 furthermore provides a connection with gable end 10.
To conform with the shape of the glazing, which it is the purpose of the glazing bars to support, the glazing bar 28 has a curved section 38 and a sloped section 40. It terminates in an end portion 42. Glazing bars 28, 30, 32, 34 and 36 have similar curved and sloped portions.
Glazing panes as comprised by the gable end 10 are indicated in various forms at 44, 46, 48, 50, 52, 54 and 56. Portions of the glazing are concealed by shade fabric as indicated at 58-60 and 62. The dwelling or other structure against which the solar greenhouse is mounted is not shown as its construction is not essential to an understanding of the present invention.
The glazing included in the front portion 12 includes glazing panes 70, 72, 74 and 76. The remaining glazing in FIG. 1 is concealed by shade fabric or shades 80, 82, 84 and 86. The number of shades and panels in FIG. 1 is illustrative only as a greater or lesser number of panels and glazing panes may be employed in accordance with the invention which is not limited thereby.
At the upper end of the solar greenhouse construction, is located a ridge structure 90. It engages the end portion of the glazing bars at the upper extremities thereof such as indicated at 42 to support and accommodate the same. The ridge structure 90 abuts at the back wall 92 against the dwelling other similar structure associated therewith as does the vertical glazing bar 26 of the gable end 10.
Also appearing in FIG. 1 is a representative sequence of rollers 94, 96, 98 and 100. These rollers in the illustrated embodiment are source rollers of shade fabric which store and supply the roller up shade fabric upon demand. Further illustrated in FIG. 1 is a guide roll 102 which guides the shades or shade fabric in a change of direction so that the edges of these shades or fabrics may be engaged in track channels provided in the vertical glazing bars as will be described in greater detail hereinbelow. It is to be noted in the diagrammatic illustration of source rollers 94, 96, 98 and 100 that interior motors 110, 112, 114 and 116 are shown. These motors are contained and concealed within the rollers and operate to drive the same. Rollers with internal motors to drive the same are commercially available. They may be obtained from Somfy Systems, Inc. of Edison, N.J. The motors are of a asynchronous capacitor start and run, single phase type rated at 120 V. and 60 Hz. They are thermally protected totally enclosed brushless type motors equipped with permanently lubricated bearings requiring no maintenance and being relatively easy to wire. They include solenoid activated disc brakes which automatically stop and hold a load in any position without slippage whenever current to the motor is interrupted. The locking action assures safety and reliability of operation of the motorized system. The system can be provided with a limit switch to set the exact length of travel in both up and down directions automatically. A planetary type gear system is employed to lower motor speed and improve torque. Other details of the motor system can be found in U.S. Pat. No. 3,718,215.
The upper motorized rollers cooperate with corresponding motorized rollers concealed in the base sill 18. In the illustration, one motorized system is exposed by the cutaway such as, for example, seen at 120. The arrangement is such that, when the rollers in the sill 18 are operated to draw shade fabric downwardly, the motorized roller systems indicated at 94, 96, 98 and 100 permit the withdrawing of shades therefrom. The electrical system and operation is reversed when the shades 80, 82, 84 and 86 are to be drawn upwardly. In this case, the motorized systems indicated at 94, 96, 98 and 100 are actuated and the concealed systems in the base sill 18 release the material for being rolled back upon the upper rollers to expose greater and greater amounts of the glazing as the operation continues. Also illustrated in FIG. 1, in diagrammatic form, is a photoelectric sensor 126. This photoelectric sensor is coupled in an electric circuit (not shown) connected with the aforementioned motors in order to drive the same in one or the other rotary directions as may be required. The photoelectric sensor 126 is representative only of any device capable of sensing an ambient condition such as solar radiation, temperature, wind and the like for purposes of automating the operation of the rollers. It will be noted, however, that, while the motorized roller systems are employed in accordance with the preferred embodiment of the invention, it is also possible that the shades be operated manually and also in connection with spring-loaded rollers as is the case in connection with domestic shades as are commonly and commercially available. In fact, a manually operated shade arrangement is indicated in association with end 10. Thus, there are no upper rollers associated with shades 58, 60 and 62, these being drawn from concealed rollers in base sill 20 by a manual operation of grasping rigid leading edge members indicated by way of example at 130, 132 and 134.
Also exposed in the illustration of FIG. 1 in diagrammatic form is a blower 140. The purpose of this blower (as will be illustrated and described in greater detail hereinbelow) is to evacuate air from between the shade and the associated glazing and to expel this air into the ambient atmosphere via an appropriate vent in order to reduce the temperature which prevails between the shades and the glazing thereby to reduce the possibility of damage to the glazing.
FIG. 2 illustrates on an enlarged scale a broken-away portion of the structure illustrated in FIG. 1 with conditions somewhat altered to show a more lowered condition of the shades. For purposes of orientation, it will be seen in FIG. 2 that there are illustrated base sill 18, vertical glazing bar 30 and shades 80 and 82. The base sill 18 includes an inner wall 150 and a first outer wall 152. The outer wall 152 supports a sloped upper wall 154 from which extends a vertical wall 156. The walls 154 and 156 cooperate to define a moisture drain 158. A bottom wall 160 extends between and connects the inner wall 150 with the outer wall 152. Drainage channels 162 and 164 are provided in horizontal disposition within the internal chamber 166 which is cooperatively defined by walls 150, 152, 154 and 160. Within the chamber 166 is accommodated the motorized roller system including the internal motor 170 and the encircling roller 172.
Each of the shades illustrated includes a bulbous lateral edge portion for purposes of being accommodated in and guided by track channels to be referred to hereinbelow.
Illustrative bulbous lateral edge portions or peripheries are indicated at 176 and 178 in FIG. 2. These constructions are commercially available and are generally of the type including wires extending through the bulbous peripheries and axially extending out of the same. Two such wires or cables are indicated at 180 and 182 in FIG. 2. They extend through and are guided by track channels 184 and 186 as will be described in greater detail hereinbelow. It is to be noted that, by reason of break-away portion 188, it is possible to see that these cables are attached to and wound onto roller 172 such as indicated 190 and 192. A winding up of these cables on the roller 172 causes the shades 80 and 82 to be drawn down towards the base sill 18 thereby to effect a greater degree of shading. This means that solar radiation passing through the glazing which is permeable thereto may be intercepted by the shades thereby to effect a greater or lesser degree of shielding as desired and as may be manually or automatically controlled. It will also be noted in FIG. 2 that the shades 80 and 82 are provided with rigid lead members 196 and 198. These members, at their extreme downward movement, come into abutting or substantially abutting relationship with cap elements 200 and 202 which are intended to cover drains such as indicated at 158 and to conceal the internal construction of the base sill 18 from viewing or from the damaging impact of dropped articles or the like. The caps 200 and 202 also constitute safety features inasmuch as they resist the penetration of probing fingers and the like which might otherwise be damaged by engagement with moving parts within the base sill 18 under inadvertent circumstances.
The cap members 200 and 202 extend generally from the vertical wall 156 to the upper lip 204 of the front wall 150. This is satisfactory in the case where the cables, such as indicated 180 and 182, extend through the glazing bar to the internal roller 172 which in this case acts take-up roller. In these circumstances, there is no need for the lead members 196 and 198 to move into the internal chamber 166 nor is there any need for the shade 80 or 82 to do likewise. In the event that it is desired to alter the construction so that the shade 80 and 82 can be directly taken-up on the roller 172 in addition to the cables 180 and 182 which they trail, the construction can be readily modified to provide a slot through which the shade 80 and 82 may pass. Thus, for example, the cap member 200 is provided with a notch 210 providing a break-away section 212 to expose a slot or passage 214 illustrative of a passageway through which the shades may enter the internal chamber 166 for engagement and being taken-up upon an associated roller. Thus, the invention includes the options whereby it is exclusively the cables which are taken-up on the lowermost roller or rollers or whereby the shades themselves are taken-up upon such roller or rollers.
FIG. 2 furthermore illustrates a second outer wall 220. This outer wall includes a protrusion 222 in facing relationship with a protrusion 224 on the outer wall 152. These two protrusions are provided with facing grooves 226 and 228 which have reentrant angles therein so that a thermal break member 230 having the form of a Maltese cross may be entrapped therein to prevent the flow of heat from the wall 152 to the wall 220.
The glazing is illustratively shown in the form of a double paned glass or plastic structure, the spaced panes being indicated at 240 and 242 with a spacing 244 therebetween To maintain this spacing, there is provided a spacer 246. The pane 242 rests against the vertical wall 156 and the glazing as a whole is entrapped between the walls 156 and 220 by means of a gasket 250 of a theremally insulative type. The upper walls of protrusions 222 and 224 define a platform at 252 and 254 upon which rests a pad 256 upon which rest the glazing and the spacer 246.
Further reference to the construction of the vertical glazing bar 30 will be made hereinbelow since the construction of this bar and other like bars in the strucutre constitute a significant feature of the invention, especially as regards the provision of the track channels 184 and 186. Before this discussion is undertaken, however, reference will next be made to FIGS. 3 and 4 which illustrate, in greater detail and/or diagrammatically, some of the features of the ridge structure 90 appearing in FIG. 1. For purposes of orientation, attention is drawn in FIGS. 3 and 4 to vertical glazing bar 30, shades 80 and 82, motorized roller system 94, guide roll 102 and blower system 140 which have been mentioned hereinabove.
From what has been stated above, it will now be obvious that the glazing bars constitute supporting members or structures for the glazing. These supporting members are accommodated in and rest against the ridge structure 90. They provide track channels for receiving and guiding the respective shades. The ridge member 90 is structurally and functionally related therewith in a manner next to be described below.
Ridge structure 90 includes a rear wall 300 consisting of upper and lower parts 302 and 304. The upper and lower parts are connected through the intermediary of a thermal break member 306 which is made of insulative material accommodated in appropriate receptacles 308 and 310 respectively provided on the upper and lower parts 302 and 304. The ridge structure 90 also include upper wall 312 and lower wall 314. Moreover, it includes a front wall indicated at 316. Cooperatively, these walls define an internal chamber 318 within which is accommodated the blower 140.
The front wall 316 is provided with a vent indicated generally at 320. Associated with this vent is a removable shutter 322 which may be employed, for example, during cold weather seasons to shut off the escape of air from within the solar greenhouse. The front wall 316 has an auxiliary portion 324 connected thereto through the intermediary of a thermal break member 326. This auxiliary member 324 supports a receptacle 328 which is a glazing receptacle to accommodate and support appropriate glazing panels at the upper extremity of the front portion of the glazing of the solar greenhouse. An exemplary panel is diagrammatically illustrated at 330. It may consist of spaced panes 332 and 334 separated, for example, by a spacer 336. The panel 330 is held in place by a gasket shown at 338. A screen for preventing the influx of insects and the like is indicated at 340. It is associated with the vent 320. A second vent is indicated at 342. Cooperating therewith is a gravity operated flap 344 which likewise prevents the influx of foreign matter. The strength of the flow of air passing outwardly through the vent 342 is sufficient to open the flap 344 to the extent required.
FIG. 4 specifically illustrates the flow of air. Flow through the vent 320 is indicated by arrows 350 and 352. Flow of air through vent 342 is indicated by arrow 354. The circuitous route is indicated by dotted line path 356. It will now be noted that the utilization of the glazing bar with its track channels 184 and 186 and the function of supporting the associated glazing defines a space between the shades and glazing. This space is indicated in FIG. 4 at S. This spacing S is a minimum of about 11/2 inches. It is intended to assist in limiting the temperature which air entrapped between the glazing and shade may reach. This function is further accomplished by the utilization of the blower 140 which displaces or withdraws air from between the glazing and the shades and propels this air along the route 356 through the vent 320 and expels this air into ambient atmosphere through the vent 342. The the ridge structure and its blower cooperate with the glazing bar and the shades in both a structurally supportative and temperature controlling manner.
It will now be noted that the end portion 360 at the upper extremity of the glazing bar 30 has an extremity indicated at 362 which is angularly related both to the longitudinal axis of bar 30 and to the rear wall 304 of the ridge structure 90. This is intended to provide a space 364 within which to accommodate at least a partial intrusion of the guide roll 102. Thus the guide roll 102 may be conveniently positioned to guide the shade 80 from the roller system 94 into the associated track channels.
Similarly, the bottom extremity of the glazing bar 30 as indicated at 366 in FIG. 2 is angularly related to the walls between which it extends. The purpose of this angular construction is different from that at the upper extremity. It is intended to provide an appropriate relationship with the drain 158 thereby to permit a proper resting of the bottom extremity of bar 130 on the upper wall 154 and to permit an ease in installing the glazing bar 30 when the structure is being assembled.
An examination of FIG. 5, which is in part, a section of glazing bar 30, will next be undertaken in conjunction with an understanding of FIGS. 2, 3, and 4. In FIG. 5 appears the track channels 184 and 186. By reference to the other figures, it will be understood that these channels extend longitudinally through the glazing bar which is itself an extended member. Associated with the channel 184 is a mouth 400. Associated with the track channel 180 is a mouth 402. These mouths are of relatively restricted dimensions. They form and constitute slots extending longitudinally along the glazing bar 30. The track channels 184 and 186 are in a preferred embodiment of the invention preferably of circular conformation. An example diameter of these track channels is indicated at D. The width of the associated mouths is indicated by way of example at W. The arrangement is such, that the width W is preferably no more than 50% of the dimension D. This, in effect, forms a reentrant angle indicated, by way of example, at A. The purpose of this is to form a track channel in which the bulbous periphery of the associated lateral edges of the corresponding shades are entrapped. This entrapment coupled with appropriate spacing of pairs of associated glazing bars enables the shades to be held in taut condition thereby avoiding sagging and the like. It also enables the bulbous portions to be vigorously guided along appropriate paths even as these paths turn through an angle associated with the curved eave portions of the overall construction. Thus the use of associated guide rolls or the like in the vicinity of the curved eave portions is avoided.
It will be noted that the glazing bar includes two side walls 404 and 406. These side walls extend between and connect inner wall 408 and outer wall 410. The arrangement of the wall is such that the glazing bar is in its preferred form quadrilateral in cross-section thereby defining four corners indicated in the drawing at 412, 414, 416 and 418. The track channels 184 and 186 are generally located at the corners 416 and 418. They are furthermore formed by interior walls indicated at 420, 422, 424 and 426. The walls 420 and 424, which partly define channels 184 and 186, have surfaces 428 and 430 which are flat. They also have surfaces 432 and 434 which conform to the shape of the channels. On the other hand, wall 422 has surfaces 436 and 438 both of which conform to the shape of the associated channel. Wall 428 likewise has surfaces 440 and 442 which conform to the shape of the associated channel 186.
In the wall 408 is provided a screw threaded groove 450. By means of this groove, attachments of various types may be provided by fastening members threadably engaged therein to provide for the connection or hanging of various types of auxiliary members or elements on the interior of the solar greenhouse. A corresponding grooved slot 452 is provided in wall 410. This provides for the utilization of fastening member 454 to sandwich glazing panes, for example, 456 and 458 against the supporting structure by means of a muntin 460 or clamping member which is entrapped by the head 462 to sandwich the glazing against the sealing members 464 and 466 accommodated in sealing receptacles 468 and 470 mounted on the outer wall 410 and constituting an integral part thereof. It will be furthermore noted that the wall 410 is provided with drainage grooves 472 and 474. The provision of these sealing receptacles and drainage has been heretofore available, but never in association with track channels and never for the partial purpose for extablishing a rigid spacing therebetween so as to provide a well defined spacing between a glazing and a associated shade arrangement as in accordance with the present invention.
Reference to FIG. 2 will show the orientation of screw threaded grooves 450 and 452 as well as seals 464 and 466 accommodated in their respective receptacles. The illustration will also show the orientation of drainage grooves 472 and 474. Not heretofore mentioned with respect to FIG. 2 is the chamber 480 defined between outer walls 152 and 220. This provides an accommodation for the upper extremity of flashing 482 the purpose of which is to provide a weather seal as between the bottom of the base sill 18 and the exterior supporting ground or other such construction.
Reference to FIG. 3 will likewise show the orientation of screw theaded grooves 450 and 452 as well as of sealing members 464 and 466 as well as drainage grooves 472 and 474.
From what has been stated above, it will be readily understood that the support arrangement of the invention, when utilized in connection with glazing or the like includes a plurality of spaced parallel glazing bars, each provided with two of the afore described track channels. These track channels are arranged in cooperating pairs and in parallel and are such that respective shades extend between these channels with the bulbous peripheries of the shades being entrapped in slidable engagement therein.
Attention is especially directed, in addition, to the horizontal base sill arrangement of the invention wherein is provided a sloped upper wall and a vertical wall extending along and upwardly from the sloped wall to define a moisture drain therewith with the vertical glazing bars including angled lower extremities accommodated in the drain formed thereby such that the lower extremities of the glazing bars and the drain have matching profiles. Attention is furthermore drawn to the fact that the sill includes a base and inner and outer walls extending upwardly from the base and defining with the upper wall and internal chamber, the upper wall extending in cantilever manner from the outer wall and terminating short of the inner wall to define a slot therewith through which the shade or the cables associated therewith can pass into the internal chamber.
Attention is furthermore directed to the generally horizontal cap members which are provided covering the drain and extending between the glazing bars, these cap members including break-away sections covering the slot at least in part and being disposable in order to provide for ingress of the shading fabric.
It will be noted that in accordance with the invention, a plurality or sequence of coaxially aligned rollers or roller segments may be provided in the internal chamber of the sill, the rollers or roller segments being respectively located between respective pairs of the vertical bars to receive and accommodate a plurality of shades or shade pannels which are respectively coupled thereto. Alternatively, a single roller may be provided to extend past a plurality of the vertical glazing bars with the shade panels being connected thereto for simultaneous operation thereby.
There will now be obvious to those skilled in the art many modifications and variations of the constructions and elements set forth hereinabove. These modifications and variations will not depart from the scope of the invention if defined by the following claims.
It is to be noted by way of example that the provisions of the invention are applicable in other situations besides solar greenhouses. Thus, for example, it is sometimes desirable to be able to erect windshields or the like in encompassing relationship to a pool area while providing the capability of being able to remove these shields or control the heights thereof at will. By utilizing vertical supporting structures of the invention embodying integrally therein, the track channels, as noted hereinabove, it will be possible while utilizing a base sill of the above noted construction to dispense to a desired degree, sheets of transparent or translucent plastic to varying freights such as to constitute a shielding. | A structural arrangement is provided which is particularly useful in connection with solar greenhouses. The structural member is suitable for use in a parallel arrangement of the same particularly for the purpose of providing controlled shading. The structural member is provided as a hollow bar of elongated form provided with at least one longitudinally extending track channel having a relatively narrow longitudinally extended slot-mouth. The bar may be provided with two such channels and these channels are substantially circular in cross-section with the mouths defining reentrant angles therewith. In a solar greenhouse, members of the above type support a glazing with a curved-eave section, the bars being curved to shape and the channels therein accommodating the bulbous lateral edges of shades which are retained therein. The shades are transferred from one roller in the direction of a second roller. The rollers may be provided with internal motors which rotate the same, although the arrangement disclosed is susceptible of being operated manually as well and additionally in conjunction with one or more spring loaded rollers. The arrangement is also suitable for selectively extending shields against wind and other such elements including rain and snow by the raising up of walls constituted by transparent sheets of plastic. | 4 |
RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 11/708,327 filed on Feb. 21, 2007 now abandoned titled READING GAME.
GOVERNMENT RIGHTS
This invention was not made with Government support. The Government does not have any rights in this invention.
BACKGROUND OF THE INVENTION
From several decades of research from the National Institute for Literacy, U.S. Department of Education, and the National Institute of Child Health and Human Development, it has been learned that learning to read can start at home. Learning to read can start before children go to school. Children can start down the road to becoming advanced readers from birth. Early experiences with spoken and written language are a foundation and set the stage for children to become successful readers. Research of the Maryland State Assessment Test from 2003 to 2006 indicates that many schools are below 70% in reading proficiency. The groups identified were African Americans, American Indians, Hispanic, those residing on farming communities, and special education students. The Maryland State Assessment Test in 2007 indicated that there was an increase of 2% to 5%. However, students are still below reading proficiency.
U.S. Pat. No. 5,273,431 discloses a game that may include “linguistic questions.”
U.S. Pat. No. 5,244,391 discloses a game that relates to illegal chemical substances.
U.S. Pat. No. 5,167,503 discloses a game that relates colors to alphanumeric characters.
What is needed is a game that helps children who have difficulty reading and non-readers, to enjoy playing a reading game, so that they will play often and learn to read sooner than they would if they did not play the game.
What is also needed is a game that young children enjoy playing so that they play often, so the non-reader or child learns to read sooner than they would if they did not play the game.
What is also needed is a board game that is an educational game designed to help early childhood and school age children build reading skills and have fun learning at the same time. What is needed is a board game that will help to teach children to read. The accumulation of points may be the result of the player or team's knowledge in spelling, parts of speech, reading comprehension, critical thinking, problem solving, and greed.
What is also needed is a board game to teach children to read, build vocabulary, develop literacy skills, and become the first player or team to accumulate a point total, such as 550 or more points. The accumulation of points may be the result of the player or team's knowledge in spelling, parts of speech, reading comprehension, critical thinking, and greed. What is needed is a board game that is designed so that teachers can incorporate the game in their reading curriculum to help build their students reading skills.
SUMMARY OF THE INVENTION
An aspect of the present invention comprises a board game ( 1 ), comprising: a game board ( 90 ); said game board ( 90 ) having a one-directional playing track ( 94 ); a spinner ( 110 ); rotatably disposed on a spinner board ( 112 ); said spinner board ( 112 ) having a category ( 130 ), said categories ( 130 ) having a greed category ( 230 ), a read category ( 200 ), a tell the story category ( 210 ), and a spelling category ( 220 ); a set of read cards ( 50 ); a set of spelling cards ( 60 ); a set of tell the story cards ( 70 ) a set of greed cards ( 80 ), whereby the spinner ( 110 ) may land on either said read category ( 200 ), said tell the story category ( 210 ), said spelling category ( 220 ), or said greed category ( 230 ), and then, based on the category ( 200 , 210 , 220 , 230 ) a card is selected from said respective set of cards ( 50 , 60 , 70 , 80 ), and the card is read to a player.
Another aspect is a process of a board game ( 1 ), comprising the steps of: rolling a pair of dice to determine the order of play; spinning a spinner ( 110 ) to determine what type of card should be selected; selecting a card ( 50 , 60 , 70 , 80 ) based on where the spinner ( 110 ) lands; responding to a question posed by the card ( 50 , 60 , 70 , 80 ); advancing a pawn ( 20 ) on along a one-directional playing track ( 94 ) disposed on a game board ( 90 ) if the player responds correctly; and placing a wink ( 40 ) over a number on the spinner board ( 112 ) when that number relating to the respective category ( 130 ) is answered.
These and other features, aspects and advantages of the present invention will become better understood with reference to the following drawings, description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a pictorial view of one embodiment of the present invention showing three steal buttons;
FIG. 2 is a pictorial view of one embodiment of the present invention showing a read pawn;
FIG. 3 is a is a pictorial view of one embodiment of the present invention showing 2 dice;
FIG. 4 is a pictorial view of one embodiment of the present invention showing a round wink;
FIG. 5 is a pictorial view of one embodiment of the present invention showing a front and back view of a read card;
FIG. 6 is a pictorial view of one embodiment of the present invention showing a front and back view of a spelling card;
FIG. 7 is a pictorial view of one embodiment of the present invention showing a front and back view of a tell the story card;
FIG. 8 is a pictorial view of one embodiment of the present invention showing a front and back view of a greed card; and
FIG. 9 is a is a pictorial view of one embodiment of a game board of the present invention showing;
FIG. 10 is a pictorial view of one embodiment of a score sheet of the present invention;
FIG. 11 is a pictorial view of one embodiment of a spinner of the present invention; and
FIG. 12 is a pictorial view of one embodiment of a bonus spinner of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description is of the best currently contemplated modes of carrying out the invention. The description is not to be taken in a limiting sense, but is made merely for illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.
REFERENCE NUMERALS
1 reading game
10 steal button
20 read pawn
30 die
40 wink
50 read card
60 spelling card
70 tell the story card
80 greed card
90 game board
92 steal indicia
94 one-directional playing track
96 starting point
97 point range
98 ending point
100 score sheet
110 spinner
112 spinner board
120 bonus spinner
130 number category (on spinner board 112 )
140 number location (on board 90 )
200 read category
210 tell the story category
220 spelling category
230 greed category
As illustrated in FIG. 9 , in one embodiment of the present invention reading game 1 , the game board 90 may be have a one-directional playing track 94 . A read pawn 20 (illustrated in FIG. 2 ) may be movably placed on the board 90 . A team or player may move a read pawn 20 along the playing track 94 based on successfully answering a question indicated on a respective card (read card 50 , spelling card 60 , tell the story card 70 , or greed card 80 ). The respective card 50 , 60 , 70 , 80 , may be chosen based on where a point of a spinner 110 of a spinner board 112 ( FIG. 11 ) lands. The spinner 110 may rotate about an axis when pushed with a finger. In a further embodiment the spinner 110 may be rotated automatically. In a further embodiment, the board 90 may be a visual on a computer screen. In a further embodiment, the spinner 110 may be a visual on a display, and the spinner 110 may be rotated via a touch screen interface.
One goal or objective of the player or team is to become the first player or team to accumulate a point total, such as 550 or more points. The accumulation of points may be the result of the player or team's knowledge in spelling, parts of speech, reading comprehension, critical thinking, and greed
To begin play, the game board 90 may be set on a table (not illustrated). The game board 90 may consist of four one-dimensional playing tracks 94 . The game may be played by four teams and/or players. The game may be played by or with a teacher. The teacher may control how the game is played by the players or teams. The teacher may be referred to herein as a scorekeeper. The teacher may also keep score.
Each separate player or team may use their own spinner board 112 , pawn 20 , and steal button 10 .
The spinner 112 may be spun to indicate what card (i.e. read card 50 , spelling card 60 , tell the story card 70 , or greed card 80 ) is drawn, from which a question may be placed on one side of the card 50 , 60 , 70 , 80 . The questions may be on the fronts of the respective cards. The back of the card 50 , 60 , 70 , 80 may have the category 150 (i.e. read, spelling, tell the story, greed) indicated. The teacher may ask the question from the card. The player or team may attempt to, and may answer the question correctly, or incorrectly. The goal is to answer the question correctly.
When the spinner 110 lands on a number category (i.e. greed category and number 50 ) that has already been answered, then the player or team may lose a turn. Then the next player or team may spin the spinner 110 . Once a number category 130 question has been answered, then the player or team may cover the number location 140 on the board 90 with a wink 40 .
Referring to FIG. 12 , if, at the end of the game, there is a tie score, then a player may use the bonus spinner 120 to break the tie. Upon successfully answering the question, the player may be awarded the points indicated on the bonus spinner until the tie may be broke. At one turn, the player may spin the bonus spinner 120 twice. If a player cannot answer the question posed after spinning the bonus spinner 120 , then another player may steal. This player may indicate their intent to steal by placing a steal button 20 on a steal indicia 92 on the game board 90 . To steal means to answer the question posed to the player who did not correctly answer the questions. The other player who stole answers the question, then that player, the “stealer” would win the game.
When a player spins the spinner 120 and it lands on the number category 130 identified as “greed,” then the greed card 80 is selected, and the player attempts to answer the question on the respective greed card 80 . The questions on the greed card 80 may be more difficult than other number categories 130 . Thus, the points may be higher. The game may also be structured so that if the player does not correctly answer the question, then that player may lose points and the other team/player can steal if they so choose. If not, then the game 1 continues clockwise.
FIG. 1 illustrates an embodiment of a steal button 10 . The steal button 10 may be placed on the board 90 , on a steal indicia 92 of the board 90 . This placement of the steal button 10 may occur when a player or team of players miss a question in any category, including a bonus question. In one embodiment the steal button 10 may be made of plastic, metal, composite, or wood. The steal 10 may be a circular disk, or it may be another shape, such as square, or even a cube.
If a player ties a second time, then the teacher may select a greed card 80 . The first player to answer two questions correctly wins the game. The game may be ended when the winning player or team shouts, “I read!”
The read cards 50 may help players learn the parts of speech and develop writing skills. For example, the read cards 50 may have text that displays words and/or sentences that the player reads correctly before advancing.
The spelling cards 60 may build vocabulary may help with spelling or reading. The spelling cards 60 may have the words spelled phonetically, which would require the player to recite the correct spelling. Or they may have pictures of figures, and the player would have to recite the correct spelling. In a further embodiment the spelling card 60 may have a picture and some of the letters, and the player would have to complete the word with the correct letters.
The tell the story cards 70 may build reading comprehension and develop critical thinking skills. The tell story cards 70 may have stories on them. In a further embodiment the tell story cards 70 may recite portions of well known tales or stories, and the player may have to correctly complete the tale or story correctly to advance on the board 90 .
The greed cards 80 may expand the player's knowledge of all subjects in school and the world. The greed cards 80 may do this by having questions regarding demographics, science, math, technology, or other subjects.
The spinner 120 may have a diameter of 5 inches. The spinner 120 may rotate upon an axis in a circular fashion. The spinner board 112 may be divided into four number categories 130 , a read category 200 , a tell the story category 210 , a spelling category 220 , and a greed category 230 . Each number category 130 may be subdivided in to point ranges, such as 10, 20 . . . etc. The point range may be from 10 to 100. The greed category 230 may have two subdivided point ranges, such as 50 and 100. This allows the team to earn the respective number of points in each category.
Referring to FIG. 11 , the spinner board 112 , when the spinner 110 lands on a tell the story region 210 , the tell the story card 70 is selected and the player is to attempt to answer the question. The teacher may read the story from the tell the story card 70 while the player or team whose turn it is, listens to comprehend what is read. The teacher may then ask a question related to the story so the player can earn the points indicated on the spinner board 112 . The tell the story cards 70 may be designed to help students build comprehension, critical thinking, and problem solving skills.
Referring to FIG. 11 , the spinner board 112 may have a spelling category 220 . When the player spins the spinner 110 , and if it lands within the spelling category 220 , then a spelling card 60 may be selected. If so, the card has a word, which the player tries to spell correctly. Spelling is essential in order to read. Spelling cards 60 , as seen in FIG. 6 , will help students build their vocabulary and read fluently.
Referring to FIG. 11 , the spinner board 112 may have a greed category 230 . If a player lands on the greed category 230 , then a greed card 80 is selected. The greed cards 80 may ask questions that are more difficult, and the points in the subdivided point sections may be worth more than the other categories 130 . This category 130 , the greed category 230 may create excitement among students that are more knowledgeable in school and world subject matter, thus building positive self-esteem as well as self-confidence to meet academic challenges.
Referring to FIG. 11 , when the spinner 110 lands on the read category 200 , a read card 50 is selected. The read card 50 may have a question on reading concepts necessary to help students build their reading and writing skills.
As illustrated in FIG. 9 , the game board 90 may have four one-directional playing tracks 94 with a starting point 96 , a running point range 97 , and an ending or finishing point 98 . There may be four (4) one-directional playing tracks 94 .
All cards 50 , 60 , 70 , 80 may have questions and answers on the respective card 50 , 60 , 70 , 80 . The cards 50 , 60 , 70 , 80 may have questions at the top and answers at the bottom.
The read cards 50 , spelling cards 60 , and tell the story cards 70 , may be placed facedown not on the game board 90 . The greed cards 80 may be placed face down on the game board 90 .
Dice 30 may be used to determine who goes first, second, etc. . . . For | An apparatus and method to improve reading, particularly the reading of young children. The game objective is to score points by answering questions posed by sets of cards. The card set is determined by a spinner. This game is designed to help children to read fluently. | 6 |
PRIORITY TO RELATED APPLICATION(S)
[0001] This application claims the benefit of European Patent Application No. 07106666.6, filed Apr. 20, 2007, which is hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] Schizophrenia is one of the major neuropsychiatric disorders, characterized by severe and chronic mental impairment. This devastating disease affects about 1% of the world's population. Symptoms begin in early adulthood and are followed by a period of interpersonal and social dysfunction. Schizophrenia manifests as auditory and visual hallucinations, paranoia, delusions (positive symptoms), blunted affect, depression, anhedonia, poverty of speech, memory and attention deficits as well as social withdrawal (negative symptoms).
[0003] For decades scientists and clinicians have made efforts with the aim of discovering an ideal agent for the pharmacological treatment of schizophrenia. However, the complexity of the disorders, due to a wide array of symptoms, has hampered those efforts. There are no specific focal characteristics for the diagnosis of schizophrenia and no single symptom is consistently present in all patients. Consequently, the diagnosis of schizophrenia as a single disorder or as a variety of different disorders has been discussed but not yet resolved. The major difficulty in the development of a new drug for schizophrenia is the lack of knowledge about the cause and nature of this disease. Some neurochemical hypotheses have been proposed on the basis of pharmacological studies to rationalize the development of a corresponding therapy: the dopamine, the serotonin and the glutamate hypotheses. But taking into account the complexity of schizophrenia, an appropriate multireceptor affinity profile might be required for efficacy against positive and negative signs and symptoms. Furthermore, an ideal drug against schizophrenia would preferably have a low dosage allowing once-per-day dosage, due to the low adherence of schizophrenic patients.
[0004] In recent years clinical studies with selective NK1 and NK2 receptor antagonists appeared in the literature showing results for the treatment of emesis, depression, anxiety, pain and migraine (NK1) and asthma (NK2 and NK1). The most exciting data were produced in the treatment of chemotherapy-induced emesis, nausea and depression with NK1 and in asthma with NK2-receptor antagonists. In contrast, no clinical data on NK3 receptor antagonists have appeared in the literature until 2000. Osanetant (SR 142,801) from Sanofi-Synthelabo was the first identified potent and selective non-peptide antagonist described for the NK3 tachykinin receptor for the potential treatment of schizophrenia, which was reported in the literature ( Current Opinion in Investigational Drugs, 2001, 2(7), 950-956 and Psychiatric Disorders Study 4 , Schizophrenia, June 2003, Decision Recources, Inc., Waltham, Mass.). The proposed drug SR 142,801 has been shown in a phase II trial as active on positive symptoms of schizophrenia, such as altered behaviour, delusion, hallucinations, extreme emotions, excited motor activity and incoherent speech, but inactive in the treatment of negative symptoms, which are depression, anhedonia, social isolation or memory and attention deficits.
[0005] The neurokinin-3 receptor antagonists have been described as useful in pain or inflammation, as well as in schizophrenia, Exp. Opinion. Ther. Patents (2000), 10(6), 939-960 and Current Opinion in Investigational Drugs, 2001, 2(7), 950-956 956 and Psychiatric Disorders Study 4, Schizophrenia, June 2003, Decision Recources, Inc., Waltham, Mass.).
[0006] In addition, EP 1 192 952 describes a pharmaceutical composition containing a combination of a NK3 receptor antagonist and a CNS penetrant NK1 receptor antagonist for the treatment of depression and anxiety.
[0007] It has been found that the combination of the antidepressant, mood enhancing properties of NK1 receptor antagonism and the antipsychotic symptoms of NK3 receptor antagonism are suitable to treat both positive and negative symptoms in schizophrenia.
[0008] This advantage may be realized in the administration of an ideal drug against schizophrenia.
[0009] They have been described as active at the NK1 receptor for the treatment of diseases related to this receptor, such as inflammatory conditions including migraine, rheumatoid arthritis, asthma, and inflammatory bowel disease as well as mediation of the emetic reflex and the modulation of central nervous system (CNS) disorders such as Parkinson's disease, anxiety, pain, headache, especially migraine, Alzheimer's disease, multiple sclerosis, attenuation of morphine withdrawal, cardiovascular changes, oedema, such as oedema caused by thermal injury, chronic inflammatory diseases such as rheumatoid arthritis, asthma/bronchial hyperreactivity and other respiratory diseases including allergic rhinitis, inflammatory diseases of the gut including ulcerative colitis and Crohn's disease, ocular injury and ocular inflammatory diseases.
[0010] The neurokinin-1 receptor antagonists are further useful for the treatment of motion sickness, for treatment induced vomiting or for the treatment of psychoimmunologic or psychosomatic disorders, see Neurosci. Res., 1996, 7, 187-214 , Can. J. Phys., 1997, 75, 612-621, Science, 1998, 281, 1640-1645 , Auton. Pharmacol., 13, 23-93, 1993, WO 95/16679, WO 95/18124 and WO 95/23798 , The New England Journal of Medicine, Vol. 340, No. 3 190-195, 1999, U.S. Pat. No. 5,972,938.
SUMMARY OF THE INVENTION
[0011] The invention provides pyrrolidine derivatives of formula I
[0000]
[0000] wherein
R 1 is hydrogen, halogen or lower alkyl; R 2 is hydrogen, halogen, lower alkoxy or lower alkyl substituted by halogen; R 3 is —(CH 2 ) p -heterocyclyl optionally substituted by lower alkyl, halogen, —S(O) 2 -lower alkyl, —C(O)-lower alkyl, —C(O)O-lower alkyl, hydroxy, lower alkyl substituted by hydroxy, —(CH 2 ) p —O-lower alkyl, or —NHCO-lower alkyl, or is C 3-6 -cycloalkyl optionally substituted by ═O, —(CH 2 ) p —O-lower alkyl or lower alkynyl, or is unsubstituted or substituted aryl or heteroaryl, wherein the substituents are selected from the group consisting of lower alkyl, CN, —S(O) 2 -lower alkyl, halogen, —C(O)-lower alkyl, hydroxy, lower alkoxy and lower alkoxy substituted by halogen; or is —(CH 2 ) p —NR 4 R 5 ; R 4 and R 5 are each independently hydrogen, lower alkyl, —(CRR′) p -lower alkyl substituted by hydroxy, —(CRR′) p —O-lower alkyl, —(CRR′) p —S-lower alkyl, —(CRR′) p —O-lower alkyl substituted by hydroxy, or C 3-6 -cycloalkyl; R and R′ are each independently hydrogen, lower alkyl or lower alkyl substituted by hydroxyl; n is 1 or 2; o is 1 or 2; and p is 0, 1, 2, 3 or 4;
and pharmaceutically active acid-addition salts thereof.
[0020] The compounds of formula I can contain asymmetric carbon atoms. Accordingly, the present invention includes all stereioisomeric forms of the compounds of formula I, including each of the individual enantiomers and mixtures thereof.
[0021] Preferred are the trans-diastereoisomers, including both enantiomers as follows:
[0000]
[0022] The present invention also provides compositions containing a compound of formula I and a pharmaceutically acceptable carrier. It further provides methods for the manufacture of compounds of formula I and the compositions containing them.
[0023] The compounds of formula I and their salts are characterized by valuable therapeutic properties. Compounds of formula I have a high affinity simultaneously to both the NK1 and the NK3 receptors (dual NK1/NK3 receptor antagonists), useful in the treatment of schizophrenia. Thus, the invention further provides a method for the treatment of schizophrenia which comprises administering to an individual a therapeutically effective amount of a compound of formula I.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The following definitions of the general terms used in the present description apply irrespective of whether the terms in question appear alone or in combination.
[0025] As used herein, the term “lower alkyl” denotes a straight- or branched-chain alkyl group containing from 1-4 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, i-butyl, t-butyl and the like. The term “alkyl” denotes a straight- or branched-chain alkyl group containing from 1-7 carbon atoms,
[0026] The term “halogen” denotes chlorine, iodine, fluorine and bromine.
[0027] The term “cycloalkyl” denotes a saturated carbocyclic group, containing 3-6 carbon atoms.
[0028] The term “heterocyclyl” denotes a saturated or partially saturated ring or ring-system, containing one or more heteroatoms, selected from N, O and S, with the rest of the ring atoms being carbon, for example morpholinyl, thiomorpholinyl, 1,1-dioxo-1-thiomorpholinyl, piperazin-1-yl, pyrrolidin-1-yl, pyrrolidin-2-yl piperidin-1-yl, piperidin-4-yl, azetidin-1-yl, tetrahydrofuran-2-yl, 2′-oxo-2′,3′-dihydro-1H, 1′H-spiro[piperidine-4,4′-quinolin]-1-yl or 1-oxo-2,3-dihydro-1H,1′H-spiro[isoquinoline-4,4′-piperidin]-1′-yl.
[0029] The term “aryl” denotes a monovalent cyclic aromatic hydrocarbon radical consisting of one or more fused rings in which at least one ring is aromatic in nature, for example phenyl or naphthyl.
[0030] The term “heteroaryl” denotes a monovalent aromatic cyclic radical, containing one or more heteroatoms, selected from N, O and S, with the rest of the ring atoms being carbon, for example pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thiazolyl, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, isothiazolyl or isoxazolyl, preferred are the pyridyl and the pyrimidinyl groups.
[0031] “Pharmaceutically acceptable” such as pharmaceutically acceptable carrier, excipient, etc., means pharmacologically acceptable and substantially non-toxic to the subject to which the particular compound is administered.
[0032] The term “pharmaceutically acceptable acid addition salts” embraces salts with inorganic and organic acids, such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, citric acid, formic acid, fumaric acid, maleic acid, acetic acid, succinic acid, tartaric acid, methanesulfonic acid, p-toluenesulfonic acid and the like.
[0033] “Therapeutically effective amount” means an amount that is effective to prevent, alleviate or ameliorate symptoms of disease or prolong the survival of the subject being treated.
[0034] One embodiment for the present invention is compounds of formula I-A
[0000]
[0000] wherein
R 1 is hydrogen, halogen or lower alkyl; R 2 is hydrogen, halogen, lower alkoxy or lower alkyl substituted by halogen; R 4 and R 5 are each independently hydrogen, lower alkyl, —(CRR′) p -lower alkyl substituted by hydroxy, —(CRR′) p —O-lower alkyl, —(CRR′) p —S-lower alkyl, —(CRR′) p —O-lower alkyl substituted by hydroxy, or C 3-6 -cycloalkyl; R and R′ are each independently hydrogen, lower alkyl or lower alkyl substituted by hydroxy; n is 1 or 2; o is 1 or 2; and p is 0, 1, 2, 3 or 4;
and pharmaceutically active acid-addition salts thereof.
[0042] Another embodiment for the present invention is compounds of formula I-B
[0000]
[0000] wherein
R 1 is hydrogen, halogen or lower alkyl; R 2 is hydrogen, halogen, lower alkoxy or lower alkyl substituted by halogen; R 4 and R 5 are each independently hydrogen, lower alkyl, —(CRR′) p -lower alkyl substituted by hydroxy, —(CRR′) p —O-lower alkyl, —(CRR′) p —S-lower alkyl, —(CRR′) p —O-lower alkyl substituted by hydroxy, or C 3-6 -cycloalkyl; R and R′ are each independently hydrogen, lower alkyl or lower alkyl substituted by hydroxy; n is 1 or 2; o is 1 or 2; and p is 0, 1, 2, 3 or 4;
and pharmaceutically active acid-addition salts thereof.
[0050] Another embodiment for the present invention are compounds of formula I-C
[0000]
[0000] wherein
R 1 is hydrogen, halogen or lower alkyl; R 2 is hydrogen, halogen, lower alkoxy or lower alkyl substituted by halogen; R 3 is —(CH 2 ) p -heterocyclyl optionally substituted by lower alkyl, halogen, —S(O) 2 -lower alkyl, —C(O)-lower alkyl, —C(O)O-lower alkyl, hydroxy, lower alkyl substituted by hydroxy, —(CH 2 ) p —O-lower alkyl or —NHCO-lower alkyl; n is 1 or 2; o is 1 or 2; and p is 0, 1, 2, 3 or 4;
and pharmaceutically active acid-addition salts thereof.
[0057] A preferred group of compounds of formula I are those, wherein the substituent (R 2 ) o is 3,5-di-CF 3 .
[0058] Preferred compounds from this group are compounds, wherein R 3 is morpholinyl, for example
rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide, rac-2-(3,5-dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide.
[0062] Further preferred are compounds, wherein R 3 is piperazinyl, substituted by S(O) 2 -lower alkyl or C(O)-lower alkyl, for example
rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide, rac-N-[(3S,4R)-1-(4-acetyl-piperazine-1-carbonyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide, rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide, rac-2-(3,5-dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide, rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide and rac-N-[(3S,4R)-4-(4-chloro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide.
[0069] Preferred compounds are further those, wherein R 3 is NR 4 R 5 for R 4 and R 5 being hydrogen or lower alkyl substituted by hydroxy, for example
rac-(3S,4R)-3-{[2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid bis-(2-hydroxy-ethyl)-amide and rac-(3S,4R)-3-{[2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid (2-hydroxy-ethyl)-amide.
[0072] The present compounds of formula I and their pharmaceutically acceptable salts can be prepared by methods known in the art, described in general schemes 1 and 2 and in specific examples 1 to 62 and, for example, by a process described below, which process comprises
[0000] a) reacting a compound of formula
[0000]
[0000] with a compound of formula
[0000] R 3 C(O)Cl III
[0000] to obtain a compound of formula
[0000]
[0000] wherein the definitions are as described above,
or
b) reacting a compound of formula
[0000]
[0000] with an amine of formula
[0000] NHR 4 R 5
[0000] to obtain a compound of formula
[0000]
[0000] wherein R 1 , R 2 , R 4 and R 5 have the significances given above, or
c) reacting a compound of formula
[0000]
[0000] with an amine of formula
[0000] NHR 4 R 5
[0000] to obtain a compound of formula
[0000]
[0000] wherein R 1 , R 2 , R 4 and R 5 have the significances given above,
and
if desired, converting the compound obtained into a pharmaceutically acceptable acid addition salt.
[0073] In the schemes and in the description of the examples the following abbreviations have been used:
[0000] TFA=trifluoroacetic acid
THF=tetrahydrofuran
RT=room temperature
[0000]
[0074] The pyrrolidines VI were prepared via a stereo specific 1,3-dipolar cycloaddition between the 2-nitrostyrene derivative IV and the azomethine ylide generated in situ from the N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine V in the presence of a catalytic amount of acid, such as TFA. Reduction of the nitro moiety using standard conditions for example SnCl 2 .H 2 O yielded VII. The amino moiety was subsequently methylated in a two step sequence, involving first the preparation of the ethyl carbamate followed by its reduction with borane to produce VIII. Reaction of VIII with an acid chloride in a presence of a base, usually Et 3 N, yielded IX. Selective N-debenzylation was then carried out using several known procedures which are compatible with the substitution patterns of the aromatic rings to afford II. Finally derivatives I were prepared via a coupling with a suitable carbamoyl chloride, acid chloride or carboxylic acide.
[0000]
[0075] Alternatively, intermediates II could be converted in a two step sequence into final compound I-A or I-B. For instance, the treatment of derivatives II with triphosgene in a presence of a base, preferably pyridine and at low temperature yielded pyrrolidine-1-carbonyl chloride derivatives X. The coupling between compounds X and a primary or secondary amine gave access to urea of formula I-A. The treatment of derivatives II with bromo-acetyl chloride in a presence of a base yielded intermediates XI. A nucleophilic substitution reaction between XI and a primary or secondary amine gave access to amide of formula I-B.
[0076] As mentioned earlier, the compounds of formula I and their pharmaceutically usable addition salts possess valuable pharmacological properties. The compounds of the present invention are dual antagonists of the Neurokinin 1 and 3 receptors.
[0077] The compounds were investigated in accordance with the tests given hereinafter.
[0000] NK 1
[0078] The affinity of test compounds for the NK 1 receptor was evaluated at human NK 1 receptors in CHO cells infected with the human NK 1 receptor (using the Semliki virus expression system) and radiolabelled with [ 3 H]substance P (final concentration 0.6 nM). Binding assays were performed in HEPES buffer (50 mM, pH 7.4) containing BSA (0.04%) leupeptin (16.8 μg/ml), MnCl 2 (3 mM) and phosphoramidon (2 μM). Binding assays consisted of 250 μl of membrane suspension (approximately 1.5 μg/well in a 96 well plate), 0.125 μl of buffer of displacing agent and 125 μl of [ 3 H]substance P. Displacement curves were determined with at least seven concentrations of the compound. The assay tubes were incubated for 60 min at room temperature after which time the tube contents were rapidly filtered under vacuum through GF/C filters presoaked for 60 min with PEI (0.3%) with 3×1 ml washes of HEPES buffer (50 mM, pH 7.4). The radioactivity retained on the filters was measured by scintillation counting. All assays were performed in duplicate in at least 2 separate experiments.
[0000] NK 3
[0079] Recombinant human NK 3 (hNK 3 ) receptor affinity was determined in a 96 well plate assay, using [ 3 H]SR142801 (final concentration 0.3 nM) to radiolabel the hNK 3 receptor in the presence of 10 concentrations of competing compound or buffer. Non specific binding was determined using 10 μM SB222200. Assay buffer consisted of Tris-HCl (50 mM, pH 7.4), BSA (0.1%), MnCl 2 (4 mM) and phosphoramidon (1 μM). Membrane preparations of hNK3 receptors (approximately 2.5 μg/well in a 96 well plate) were used to initiate the incubation for 90 min at room temperature. This assay was terminated by rapid filtration under vacuum through GF/C filters, presoaked for 90 min with PEI (0.3%), with 3×0.5 ml washes of ice-cold Tris buffer (50 mM, pH 7.4) containing 0.1% BSA. The radioactivity retained on the filters was measured by scintillation counting. All assays were performed in duplicate in at least two separate experiments.
[0080] The activity of the present compounds is described in the table below:
[0000]
Example No.
Ki NK1(μM)
Ki NK3 (μM)
2
0.002348
0.4568
15
0.002057
0.155
16
0.001407
0.3091
21
0.001077
0.2038
22
0.000875
0.2034
23
0.001118
0.0924
24
0.001921
0.1998
26
0.000634
0.2116
27
0.000341
0.2756
28
0.000689
0.1373
55
0.003157
0.03
[0081] The present invention also provides pharmaceutical compositions containing compounds of the invention, for example compounds of formula I and their pharmaceutically suitable acid addition salts, and a pharmaceutically acceptable carrier. Such pharmaceutical compositions can be in the form of tablets, coated tablets, dragées, hard and soft gelatin capsules, solutions, emulsions or suspensions. The pharmaceutical compositions also can be in the form of suppositories or injectable solutions.
[0082] The pharmaceutical compounds of the invention, in addition to one or more compounds of the invention, contain a pharmaceutically acceptable carrier. Suitable pharmaceutically acceptable carriers include pharmaceutically inert, inorganic and organic carriers. Lactose, corn starch or derivatives thereof, talc, stearic acid or its salts etc can be used as such excipients e.g. for tablets, dragées and hard gelatin capsules. Suitable excipients for soft gelatin capsules are e.g. vegetable oils, waxes, fats, semi-solid and liquid polyols etc. Suitable excipients for the manufacture of solutions and syrups are e.g. water, polyols, saccharose, invert sugar, glucose etc. Suitable excipients for injection solutions are e.g. water, alcohols, polyols, glycerol, vegetable oils etc. Suitable excipients for suppositories are e.g. natural or hardened oils, waxes, fats, semi-liquid or liquid polyols etc.
[0083] Moreover, the pharmaceutical compositions can contain preservatives, solubilizers, stabilizers, wetting agents, emulsifiers, sweeteners, colorants, flavorants, salts for varying the osmotic pressure, buffers, masking agents or antioxidants. They can also contain still other therapeutically valuable substances.
[0084] The dosage at which compounds of the invention can be administered can vary within wide limits and will, of course, be fitted to the individual requirements in each particular case. In general, in the case of oral administration a daily dosage of about 10 to 1000 mg per person of a compound of general formula I should be appropriate, although the above upper limit can also be exceeded when necessary.
[0085] The following Examples illustrate the present invention without limiting it. All temperatures are given in degrees Celsius.
EXAMPLE A
[0086] Tablets of the following composition can be manufactured in the usual manner:
[0000]
mg/tablet
Active substance
5
Lactose
45
Corn starch
15
Microcrystalline cellulose
34
Magnesium stearate
1
Tablet weight
100
EXAMPLE B
[0087] Capsules of the following composition can be manufactured:
[0000]
mg/capsule
Active substance
10
Lactose
155
Corn starch
30
Talc
5
Capsule fill weight
200
[0088] The active substance, lactose and corn starch can be firstly mixed in a mixer and then in a comminuting machine. The mixture then can be returned to the mixer, the talc can be added thereto and mixed thoroughly. The mixture can be filled by machine into hard gelatin capsules.
EXAMPLE C
[0089] Suppositories of the following composition can be manufactured:
[0000]
mg/supp.
Active substance
15
Suppository mass
1285
Total
1300
[0090] The suppository mass can be melted in a glass or steel vessel, mixed thoroughly and cooled to 45° C.
[0091] Thereupon, the finely powdered active substance can be added thereto and stirred until it has dispersed completely. The mixture then can be poured into suppository moulds of suitable size, left to cool, the suppositories are then removed from the moulds and packed individually in wax paper or metal foil.
Experimental Part
[0092]
[0093] To a stirred solution of a pyrrolidine intermediate (1 mmol) in CH 2 Cl 2 (15 ml) at RT were added ethyl-diisopropyl-amine (2 mmol) and a carbamoyl chloride or acid chloride of formula R 3 COCl (1.1 mmol). Stirring was continued until completion of the reaction. The reaction mixture was then concentrated under vacuo and purification by flash chromatography on SiO 2 or preparative HPLC.
[0000]
[0094] To a stirred solution of a pyrrolidine carbonyl chloride intermediate (1 mmol) in CH 2 Cl 2 (15 ml) at RT were added ethyl-diisopropyl-amine (1.2 mmol) and a amine (1.1 mmol). Stirring was continued until completion of the reaction. The reaction mixture was then concentrated under vacuo and purification by flash chromatography on SiO 2 or preparative HPLC.
[0000]
[0095] To a stirred solution of a pyrrolidine acetyl bromid intermediate (1 mmol) in THF (15 ml) at RT were added ethyl-diisopropyl-amine (1.2 mmol) and a amine (4 mmol). Stirring was continued until completion of the reaction. The reaction mixture was then concentrated under vacuo and purification by flash chromatography on SiO 2 or preparative HPLC.
Process for Preparation of Pyrrolidine Intermediates of Formula II
Pyrrolidine II-1 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide
[0096]
a) rac-(3S,4R)-1-Benzyl-3-nitro-4-phenyl-pyrrolidine (III-1)
[0097] A solution of N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine (0.50 g, 2.02 mmol) in CH 2 Cl 2 (15 ml) was added drop wise, over a 30 minutes period, to a stirred solution of ((E)-2-nitro-vinyl)-benzene (0.30 g, 2.02 mmol) and trifluoroacetic acid (0.17 ml, 0.2 mmol) in CH 2 Cl 2 (10 ml) at 0° C. The ice bath was removed, and the solution was stirred at 25° C. for an additional 48 h. It was then concentrated and purification by flash chromatography (SiO 2 , EtOAc/H 1:6) afforded 0.38 g (68%) of the title compound as a colorless oil. ES-MS m/e: 283 (M+H + ).
b) rac-(3S,4R)-1-Benzyl-4-phenyl-pyrrolidin-3-ylamine (IV-1)
[0098] To a stirred solution of rac-(3S,4R)-1-benzyl-3-nitro-4-phenyl-pyrrolidine (1.0 g, 3.54 mmol) in EtOAc (50 ml) was added in one portion SnCl 2 .2H 2 O (3.99 g, 17.70 mmol). The reaction mixture was then heated at reflux for 2 hours, cooled down to RT and a saturated aqueous solution of NaHCO 3 (100 ml) was added. The salts were filtered off and the product extracted with EtOAc. The organic phases were then dried over Na 2 SO 4 , and concentration under vacuum gave 0.72 g (80%) of rac-(3S,4R)-1-benzyl-4-phenyl-pyrrolidin-3-ylamine as a light yellow oil. The product was then used in the next step without further purification.
c) rac-((3S,4R)-1-Benzyl-4-phenyl-pyrrolidin-3-yl)-methyl-amine (V-1)
[0099] To a solution of rac-(3S,4R)-1-benzyl-4-phenyl-pyrrolidin-3-ylamine (0.25 g, 1.0 mmol) in THF (5 ml) was added a solution of K 2 CO 3 (0.25 g, 1.8 mmol) in H 2 O (2 ml). After 10 minutes, ethyl chloroformate (0.119 g, 1.1 mmol) was added and stirring was continued at RT for an additional 4 h. The intermediate carbamate was then extracted with Et 2 O, dried over Na 2 SO 4 and concentrated under vacuo to give viscous oil. The oil was taken up in THF (5 ml) and a solution of borane in THF (1M) was added (3.5 ml). The reaction mixture was then heated at 65° C. over night, cooled to RT and carefully quenched with conc. HCl (0.5 ml). The mixture was then heated at 80° C. for 2 h, cooled to RT, concentrated under vacuo, diluted with Et 2 O (20 ml) and neutralized with an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 and the product purified by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 9:1) to afford 0.21 g (82%) of rac-((3S,4R)-1-benzyl-4-phenyl-pyrrolidin-3-yl)-methyl-amine as a colorless oil.
d) rac-N-((3S,4R)-1-Benzyl-4-phenyl-pyrrolidin-3-yl)-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-1)
[0100] A solution of 2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2002079134) (0.88 g, 2.76 mmol) in CH 2 Cl 2 (2 ml) was added drop wise to a stirred solution of rac-((3S,4R)-1-benzyl-4-phenyl-pyrrolidin-3-yl)-methyl-amine (0.72 g, 2.70 mmol) and ethyl-diisopropyl-amine (0.64 ml, 3.76 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 1 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 1.05 g (74%) of the title product as colorless foam.
e) rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (VII-1)
[0101] To a solution of rac-N-((3S,4R)-1-Benzyl-4-phenyl-pyrrolidin-3-yl)-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (1.0 g, 1.82 mmol) in MeOH (30 ml) was added ammonium formate (0.59 g, 9.3 mmol) and Pd/C 10% (0.25 g). Stirring was continued at RT for 1 h, the reaction mixture was then filtered through celite, concentrated under vacuo. Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 8:2) yielded 0.87 g (84%) of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide as a colorless oil. ES-MS m/e: 459.4 (M+H + ).
Pyrrolidine II-2 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0102]
a) rac-(3R,4S)-1-Benzyl-3-(4-chloro-phenyl)-4-nitro-pyrrolidine (III-2)
[0103] A solution of N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine (6.70 g, 28.2 mmol) in CH 2 Cl 2 (100 ml) was added drop wise, over a 30 minutes period, to a stirred solution of 1-chloro-4-((E)-2-nitro-vinyl)-benzene (4.97 g, 27.1 mmol) and trifluoroacetic acid (0.31 g, 2.7 mmol) in CH 2 Cl 2 (150 ml) at 0° C. The ice bath was removed, and the solution was stirred at 25° C. for an additional 48 h. It was then concentrated and purification by flash chromatography (SiO 2 , EtOAc/H 1:4) afforded 6.75 g (79%) of the title compound as a colorless oil.
b) rac-(3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-ylamine (IV-2)
[0104] Titanium (IV) chloride (0.36 g, 1.89 mmol) was added drop wise to a suspension of zinc powder (0.25 g, 3.78 mmol) in THF (3 ml). This solution was heated at 68° C. for one hour, then cooled to RT before rac-(3R,4S)-1-benzyl-3-(4-chloro-phenyl)-4-nitro-pyrrolidine (0.20 g, 0.63 mmol) in THF (2 ml) was added. The reaction mixture was then stirred at reflux over night. The reaction was cooled to RT, diluted with 300 ml of Et 2 O, washed with an aqueous solution of NaHCO 3 and the organic phases were dried over Na 2 SO 4 . Flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH, 9:1) yielded 0.10 g (57%) of rac-(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-ylamine as a light yellow oil.
c) rac-[(3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-methyl-amine (V-2)
[0105] To a solution of rac-(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-ylamine (1.86 g, 6.51 mmol) in THF (20 ml) was added a solution of K 2 CO 3 (1.80 g, 13.02 mmol) in H 2 O (15 ml). After 10 minutes, ethyl chloroformate (0.68 ml, 7.16 mmol) was added and stirring was continued at RT for an additional 4 h. The intermediate carbamate was then extracted with Et 2 O, dried over Na 2 SO 4 and concentrated under vacuo to give viscous oil. The oil was taken up in THF (20 ml) and a solution of borane in THF (1M) was added (26 ml). The reaction mixture was then heated at 65° C. over night, cooled to RT and carefully quenched with conc. HCl (5 ml). The mixture was then heated at 80° C. for 2 h, cooled to RT, concentrated under vacuo, diluted with Et 2 O (100 ml) and neutralized with an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 and the product purified by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 9:1) to afford 1.51 g (77%) of rac-[(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-methyl-amine_as a colorless oil.
d) rac-N-[(3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-2)
[0106] A solution of 2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2002079134) (1.05 g, 3.30 mmol) in CH 2 Cl 2 (10 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-methyl-amine-(0.90 g, 3.00 mmol) and ethyl-diisopropyl-amine (0.77 ml, 4.50 mmol) in CH 2 Cl 2 (10 ml). The reaction mixture was stirred 1 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 1.53 g (87%) of the title product as light brown oil.
e) rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-2)
[0107] To a solution of rac-N-[(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide_(1.46 g, 2.50 mmol) in toluene (15 ml) was added chloroethyl chloroformate (0.70 g, 5.00 mmol). Stirring was continued at 110° C. for 18 h, cooled to RT and MeOH (15 ml) was added. The solution was stirred at 80° C. over night, concentrated under vacuo, taken up in EtOAc, washed with an aqueous solution of NaHCO 3 and the organic phases dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 95:5) yielded 0.52 g (42%) of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide_as a light brown oil. ES-MS m/e: 493.7 (M+H + ).
Pyrrolidine II-3 rac-N-[(3S,4R)-4-(4-Chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide
[0108]
a) rac-N-[3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-3)
[0109] A solution of 2-(3,5-Dichloro-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2005002577) (0.40 g, 1.59 mmol) in CH 2 Cl 2 (5 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-methyl-amine (the preparation of which is described herein above) (0.57 g, 1.90 mmol) and ethyl-diisopropyl-amine (0.41 ml, 2.38 mmol) in CH 2 Cl 2 (10 ml). The reaction mixture was stirred 2 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 0.25 g (31%) of the title product as light brown oil.
b) rac-N-[(3S,4R)-4-(4-Chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide (VII-3)
[0110] To a solution of rac-N-[(3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide_(0.21 g, 0.41 mmol) in MeOH (20 ml) and H 2 O (10 ml) were added sodium hypophosphite monohydrate (NaH 2 PO 2 .H 2 O, 87 mg, 0.82 mmol), a solution of sodium chloride (5 ml, 15 wt %) and Pd on charcoal (30 mg). Stirring was continued at 65° C. for 4 h, then at RT over night. The reaction mixture was filtered on celite, concentrated under vacuo and the product extracted with CH 2 Cl 2 . Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 90:10) yielded 85 mg (48%) of rac-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide_as a light brown oil. ES-MS m/e: 427.2 (M+H + ).
Pyrrolidine II-4 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0111]
a) rac-(3R,4S)-1-Benzyl-3-(4-fluoro-phenyl)-4-nitro-pyrrolidine (III-4)
[0112] A solution of N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine (8.00 g, 33.6 mmol) in CH 2 Cl 2 (140 ml) was added drop wise, over a 30 minutes period, to a stirred solution of 1-fluoro-4-((E)-2-nitro-vinyl)-benzene (5.12 g, 30.6 mmol) and trifluoroacetic acid (0.23 ml, 3.1 mmol) in CH 2 Cl 2 (200 ml) at 0° C. The ice bath was removed, and the solution was stirred at 25° C. for an additional 48 h. It was then concentrated and purification by flash chromatography (SiO 2 , EtOAc/H 1:4) afforded 6.60 g (72%) of the title compound as a light yellow oil.
b) rac-(3S,4R)-1-Benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-ylamine (IV-4)
[0113] Titanium (IV) chloride (179.4 g, 0.94 mol) was added drop wise to a suspension of zinc powder (123.6 g, 1.89 mol) in THF (1200 ml). This solution was heated at 68° C. for one hour, then cooled to RT before rac-(3R,4S)-1-benzyl-3-(4-fluoro-phenyl)-4-nitro-pyrrolidine (94 g, 0.31 mol) in THF (400 ml) was added. The reaction mixture was then stirred at reflux over night. The reaction was cooled to RT, diluted with 3000 ml of Et 2 O, washed with an aqueous solution of NaHCO 3 and the organic phases were dried over Na 2 SO 4 . Flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH, 9:1) yielded 18.9 g (22%) of rac-(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-ylamine as a brown oil.
c) rac-[(3S,4R)-1-Benzyl-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-methyl-amine (V-4)
[0114] To a solution of rac-(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-ylamine (2.30 g, 8.50 mmol) in THF (25 ml) was added a solution of K 2 CO 3 (2.35 g, 17.00 mmol) in H 2 O (17 ml). After 10 minutes, ethyl chloroformate (0.89 ml, 9.36 mmol) was added and stirring was continued at RT for an additional 2 h. The intermediate carbamate was then extracted with Et 2 O, dried over Na 2 SO 4 and concentrated under vacuo to give viscous oil. The oil was taken up in THF (25 ml) and a solution of borane in THF (1M) was added (34 ml). The reaction mixture was then heated at 65° C. over night, cooled to RT and carefully quenched with conc. HCl (5 ml). The mixture was then heated at 80° C. for 2 h, cooled to RT, concentrated under vacuo, diluted with Et 2 O (100 ml) and neutralized with an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 and the product purified by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 9:1) to afford 0.69 g (29%) of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-methyl-amine_as a colorless oil. ES-MS m/e: 285.1 (M+H + ).
d) rac-N-[(3S,4R)-1-Benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-4)
[0115] A solution of 2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2002079134) (0.88 g, 2.76 mmol) in CH 2 Cl 2 (5 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-methyl-amine (0.72 g, 2.53 mmol) and ethyl-diisopropyl-amine (0.64 ml, 3.78 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 1 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 1.06 g (74%) of the title product as colorless foam. ES-MS m/e: 567.3 (M+H + ).
e) rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0116] To a solution of rac-N-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (1.06 g, 1.87 mmol) in MeOH (30 ml) was added ammonium formate (0.59 g, 9.3 mmol) and Pd/C 10% (0.25 g). Stirring was continued at RT for 1 h, the reaction mixture was then filtered through celite, concentrated under vacuo. Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 8:2) yielded 0.85 g (82%) of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide_as a colorless oil. ES-MS m/e: 477.1 (M+H + ).
Pyrrolidine II-5 rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0117]
a) rac-N-[(3S,4R)-1-Benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide (VI-5)
[0118] A solution of 2-(3,5-dichloro-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2005002577) (0.146 g, 0.58 mmol) in CH 2 Cl 2 (4 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-methyl-amine (the preparation of which is described herein above) (0.15 g, 0.52 mmol) and ethyl-diisopropyl-amine (0.13 ml, 0.79 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 2 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 0.18 g (68%) of the title product as light brown oil.
b) rac-N-[(3S,4R)-4-(4-Fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide (VII-5)
[0119] To a solution of rac-N-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide_(0.18 g, 0.36 mmol) in toluene (2 ml) was added chloroethyl chloroformate (77 mg, 0.54 mmol). Stirring was continued at 110° C. for 18 h, cooled to RT and MeOH (4 ml) was added. The solution was stirred at 80° C. over night, concentrated under vacuo, taken up in EtOAc, washed with an aqueous solution of NaHCO 3 and the organic phases dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 90:10) yielded 90 mg (61%) of 2-(3,5-dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide as a light brown oil. ES-MS m/e: 409.2 (M+H + ).
Pyrrolidine II-6 rac-2-(3-Chloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0120]
a) N-[3S,4R)-1-Benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3-chloro-phenyl)-N-methyl-isobutyramide (VI-6)
[0121] A solution of 2-(3-chloro-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in DE2659404) (0.10 g, 0.46 mmol) in CH 2 Cl 2 (4 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-methyl-amine (the preparation of which is described herein above) (0.11 g, 0.38 mmol) and ethyl-diisopropyl-amine (0.10 ml, 0.58 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 2 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:3) yielded 0.14 g (80%) of the title product as light yellow oil. ES-MS m/e: 465.2 (M+H + ).
b) rac-2-(3-Chloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-6)
[0122] To a solution of N-[(3S,4R)-1-benzyl-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3-chloro-phenyl)-N-methyl-isobutyramide_(0.14 g, 0.31 mmol) in toluene (2 ml) was added chloroethyl chloroformate (66 mg, 0.46 mmol). Stirring was continued at 110° C. for 18 h, cooled to RT and MeOH (4 ml) was added. The solution was stirred at 80° C. over night, concentrated under vacuo, taken up in EtOAc, washed with an aqueous solution of NaHCO 3 and the organic phases dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 90:10) yielded 33 mg (28%) of the title compound as light brown oil. ES-MS m/e: 375.3 (M+H + ).
Pyrrolidine II-7 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0123]
[0000] a) rac-(3R,4S)-1-Benzyl-3-(4-fluoro-2-methyl-phenyl)-4-nitro-pyrrolidine (III-7)
[0124] A solution of N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine (1.95 g, 8.21 mmol) in CH 2 Cl 2 (30 ml) was added drop wise, over a 30 minutes period, to a stirred solution of 4-fluoro-2-methyl-1-((E)-2-nitro-vinyl)-benzene (1.49 g, 8.22 mmol) and trifluoroacetic acid (0.60 ml, 0.82 mmol) in CH 2 Cl 2 (30 ml) at 0° C. The ice bath was removed, and the solution was stirred at 25° C. for an additional 48 h. It was then concentrated and purification by flash chromatography (SiO 2 , EtOAc/H 1:6) afforded 0.77 g (30%) of the title compound as a light yellow oil. ES-MS m/e: 315.2 (M+H + ).
b) rac-(3S,4R)-1-Benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-ylamine (IV-7)
[0125] To a stirred solution of rac-(3R,4S)-1-benzyl-3-(4-fluoro-2-methyl-phenyl)-4-nitro-pyrrolidine (56 mg, 0.18 mmol) in EtOAc (5 ml) was added in one portion SnCl 2 .2H 2 O (201 mg, 0.89 mmol). The reaction mixture was then heated at reflux for 2 hours, cooled down to RT and a saturated aqueous solution of NaHCO 3 (100 ml) was added. The salts were filtered off and the product extracted with EtOAc. The organic phases were then dried over Na 2 SO 4 , and concentration under vacuum gave 40 mg (79%) of rac-(3S,4R)-1-benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-ylamine as a light yellow oil. The product was then used in the next step without further purification. ES-MS m/e: 285.3 (M+H + ).
c) rac-[(3S,4R)-1-Benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-methyl-amine (V-7)
[0126] To a solution of rac-(3S,4R)-1-benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-ylamine (130 mg, 0.46 mmol) in THF (6 ml) was added a solution of K 2 CO 3 (126 mg, 0.91 mmol) in H 2 O (2 ml). After 10 minutes, ethyl chloroformate (0.05 ml, 0.48 mmol) was added and stirring was continued at RT for an additional 2 h. The intermediate carbamate was then extracted with Et 2 O, dried over Na 2 SO 4 and concentrated under vacuo to give viscous oil. The oil was taken up in THF (5 ml) and a solution of borane in THF (1M) was added (1.9 ml). The reaction mixture was then heated at 65° C. over night, cooled to RT and carefully quenched with conc. HCl (2 ml). The mixture was then heated at 80° C. for 2 h, cooled to RT, concentrated under vacuo, diluted with Et 2 O (30 ml) and neutralized with an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 and the product purified by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 9:1) to afford 77 mg (56%) of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-methyl-amine as a colorless oil. ES-MS m/e: 299.3 (M+H + ).
d) rac-N-[(3S,4R)-1-Benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-7)
[0127] A solution of 2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2002079134) (90 mg, 0.28 mmol) in CH 2 Cl 2 (5 ml) was added drop wise to a stirred solution of rac-[(3S,4R)-1-benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-methyl-amine (77 mg, 0.26 mmol) and ethyl-diisopropyl-amine (0.07 ml, 0.38 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 1 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:4) yielded 80 mg (54%) of the title product as colorless oil. ES-MS m/e: 581.2 (M+H + ).
e) rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-7)
[0128] To a solution of rac-N-[(3S,4R)-1-benzyl-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide_(0.10 g, 0.17 mmol) in MeOH (5 ml) was added ammonium formate (43 mg, 0.68 mmol) and Pd/C 10% (20 mg). Stirring was continued at RT for 2.5 h, the reaction mixture was then filtered through celite, concentrated under vacuo. Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 8:2) yielded 68 mg (80%) of the title compound as colorless oil. ES-MS m/e: 491.1 (M+H + ).
Pyrrolidine II-8 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide
[0129]
a) rac-(3S,4R)-1-Benzyl-3-nitro-4-o-tolyl-pyrrolidine (III-8)
[0130] A solution of N-(methoxymethyl)-N-(phenylmethyl)-N-(trimethylsilyl)methylamine (3.93 g, 16.55 mmol) in CH 2 Cl 2 (60 ml) was added drop wise, over a 30 minutes period, to a stirred solution of 1-methyl-2-((E)-2-nitro-vinyl)-benzene (2.70 g, 16.55 mmol) and trifluoroacetic acid (0.13 ml, 1.65 mmol) in CH 2 Cl 2 (30 ml) at 0° C. The ice bath was removed, and the solution was stirred at 25° C. for an additional 48 h. It was then concentrated and purification by flash chromatography (SiO 2 , EtOAc/H 1:6) afforded 1.01 g (21%) of the title compound as a light yellow oil. ES-MS m/e: 297.4 (M+H + ).
b) rac-(3S,4R)-1-Benzyl-4-o-tolyl-pyrrolidin-3-ylamine (IV-8)
[0131] To a stirred solution of rac-(3S,4R)-1-benzyl-3-nitro-4-o-tolyl-pyrrolidine-(1.01 g, 3.40 mmol) in EtOAc (50 ml) was added in one portion SnCl 2 .2H 2 O (3.85 g, 17.04 mmol). The reaction mixture was then heated at reflux for 2 hours, cooled down to RT and a saturated aqueous solution of NaHCO 3 (100 ml) was added. The salts were filtered off and the product extracted with EtOAc. The organic phases were then dried over Na 2 SO 4 , and concentration under vacuum gave 0.73 g (81%) of rac-(3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-ylamine as a light yellow oil. The product was then used in the next step without further purification. ES-MS m/e: 267.4 (M+H + ).
c) rac-((3S,4R)-1-Benzyl-4-o-tolyl-pyrrolidin-3-yl)-methyl-amine (V-8)
[0132] To a solution of rac-(3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-ylamine (0.73 g, 2.74 mmol) in THF (15 ml) was added a solution of K 2 CO 3 (0.75 mg, 5.48 mmol) in H 2 O (5 ml). After 10 minutes, ethyl chloroformate (0.27 ml, 2.87 mmol) was added and stirring was continued at RT for an additional 2 h. The intermediate carbamate was then extracted with Et 2 O, dried over Na 2 SO 4 and concentrated under vacuo to give viscous oil. The oil was taken up in THF (10 ml) and a solution of borane in THF (1M) was added (11 ml). The reaction mixture was then heated at 65° C. over night, cooled to RT and carefully quenched with conc. HCl (5 ml). The mixture was then heated at 80° C. for 2 h, cooled to RT, concentrated under vacuo, diluted with Et 2 O (60 ml) and neutralized with an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 and the product purified by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 9:1) to afford 0.27 g (35%) of rac-((3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-yl)-methyl-amine as a colorless oil. ES-MS m/e: 281.3 (M+H + ).
d) rac-N-((3S,4R)-1-Benzyl-4-o-tolyl-pyrrolidin-3-yl)-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide (VI-8)
[0133] A solution of 2-(3,5-bis-trifluoromethyl-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2002079134) (170 mg, 0.53 mmol) in CH 2 Cl 2 (5 ml) was added drop wise to a stirred solution of rac-((3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-yl)-methyl-amine-(135 mg, 0.48 mmol) and ethyl-diisopropyl-amine (0.12 ml, 0.72 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 1 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:3) yielded 180 mg (66%) of the title product as colorless oil. ES-MS m/e: 563.7 (M+H + ).
e) rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-8)
[0134] To a solution of rac-N-((3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-yl)-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide-(0.10 g, 0.17 mmol) in MeOH (5 ml) was added ammonium formate (45 mg, 0.71 mmol) and Pd/C 10% (20 mg). Stirring was continued at RT for 2.5 h, the reaction mixture was then filtered through celite, concentrated under vacuo. Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 8:2) yielded 75 mg (89%) of the title compound as colorless oil. ES-MS m/e: 473.3 (M+H + ).
Pyrrolidine II-9 rac-2-(3,5-Dichloro-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide
[0135]
a) rac-N-((3S,4R)-1-Benzyl-4-o-tolyl-pyrrolidin-3-yl)-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide (VI-9)
[0136] A solution of 2-(3,5-dichloro-phenyl)-2-methyl-propionyl chloride (the preparation of which is described in WO2005002577) (127 mg, 0.50 mmol) in CH 2 Cl 2 (5 ml) was added drop wise to a stirred solution of ((3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-yl)-methyl-amine (the preparation of which is described herein above) (135 mg, 0.48 mmol) and ethyl-diisopropyl-amine (0.12 ml, 0.72 mmol) in CH 2 Cl 2 (5 ml). The reaction mixture was stirred 2 h, concentrated under vacuo and purification by flash chromatography (SiO 2 , EtOAc/H, 1:3) yielded 0.18 g (75%) of the title product as colorless oil.
b) rac-2-(3,5-Dichloro-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide (VII-9)
[0137] To a solution of rac-N-((3S,4R)-1-benzyl-4-o-tolyl-pyrrolidin-3-yl)-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide_(0.18 g, 0.36 mmol) in toluene (2 ml) was added chloroethyl chloroformate (78 mg, 0.54 mmol). Stirring was continued at 110° C. for 18 h, cooled to RT and MeOH (4 ml) was added. The solution was stirred at 80° C. over night, concentrated under vacuo, taken up in EtOAc, washed with an aqueous solution of NaHCO 3 and the organic phases were dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , CH 2 Cl 2 /MeOH 90:10) yielded 35 mg (24%) of rac-2-(3,5-dichloro-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide as_a light yellow oil. ES-MS m/e: 405.3 (M+H + ).
Pyrrolidine Intermediates of Formula X
Pyrrolidine X-1 rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride
[0138]
[0139] To a stirred solution of carbonic acid ditrichloromethyl ester (triphosgene) (106 mg, 0.36 mmol) in CH 2 Cl 2 (15 ml) at −78° C., was added a solution of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1), (410 mg, 0.89 mmol) and pyridine (0.16 ml, 1.97 mmol) in CH 2 Cl 2 (5 ml) over 30 minutes. The temperature was raised to RT, and stirring was continued for 2 hours. The organic phase was washed with H 2 O, dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , EtOAc/Hx 1:1) yielded 428 mg (92%) of the title compound as_colorless oil.
[0140] ES-MS m/e: 521.2 (M+H + ).
Pyrrolidine X-4 rac-((3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride
[0141]
[0142] To a stirred solution of carbonic acid ditrichloromethyl ester (triphosgene) (31 mg, 0.10 mmol) in CH 2 Cl 2 (5 ml) at 0° C., was added a solution of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (Intermediate VII-4), (100 mg, 0.21 mmol) and pyridine (0.02 ml, 0.22 mmol) in CH 2 Cl 2 (2 ml) over 30 minutes. The temperature was raised to RT, and stirring was continued for 2 hours. The organic phase was washed with H 2 O, dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , EtOAc/Hx 1:1) yielded 25 mg (22%) of the title compound as_colorless oil.
[0143] ES-MS m/e: 539.3 (M+H + ).
Pyrrolidine X-5 rac-(3S,4R)-3-{[2-(3,5-Dichloro-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride
[0144]
[0145] To a stirred solution of carbonic acid ditrichloromethyl ester (triphosgene) (12 mg, 0.040 mmol) in CH 2 Cl 2 (3 ml) at −78° C., was added a solution of rac-2-(3,5-dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (Intermediate VII-5), (41 mg, 0.10 mmol) and pyridine (0.02 ml, 0.22 mmol) in CH 2 Cl 2 (2 ml) over 30 minutes. The temperature was raised to RT, and stirring was continued for 2 hours. The organic phase was washed with H 2 O, dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , EtOAc/Hx 1:1) yielded 37 mg (79%) of the title compound as_colorless oil.
[0146] ES-MS m/e: 473.0 (M+H + ).
Pyrrolidine Intermediates of Formula XI
Pyrrolidine XI-4 rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0147]
[0148] To a stirred solution of bromo-acetyl chloride (0.80 g, 4 mmol) in CH 2 Cl 2 (5 ml) at 0° C. was added over 1 hour a solution of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (pyrrolidine interm. VII-4 described herein above, 0.94 g, 1.97 mmol) and ethyl-diisopropyl-amine (0.37 ml, 2.17 mmol) in CH 2 Cl 2 (10 mL). The reaction was stirred over night, quenched by addition of an aqueous solution of NaHCO 3 , and the product extracted with CH 2 Cl 2 . Purification by flash chromatography (SiO 2 , EtOAc/Hx 1:1) yielded 0.83 g (70%) of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide as a white foam.
[0149] ES-MS m/e: 598.4 (M+H + ).
EXAMPLE 1
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-[(3S,4R)-1-(morpholine-4-carbonyl)-4-phenyl-pyrrolidin-3-yl]-isobutyramide
[0150]
[0151] Coupling according to general procedure I:
[0152] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (VII-1),
[0153] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available),
[0154] ES-MS m/e: 572.1 (M+H + ).
EXAMPLE 2
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0155]
[0156] Coupling according to general procedure I:
[0157] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-2)
[0158] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available),
[0159] ES-MS m/e: 606.0 (M+H + ).
EXAMPLE 3
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0160]
[0161] Coupling according to general procedure I:
[0162] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0163] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available),
EXAMPLE 4
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-1-cyclopropanecarbonyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0164]
[0165] Coupling according to general procedure I:
[0166] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-chloro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-2)
[0167] Acid chloride: Cyclopropanecarbonyl chloride (commercially available),
[0168] ES-MS m/e: 561.3 (M+H + ).
EXAMPLE 5
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(thiomorpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0169]
[0170] Coupling according to general procedure I:
[0171] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0172] Carbamoyl chloride: Thiomorpholine-4-carbonyl chloride (described in EP521827),
[0173] ES-MS m/e: 606.0 (M+H + ).
EXAMPLE 6
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(1,1-dioxo-1-thiomorpholine-4-carbonyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0174]
[0175] To a stirred solution of rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(thiomorpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (0.20 g, 0.33 mmol, described herein above) in MeOH (2 ml) at RT, was added potassium monopersulfate triple salt (0.30 g, 0.49 mmol). Stirring was continued an additional 3 hours, then a solution of NaHSO 3 (40%) was added, the ph was adjusted to 9 with an aqueous solution of NaHCO 3 , and finally the product was extracted with Et 2 O. Purification by flash chromatography (SiO 2 , EtOAc/Hx 1:1) yielded 185 mg (88%) of the title compound as_white foam.
[0176] ES-MS m/e: 638.2 (M+H + ).
EXAMPLE 7
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0177]
[0178] Coupling according to general procedure I:
[0179] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0180] Carbamoyl chloride: 4-Methyl-piperazine-1-carbonyl chloride (commercially available),
[0181] ES-MS m/e: 603.2 (M+H + ).
EXAMPLE 8
rac-(3S,4R)-3-[{2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid dimethylamide
[0182]
[0183] Coupling according to general procedure I:
[0184] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0185] Carbamoyl chloride: N,N-Dimethylcarbamyl chloride (commercially available),
[0186] ES-MS m/e: 548.3 (M+H + ).
EXAMPLE 9
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(pyrrolidine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0187]
[0188] Coupling according to general procedure I:
[0189] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0190] Carbamoyl chloride: Pyrrolidine-1-carbonyl chloride (commercially available),
[0191] ES-MS m/e: 574.2 (M+H + ).
EXAMPLE 10
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-[2-(1,1-dioxo-1-thiomorpholin-4-yl)-acetyl]-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0192]
[0193] Coupling according to general procedure 3:
[0194] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0195] Amine: Thiomorpholine 1,1-dioxide (commercially available),
[0196] ES-MS m/e: 652.1 (M+H + ).
EXAMPLE 11
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-cyclopropylamino-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0197]
[0198] Coupling according to general procedure 3:
[0199] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0200] Amine: Cyclopropylamine (commercially available),
[0201] ES-MS m/e: 574.2 (M+H + ).
EXAMPLE 12
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-dimethylamino-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0202]
[0203] Coupling according to general procedure 3:
[0204] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0205] Amine: Dimethyl-amine (commercially available),
[0206] ES-MS m/e: 562.3 (M+H + ).
EXAMPLE 13
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-{(3S,4R)-4-(4-fluoro-phenyl)-1-[2-(4-methanesulfonyl-piperazin-1-yl)-acetyl]-pyrrolidin-3-yl}-N-methyl-isobutyramide
[0207]
[0208] Coupling according to general procedure 3:
[0209] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0210] Amine: 1-Methanesulfonyl-piperazine (commercially available),
[0211] ES-MS m/e: 681.3 (M+H + ).
EXAMPLE 14
rac-N-[(3S,4R)-1-[2-(4-Acetyl-piperazin-1-yl)-acetyl]-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide
[0212]
[0213] Coupling according to general procedure 3:
[0214] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0215] Amine: 1-piperazin-1-yl-ethanone (commercially available),
[0216] ES-MS m/e: 645.4 (M+H + ).
EXAMPLE 15
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0217]
[0218] Coupling according to general procedure I:
[0219] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0220] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride
[0221] ES-MS m/e: 667.3 (M+H + ).
4-Methanesulfonyl-piperazine-1-carbonyl chloride
[0222] To a stirred solution of carbonic acid ditrichloromethyl ester (triphosgene) (1.81 g, 6.09 mmol) in CH 2 Cl 2 (30 ml) at 0° C., was added a solution of 1-methanesulfonyl-piperazine (2.0 g, 12.2 mmol) and pyridine (1.08 ml, 13.4 mmol) in CH 2 Cl 2 (5 ml) over 30 minutes. The temperature was raised to RT, and stirring was continued over night. The organic phase was washed with H 2 O, dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , EtOAc) yielded 2.20 g (79%) of the title compound as white solid.
EXAMPLE 16
rac-N-[(3S,4R)-1-(4-Acetyl-piperazine-1-carbonyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide
[0223]
[0224] Coupling according to general procedure I:
[0225] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0226] Carbamoyl chloride: 4-Acetyl-piperazine-1-carbonyl chloride
[0227] ES-MS m/e: 631.5 (M+H + ).
4-Acetyl-piperazine-1-carbonyl chloride
[0228] To a stirred solution of carbonic acid ditrichloromethyl ester (triphosgene) (2.31 g, 7.80 mmol) in CH 2 Cl 2 (30 ml) at 0° C., was added a solution of 1-piperazin-1-yl-ethanone (2.0 g, 15.6 mmol) and pyridine (1.38 ml, 17.2 mmol) in CH 2 Cl 2 (5 ml) over 30 minutes. The temperature was raised to RT, and stirring was continued over night. The organic phase was washed with H 2 O, dried over Na 2 SO 4 . Purification by flash chromatography (SiO 2 , EtOAc) yielded 1.12 g (38%) of the title compound as white solid.
EXAMPLE 17
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(2-morpholin-4-yl-acetyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0229]
[0230] Coupling according to general procedure 3:
[0231] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(2-bromo-acetyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (IX-4)
[0232] Amine: Morpholine (commercially available),
[0233] ES-MS m/e: 604.3 (M+H + ).
EXAMPLE 18
rac-4-[(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl]-piperazine-1-carboxylic acid tert-butyl ester
[0234]
[0235] Coupling according to general procedure I:
[0236] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0237] Carbamoyl chloride: 4-Chlorocarbonyl-piperazine-1-carboxylic acid tert-butyl ester (commercially available)
[0238] ES-MS m/e: 689.3 (M+H + ).
EXAMPLE 19
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0239]
[0240] To a stirred solution of rac-4-[(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl]-piperazine-1-carboxylic acid tert-butyl ester (21 mg, 0.30 mmol) in CH 2 Cl 2 (4 ml) at RT, was added TFA (1 ml). After 1 hour, the reaction mixture was neutralized by addition of an aqueous solution of NaHCO 3 . The organic phases were dried over Na 2 SO 4 to yield the title compound as a white solid.
[0241] ES-MS m/e: 589.5 (M+H + ).
EXAMPLE 20
rac-N-[(3S,4R)-1-(1-Acetyl-piperidine-4-carbonyl)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide
[0242]
[0243] Coupling according to general procedure I:
[0244] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0245] Acid chloride: 1-Acetyl-piperidine-4-carbonyl chloride (commercially available)
[0246] ES-MS m/e: 630.5 (M+H + ).
EXAMPLE 21
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid bis-(2-hydroxy-ethyl)-amide
[0247]
[0248] Coupling according to general procedure II:
[0249] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride (VIII-4)
[0250] Amine: 2-(2-Hydroxy-ethylamino)-ethanol (commercially available).
[0251] ES-MS m/e: 608.3 (M+H + ).
EXAMPLE 22
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0252]
[0253] Coupling according to general procedure I:
[0254] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0255] (VII-1)
[0256] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above)
[0257] ES-MS m/e: 649.5 (M+H + ).
EXAMPLE 23
rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0258]
[0259] Coupling according to general procedure I:
[0260] Pyrrolidine intermediate: rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-5)
[0261] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above)
[0262] ES-MS m/e: 599.2 (M+H + ).
EXAMPLE 24
rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0263]
[0264] Coupling according to general procedure I:
[0265] Pyrrolidine intermediate: rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-5)
[0266] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available)
[0267] ES-MS m/e: 522.3 (M+H + ).
EXAMPLE 25
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-oxo-cyclohexanecarbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0268]
[0269] Coupling according to general procedure I:
[0270] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-4)
[0271] Acid chloride: 4-Oxo-cyclohexanecarbonyl chloride
[0272] ES-MS m/e: 601.5 (M+H + ).
4-Oxo-cyclohexanecarbonyl chloride
[0273] To a stirred solution of 4-oxo-cyclohexanecarboxylic acid (commercially available) (115 mg, 0.81 mmol) in CH 2 Cl 2 (3 ml) was added oxalyl chloride (205 mg, 1.61 mmol). The reaction mixture was stirred at RT over night, and then concentrated under vacuo. The product was used directly in the next step without further purification.
EXAMPLE 26
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid (2-hydroxy-ethyl)-amide
[0274]
[0275] Coupling according to general procedure II:
[0276] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride (VIII-4)
[0277] Amine: 2-Amino-ethanol (commercially available).
[0278] ES-MS m/e: 564.3 (M+H + ).
EXAMPLE 27
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-1-(morpholine-4-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0279]
[0280] Coupling according to general procedure I:
[0281] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-7)
[0282] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available)
[0283] ES-MS m/e: 604.5 (M+H + ).
EXAMPLE 28
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0284]
[0285] Coupling according to general procedure I:
[0286] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-4-(4-fluoro-2-methyl-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-7)
[0287] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above).
[0288] ES-MS m/e: 681.5 (M+H + ).
EXAMPLE 29
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(3-hydroxy-azetidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0289]
[0290] Coupling according to general procedure II:
[0291] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0292] Amine: Azetidin-3-ol (commercially available).
[0293] ES-MS m/e: 558.2 (M+H + ).
EXAMPLE 30
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-hydroxy-piperidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0294]
[0295] Coupling according to general procedure II:
[0296] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0297] Amine: Piperidin-4-ol (commercially available).
[0298] ES-MS m/e: 586.5 (M+H + ).
EXAMPLE 31
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid (2-hydroxy-ethyl)-methyl-amide
[0299]
[0300] Coupling according to general procedure II:
[0301] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0302] Amine: 2-Methylamino-ethanol (commercially available).
[0303] ES-MS m/e: 560.5 (M+H + ).
EXAMPLE 32
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid (2-methoxy-ethyl)-amide
[0304]
[0305] Coupling according to general procedure II:
[0306] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0307] Amine: 2-Methoxy-ethylamine (commercially available).
[0308] ES-MS m/e: 560.3 (M+H + ).
EXAMPLE 33
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid (2-hydroxy-1-hydroxymethyl-ethyl)-amide
[0309]
[0310] Coupling according to general procedure II:
[0311] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0312] Amine: 2-Amino-propane-1,3-diol (commercially available).
[0313] ES-MS m/e: 576.7 (M+H + ).
EXAMPLE 34
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid (3-hydroxy-propyl)-amide
[0314]
[0315] Coupling according to general procedure II:
[0316] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0317] Amine: 3-Amino-propan-1-ol (commercially available).
[0318] ES-MS m/e: 560.5 (M+H + ).
EXAMPLE 35
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid [2-(2-hydroxy-ethoxy)-ethyl]-amide
[0319]
[0320] Coupling according to general procedure II:
[0321] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0322] Amine: 2-(2-Amino-ethoxy)-ethanol (commercially available).
[0323] ES-MS m/e: 590.7 (M+H + ).
EXAMPLE 36
rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid (2-hydroxy-1,1-dimethyl-ethyl)-amide
[0324]
[0325] Coupling according to general procedure II:
[0326] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0327] Amine: 2-Amino-2-methyl-propan-1-ol (commercially available).
[0328] ES-MS m/e: 574.5 (M+H + ).
EXAMPLE 37
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-[(3S,4R)-1-(morpholine-4-carbonyl)-4-O— tolyl-pyrrolidin-3-yl]-isobutyramide
[0329]
[0330] Coupling according to general procedure I:
[0331] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-O— tolyl-pyrrolidin-3-yl)-isobutyramide (VII-8)
[0332] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available)
[0333] ES-MS m/e: 586.5 (M+H + ).
EXAMPLE 38
rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-4-o-tolyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0334]
[0335] Coupling according to general procedure I:
[0336] Pyrrolidine intermediate: rac-2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-O— tolyl-pyrrolidin-3-yl)-isobutyramide (VII-8)
[0337] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above).
[0338] ES-MS m/e: 663.3 (M+H + ).
EXAMPLE 39
rac-2-(3,5-Dichloro-phenyl)-N-methyl-N-[(3S,4R)-1-(morpholine-4-carbonyl)-4-o-tolyl-pyrrolidin-3-yl]-isobutyramide
[0339]
[0340] Coupling according to general procedure I:
[0341] Pyrrolidine intermediate: rac-2-(3,5-Dichloro-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide (VII-9)
[0342] Carbamoyl chloride: Morpholine-4-carbonyl chloride (commercially available)
[0343] ES-MS m/e: 518.5 (M+H + ).
EXAMPLE 40
rac-2-(3,5-Dichloro-phenyl)-N-[(3S,4R)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-4-O— tolyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0344]
[0345] Coupling according to general procedure I:
[0346] Pyrrolidine intermediate: rac-2-(3,5-Dichloro-phenyl)-N-methyl-N-((3S,4R)-4-o-tolyl-pyrrolidin-3-yl)-isobutyramide (VII-9)
[0347] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above).
[0348] ES-MS m/e: 597.1 (M+H + ).
EXAMPLE 41
rac-2-(3-Chloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0349]
[0350] Coupling according to general procedure I:
[0351] Pyrrolidine intermediate: rac-2-(3-Chloro-phenyl)-N-[(3S,4R)-4-(4-fluoro-phenyl)-pyrrolidin-3-yl]-N-methyl-isobutyramide (VII-6)
[0352] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above).
[0353] ES-MS m/e: 565.3 (M+H + ).
EXAMPLE 42
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((S)-1-hydroxymethyl-3-methylsulfanyl-propyl)-amide
[0354]
[0355] Coupling according to general procedure II:
[0356] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0357] Amine: (S)-2-Amino-4-methylsulfanyl-butan-1-ol (L-Methioninol, commercially available).
[0358] ES-MS m/e: 620.3 (M+H + ).
EXAMPLE 43
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((S)-1-hydroxymethyl-3-methyl-butyl)-amide
[0359]
[0360] Coupling according to general procedure II:
[0361] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0362] Amine: (S)-2-Amino-4-methyl-pentan-1-ol (L-leucinol, commercially available).
[0363] ES-MS m/e: 602.5 (M+H + ).
EXAMPLE 44
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((R)-2-hydroxy-1-methyl-ethyl)-amide
[0364]
[0365] Coupling according to general procedure II:
[0366] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0367] Amine: (R)-2-Amino-propan-1-ol (D-alaminol, commercially available).
[0368] ES-MS m/e: 560.5 (M+H + ).
EXAMPLE 45
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((S)-1-hydroxymethyl-2-methyl-propyl)-amide
[0369]
[0370] Coupling according to general procedure II:
[0371] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0372] Amine: (S)-2-Amino-3-methyl-butan-1-ol (L-valinol, commercially available).
[0373] ES-MS m/e: 588.5 (M+H + ).
EXAMPLE 46
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((S)-2-hydroxy-propyl)-amide
[0374]
[0375] Coupling according to general procedure II:
[0376] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0377] Amine: (S)-1-Amino-propan-2-ol (commercially available).
[0378] ES-MS m/e: 560.3 (M+H + ).
EXAMPLE 47
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[((3S,4R)-1-((S)-2-hydroxymethyl-pyrrolidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0379]
[0380] Coupling according to general procedure II:
[0381] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0382] Amine: (S)-1-Pyrrolidin-2-yl-methanol (commercially available).
[0383] ES-MS m/e: 586.5 (M+H + ).
EXAMPLE 48
(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carboxylic acid ((R)-2-hydroxy-propyl)-amide
[0384]
[0385] Coupling according to general procedure II:
[0386] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0387] Amine: (R)-1-Amino-propan-2-ol (commercially available).
[0388] ES-MS m/e: 560.5 (M+H + ).
EXAMPLE 49
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-((2R,3S)-3-hydroxy-2-hydroxymethyl-pyrrolidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0389]
[0390] Coupling according to general procedure II:
[0391] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0392] Amine: (2R,3S)-2-Hydroxymethyl-pyrrolidin-3-ol (described in J. Org. Chem. 1989, 54(20), 4812).
[0393] ES-MS m/e: 602.3 (M+H + ).
EXAMPLE 50
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-((S)-3-hydroxy-pyrrolidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0394]
[0395] Coupling according to general procedure II:
[0396] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0397] Amine: (S)-Pyrrolidin-3-ol (described in WO2007011162).
[0398] ES-MS m/e: 572.3 (M+H + ).
EXAMPLE 51
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-((S)-2-methoxymethyl-pyrrolidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0399]
[0400] Coupling according to general procedure II:
[0401] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0402] Amine: (S)-2-Methoxymethyl-pyrrolidine (commercially available).
[0403] ES-MS m/e: 600.3 (M+H + ).
EXAMPLE 52
N-[(3S,4R)-1-((R)-3-Acetylamino-pyrrolidine-1-carbonyl)-4-phenyl-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide
[0404]
[0405] Coupling according to general procedure II:
[0406] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0407] Amine: (R)—N-Pyrrolidin-3-yl-acetamide (commercially available).
[0408] ES-MS m/e: 613.3 (M+H + ).
EXAMPLE 53
rac-(3S,4R)-3-{[2-(3,5-Dichloro-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid (3-hydroxy-propyl)-amide
[0409]
[0410] Coupling according to general procedure II:
[0411] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Dichloro-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride (VIII-5)
[0412] Amine: 3-Amino-propan-1-ol (commercially available).
[0413] ES-MS m/e: 510.3 (M+H + ).
EXAMPLE 54
rac-(3S,4R)-3-{[2-(3,5-Dichloro-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carboxylic acid bis-(2-hydroxy-ethyl)-amide
[0414]
[0415] Coupling according to general procedure II:
[0416] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Dichloro-phenyl)-2-methyl-propionyl]-methyl-amino}-4-(4-fluoro-phenyl)-pyrrolidine-1-carbonyl chloride (VIII-5)
[0417] Amine: 2-(2-Hydroxy-ethylamino)-ethanol (commercially available).
[0418] ES-MS m/e: 540.3 (M+H + ).
EXAMPLE 55
rac-N-[(3S,4R)-4-(4-Chloro-phenyl)-1-(4-methanesulfonyl-piperazine-1-carbonyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide
[0419]
[0420] Coupling according to general procedure I:
[0421] Pyrrolidine intermediate: rac-N-[(3S,4R)-4-(4-Chloro-phenyl)-pyrrolidin-3-yl]-2-(3,5-dichloro-phenyl)-N-methyl-isobutyramide (VII-3)
[0422] Carbamoyl chloride: 4-Methanesulfonyl-piperazine-1-carbonyl chloride (described herein above)
[0423] ES-MS m/e: 617.3 (M+H + ).
EXAMPLE 56
2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-[(3S,4R)-4-phenyl-1-((R)-tetrahydro-furan-2-carbonyl)-pyrrolidin-3-yl]-isobutyramide
[0424]
[0425] To a stirred solution of (R)-tetrahydro-furan-2-carboxylic acid (described in Tetrahedron Asymmetry, 2003, 14(10, 1385) (5.0 mg, 0.043 mmol) in THF (2 ml) at RT were added Et 3 N (12 μl, 0.086 mmol), BOP (25 mg, 0.057 mmol) and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1) (20 mg, 0.043 mmol). Stirring was continued at 40° C. for 48 hours. Concentration and purification by preparative HPLC afforded 5.8 mg (28%) of the title compound.
[0426] ES-MS m/e: 557.2 (M+H + ).
EXAMPLE 57
2-(3,5-Bis-trifluoromethyl-phenyl)-N-methyl-N-[(3S,4R)-4-phenyl-1-((S)-tetrahydro-furan-2-carbonyl)-pyrrolidin-3-yl]-isobutyramide
[0427]
[0428] To a stirred solution of (S)-tetrahydro-furan-2-carboxylic acid (described in J. Med. Chem., 1995, 38(15, 2830) (5.0 mg, 0.043 mmol) in THF (2 ml) at RT were added Et 3 N (12 μl, 0.086 mmol), BOP (25 mg, 0.057 mmol) and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1) (20 mg, 0.043 mmol). Stirring was continued at 40° C. for 48 hours. Concentration and purification by preparative HPLC afforded 5.1 mg (25%) of the title compound.
[0429] ES-MS m/e: 557.2 (M+H + ).
EXAMPLE 58
N-[(3S,4R)-1-((2S,4R)-1-Acetyl-4-hydroxy-pyrrolidine-2-carbonyl)-4-phenyl-pyrrolidin-3-yl]-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-isobutyramide
[0430]
[0431] To a stirred solution of (2S,4R)-1-acetyl-4-hydroxy-pyrrolidine-2-carboxylic acid (commercially available) (7.5 mg, 0.043 mmol) in THF (2 ml) at RT were added Et 3 N (12 μl, 0.086 mmol), BOP (25 mg, 0.057 mmol) and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1) (20 mg, 0.043 mmol). Stirring was continued at 40° C. for 48 hours. Concentration and purification by preparative HPLC afforded 7.6 mg (29%) of the title compound.
[0432] ES-MS m/e: 614.5 (M+H + ).
EXAMPLE 59
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-methoxymethyl-cyclohexanecarbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0433]
[0434] To a stirred solution of 4-methoxymethyl-cyclohexanecarboxylic acid (described in JP60258141) (7.4 mg, 0.043 mmol) in THF (2 ml) at RT were added Et 3 N (12 μl, 0.086 mmol), BOP (25 mg, 0.057 mmol) and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1) (20 mg, 0.043 mmol). Stirring was continued at 40° C. for 48 hours. Concentration and purification by preparative HPLC afforded 12.7 mg (48%) of the title compound.
[0435] ES-MS m/e: 613.3 (M+H + ).
EXAMPLE 60
2-(3,5-Bis-trifluoromethyl-phenyl)-N-[(3S,4R)-1-(4-ethynyl-cyclohexanecarbonyl)-4-phenyl-pyrrolidin-3-yl]-N-methyl-isobutyramide
[0436]
[0437] To a stirred solution of 4-ethynyl-cyclohexanecarboxylic acid (commercially available) (6.5 mg, 0.043 mmol) in THF (2 ml) at RT were added Et 3 N (12 μl, 0.086 mmol), BOP (25 mg, 0.057 mmol) and rac-2-(3,5-bis-trifluoromethyl-phenyl)-N-methyl-N-((3S,4R)-4-phenyl-pyrrolidin-3-yl)-isobutyramide (Intermediate VII-1) (20 mg, 0.043 mmol). Stirring was continued at 40° C. for 48 hours. Concentration and purification by preparative HPLC afforded 13.7 mg (54%) of the title compound.
[0438] ES-MS m/e: 593.5 (M+H + ).
EXAMPLE 61
rac-2-[3,5-bis(trifluoromethyl)phenyl]-N-{(3R,4S)-1-[(6′-bromo-2′-oxo-2′,3′-dihydro-1H,1′H-spiro[piperidine-4,4′-quinolin]-1-yl)carbonyl]-4-phenylpyrrolidin-3-yl}-N,2-dimethylpropanamide
[0439]
[0440] Coupling according to general procedure II:
[0441] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0442] Amine: 6′-bromo-1′H-spiro[piperidine-4,4′-quinolin]-2′(3′H)-one
[0443] ES-MS m/e: 779.5 (M+H + ).
EXAMPLE 62
rac-2-[3,5-bis(trifluoromethyl)phenyl]-N,2-dimethyl-N-{(3R,4S)-1-[(1-oxo-2,3-dihydro-1H,1′H-spiro[isoquinoline-4,4′-piperidin]-1′-yl)carbonyl]-4-phenylpyrrolidin-3-yl}propanamide
[0444]
[0445] Coupling according to general procedure II:
[0446] Pyrrolidine intermediate: rac-(3S,4R)-3-{[2-(3,5-Bis-trifluoromethyl-phenyl)-2-methyl-propionyl]-methyl-amino}-4-phenyl-pyrrolidine-1-carbonyl chloride (VIII-1)
[0447] Amine: 2,3-dihydro-1H-spiro[isoquinoline-4,4′-piperidin]-1-one
[0448] ES-MS m/e: 701.5 (M+H + ). | The invention relates to pyrrolidine derivatives of formula
wherein
R 1 , R 2 , R 3 , n, and o are defined in the specification and to pharmaceutically active acid-addition salts thereof. Compounds of formula I have a high affinity simultaneously to both the NK1 and the NK3 receptors (dual NK1/NK3 receptor antagonists), useful in the treatment of schizophrenia. | 2 |
PRIORITY APPLICATION
[0001] This is a continuation patent application drawing priority from U.S. patent application Ser. No. 14/971,320; filed Dec. 16, 2015. This present patent application draws priority from the referenced patent application. The entire disclosure of the referenced patent application is considered part of the disclosure of the present application and is hereby incorporated by reference herein in its entirety.
TECHNICAL FIELD
[0002] The application of innovative micro and nano vesicle forming technologies to effect beneficial results through the application of synthetic and natural ingredients to the skin has shown a great potential to significantly benefit the cosmetic formulation practice, offering solutions to many of the current limitations in ingredients, treatment style and management of human skin effected by environmental and physiological impact.
BACKGROUND
[0003] A liposome vesicle encapsulates a region of aqueous solution inside a hydrophobic membrane; dissolved hydrophilic solutes cannot readily pass through the lipids. Hydrophobic chemicals can be dissolved into the membrane, and in this way liposome can carry both hydrophobic molecules and hydrophilic molecules.
[0004] Several CFs (Compressed Fluid) methodologies have been used to generate vesicles, some of them already existed and others were developed for this specific application. Most of the methods involve a mixture between the compressed CO2, the vesicle membrane constituents and an organic solvent for producing the vesicles upon contact with an aqueous phase.
[0005] Depending on the role of the compressed CO2 used in each method, they can be classified as: Process involving the use of CO2 as a solvent (e.g. Supercritical Liposome Method and Rapid Expansion of Supercritical Solutions), Processes involving the use of CO2 as an antisolvent (e.g. Gas Antisolvent Precipitation and Aerosol Solvent Extraction System) and Processes involving the use of CO2 as a co-solvent or a processing aid (e.g. Depressurization of an Expanded Liquid Organic Solution-Suspension and Supercritical Reverse Phase Evaporation).
[0006] Model hydrophilic and hydrophobic compounds, such as fluorescent dyes, sugars and cholesterol, have been encapsulated into vesicles using these methodologies whereas biomolecules like proteins, anticancer drugs and antibiotic, have been integrated in less extent.
[0007] Transdermal delivery systems (TDS) were introduced onto the US market in the late 1970s), but transdermal delivery of drugs had been around for a very long time. There have been previous reports about the use of mustard plasters to alleviate chest congestion and belladonna plasters used as analgesics. The mustard plasters were homemade as well as available commercially where mustard seeds were ground and mixed with water to form a paste, which was in turn used to form a dispersion type of delivery system.
[0008] Once applied to the skin, enzymes activated by body heat led to the formation of an active ingredient (allyl isothiocyanate). Transport of the active drug component took place by passive diffusion across the skin—the very basis of transdermal drug delivery.
[0009] The epi-dermis undergoes changes in structure and function which result in many of the characteristics of aged skin, including loss of elasticity, formation of wrinkles, loss of water-holding capacity, sagging, and poor microcirculation. At the molecular level, these changes have been correlated with biochemical changes in the content and structure of the extracellular matrix to which the major cells of the epi-dermis (i.e., the fibroblasts) reside. Collagen becomes highly cross-linked and inelastic, elastin is reduced in amounts and is incorrectly distributed, which results in reduced intercellular water for reduction and repair of these changes. Nonsurgical options include chemical peels and chemicals with minor irritant properties (e.g., topical retinoid, salicylic acid, and alpha-hydroxy acids), are based on the principle of wounding the stratum corneum—the skin's primary defense against the transit of exogenous materials into the epidermis and dermis—to allow the penetration of constituents through the disrupted skin, which stimulates the desired response, typically restorative healing. All of these techniques require a wound healing response to the skins being intentionally wounded as a method to initiate the rejuvenation process.
[0010] Owing to the selective nature of the skin barrier, only a small pool of ingredients can be delivered non-systemically or systemically at therapeutically relevant rates. Besides great potency, the physicochemical ingredient characteristics often evoked as favorable for percutaneous delivery include moderate lipophilicity and low-molecular-weight. However, a large number of skin damage mitigating active agents do not fulfill these criteria.
[0011] Chemical permeation enhancers facilitate drug permeation across the skin by increasing drug partitioning into the barrier domain of the stratum corneum, increasing drug diffusivity in the barrier domain of the stratum corneum or the combination of both (2).
[0012] The heterogeneous stratum corneum is composed of keratin ‘bricks’ and intercellular continuous lipid ‘mortar’ organized in multilamellar strata (3)(4)(5). Depending on the nature of the drug or ingredient, either of these two environments may be the rate-limiting milieu (barrier domain) for the percutaneous transport.
[0013] As a consequence, it is anticipated that the magnitude of permeation improvement obtained with a given permeation enhancer will vary between lipophilic and hydrophilic ingredients. Several mechanisms of action are known: increasing fluidity of stratum corneum lipid bilayers, extraction of intercellular lipids, increase of ingredient's thermodynamic activity, increase in stratum corneum hydration, alteration of proteinaceous corneocyte components and others.
[0014] The stratum corneum is a formidable barrier to exogenous agents including cosmeceutical ingredients. Therefore, it is often necessary to add permeation-enhancing chemicals to aid beneficial constituents in passing through the stratum corneum. Permeation-enhancing chemicals include fatty acids, organic solvents (i.e., acetone and ethanol), alcohols, esters and surfactants.
[0015] It is generally understood that for enhancers, increased potency is directly correlated with increased skin irritation. Difficulty in reducing the irritation of these agents has been expressed since the same mechanisms responsible for increasing permeation cause irritation. While potent enhancers are effective at transiently compromising the integrity of the stratum corneum barrier, their action is not entirely limited to the stratum corneum and the interaction with viable epidermis can cause cytotoxicity and irritation. Published methods for reducing the skin irritation of permeation enhancers include combining permeation enhancers (synergistic mixtures) and manipulation of their chemical structures.
[0016] Conventional lipid or niosome vesicle production techniques have drawbacks such as complex and time consuming procedures involving organic solvents. For liposomes, conventional methods can involve harsh conditions that result in denaturation of the lipids and active ingredients, and also cause poor ingredient encapsulation efficiency.
[0017] Since the liposomes were first used as drug carriers in 1970s. Many methods, such as Supercritical fluids (SCFs), for preparing liposomes have been developed, but these methods require large amounts of organic solvents like chloroform, ether, freon, methylenechloride and methanol that are harmful to the environment and the human body, and very few methods have been developed that yield liposomes that have a high trapping efficiency for water soluble substances without using any organic solvent.
[0018] Additionally, all these methods are not suitable for mass production of liposomes because they consist of many steps. With the advent of Green Chemistry in the early 1990s, the surge of supercritical fluids (SCFs) increased vastly.
[0019] The supercritical state of a fluid (SCF) is intermediate between that of gas and liquids. The SCF has been used widely in pharmaceutical industrial operations including crystallization, particle size reduction, drug delivery preparation, coating and product sterilization. In the pharmaceutical field, supercritical carbon dioxide (scCO2) is by far the most commonly used gas, which can become supercritical at conditions that are equal or exceed its critical temperature of 31.1° C. and its critical pressure of 7.38 Megapascals (Mpa).
[0020] The encapsulation degree of any drug into vesicles is influenced by several parameters related to the: a) vesicle composition, b) the nature of the cosmeceutical ingredient and c) the preparation methodology. Regarding the vesicle composition, besides the selection of the lipids forming the membrane and the presence of charges on it, the type of vesicle plays also an important role. Thus, for hydrophilic drugs, such as proteins or peptides, the encapsulation degree appears to increase in the following order: MLV<SUV<LUV. ( FIG. 1.0 ) Nevertheless in the case of hydrophobic drugs, the size and type of liposomes do not seem to play a major role.
[0021] Liposomes with a single bilayer are known as unilamellar vesicles (UV). UVs may be made extremely small (SUVs) or large (LUVs) ( FIG. 3.0 ). Liposomes are prepared in the laboratory by sonication, detergent dialysis, ethanol injection, French press extrusion, ether infusion, and reverse phase evaporation.
[0022] These methods often leave residuals such as detergents or organics with the final liposome. From a production standpoint, it is clearly preferable to utilize procedures which do not use organic solvents since these materials must be subsequently removed.
[0023] Some of the methods impose harsh or extreme conditions which can result in the denaturation of the phospholipid raw material and encapsulated ingredients. These methods are not readily scalable for mass production of large volumes of liposomes.
[0024] Several methods, such as energy input in the form of sonic energy (sonication) or mechanical energy (extrusion), exist for producing MLVs (multilamellar vesicles), LUVs and SUVs without the use of organic solvents.
[0025] MLVs (multilamellar vesicles), free of organic solvents, are usually prepared by agitating lipids in the presence of water. The MLVs are then subjected to several cycles of freeze thawing in order to increase the trapping efficiencies for water soluble ingredients.
[0026] MLVs are also used as the starting materials for LUV and SUV production. One approach of creating LUVs, free of organic solvents, involves the high pressure extrusion of MLVs through polycarbonate filters of controlled pore size. SUVs can be produced from MLVs by sonication,
[0027] French press or high pressure homogenization techniques. High pressure homogenization has certain limitations. High pressure homogenization is useful only for the formation of SUVs. In addition, high pressure homogenization may create excessively high temperatures.
[0028] Contrary to the present embodiment, extremely high pressures are associated with equipment failures. High pressure homogenization does not insure end product sterility. High pressure homogenization is associated with poor operability because of valve plugging and poor solution recycling.
[0029] The use of liposomes for the delivery and controlled release of therapeutic drugs requires relatively large supplies of liposomes suitable for in vivo use ( FIG. 6.0 ). Present laboratory scale methods lack reproducibility, in terms of quantity and quality of encapsulated ingredients, lipid content and integrity, and liposome size distribution and captured volume.
[0030] The multidimensional characteristics of the ingredient and the liposome, as well as potential raw material variability, influence reproducibility. Present state-of-the-art liposome and niosome products are not stable. It is desirable to have final formulations which are stable for six months to two years at room temperature or at refrigeration temperature.
[0031] Present liposome products are difficult to sterilize. Sterility is currently accomplished by independently sterilizing the component parts lipid, buffer, ingredient and watery autoclave or filtration and then mixing in a sterile environment.
[0032] This sterilization process is difficult, time consuming and expensive since the product must be demonstratively sterile after several processing steps. Heat sterilization of the finished product is not possible since heating liposomes or niosomes does irreparable damage. Filtration through 0.22 micron filters may also alter the features of multilayered liposomes and elastic niosomes.
[0033] Gamma ray treatment, not commonly used in the pharmaceutical industry, may disrupt liposome or elastic niosome membranes. Picosecond laser sterilization is still experimental and has not yet been applied to the sterilization of any commercial pharmaceutical.
[0034] In the past two decades, several cosmetic formulations based on ingredient delivery systems have been successfully introduced for the treatment of skin disorders. Many problems exhibited by free active cosmetic ingredients (ACIs), such as poor solubility, toxicity, rapid in vivo breakdown, unfavorable pharmacokinetics, poor bio distribution and lack of selectivity for target tissues can be ameliorated by the use of a VDS (vesicle delivery system) as offered by the current embodiment. Although a whole range of delivery agents exist nowadays, the main components typically include a nanocarrier, a targeting moiety conjugated to the nanocarrier, and a cargo, such as the desired cosmeceutical ingredient.
[0035] In 1846, Gobley separated phospholipids from egg yolk. The term “lecithin” which is derived from the Greek lekithos was first used to describe a sticky orange material isolated from egg yolk. “Lecithin” refers to the lipids containing phosphorus isolated from eggs and brains; (3) from a scientific point of view, “lecithin” refers to PCs (phosphatidylcholine) the most common phospholipid, egg yolks, liver, wheat germ and peanuts contain the phospholipid lecithin.
[0036] Phospholipids ( FIG. 3.0 ) have excellent biocompatibility. In addition, phospholipids are renowned for their amphiphilic structures. The amphiphilicity confers phospholipids with self-assembly, emulsifying and wetting characteristics. When introduced into aqueous milieu, phospholipids self-assembly generates different super molecular structures which are dependent on their specific properties and conditions.
[0037] In the need for synthetic analogs of natural phospholipids, further synthetic phospholipids were for instance designed to optimize the targeting properties of liposomes. Examples are the PEG-ylated phospholipids and the cationic phospholipid 1,2-diacyl-P—O ethylphosphatidylcholine. Also attempts were made to convert by organic chemical means phospholipids into pharmacological active molecules (for instance ether phospholipids or to make phospholipid pro-drugs.
[0038] DPPC is the major constituent of stratum corneum surfactants which controls the dynamic surface tension (DST) and helps maintaining the epi-dermis health. It is also one of the most popular phospholipids used for preparing lipid or niosome bilayers and model biological membranes.
SUMMARY
[0039] The present embodiment features methods and apparatus for producing liposomes and niosomes containing hydrophobic and hydrophilic ingredients know to be beneficial to the repair and rejuvenation to the stratum corneum and underlying epi-dermis with the ability to effect non-systemic drug absorption and transportation are influenced by various factors. The methods and apparatus are suitable for large scale production of pharmaceutical grade liposomes which are sterile, of a predetermined size, and are substantially free of organic solvents. The present embodiment features a method of making liposomes and elastic niosomes using low pressure fluids.
[0040] As constructed according to the present embodiment example, nano and macro carriers can be either unimolecular (i.e.: dendrimers, carbon nanotubes, polymer-conjugate drug/protein, etc.) or multimolecular carries, based on molecular self-assemblies (nanoshells, vesicles, etc.). Their major constituents are either lipids or polymers and they all have in common that the final arrangement is governed by the nature of the initial components and the methodology used in their preparation. Some of the advantages are the incorporation of ACIs (active cosmeceutical ingredients).
[0041] One method of the example embodiment comprises the steps of forming a solution or mixture of a phospholipid, a hydrophobic or hydrophilic cosmeceutical ingredient, an aqueous phase and a low pressure fluid. The solution or mixture is decompressed to separate the low pressure, critical fluid, from the phospholipid and aqueous medium, to form one or more liposomes. This method is referred to as the decompression method of forming liposomes in the embodiment. Preferably, the rate of depressurization influences the size of the liposomes formed.
[0042] According to the procedure of the example embodiment, schematically represented in FIG. 4.0 , operating always under mild conditions to preserve the activity of the labile biomolecules. The general method consists in loading a solution of the membrane lipid components and the desired hydrophobic bio-actives in an organic solvent (e.g. ethanol), into the high-pressure reactor previously driven to the preferred working temperature ( FIG. 4.0 A). The reactor is then pressurized, in a second stage, with a large amount of compressed CO2 until reaching the working pressure (10 MPa) ( FIG. 4.0 B).
[0043] Finally in the third stage, the vesicular conjugates are formed by depressurizing the resulting CO2-expanded solution over an aqueous phase, which might contain water soluble surfactants and hydrophilic bio-actives ( FIG. 4.0 C). In this step a flow of N2 at the working pressure is used in order to push down the CO2-expanded solution and to keep constant the pressure inside the reactor. It is worth to note that no further energy input is required for achieving the desired SUVs (small unilamellar vesicles) structural characteristics, neither for increasing the loading or functionalization.
[0044] In applications utilizing the example embodiment with low pressure fluids, the properties of the coating material and particularly the interactions of coating materials with low pressure low temperature fluids are especially important.
[0045] These interactions may be important for enabling the incorporation of cosmeceutical essential oils into carrier materials, for example by facilitating the diffusion of the essential oil due to the swelling and opening of the pores of carrier material particles.
[0046] One method comprises the steps of (1) forming a solution or mixture of a phospholipid, (2) an aqueous phase and low pressure low temperature methodologies. (3) The solution or mixture is decompressed to separate the fluid, from the phospholipid and aqueous media, to form one or more liposomes.
[0047] In some embodiments, the aqueous, or addition phase, has a therapeutic cosmeceutical agent included. As used herein, the term “therapeutic cosmeceutical agent” means a chemical or ingredient capable of effecting a desirable response in an individual subject. This embodiment is ideally suited for therapeutic cosmeceutical agents which are not shear sensitive.
[0048] Preferably the compressed fluid is recycled. To the extent that phospholipids and aqueous phase are carried over with the CF, such components may also be recycled. For convenience, liposomes formed with CF fluid in the current embodiment are referred to as “LPLTVs.”
[0049] An example embodiment features an apparatus for forming liposomes/niosomes (non-ionic) vesicles. The apparatus comprises a first vessel wherein a phospholipid, an aqueous phase and a CF are combined to form a mixture or solution. The apparatus further comprises a second vessel in communication with the first vessel for expansion.
[0050] The apparatus of the embodiment further comprises a third vessel for depressurization as a means capable of reducing the pressure of the solution or mixture. Depressurization means may be interposed between the first and second vessels or may be integral with a third vessel. The third vessel receives the solution or mixture of phospholipids and an aqueous phase which form liposomes upon depressurization.
[0051] Preferably, the CF is removed from depressurization means and/or the third vessel and recycled.
[0052] One example embodiment comprises the steps of forming a solution or mixture of a phospholipid and a compressed fluid. The solution or mixture is then decompressed through a tip or orifice into an aqueous phase to form one or more liposomes. As a result of the decompression, the CF is separated from the phospholipids and the aqueous phase. The released CF is either vented or recycled to form a solution or mixture of phospholipid.
[0053] A further example embodiment features a method of making liposomes or niosomes comprising the steps of forming a solution or mixture of a phospholipid and a CF. The solution or mixture is injected into an aqueous phase to form one or more liposomes or niosomes as the phospholipids and CFs are decompressed.
[0054] Preferably, the aqueous phase or phospholipids contain a cosmeceutical therapeutic agent which is incorporated into the liposome or niosomes.
[0055] Embodiments of the present method are ideally suited for skin rejuvenating agents which are shear sensitive such as botanicals, proteins and peptides. Embodiments of the present method do not subject botanicals, proteins and peptides to extreme shear forces or temperatures.
[0056] Example embodiments are ideally suited to form unilamellar liposome or niosome vesicles. The size of the liposome or niosome is determined by the rate of decompression.
[0057] A preferred method uses a CF selected from the group of compositions capable of forming a critical fluid comprising carbon dioxide; nitrous oxide; halo-hydrocarbons, such as FREON; alkanes such as propane and ethane; and alkanes such as ethylene.
[0058] One example embodiment features an apparatus for forming liposomes and niosomes. The apparatus comprises a first vessel for containing a solution or mixture of a phospholipid and a compressed fluid. The apparatus further comprises a second vessel for containing an aqueous phase. The first vessel and the second vessel are in communication by means of injection means for injecting the phospholipid and CF fluid mixture into the aqueous phase. Upon injection into the aqueous phase in the third vessel, liposomes are formed.
[0059] Preferably, the aqueous phase contains a cosmeceutically therapeutic agent which cosmeceutical therapeutic agent is encapsulated within the liposome.
[0060] Conjugation of cosmeceutical bio-beneficial ingredients to nano carriers can offer over the free ingredient the protection from premature degradation, a higher stability, an enhance permeability through biological membranes, a higher control of the pharmacokinetics, a better ingredient tissue distribution profile, and an improvement of intracellular, intercellular, and intra-follicular penetration and the ability to control whether the nano-carrier goes systemic or non-systemic.
BRIEF DESCRIPTION OF THE DRAWINGS
[0061] For a better understanding of the example embodiments, reference should be made to the following detailed description disclosed in conjunction with the accompanying drawings, in which:
[0062] FIG. 1.0 illustrates the classification of vesicles regarding size and lamellarity.
[0063] FIG. 2.0 illustrates the construction and composition of phospholipids
[0064] FIG. 3.0 illustrates the major classifications of liposomes as vesicular systems according to their size and membrane lamellarity.
[0065] FIG. 4.0 (A, B, C) is a representation of the steps of forming a solution or mixture of a phospholipid, an aqueous phase and low pressure low temperature methodologies.
[0066] FIG. 5.0 is a TEM image of liposomes produced in the LPLTVs process.
[0067] FIG. 6.0 is an image of the appearance of small spheres aggregating into larger spheres or captured within larger spheres in the LPLTVs liposomal forming process.
[0068] FIG. 7.0 shows rod or coffee-bean morphology observed in the liposomes samples produced by the LPLTVs process.
[0069] FIG. 8.0 is a schematic representation of the LPLTV process method.
[0070] FIG. 9.0 shows a solubility curve of hyaluronic acid and cholesterol, in ethanol/CO2 at 10 MPa and 308 K.
[0071] FIG. 10.0 is a schematic illustration of the formation of (a) the hyaluronic acid cholesterol/CTAB bimolecular amphiphile and (b) their self-assembling into bilayer vesicles based on the packing parameter concept.
[0072] FIG. 11.0 is a chart showing Hyaluronic Acid levels in active and control samples.
DETAILED DESCRIPTION
[0073] The present embodiment features methods and apparatus for producing cosmeceutically benevolent ingredient content liposomes and niosomes. The methods and apparatus are suitable for large scale production of pharmaceutical and cosmeceutical grade vesicles for the treatment of skin anomalies created as a result of aging skin or chronic environmental insult which are sterile, of a predetermined size, and are substantially free of organic solvents.
Definitions
[0074] As used herein, the word “hydrophilic” in relation to the material means that that material is above 10% soluble in water by weight at standard temperature and pressure (STP).
[0075] As used herein, the word “hydrophobic” as used in relation to a material means that that material is less than 0.1% soluble in water by weight at standard temperature and pressure (STP).
[0076] As used herein, the term (IDS) as used in relation to the explanation of the current embodiment means Ingredient Delivery Systems.
[0077] As used herein, the word “micelle” as used in relation to a material means “molecules having both polar or charged groups and non-polar regions (amphiphilic molecules) formed aggregates”.
[0078] As used herein, the word “vesicle” as used in relation to one prepared artificially, in which case they are called liposomes. If there is only one phospholipid bilayer, they are called unilamellar liposome vesicles; otherwise they are called multilamellar.
[0079] As used herein, the word “niosome” as used in relation to a non-ionic surfactant-based Vesicle formed mostly by non-ionic surfactant and cholesterol incorporation as an excipient.
[0080] As used herein, the term “LPLTVs as used means Low Pressure Low Temperature alternative construction of Vesicles based on milder conditions of pressure (<10 MPa) and temperature (<308 K) than the previously described methodologies based on CFs (Compressed Fluids).
[0081] As used herein, the term Active Cosmetic Ingredients (ACIs) as used means but is not limited to such substances as synthetic or natural skin rejuvenating ingredients, sunscreen ingredients, skin-lightening agents, and anti-acne ingredients.
[0082] As used herein, the term CFs as used means such substances made from compressed fluids based technologies to produce niosomes or vesicles.
[0083] As used herein, the term phospholipids as used means lipids containing phosphorus, a polar potion and non-polar potion in their structures.
[0084] As used herein, the term niosomes are microscopic lamellar vesicular structures, which are formed on the admixture of non-ionic surfactant and cholesterol with subsequent hydration in aqueous media.
[0085] One example embodiment features an apparatus for forming liposomes and niosomes. The apparatus comprises a first vessel or mixing the organic phase, a second vessel for containing a mixture of multi-lamellar vesicles and a compressed fluid and a third vessel for decompressing into the aqueous phase. The first vessel is in communication with a second vessel which second vessel is in communication with a third vessel capable of decompressing the mixture to remove the compressed fluid. During decompression, one or more liposomes or niosomes are formed.
[0086] Another embodiment further comprises a third vessel for forming multilamellar vesicles by hydrating phospholipids in an aqueous phase.
[0087] In the embodiment, the aqueous phase or the phospholipids may contain a therapeutic agent to impart special qualities to the liposome for beneficial partitioning of the stratum corneum to aid in transiting cosmeceutically beneficial liposomes or niosomes to the epi-dermis.
[0088] An embodiment further features control means for determining the rate of decompression. The rate of decompression determines the size of liposomes or niosomes.
[0089] Preferably, compressed fluid removed from the liposome preparation in the decompression vessel is recycled to the first vessel to form additional mixtures of multilamellar vesicles and compressed fluid.
[0090] Contact with compressed fluid may cause destruction of the cellular structures particularly upon rapid decompression. Thus, embodiments are, for the most part, self-sterilizing.
[0091] Methods and apparatus of the example embodiment are capable of forming liposomes or niosomes which carry a cosmeceutical therapeutic agent. The cosmeceutical therapeutic agent can be incorporated into ingredients which are used to form the liposome or niosome or the liposome or niosome can be loaded with the cosmeceutical therapeutic agent after the liposome or niosome is formed.
[0092] Embodiments allow the recovery of raw materials, lipids and solvents which are not incorporated into the final liposome or niosome product. Example embodiments feature efficient cosmeceutical ingredient entrapment and recovery of un-encapsulated cosmeceutical ingredient. The operating parameters of the apparatus and method are consistent with other industrially applied processes. The method and apparatus are capable of operating continuously.
[0093] These and other features, aspects, and advantages of the embodiment will become evident to those of ordinary skill in the art from a reading of the present disclosure.
[0094] During the depressurization step of the example embodiment, the expanded organic solution experiences a large, abrupt and extremely homogenous temperature decrease produced by the CO2 evaporation from the expanded solution. This is the reason that explains the obtaining of homogenous vesicles regarding size, lamellarity and morphology compared with the same system but prepared by a conventional mixing method.
[0095] However, changes in the procedures and equipment, as in the present embodiment, result in vesicular systems with differentiated characteristics. The processes can also be distinguished by the latter hydration step that can occur either during the pressurization or the depressurization step.
[0096] These lipid or niosome vesicles of the present embodiment allow the physicochemical properties of ingredient molecules, of a higher molecular weight in excess of 700 kDa, in a liposomal system to be changed, which facilitates crossing of the stratum corneum barrier into the epi-dermis.
[0097] The size of the liposome can be controlled by the rate of decompression to form liposomes or niosomes of predetermined size to control the volume and depth of penetration.
[0098] Among the various approaches for exploiting developments in nano and micro technology for cosmetic applications, ingredient delivery systems (IDS) have already had an enormous impact on cosmetic formulation technology, improving the performance of many existing ingredients and enabling the use of entirely new therapies. The fact that IDSs can protect sensitive molecules, such as hormones, enzymes and proteins, from degradation and the in-vivo attack of the immune system providing longer resident times, have been used to improve the effectiveness and delivery of these ingredients. Although nano and micro particulate carriers can be made from a variety of organic and inorganic materials, vesicle and polymer based-nanocarriers are perhaps the most widely used for ingredient delivery purposes.
[0099] Particularly vesicles, liposome and noisome, have served as convenient delivery vehicles for biologically active compounds because they are non-toxic, biodegradable and non-immunogenic. Contrary to products where the active substance is in simple solution, the pharmacological properties of vesicle-based delivery systems strongly depend on the structural characteristics of the conjugates. Indeed, a high degree of structural homogeneity regarding size, morphology and vesicle organization in the membrane is crucial, for their optimum performance as functional entities.
[0100] Liposomes and niosomes are vesicles in which, in the current embodiment, cosmeceutical ingredients can be trapped and administered more efficiently. However, these vesicles, micelle, liposome and niosome, are not similar to each other. In a comparison, micelles vs. liposomes, and or elastic niosomes, the differences between the two are explained as; Micelles are structures composed of a monolayer of amphipathic molecules. In a biological system, the molecules tend to arrange themselves in such a manner that the inner core of these structures are hydrophobic and the outer layers are hydrophilic in nature.
[0101] Liposomes as in the present embodiment, are composed of a bilayer of amphipathic molecules, the molecules are arranged in two concentric circles, such that the hydrophilic heads of the outer layer are exposed to the outer environment, and the hydrophilic heads of the inner layer make the inner hydrophilic core. The hydrophobic tails are tucked between the two layers.
[0102] In the present embodiment, elastic liposomes are microscopic vesicles having single or multiple phospholipid bilayers which can entrap hydrophilic compounds within their aqueous cores.
[0103] Elastic niosomes are composed of nonionic surfactants, ethanol and water. They are superior to conventional niosomes because they enhance penetration of a drug through intact skin by passing through pores in the stratum corneum, which are smaller than the vesicles. In fact, their elasticity allows them to pass through channels that are less than one tenth of their own diameter. Thus they can deliver ingredients or compounds of both low and high molecular weight. Furthermore, they can provide prolonged action and demonstrate superior biological activity compared to conventional niosomes. The transport of these elastic vesicles is concentration independent and driven by trans-epidermal hydration.
[0104] To deliver the molecules to sites of action, the lipid or niosome bilayer can fuse with other bilayers such as the cell membrane, thus delivering the liposome contents. By making liposomes in a solution of natural or synthetic ingredients that can effect a beneficial change to the skin, (which would normally be unable to diffuse through the membrane) they can be (indiscriminately) delivered past the lipid bilayer. A liposome or niosome vesicle does not necessarily have lipophobic contents, such as water, although, in the case of the present embodiment, it usually does.
[0105] The preferred phospholipid in the current process embodiment is naturally derived, for example phospholipids obtained from plant or animal sources. Natural phospholipids are purified from, e.g., soybean, rapeseed, and sunflower seed. The phospholipid may be salted or desalted, hydrogenated or partially hydrogenated or natural, semi-synthetic or synthetic.
[0106] Liposomes, niosomes and in general vesicles, are undoubtedly one of the most promising carriers in nano and micro cosmeceutical ingredient delivery. They are particularly important in the stratum corneum percutaneous transit field due to their great versatility respect to size, composition, surface characteristics, biocompatibility, biodegradability, low toxicity, capacity for entrapping and/or integrating hydrophilic and/or hydrophobic molecules and possibility of surface functionalization. Vesicles of the present process embodiment are spherical objects enclosing a liquid compartment, with a diameter ranging from 20 nm to a few thousand of nanometers, separated from its surroundings by at least one thin membrane consisting of a bilayer (unilamellar) or several layers (multilamellar) of amphiphilic molecules.
[0107] Sometimes the terms liposome, niosome and vesicle are used interchangeably, although a liposome is a type of vesicle composed mainly by phospholipids, a niosome as a non-ionic surfactant-based vesicle formed mostly by non-ionic surfactant and cholesterol incorporation as an excipient. Vesicles can be formed also by non-lipid building blocks, such as block co-polymers or cationic or non-ionic surfactants.
[0108] A liposome or niosome is an artificially-prepared vesicle composed of a lipid bilayer. The liposome or niosome can be used as a vehicle for administration of percutaneous skin nutrients and pharmaceutical drugs. Liposomes and niosomes are composed of natural phospholipids, and may also contain mixed lipid chains with surfactant properties (e.g., egg phosphatidylethanolamine). According to the present process embodiment, a liposome design may employ surface ligands for attaching to unhealthy tissue.
[0109] In the present embodiment, phospholipids have a propensity to form liposomes and niosomes, which can be employed as the cosmetic ingredient carriers. Phospholipids have good emulsifying property which can stabilize the cosmetic serum emulsions. In addition, phospholipids as surface-active wetting agents which can coat on the surface of crystals to enhance the hydrophilicity of hydrophobic ingredients. The above properties are successfully employed in the LPLTVs design.
[0110] As used herein, in the current embodiment example, the term “phospholipid” refers to compositions which are esters of fatty acids in which the alcohol component of the molecule contains a phosphate group as an integral part ( FIG. 2.0 ).
[0111] In order to extend LPLTVs (Low Pressure Low Temperature alternative construction of Vesicles) to the preparation of other kinds of vesicle systems taking full advantage of the possibilities offered by this process were also undertaken. Phospholipids-based formulations are widely used for delivery purposes and for this reason 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) was selected as a membrane component for the liposome preparation with LPLTVs.
[0112] Phospholipids comprise the glycerol-phosphatides, containing glycerol, and the sphingomyelins containing sphingosine.
[0113] According to the alcohols contained in the phospholipids, they can be divided into glycerophospholipids and sphingomyelins.
[0114] For the present embodiment, the use of Glycerophospholipids, which are the main phospholipids in eukaryotic cells, refer to the phospholipids in which glycerol is the backbone are preferred. All naturally occurring glycerophospholipids possess α-structure and L-configuration.
[0115] Preferred phospholipids used in the embodiment comprise phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine and sphingomyelin; and although not preferred, in the present embodiment, synthetic phospholipids comprising dimyristoyl phosphatidylcholine, dipalmitoyl phosphatidylcholine, distearoyl phosphatidylcholine, distearoyl phosphatidylglycerol, dipalmitoyl phosphatidylglycerol, dimyristoyl phosphatidylserine, distearoyl phosphatidylserine, and dipalmitoyl serine.
[0116] In the case of the present method embodiment, liposomes or niosomes are used as carriers for beneficial ingredients for the treatment of skin anomalies. Liposomes and niosomes can be made with different features can enhance an ingredients efficacy, reduce an ingredients toxicity, restriction from going systemic and prolong the ingredients therapeutic effect.
[0117] Niosomes are self-assembled vesicles composed primarily of synthetic surfactants and cholesterol. They are analogous in structure to the more widely studied liposomes formed from biologically derived phospholipids.
[0118] The type of epi-dermal activity resulting from the application of the current embodiment's content of natural or synthetic ingredients to be beneficial includes: Hydration • Skin lightening • Anti-wrinkle/skin smoothing • Antioxidant activity/free radical scavenger • Anti-inflammatory/anti-irritant • Collagen stimulation • Cell regeneration/stimulation • Sebum regulation • Anti-cellulite • Antimicrobial • Antibacterial.
[0119] With chronological age and chronic exposure to adverse environmental factors, (notably UVA, UVB, and IR radiation) the visual appearance, physical properties, and physiological functions of skin change in ways that are considered cosmetically undesirable. The most notable and obvious changes include the development of fine lines and wrinkles, loss of elasticity, increased sagging, loss of firmness, loss of color evenness (tone), coarse surface texture, and mottled pigmentation.
[0120] Less obvious, but measurable changes which occur as skin ages or endures chronic environmental insult include a general reduction in cellular and tissue vitality, reduction in cell replication rates, reduced cutaneous blood flow, reduced moisture content, accumulated errors in structure and function, and a reduction in the skin's ability to remodel and repair itself.
[0121] Many of the above alterations in appearance and function are caused by changes in the outer epidermal layer of the skin, while others are caused by changes in the lower dermis.
[0122] Regardless of the stimulus for skin damage, when damage occurs, numerous natural and complex biochemical mechanisms are set into motion in attempts to repair the damage.
[0123] The present embodiment relates generally to construct a process for a vesicle-driven treatment method and composition for improving the skin's visual appearance, function, and clinical/biophysical properties which have been changed by factors such as chronological age, chronic sun exposure, adverse environmental pollutants, household chemicals, disease pathologies, smoking, and malnutrition. In particular, the present embodiment relates to a process to create a method of treating skin by increasing the skin's stratum corneum transit of known beneficial ingredients through dynamic infusion of vesicles (DIV) generated from natural and biocompatible phospholipids with an aqueous volume enclosed within a lipid or niosome membrane.
[0124] The result of the present process embodiment is to deliver larger molecular weight, longer lasting, beneficial ingredients to areas of the epi-dermis depleted of needed vitamins, hydration, nourishment and complimentary ingredients need for the rejuvenation of elastin and collagen.
[0125] Now, in the current embodiment, comes the development of a new, single process, ingredient vesicle methodology based on a Low Pressure Low Temperature alternative construction of liposome or niosome Vesicles process (LPLTVs) for the direct, robust and scalable encapsulation of biomolecules in vesicles. The development of reproducible and scalable methodologies in order to functionalize those vesicles with targeting/protective units enabling greater selectivity of the therapeutic epidermal targets and therefore more effective treatments.
[0126] The use of the biomolecules-vesicles conjugates prepared by LPLTVs can be used in the treatment of different skin anomalies. The embodiments process uses milder conditions of pressure (<10 MPa) and temperature (<308 K) than previous methodologies based on CFs, allowing the processing of heat labile compounds and reducing the investment cost of a high pressure plant when the process is scaled-up.
[0127] The present embodiment encompasses compressed fluid-based methodologies (CF), also called dense gas technologies, for the production of lipid-based ingredient carrier systems with structural characteristics not reachable by already existing procedures using liquid organic solvents. In the present embodiment, we have improved the processing of vesicles and niosomes because they provide the ability to reduce the amount of organic solvent required by conventional methods and allow a better control over the final vesicle structural characteristics. Moreover compressed fluid processing offers sterile operating conditions and the ability for one-step production processes, which is convenient in transferring the technology to larger scale operations.
[0128] The present embodiment's compressed fluid technology was developed as a platform for producing lipid and niosome-based cosmetic ingredient carrier systems that can address most of the limitations of conventional methods.
[0129] LPLTVs methodology allows an easy and direct preparation of different liposome-biomolecule conjugates with micro and nano scopic sizes and great degrees of unilamelarity.
[0130] The stability time of the liposome-based conjugates is somewhat smaller than those of LPLT Vesicle-based conjugates. This stability is improved by the addition of stabilizing/targeting units to the formulation.
[0131] Bioactivity of the integrated biomolecules is unaffected under the processing conditions with CO2-expanded solvents.
[0132] Liposomes and Niosomes prepared by the current embodiment's process of LPLTVs, fulfill the structural and physio-chemical requirements to be a platform for the percutaneous delivery of synthetic or natural ACIs (active cosmeceutical ingredients).
[0133] Major advantages of the embodiment's application of CFs technology are that sterile and stable liposomal and niosomal formulations can be produced with minimum amounts of organic solvents.
[0134] In the case of blemished or compromised complexion of the skin the following properties could be desirable: • Sebum regulating • Anti-bacterial • Anti-inflammatory/anti-irritant • Soothing/calming • Skin healing and regeneration • uniform complexion • lightening and brightening.
[0135] These and other advantages will be apparent to individuals skilled in the art in view of the drawings and detailed description which follow.
[0136] Examples of some preferred preparation ingredients in the present embodiment include natural botanicals, those ingredients that that originates from plants, herbs, roots, flowers, fruits, leaves or seeds such as: aloe vera, almond oil, avocado oil, coconut oil, hazelnut oil, jojoba oil, olive oil, palm oil, pumpkin seed oil, sesame oil, sunflower oil, tamanu oil, candeia oil, arnica,
[0137] chamomile, oat extract, hibiscus flower, boswellia serratta, cocoa powder, green and white tea, gotu kola, chamomile extract, L-arginine, glutamine, pantothenic acid, white willow bark extract, tetrahydrocurcuminoids, alpha-arbutin, aloesin, alpha glucosyl hesperidin, niacinimide, fucoidan, magnesium asorbyl phosphate, azelaic acid, N-acetyl-D-glucosamine, glutathione, mulberry, pomegranate seed oil, cyprus rotund root extract, licorice, licorice-glabrin root extract, kojic acid, panax ginseng root extract, ginko bilbao, salicylic acid, Lauric acid, glycerin, caffeine, tocopheryl acetate, copper peptide, retinyl palmitate, asorbyl palmitate, wakame, dimethylethanolamine, beta glucan, triglyceride as well as hyaluronic acid (Hyaluronic acid is a natural and sugar-like biopolymer in the human body that alternately consists of D-glucuronic acid and N-acetyl-D-glucosamine-units).
[0138] Additionally, preferred natural polymers for the current embodiment such as starch, starch, xanthan or guar gum, carrageenan, alginates, polysaccharides, pectin, gelatin, agar, and cellulose derivatives can be used to this end. On the synthetic side, polyacrylate derivatives and polyacrylamide polymers can be incorporated in to the carrier system of the present embodiment. More recent developments include combining hydrophobic and hydrophilic polymers into block and star copolymers and thermally responsive systems.
[0139] Polymers are particularly susceptible to the construction of vesicle that can physically entrap the active component, preserving its biological stability, or the bioactive component can be incorporated chemically into a polymer chain or pendant group, then released through hydrolysis. For example, salicylic acid (an anti-acne ingredient) can be incorporated into the main chain of polyanhydride ester and released within a short time.
[0140] The current example embodiment also applies to the construction of vesicle encapsulated polymers that are routinely used in many personal care and cosmetic products.
[0141] The current embodiment takes advantage of the various properties of these polymers to impart unique benefits to their formulations. The range of properties is as varied as the class of polymers that have been utilized. Using polymers, cosmetic chemists can create high performance products. Broad spectrums of polymers; natural polymers, synthetic polymers, organic polymers as well as silicones are used in a wide range of cosmetic and personal care products as film-formers, emulsifiers, thickeners, modifiers, protective barriers, and as aesthetic enhancers.
[0142] A further embodiment features a method of making liposomes comprising forming a mixture of multilamellar vesicles and a CF. The mixture is decompressed to remove the CF to form one or more liposomes or niosomes.
[0143] Preferably, multilamellar vesicles are made by hydrating phospholipids in an aqueous phase. Preferably, the aqueous phase or the phospholipids contain a cosmeceutical therapeutic agent.
Example 1
Phase Behavior Studies for the Low Pressure Low Temperature Alternative Construction of a Liposome and Niosome Vesicles (LPLTVs)—CO2-Solvent System
[0144] Prior to liposome or niosome formation, the phase behavior and solubility of the chosen lipid in dense CO2 were investigated to verify the suitability of the lipid for dense gas processing and, in particular LPLTVs processing.
[0145] Knowledge of the threshold pressure for precipitation of lipid from solution is also a key factor for design of the LPLTVs process in order to determine the maximum pressure for the technique so that yield is enhanced and loss of lipid in the expansion chamber minimized. The solid state of 1,2 distearoyl-sn-glycero-3-phosphocholine (DSPC) was maintained when the lipid was exposed to CO2 below 350 bar at 50° C. and 150 bar at 70° C. The solubility of DSPC in pure CO2 at 50° C. and pressures up to 280 bar was considered negligible. The addition of 5 mol % ethanol co-solvent did not significantly improve the solubility of DSPC in CO2 at 50° C. and 250 bar. Use of higher pressures or larger amounts of organic solvent are undesirable, thus the results of the solubility study are in agreement with the literature in concluding that effects arising from poor solubility of lipids in dense CO2 are not easily overcome.
[0146] In prior art, at 50° C. and 250 bar, DSPC required the addition of 4.8% v/v ethanol as well as the use of a recycling system for homogeneous dissolution of the lipid in CO2. In the current embodiment, the use of the LPLTVs process eliminates the current limitations of dense gas techniques associated with solubilizing lipids using a supercritical fluid and simply utilizes a dense gas as an aerosolization aid. The threshold pressure for the precipitation of DSPC from a 10 mg/mL ethanol solution at 22° C. was 55 bar.
[0147] Precipitation was first observed at 58, 55, and 56 bar for the 5, 10, and 20 mg/mL solutions of DSPC and cholesterol (70:30 lipid to cholesterol weight ratio) in ethanol at 22° C., respectively. Therefore it can be seen that cholesterol had negligible effect on the threshold pressure. When the pressurization rate for the 5 mg/mL lipid/cholesterol solution was dramatically increased, precipitation was not observed until 60 bar was reached. A faster pressurization rate is preferable for the embodiments LPLTVs process in order to minimize the time requirement for each experiment. During this experiment, noticeable expansion only started to occur after 50 bar was reached. Solution expansion is desired to maximize the effect of utilizing CO2 as an aerosolization aid to disperse the lipid solutions throughout the aqueous phase. Therefore, the expansion pressure used in the LPLTVs experiments to avoid solute precipitation and enhance the yield for or niosome formation from ethanol solutions was between 50 and 55 bar at 22° C.
[0148] The threshold pressure for the precipitation of a 20 mg/mL DSPC/cholesterol chloroform solution (90:10 lipid/cholesterol weight ratio) at 22° C. was 41 bar. The solvent volume had significantly expanded (doubled) by the time 40 bar was reached in the chloroform experiments. Therefore, expansion pressures between 38 and 40 bar were used for the LPLTVs chloroform experiments to achieve maximum expansion without lipid precipitation.
Example 2
Effects of Process Variables on LPLTVs Operation
[0149] The effects of solute composition, solute concentration, type of solvent, nozzle diameter, type of aqueous media, temperature of vesicle formation chamber, and volume of dense gas used for spraying on both the ease of operation of the embodiments LPLTVs process and the product were investigated. The results obtained for liposome formation are summarized in Table 1. Preliminary trials were conducted to establish viable nozzle options for the LPLTVs system. A variety of nozzles were tested including 102, 178, 254, 508, and 1016 μm i.d. stainless steel tubing and 100 μm i.d. Peeksil tubing (polymer tubing with fused silica lining). The most suitable nozzle for the LPLTVs apparatus, to control the flow rate and prevent blockages, was the 178 μm i.d. stainless steel tubing. The 254 μm nozzle was used in Set 1 (Table 1); however, there were difficulties in controlling the flow rate and maintaining constant pressure in the expansion chamber. Other nozzle dimensions may be selected depending on the pump capacity and vessel dimensions.
[0150] The LPLTVs process of the present example embodiment is robust and, within the range examined, variation of solute concentration and composition, type of solvent, type of aqueous media, and volume of CO2 used for spraying had minimal effect on the operation of the LPLTVs process. The temperature of the vesicle formation chamber did, however, significantly affect the process since a smaller amount of liposomal product was obtained at 90° C. (Set 5) compared with 75° C. The smaller volume can be attributed to the aqueous medium being closer to its boiling point at 90° C., and thus some of the water was lost to the solvent trap via evaporation.
Example 3
Characterization of Liposomes Produced by the LPLTVs Process
[0151] The liposome morphology.
[0152] TEM (Transmission electron microscopy) was used to investigate the morphology of the particles produced in the embodiments LPLTVs process. At all conditions studied, submicron spheres were observed that possessed a similar structure to liposomes previously reported in the literature. The image shown in FIG. 5.0 indicates that spherical particles, generally ranging in size from 35 to 200 nm and more commonly 35-100 nm, were formed using the LPLTVs process. Images collected suggest that the liposomes were unilamellar. Not only were the spheres of a size range common to unilamellar liposomes, but in many images a single, thin wall can be seen at the edge of each particle. However, the arguments against positive identification of lamellarity using negative staining and TEM have been well documented in the literature. 18 Staining artifacts are difficult to identify and are often interpreted as unexpected morphologies. Confirmation that the particles formed were in fact liposomes was found by utilizing SANS (Small-Angle Neutron Scattering) to identify an aqueous core, as discussed below. The spherical particles shown in FIG. 5.0 are a general indication of the liposomes formed; however, some other features have also been observed. In several samples, a large quantity of smaller spherical particles (10-20 nm) was observed, which are at or below the lower size limit at which liposomes can be formed and may be considered as micelles. In some samples, small vesicles appear to be aggregated into or contained within a larger liposome vesicle, as shown in FIG. 6.0 .
[0153] A vesicle-in-vesicle structure may be formed in the last stage of the LPLTVs process due to liposomes forming in the presence of existing vesicles. However, the lipid vesicles are more likely to have formed into aggregate structures during the negative staining process in order to minimize any deleterious effects when the aqueous phase was removed or to minimize the interactions of the lipid with the stain. The artifact of these aggregated systems could also result from a larger vesicle superimposed upon smaller vesicles, which is a common feature in TEM analysis. The particle size and morphology of the LPLTVs liposomes was not significantly changed within the range of process parameters varied. However, rods or coffee bean morphology (liposomes exhibiting a characteristic ‘coffee-bean’ appearance due to the presence of an inner structure apparently separating the LUV into two sections) appeared in a few samples in addition to spherical particles, as shown in FIG. 7.0 . It is suggested that the coffee bean morphology was formed due to the collapse of vesicles, predominantly for the smaller particles. This effect can be attributed to the lower stability of small vesicles due to the high curvature of the membrane.
[0154] The unilamellar liposomes produced using a conventional technique were stained with ammonium molybdate with and without the presence of protein. The images of the liposomes stained without protein showed “cup-like structures” and vesicles consisting of two lipid membranes. When protein was included in the staining process, the images showed vesicles consisting of a single lipid bilayer.
[0155] In the present embodiment, it is concluded that the liposomes in both images were unilamellar and that the vesicles had collapsed in the absence of protein. The double membrane feature can therefore be explained by the thick edge of the collapsed sphere, and the “cup-like structures” can be observed if the collapsed spheres are rotated.
[0156] The correct choice of vesicle or niosome preparation method in the current embodiment depends on the following parameters: the physicochemical characteristics of the material to be entrapped and those of the liposomal or niosomal ingredients; the nature of the medium in which the vesicles are dispersed; the effective concentration of the entrapped substance and its potential toxicity; additional processes involved during application/delivery of the vesicles; optimum size, polydispersity and shelf-life of the vesicles for the intended application; and, batch-to-batch reproducibility and possibility of large-scale production of safe and efficient liposomal products.
[0000]
TABLE 1
Summary of the Conditions Investigated and the Results Obtained for Producing Liposomes via the embodiments of the LPLTVs Process.
set
1
2
3
4
5
6
7
8
9
nozzle diameter
254
178
178
178
178
178
178
178
178
(μm)
solute lipid
70
70
90
90
90
90
90
90
90
content (% w/w)
solute conc.
20
20
20
5
20
20
20
20
20
(mg/mL)
VFC temp.
75
75
75
75
90
75
75
75
75
(° C. ±2.5)
CO 2 spraying
200
200
200
200
200
50
200
200
200
vol. (mL)
aqueous media
RO H 2 O
RO H 2 O
RO H 2 O
RO H 2 O
RO H 2 O
RO H 2 O
DI H 2 O
TBS
RO H 2 O
organic solvent
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
Chlfm
effective diameter
156 ± 2
166 ± 5
121 ± 1
152 ± 23
207 ± 75
122 ± 2
119 ± 3
143 ± 5
3 7 ± 64
(nm)
polydispersity
0.27 ± 0.001
0.27 ± 0.01
0.15 ± 0.01
0.19 ± 0.01
0.18 ± 0.01
0.15 ± 0.01
0.17 ± 0.02
0.18 ± 0.02
0.29 ± 0.03
product lipid
75.2 ± 1.9
77.3 ± 1.8
82.4 ± 0.4
76.1 ± 0.1
81.8 ± 0.5
80.5 ± 0.2
80.9 ± 0.3
80.1 ± 0.6
81.8 ± 1.3
content
(% w/w)
residual solvent
3.1 ± 0.4
1.6 ± 0.8
1.4 ± 0.4
2.2 ± 0.3
1.9 ± 0.7
3.9 ± 0.2
1.8 ± 0.4
2.0 ± 0.8
0.4 ± 0.3
(% v/v)
* VFC: vescile formation chamber; RO H 2 O: water purified via reverse osmosis; DI H 2 O: deionized water: TBS: TRIS buffered saline; EtOH: ethanol: Chlfm: chloroform.
indicates data missing or illegible when filed
[0157] Collapsed spheres were present in all LPLTVs samples; however, rods or “coffee bean” particles were rare except in those samples from Sets 1 and 2, where a higher proportion of cholesterol was used compared with other samples.
[0000]
TABLE 3
SANS Fitted parameters for the LPLT liposome sample
fitted parameter (Å −2 )
value
core SLD
6.30 × 10 −5
shell SLD
3.85 × 10 −5
solvent SLD
6.82 × 10 −5
[0000]
TABLE 2
The calculated SLD for the components
LPLT Vs of the LPLT Vs liposome samples
material
SLD (×10 − Å −2 )
H 2 O
−0.56
D 2 O
6.33
hydrocarbon chain (CH 2 )
−0.44
cholesterol (C H OH)
0.21
lipid headgroup (C H O NP)
1.12
indicates data missing or illegible when filed
[0158] Cholesterol was incorporated in order to improve stability, and it has been reported in the literature that the incorporation of cholesterol causes larger liposomes or niosomes to form.
[0159] However, the rod-shaped particles were at the smaller end of the size range for the LPLTVs. Comparison of images from a number of samples indicated that the presence of rods may be promoted by the level of stain as well as the size of the vesicles. It is therefore also possible that the relative proportion of rods found in Sets 1 and 2 was amplified by the staining process. Because of the improved spherical morphology observed in Set 3, the experiments were carried out using a preferred lipid/cholesterol ratio of 90:10.
Advantages of the Current Embodiments LPLTVs Process for Bulk Liposome or Niosome Vesicle Formation.
[0160] The LPLTVs process has many advantages over conventional liposome or niosome formation techniques. These advantages include the fact that it is a simple and rapid process for bulk production of unilamellar liposomes or niosomes. A conventional liposome standard was produced, and the formation process took almost 24 h and multiple stages to complete. The embodiments LPLTVs process produced a greater volume of the same formulation in less than half an hour, clearly demonstrating the dramatic reduction in processing time.
[0161] The conventional ethanol and ether injection methods exhibit some similarities to the embodiments LPLTVs process since they involve the dissolution of a lipid into an organic phase, followed by the injection of the lipid solution into aqueous media forming liposomes. The drawbacks of the ethanol injection method as opposed to the examples of the present embodiment, are the poor homogeneity of the vesicles if there is not adequate mixing and the residual solvent levels in the product.
[0162] Either injection method eliminates the residual solvent issue by having a heated aqueous phase, but is a time-consuming technique. It has been suggested that injecting the ether solution at a rate faster than 0.2 mL/min can cause cooling of the aqueous phase due to evaporation, and that pre-evaporation of ether can cause nozzle blockages and the formation of multilamellar vesicles. The LPLTVs process of the present embodiment for the formation of liposomes or niosomes formed around cosmeceutically benevolent ingredients has significant advantages over both the ethanol and ether injection methods since the depressurization from a high pressure environment creates outstanding dispersion of the lipid solution and mixing with the aqueous environment. The incorporation of both heating and dense gas washing enables the solvent to be efficiently removed. The LPLTVs process can also produce an equivalent volume of product in a significantly reduced time span. Compared with other dense gas processes developed for liposome formation, the LPLTVs process is beneficial due to its simplicity and the incorporation of residual solvent removal measures into the method. The LPLTVs process also operates at pressures generally less than 60 bar and moderate temperatures, therefore making the process more cost-effective and avoiding the concerns of uncontrollable foam formation present in the low pressure liposome method. A significant advantage of the LPLTVs process is that it can be used to process a broad range of materials since there is no requirement for the compound to be solubilized in the dense gas and there are no high shear forces. Furthermore, time-consuming solubility studies and recycling loops for lipid solubilization are not needed. The only preliminary investigation required is the determination of the threshold pressure for precipitation of the solutes from expanded solution, such that the solution expansion can be carried out without precipitation.
[0163] In the LPLTVs process of the current embodiment, the entrapment of hydrophilic compounds may be achieved through the dissolution of the target compound into the aqueous media prior to release of the lipid solution. The liposomes or niosomes would then form, entrapping the hydrophilic or hydrophobic compound within the aqueous interior of the vesicle.
[0164] To entrap a hydrophobic, hydrophilic, lipophilic, or amphipathic compound into liposomes or niosomes using the LPLTVs process, the compound is dissolved along with the phospholipid and other solutes in the liquid solvent.
[0165] The compound then becomes entrapped within the phospholipid membrane as a result of the affinity of the compound for the membrane rather than the aqueous phase.
[0166] The suitability of the LPLTVs process for entrapping hydrophobic compounds has already been demonstrated through incorporating up to 25% w/w cholesterol into the liposome formulation. The LPLTVs technique can also be applied to the formation of structures other than liposomes. Micro particles of hydrophobic compounds could be produced through precipitation into aqueous media in the LPLTVs process.
[0167] Liposomal Particle Size Distribution and Stability. Photon correlation spectroscopy (PCS) was used to assess the particle size distribution of the liposomal population using the Brookhaven ZetaPlus. Each liposomal sample was diluted in RO or DI water and placed in a disposable polypropylene cuvette. Ten runs, each of 1 min duration, were conducted at 23-25° C. for each sample. A laser wavelength of 678 nm was used with a destination angle of 90o. The dust cutoff was set between 20 and 50 μm. The instrument calculates an effective diameter for each run and an overall effective diameter for the 10 runs combined. The effective diameter is the mean diameter that is calculated by the following equation:
[0000]
Effective
diameter
=
(
1
d
k
)
-
1
=
∑
i
N
i
d
i
6
P
i
∑
i
N
i
d
i
5
P
i
[0168] Where Ni refers to the number per scattering volume of the ith particle, and Pi accounts for angular scattering effect for particles larger than λ/20. Pi is calculated using Mie theory and requires the particle refractive index; however, for Rayleigh scatters and at sufficiently low angles, Pi=1 is used in the program.
Example 4
A Formulation for the Treatment of Acne Made Using the Current LPLTVs Embodiment
[0169] A solution for treating Acne vulgaris or Propionibacterium acnes containing lipids formed of the following ingredients utilizing the science of the present embodiment may be formulated using the constructed phospholipids of the following volumes;
[0170] D.I. water 50% to 95% (preferably 60 to 90%, ethanol 15 to 40% (preferably 25 to 30%), hyaluronic acid 5 to 50% (preferably 12 to 18%) propanediol 10 to 80% (preferably 20 to 25%), aloe vera 0.2 to 20% (preferably 0.5 to 5%), azelaic acid 2 to 50% (preferably 4 to 8%), salicylic acid 0.2 to 20% (preferably 0.5 to 5.0%), lauric acid 0.2 to 20% (preferably 0.5 to 5.0%), asorbyl palmitate 0.1 to 20% (preferably 0.2 to 8%) niacinimide 0.2 to 20.0% (preferably 0.5 to 5%), lecithin 0.2 to 10% (preferably 0.5 to 5.0%), glycerin 0.5 to 25% (preferably 2 to 10%), caffeine 0.2 to 20% (preferably 0.5 to 10%)
Example 5
A Formulation for the Enhanced Hydration and the Reduction of Fine Lines and Wrinkles Made Using the Current Embodiment
[0171] A solution for treatment of lack of skin hydration and the reduction of fine lines and wrinkles containing lipids formed of the following ingredients utilizing the science of the present embodiment may be formulated using the constructed phospholipids of the following volumes; D.I. water 50% to 95% (preferably 60 to 90% ethanol 15 to 40% (preferably 25 to 30%), hyaluronic acid 5 to 50% (preferably 12 to 18%) propanediol 10 to 80% (preferably 20 to 25%), aloe vera 0.2 to 20% (preferably 0.5 to 5%), hexa-peptide 8 2% to 50% (preferably 5% to 20%), caffeine 0.2 to 20% (preferably 0.5 to 10%), glycerin 0.5 to 25% (preferably 2 to 10%), tocopheryl acetate 0.1 to 10% (preferably 0.5 to 8%), retinyl palmitate 0.1 to 10% (preferably 0.5 to 8%), asorbyl palmitate 0.1 to 20% (preferably 0.2 to 8%), Copper tri-peptide GHK-Cu 0.1 to 20% (preferably 0.2 to 8%), hesperidin 0.1 to 20% (preferably 0.2 to 8%), dimethylethanolamine (DMAE) 0.05 to 20% (preferably 0.08 to 8%), sesame oil 2 to 50% (preferably 3 to 20%) beta glucan 0.1 to 20% (preferably 0.2 to 8%)
Test 1
LPLTVs Method for the Preparation of Hyaluronic Acid-Rich Vesicles
[0172] The present embodiment is based on the use of compressed CO2 in a process called LPLTVs for the production of micron-sized and submicron-sized crystalline particles from an organic solution. As novelty the process used the CO2 as co-solvent being completely miscible at a given pressure and temperature with a specific solution of an organic solvent containing the solute to be crystallized. In order to take full advantage of compressed fluid processing without using severe working conditions a novel and improved procedure based on the LPLTVs process was developed. This method, named as LPLTVs (Low Pressure Low Temperature alternative construction of Liposome Vesicles), enabled the preparation of cholesterol rich-hyaluronic acid vesicles. The process uses milder conditions of pressure (<10 MPa) and temperature (<308 K) than the previously described methodologies based on CFs, allowing the processing of heat labile compounds and reducing the investment cost of a high pressure plant when the process is scale-up. Using this procedure, homogeneous nanovesicles composed of hyaluronic acid, cholesterol and the cationic surfactant CTAB (cetyltrimethylammonium bromide, in a molar ratio 1:1, were prepared by depressurizing a volumetric expanded organic solution containing the cholesterol and hyaluronic acid over a flow of an aqueous solution containing the CTAB surfactant ( FIG. 5.0 ). An alternate non-ionically formed elastic noisome can be constructed using the same apparatus.
[0173] During the depressurization step, the expanded organic solution experiences a large, abrupt and extremely homogenous temperature decrease produced by the CO2 evaporation from the expanded solution. This explains the obtaining of homogenous vesicles regarding size, lamellarity and morphology.
[0174] In order to prepare any vesicular system using LPLTVs is necessary that the lipids forming the membrane are completely soluble in the CO2-expanded organic solvent, presenting one phase at the working conditions of pressure, P w, temperature, T w and CO2 molar fraction, X2. Therefore for the preparation of cholesterol rich-hyaluronic acid vesicles by LPLTVs method is always necessary to analyze the solubility behavior of the used sterol in CO2-expanded solvents, by means of a detailed phase diagram study, like the one showed in FIG. 6.0 .
[0175] An important prerequisite for the effective use of vesicles as a cosmeceutical ingredient carrier as described above is to control their stability, which can be defined as the extent to which the carrier retains its ingredient contents either in vitro or in vivo studies. One of the major disadvantages when using classical vesicles based on phospholipids, is the leakage of the encapsulated ingredient during their storage. One variant that can enhance the retention of drugs and promote the stability of liposomes or niosomes is the presence of hyaluronic acid in the formulation. Another variant is the preparation of liposomes from non-phospholipid amphiphiles, such as surfactants or polymers.
[0176] This kind of vesicular formulations show low passive leakage in comparison to liposomal systems based only on phospholipids and therefore a higher retention of the encapsulated materials, as for example epi-dermal therapeutically active molecules.
[0177] In the present example embodiment for the preparation of positively charged vesicles composed by cholesterol, hyaluronic acid and the cationic surfactant hexadecyltrimethylammonium bromide (CTAB). More recently nanoscopic vesicles, composed by different sterols and other quaternary ammonium surfactants have been also successfully prepared. This is why it was decided to name this kind of formulations as LPLTV (low pressure low temperature vesicles) that are stable for periods as long as several years, their morphology do not change upon rising the temperature or by dilution and they show a great homogeneity regarding size and morphology.
[0178] Studies at molecular level of the self-assembling of cholesterol hyaluronic acid and CTAB molecule in aqueous medium showed that a pure vesicular phase is only formed at equimolar ratios of both components. Moreover molecular dynamic (MD) simulations revealed that the cholesterol, hyaluronic acid and the CTAB self-assemble in a unique bimolecular synthon that can be considered as a single entity which further self-assembles in particularly stable vesicles ( FIG. 7.0 ) ( FIG. 10 ). Moreover, MD simulations have provided a theoretical support to justify the experimental high thermal stability and the exceptional morphological properties attributed to cholesterol, hyaluronic acid/CTAB vesicles at 1:1 molar ratio.
Test 2
Analysis of Active and Placebo Tape Strips from an In-Vivo Study of Skin Permeation of 800 KDa Hyaluronic Acid Using the Embodiments LPLTVs Formation Process
Introduction:
[0179] The test was to extract and analyze tape strips and blanks from an in vivo tape stripping study of 800 KDa Hyaluronic Acid skin penetration transport.
[0180] HA distribution in stratum corneum (SC) layer was investigated. Distribution in SC was studied using a tape-stripping method.
Methods:
[0181] Each tape sample will be extracted individually by extraction solvent: 1×PBS with 0.2% NaN3/acetonitrile (50/50 v). Samples with extraction solvent were vortexed at high speed for 1 minute followed with centrifugation at 12,000 rpm for 10 minutes (chill the samples on ice at 4° C. and then centrifuge). The supernatant solution was then collected from each tube/container and stored at 4° C. and ready for analysis.
Outcome:
[0182] See the chart in FIG. 11.0 showing Hyaluronic Acid levels in active and control samples.
[0183] Abstract of the Disclosure is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed embodiment. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separate embodiment. | The skin serves as a barrier that protects the body from the external environment and prevents water loss. This barrier function also prevents most hydrophilic or hydrophobic and large molecular weight ingredients (>500 kDa) from penetrating intact skin. Until recently, methods to increase stratum corneum permeability were generally not effective enough to make the stratum corneum so permeable that the barrier posed by the viable epidermis mattered. However, that has now changed with the development of the present embodiment's physical methods and highly optimized chemical formulations, such that we revisited the permeability of the full epidermis with the example embodiment's constructs and not focus only on the stratum corneum. This example embodiment therefore tests the hypothesis that the viable epidermis offers a significant permeability barrier to both small molecules and macromolecules that becomes the rate limiting step. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to stitch length control mechanism for a sewing machine.
2. Description of the Prior Art
Sewing machines are commonly provided with stitch length control mechanism. Such mechanism may include a stitch length control lever in association with a pivoted lever which is spring biased against a camming surface on the stitch length control lever and operably connected to feed regulating mechanism of the kind shown for example in U.S. Pat. No. 3,527,183, of Jan Szostak for "Work Feeding Mechanism for Sewing Machines", issued Sept. 8, 1970. The stitch length control lever may then be used to selectively position the spring biased lever and thereby control operation of the feed regulating mechanism. However, the feed regulating mechanism in such an arrangement tends to impart vibrational movements to the spring biased lever. This causes the spring biased lever to impact repetitevely against the stitch control lever and produce an unacceptable amount of noise.
It is a prime object of the present invention to eliminate objectionable noise in stitch length control mechanism for a sewing machine.
It is another object of the invention to dampen impact noise in a sewing machine between a stitch length control lever and a pivoted spring biased lever which is operably connected to feed regulating mechanism in the machine.
Other objects and advantages of the invention will become apparent during a reading of the specification taken in connection with the accompanying drawings.
SUMMARY OF THE INVENTION
A sewing machine according to the invention includes feed regulating mechanism, a pivoted lever operably connected with the feed regulating mechanism, a stitch length control lever, and a spring which biases said pivoted lever toward the stitch length control lever. The stitch length control lever includes a low friction plunger with a camming surface which engages the spring biased lever, and which, in response to movement of the stitch length control lever, positions the spring biased pivoted lever to control operation of the feed regulating mechanism and thereby stitch length. The stitch length control lever is provided with a resilient shock absorber under the plunger to dampen vibrations of the spring biased pivoted lever as occassioned by operation of the feed regulating mechanism.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view showing stitch length control mechanism according to the invention;
FIG. 2 is a top plan view of a stitch length control lever according to the invention;
FIG. 3 is an elevational view of the stitch length control lever;
FIG. 4 is a sectional view on the plane of the line 4--4 of FIG. 2 showing a cam assembly for use on the stitch length control lever; and
FIG. 5 is an exploded perspective view of the cam assembly.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, reference character 10 generally designates a sewing machine including a bed 12, a standard 14 rising from the bed, and a bracket arm 16 projecting from the standard to overhang the bed. The bracket arm terminates in a sewing head 18 wherein a needle bar 20 having a needle 22 attached thereto is supported for endwise reciprocation in a needle bar gate 24. The gate is preferably mounted for pivotal movement in head 18 to accommodate lateral jogging of the needle 22 by bite controlling mechanism which may be of the type shown for example, in U.S. Pat. No. 4,188,895, of R. E. Johnson for "Needle Bight Control Mechanism", issued Feb. 19, 1980. Conventional needle bar driving mechanism (not shown) for imparting endwise reciprocation to the needle operably connects through a timing belt 26, sprocket 28, bed shaft 30 and bevel gears 32 and 34 with a looptaker 36 which is driven in timed relation to the operation of the needle.
Work is movable under the needle 22 by a feed dog 38 which is controlled by feed regulating mechanism of the type disclosed in U.S. Pat. No. 3,527,183, of Jan Szostak for "Work Feeding Mechanisms For Sewing Machines". As shown, such feed regulating mechanism includes a feed bar 40 which is mounted at shafts 42 and 44 so that it may be oscillated in mutually perpendicular directions to impart vertical and horizontal motion to the feed dog, the feed dog being carried by a bracket 46 that is secured to a pivot pin 48 journalled in the feed bar. The feed regulating mechanism also includes a shaft 50 which is driven by bed shaft 30 through gears 52 and 54, a lift cam 56, a feed advance eccentric 58 in a pitman 60, a slide block 62, and a feed regulating block 64. The lift cam imparts vertical motion to the feed bar through a bifurcated lever 66, a link 68, and a pin and boss assembly indicated generally by reference numeral 72. Transverse motion is imparted to the feed bar by means of the feed advance eccentric 58, pitman 60, a pivot pin 74, slide block 62, feed regulating block 64 and a link 76. Such transverse motion, and therefore stitch length as well as feed direction, is determined according to the position of feed regulating block 64. The block is positionable by a lever 78 acting through links 80 and 82, and a rock shaft 84 to which the block is affixed. Lever 78 is positionable by a stitch length control lever 86.
As shown, lever 78 is pivoted at 88 on a bracket 90 which is affixed in the bed of the machine with a screw 92. A spring 94 having one end 96 restrained in the machine, and the other end 95 affixed in a collar 97 which is attached to rock shaft 84 biases lever 78 downwardly into engagement with a camming surface 98 which is fixedly located on the stitch length control lever 86. The camming surface 98 is formed on the head 100 of a plastic plunger 102 which is located in a carrier 104 having a recess 106 on the underside thereof. The carrier straddles control lever 86 at recess 106 and is secured thereto with a resilient strap 108. Plunger 102 extends into a well 110 in carrier 106, as shown, and is resiliently supported therein by two O-rings 112 and 114 of elastomeric material located under head 100 and extending about the neck 116 of the plunger. A bifrucated enlarged end 118 of neck 116 extending through a restricted opening 120 in the carrier retains the plunger 102 in well 110.
Stitch length control lever 86 is pivoted at one end under a spring 121 on the shoulder 122 of a screw 124 which is affixed in a platform 125. The opposite end of the lever 86 carries a knob 126 for use in moving the control lever about its pivotal axis, which is perpendicular to the pivotal axis of lever 78, to position camming surface 98 along the length of an engaging curvilinear undersurface 128 of spring biased lever 78. By pivotally moving control lever 86, an operator can select a position for lever 78 and thereby control the operation of the feed regulating mechanism to determine stitch length. The length of the stitch length control lever between its pivotal axis and camming surface 98 is of a length which is sufficient to prevent disengagement of surfaces 98 and 128 throughout control movements of lever 86.
Vibrational forces are imparted to lever 78 by the feed regulating mechanism during operation of the machine, and cause the lever to impact against camming surface 98 on plunger 102. However, undue noise resulting from such impacts is prevented both by operation of the plunger and by the sound deadening nature of the materials used in the plunger, O-ring assembly. The plunger is of a plastic material, such as "Delrin" or "Celcon", having a low friction coefficient enabling the plunger head 100 to slide easily on the wall of well 110 in carrier 104, and camming surface 98 to be moved with little frictional resistance across the undersurface 128 of lever 78; whereas the O-rings 112 and 114 are of an elastomeric shock absorbing material such as rubber or a urethane plastic, and as such resist downward movement of the plunger in well 110 to dampen the vibration of lever 78.
It is to be understood that the present disclosure relates to a preferred embodiment of the invention which is for purposes of illustration only and is not to be construed as limiting the invention. Numerous alterations and modifications of the structure herein disclosed will suggest themselves to those skilled in the art, and all such modifications and alterations which do not depart from the spirit and scope of the invention are intended to be included within the scope of the appended claims. | Vibrational movements of a spring biased lever, which is selectively positionable by a stitch length control lever and controls the operation of feed regulating mechanism in a sewing machine accordingly, are dampened by the operation of a plunger that is carried by said control lever and has a camming surface thereon to engage and lift the spring biased lever when the control lever is moved. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to teeth, and more particularly to a method for replacing natural teeth with synthetic teeth.
Generally, teeth consist of three regions: an exposed portion, the crown; a root, which embeds in the jawbone; and a slightly constricted neck at the gum level. The three layers of a tooth are the dentin, which makes up most of the tooth; a hard enamel, which covers the dentin of the crown; and the pulp, composed of connective tissue rich in nerves and blood vessels. These vessels and nerves enter and leave the tooth through the apical foramen. The periodontal membrane lines the tooth socket and secretes the bony cementum that holds the tooth in place.
When such teeth are removed and replaced, it is generally a lengthy and costly procedure in which the individual is usually without the use of any permanent teeth. The cost of such dental procedure is most times too expensive and those needing a tooth or teeth replaced have to go without or have inexpensive and, most times, insecure, sloppy-fitting teeth to replace their natural teeth.
Thus, it is an object of this invention to provide a means of replacing removed teeth with secure, effective teeth, in a short time, almost immediately, at little cost. These teeth effectively replace original teeth so that one ca be assured of good looking, strong teeth.
SUMMARY OF THE INVENTION
A method for installing a synthetic tooth composed of a crown and flexible plastic sack secured thereto that is arranged to fit securely in the socket of a removed tooth. The method comprises:
(a) heating the flexible sack to a state where such is able to be conformed with the walls of the tooth socket;
(b) placing the crown and heated sack over the socket;
(c) injecting air through a valve opening of the crown to expand the heated sack snugly in the socket;
(d) venting any air/liquid build-up in the bottom of the tooth socket; and
(e) injecting a heated plastic material through a second crown valve opening to fill the sack and form a solid tooth in the socket, whereby the tooth is secure in the socket of the removed tooth.
DRAWINGS
The present invention will be better understood by considering the following drawings with the detailed description below. The drawings are:
FIG. 1 is a perspective view of a clamp arranged around the socket into Which a synthetic tooth will be placed according to the present invention;
FlGS. 2A and 2B illustrate, respectively, two-component, back and front, synthetic teeth according to the present invention;
FIGS. 3A and 3B illustrate, respectively, single-component back and front synthetic teeth according to the present invention;
FIG. 4 is a side-elevational view of a synthetic tooth of the present invention positioned over the socket of a removed tooth;
FIG. 5 is an elevational view of the sYnthetic tooth of FIG. 4 illustrating the flexible sack and its air/liquid venting means, and where the flexible sack is being expanded in various degrees to conform with the socket of the removed tooth; and
FIG. 6 is an elevational view of the synthetic tooth of FlGS. 4 and 5 fully constructed and secured in the socket of the removed tooth.
DETAILED DESCRIPTION OF THE INVENTION
The synthetic teeth of this invention are constructed in a way that renders them to have the same form as natural teeth with better durability and performance, and these synthetic teeth, according to the present invention, are able to be constructed and placed in the socket of a removed tooth with ease and in a very short period of time after the natural tooth is removed.
And, the cost for such procedure is at a substantial savings for the individual. The cost is generally about one-tenth the cost today for replacing a removed tooth. According to the present invention, an important and necessary feature for individuals is that they can have a fully effective tooth replacing the removed tooth in a fraction of the time needed today. The new functioning tooth may be placed securely within the socket in less than about one-half hour.
According to the present invention, the replacement tooth, i.e., the crown and sack to be conformed to the socket of the removed tooth is generally made in one process out of the same material. The crown and flexible sack may be made separately out of different materials and sealed together to be conformed and filled in the socket of the removed tooth. Also, it is intended by this invention that a removed tooth may be replaced long after it has been removed, as well as immediately after being removed. This may require some minor surgery by the dentist to remove the skin and flesh covering the socket of the removed tooth.
In the event the socket walls are damaged or the socket is too shallow, the socket may be opened wider and/or deeper with grooves in the socket wall by known dental procedures.
In the process of making a crown and flexible sack in one unit, a particular plastic material may be die-casted to form the crown and the flexible sack in one unit. AccordinglY, the crown is a thicker portion of this plastic material, whereas the flexible sack is a thinner portion of this material which can be heated to conform to the walls of the socket of the removed tooth.
When making the single-component, synthetic tooth, i.e., a crown and flexible sack, the open ends of the sack will be sealed and cut to be conformable with the socket of a removed tooth. Before the flexible sack has its cut-off ends sealed, an air/liquid venting means by its by its tubing and head is placed in the bottom of the sack and sealed.
According to the present invention, the flexible sack is preferably made out of a plastic material that can be heated to become flexible to conform with the socket of the removed tooth and when cooled, it will adhere to and be compatible with the socket walls.
As indicated above, the flexible sack, before being used, is cured with the crown in the die-cast. Just before use, the flexible sack is heated to be able to be conformed to the socket of the removed tooth.
The synthetic tooth made according to the present invention is comprised of a crown, a flexible sack securely sealed to the crown and filled with a plastic material to conform with any shape and form of a tooth socket.
Referring to FIG. 1, there is a socket (18) of a removed tooth where a clamp (8) is arranged around the socket (18) into which the synthetic tooth (10) is to be placed. As shown in FIG. i, the clamp (8) is attached to the teeth surrounding the socket (18) and the upper (30) or lower (28) jawbone.
As shown in FIG. 4, the crown (12) of the synthetic tooth (10) is secured within the clamp (8) after a satisfactory bite test is made for the tooth (10). In order to flex and conform the sack (14) with socket walls (20), the crown (12) has an air pressure intake control valve (13) for the air to flex and inflate the sack (14) and hold the air pressure until the sack (14) is hardened.
In order to prevent the air pressure and liquid build-up in the bottom of the tooth socket, it is necessary to provide the flexible sack and tooth with an air/liquid venting means as shown in FlGS. 4, 5, and 6.
As shown in FIGS. 4, 5, and 6, the air/liquid venting means (40) includes for each root of the removed tooth a tubing (42) having a head (44) sealed in the bottom of the sack (14), and a tubing opening.
After the sack (14) is hardened, the overflow valve (15) is opened to release the air. Then, a liquid plastic material is funneled through the control valve (13) to fill entirely the hardened sack (14). The overflow plastic material exits through the overflow valve (15).
After the air and liquid build-up has been vented, the tubing (42) is temporarilY plugged, and then, when the tooth socket is satisfactory to the dentist, the tubing is permanentlY sealed in a manner similar to a root canal.
The tubing (42) may be made of any suitable plastic material.
Referring to FlG. 5, the heated flexible sack (14) is expanded and inflated by air pumped through the control valve (13). As shown by the expansion lines (25), the sack (14) is inflated and expanded to conform with the socket and walls (20) of the removed tooth.
As shown in FlGS. 2A and 2B, the teeth used in the present procedure may be a two-component unit in which the flexible sack (14) and crown (12) are made of different materials and secured together at points (17), (19), (21) and (23).
The crown (12) may be made of a material selected from the group consisting of a plastic, iron, gold, silver, titanium, and porcelain. And, the flexible sack may be made out of any plastic material which can be expanded to fill all sockets of removed teeth, securely adhere to the walls of the sockets, and which is compatible with the walls of the sockets of the removed tooth.
The tooth (10) of FlG. 2A may be used to replace removed molars, whereas the tooth (10) of FIG. 2B may be used for incisor and canine teeth.
The teeth shown in FIGS. 3A and 3B are examples of teeth that are a one-component unit that may be used to replace, respectively, molars and incisors. The teeth of FIGS. 3A and 3B may be made of the same material for both the crown (12) and sack (14).
As indicated bY FIG. 6, after the liquid plastic has hardened and set in the sack (14) of the tooth, the clamp (8) is removed. The overflow from valve (15) is ground off and the intake valve (13) is filled and both areas are smoothed down and polished to conform with the rest of the tooth.
According to the present invention, the synthetic tooth described herein maY be treated as, and will perform as well as, if not better, than the natural tooth it will replace. That is, the tooth may be ground, cleaned, polished, reworked with plastic materials, and will be stronger and less destructible than a natural tooth.
The teeth (i.e., crown and sack) of this invention may be made of any material that is approved by the Dental Society. The flexible sack should be made of a material that is flexible, able to set on cooling, and one that is compatible with the walls of the tooth socket. | A synthetic tooth for replacing an actual tooth by inserting a flexible crowned member into the socket of the removed tooth. The synthetic tooth is conformed to the tooth socket and filled to replace the actual tooth therein. | 0 |
The present invention relates to a process for obtaining and to a new protein capable of being biotinylated in ripe seeds of plants belonging to leguminous, carrot and beet species and to its use as a molecular marker of the germination of these seeds.
BACKGROUND OF THE INVENTION
Germination is a complex development process for which there is currently available only a small amount of specific molecular data. This development programme, during which the cells of the embryo pass from a resting state to a state of intense metabolic activity, essentially begins during the imbibition phase. It ends, in the physiological sense, in the piercing of an organ of the nascent plantlet through the coats of the seed, Bewley et al. (1983).
The main techniques used to define the competence of seeds to germinate use conventional germination tests, that is to say that, for a given batch of seeds and under codified conditions (temperature, humidity, light, substrate), the percentage of germination at various times after sowing is measured. The criterion generally used to quantify the germination is the piercing of the coat of the seeds by an organ of the nascent plant. The majority of biochemical markers described to date are correlated with this phase. It therefore does not concern markers sensu stricto of germination but rather of the initial phases of growth (Fincher, 1989). For the moment, only a single example of an early marker is well documented. It relates to germine in cereals, a protein of the embryo, whose kinetics of appearance very closely follow the kinetics of imbibition (Lane et al., 1992). It should be noted that the initial imbibition phase is reversible up to a certain point. Following a controlled hydration of seeds, it is possible to dry them while retaining their biological integrity and their germinating ability. As soon as the plantlet appears, the commitment of the latter to its growth becomes irreversible. In fact, a dehydration at this stage irremediably leads to the death of the plantlets (Bewley & Black, 1983).
The pre-germination ("priming") processes developed by seed companies are based on the reversibility of the initial imbibition phase. The seeds are generally hydrated in a controlled way and are then dried (Karsen et al., 1989; Tarquis & Bradford, 1992). These processes contribute a true added value to the seeds because they:
1) make it possible to homogenize the batches of seeds with respect to germination,
2) make possible an appreciable saving in time for the emergence after sowing, since a certain number of biochemical processes necessary for accomplishing germination would already be carried out during priming,
3) make possible an improvement in the germinal quality of batches of aged seeds, probably due to the fact that mechanisms for repairing biological structures damaged during the final ripening of the seeds are deployed during the priming.
As markers of early stages of germination are not available, optimization of such processes rests solely on carrying out germination tests, which require several days of experimentation. Moreover, if the treatment fails (as batches of seeds are by nature heterogeneous, it is therefore necessary to optimize the treatment for each of the batches), the batch is lost. There therefore exists a significant need to find a molecular marker which is easy to detect and the possibility of continuously monitoring the imbibition phase, via such a molecular marker, would therefore constitute a considerable advance, making it possible to adapt the priming to each batch of seeds.
Plant cells are capable of synthesizing the main vitamins. One of them, biotin, acts as cofactor to a small number of enzymes, which play an essential role in cell metabolism, known under the name of biotin carboxylases (Knowles, 1989; Wurtele & Nikolau, 1990; Alban et al., 1993): acetyl-CoA carboxylase (EC 6.4.1.2), 3-methylcrotonyl-CoA carboxylase (EC 6.4.1.4), propionyl-CoA carboxylase (EC 6.4.1.3) and pyruvate carboxylase (EC 6.4.1.1). The study of these proteins is therefore of major importance in understanding the resurgence of metabolism during the germination of the seeds. Acetyl-CoA carboxylase is, in plants, the most studied of the biotin enzymes, because it constitutes the target of powerful herbicides in monocotyledon plants (Hoppe & Zacher, 1985; Burton et al., 1987a,b). This enzyme, in fact, plays a key role in the synthesis of fatty acids. The role of the other three biotin carboxylases in plants remains unknown for the moment. It is known that seeds containing lipid stores (Stumpf, 1980; Harwood, 1988), as well as pea seeds (Bettey et al., 1992), contain an acetyl-CoA carboxylase activity which is probably involved in the synthesis of storage triglycerides. On the other hand, it is not known if the seeds contain other biotinylated proteins and if they play a role during germination.
SUMMARY OF THE INVENTION
The subject of the present invention is therefore a pure protein of plant origin which is capable of being biotinylated, characterized in that it results from a seed of a species of crop plant and in that it comprises at least one unit of 50 to 85 kDa, is expressed in the seeds and in no other organ of the plant and disappears rapidly during the early phases of germination.
The subject of the present invention is more particularly a pure protein which is capable of being biotinylated and which results from the seed of leguminous species, for example pea, bean, lupin, lucerne, soya or lentil, but also in other species such as, for example, the umbelliferous species such as, for example, carrot or alternatively the Chenopodiaceae such as, for example, beet. In the case of pea, the protein is named SBP65. It also relates to the proteins equivalent to the latter which establish an interaction with biotin.
The invention also relates to new antibodies, characterized in that they recognize the protein SBP65.
It also relates to molecular probes, characterized in that they are derived from the protein SBP65 or from the equivalent proteins.
It also relates to the use of the specificity of tissue expression and of the pattern of development of these markers in order to measure as precisely as possible the state of progress of the germination, more particularly in the early imbibition phase, and in particular to their use as a protein and nucleic and molecular marker of germination in leguminous seeds, for example, pea, bean, lupin, lucerne, soya or lentil, but also in other species such as, for example, umbelliferous species such as, for example, carrot or alternatively the Chenopodiaceae such as, for example, beet. Detection of these markers can be carried out either by detection with specific antibodies, in the case of use in leguminous species, or directly using coloured visualization of biotin in the case of other crops such as carrot or beet.
This detection can be carried out using a device (kit), which also forms part of the invention.
Another subject of the invention is a process for the transformation of plant cells by DNA sequences encoding the protein SBP65 or an equivalent protein.
It likewise relates to a process for the transformation of plant cells by DNA sequences encoding an antisense RNA of the protein SBP65, or any equivalent biotinylated protein from the viewpoint of the pattern of development and the tissue expression, in order to inhibit the synthesis of such proteins and thus to create sterile plants.
A further subject of the invention is a process for the transformation of plants cells by DNA sequences expressing an RNA encoding a protein which could differ from SBP65 by its sequence and its method of interaction with biotin but whose construction would make it possible to provide for a specificity of tissue expression analogous to that of the protein SBP65 and the possibility of trapping, in the developing seeds, free biotin newly synthesized and/or absorbed from the soil by the plant with the aim of creating sterile plants.
The final subject of the invention is the plant cells transformed according to the above processes and the transformed plants obtained by regeneration of these transformed cells.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 graphically depicts levels of total proteins (▪) versus levels of SBP65 protein (∘) in peas seeds as germination progresses.
DETAILED DESCRIPTION OF THE INVENTION
Characterization of proteins capable of being biotinylated:
Pea seed (pisum sativum cv. Douce Provence) is used as model. By virtue of the use of ELISA techniques and of specific marking with streptavidin bacterial protein endowed with a very high specific affinity for biotin (Green, 1990)! coupled to peroxidase (Sigma), the biotinylated proteins are easily detectable in a total protein extract produced from a single seed. This quantification requires only a small number of stages which are easy to implement: grinding the seeds in a mixer of Waring blender type (30 sec), taking the powder up in a homogenization buffer (Hepes pH 8.0, containing various protease inhibitors; Alban et al., Plant Physiol. 102, 957-965, 1993), centrifuging (15 min at 20,000 g in Eppendorf-type centrifuging tubes) in order to remove the cell debris, and carrying out tests based on conventional ELISA techniques.
The proteins, which are capable of being biotinylated, of the crude extract can also be easily located, no longer as a mixture but individually, following the separation of the proteins of the total extract in a polyacrylamide gel in the presence of sodium dodecylsulfonate (SDS), electrotransfer of the proteins on a nitrocellulose membrane and specific visualization with streptavidin coupled to peroxidase (Nikolau et al., 1985; Alban et al., Plant Physiol. 102, 957-965, 1993). The latter technique has been optimized with the aim of making it possible to use equipment for the electrophoretic microanalysis of proteins in preformed polyacrylamide gels (PhastSystem and PhastTransfer of Pharmacia), which have the advantage of leading to a very rapid analysis of samples.
Using these methods, we have observed that ripe pea seeds contain a major protein capable of being biotinylated and which has a molecular weight of 65 kDa.
Measurements of enzymatic activity carried out as described by Alban et al. (1993) show that the crude extract contains two biotin carboxylase activities: acetyl-CoA carboxylase and 3-methylcrotonyl-CoA carboxylase. The propionyl-CoA carboxylase and pyruvate carboxylase activities are not detectable.
The protein SBP65 was purified to the state of homogeneity from a pea seed extract produced as described above and by using a chromatography technique on an affinity column consisting of avidin-Sepharose (Kohanski & Lane, 1990; Alban et al., 1993) avidin is a chicken egg protein which, like bacterial streptavidin, is endowed with a very high specific affinity for biotin (Green, 1990)!. This method makes it possible to purify all the proteins capable of being biotinylated contained in the crude extract. In a subsequent stage, it is possible, by carrying out ion exchange chromatography on a Mono-Q HR 5/5 column (Pharmacia), to separate these proteins into two distinct fractions. One, not retained by the column, contains the pure protein SBP65. The other, retained by this column, is eluted in the presence of 0.3M KCl and contains the two main biotin carboxylase activities present in the crude extract: acetyl-CoA carboxylase and 3-methylcrotonyl-CoA carboxylase.
The main results of this purification are the following:
1) The protein SBP65 does not carry any of the biotin carboxylase activities (EC 6.4.1.1, EC 6.4.1.2, EC 6.4.1.3, and EC 6.4.1.4) described in micro-organisms, yeast and eukaryotes (Knowles, 1989). It contains one mole of biotin per mole of 65 kDa polypeptide, the binding of biotin to the protein being strong in nature, especially strong ionic or covalent in nature. Its molecular weight, estimated by gel filtration (Sephacryl S-300 HR, Pharmacia) is, in the native form, 450±60 kDa. This indicates that the native form of the protein SBP65 corresponds to the combination of six to eight identical subunits, each having a molecular weight of 65 kDa.
2) The acetyl-CoA carboxylase activity is carried by a biotinylated polypeptide of 200 kDa as described by Bettey et al. (1992).
3) The 3-methylcrotonyl-CoA carboxylase activity is carried by two polypeptides constituting the two subunits of the enzyme: one, biotinylated, of 75 kDa and the other, non-biotinylated, of 50 kDa, in agreement with the results of Alban et al. (1993) regarding the purification to the state of homogeneity of this enzyme from pea leaf.
SBP65 therefore corresponds to a new protein of plant origin capable of being biotinylated.
Tissue Distribution of the Protein
The purification to the state of homogeneity of the protein SBP65 has made it possible, by immunization of a rabbit, to obtain new specific antibodies which also form part of the invention. The use of these antibodies shows that the expression of the protein is specific to the seeds. It is not detected in any other organ of the plant (leaves, stems, roots, pods and flowers), whatever the state of development of the plant. Such tissue specificity is not found for the biotincarboxylases. The acetyl-CoA carboxylase and 3-methylcrotonyl-CoA carboxylase activities are, in fact, detectable in all organs of the plant.
Cloning of the cDNA Encoding the Protein
The anti-SBP65 antibodies were used to screen a cDNA bank corresponding to the polyadenylated mRNAs isolated from pea seeds. A recombinant bacterial clone (host:Escherichia coli K 12; cloning system: predigested lambda ZAP® II/Eco RI cloning kit, Stratagene), expressing a protein recognized by the anti-SBP65 antibodies, was isolated and the cDNA thus cloned was characterized. Its length is of the order of 2000 bases.
Sequencing experiments show that the cDNA contains, in the direction of the translation SEQ ID NOs: 5 and 7;
1) a consensus sequence for initiating the translation in plants: ATCAATGGC, (SEQ ID NO:1) is found at nucleotides 72-80 and 48-55 in SEQ ID NOs: 5 and 7 respectively.
2) a consensus signal for polyadenylation: AATAAA, (SEQ ID NO:2) is located at nucleotides 59-64 and 1829-1834 of SEQ ID NOs: 6 and 7 respectively.
3) a poly(A) tail consisting of 18 A residues (SEQ ID NO:2).
Moreover, the 5'-end of this cDNA contains sequence units corresponding exactly to those which we have determined by sequencing the protein from peptides obtained by cutting SBP65 with cyanogen bromide and trypsin. These sequence units correspond to 44 amino acid residues localized at the N-terminal end of SBP65 i.e., amino acid residues 17-27, 29-35, 37-49, and 62-74 of SEQ ID NOs: 5 and 7. Sequencing experiments of the protein SBP65 have additionally made it possible to identify the Lysine 103 as representing the amino acid residue carrying biotin.
SEQ ID NO:7 is the complete sequence of the cDNA encoding the protein according to the invention and which also forms part of the invention: its length is 1969 nucleotides. The region encoding the entire protein is 1653 nucleotides, from the nucleotide 51 to the nucleotide 1703. The sequence, from the nucleotide 47 to the nucleotide 55, corresponds to the consensus sequence found at the initiation codon of dicotyledon plants (AACAATGGC) SEQ ID NO:4. Nucloetides 1828 to 1838 correspond to the polyadenylation signal sequence. Sequence SEQ ID NO:7 also has the protein sequence translated from this cDNA, containing 551 residues. Peptide sequences obtained by microsequencing consist of amino acid residues 93-125 and amino acid residues 129-146 of SEQ ID NO:7. The Lysine residue in position 103 is that for binding biotin covalently (biocytin residue).
Comparison of the nucleotide and protein sequences obtained for the protein SBP65 with those contained in the Swiss-Prot and Gene Bank banks does not reveal any homology with a currently known protein. Presence of proteins equivalent to SBP65 in other seed species.
The use of anti-SBP65 antibodies shows that the protein is present in different varieties of pea seeds (Cador, Finale, Cash, Progreta, Twigy), and in different leguminous species (bean, soya, lentil, lupin, lucerne). For species not belonging to the leguminous family, the reactivity of the anti-SBP65 antibodies is low. However, in the case of carrot, two major biotinylated proteins of 62±2 kDa and 30±2 kDa are detected in ripe seeds, probably corresponding to the polypeptides revealed beforehand in the somatic embryo (Wurtele & Nikolau, 1992; Caffrey et al., 1993). These proteins disappear very rapidly during germination, before the appearance of the radicle is observed. The same type of results is obtained in the case of beet. Yet again a biotinylated protein of 62±2 kDa is easily recognizable in crude extracts of dry seeds, disappearing at a high rate during early phases of germination.
EXAMPLE 1
Development of the Total Proteins and of the Protein SBP65 During the Germination of Pea Seeds
Germination experiments are carried out under glass, at 20° C., and under controlled light (photoperiod 12 h, white light in fluorescent tubes, 10-40 μE m -2 s -1 ). Ripe pea seeds (var. Douce Provence) are germinated on compost at zero-time; they are sprinkled each day with water. The seeds are withdrawn as a function of time. The arrow shows the piercing by the radicle. A crude extract is produced for each sample as indicated. FIG. 1 represents a curve showing the development, with time, of the relative content (1=100%) of the seeds in total proteins (▪) i.e. the storage proteins, the major proteins of the seeds (Bewley & Black, 1983)! and in protein SBP65 (∘), the latter being specifically revealed by carrying out ELISA tests with anti-SBP65 antibodies. The results are displayed in standardized form with respect to the measurements carried out with the ripe seeds (zero-time). It may be observed that the protein SBP65 disappears very quickly during germination. A remarkable fact is that a considerable part of the initial content (of the order of 60%) disappears before the piercing by the radicle is observed (the latter is indicated by a vertical arrow). The kinetics of disappearance of SBP65 are thus much faster than those of the storage proteins of the seed. It is known that the mobilization of these stores begins when the radicle pierces the coats (Bewley et al., 1983). These results demonstrate that SBP65 is a marker of the early phases of germination.
EXAMPLE 2
To complement this study on the germination, the development in time of the expression of the protein SBP65 and of free biotin, that is to say the vitamin which is not complexed to proteins, during the ripening of the pea seeds is studied (by using the method described by Baldet et al., 1993). It is known that the plant cells have the enzymatic equipment necessary for the biosynthesis of this vitamin and that, moreover, the vitamin in its free form is found in the plant tissues such as the leaves in excess with respect to biotin bonded to proteins (Baldet et al., 1993). The main results obtained are the following:
1) In very young seeds, protein SBP65 is not yet present and free biotin is always in excess with respect to bonded biotin.
2) The maximum level of the protein SBP65 is detected in the final phase of ripening of the seeds, at the same time as the main storage substances, proteins, starch and triglycerides, accumulate and as the seeds enter into a dehydration phase. At this stage of development, bonded biotin (that is to say biotin mainly bonded to the protein SBP65, since the latter becomes, at this stage, the major biotinylated protein of the seeds) is in excess with respect to free biotin.
All these results show the biological role of the protein SBP65:
1) It constitutes a biotin store, used in germination for restarting the metabolism.
2) The protein SBP65 regulates the level of free biotin in the embryonic cell.
BIBLIOGRAPHIC REFERENCES
Alban, C., Baldet, P., Axiotis, S. & Douce, R. (1993), Plant Physiol., 102, 957-965
Baldet, P., Alban, C., Axiotis, S. & Douce, R. (1993), Arc. Biochem. Biophys., 303, 67-73
Bewley et al., (1983) in Physiology and Biochemistry of Seeds in Relation to Germination, Vol. 1, pp. 177-244, Springer-Verlag, Berlin
Burton, J. D., Gronwald, J. W., Somers, D. A., Connelly, J. A., Gengenbach, B. G. & Wyse, D. L. (1987a), Biochem. Biophys. Res. Commun., 148, 1039-1044
Burton, J. D., Gronwald, J. W., Somers, D. A., Gengenbach, B. G. & Wyse, D. L. (1987b), Pestic. Biochem. Physiol., 34, 76-85
Caffrey, J. J., Keller, G., Wurtele, E. S. & Nikolau, B. J. (1993), Plant Physiol., 102, Abstract 524
Fincher, G. B. (1989), Annu. Rev. Plant Physiol. Plant Mol. Biol., 40, 305-346
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Hoppe, H. H. & Zacher, H. (1985), Pestic. Biochem. Physiol., 24, 298-305
Karsen, C. M., Haigh, A., van der Toorn, P. & Weges, R. (1989), in Recent Advances in the Development and Germination of Seeds (Taylorson, R. B., ed.) NATO ASI series, Series A, Life sciences, Vol. 187, pp. 269-280
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__________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 7(2) INFORMATION FOR SEQ ID NO:1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 9 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:ATCAATGGC9(2) INFORMATION FOR SEQ ID NO:2:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 6 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:2:AATAAA6(2) INFORMATION FOR SEQ ID NO:3:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 18 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:3:AAAAAAAAAAAAAAAAAA18(2) INFORMATION FOR SEQ ID NO:4:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 9 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(xi) SEQUENCE DESCRIPTION: SEQ ID NO:4:AACAATGGC9(2) INFORMATION FOR SEQ ID NO:5:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 530 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(ix) FEATURE:(A) NAME/KEY: CDS(B) LOCATION: 76..528(xi) SEQUENCE DESCRIPTION: SEQ ID NO:5:GAATTCGAGGATCCGGGTACCATGGTTTTTTTTTTTTTCATAACCAATACAGAGAAAAAC60GCACATCCATTATCAATGGCATCTGAACAATTATCTCGCAGAGAAAACATC111MetAlaSerGluGlnLeuSerArgArgGluAsnIle1510ACAACCGAGAGAAAGATTCAAAACGCGGAAGACAGTGTCCCTCAAAGG159ThrThrGluArgLysIleGlnAsnAlaGluAspSerValProGlnArg152025ACAACCCACTTCGAGCTTAGAGAGACCCACGAACTTGGACCAAACTTT207ThrThrHisPheGluLeuArgGluThrHisGluLeuGlyProAsnPhe303540CAGTCTCTCCCTCGCAACGAGAATCAAGCTTACCTTGACCGTGGTGCA255GlnSerLeuProArgAsnGluAsnGlnAlaTyrLeuAspArgGlyAla45505560CGTGCTCCTTTGAGTGCAAATGTATCAGAAAGTTACCTTGATCGTGCA303ArgAlaProLeuSerAlaAsnValSerGluSerTyrLeuAspArgAla657075CGTGTTCCTTTGAATGCAAATATACCAGAACACAGAGTTAGAGAAAAA351ArgValProLeuAsnAlaAsnIleProGluHisArgValArgGluLys808590GAAGATTTTGGTGGTGTTCGTGATATGGGAAAGTTTCAGATGGAATCG399GluAspPheGlyGlyValArgAspMetGlyLysPheGlnMetGluSer95100105AAAGGAGGGAATAAGAGTTTGGCCGAAGATAGAGAAACTCTCGATACA447LysGlyGlyAsnLysSerLeuAlaGluAspArgGluThrLeuAspThr110115120CGATCTAGAATGGTTACTGGAACACCTCACATTAAAGAAGCATCGGGA495ArgSerArgMetValThrGlyThrProHisIleLysGluAlaSerGly125130135140AAAGGACAAGTTGTGGAGGAAAGAGAGAGAGCGAG530LysGlyGlnValValGluGluArgGluArgAla145150(2) 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NO:6:GTCGACAGTGGATGGAACTAGGGCTGCTGCGAATGCTGTTGAAGGAGCGGTTGGGTATGT60TGCACTTAAAGCTTCTGAGCTTGCGGCGAAATCGGTGGAAACTGTTAAGGGTTTGGCTGC120TTCTGCTGGTGAAACTGCTAAGGAGTTTACTGCTAGGAAGAAAGAAGAATCATGGCGGGA180ATATGAGGCTAAAAGGGCTTCTCAACTTCAGGAAGGTGAAGAAATCTTGCCATCTACCGG240AGGTATCGGAAAAGTGTTACCCAGTGGAGAAAGAACTCAAGCACAAGGAACCAATCTTCA300AGAGAAGGTACAAGGAAAAGGAAGTGATATATTAGGAGCTGTGACTGAAACTGTGAGTGA360CATTGGAAGTAGCATGATTAAACCAATAGATAATGCTAATACTAAAGTTAAGGAACATGG420TGGCACTACTATTACACCAAAAGGACAAGATGCTGGTGGTGTTTTGGATGCTATTGGTGA480AACTATAGCTGAGATTGCACATACAACTAAAGTCATTGTTGTTGGTGAAGATGATGAAGT540AGAAAAGTCAATGCAGAAGAATATTGGGTCAGATTCTCACTCTCTTGATCGTGCCAAGCA600TGAAGGATATAGAGCACCAAAGAATAATGTTTCTTAATTCCAAAGTTTGAAGACAATGAA660TGTGTTTGTTTGATGCAGAAGTTTAGTAATATGTTAATCTTAATTAGCTGTCAGTGAAGA720AGTTCAATGTTTTGTGGCTTTGTTTTATGGAGTTGTGTGAATAAATTACAATCTCATTCT780TGAGATTGTCAATAATAGCAAATATATCTTATGCTTATGTCTTTTGTAAGTCAATGTTGT840AATGTAATAATATATACTTTTATTTAATATTCTGTTATTGCTAAAAAAAAAAAAAAAAAA900CCATGGTACCCGGATCCTCGAATTC925(2) INFORMATION FOR SEQ ID NO:7:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 1969 base pairs(B) TYPE: nucleic acid(C) STRANDEDNESS: double(D) TOPOLOGY: linear(ii) MOLECULE TYPE: cDNA(ix) FEATURE:(A) NAME/KEY: CDS(B) LOCATION: 51..1703(xi) SEQUENCE DESCRIPTION: SEQ ID NO:7:TTTTTTTTTTTTTCATAACCAATACAGAGAAAAACGCACATCCATTATCAATGGCA56MetAlaTCTGAACAATTATCTCGCAGAGAAAACATCACAACCGAGAGAAAGATT104SerGluGlnLeuSerArgArgGluAsnIleThrThrGluArgLysIle51015CAAAACGCGGAAGACAGTGTCCCTCAAAGGACAACCCACTTCGAGCTT152GlnAsnAlaGluAspSerValProGlnArgThrThrHisPheGluLeu202530AGAGAGACCCACGAACTTGGACCAAACTTTCAGTCTCTCCCTCGCAAC200ArgGluThrHisGluLeuGlyProAsnPheGlnSerLeuProArgAsn35404550GAGAATCAAGCTTACCTTGACCGTGGTGCACGTGCTCCTTTGAGTGCA248GluAsnGlnAlaTyrLeuAspArgGlyAlaArgAlaProLeuSerAla556065AATGTATCAGAAAGTTACCTTGATCGTGCACGTGTTCCTTTGAATGCA296AsnValSerGluSerTyrLeuAspArgAlaArgValProLeuAsnAla707580AATATACCAGAACACAGAGTTAGAGAAAAAGAAGATTTTGGTGGTGTT344AsnIleProGluHisArgValArgGluLysGluAspPheGlyGlyVal859095CGTGATATGGGAAAGTTTCAGATGGAATCGAAAGGAGGGAATAAGAGT392ArgAspMetGlyLysPheGlnMetGluSerLysGlyGlyAsnLysSer100105110TTGGCCGAAGATAGAGAAACTCTCGATACACGATCTAGAATGGTTACT440LeuAlaGluAspArgGluThrLeuAspThrArgSerArgMetValThr115120125130GGAACACCTCACATTAAAGAAGCATCGGGAAAAGGACAAGTTGTGGAG488GlyThrProHisIleLysGluAlaSerGlyLysGlyGlnValValGlu135140145GAAAGAGAGAGAGCGAGAGAAAGAGCAATGGAAGAAGAAGAGAAAAGG536GluArgGluArgAlaArgGluArgAlaMetGluGluGluGluLysArg150155160TTAACAATGGAAGAGATATCGAAGTATAGAAACCAAGCTCAACAAAGT584LeuThrMetGluGluIleSerLysTyrArgAsnGlnAlaGlnGlnSer165170175GCATTGGAAGCGCTTTCAGCAGCACAAGAGAAATACGAAAGAGCGAAA632AlaLeuGluAlaLeuSerAlaAlaGlnGluLysTyrGluArgAlaLys180185190CAAGCAACAAATGAAACACTACGCAACACGACACAGGCTGCACAAGAG680GlnAlaThrAsnGluThrLeuArgAsnThrThrGlnAlaAlaGlnGlu195200205210AAAGGAGAAGCAGCACAAGCGAAAGATGCAACTTTTGAGAAAACACAA728LysGlyGluAlaAlaGlnAlaLysAspAlaThrPheGluLysThrGln215220225CAAGGTTATGAAATGACAGGAGACACAGTTTCAAATTCTGCAAGAACT776GlnGlyTyrGluMetThrGlyAspThrValSerAsnSerAlaArgThr230235240GCTTCTGAGAAAGCAGCACAGGCTAAAAATACAACTCTTGGAAAGACA824AlaSerGluLysAlaAlaGlnAlaLysAsnThrThrLeuGlyLysThr245250255CAACAAGGTTATGAGGCAACAAGAGACACAGTTTCAAATGCTGCAAGA872GlnGlnGlyTyrGluAlaThrArgAspThrValSerAsnAlaAlaArg260265270ACTGCGGCGGAGTATGCTACTCCTGCTGCGGAGAAAGCCAGGTGTGTG920ThrAlaAlaGluTyrAlaThrProAlaAlaGluLysAlaArgCysVal275280285290GCTGTTCAGGCGAAAGATGTTACTCTGGAAACAGGTAAGACAGCGGCG968AlaValGlnAlaLysAspValThrLeuGluThrGlyLysThrAlaAla295300305GAGAAAGCCAAGTGTGCCGCGGAAATTGCTGCCAAAGTGGCGGTTGAT1016GluLysAlaLysCysAlaAlaGluIleAlaAlaLysValAlaValAsp310315320TTGAAGGAGAAGGCCACTGTGGCAGGGTGGACTGCGTCGCATTATGCC1064LeuLysGluLysAlaThrValAlaGlyTrpThrAlaSerHisTyrAla325330335ACACAGTTGACAGTGGATGGAACTAGGGCTGCTGCGAATGCTGTTGAA1112ThrGlnLeuThrValAspGlyThrArgAlaAlaAlaAsnAlaValGlu340345350GGAGCGGTTGGGTATGTTGCACCTAAAGCTTCTGAGCTTGCGGCGAAA1160GlyAlaValGlyTyrValAlaProLysAlaSerGluLeuAlaAlaLys355360365370TCGGTGGAAACTGTTAAGGGTTTGGCTGCTTCTGCTGGTGAAACTGCT1208SerValGluThrValLysGlyLeuAlaAlaSerAlaGlyGluThrAla375380385AAGGAGTTTACTGCTAGGAAGAAAGAAGAATCATGGCGGGAATATGAG1256LysGluPheThrAlaArgLysLysGluGluSerTrpArgGluTyrGlu390395400GCTAAAAGGGCTTCTCAACTTCAGGAAGGTGAAGAAATCTTGCCATCT1304AlaLysArgAlaSerGlnLeuGlnGluGlyGluGluIleLeuProSer405410415ACCGGAGGTATCGGAAAAGTGTTACCCAGTGGAGAAAGAACTCAAGCA1352ThrGlyGlyIleGlyLysValLeuProSerGlyGluArgThrGlnAla420425430CAAGGAACCAATCTTCAAGAGAAGGTACAAGGAAAAGGAAGTGATATA1400GlnGlyThrAsnLeuGlnGluLysValGlnGlyLysGlySerAspIle435440445450TTAGGAGCTGTGACTGAAACTGTGAGTGACATTGGAAGTAGCATGATT1448LeuGlyAlaValThrGluThrValSerAspIleGlySerSerMetIle455460465AAACCAATAGATAATGCTAATACTAAAGTTAAGGAACATGGTGGCACT1496LysProIleAspAsnAlaAsnThrLysValLysGluHisGlyGlyThr470475480ACTATTACACCAAAAGGACAAGATGCTGGTGGTGTTTTGGATGCTATT1544ThrIleThrProLysGlyGlnAspAlaGlyGlyValLeuAspAlaIle485490495GGTGAAACTATAGCTGAGATTGCACATACAACTAAAGTCATTGTTGTT1592GlyGluThrIleAlaGluIleAlaHisThrThrLysValIleValVal500505510GGTGAAGATGATGAAGTAGAAAAGTCAATGCAGAAGAATATTGGGTCA1640GlyGluAspAspGluValGluLysSerMetGlnLysAsnIleGlySer515520525530GATTCTCACTCTCTTGATCGTGCCAAGCATGAAGGATATAGAGCACCA1688AspSerHisSerLeuAspArgAlaLysHisGluGlyTyrArgAlaPro535540545AAGAATAATGTTTCTTAATTCCAAAGTTTGAAGACAATGAATGTGTTTGTTTGAT1743LysAsnAsnValSer550GCAGAAGTTTAGTAATATGTTAATCTTAATTAGCTGTCAGTGAAGAAGTTCAATGTTTTG1803TGGCTTTGTTTTATGGAGTTGTGTGAATAAATTACAATCTCATTCTTGAGATTGTCAATA1863ATAGCAAATATATCTTATGCTTATGTCTTTTGTAAGTCAATGTTGTAATGTAATAATATA1923TACTTTTATTTAATATTCTGTTATTGCTAAAAAAAAAAAAAAAAAA1969__________________________________________________________________________ | A biotinylated protein is disclosed which is obtained from the seeds of leguminous plants and which is expressed exclusively in the seeds and in no other tissue. The protein comprises at least one subunit of 50-85 kDa. Levels of the protein decrease rapidly as germination of the seed progresses. The protein does not exhibit the activity of either acetyl-CoA carboxylase or 3-methyl crotonyl-CoA carboxylase. In the pea, Pisum sativum, the protein is designated SBP65 and comprises 6-8 identical subunits, each having a molecular weight of about 65 kDa. The protein may be a useful marker for determining the germination stage of seeds. | 2 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application No. 61/044,336, filed Apr. 11, 2008, entitled “Hydrogen Generation Process”, which application is incorporated herein by reference.
TECHNICAL FIELD
This description relates to electrochemical systems, particularly hydrogen generation systems and, more particularly, to the electrolysis of water to produce hydrogen.
BACKGROUND
Hydrogen can provide clean energy for powering automobiles as well as for cooking, space heating, heating hot water, and supplying power to absorption air conditioning and refrigeration units. In addition, unlike conventional electricity, it may be stored for later use. As currently envisioned, widespread use of hydrogen will require a significant infrastructure for the efficient distribution and use of this fuel. Costs of hydrogen generation may also be a factor in its widespread use.
Hydrogen may be produced by the electrolysis of water, a readily available and inexpensive feedstock, by passing an electric current through the water. A source of direct current electricity is connected to an anode and a cathode placed in contact with the water and hydrogen is generated at the cathode and oxygen is generated at the anode. A membrane is interposed between the anode and the cathode and hydrogen ions move across the membrane, where they combine with electrons to form hydrogen gas. The membrane must be durable enough to withstand the caustic environment of the electrolysis process as well as the physical stress of the sometimes violent production of hydrogen and oxygen gas. Waste heat is also generated in the process, which, if recovered, may result in an increase in the overall efficiency of the electrolytic process.
There are many sources of the electric energy needed to generate hydrogen by the process of electrolysis. Traditional sources include burning fossil fuels such as coal, petroleum derivatives, and natural gas and nuclear plants and non-traditional sources such as wind power and solar panels may also be used. The flexibility to utilize electricity generated by a variety of sources can provide greater reliability of hydrogen generation. Utilizing electricity to generate hydrogen can also provide a convenient storage medium which may be used to dampen time-dependent fluctuations in power supply and energy demand.
SUMMARY
Electrochemical apparatus can utilize electricity to induce a chemical reaction, such as the separation of water into its component element hydrogen and oxygen in an electrolyzer, or to provide electrical energy by combining hydrogen and oxygen to produce water, as in a fuel cell.
A comprehensive electrolytic hydrogen generation process may effectively utilize clean alternative power, make hydrogen fuel available without relying upon a complex and expensive hydrogen distribution infrastructure, and eliminate complex and expensive waste disposal problems.
Included is a ripstop nylon fabric membrane for an electrochemical apparatus that is both durable and low-cost. Optionally, the ripstop nylon membrane is combined with a plastisol-based gasket in a membrane assembly. Also included are light-weight, low-cost high-density polyethylene (HDPE) components, which components can be formed to frame both single electrodes and single membranes in one-piece modules. Multiple electrode modules and membrane modules can be combined to produce a multi-cell electrolyzer system. Also included are small inter-electrode gaps and high electrode-water contact areas to help effect high-efficiency electrolyzer operation. Included, too, are effective and low-cost safety and process control features that help reduce or minimize the dangers of the electrolytic generation of hydrogen.
An electrolyzer can flexibly utilize electrical power from a variety of sources. Wind of any speed sufficient to turn a wind turbine may be utilized. Either wind or solar power can be converted to hydrogen and stored during off-peak times or when such generated electrical power is more than required to meet demand. A rectifier may be provided to convert conventional AC power to provide DC to the electrolyzer if desired. Batteries may be charged by either wind or solar power and later used to power the electrolyzer or to smooth out changes in source.
Waste heat may be captured and put to other uses. For example, by enclosing the electrolyzer, water or other heat transfer medium may be circulated to provide heat for a residence or office. By enclosing the hydrogen and oxygen collection towers, air or other suitable heat transfer media may be circulated to collect additional waste heat. Further efficiencies may be obtained by circulating water or other suitable heat transfer medium through heat-transfer coils included within the towers.
In one embodiment, an apparatus comprises a first compression plate; a first insulator plate next to the first compression plate; a first electrode next to the first insulator plate; a first end frame next to the first electrode, the first end frame having an aperture, a liquid inlet, a channel formed between the aperture and the liquid inlet, a gas outlet, and a channel formed between the aperture and the gas outlet; the apparatus further comprising at least one membrane-electrode assembly, the at least one membrane-electrode assembly next to the first end frame and comprising a membrane assembly, the membrane assembly comprising a ripstop nylon membrane and a gasket affixed to a border of the membrane; the at least one membrane-electrode assembly further comprising a first interior frame, the first interior frame comprising an aperture, at least one liquid inlet, a channel formed between the aperture and the liquid inlet, a gas outlet, and a channel formed between the aperture and the gas outlet; the at least one membrane-electrode assembly further comprising an interior electrode and a second interior frame, the second interior frame comprising an aperture, at least one liquid inlet, a channel formed between the aperture and the liquid inlet, a gas outlet, and a channel formed between the aperture and the gas outlet; the apparatus further comprising a further membrane assembly, the further membrane assembly next to the membrane-electrode assembly and comprising a ripstop nylon membrane and a gasket affixed to a border of the membrane; the apparatus further comprising a second end frame, the second next to the further membrane assembly and comprising an aperture, a liquid inlet, a channel formed between the aperture and the liquid inlet, a gas outlet, and a channel formed between the aperture and the gas outlet; the apparatus further comprising a further electrode, the further electrode next to the second end frame; a second insulator plate, the second insulator plate next to the further electrode; and a second compression plate, the second compression plate next to the second insulator plate. The further electrode, the second insulator plate, and the second compression plate may each further include a liquid inlet and a gas outlet.
As will be appreciated by those skilled in the relevant art, these elements will be interleaved with one another to create an electrochemical apparatus, and especially an electrolyzer.
In a further embodiment, a membrane for an electrolyzer comprises a synthetic fabric. In a further embodiment, the synthetic fabric comprises nylon. In a further embodiment, the nylon comprises ripstop nylon.
In a further embodiment, a method comprises impressing a DC electric current across a ripstop nylon membrane.
In a further embodiment, a method comprises applying a plastisol border to a ripstop nylon membrane.
In a further embodiment, a method comprises (a) placing a first side of a first insulator plate against a second side of a first compression plate; (b) placing a first side of a first electrode against a second side of the first insulator plate; (c) placing a first side of a first end frame against a second side of the first electrode, the first end frame comprising: a second side; a liquid inlet forming a hole between the first side and the second side; a channel formed on the first side between the aperture and the liquid inlet; a gas outlet forming a hole between the first side and the second side; and a channel formed on the first side between the aperture and the gas outlet; (d) placing a first membrane assembly side of at least one membrane-electrode assembly against the second side of the first end frame, the at least one membrane-electrode assembly comprising: a membrane assembly, the membrane assembly comprising: a ripstop nylon membrane; and a gasket affixed to a border of at least one side of the membrane; a first frame, the first frame defining an aperture, and comprising: a first side, the first side facing and abutting a second side of the membrane assembly; a second side; a liquid inlet forming a hole between the first side and the second side; a channel formed on the second side between the aperture and the liquid inlet; a gas outlet forming a hole between the first side and the second side; and a channel formed on the second side between the aperture and the gas outlet; an interior electrode, a first side of the interior electrode facing and abutting the second side of the first interior frame; and a second frame, the second frame defining an aperture, and comprising: a first side, the first side facing and abutting a second side of the interior electrode; a second side; a liquid inlet forming a hole between the first side and the second side; a channel formed on the first side between the aperture and the liquid inlet; a gas outlet forming a hole between the first side and the second side; and a channel formed on the first side between the aperture and the gas outlet; (e) placing a first side of a further membrane assembly against the second side of the second frame of the membrane-electrode assembly; (f) placing a first side of a second end frame against a second side of the further membrane assembly; (g) placing a first side of a further electrode against a second side of the second end frame; (h) placing the first side of a second insulator plate against a second side of the further electrode; and (i) placing a first side of a second compression plate against a second side of the second insulator plate. The further electrode, the second insulator plate, and the second compression plate may each further include a liquid inlet and a gas outlet.
The details of one or more implementations are set forth in the accompanying drawings and the description below. Other features will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The accompanying drawings, which are incorporated in, and constitute a part of, this specification, illustrate several embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.
FIG. 1 is a block diagram illustrating a hydrogen system.
FIG. 2 is a partial cutaway view illustrating an electrolyzer and associated collection towers along with enclosures.
FIGS. 3 and 4 combine to give an exploded view illustrating components of an electrolyzer.
FIG. 5 illustrates the detail of a channel.
FIG. 6 illustrates the detail of a membrane fabric.
FIG. 7 is a process diagram illustrating an electrolyzer and associated ancillary equipment and controls.
FIGS. 8 and 9 are circuit diagrams illustrating monitoring and control circuits for an electrolyzer and associated ancillary equipment.
FIG. 10 is a circuit diagram illustrating an oxygen sensor and associated control circuit.
FIG. 11 is an exploded view of a framed electrode.
FIG. 12 is an exploded view of a framed membrane.
DETAILED DESCRIPTION
Referring to FIG. 1 , a hydrogen system 10 includes an electrolyzer process 100 (shown also in FIGS. 2 and 7 ) adapted to produce hydrogen 32 from water 34 using electricity 28 . The electrolyzer process 100 converts water 34 into its component parts of hydrogen 32 and oxygen 30 . An electrolyte 36 is combined with the water 34 in a feedwater tank 38 and introduced into the electrolyzer process 100 as feedwater 40 . Typically, the electrolyte 36 is sodium hydroxide (NaOH) or potassium hydroxide (KOH), but cations such as, but not limited to, lithium (Li + ), rubidium (Rb + ), potassium (K + ), cesium (Cs + ), barium (Ba 2+ ), strontium (Sr 2+ ), calcium (Ca 2+ ), sodium (Na + ), and magnesium (Mg 2+ ) may also be used. Those skilled in the relevant art will recognize that other compounds are suitable for providing an electrolyte 36 to the electrolyzer process 100 . Direct current (DC) electricity 28 fed to the electrolyzer process 100 provides the necessary electricity 28 for producing hydrogen 32 . Makeup water 34 is added as required. Electrolyte 36 is added as needed to maintain proper concentration.
An electrical power selection and conditioning module 14 enables the hydrogen system 10 to provide DC electricity 28 from a variety of sources which are appropriately connected thereto. By way of example only, such sources include solar panels 22 , wind turbines 24 , batteries 26 , and the conventional power grid 16 , which alternating current (AC) electricity 18 may be converted to DC by an AC-DC rectifier which may be included in the power selection and conditioning module 14 . It will be appreciated by those skilled in the relevant art that sources other than those shown and discussed may also provide the necessary electric power 28 . Advantageously, excess power from, for example, solar panels 22 or wind turbines 24 , not required to operate the electrolyzer process 100 , may be fed back into the grid 16 for credit or utilized in a residence, business, or other property.
As shown in FIG. 1 , oxygen 30 may be vented to the atmosphere or further processed for other uses. Hydrogen 32 produced by the electrolyzer process 100 may be sent to storage 12 for further use and may be compressed (not shown) for storage at higher pressures as required. In a residential setting, for example, the hydrogen 32 may be used to fill an onboard supply vessel, for example, with a vehicle 42 . Conventional stationary appliances 44 such a furnace, water heater, stove or oven, an absorption air conditioner or refrigerator, electrical generator, or fuel cell may be powered by the hydrogen 32 . Finally, excess heat from the electrolyzer 102 or a hydrogen or oxygen collector 104 , 106 (described more fully below) may help further reduce heat demands.
The electrolyzer 102 and selected ancillary components are shown in FIG. 2 . An electrolyzer 102 (described more fully below) receives water via the hydrogen collector 104 and the oxygen collector 106 (both described more fully below). The hydrogen collector 104 collects hydrogen 32 generated by the electrolyzer 102 and the oxygen collector 106 collects oxygen 30 generated by the electrolyzer 102 .
In an exemplary embodiment as shown in FIG. 2 , the electrolyzer 102 is enclosed within a sealed electrolyzer enclosure 108 and the hydrogen and oxygen collectors 104 , 106 are enclosed within a sealed collector enclosure 110 . Water or other suitable heat transfer fluid may be circulated through the electrolyzer enclosure 108 and around the electrolyzer 102 as indicated by electrolyzer enclosure circulating heat transfer fluid in 112 and electrolyzer enclosure circulating heat transfer fluid out 114 . The electrolyzer enclosure circulating heat transfer fluid circulating through the electrolyzer enclosure 108 may be heated by the electrolyzer 102 to, for example, 115 deg. F. and may be subsequently used for space heating or for heating hot water, especially in a residence. Air or other suitable heat transfer fluid may be circulated through the collector enclosure 110 and around the hydrogen and oxygen collectors 104 , 106 as indicated by collector enclosure circulating heat transfer fluid in 116 and collector enclosure circulating heat transfer fluid out 118 . The collector enclosure circulating heat transfer fluid circulating through the collector enclosure 110 is heated by the hydrogen and oxygen collectors 104 , 106 to, for example, 130 deg. F. and may subsequently be used for space heating, heating hot water, or for powering an absorption air conditioner or refrigerator. In an exemplary embodiment, the electrolyzer enclosure 108 and the collector enclosure 110 are constructed with ¾-inch high density polyethylene (HDPE) panels and appropriately sealed to contain the circulating heat transfer fluid.
FIGS. 3 and 4 combine to illustrate an exemplary embodiment of a multi-cell electrolyzer 102 . Going through in order, first is a stack closed end compression plate 200 . In the illustrated embodiment, the stack closed end compression plate 200 has no means for allowing process streams in or out. Such connections are at the far end of the stack 102 . In an exemplary embodiment, the stack closed end compression plate 200 is ¾-inch hot-rolled steel. The stack closed end compression plate 200 may also comprise a material such as cold-rolled steel, composite, or other material with sufficient strength. The stack closed end compression plate 200 includes a plurality of stack compression bolt holes 202 . In the illustrated embodiment, there are 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). The stack closed end compression plate 200 cooperates with a stack open end compression plate 290 ( FIG. 4 ) and the plurality of stack compression bolts (not shown) to hold together and compress the electrolyzer 102 . Also, in an exemplary embodiment, the stack closed end compression plate 200 includes an electrical stud hole 204 to receive, and to allow for protrusion of, an electrical stud 232 attached to an anode 230 . The electrical stud 232 enables electrical current to be applied to the electrolyzer 102 . As will be appreciated by those skilled in the relevant art, the anode 230 and the cathode 231 ( FIG. 4 ) may be reversed and the ancillary collection equipment modified accordingly. In the illustrated embodiment, the stack closed end compression plate 200 further includes a stack lift tongue 206 including a stack lift hole 208 for facilitating lifting and transporting the electrolyzer 102 . In an exemplary embodiment, the surface of the stack closed end compression plate 200 facing the stack closed end insulator plate 220 is treated with blanchard grinding.
Adjacent the stack closed end compression plate 200 is a stack closed end insulator plate 220 . In an exemplary embodiment, the stack closed end insulator plate 220 is ¾-inch HDPE. Other non-conductive materials with sufficient strength and heat resistant properties, such as low density polyethylene (LDPE), polyurethane, nylon, and ceramic materials could be satisfactory. The stack closed end insulator plate 220 includes a series of stack compression bolt holes 202 . In the illustrated embodiment, there are 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). Also, in an exemplary embodiment, the stack closed end insulator plate 220 includes an electrical stud hole 204 to receive, and to allow for protrusion of, the electrical stud 232 attached to the anode 230 . The stack closed end insulator plate 220 may further include a set of seals (not shown) such as O-rings seated in a like set of seal grooves (not shown) formed to seal one or more water inlets 234 an oxygen outlet 236 and a hydrogen outlet 238 formed in the anode 230 .
Adjacent to the stack closed end insulator plate 220 is the anode 230 . The anode 230 includes the electrical stud 232 attached thereto which may be threaded for ease of connection to DC electrical power. As will be appreciated by those skilled in the relevant art, the anode 230 may be connected to DC electrical power in a number of ways, including, but not limited to, one or more tabs along the side edges of the anode 230 . In an exemplary embodiment, the anode 230 is constructed of 11-gauge 316 stainless steel. In the illustrated embodiment, the anode 230 includes 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). As assembled, the anode 230 is placed so its electrical stud 232 protrudes through the electrical stud holes 204 formed in the stack closed end insulator plate 220 and the stack closed end compression plate 200 and is connected to DC electrical power. In an exemplary embodiment, the anode 230 is formed with an oxygen outlet 236 , a hydrogen outlet 238 , and one or more water inlets 234 .
Adjacent to the anode 230 is a first end frame 240 . Shown in FIG. 3 is the anode side of the first end frame 240 . In an exemplary embodiment, the first end frame 240 is HDPE. As with the insulator plates 220 , 280 ( FIG. 4 ), and the interior frames 260 ( FIGS. 3 and 4 ), the end frames 240 could comprise LDPE, polyurethane, nylon, or ceramic material. The first end frame 240 includes a chamber aperture 248 and, in the illustrated embodiment, 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). The first end frame 240 further includes at least one water inlet 234 . In the illustrated embodiment, the anode side of the first end frame 240 includes at least one channel 244 formed between the at least one water inlet 234 and the chamber aperture 248 and, thus, provides fluid connectivity between the water inlet 234 and the chamber aperture 248 . In the illustrated embodiment, the anode side of the first end frame 240 includes at least one channel support 246 . (Shown in analogous fashion in FIG. 5 .) The at least one channel support 246 helps maintain the integrity of the channel 244 when the electrolyzer 102 is under compression.
The first end frame 240 further includes an oxygen outlet 236 and a hydrogen outlet 238 . In the illustrated embodiment, the anode side of the first end frame 240 includes a channel 244 formed between the oxygen outlet 238 and the chamber aperture 248 . In the illustrated embodiment, the anode side of the first end frame 240 includes at least one channel support 246 ( FIG. 5 ). The reverse side of the first end frame 240 , which faces, and is adjacent to, a first membrane assembly 250 , is described herein below when describing a membrane assembly side of a first interior frame 260 .
Referring again to FIG. 3 , adjacent to the first end frame is the first membrane assembly 250 . In an exemplary embodiment, the first membrane assembly 250 comprises a membrane 256 and an associated membrane gasket 254 . In a further exemplary embodiment, the membrane 256 is ripstop nylon with a thread count per square inch of 118×92 and with a weight per square yard of about two ounces. Ripstop nylon is durable and less-expensive than alternative materials and it is resistant to chemical attack by caustic feedwater 40 . In an exemplary embodiment, the nylon used in the membrane material is nylon 6,6. In a further exemplary embodiment, the nylon used in the membrane material is nylon 6. In an exemplary embodiment, the ripstop nylon membrane 256 is treated with a fluorocarbon-based water-repellent. In a further exemplary embodiment the ripstop nylon membrane 256 is not so treated. When wet, the membrane 256 enables electrons to selectively pass through. Additionally, and although not wishing to be bound by any particular theory, it is believed that the structure of the ripstop nylon material, with its inter-woven ripstop reinforcement threads in a crosshatch pattern, may effect a concentration of current density and improve cell efficiency.
In an exemplary embodiment, the membrane may also comprise other synthetic fabric materials. Polyamides, of which nylon is at type, also include aramids, a class of strong, heat-resistant fibers comprising aromatics.
The membrane gasket 254 effects a seal of the membrane 256 when included in the electrolyzer 102 . In an exemplary embodiment, the membrane gasket 254 comprises plastisol bonded to a border of the membrane 256 . The plastisol may be applied via a silkscreen process. The border of one side of the membrane 256 is coated with plastisol and heated, typically in an oven, sufficiently to bond the plastisol to the membrane 256 , in one exemplary embodiment, generally between about 140 deg. C. and about 170 deg. C. for between about 45 seconds and about 60 seconds. In another exemplary embodiment, about 175 deg. C. for about 90 seconds. The membrane 256 is then turned over and the border of the other side of the membrane 256 is coated with plastisol and heated as before. The bonds are complete after about 72 hours. Before treating with plastisol to form the membrane gasket 254 , the original dimensions of the membrane 256 are larger to accommodate shrinkage in the heating process.
The membrane gasket 254 comprises at least one water inlet 234 , an oxygen outlet 236 , a hydrogen outlet 238 , and a series of stack compression bolt holes 202 . A die punch may be used to form these holes, inlets, and outlets and may include a series of alignment jig posts (not shown). A series of alignment marks or holes 252 may be included on the membrane assembly 250 which cooperate with the die punch alignment jig posts to enable the membrane assembly 250 to be properly aligned on the die punch.
Plastisols are used to print textiles and are composed primarily of polyvinyl chloride (PVC) resin, typically a white powder, and a plasticizer, typically a thick, clear liquid. Optionally, a colorant may be added. The inks must be heated to cure, generally at temperatures in the range of 140-170 deg. C., as discussed above. The porosity of the textile permits good plastisol penetration and, therefore, good adhesion of the plastisol to the textile. When used with tightly-woven ripstop nylon, however, the plastisol may be combined with a nylon binding agent such as Nylobond™ Bonding Agent (NYBD-9120) (Union Ink Co., Ridgefield, N.J.). In an exemplary embodiment, the ink is Ultrasoft PLUS (PLUS-6000) (Union Ink Co.) and is formulated.
In a further exemplary embodiment, the plastisol is 900-series, such as 902LF, from International Coatings Co. (Cerritos, Calif.). These plastisol formulations include a premixed bonding agent catalyst. Exemplary curing is about 175 deg. C. for about 90 seconds.
In an exemplary embodiment, the membrane assembly 250 is about 0.009 inches thick at the membrane gasket 254 . Under compression in the electrolyzer 102 , the membrane gasket 254 compresses and the membrane assembly 250 compresses to about 0.005 inches.
Referring again to FIG. 3 , adjacent to the first membrane assembly 250 is a first interior frame 260 . Shown in FIG. 3 is the first membrane side of the first interior frame 260 . In an exemplary embodiment, the first interior frame 260 is HDPE. The first interior frame includes a chamber aperture 248 and, in the illustrated embodiment, 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). The first interior frame 260 also includes at least one water inlet 234 , an oxygen outlet 236 , and a hydrogen outlet 238 .
The side of the first interior frame 260 which faces an interior electrode 270 is further described herein below with the second interior frame 260 . On the interior electrode side of the first interior frame 260 is an electrode ledge 272 formed around the chamber aperture 248 into which the interior electrode 270 may nest. In an exemplary embodiment, the electrode ledge 272 has a depth of one-half the thickness of the interior electrode 270 . As will be appreciated by those skilled in the art, the interior electrode side of the first interior frame 260 , discussed below with the second interior frame 260 , and shown in detail in FIG. 4 , includes a channel 244 (not shown, but illustrated analogously with the second interior frame 260 of FIG. 4 ), analogous to the channel 244 , formed between the hydrogen outlet 238 (not shown, but illustrated analogously with the second interior frame 260 in FIG. 4 ) and the chamber aperture 248 . The channel 244 may further include at least one channel support 246 ( FIG. 5 ).
Turning now to FIG. 4 , adjacent to the first interior frame 260 is an interior electrode 270 . As will be appreciated by one skilled in the relevant art, the interior electrode 270 operates as a bi-polar electrode. In an exemplary embodiment, the interior electrode 270 is sized to nest within the electrode side of each interior frame 260 . In an exemplary embodiment, the interior electrode 270 is 18-gauge 316 stainless steel.
Adjacent to the interior electrode 270 is a second interior frame 260 . As shown in FIG. 4 , the interior electrode side of the second interior frame 260 faces the interior electrode 270 . In an exemplary embodiment, the second interior frame 260 is HDPE. The second interior frame 260 includes a chamber aperture 248 and, in the illustrated embodiment, 16 stack compression bolt holes 202 , which receive a like number of stack compression bolts (not shown). The second interior frame 260 also includes at least one water inlet 234 , and oxygen outlet 236 , and a hydrogen outlet 238 .
The side of the second interior frame 260 which faces the interior electrode 270 includes an electrode ledge 272 formed around the chamber aperture 248 into which the interior electrode 270 may nest. In an exemplary embodiment, the electrode ledge 272 has a depth of one-half the thickness of the interior electrode 270 . The interior electrode side of the second interior frame 260 includes a channel 244 formed between the oxygen outlet 236 and the chamber aperture 248 . The channel 244 may further include at least one channel support 246 ( FIG. 5 ).
The side of the second interior frame 260 which is adjacent to, and faces, a second membrane assembly 250 is analogously shown in detail and described with the side facing the first membrane assembly 250 of the first interior frame 260 ( FIG. 3 ).
Adjacent to the second membrane assembly side of the second interior frame 260 is a second membrane assembly 250 , which has been described herein above with the first membrane assembly 250 .
Adjacent to the second membrane assembly 250 is a second end frame 240 . In an exemplary embodiment, the second end frame 240 is HDPE. The second end frame 240 includes a chamber aperture 248 and, in the illustrated embodiment, 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). The second end frame 240 further includes at least one water inlet 234 , an oxygen outlet 236 , and a hydrogen outlet 238 . Shown in analogous detail in FIG. 3 , and as described analogously above in reference to the first end frame 240 , the cathode side of the second end frame 240 further includes a channel 244 (shown in analogously in FIG. 3 and discussed above with the first end frame 240 ) formed between the chamber aperture 248 and the hydrogen outlet 238 . Further, the channel 244 may include at least one channel support 246 .
Likewise, the cathode side of the second end frame 240 further includes a channel 244 formed between the chamber aperture 248 and the at least one water inlet 234 . Further, this channel 244 may include at least one channel support 246 .
Adjacent to the cathode side of the second end frame 240 is the cathode 231 . The description of the cathode 231 is similar to that of the anode 230 . The cathode 231 further includes an oxygen outlet 236 , a hydrogen outlet 238 , and one or more water inlets 234 .
Adjacent to the cathode 231 , and interposed between the cathode 231 and a stack open end compression plate 290 , is a stack open end insulator plate 280 . While the stack open end insulator plate 280 is formed similarly to the stack closed end insulator plate 220 , the stack open end insulator plate 280 further includes at least one water inlet 234 , an oxygen outlet 236 , and a hydrogen outlet 238 . In an exemplary embodiment, the stack open end insulator plate 280 is ¾-inch HDPE. The stack open end insulator plate 280 includes a series of stack compression bolt holes 202 . In the illustrated embodiment, there are 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). Also, in an exemplary embodiment, the stack open end insulator plate 280 includes an electrical stud hole 204 to receive, and to allow for protrusion of, the electrical stud 232 attached to the cathode 231 . On the cathode side of the stack open end insulator plate 280 may further include a set of seals such as O-rings (not shown) seated in a like set of grooves 284 formed to seal the one or more water inlets 234 , the oxygen outlet 236 , and the hydrogen outlet 238 formed in the cathode 231 . Likewise, a similar set of grooves 284 and seals may be included in the open end compression plate side of the open end insulator plate 280 .
Adjacent to the stack open end insulator plate 280 is the stack open end compression plate 290 . In an exemplary embodiment, the stack open end compression plate 290 is ¾-inch hot-rolled steel plate. The stack open end compression plate 280 may also comprise a material such as cold-rolled steel, composite, or other material with sufficient strength. In an exemplary embodiment, the surface of the stack open end compression plate 290 facing the stack open end insulator plate 280 is treated with blanchard grinding. The stack open end compression plate 290 also includes at least one water inlet 234 , an oxygen outlet 236 , and a hydrogen outlet 238 . Along a periphery of the stack open end compression plate 290 are a plurality of stack compression bolt holes 202 . In the illustrated embodiment, there are 16 stack compression bolt holes 202 which receive a like number of stack compression bolts (not shown). Also, in an exemplary embodiment, the stack open end compression plate 290 includes an electrical stud hole 204 to receive, and to allow for protrusion of, an electrical stud 232 attached to the cathode 231 .
The exemplary embodiment illustrated in FIGS. 3 and 4 shows one interior electrode 270 . Larger capacities may be assembled by adding additional interior parts. For example, a plurality of assemblies, each assembly comprising a membrane assembly 250 , a first interior frame 260 , an interior electrode 270 , and a second interior frame 260 , may be included. As appropriate, a first end frame 240 , an additional membrane assembly 250 , and a second end frame 240 , would be required.
Although not shown, the electrolyzer 102 may be held together with a plurality of stack compression bolts spanning the electrolyzer 102 from the stack closed end compression plate 200 and the stack open end compression plate 290 . Each compression bolt may be surrounded, substantially along its entire length, by a seal (not shown), which may also function as an insulator. By way of example only, such seal could be Parflex® (Parflex Division, Parker-Hannifin, Ravenna, Ohio) 588N-10 non-conducting, high-pressure hose. In an exemplary embodiment, the compression bolts are torqued to 55 pounds.
Turning now to FIG. 11 , in an exploded view of a further exemplary embodiment, a framed electrode 270 ′ may be provided and used in multi-cell electrolyzer. The electrode 270 is partially encased within, and formed as one with, two interior frames 320 which frames 320 may comprise HDPE. In the illustrated embodiment, the channels 244 have a depth that extends to the surface of the electrode 270 . Channel supports 246 may be omitted. As illustrated in FIG. 11 , one side of the framed electrode 270 ′ may comprise a tongue 264 and the other side a coordinating groove 266 to enhance fit and seal. Multiple framed electrodes 270 ′ could be combined with, for example, multiple framed membranes 256 ′, described below.
In a further exemplary embodiment shown in FIG. 12 , a framed membrane 256 ′ may also be provided and used in multi-cell electrolyzers 102 . A membrane 256 , which may not include a membrane gasket 254 , is partially encased within, and formed as one with, two frames 330 . As shown in FIG. 12 , the membrane 256 is large enough to extend beyond the water inlets 234 and the hydrogen 238 and oxygen 236 outlets. In addition, the associated holes in the membrane 256 (shown as 234 ′, 238 ′, and 236 ′, respectively) are larger than their counterparts. This enables the frame material (e.g., HDPE) to seal the holes 234 , 238 , and 236 . In addition, where peripheral bolt holes 202 (not shown in FIG. 12 ) are included, such holes in the membrane 256 may also be larger. In the illustrated embodiment, the channels 244 have a depth that does not extend to the surface of the membrane. As illustrated in FIG. 12 , one side of the framed membrane 256 ′ may comprise a tongue 264 and the other side a coordinating groove 266 to enhance fit and seal.
In a further exemplary embodiment, the framed membrane 256 ′ further comprises an electrode ledge 272 ( FIG. 4 , shown associated with the interior frame 260 , e.g.) formed therein. As constructed, then, a plurality of framed membranes 256 ′ may be stacked with an interior electrode 270 inserted therebetween.
In an exemplary embodiment, interior frames 260 have a gross thickness at the borders of about 0.110 in. The thickness of the interior frame 260 along the edge of the electrode ledge is about 0.086 in. When torqued, the membrane assembly is about 0.005 in. This configuration results in an inter-electrode gap of about 0.177 in.
FIG. 6 illustrates the detail of the fabric of a ripstop nylon membrane 256 . As shown, the membrane 256 includes a pattern of ribs 300 comprising interwoven ripstop reinforcement threads in a crosshatch pattern with fabric planes 302 therebetween.
FIG. 5 illustrates the detail of a channel 244 between an illustrative oxygen outlet 236 and an aperture 248 . One or more channel supports 246 are shown which help keep the channel 244 from collapsing under the compressive load. Also shown in FIG. 5 is the electrode ledge 272 for providing fit and sealing to the interior electrode 270 ( FIG. 4 ).
Turning now to FIG. 7 , shown generally is the electrolyzer process 100 , the electrolyzer 102 is shown, along with the hydrogen collector 104 , the oxygen collector 106 , and a hydrogen expansion tank 105 . Feedwater 40 , which is formed from the water supply 34 and the electrolyte supply 36 , is drawn from the feedwater tank 38 ( FIG. 1 ). Feedwater 40 is supplied by a pump 126 and managed by a solenoid valve 132 which are described more fully herein below. As can be seen in FIG. 7 , feedwater 40 may be balanced throughout the electrolyzer process 100 and provides feedwater 40 in the electrolyzer 102 , the hydrogen collector 104 , and the oxygen collector 106 . The feedwater 40 enters the electrolyzer 102 through the one or more water inlet 234 , shown illustratively in FIG. 7 as two water inlets 234 . Feedwater 40 also provides a controlled liquid level in the hydrogen collector 104 and the oxygen collector 106 , the control of which is described more fully herein below. An electrical supply 156 and power supply 134 are also provided and shown in FIG. 7 . In the illustrated embodiment, 250VDC power is supplied to the cathode 231 (not shown) and to the anode 230 (not shown) through the electrical studs 232 . During operation, hydrogen 32 and oxygen 30 are withdrawn from the electrolyzer 102 through the hydrogen outlet 238 and oxygen outlet 236 , respectively.
The hydrogen collector 104 may include appropriate liquid level sensors and transmitters. Four such instruments are shown in FIG. 7 . A water level high transmitter 136 indicates when the water level in the hydrogen collector 104 is high. A water level low transmitter 148 indicates when the water level in the hydrogen collector 104 is low. A pair of water level transmitters 140 , 144 initiate turning off and on, respectively, the feedwater pump 126 . As will be appreciated by those skilled in the art, the functions of these multiple level transmitters may be provided by as few as one sophisticated level transmitter. At the outlet of the hydrogen collector 104 is a hydrogen relief valve 128 .
The illustrative embodiment shown in FIG. 7 further includes a hydrogen expansion tank 105 downstream of the hydrogen collector 104 . In an exemplary embodiment, the hydrogen expansion tank 105 helps stabilize the levels of water in the hydrogen collector 104 and the oxygen collector 106 when starting up with pressure preexisting in the hydrogen storage 12 ( FIG. 1 ). A hydrogen expansion tank 105 having a volume of about 0.58 times the oxygen collector 106 should accomplish feedwater level stability long enough for the pressure in the electrolyzer process 100 to rise above the pressure in the hydrogen storage 12 ( FIG. 1 ) and allow hydrogen to flow from the hydrogen collector 104 to the hydrogen storage 12 ( FIG. 1 ). Lacking this feature, the feedwater level in the hydrogen collector 104 could drop enough to prematurely activate the feedwater pump 126 which could cause the electrolyzer process 100 to overfill with feedwater 40 . In such case, as the electrolyzer process 100 becomes overfilled, as described above, when the system reaches pressure above that of the hydrogen storage 12 , the water in the hydrogen collector 104 will reach the high water level fault indicator before the oxygen release valve 130 on the oxygen collector 106 is triggered by the level transmitter 150 . Thus, unwanted or unnecessary shutdowns are avoided. Alternatively, the hydrogen collector 104 may be sized sufficiently larger than the oxygen collector 106 .
Associated with the oxygen collector 106 , and downstream thereof, is an oxygen sensor 158 (e.g., Bosch 13275). The oxygen sensor 158 is used to detect, by inference, hydrogen in the oxygen 30 . Of course, a second oxygen sensor 158 could be used to detect oxygen in the hydrogen 32 . Also included with the oxygen collector 106 may be a pressure relief valve 172 .
The oxygen collector 106 may also include appropriate liquid level sensors and transmitters. Six such instruments are shown in FIG. 7 . A water level high transmitter 138 indicates when the water level in the oxygen collector 106 is high. A water level low transmitter 154 indicates when the water level in the oxygen collector 106 is low. In addition, a series of sensors and transmitters control the discharge of oxygen 30 from the oxygen collector 106 . In the illustrated embodiment, there are a pair of oxygen-off transmitters 142 , 146 that effect the closing of an oxygen release control valve 130 . In operation, when the water level in the oxygen collector 106 rises to either oxygen-off transmitter 142 , 146 , the oxygen release control valve 130 is closed and remains closed until the water level lowers to a point which activates either oxygen-on transmitter 150 , 152 at which time the oxygen release control valve 130 is opened and remains open until the water level rises and actuates oxygen-off transmitter 142 , 146 at which time the oxygen release control valve 130 is closed. During operation this cycle repeats to continuously balance the electrolyzer process 100 and remains active even if the electrolyzer process 100 is not active. As will be appreciated by those skilled in the relevant art, the functions of these multiple level transmitters may be provided by as few as one sophisticated level transmitter.
Further illustrated in the exemplary embodiment shown in FIG. 7 are one or more heat transfer coils 107 which can effectively utilize excess heat. Shown in FIG. 7 is a coil 107 within each collector 104 , 106 and in combination with a fan 120 . A pump 124 circulates a suitable heat transfer fluid (e.g., water) through the collectors 104 , 106 and the heat sink 107 associated with the fan 120 . The excess heat recovered from the collectors 104 , 106 may be utilized, for example, in space heating or by placing a coil 107 downstream of the air handler of a forced air furnace.
Circuit Diagrams
The following tables are intended to provide exemplary values for the electronic circuit elements shown in FIGS. 8-10 and described herein.
Resistors (Ω)
R1 = 100K
R2 = 100K
R3 = 10
R4 = 47K
R5 = 100K
R6 = 100
R7 = 22K
R8 = 470
R9 = 100K
R10 = 100K
R11 = 470
R12 = 470
R13 = 100
R14 = 100
R15 = 100K
R16 = 100K
R17 = 470
R18 = 47K
R19 = 100K
R20 = 470
R21 = 22K
R22 = 100K
R23 = 100K
R24 = 470
R25 = 47
R26 = 100
R27 = 100K
R28 = 47K
R29 = 22K
R30 = 470
R31 = 10 meg
R32 = 100K
R33 = 100K
R34 = 0.001
Capacitors (μf)
C1 =
C2 =
C3 = 100
C4 = 100
C5 = 0.1
C6 = 0.001
0.001
0.001
C7 =
C8 =
C9 = 0.001
C10 = 4700
C11 = 0.001
C12 = 0.001
0.001
0.001
C13 =
0.001
Transistors (MOSFET)
T1 = 2984
T2 = 2984
T3 = 2984
T4 = 2984
T5 = 2984
T6 = 2984
T7 = 2984
T8 = 2984
T9 = 2984
T10 = 2984
Amplifiers
A1 = NTE 943
A2 = NTE 943
A3 = NTE 943
Integrated Circuits
IC1 =
IC2 = 555
IC3 = 960
IC4 = 4013
IC5 = 960
IC6 = 4013
4013
IC7 =
4013
Diodes
D1 = high
D2 = 1N914
D3 = power
D4 = H 2 storage
D5 = 1N914
D6 = water
temperature
on
tank full
level fault
D7 = 1N914
D8 = H2 in
D9 = pump
D10 = 1N914
D11 = 1N914
D12 = system
O 2 fault
on
warm
Switches
S1 = control
S2 = control
S3 = continuous
S4 = 136-H 2
S5 = 138-O 2
S6 = 148-H 2
system off
system on
or pulsed
water high
water high
water low
operation
S7 = 154-O 2
S8 = 142-O 2
S9 = 146-O 2
S10 = 150-O 2
S11 = 152-O 2
S12 = 140-
water low
release closed
release closed
release open
release open
feedwater
pump off
S13 = 144-
feedwater
pump on
Contactors
Coil K1 and
Coil K2 and
Coil K3 and
K4 = K4-over
K5 = K5-
K6 = K6-
contact K1-
contact K2-
contact K3-
temperature
solid state relay
solid state relay
energizes coil
time delay
battery saver
redundancy
K2
operates
circuit
pump and water
input solenoid
Looking first at FIG. 8 , a power logic circuit 400 controls the overall control scheme. Power logic circuit 400 cooperates with the water level fault circuit 440 to shut off power if the water level becomes unbalanced. For example, if either of switches S 4 -S 7 are closed (see, also, FIG. 7 ), a fault condition is indicated at D 6 and a fault condition goes from fault output 442 to fault input 402 . The power logic circuit 440 also cooperates with the oxygen sensor circuit 460 ( FIG. 10 ) to shut off power if an unsafe level of hydrogen arises in the oxygen (see, also, FIG. 7 ). For example, if the oxygen sensor 158 detects an unsafe level of hydrogen in the oxygen, a fault condition is indicated at D 8 and a fault condition goes from fault output 462 to fault input 402 .
An operational temperature circuit 410 monitors heat levels in the electrolyzer 102 . A thermistor 174 (see, also, FIG. 7 ) actuates when an unsafe temperature level (e.g., 160 deg. F.) is reached. This condition is indicated by LED D 1 . This shuts off the power to the electrolyzer 102 , which remains off until the temperature drops below the preset temperature level. Thus, the electrolyzer 102 turns on and off to keep the electrolyzer 102 within a safe temperature regime.
An intermittent/pulsed operation circuit 420 provides adjustable intermittent power through a switch S 3 to the electrolyzer 102 to regulate heat and to improve efficiency. This circuit also enables varying modes of operation of the electrolyzer 102 . For example, the circuit may be cycled on-and-off at intervals from about one second to about two minutes or greater. This allows the hydrogen and oxygen to clear the electrodes, thereby increasing the effective surface area of the electrode. In addition, such intermittent operation assists in controlling the heat of the hydrogen generation system. In addition, the intermittent/pulsed operation circuit can enable the hydrogen system 10 to more effectively utilize power available from the wind turbine 24 ( FIG. 1 ). An intermittent no-load condition of the wind turbine 24 allows it to gain inertia in low wind conditions. Then, when a load is applied, the kinetic energy of the spinning turbine 24 is applied to the electrolyzer 102 .
A pressure switch circuit 430 controls the pressure in the hydrogen storage 12 ( FIG. 1 ) via a pressure switch 170 . As long as the pressure switch 170 is closed, indicating below preset maximum pressure in the hydrogen storage 12 , MOFSET T 4 conducts to coils K 5 and K 6 which are operably connected to contacts K 5 and K 6 (shown in the power supply circuit 490 , FIG. 9 , discussed below) and power remains on. When the pressure in the hydrogen storage 12 reaches the preset maximum pressure, power to the electrolyzer 102 is shut off. Normal operation is indicated at an LED D 3 and a full pressure condition in the hydrogen storage 12 is indicated at an LED D 4 . When the pressure in the hydrogen storage 12 drops below a preset pressure condition, indicating there is room for more hydrogen in the hydrogen storage 12 , power to the electrolyzer 102 is turned back on.
A water level fault circuit 440 monitors the water levels in the collection towers 104 , 106 and shuts off power if the water level becomes unbalanced. The water level fault circuit 440 cooperates with the power logic circuit 400 discussed above.
Associated with the pump control circuit 450 a , shown in FIG. 8 , is a pump control circuit 450 b shown in FIG. 9 . And, shown associated with the pump control circuit 450 b are two switches, switch S 12 , which is operably connected to the water pump off level transmitter 140 on the hydrogen collector 104 , and switch S 13 , which is operably connected to the water pump on level transmitter 144 on the hydrogen collector 104 . In operation, when level transmitter 144 senses a need for feedwater 40 , coil K 1 is energized in the pump control circuit 450 b ( FIG. 9 ) which closes contact K 1 in the pump control circuit 450 a ( FIG. 8 ). The closing of contact K 1 energizes coil K 2 of the pump control circuit 450 a which closes contact K 2 of the pump control circuit 450 a , thus powering the feedwater pump 126 ( FIGS. 7 and 8 ) and opening the feedwater solenoid valve 132 ( FIG. 7 ). When the level transmitter 140 on the hydrogen collector 104 senses sufficient feedwater 40 , coil K 1 is de-energized and the feedwater pump 126 is turned off and the feedwater solenoid valve 132 is closed. Coil K 2 de-energizes after a preset time and must be reset in order to be reactivated. This provides protection to the pump 126 in such case when the feedwater 40 has been turned off or is empty. It also helps prevent overfilling in the event water level transmitter 140 fails.
Turning now to FIG. 10 , the oxygen sensor circuit 460 interprets the voltage levels of the oxygen sensor as it correlates to the proportion of hydrogen in the oxygen. The oxygen sensor circuit 460 cooperates with the power logic circuit 400 ( FIG. 8 ). The oxygen sensor circuit 460 will shut down the electrolyzer process 102 if the level of hydrogen in the oxygen 30 reaches unsafe levels by energizing a fault output 462 which is fed into the fault input 402 of the power logic circuit 400 . An indicator LED D 8 is also illuminated.
A battery saver circuit 470 shown in FIG. 9 is designed to automatically disconnect a battery 476 from the control circuits, thus preventing complete discharge of the battery 476 in the event of an extended power failure. This disconnect will occur if a power interruption lasts longer than about eight hours. The battery saver circuit 470 automatically reconnects the battery 476 when power is restored. The eight hours of standby allows for cool down and release of pressure by the control circuits in case of a power failure. This helps prevent the control circuits from draining the battery 476 in the event of an extended power outage.
In operation, when AC power is present, the standby transformer 472 supplies power to the rectifier diode D 10 which feeds IC 5 . The output of IC 5 then charges capacitor C 10 through blocking diode D 1 . When charge is sufficient, the logic level MOSFET T 10 conducts and energizes coil K 3 . This connects the battery 476 to the control circuits and a 12VDC power supply via a normally-open contact K 3 . If AC power is removed, or a power outage is experienced for e.g., eight hours or other preset time, the MOSFET T 10 de-energizes K 3 which effectively disconnects the battery 476 .
A warm-up circuit 480 monitors the warm-up phase of the operation of the electrolyzer process 100 and regulates the pressure inside the electrolyzer 102 . An LED D 12 is illuminated when the electrolyzer process 100 reaches operational temperature. With further reference to FIG. 7 , during the warm-up phase, a hydrogen relief valve 128 is opened to vent the hydrogen 32 being produced to prevent any pressure from developing until the electrolyzer 102 reaches a preset and adjustable temperature that causes the electrolyzer 102 to expand and tightens the seals to hold pressure. In the alternative, a flare system may be provided to burn hydrogen being vented. The hydrogen relief valve 128 is then closed and the hydrogen 32 is further processed, in, for example, a dryer 122 and sent to hydrogen storage 12 ( FIG. 1 ). If power to the electrolyzer process 100 is shut down for a period of time that would be sufficient for the electrolyzer 102 to contract, the bypass valve 128 is reopened to relieve all pressure from the electrolyzer 102 to prevent damage.
A power supply circuit 490 controls the main power to the electrolyzer 102 . In an exemplary embodiment, a rectifier 498 converts 240VAC to 250VDC using two NTE6036 diodes and two NTE6037 diodes. As a redundant backup to the high temperature circuit 410 which includes thermistor 174 , a thermal fuse 496 , set to 180 deg. F. or whatever reform temperature of the material used in the electrolyzer 102 , for example HDPE, helps protect the electrolyzer 102 from a thermal overload. If the thermal fuse 496 is tripped, a coil K 4 is de-energized and two contacts K 4 are opened, shutting off power to the electrolyzer 102 . In addition, de-energizing coils K 5 and K 6 opens contacts K 5 and K 6 to shut off power to the electrolyzer 102 . This may be effected by such conditions as a water level fault 442 , the off button SI, a high temperature condition, oxygen mix, the intermittent circuit 420 , or the pressure switch 170 . Also shown in FIG. 9 is a fan 499 to help cool the rectifier 498 and solid state relays K 5 and K 6 .
Also shown in FIG. 9 is a water level balance circuit 500 which is operably connected to the electrolyzer process 100 . Switches S 8 and S 9 , associated with level transmitters 142 and 146 , respectively, cause the oxygen release solenoid 130 ( FIGS. 7 and 9 ) to be closed. Conversely, switches S 10 and S 11 , associated with level transmitters 150 and 152 , respectively, cause the oxygen release solenoid 130 to be open. Thus, the water level in the electrolyzer process 100 is balanced.
Test Results
Tests were performed on an electrolyzer having the following configuration:
Number of Cells
111 cells
Electrode Size
11 × 11 inches
Inter-electrode Gap
0.177 inches
Feedwater
5 oz. NaOH per
Nominal Voltage
240 VAC (converted
5 gal. distilled water
to DC with four 85-amp diodes
in a bridge configuration)
Test 1
Time
4.5 minutes
Average
253.3 V
Voltage
Average Amperage
27.43 amps
KWH
0.5211 KWH
H2 Produced
4.32 scf
H2 Conversion
0.0791 KWH/cu. ft.
H2
H2 KWH
0.34 KWH
Efficiency
65.2 percent
Equivalent
Test 2
Time
1 hour
Average
240 V
Voltage
Average Amperage
35 amps
KWH
8.4 KWH
H2 Produced
66.84 scf
H2 Conversion
0.0791 KWH/cu. ft.
H2
H2 KWH
5.28 KWH
Efficiency
62.9 percent
Equivalent
Test 3
Time
9 minutes
Average
246.5 V
Voltage
Average Amperage
36.76 amps
KWH
1.36 KWH
H2 Produced
11.36 scf
H2 Conversion
0.0791 KWH/cu. ft.
H2
H2 KWH
0.90 KWH
Efficiency
66.1 percent
Equivalent
While certain preferred embodiments of the present invention have been disclosed in detail, it is to be understood that various modifications may be adopted without departing from the spirit of the invention of scope of the following claims. | A membrane for use with an electrochemical apparatus is provided. The electrochemical apparatus may include a fuel cell or electrolyzer, for example, an electrolyzer adapted to produce hydrogen. The membrane comprises a fabric made from a synthetic fiber such as nylon where the nylon, in an exemplary embodiment, is woven into ripstop nylon fabric. The electrochemical apparatus is constructed with frames comprising high-density polyethylene (HDPE) which provide support and structure to the membranes as well as to internal electrodes. A method of making an electrochemical apparatus, such as an electrolyzer, containing a membrane comprising ripstop nylon is also disclosed, as is a method for producing hydrogen gas with an electrolyzer containing a membrane comprising ripstop nylon. | 8 |
CROSS REFERENCE TO CO-PENDING APPLICATIONS
The present application is related to U.S. Pat. application Ser. No. 08/235,196, which is a continuation of application Ser. No. 07/762,276, entitled "Data Coherency Protocol for Multi-level Cached High Performance Multiprocessor System", filed Sep. 19, 1991 and assigned to the assignee of the present invention. The related patent application is herein incorporated by reference.
BACKGROUND OF THE INVENTION
A. Field of Invention
This invention relates to the area of data processing systems where a plurality of processors are competing for exclusive access to a portion of an addressable memory.
B. Status of the Prior Art
In data processing systems having multiple processors sharing a common addressable memory, a plurality of programs or processes are executed in parallel. This yields the advantage of increased throughput performance over machines where there is a single processor executing a single process.
Where there are multiple processes cooperating to perform a programmed function, a high level of coordination is necessary to ensure proper operation where resources are shared. One resource which may be shared in multi-processor data processing systems is addressable memory. It is well known in the art that machine language macro-instructions such as the biased-fetch, test-and-set, increment-and-test, or conditional-replace can be provided to accommodate the sharing of addressable memory. During execution of these instructions, the portion of memory upon which the operation is being performed is exclusively held, or "locked", by the processor executing the instruction; thus, they are referred to as "storage lock instructions". Should another processor attempt to execute a similar type of instruction on the same portion of memory while the first processor has that portion of memory locked, the second processor will be denied access to the storage location until the first processor has completed its exclusive use operation and has released the lock.
Each new generation of data processing systems has brought architectures having more and faster processors to drive the system. With respect to storage lock instructions, each generation has sought to keep the time required to coordinate lock processing to a minimum and maximize system performance.
The two basic approaches to storage lock operations are the "distributed" and "centralized" approaches. In the centralized approach to locking storage, the particular storage unit being locked contains the locking logic, and a lock granted signal must be provided to the processor requesting the lock to indicate that it has exclusive use of the requested storage location. In contrast, the distributed approach places the locking logic within each processor. Where each processor has the locking logic, a high level of coordination between the processors is necessary to ensure that a deadlock situation does not occur.
The distributed approach to processing storage lock instructions is shown in U.S. Pat. No. 4,984,153 issued Jan. 8, 1991 to Glen Kregness et al. for a "Storage Locking Control for a Plurality of Processors Which Share a Common Storage Unit" and assigned to Unisys Corporation, wherein each of the processors keeps a copy of each location in the shared storage which is locked by each of the processors. Special arbitration logic is provided to deal with the case where two processors request a lock simultaneously. This approach places the arbitration and locking logic at the processor level of the architecture, and results in lock processing overhead for the processor which is directly proportional to the number of processors in the system. Furthermore, with the point-to-point communications shown, the space required for inter-processor cabling drastically increases as each additional processor requires cables between the it and each processor already in the system.
The "Lock Control for a Shared Storage in a Data Processing System" described in U.S. Pat. No. 4,733,352, issued Mar. 22, 1988 to Kouji Nakamura et al., shows a plurality of processors sharing a main storage through a plurality of storage controllers. Each storage controller is coupled to a main storage unit and processes the main storage requests for each of the coupled processors. While the described locking mechanism removes the locking logic from the processors and thereby reduces the cabling between the processors, its locking mechanism has each locking unit maintaining a copy of lock information stored in the other locking unit. When the lock information is duplicated in the lock units, extra logic hardware is required to synchronize the lock operation between each of the lock units.
The "Shared Resource Locking Apparatus" described by Starr in the International Patent Application published under the Patent Cooperation Treaty, International Pub. No. WO 83/04117, has a hardware lock unit for limiting concurrent use of shared memory in a data processing system with a bus architecture. The publication shows that where the lock unit is centralized with respect to the resource being locked, logic for coordinating between lock units is unnecessary. When a processor wishes to lock a selected portion of addressable memory, it sends its processor identification, a read command, and an address indicating the memory portion to be locked over the system bus to the shared memory unit. The shared memory unit then checks whether the memory portion indicated is already locked by another processor. If so, the lock request is held and the read from memory is not performed. The requesting processor must await its turn to lock the indicated portion of memory, and the shared memory unit waits until the lock is granted to perform the read operation. Each portion of the shared memory that is to be treated as a separate lockable resource has a lock register. The lock register contains an identifier for the requestor currently having the resource locked, and a bit map field indicating which processors have lock requests outstanding for the resource.
The above-referenced patents do not disclose the system of the present invention for locking a portion of addressable memory. The system set forth reduces the locking logic by centralizing the locking control, minimizes the point-to-point cabling necessary for multiple processors, performs the lock control and memory read operations in parallel, and detects when processors become inoperative to avoid deadlock. These and other advantages are described in more detail in the following discussion.
OBJECTS OF THE INVENTION
It is therefore a primary object of the present invention to provide an improved storage locking system for data processing systems having a plurality of processors contending for exclusive use of a portion of addressable memory.
Yet another object of the present invention is to minimize the processing overhead for processors requesting exclusive use of a portion of addressable memory.
It is a further object of the present invention to perform a storage lock operation and storage read operation concurrently.
It is also an object of the present invention to avoid deadlock situations by releasing a storage lock when a processor, which has been granted a lock on a portion of memory, becomes inoperative.
It is still a further object of the present invention to provide a storage locking system for data processing systems having a plurality of processors and a plurality of addressable memories of which a selected portion can be locked.
It is a further object of the present invention to eliminate the point-to-point connections between a plurality of processors requesting lock operations on a plurality of shared addressable memories.
SUMMARY OF THE INVENTION
According to the present invention, a set of lock registers is provided for storing the address of the selected portions of memory which are in exclusive use by the processors in the data processing system. An associated lock register is provided for each processor in the system. When a processor requests and is granted exclusive use of the selected portion of memory, a lock bit associated with the particular lock register is set to indicate that the associated processor has exclusive use of the selected portion of memory indicated by the address stored in the lock register; and a lock granted signal is returned to the requesting processor. If the selected portion of memory upon which the processor requests exclusive use is already locked by another processor, a lock request bit associated the particular lock register is set to indicate that the requesting processor has requested exclusive use of the selected portion of memory indicated by the address stored in the associated lock register.
When a processor releases the exclusively held selected portion of memory after completing execution of a storage lock instruction, the lock bit associated with the lock register for the processor is cleared. Lock-priority logic selects one of the processors which has its lock request bit set and whose address stored in the associated lock register is equal to the address stored in the lock register of the processor releasing the lock, to be the next processor to receive exclusive use of the selected portion of memory. The priority logic utilizes a round-robin priority scheme. The lock-bit associated with the selected processor is set, a lock-granted signal is returned to the requesting processor, and the lock-request bit for the selected processor is cleared.
In another aspect of the present invention, the lock-control logic is distributed among a plurality of storage controllers, wherein each of the storage controllers controls access to the memory to which it is directly coupled. Each storage controller also has a plurality of processors to which it is directly coupled. Furthermore, each storage controller is directly coupled to each of the other storage controllers, thereby providing a directly coupled processor with indirect access to the addressable memory directly coupled to another storage controller. A processor seeking access to addressable memory first sends the memory request (an example being a lock-request) to its directly coupled storage controller. If the requested address is in the addressable memory controlled by the directly coupled storage controller, it processes the request. If the requested address is not in its addressable memory, the storage controller sends the request to the appropriate storage controller. A lock-request is sent to the lock-control logic in the storage controller for which the memory request was requested and processed as described above.
Three particular advantages are realized with the design of the present invention. First, the advantages of point-to-point communication with the advantages of centralized locking logic. The controllers which control the resource to be locked are directly coupled one to another, thereby minimizing the time required to communicate with one another. Furthermore, the locking logic is centralized in each of the controllers, and each controller is directly coupled to a plurality of processors which may make a lock request. Centralizing the lock logic in the controllers removes the lock processing overhead from the requesting processors and further eliminates the interprocessor cabling necessary when the lock logic is distributed among the requesting processors.
Second, increased performance via a parallel processing of read-lock operation is realized. Overall throughput is increased by allowing a memory read operation to proceed in parallel with the lock logic processing. This eliminates the two step process evident in the prior art where first a lock was requested and granted before the memory read request could be processed. By processing the lock and memory read operations in parallel, the requested data is made available to the requesting processor independent of the arrival of the lock-granted signal.
Third, deadlock situations are avoided by monitoring the status of each processor which makes storage lock-requests. If a processor becomes inoperative during the time which it has a storage location locked, the storage location which is locked by the inoperative processor is released and another processor waiting for the locked storage location is granted the lock.
The foregoing and various other aspects of the invention will become apparent from a consideration of the Drawings and the following detailed Description of the Preferred Embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of the overall data processing system in which present invention is utilized;
FIG. 2 is a block diagram of an Instruction Processor for executing instructions which is coupled to a Storage Controller;
FIG. 3 is a logic diagram of the IP Lock Control for coordination of lock processing;
FIG. 4 is a block diagram of the overall Lock Control within a Storage Controller for managing storage lock operations;
FIG. 5 is a logic diagram for the Lock Control Logic in the Storage Controller and the affected Lock Registers; and
FIG. 6 is a general timing diagram of Lock Request processing with a single Storage Controller and two Instruction Processors.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a block diagram of the overall data processing system in which the present invention is utilized. The system show is that of the 2200/900 Series data processing system, commercially available from Unisys Corporation. The fully populated system consists of a configuration built around four Storage Controllers 10, 12, 14, and 16, respectively. Storage Controller 10 is exemplary of the other Storage Controllers 12, 14, and 16 and will be used in the following general discussion. It should be understood that the general operation of Storage Controllers 12, 14, and 16 can be understood from the following discussion of Storage Controller 10.
Storage Controller 10 controls access to two locally associated addressable Memory Units 20 and 22. Each addressable Memory Unit 20 and 22 contains addressable memory space for purposes of storing data and computer instructions. Similarly, Storage Controller 12 controls access to locally associated addressable Memory Units 24 and 26, Storage Controller 14 controls access to locally associated addressable Memory Units 28 and 30, and Storage Controller 16 controls access to its locally associated addressable Memory Units 32 and 34.
Two local Instruction Processors, IP 40 and IP 42 are directly coupled to the Storage Controller 10. The Instruction Processors 40 and 42 can send requests for access to specified locations in addressable memory to the Storage Controller 10. If the address requested is contained within local addressable Memory Unit 20 or Memory Unit 22 controlled by Storage Controller 10, the request is processed locally. Otherwise, the memory request is sent by Storage Controller 10 to the appropriate remote Storage Controller 12, 14, or 16 depending upon the particular address requested. The Storage Controllers 12, 14, and 16 are also shown with their local directly coupled Instruction Processors IP 44 and IP 46, IP 48 and IP 50, and IP 52 and IP 54.
Storage Controller 10 also has an Input Output Controller, IOC 60. IOC 60 controls the transfer of data between peripheral data storage devices, such as tapes and disks, show collectively as Peripheral Devices 61, and Storage Controller 10. IOC 62, IOC 64, and IOC 66 are similarly coupled to the respective Storage Controllers 12, 14, and 16, and are coupled to associated Peripheral Devices 63, 65, and 67 respectively.
Storage Controller 10 is directly coupled (not bussed) to each of Storage Controllers 12, 14, and 16. Coupling 82 represents the direct coupling for sending memory and lock requests from Storage Controller 10 to Storage Controller 12, and Coupling 84 represents the direct coupling for sending memory and lock requests from Storage Controller 12 to Storage Controller 10. The remaining inter-couplings are similar in function and are shown by lines 86, 88, 90, 92, 94, 96, 98, 100, 102 and 104.
FIG. 2 is a block diagram of an Instruction Processor for executing instructions which is coupled to a Storage Controller. IP 40 provides instruction execution for programs stored in Memory Units 20 and 30. Each IP is functional to call instructions from the addressable Memory Units 20, 22, 24, 26, 28, 30, 32, and 34, execute the instructions, and, in general, do data manipulation. The Instruction Processor 40 has an Execution Unit 150 for executing instructions retrieved from memory and manipulating data. An Interrupt Control 154 is coupled to all units within the Instruction Processor 40 for signalling interrupts due to error detection and other preemption conditions.
The Instruction Processor 40 has a Cache Control and Storage 156 consisting of an instruction cache and an operand cache for providing high speed access to the data stored within. The Cache Control 156 is coupled to a Storage Controller Function Generator 158 which generates various request functions to the Storage Controller 10. An example case is where the Execution Unit 150 seeks access to a memory location via Cache Control 156. If Cache Control 156 determines that the requested address is not available in the cache storage, a signal is provided to the SC (Storage Controller) Function Generator 158 indicating that the requested address is not available in the cache storage and must be retrieved. The operation code (also referred to as a request) generated by the SC Function Generator 158 is forwarded to the IP-to-SC Interface Control 160 to be transmitted to the coupled Storage Controller 10. The operation code contains an address code portion indicating the desired address and a function code portion indicating the desired operation, such as a lock request.
IP Lock Control 162 coordinates the processing of storage lock instructions. The Instruction Processor Lock Control 162 signals the Execution Unit 150 when exclusive control of the requested location has been granted by Lock Control 206 and coordinates the release of the locked memory location when execution of the special instruction is complete.
The main function of Storage Controller 10 is to manage the data traffic of the system. Requests for Memory Units 20 and 22 are processed within the Storage Controller 10. Requests for any of the other addressable Memory Units 24 and 26, 28 and 30, and 32 and 34 (shown in FIG. 1) are routed to the appropriate Storage Controller 12, 14, or 16. IP 40, IP 42, and IOC 60 will be referred to as "local requesters" when they request access to Memory Units 20 or 22 which are controlled by the Storage Controller 10 to which the requesters are directly coupled. IP 40, IP 42, and IOC 60 will be referred to as "remote requesters" when they request access to Memory Units 24 and 26, 28 and 30, and 32 and 34 which are controlled by a Storage Controllers 12, 14, and 16 respectively, other than the Storage Controller 10 to which the requesters are directly coupled.
Within Storage Controller 10 is the IP (Instruction Processor) and IOC (Input/Output Controller)-to-SC (Storage Controller) Interface Control 170. This logic controls the communication between the Storage Controller 10 and each directly coupled (not bussed) IP 40, IP 42 and IOC 60. Line 172 represents the coupling between Storage Controller 10 and IP 40; line 174 represents the coupling between Storage Controller 10 and IP 42 (not shown); and line 176 couples Storage Controller 10 to IOC 60 (not shown).
Storage Controller 10 also has a Storage Controller (SC) to SC Interface Control 178 for controlling communications between Storage Controller 10 and Storage Controllers 12, 14, and 16. The 2200/900 Series data processing system, in which the present invention is implemented, has possible configurations consisting of one to four Storage Controllers. Lines 82 and 84, 94 and 96, and 102 and 104 represent the coupling between Storage Controller 10 and Storage Controllers 12, 14, and 16 respectively. The coupling between each pair of Storage Controllers is direct, not bussed, and has separate lines for requests received by a Storage Controller and requests sent from a Storage Controller.
Storage Controller 10 also provides caching of data stored in the addressable Memory Units 20 and 22. The Storage Controller 10 reduces access time to data stored in Memory Units 20 and 22 by caching data from the Memory Units in Second Level Caches 186 and 188. Second Level Cache 186 buffers data for Memory Unit 20 and Second Level Cache 188 buffers data for Memory Unit 22. When Second Level Cache 186 detects that the requested memory address is present in its buffer storage, that data is returned to the requester via line 190. In the case of a local requester, the data passes to the local requester via the IP and IOC-to-SC Interface Control 170; in the case of a remote requester, the data passes to the Storage Controller controlling the remote requester via the SC-to-SC Interface Control 178. Similarly, data returned from Second Level Cache 188 passes via line 192.
Priority Controls 194 and 196 select a single memory request to present to the corresponding Second Level Caches 186 and 188. Because memory requests can come from the local IPs, 40 and 42, the local IOC 60, and remote Storage Controllers 12, 14, and 16 simultaneously, a priority mechanism is necessary to select one of the multiple requesters for which the memory access is directed to the respective Second Level Cache. Lines 198 are input requests from the SC-to-SC Interface Control 178 to the Priority Controls 194 and 196; they represent the requests made by the remote requesters coupled to Storage Controllers 12, 14, and 16. Lines 200 are inputs from the IP and IOC-to-SC Interface Control 170 to the Priority Controls 194 and 196; and they represent the requests made by the local requesters: IP 40, IP 42, and IOC 60.
When a memory request is selected by Priority Controls 194 and 196 for processing by the Second Level Caches 186 and 188, the requests are also forwarded via lines 202 and 204 to Lock Control 206. Lock Control 206 coordinates the requests for exclusive lock access to memory addresses within the domain of Memory Units 20 and 22. A request signal indicating that a processor desires exclusive lock access to a address in memory is called a "Lock-Request." As a memory request is processed by the Second Level Caches 186 and 188, the request is simultaneously processed by Lock Control 206. When Lock Control 206 determines that it is appropriate for a requester to have exclusive lock access to a memory location, a Lock-Granted signal is sent to the requester via line 208 and the Interface Controls 170 and 178. Line 209 is input from the SC-to-SC Interface Control 178 to the Lock Control 206 line 209 contains Lock-Granted signals received at Storage Controller 10 from Storage Controllers 12, 14, and 16; lines 210 and 212 provide timing signals between the Lock Control 206, Priority Controls 194 and 196, and Second Level Caches 186 and 188 for ensuring that buffers within the Lock Control 206 are not written to before the Lock-Requests are processed. The details concerning these timing signals will be described in greater detail with FIG. 4.
FIG. 3 is a more detailed logic diagram of the IP Lock Control 162 (Shown in FIG. 2) for coordination of lock processing. Control can be traced by beginning with the IP Lock Instruction Signal 300. When IP 40 decodes an instruction and detects an instruction for which a storage lock is necessary, the Lock Instruction Signal 300 is captured by Register 302. The output signal is passed over line 304 from Register 302 and is supplied to AND Gate 306. If there is no Lock-Pending Wait at Register 430, the inverted Lock Pending Wait Signal on line 308 and the IP Lock Instruction on line 304 satisfy AND Gate 306. The output of AND Gate 306 is routed to AND Gate 310 via Signal line 312. When an active Signal line 312 is present and the Slave Lock Instruction In Progress Signal 314 from Register 316 is not active on line 315, Register 318 is set from the output of AND gate 310. Register 318 then supplies the Lock Request Signal on line 320 to Function Code Generator Logic 322.
Function Code Generator 322 takes the Lock Request Signal 320, a Function Code on line 324 from the Cache Control 156 (Shown in FIG. 2), and the Lock Granted Received Signal 326 as input, and generates a function code request which is routed to the Selector Circuit 328 via line 331. Function Code line 324 is a set of signals sent from the Cache Control 156 (Shown in FIG. 2) to the Storage Controller Function Generator 158 for the generation of a request to send to the Storage Controller 10 (Shown in FIG. 2). One example Function Code sent over line 324 would be where the Cache Control 156 detects that the address specified by a read instruction is not present in its cache memory and sends a Read Function Code along with the requested address. A second example is where the Cache Control performs a store operation resulting in a store-through cache operation, and thereafter sends a Write Function Code to the Function Code Generator 322.
For the purposes of this invention Function Code Generator 322 generates one of three function code requests on lines 330 and 331. Each type of request is defined below:
a) Read with Lock--A Read with Lock request is sent on Line 330 when the Lock Request Signal is active on line 320 and Function Code 324 indicates that a memory read is necessary. When the proper Storage Controller receives the Read with Lock request, the Lock and Read portions of the function are processed in parallel as described in FIG. 2.
b) NOP-Read with Lock--A No-Operand-Read (NOP-Read) with Lock request is sent on lines 330 and 331 when the Cache Control 156 detects that the address upon which a lock is desired is present in its cache memory and sends a Function Code 324 indicating that a read is not necessary, and the Lock Request Signal on line 320 is active. When the proper Storage Controller receives the NOP-Read with Lock request, the NOP-Read portion is essentially ignored and the Lock portion is sent to Lock Control 206 (see FIG. 2).
c) Write with Lock Release--A Write with Lock Release request is sent on lines 330 and 331 when Lock Granted Received Signal is active on line 326 and the Cache Control 156 has sent a Function Code 324 with an appropriate write function. The Write portion of the request indicates the data that the Second Level Cache 186 or 188 is to store in
the Second Level Cache memory or one of Memory Units 20 or 22. The Lock Release portion of the function code indicates that the Lock Control 206 can release the exclusive hold on the specified memory location.
It should be noted that normal Read Requests and Write Requests are also generated in Function Code Generator 322, but for the purpose of this invention, they need not be described.
The Write CAM 332 is the first-in first-out memory with a content addressable memory mechanism. All function codes having a write request pass through Write CAM 332 on a first-in first-out priority scheme. One method for increasing the performance of a processor is to maximize the time the processor performs useful functions and minimize the time the processor spends waiting. In the case of the write-through cache, it can be seen that if all Read and Write Requests are sent to the Storage Controller 10 on a simple first-come-first-served basis, the Instruction Processor 40 may be kept waiting for data where there are Write Requests ahead of the Read Request in the queue. Therefore, the system in which the present invention is used has a "read-priority" scheme to maximize processor utilization. With read-priority, if there are Write Requests already in the Write CAM 332 and a Read Request is sent from Cache Control 156, the Read Request receives priority, unless there is a write/read conflict, and is processed first, effectively keeping the Instruction Processor 40 busy by providing it with data as soon as possible.
While the read-priority scheme ensures that an instruction processor is kept busy, care must be taken to ensure that the proper data is returned from the Storage Controller 10. The specific case where old data could be returned from the Storage Controller 10 in a strict read-priority scheme is where Cache Control first sends a Write Request for a particular address and then sends a Read Request for the same address as that specified in the Write Request. If a strict read-priority scheme was followed, the Read Request would be sent to the Storage Controller 10 before the Write Request, and the data returned would be incorrect because the Write Request would not yet have been processed. To deal with this situation, the Conflict Detection Logic 334 is designed to detect when a Read Request sent to the Write CAM 332 is for the same address as that specified in an outstanding Write Request. Conflict Detection Logic 334 receives an input on signal line 335 from OR Gate 342. OR Gate 342 provides an active signal at its output when either the Read Request Signal is active on line 340 or the Lock Request Signal is active on line 320. If no conflict is detected, the signal provided on line 346 causes AND Gate 346 to provide an active Read Request Signal on line 348 to the Storage Controller 10. If Conflict Detection Logic 334 detects that a Read or Read with Lock Request conflicts with an outstanding Write Request in the Write CAM 332, the signal on line 344 disables AND Gate 346 and allows the outstanding Write Request to be processed first.
Cable 336 from Write CAM 332 carries a function code from the Write CAM to Selector Circuit 328. When a Write Request is selected, the Signal on line 337 signals the Storage Controller 10 that a Write Request is forthcoming. If neither Read Request Signal on line 340 nor Lock Request Signal on line 320 is active, the output of OR Gate 342 is inactive and Conflict Detection Logic 344 will not detect a read/write conflict.
The signal on line 312 from AND Gate 306 is also routed to OR Gate 360 via line 361. When the signal on line 312 is active the output signal from OR Gate 360 is active. AND Gate 363 takes the inverted signal from line 364 and the output signal from OR Gate 360, and, when both are active, Register 316 is set to indicate that a Lock Request is being processed. The output of Register 316 is fed back to input of OR Gate 360 via line 362, and the Register 316 maintains Lock Instruction In Progress signal on line 314 until the signal on line 364 becomes active. The Lock Instruction In Progress signal on line 314 from Register 316 is also routed to OR Gate 366 which issues an IP Wait signal on line 368. The IP Wait signal on line 368 is returned to the Execution Unit 150 (Shown in FIG. 2) to indicate to the Execution Unit that it should suspend activities until the signal is removed. It should be noted that the IP Wait signal on line 368 can be active when either the signal on line 314 is active, the Lock Pending Wait signal on line 308 is active, or the Cache Control 156 (see FIG. 2) establishes Other Wait Conditions 370. Other Wait Conditions 370 are shown to merely illustrate that there could be other signals routed to OR Gate 366 for the purpose of activating the IP Wait signal on line 368. Further explanation of these signals is unnecessary for the purpose of understanding this invention.
The Slave Lock In Progress signal on line 365 is routed to AND Gates 372, 376, and 378. Until an active Lock Granted signal on line 380 is returned from the Storage Controller 10, none of the outputs from AND Gates 374, 376, and 378 will be active, thereby driving the output Signal 364 of OR Gate 382 to inactive. The signal in line 364 is inverted and provided as input to AND Gate 362 for resetting the Register 316 as described above.
Once the Storage Controller 10 (Shown in FIG. 2) has processed the Lock Request (described further in FIGS. 4 and 5), a Lock-Granted signal on line 380 is returned to the IP Lock Control 162 (See FIG. 2). The Lock-Granted signal on line 380 is combined with the Slave Lock Instruction In Progress signal on line 365, Cache Read Miss Wait signal on line 384, Cache Read Miss Acknowledge signal on line 386 from the Second Level Cache 186 or 188, and Interrupt signal on line 388 to change the state of the IP Lock Control Logic 162.
The Cache Read Miss Wait signal on line 384 is active when the Cache Control 156 detects that a requested address is not in its cache memory; the Cache Read Miss Acknowledge signal on line 386 is active when the Cache Control has received the acknowledgement from the Second Level Cache 186 or 188 indicating that data is forthcoming. When any one of the outputs of AND Gates 374, 376, or 378 is active, the signal line 364 from OR Gate 382 will be active. The inverted signal on line 364 is routed to AND Gate 362 and will effectively clear Register 316 and drive Lock Instruction In Progress on signal line 314 to an inactive state. If the Lock Instruction In Progress on signal line 314 is what caused the IP Wait signal on line 368 to be active, when the signal on line 314 goes inactive, so will the IP Wait signal on line 368.
AND Gate 410 receives input signals from the Lock Instruction In Progress on signal line 411, signal line 364, and the inverted slave output signal on line 412 from Register 414. Register 414 remains in a cleared state until both the signal on line 411 and the signal on line 364 are active, and AND Gate 410 and Register 414 effectively generate Lock Granted Received signal on line 326. The master output, Qm, of Register 414 represents the Lock Granted Received signal on line 326, and is routed to OR Gate 416 via line 417, Function Code Generator 322 on line 326, and OR Gate 418 on line 419.
Register 420 is set when the Instruction Processor has received a Lock-Granted signal on line 380 and is performing the specified operations on the locked memory location. In particular, Register 420 is set when the Lock-Granted Received signal on line 419 is active, and Register 420 remains set until the Lock Complete signal on line 422 is active. Note that the Lock Complete signal on line 422 is asserted when all processing, including that in the Storage Controller 10, associated with the address locked by the Instruction Processor 40 is complete. The Lock-Granted Received signal on line 419 and the slave output of Register 420 are routed to OR Gate 418. The output of OR Gate 420 and the inverted Lock Complete signal on line 422 are provided to AND Gate 424 whose output is used to set and clear Register 420.
The logic provided by AND Gate 426 and OR Gate 428 is used to set Register 430. As shown, Register 430 establishes the Lock Pending Wait signal on line 308 which is routed to OR Gate 366. The significance of Register 430 is that any subsequent Lock type instructions will be held until the current Lock type instruction is complete. This is shown in the logic where the Lock Pending Wait signal is also routed via line 431 to AND Gate 306 and inverted. The signal on line 312 is activated to trigger lock processing when the Lock Pending Wait signal on line 308 is not activated and the signal on line 304 is active, namely, when there currently is not a storage lock instruction being processed and a storage lock instruction is requested. Other Related Lock Pending Conditions 432 are merely shown to illustrate that there could be other signals routed to OR Gate 428 for the purpose of asserting the Lock Pending Wait signal on lines 308 and 431. Further explanation of these signals is unnecessary for the purpose of understanding this invention.
The process of releasing a locked memory location begins with the receipt of a Write Request signal on line 442, which is routed from the Cache Control 156 to OR Gate 416. Along with the Write Request, Cable 324 carries a function code specifying a Write and Lock Release request to the Function Code Generator 322. The function code contains the address, data, and operation to perform.
The Write With Lock Release Function Code received on line 324 is routed to the Function Code Generator Logic 322 upon which the proper function code is generated and routed to the Write CAM 332 and Selector Circuit 328. When the Write With Lock Release request receives priority in the Write CAM, line 336 routes the Write Request portion of the function code to Selector Circuit 328 and the Write Request signal is provided on line 337 is asserted. When the Storage Controller 10 has received the Write Request, the Write Acknowledge signal on line 444 is applied thereby setting Register 446. The output signal on line 448 from Register 446 is routed to the Write CAM 332 through OR Gate 416.
Once the Storage Controller 10 has acknowledged the Write Request, the second part of the Write With Lock Release sequence can be performed, namely, a NOP-Write With Lock Release is sent to the Storage Controller. Upon receipt of the Write Acknowledge, the Write CAM provides the Lock Release signal on line 450 to AND Gate 452; Cable 336 carries the NOP-Write With Lock Release function code to Selector Circuit 328; and the Write Request signal is provided on line 337 along with the NOP-Write With Lock Release function code to the Storage Controller 10. A brief explanation of the reason for sending the Write With Lock Release request to the Storage Controller 10 as two requests follows.
Because the Lock Control 206 (Shown in FIG. 2) and Second Level Caches 194 and 196 within Storage Controller 10 process concurrently, parallel processing of the Write With Lock Release function presents the danger that the Lock Release portion could be completed before the Write portion of the request. If this sequence is allowed, there is a risk that another processor could be waiting to read the data from the address just unlocked. If the Lock Release is completed before the Write portion, the processor requesting the data may have or receive old data as the Write portion of the Write With Lock Release request has not completed. To address this scenario, the Instruction Processor 40 sequences the Write With Lock Release function in two stages: First, the Write Request is sent to the Storage Controller 10. Second, when a Write Acknowledge signal from the Storage Controller 10 has been received on line 444, a NOP-Write with Lock Release function is sent to the Storage Controller 10. Storage Controller 10 interprets the NOP-Write portion of the function code as being a dummy write request whereby the NOP-Write portion is effectively ignored; the Lock Release portion is routed to the Lock Control 206 (Shown in FIG. 2).
Returning to the logic trace, when both the Lock Release signal on line 450 and the Write Request signal on line 337 are active, the AND Gate 452 output signal on line 456 is routed to OR Gate 458. The output of OR Gate 458 is routed to AND Gate 460, which also receives an inverted Write Acknowledge signal on line 448. When the Write Acknowledge signal on line 444 falls to an inactive state, Register 446 is cleared and the signal on line 448 goes inactive. Thus when the signal on line 456 is active and the signal on line 448 is not active, the output of AND Gate 460 goes active and Register 462 is set. The master signal Qm 464 of Register 462 is routed to AND Gate 466 via line 464. When the Storage Controller 10 acknowledges receipt of the NOP-Write With Lock Release function code with an active Write Acknowledge signal on line 444, line 448 is active and routed to AND Gate 466 via line 448 thereby activating the Lock Complete signal on line 422.
The inverted Lock Complete signal on line 422 is supplied to AND Gate 424 whose output when the Lock Complete signal on line 422 is active, is inactive. This clears Register 410 and the Lock In Progress signal on line 468 is thereby forced into an inactive. This in turn drives the output of AND Gate 426 active, and if all Other Lock Pending Conditions 432 are inactive, OR Gate 428 clears Register 430 upon which the Lock Pending Wait signal on line 308 goes inactive. Once the Lock Pending Wait signal on line 308 is cleared, any subsequent lock type instructions can be processed.
FIG. 4 is a block diagram of the overall Lock Control within a Storage Controller for managing storage lock operations. The Lock Control has two Request Registers 502 and 504. The Request Registers 502 and 504 receive input from Priority Controls 194 and 196 (Shown in FIG. 2) respectively. As memory requests are routed to the Second Level Caches 186 and 188, the requests are simultaneously routed to the Request Registers 502 and 504. Processing of Lock Requests proceeds in parallel with processing of the memory request in the Second Level Caches 186 and 188 (see FIG. 2).
Selector 506 selects the contents of either Request Register 502 or Request Register 504 for processing by the Lock Unit 508 based upon the Selector Signal 510 from Input Control 512. Input Control 512 detects Lock Requests and Release Requests as indicated by the Function Portions 514 and 516 of Request Registers 502 and 504. Upon decoding the Function Portions, Input Control 512 generates control signals for the sequencing of the Lock Unit 508.
TAG Request signals on line 212 are active when a request has gained priority to the Second Level Caches 186 and 188. There is a separate signal for each Second Level Cache. When asserted together, these signals indicate that both Second Level Cache 186 and Second Level Cache 188 are processing a simultaneous requests. If Input Control 512 detects that each Function Portion 514 and 516 of Request Registers 502 and 504 contains a Lock Request or a Lock Release Request, the signal on line 510 is active and routed to Selector 506 upon which Selector 506 selects Request Register 502 for processing by the Lock Unit 508. Furthermore, a Cabinet Priority Inhibit signal on line 210 is activated to indicate to Priority Controls 194 and 196 that no new requests should be granted priority to either Second Level Cache 186 or Second Level Cache 188 until the Cabinet Priority Inhibit signal on line 210 goes inactive. This ensures that the requests in Request Registers 502 and 504 are processed before being overwritten with subsequent requests. After the Lock Unit 508 has had time to complete processing of the contents of Request Register 502, Input Control 512 deactivates the signal on line 510 to indicate to Selector 506 that Request Register 504 should be selected for processing by Lock Unit 508. After Lock Unit 508 has had time to process the contents of Request Register 504, the Cabinet Priority Inhibit signal on line 210 is deactivated so that Priority Controls 194 and 196 can resume processing.
Additional inputs to Lock Unit 508 include the IP Operative signal on line 518 and output from the Lock Granted Input Register 520 on line 521. The IP Operative line 518 consists of signals which indicate the status of each IP 40, 42, 44, 46, 48, 50, 52, and 54. An inactive IP Operative signal indicates that the Instruction Processor associated with the signal line is inoperative for further processing. An example would be where the Instruction Processor detects an unrecoverable hardware error and aborts processing.
The Lock Granted Input Register 520 latches Lock Granted signals from the other Storage Controllers 12, 14, and 16 and routes them to Lock Unit 508 where they are routed directly to the Lock Output Register 526 as will be described shortly.
Lock Unit 508 has a set of Lock Registers 522 and Lock Control Logic 524 to manage the contents of the Lock Registers. A Lock Register is provided for each processor in the configuration, wherein each register contains the address for which the processor is requesting a lock or currently has an outstanding lock granted. When Lock Unit 508 generates a Lock Granted signal, the result is made available in Lock Output Register 526 via line 528. Lock Unit 508 is discussed in greater detail with FIG. 5.
FIG. 5 is the logic diagram for the Lock Control Logic and the affected Lock Registers. While the diagram shows only one Lock Register 522, it should be noted that the Lock Register shown is one of a possible plurality. Likewise, most of the logic shown is repeated for each Lock Register with the exceptions noted in the following discussion.
In general, the Lock Unit 508 (See FIG. 4) works as follows: A request containing a processor identifier, an address code, and a function code are presented to the Lock Unit 508. The address code is stored in Address Register 556, the processor identifier is stored in ID Register 554, and the function code is decoded (not shown) and either the Lock Request Register 558 is set or the Release Request Register 560 is set. The Address Register 556 is compared against the Address Portion 562 of Lock Register 552 by Compare Logic 564. The comparison is performed across all Lock Registers 522 simultaneously. If the logic detects that the address code of Address Register 556 is not present in any of the Lock Registers 522 and the Lock Request Register 558 is set, the Locked-Bit Register 566 is set for the appropriate processor and a Lock Granted Signal 528 is routed to the Lock Output Register 526 (Shown in FIG. 4). If the logic detects that the address code of Address Register 556 is present in one or more of Lock Registers 522, lock request is queued by setting the Lock-Requested-Bit Register 570 in the Lock Register 552 associated with the processor identifier of ID Register 554. In either case the Address Register 556 is loaded into the Address Portion 562 of the Lock Register 552.
When the logic detects that the address code in Address Register 556 is present in one or more of the Lock Registers 522 and the Release Request Register 560 is set, Priority Logic 572 is triggered. There is only one Priority Logic 572 present in the Lock Unit 508; it receives inputs from the comparisons done on each of the Lock Registers 522 and selects one of the Lock Registers for which the associated requester will receive a Lock Granted Signal 528. Upon selection for receiving the Lock Granted signal on line 528, the Lock-Requested-Bit Register 570 is cleared and the Locked-Bit Register 566 is set in the Lock Register 552 associated with the requester for which the lock was granted. The type of priority selection algorithm chosen in this embodiment is a Round-Robin scheme. Those skilled in the art will recognize that other algorithms may be substituted.
The following discussion traces the logic flow of FIG. 5. A request which includes a Processor Identifier, an Address, and a Function is presented to the Lock Control Logic 524 (Shown in FIG. 4). The request is stored in a Processor Identifier Register 554, an Address Register 556, a Lock Request Register 558, and a Release Request Register 560.
The contents of the Address Register 556 are compared against the Address 562 stored in the Lock Register 552 by Compare Logic 564. If the contents match, the signal on line 574 is activated and routed to AND Gate 576. AND Gate 576 receives input on signal lines 574 and 578. If both Signals 574 and 578 are active, the signal on line 580 is activated and routed to OR Gate 582. OR Gate 582 receives as input, signals from each of the AND Gates corresponding to AND Gate 576 for each available Lock Register 552. Lines 584 represent these input signals from the logic associated with the other Lock Registers.
If any of signals on lines 584 or line 580 is active, the output of OR Gate 582, namely, the Hit signal on line 586, is active. This signifies that one of the Lock Registers 522 contains an Address 562 which matches the requested Address 556 and currently has the memory location locked, as indicated by Locked-Bit Register 566. Hit Signal 586 is routed to AND Gate 588. AND Gate 588 also receives input signals from Lock Request Register 558 and the IP Operative signal on line 518. For each Lock Register 552, there is a separate IP Operative Line 518 which signals availability of the Instruction Processor which is associated with the particular Lock Register 552. When AND Gate 588 detects that Lock Request Register 558 is set, the IP Operative signal on line 518 is active, and the Hit signal on line 586 is activated, the output signal on line 592 goes active for setting the Lock-Requested-Bit Register 570.
AND Gate 594 receives as input the Compare signal on line 574, and Request Bit signal on line 596 from Lock-Requested-Bit Register 570. If Compare Logic 564 finds that the requested Address 556 matches the Address 562 of Lock Register 552 and thereby asserts Signal 574, and if the Lock-Requested- Bit Register 570 is set, AND Gate 594 asserts its output signal on line 598 and routes it to Priority Logic 572. Similarly lines 600 are inputs from the AND Gates corresponding to AND Gate 594 of the logic associated with the other Lock Registers 522. One or more of these lines 600 and the signal on line 598 may be asserted. Priority Logic 572 selects one of the requesters vis-a-vis the inputs of line 598 and lines 600, and asserts one of lines 602 to indicate that a requester has been given priority. The Priority signal on line 604 is routed to OR Gate 606.
If OR Gate 606 detects an active Priority signal on line 604, the Remote Lock-Granted signal on line 521, or the output of AND Gate 610 is active, the Lock Granted signal on line 528 is activated and routed to the Lock Output Register 526 (Shown in FIG. 4). It should be noted that the output from AND Gate 610 is active when the Lock Request Register 558 is set and the Hit signal on line 586 is inactive.
The Hit signal on line 586 and the Priority signal on line 604 are further routed to AND Gates 612 and 614 for setting or clearing the Locked-Bit Register 566 of Lock Register 552. The output of OR Gate 616 is active when either the output of AND Gate 612 or AND Gate 614 is active. The output from AND Gate 612 is active when the Lock Request Register 558 is set, the IP Operative signal on line 518 is active, the Release Request Register 560 is not set, and Hit signal on line 586 is inactive. The output of AND Gate 614 goes active when the Release Request Register 560 is set, the IP Operative signal on line 518 is active, and the Priority signal on line 604 is active. When these conditions are satisfied, OR Gate 616 activates its output for setting Locked Bit 552.
A Write Enable signal on line 618 is activated for updating the contents of the Lock Register 552. Neither the Address 562, Locked-Bit Register 566, nor the Lock-Requested-Bit Register 570 are changed until the Write Enable signal on line 618 is active. OR Gate 620 activates the Write Enable signal on line 618 when either the IP Operative signal on line 518 is not active, the output of AND Gate 614 is active, or the output of AND Gate 622 is active. AND Gate 614 is described in the previous paragraph.
Turning to AND Gate 622, its output goes active when either the Lock Request Register 558 or the Release Request Register 560 is set as detected by OR Gate 624, and Decoder 626 activates the signal on line 628. Lines 630 emanating from Decoder 626 are routed to the logic associated with each of the other Lock Registers 522 within the Lock Unit 508. Only one of lines 630 or 628 is active, depending on the contents of the Processor Identifier Register 554 as decoded by Decoder 626.
Those skilled in the art will recognize that although the Lock Register 552 is shown as including a Lock-Requested-Bit Register 570, some processors, such as the IOC (Input/Output Controller) 60 (Shown in FIG. 1) should not be idled while waiting for a lock Granted Signal 528. Therefore, the Lock Register 552 associated with an IOC 60 requester has the Address 562 and Locked-Bit Register 566 portions, but no Lock-Requested-Bit Register 570. When the Hit signal on line 586 goes active upon processing a lock request from IOC 60, instead of setting Lock-Requested-Bit Register 570, a lock rejected signal (not shown) is returned to the requester. To obtain the lock, the requester must retry the lock request.
FIG. 6 is a general timing diagram of Lock Request processing with a single Storage Controller 10 and two requesters, IP 40 and IP 42. In particular, FIG. 6 shows the timing relationships between various stages of processing within a Storage Controller 10, a first Instruction Processor, IP 40, and a second Instruction Processor, IP 42. The horizontal lines indicate the time periods during which the respective processing steps are active, and the lines with arrows are used to indicate the succeeding step(s) which are triggered by a particular processing step. It should be understood that the relative lengths of the horizontal lines in FIG. 6 are shown only to indicate the timing relationships between the processings phases and are not scaled to actual time periods.
Processing begins with an active Lock Instruction signal 808, indicating that IP 40 has decoded an instruction requiring exclusive access to a predetermined address. During the time which IP 40 is waiting for a Lock Granted signal back from the Storage Controller 10, an IP Wait signal 810 is active and IP 40 suspends processing activities. Some time after the Lock Instruction signal 808 has been asserted, a Read With Lock Instruction 812 (an example operation code) is sent to Storage Controller 10. The Read portion of the Read With Lock Instruction is sent when the Cache Control 156 (Shown in FIG. 2) detects that the memory address requested is not present it its storage, and the Lock portion is determined when Execution Unit 150 (Shown in FIG. 2) decodes an instruction and detects a request for exclusive access to the requested address.
After receiving the Read With Lock Instruction, the request is routed to Priority Controls 194 and 196 (Shown in FIG. 2) for Storage Controller 10 processing. The request will receive service from the Priority Control associated with the Memory Unit 20 or 22 (Shown in FIG. 2) having the requested address. SC (Storage Controller) Priority 814 represents the time during which the request is awaiting service. Upon selection for service, a read request along with the specified address is routed to a Second Level Cache (SLC) 186 or 188 (Shown in FIG. 2). An SLC Search 816 is performed to determine whether or not the requested address is in the storage of the Second Level Cache 186 or 188. At substantially the same time as the SLC Search 816 is proceeding, a Lock signal 818 is asserted in Lock Control 206 (Shown in FIG. 2). Lock Request signal 818 causes an activate Write Enable signal 822 for storing appropriate information in the Lock Register 552 (Shown in FIG. 5) associated with Instruction Processor 40. In addition, Lock signal 818 triggers Compare Operation 820 for checking each of the Lock Registers 522 (Shown in FIG. 4) against the address for which the lock is requested. In this example it is assumed that the Compare processing does not find a matching address in the Lock Registers 522 (Shown in FIG. 4). When there is no match detected, a Lock Granted signal 824 is sent to IP 40. When IP 40 receives the Lock Granted signal 824, the IP Wait Condition 810 deactivated, thereby allowing IP 40 to continue its processing activities. In addition, the Lock Granted signal 380 activates the Lock In Progress signal 825. As long as the Lock In Progress signal 424 is active, IP 40 is not allowed to issue another lock request to the Storage Controller 10.
Once the Second Level Cache Search 816 has located the requested address and sent the data to IP 40, a Read Acknowledge signal 826 is activated and routed to IP 40. After receiving the requested data, as indicated by Read Acknowledge signal 826, IP Lock Instruction Processing 828 can continue.
The example of FIG. 6 involves a second requester, IP 42, processing a lock type instruction during the time period during which IP 40 is Processing a Lock Instruction 828. The processing of a lock type instruction by IP 42 during IP Processing 828 is encompassed within the area bound by dashed line 830.
A Lock Instruction signal 832 goes active when a lock type instruction is decoded by IP 42. An active Lock Instruction signal 832 activates the IP Wait signal 834 thereby halting processing by IP 42 until a Lock Granted signal 836 is received. Lock Instruction 832 also triggers processing for sending the necessary function code to the Storage Controller 10. For the IP 42 lock instruction it is assumed that the requested data is present in the cache unit for IP 42; therefore, a NOP-Read With Lock Request 838 is sent to Storage Controller 10. The NOP-Read portion of the function codes indicates to the Storage Controller 10 that a read of data need not be performed.
The NOP-Read With Lock Request is serviced during SC Priority Processing 840. When the request receives priority, a Lock Request signal 842 is activated thereby triggering an active Write Enable signal 844 for the Lock Register 552 (Shown in FIG. 5) associated with IP 42. At substantially the same time, a Compare Operation 846 is performed to check whether any of the Lock Registers 522 (Shown in FIG. 4) has requested or currently has a lock on the address specified by IP 42. In this example it is assumed that IP 42 has requested the same address which IP 40 currently has locked. Therefore, Storage Controller 10 detects a hit in the Compare Operation 846 and Sets a Request Bit Register 848. Processing for IP 42 is then held, as indicated by the IP Wait signal 834, until it receives the Lock Granted signal 836.
Returning to IP 40 Lock Processing 828, it is shown that when complete, the lock release processing begins with a Write Request 862 being sent to the Storage Controller 10. The Write Request is serviced during SC Priority Processing 864. The Storage Controller 10 responds with an active Write Acknowledge signal 865 when it has received the Write Request, upon which a NOP-Write With Lock Release 868 instruction is sent to Storage Controller 10. When the Write Request receives priority, an IP 40 Invalidate signal 866 is activated to inhibit priority for any subsequent write requests made by IP 40. As set forth in the description accompanying FIG. 3, when the locked location is to be modified, the IP 40 will send a write request, address, and data to the SC. This will be followed with a NOP-Write With Lock Release Request 868.
Where the locked location is not modified, the IP 40 simply sends a NOP-Write Request With Lock Release. In the case where IP 40 modifies the locked location, there are two write requests made to the Storage Controller 10. The second write request (NOP-Write Request With Lock Release) will not be allowed priority until the invalidate for the first write request (Write Request 862) has been acknowledged. The reason for this is that any processor having the data from locked location in its local cache must be notified that the current data is invalid before being allowed to access to the locked location. When all invalidate acknowledge signals have been received by Storage Controller 10 (signals not shown for clarity), SC Priority Processing 870 selects the Lock Release Request for processing by Lock Control 206 (Shown in FIG. 2) and activates Write Acknowledge Signal 871. Receipt of the Write Acknowledge Signal 871 deactivates the Lock In Progress Signal 825.
An active Release signal 872 causes an active Write Enable signal 874 for storing appropriate information in the Lock Register 552 (Shown in FIG. 5) associated with IP 42. At substantially the same time, a Compare Operation 876 is done to determine whether any other processors have requested a lock for the address being released.
In this example, IP 42 has requested a lock for the address so Operation 878 entails: selecting IP 42 as having priority for receiving the lock on the requested address; clearing the Locked-Bit Register 566 (Shown in FIG. 5) associated with the Lock Register 552 for IP 40; setting the Locked-Bit Register 566 (Shown in FIG. 5) associated with the Lock Register 552 for IP 42; and clearing the Lock-Requested-Bit Register 570 (Shown in FIG. 5) associated with the Lock Register 552 for IP 42.
After determining that the lock request from IP 42 has priority, an active Lock Granted signal 836 is supplied to IP 42, which in turn deactivates the IP Wait signal 834.
While only one embodiment of the present invention has been described, it should be understood that those skilled in the art will recognize that alternate embodiments exist which fall within the scope and spirit of the claims set forth below. | A method and apparatus for granting exclusive access to a selected portion of addressable memory to a requesting processor in a large scale multiprocessor system. An instruction processor having a store-through operand cache executes an instruction requiring exclusive access to an address in a shared memory. If the address upon which the lock is requested is not in the local cache, the instruction processor simultaneously sends a lock and read request to the coupled storage controller. Otherwise, a no-operand-read and lock request is sent to the storage controller. If, while processing the lock request, no conflict is detected by the storage controller, the address is marked as locked and a lock granted signal is issued to the requesting processor. Concurrent with the processing the lock request the storage controller processes the read request. The lock granted signal and requested data are returned to the requesting processor asynchronously. The requesting processor can continue processing the lock instruction when the lock granted and required data have been returned from the storage controller. When two or more processors contend for a lock on a the same portion of addressable memory, one processor is granted the lock while the other contending processor(s) are forced to wait. Lock contention is arbitrated by a round robin priority scheme. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a transducer for effecting conversion between stress wave and electrical energy and to a method of making such a transducer.
The invention has been developed in relation to transducers required for certain forms of apparatus (hereinafter referred to as being of the kind specified) but is capable of application generally to stress wave-electrical tranducers.
Apparatus of the kind specified is intended to provide data relating to an object (including, for example, data as to the existence or position of the object or one or more characteristics of the object) otherwise than by direct vision, and the object data may be ascertained or read either by human perception (as by visual display or by audible or tactile display) or by machine vision.
In a specific form of apparatus of the kind specified the apparatus comprises a combination of
(a) transmitting means for transmitting stress wave energy (hereinafter called the transmitted signal) to a field of view to illuminate the object with such energy,
(b) receiving means for receiving at least part of the energy (herein called the received signal) reflected from the object when in the field of view and effectively forming an image in respect of the illumination of the object by the transmitted signal,
(c) means for imposing predetermined characteristics upon at least part of the signals giving rise to the image in respect of at least one of the parameters pertaining thereto and selected to establish that the image shall contain the required object data,
(d) means for analysing the image derived from the stress wave energy.
The term "image" used herein is to be deemed to include a plurality of signals (readable by human perception or by machine, as appropriate) whether presented serially in time or in spacial juxtaposition or separation and collectively representing the existence, position or attitude of the object, or one or more dimensions thereof, or the configuration or area of the object viewed from any direction.
In a particular form of apparatus of the kind specified the means for imposing predetermined characteristics upon the signals giving rise to the image may differ widely in accordance with the particular data concerning the object which the received signal is required to carry. Thus, if one of the characteristics which the image is required to present is the range or distance of the object or some part thereof from a predetermined point, e.g. the station at which the transmitting means is situated, then the means for imposing the predetermined characteristic may comprise a means for frequency modulating the stress wave transmitted signal in a mode such that the frequency difference between the transmitted signal and the received signal, due to the elapse of transit time between initial radiation of the signal and receipt of the reflection, is representative of the range or distance. In such a case the means for imposing the predetermined characteristic would appropriately impose a frequency sweep on the transmitted signal which may be linear or non-linear but preferably of saw-tooth form.
If the required object data includes information concerning the lateral or angular position of the object, or a part thereof, or the angular width subtended by the object at a predetermined point, e.g. that at which the transmitting means is situated, then the means for imposing a predetermined characteristic may include means to establish that the transmitted signal and/or the received signal is radiated and/or received respectively by way of a beam represented conveniently as a polar diagram with the radius vector centered on a predetermined point and having a maximum value in the central region of said beam and a minimum value at each of two opposite boundaries thereof in a reference plane. The reference plane may be horizontal, vertical, or in some intermediate angular position.
In some cases it may be advantageous to provide transmitting and/or receiving means in which the beam is convergent to a focus or a focal region spaced longitudinally of the transmitting and/or receiving means along an axis extending outwardly into the field of view.
The means for imposing predetermined characteristics on the transmitted and/or received stress wave signals may further include means for scanning the beam angularly through the field of view between boundaries thereof, e.g. in an azimuthal plane or in an elevational plane, or both, or in some intermediate plane.
Transducers for effecting conversion between stress wave energy and electrical energy are required for incorporation in the transmitting means and the receiving means. Possibly a transducer common to both the transmitting means and the receiving means may be used.
The speed or frequency at which such mode of operation is required to be carried out often precludes the use of mounting means for the transducers permitting the transducers to be moved physically to the different angular positions required.
It is known that such beams may be moved angularly or scanned by the use of a transducer which comprises an array of transducer elements connected to the power amplifier or output element of the transmitting means or to the input element of the receiving means through respective channels which include means for imposing a phase difference or time difference between the signals fed to the transducer elements or received therefrom as the case may be, thereby electronically effecting angular deflection of the beam.
The performance of such an array is adversely affected by the need to provide individual transducer elements to form such array and one of the principal objects of the present invention is to avoid or reduce this disadvantage as well as to provide for reduction in the cost of manufacturing such a transducer array.
Further, in cases where it is required to provide a beam either for the transmitting or receiving means of a form which is convergent to a focus or focal region spaced longitudinally from the transducer means along said axis, the need to provide individual tranducer elements imposes considerable complications and contributes to the cost of providing an appropriate array, and imposes considerable limitations on the extent to which the size of the array can be reduced.
SUMMARY OF THE INVENTION
According to the invention there is provided a transducer for effecting conversion between stress wave energy and electrical energy comprising a plurality of transducer elements collectively forming an array and each of which includes opposing conductive electrode means and an intervening dielectric element wherein at least the dielectric element comprises a lamina (the first lamina) common to the tranducer elements.
Advantageously, one of the opposing electrode means may also comprise a further lamina (the second lamina) which is common to the transducer elements.
In a preferred form the invention applicable to airborne stress wave energy comprises a transducer for effecting conversion between airborne stress wave energy and electrical energy comprising a plurality of individual electrically conductive electrode elements presenting an array of coplanar electrode element faces, an opposing sheet of dielectric material carrying an electrically conductive film or coating on its side remote from the individual electrode elements and which is common to the individual electrode elements, means for supporting the sheet peripherally to lie freely on, but in tension over, the coplanar faces of the individual electrode elements, adjacent ones of which are spaced from each other by gaps which are sufficiently large compared with the thickness of the sheet to avoid or minimise shear stress transmission between adjacent areas of the sheet overlying respective adjacent individual electrode elements.
The transducer may be combined with time delay means connected to each of, or selected, channels or conductors connected to respective electrode elements of the array, the time delay means imposing respective time delays of such magnitude as to establish a convergent or focused beam.
Further, the transducer may be combined with variable time delay means connected to each of, or selected, channels or conductors connected to respective electrode elements of the array, and means for varying the magnitudes of the respective time delays to establish scanning of a beam provided by the array.
The first lamina may be in the form of a sheet of dielectric material and the second lamina may comprise an electrically conductive film or coating on the sheet.
From a further aspect the invention resides in a method of making a multi-channel transducer for effecting conversion between airborne stress wave energy and electrical energy, such method comprising laying a sheet of dielectric material over coplanar faces of an array of spaced apart, electrically conductive, electrode elements, securing the sheet peripherally around the array, and providing a further conductive electrode means on the side of the lamina opposite to the array.
The further conductive electrode means may conveniently comprise a further lamina (the second lamina) formed as a film or coating on the first lamina.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described, by way of example, with reference to the accompanying drawings wherein:
FIG. 1 is a view in cross-section on the line A--A of FIG. 2 through one embodiment of transducer in accordance with the invention and made by the method thereof;
FIG. 2 is a view in cross-section on the line B--B of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Echo location systems (being one form of apparatus of the kind specified) operating in air as aids for the blind commonly use solid dielectric transducers for both radiating and receiving ultrasonic waves. One such system is described by KAY in the Radio and Electronic Engineer, Volume 44, No. 11, pp. 605-627 and dated November, 1974. On page 610 is described the transducer design used in the system. The radiation and receiving field of the transducer is fixed in space relative to the active face and can be moved only by physically moving the transducer.
A line array of transducers of the type described can be used to form a radiation field by suitably coupling them together through an electrical network. When all the signals at the transducer terminals are in phase coincidence a narrower beam is formed which is perpendicular to the active face of the array. Applying a phase delay between each element causes the beam to be deflected from the perpendicular direction by an amount determined by the phase delay. Alternatively, a time delay can be used between each element to produce a deflection of the beam from the perpendicular. Both of these methods of beam deflection or beam scanning are now well known principles used in radar, sonar and ultrasonic testing in solids or body tissue.
The embodiment of the present invention now illustrated and described in effect provides a transducer array as a single unit but with individual channel access to elements of the array. It is not only more convenient to incorporate in apparatus of the kind specified and other forms of apparatus than would be the case were individual transducer elements utilized to form the array, but can also be manufactured more economically and provide improved performance as regards beam deflection or scanning whilst avoiding the necessity to move the array physically.
In the embodiment illustrated a plurality of electrically conductive electrode elements 10 are provided. These may be of electrically conductive metal or a conductive plastics material, or of a plastics material (an insulator) coated with electrically conductive metal.
The elements may conveniently be of cubic form, although the height dimension as seen in FIG. 1 and the width dimensions as seen in FIG. 2 need not necessarily be equal.
The elements 10 are mounted in an array with their top faces 11, as seen in FIG. 2, coplanar and their bottom faces supported by a base plate 12 through the intermediary of an intervening plate 13 of insulating material.
The plate 12 may be formed integrally with an outer frame 14, the top face of which is coplanar with the top faces 11 of the elements 10. The frame 14 and the base plate 12 may be formed of metal or a plastics (insulating) material as desired.
The base plate has openings in alignment with respective elements 10 to provide for passage of conductors 15 for connection to respective electrode elements 10. The latter may be made of metal or conductive plastics material, or may be made of insulating material with an electrically conductive coating on at least their top faces to which, in this case, the conductors 15 would be connected.
On the top faces 11 of the electrode elements 10 is laid a sheet of dielectric material such as "Mylar" (the first lamina hereinbefore referred to) and which is coated on its top surface remote from the electrode elements 10 with a film of conducting material, for example aluminium or gold (the second lamina hereinbefore mentioned).
Because of the scale of the drawings these two laminae are not shown separately and a single reference 16 designates them collectively.
Conveniently the sheet 16 is secured to the top surface of the frame 14 adhesively. For this purpose the top surface of the frame 14 is preferably roughened on a suitable flat scratching material. The top surfaces of the electrode elements 10 may be roughened as indicated at 21 (shown in two instances only). This assists in establishing the existence of an air film between the sheet 16 and the top surfaces of the electrodes and determines the frequency response characteristic of the transducer over a (higher) range of frequencies, typically 70 KHz to 300 KHz. Conveniently the roughening of these surfaces of the electrode elements and the top surface of the frame 14 may be carried out at the same time in a single operation, although this is not essential. A typical grit size of 60-280 may be used for effecting the roughening, for example, according to the frequency response required from the transducer. The top surface of the elements may be appropriately machined to produce grooves as seen at 20. This controls the frequency response characteristic in another (lower) range of frequencies, typically 30 KHz to 100 KHz. This would preferably be done additionally to roughening, although for simplification roughening and grooving has been shown only on separate elements in the drawings. Likewise the top surface of the frame may be machined either separately or at the same time.
The roughening and grooving may be carried out on all of the electrode elements or selected elements only as determined by the characteristics to be achieved.
The thickness of the sheet 16 may typically be 5.0 microns and the film or coating of conductive material 0.05 microns. Preparatory to coating the top surface of the frame 14 with glue and laying the sheet 16 thereover, the sheet may be tensioned in its own plane by an amount depending upon the frequency response required. In some circumstances the tension need be sufficient only to remove any wrinkles from the sheet. Clamps 19 may be provided to embrace and protect the peripheral margin of the sheet 16 and the frame 14 and left in position permanently to provide an electrical connection to the conducting lamina--the second lamina.
The electrode elements 10 are insulated electrically from each other by the provision of lateral gaps 17 and 18 between them. These may be air gaps but could contain solid state insulating material if required.
The sheet 16 is not fixed to the top faces of the electrode elements 10, nor is the sheet 16 clamped or similarly constrained over those areas which lie above the gaps 17 and 18 between individual electrode elements 10 whether the gaps are air-filled or contain solid state insulating material. The sheet lies freely on the coplanar faces of the electrode elements but without excluding an air layer between these faces and the sheet, the boundaries of the air layer being, in effect, defined by the roughened and grooved faces of the elements 10 and the overlying face of the sheet.
The gaps 17 and 18 extending in mutually perpendicular directions of the array may be equal and are preferably substantially greater than the thickness of the sheet 16. A typical value for the thickness of the sheet would be, as mentioned, 5 microns whereas each of the gaps 17 and 18 would typically be 500 microns. This provides for satisfactory operation of the transducer in the frequency range 30 KHz to 300 KHz, although if desired the range may be limited to 100 KHz to 200 KHz.
Because each electrode element 10 is required to radiate or receive signals independently, or nearly independently, of each other, and since radiation action is one of movement of deformation of the dielectric lamina either towards or away from the top face of the electrode element 10, it would seem natural to clamp the dielectric sheet in the gaps 17 and 18 between the elements. It is one of the primary features of the invention that the dielectric is not clamped opposite these gaps and this materially contributes to reducing the difficulty and cost of manufacture.
By adoption of a gap width for the gaps 17 and 18 which is wide compared with the thickness of the dielectric, shear forces which could propogate through the dielectric across the gaps 17 and 18 are attenuated sufficiently to make them negligible and avoid or reduce stress coupling between the transducer elements each constituted by an electrode element 10, the portion of the dielectric sheet lying on top of such element, and the further electrode means comprising the film or coating of conductive material (the second lamina) on top of the sheet.
Although the specific embodiment described and illustrated shows the top surfaces of the electrode elements as lying in a single flat plane, it will be understood that it would be within the scope of the invention for these surfaces (collectively) to present some other shape consistent with ability to stretch a sheet such as 16 over the exposed surfaces of these elements in contact therewith but without air exclusion, preferably the form of the air layer being controlled by roughening and grooving as previously described. Thus, the upper surfaces of the elements 10 could thus collectively present a convex cylindrical shape should this be desired, and the term "coplanar" is to be deemed to include such arrangements.
An application of the invention to a transducer required to provide a convergent or focus beam would include time delay means connected in series with each of, or a selected number of, the conductors 15 to impose increments of time delay in radiation (or reception) of wave energy from the electrode elements 10 systematically over the array.
To effect scanning further variable time delay means may be provided in each of the conductors or selected conductors 15. Such variable time delay means is preferably activated electronically to achieve rapid cyclic scanning movements of the beam to establish scanning of the field of view. | A transducer for effecting conversion between stress wave energy and electrical energy comprising a plurality of individual electrically conductive electrode elements presenting an array of coplanar electrode element faces, an overlying sheet of dielectric material carrying an electrically conductive film or coating on its side remote from the individual electrode elements and which is common to the individual electrode elements, means for supporting the sheet peripherally to lie freely on, but in tension over, the coplanar faces of the individual electrode elements, adjacent areas of which are spaced from each other by gaps which are sufficiently large compared with the thickness of the sheet to avoid or minimize shear stress transmission between adjacent areas of the sheet overlying respective adjacent individual electrode elements. | 8 |
FIELD OF INVENTION
The invention relates to an adaptable latch. More particularly, the invention relates to a latch being adaptable to form either a short-length latch or a long-length latch.
BACKGROUND
Early on, industry manufactured both short- and long-length door latches. The short-length latch resulted in the door handle axle being about 60 mm from the door's edge. The long-length latch resulted in the door handle axle being about 70 mm from the door's edge.
Use of short- and long-length latches resulted in many doors existing in the marketplace having perforations, either for the long-length or the short-length latch. The existence of two distinct types of doors required services of door latches to stock both short and long latches. Services had to stock long latches to service doors previously perforated for long latches, and services had to stock short latches for doors previously perforated for short latches. In addition, manufacturers had to make both short and long door latches to fulfill the needs of their customers. It became very expensive to stock and manufacture both long and short door latches.
To solve the problem, industry developed a single latch capable of being adapted to fit either a door previously perforated for a short latch or previously perforated for a long latch. Some adaptable latches adapt by providing a linkage between an eccentric and two possible pre-established positions on a bolt tail. The design complicates the latch. The linkage requires provisions to provide for door axle rotation at either of the two linkage positions on the bolt tail.
Other devices provide for the adaptation within the bolt case. Some of these devices produce a helical movement between the extreme positions of 60 mm and 70 mm. Some of the devices produce the movement by a right side-up or upside-down U-shaped movement between the positions.
Accordingly, the present invention seeks to improve upon previous adaptable latches by providing a bolt head having a bolt head catch, and by providing a bolt tail having a bolt tail appendage. The bolt tail appendage has a bolt tail appendage first catch and a bolt tail appendage second catch. The bolt tail appendage first catch and the bolt tail appendage second catch are longitudinally spaced from each other along a longitudinal length of the latch. The bolt head catch locks with either the appendage first catch or the appendage second catch.
The invention further provides advantages by providing a bolt case extension having a bolt case extension first catch and a bolt case extension second catch. The case extension first catch and the case extension second catch are longitudinally spaced apart along the longitudinal length of the latch. A resilient catch coupled to the bolt case locks with either the bolt case extension first catch or the bolt case extension second catch.
The invention provides still a further advantage by providing a bolt tail protrusion which has a pressed position. The protrusion, when in the pressed position, unlocks the resilient catch from the case extension first catch or case extension second catch. In addition, it unlocks said bolt head catch from the bolt tail appendage first catch or the bolt tail appendage second catch.
The invention further improves upon prior latches by providing a spring-loaded lug which co-acts with both said bolt tail appendage and said resilient catch to provide for a simultaneous unlocking of said bolt head catch from said appendage and said resilient catch from said case extension.
SUMMARY
An adaptable latch having a bolt case. The bolt case has a bolt case opening. The bolt case has a resilient catch connected thereto. The latch further includes a bolt head. The bolt head has a bolt head interior surface defining a bolt head hollow. The bolt head is disposed in the bolt case and has a bolt head first section and a bolt head second section.
The latch has a bolt tail with a bolt tail first section and a bolt tail second section. A bolt tail appendage is connected to the bolt tail first section and disposed in the bolt tail hollow. The bolt tail appendage has a bolt tail appendage first catch and a bolt tail appendage second catch. The first catch is spaced from the second catch along the longitudinal length of the latch. A bolt head catch is disposed in the bolt head hollow. The bolt head catch and the bolt tail appendage have a variable positional relationship selected from a group consisting of the bolt head catch locked with the bolt tail appendage first catch, the bolt head catch locked with the bolt tail appendage second catch, and the bolt head catch unlocked from the bolt tail appendage.
A bolt case extension has a bolt case extension first catch and a bolt case extension second catch. The resilient catch and the bolt case extension have a variable positional relationship selected from a group consisting of the resilient catch locked with the bolt case extension first catch, the resilient catch locked with the bolt case extension second catch, and the resilient catch unlocked from the case extension.
Other desires, results and novel features of the present invention will become more apparent from the following drawings, detailed description and the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B shows the longitudinal section, in its median vertical elevation, of a latch according to the invention in its state of short latch, including an enlargement of the area surrounded in the complete latch view.
FIG. 2 is a partial view in upper elevation of the case extension 33 according to section II--II shown in the enlarged detail on FIG. 1B
FIG. 3 shows on a smaller scale the latch in FIG. 1 with the push button 29 activated.
FIG. 4 is FIG. 3 after having extended the latch to its long latch state while the push button 29 is still being pressed.
FIG. 5 is the same as FIG. 4 once the push button 29 has ceased to be activated.
FIG. 6 shows enlarged, sections along VI--VI in FIG. 1A.
FIGS. 7A, 7B and 8A, 8B show a diagram of the sequential operation of switching from short latch to long latch (from FIG. 7A to FIG. 8A) and conversely (from FIG. 8A to FIG. 7A) showing the respective status of FIGS. 3 and 4 and including enlarged illustrative details of the position of the flange 105.
FIG. 9 shows the bolt tail individually 25 as it appears in FIG. 1A.
FIG. 10 is the section cut along X--X in FIG. 9.
The back end of the bolt pin 107 of the bolt head 19 is seen outlined on FIG. 1A as a broken line for clarity's sake; this broken line has been eliminated in FIGS. 3, 4, and 5.
DETAILED DESCRIPTION
The latch has advantages in that it is adjustable to a short-length latch or to a long-length latch. The latch, when adjusted to be a short-length latch, is locked in a short position (FIG. 1). The latch, when adjusted to be a long-length latch, is locked in a long position (FIG. 5). In the long position the single bolt (bolt head and bolt tail) has a longer longitudinal length than when in the short position.
An installer locks the latch in either the long position or the short position prior to installation of the latch. The installer selects either the short position or the long position to conform the latch's length to existing door perforations or desired door perforations. The latch, once installed, remains locked in either the short position or the long position. The latch position, however, can be easily unlocked and reset to either the long position or short position. The latch remains locked in the selected short or long position during longitudinal movement imparted by a door handle or a doorknob.
The door latch and its constituent components are designed to be installed in a door. The door latch includes a bolt case 15. The bolt case has a bolt case opening 17 which is designed to be flush with a door's edge (not shown). A bolt head 19 is disposed in the bolt case. The bolt head can occupy an extended position in which the bolt head extends through the bolt case opening. The bolt head can also occupy an opposite retracted position. The latch is shown with the bolt head in the retracted position.
The bolt head has a longitudinal length which is aligned along the longitudinal length of the latch. The bolt head has a bolt head first section 21 facing towards the bolt case opening 17. The bolt head has a bolt head second section 23 opposite the bolt head first section.
A bolt tail 25 is adjustably coupled to the bolt head 19. The bolt tail has a bolt tail first section 27 disposed towards the bolt head second section. The bolt tail includes a bolt tail protrusion 29, a push button. The bolt tail has a bolt tail second section 31.
A bolt case extension 33 has a bolt case extension first section 35 which is disposed between an interior longitudinally extending bolt case surface 37 and an exterior longitudinally extending bolt head surface 39. Thus, the bolt case extension is near the bolt case. The bolt case has a bolt case extension second section 41. The bolt case extension has a longitudinal length aligned with the longitudinal length of the latch. The bolt case extension has a first half 43a and a second half 43b.
An eccentric 45 is coupled to the bolt tail at the bolt tail second section 31. A doorknob axle 41 is disposed coaxially with the eccentric. The doorknob axle when rotated, for instance by a doorknob, imparts a rotation to the eccentric. The eccentric imparts a longitudinal movement on the bolt tail and bolt head. The bolt tail and bolt head remain fixed relative to each other and move longitudinally as a single bolt. The single bolt (bolt head and bolt tail) slides longitudinally relative to the bolt case and bolt case extension. The bolt case and bolt case extension remain fixed relative to the door during the longitudinal movement. The extension second section has a guide 42 which guides the eccentric and bolt tail during the longitudinal movement. During positioning to the long position from the short position, the bolt tail first section 27 is moved longitudinally away from the bolt head second section 23. The latch is adjusted from the long position to the short position by a reverse movement of the bolt tail and bolt head. The bolt head and bolt tail remain connected before, during and after adjustment from the short to long position, and vice versa.
The bolt case extension 33 is adjusted concurrently with the bolt tail 25 during adjustment of the latch to the preferred short or long position.
The bolt head has a bolt head interior surface 49 which defines a bolt head hollow 51. The bolt head has a bolt head catch 57 on a first bolt head interior surface 59. The bolt head catch 57 is a bolt lug which extends radially towards a second bolt head interior surface 61.
The second bolt head interior surface 61 faces towards the first bolt head interior surface 59. A bolt head hole 63 extends transversely through the second bolt head interior surface 61 and through the bolt head 19, thereby connecting the bolt head hollow 51 to an area exterior to the bolt head.
A spring-loaded lug 65 has a lug shaft 66 which is disposed in the bolt head hole 63. The spring-loaded lug has a lug head 67a, 67b at one end of the lug shaft. The spring-loaded lug has a lug shaft-end 69 opposite the lug head. The lug head 67a, 67b is disposed in the bolt head hollow. The section of the lug head towards the second bolt head interior surface 61 forms a collar 67b. A helical spring 71 is disposed around the lug shaft 66. The helical spring 71 is between the collar 67b and the second bolt head interior surface 61.
The spring-loaded lug has a lug retracted position (FIG. 3, FIG. 4). In the lug retracted position the spring has an increased potential energy. The lug shaft-end 69 extends out of the bolt head hole 63 away from the bolt head hollow 51. The lug shaft-end 69 also extends through a longitudinally extending hole 73 in the bolt case extension first section 35. The lug shaft-end 69 also extends through a bolt case hole 75. The lug shaft-end passes through the bolt case hole exit and connects with a resilient catch 77.
In the retracted position, the lug shaft-end 69 pushes the resilient catch 77 away from an exterior surface of the bolt case (FIG. 3, FIG. 4). The resilient catch is also dislodged from the bolt case extension 33.
The spring-loaded lug also has an extended position (FIG. 1, FIG. 5). In the extended position, the spring has less potential energy than when the spring-loaded lug is in the retracted position. The spring-loaded lug extends further into the bolt head hollow 51 when in the extended position than when in the retracted position.
In the extended position the collar 67b is pushing on a bolt tail appendage 79 disposed in the bolt head hollow. The collar pushes on the bolt tail appendage in a direction towards the first bolt head interior surface. In the extended position, the- lug shaft-end 69 is not pushing on the resilient catch 77. The lug shaft-end is not extended through either the bolt case hole 75, the longitudinally extending hole 73 or the bolt head hole 63. The spring-loaded lug and the bolt head catch have their respective vertical axes situated on the median longitudinal plane.
The bolt tail appendage 79 is elongated and extends into the bolt head hollow and away from the bolt tail first section. The bolt tail appendage 79 at its base is integral with the bolt tail first section. The bolt tail appendage includes a bolt tail appendage first catch 81 and a bolt tail appendage second catch 83. The catches 81 and 83 are both shown as openings in an appendage exterior surface facing the first bolt head interior surface 59.
The bolt tail appendage 79 has an appendage interior surface which defines a longitudinally extending chasm 85. The chasm has a longitudinally extending floor bounded by two longitudinally extending lateral walls. The lateral walls have longitudinally extending end surfaces 87 which face the second bolt head interior surface 61. The chasm 85 has a U-shaped cross section. The collar 67 pushes down on the lateral wall end surfaces. A bulbous portion 67a of the lug head extends into the chasm.
The pushing force of the collar 67b helps to keep the bolt head catch 57 locked with the bolt tail appendage first catch 81 when the latch is in the short position, and helps to keep the bolt head catch locked with the bolt tail appendage second catch 83 when the latch is in the long position. The appendage first 81 and second catches 83 are longitudinally spaced apart a pre-determined distance 88 to coincide with the desired short latch length and the desired long latch length.
The bolt case extension first section 35 has a first catch 89 longitudinally spaced apart from a second catch 91. The case extension first catch 89 is between the longitudinally extending hole 73 and the case extension second section 41. The first catch 89 and second catches 91 are apertures.
The longitudinally extending hole 73 has a longitudinally extending hole first end 93. The longitudinally extending hole has a longitudinally extending hole second end 95 opposite the longitudinally extending hole first end. The longitudinal length 88 of the longitudinally extending hole, measured from the first end 93 to the second end 95, is equal to the longitudinal spacing of the bolt tail appendage first catch 81 and the bolt tail appendage second catch 83.
The case extension second catch 91 is formed by two notches. A first notch 97 is disposed in a first longitudinally extending side of the longitudinally extending hole 73. A second notch 99 is disposed opposite said first notch in a second longitudinally extending side of the longitudinally extending hole 73. The case extension second catch 91 is longitudinally closer to the longitudinally extending hole second end 95 than to the longitudinally extending hole first end 93. The longitudinal distance 88 between the case extension first catch and the case extension second catch is equal to the longitudinal spacing between the bolt tail appendage first catch 81 and the bolt tail appendage second catch 83.
The resilient catch 77 is connected to the bolt case along a side of the bolt case having a bolt case surface facing in the same direction as the exterior longitudinally extending bolt head surface 39. The resilient catch 77 has a resilient catch first section 101 anchored to the bolt case. The resilient catch has a resilient catch second section 103 resiliently displaceable away from the bolt case surface and away from the bolt case hole. The resilient catch second section 103 is displaced by the pushing of the lug shaft-end 69 on the resilient catch when the spring-loaded lug is in the retracted position. The resilient catch second section 103 closely covers the bolt case hole when the spring-loaded lug is in the extended position and thus not pushing on the resilient catch second section 103. The resilient catch second section has a flange 105 which is disposed in the bolt case extension first catch 89 when the latch is in the short position. The resilient catch flange 105 is disposed in the case extension second catch 91 when the latch is in the long position.
In an intermediate position between the short and long latch positions, the push button 29 is depressed and the spring-loaded lug 65 is retracted. The lug shaft 66 abuts up against the longitudinally extending hole first end 93. The lug shaft-end 69 pushes up against the resilient catch 77. The resilient catch is in an unrelaxed position. The case extension first catch 89 is aligned with the resilient catch flange 105. The bolt tail appendage first latch 81 is aligned over the bolt head catch 57. Releasing the push button 29 locks the latch in the short position.
In the short position the spring-loaded lug 65 is extended. The resilient catch flange 105 is locked with the case extension first catch 89. The resilient catch 77 is in the relaxed state closely covering the bolt case hole 75. The bolt head catch 57 is locked with the bolt tail appendage first catch 81.
Adjusting the latch from the short position to the long position is accomplished with relative ease. An installer pushes the bolt tail protrusion 29 in a direction towards the resilient catch. The pushing causes the bolt tail to tilt and the bolt tail appendage first catch 81 to dislodge from the bolt head catch 57. The pushing also causes the bolt tail appendage to push the spring-loaded lug 65 to its retracted position. The retraction causes the lug shaft-end to push the resilient catch 77 away from the bolt case 15. The movement dislodges the resilient catch flange 105 from the case extension first catch 89. The variable positional relationship of the bolt head catch to the bolt tail appendage and the variable positional relationship of the resilient catch to the case extension is thus mutually dependent.
The installer while pushing the bolt tail protrusion 29 also slides the bolt tail 25, case extension 33, and eccentric 45 longitudinally away from the bolt head 19. During this longitudinal movement the case extension first section 35 slides between the longitudinally extending bolt head exterior surface and the longitudinally extending bolt case interior surface. The case extension first section 35 slides in a longitudinal direction away from the bolt head first section 21.
The bolt tail 21, case extension 33, and eccentric 45 slide in unison longitudinally away from the bolt head. During the sliding the longitudinally extending hole second end 95 moves closer to the lug shaft 66. When the latch is ready to be locked in the long position, the lug shaft contacts the longitudinally extending hole second end 95.
The installer releases the push button. The spring-loaded lug enters the extended position. The resilient catch flange 105 locks with the case extension second catch 91. The bolt head catch locks with the bolt tail appendage second catch 83. The resilient catch relaxes and closely covers the bolt case hole 75. The latch is locked in the long position. The simultaneous locking of the bolt head catch and the resilient catch flange demonstrates a mutual dependence between the resilient catch and the bolt head catch.
The installer, to adjust the latch from the long position to the short position, simply repeats the above process but obviously slides the bolt tail, case extension, and eccentric in the opposite direction.
The spring-loaded lug is extended in both the short and long positions. It should also be noted that the adjustment to the short and long positions is shown with the bolt head in the retracted position.
Further, the U-shaped bolt tail appendage should be noted. The configuration helps to stabilize a normal center-mounted bolt pin 107 during the adjustment of the bolt tail from the short to the long position or vice versa. As shown, the bolt pin 107 co-acts with the bolt tail to open and close the bolt head 19.
Additionally, the bolt case extension second section has holes 109 for door mounting pins.
It is important to note that the present invention has been described with reference to an example of an embodiment of the invention. It would be apparent to those skilled in the art that a person understanding this invention may conceive of changes or other embodiments or variations which utilize the principles of the invention without departing from the broader spirit and scope of the invention as set forth in the appended claims. All are considered within the spirit and scope of the invention. The specifications and drawings are therefore to be regarded in an illustrative rather than a restrictive sense. Accordingly, it is not intended that the invention be limited except as may be necessary in view of the appended claims. | An adaptable latch having a bolt case. A bolt case extension is connected to the rear of the bolt case. The bolt case extension can be locked in position with the bolt case to place the latch in a short-length position or a long-length position. A bolt head is disposed in the bolt case. A bolt tail is connected to the rear of the bolt case. The bolt tail can be locked in position with the bolt head to place the latch in the short-length position or the long-length position. A spring-loaded lug allows for simultaneous unlocking of the bolt tail from the bolt head and the case extension from the bolt case. The bolt tail and case extension, when unlocked from a previous locked position, can be placed in another locked position to lock the latch in either the desired long-length position or the short-length position. The bolt tail is locked into position with the bolt head by way of a bolt tail appendage extending into a bolt head hollow. The bolt tail appendage locks with a bolt head catch in the bolt head hollow. | 8 |
TECHNICAL FIELD
[0001] This invention relates to a continuous rolling method for efficiently manufacturing steel rod, wire, and the like by successively joining traveling high temperature steel pieces by flash welding (also called as flash-butt welding), and then by rolling thus formed endless steel piece, and to a continuous rolling apparatus therefor.
BACKGROUND
[0002] Conventional rolling lines of steel rods, wires, and the like manufacture the products by rolling steel pieces such as blooms and billets one by one. In recent years, however, there has been proposed a technology of preventing the reduction of product yield resulting from cutting to remove the crops of leading and trailing ends of steel pieces and improving productivity by eliminating idle time between steel pieces. According to that technology, pluralities of steel pieces delivered from a heating furnace or directly fed from a continuous casting machine are welded with each other while traveling by a traveling flash welding machine at an upstream side of the rolling mill train or in the rolling mill train to form an endless steel piece. Thus formed endless steel piece is continuously rolled as disclosed in Japanese Patent Publication Nos. 52-43754 and 9-66301.
[0003] During the operation of the above technology, the welded parts of steel pieces which were joined together by flash welding form welding burrs. Since the welding burrs are relatively large, they generate flaws in the succeeding rolling step to decrease the product yield, and they may cause a break or the like in the rolling step. Consequently, those welding burrs have to be removed before rolling after the welding.
[0004] There is a known deburring machine to remove welding burrs from flash welded parts, which is a deburring machine built in a traveling flash welding machine. FIG. 12 shows a continuous rolling apparatus provided with that type of deburring machine, and FIG. 13 shows a perspective view of a core part of that deburring machine.
[0005] In FIG. 12 , the rolling line has a heating furnace 10 , a traveling flash welding machine 20 , and a rolling mill 60 , in sequential order. The traveling flash welding machine 20 has a deburring machine 30 . As illustrated in FIG. 13 , the deburring machine 30 is equipped with a vertical deburring cutter 31 in a downward-opening angular U-shape, a hydraulic cylinder 32 to drive the vertical deburring cutter 31 in the vertical directions, a horizontal deburring cutter 33 in a side-opening angular U-shape, and a hydraulic cylinder 34 to drive the horizontal deburring cutter 33 in the horizontal directions. The reference numbers 21 a and 22 b in FIG. 13 signify welding clamps to conduct flash welding while clamping to upset a preceding billet 1 a and a succeeding billet 1 b , respectively.
[0006] In such a structured rolling line, the leading end of the succeeding billet 1 b delivered from the heating furnace 10 and the trailing end of the preceding billet 1 a are welded together by the traveling flash welding machine 20 , and welding burrs 2 formed on the welded part are removed by the deburring machine 30 . Then, thus formed endless billet 1 is continuously rolled by the rolling mill 60 . In FIG. 12 , the “H” position is the home position of the traveling flash welding machine 20 . The welding by the traveling flash welding machine 20 begins from the home position, and the welding terminates at the “A” position in the figure. After that, deburring by the deburring machine 30 begins from the “A” position, and the deburring terminates at the “B” position. FIG. 14 illustrates the conditions of deburring by the deburring machine 30 . As illustrated in FIG. 14A , the vertical deburring cutter 31 descends toward the welded part, driven by the hydraulic cylinder 32 , thereby removing the welding burrs on both left and right sides of the welded part. Then, as illustrated in FIG. 14B , the horizontal deburring cutter 33 travels in the horizontal direction toward the welded part, driven by the hydraulic cylinder 34 , thereby removing the welding burrs from both top and bottom sides of the welded part.
[0007] According to the deburring by the deburring machine 30 , there are problems of forming fins 3 at corners of the cross section of the welded part upon conducting deburring at the welded part using the vertical deburring cutter 31 or the horizontal deburring cutter 33 , as shown in FIG. 14A and FIG. 14B , and giving fins 3 , formed by deburring, left behind at corners of cross section of the welded part of the billet 1 , as shown in FIG. 14C . The presence of such fins generates flaws in succeeding rolling step, thus inducing deterioration of product quality and reducing the product yield in some cases.
[0008] There is another known deburring machine to remove welding burrs from the flash welded part, which is a rotary-blade type deburring machine, located at the downstream side of the traveling flash welding machine, to cut the welding burrs by pressing the rotating circular cutting edge against the welding burrs as disclosed in European Published Patent Application No. EP 1 057 563 A1. FIG. 15 illustrates a continuous rolling line provided with that type of deburring machine, and FIG. 16 shows a perspective view of a core part of that deburring machine.
[0009] As shown in FIG. 15 , the rolling line arranges the heating furnace 10 , the traveling flash welding machine 20 , the deburring machine 40 , and the rolling mill 60 in this sequential order. As seen in FIG. 16 , the deburring machine 40 has cutting blades 41 a and 41 b , each having a rotating circular cutting edge. With the cutting blades 41 a and 41 b , the welding burr 2 formed on the top face of the welded part is removed. The cutting blades to remove the welding burrs on other faces of the welded part, (bottom face and right and left side faces) are also provided, though FIG. 16 does not show them.
[0010] According to thus structured rolling line, the leading end of the succeeding billet 1 b delivered from the heating furnace 10 and the trailing end of the preceding billet 1 a are welded to join together while traveling them using the traveling flash welding machine 20 , and the welding burrs 2 formed on the welded part are removed by the deburring machine 40 , and then thus formed endless billet 1 is continuously rolled by the rolling mill 60 . In FIG. 15 , the “H” position is the home position of the traveling flash welding machine 20 . The welding by the traveling flash welding machine 20 begins from the home position, and the welding terminates at the “A” position in the figure. The welding burrs 2 at the welded part are removed while the billet 1 passes through the deburring machine 40 . The deburring operation with that type of deburring machine 40 avoids the generation of fins 3 which raise a problem in deburring operation with the deburring machine 30 , which is illustrated in FIGS. 12 to 14 .
[0011] There are, however, problems in the deburring using the above deburring machine 40 . That is, as illustrated in FIG. 17 , when the continuously cast billet 1 is cut to a specified length in a continuous casting process using a mechanical diagonal cutter 71 equipped with a mobile cutting blade 72 a and stationary cutting blade 72 b , ( FIG. 17A ), the cut section deforms, ( FIG. 17B ). In this state, if the cross sections of the preceding billet 1 a and the succeeding billet 1 b are butted against each other, a significant misalignment 4 appears particularly at corners (edges) of the cross sections, ( FIG. 17C ). If flash welding is applied to these billets 1 a and 1 b , having that misalignment 4 , ( FIG. 17D ), the portions near the misalignment 4 are not fully welded and result in a defect 6 caused by the misalignment 4 left behind at the welded part, ( FIG. 17E ). Since that type of defect 6 caused by the misalignment 4 cannot be removed by deburring (hatched part 5 ) by the deburring machine 40 , ( FIG. 17F ), the defect 6 caused by the misalignment 4 is left behind at corners of the cross section of the billet 1 before rolling, ( FIG. 17G ). As a result, flaws appear in the succeeding rolling step, which may deteriorate the product quality and decrease the product yield.
[0012] As described above, the continuous rolling technology in the related art raises problem that, when the welding burrs formed at the flash welded part are removed by a deburring machine, defects caused by fins or misalignment are left behind at corners of cross section at the welded part, which defects become flaws in the succeeding rolling step, thereby deteriorating the product quality and decreasing the product yield.
[0013] It would therefore be helpful to provide a continuous rolling method and a continuous rolling apparatus to attain good product quality and product yield by preventing the generation of flaws during rolling in the continuous rolling technology to manufacture steel rods, wires, and the like.
SUMMARY
[0014] A continuous rolling method is disclosed that has the steps of: flash welding a trailing end of a preceding steel piece and a leading end of a succeeding steel piece to join them together while they are traveling; deburring to remove burrs from the welded part; and rolling thus joined steel pieces; wherein the step of trimming for trimming corners of cross section of the deburred welded part is provided after the step of deburring.
[0015] A continuous rolling apparatus is also disclosed that has: a traveling flash welding machine which joins a trailing end of a preceding steel piece and a leading end of a succeeding steel piece together by flash welding while they are traveling; and a deburring machine which removes burrs from the welded part, and a rolling mill which rolls thus joined steel pieces; wherein a trimming machine to trim corners of cross section of the deburred welded part is located in the apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 shows a block flow diagram of selected aspects of the method.
[0017] FIG. 2 illustrates the structure of selected aspects of the apparatus.
[0018] FIG. 3A and FIG. 3B illustrate a trimming machine.
[0019] FIG. 4A , FIG. 4B , FIG. 4C , and FIG. 4D illustrate the state of deburring and trimming.
[0020] FIG. 5A and FIG. 5B illustrate another trimming machine.
[0021] FIG. 6A and FIG. 6B illustrate a further trimming machine.
[0022] FIG. 7 illustrates still another trimming machine.
[0023] FIG. 8 illustrates yet another trimming machine.
[0024] FIG. 9A and FIG. 9B illustrate yet still another trimming machine.
[0025] FIG. 10 illustrates the structure of another apparatus.
[0026] FIG. 11A , FIG. 11B , FIG. 11C , FIG. 11D , and FIG. 11E illustrate the state of trimming of another selected aspect.
[0027] FIG. 12 illustrates the related art.
[0028] FIG. 13 illustrates the related art.
[0029] FIG. 14A , FIG. 14B , and FIG. 14C illustrate the related art.
[0030] FIG. 15 illustrates the related art.
[0031] FIG. 16 illustrates the related art.
[0032] FIG. 17A , FIG. 17B , FIG. 17C , FIG. 17D , FIG. 17E , FIG. 17F , and FIG. 17G illustrate the related art.
[0033] FIG. 17G illustrates the related art.
DETAILED DESCRIPTION
[0034] It will be appreciated that the following description is intended to refer to specific aspects of this disclosure selected for illustration in the drawings and is not intended to define or limit the scope of the subject matter herein, other than in the:appended claims.
[0035] FIG. 1 shows a block flow diagram of a heating step for heating steel pieces, (hereinafter represented by billets), to a specified temperature; a flash welding step for joining the trailing end of a preceding billet with the leading end of a succeeding billet while they are traveling using flash welding; a deburring step for removing burrs from the welded part; an edge trimming step for trimming corners (edges) of cross section of the deburred welded part; and a rolling step for rolling the joined billets. As illustrated in FIG. 1 , the heating step may be replaced by a direct-feeding step for continuously and directly feeding the continuously cast billet. Furthermore, a preliminary rolling step for rolling the billet, which was heated in the heating step, to a specified cross section may be inserted between the heating step and the flash welding step.
[0036] FIG. 2 illustrates the structure of apparatus that has a rolling line with a heating furnace 10 , the traveling flash welding machine 20 , the trimming machine 50 , and the rolling mill 60 , in this sequential order. The traveling flash welding machine 20 is equipped with the deburring machine 30 .
[0037] As shown in FIG. 13 , the deburring machine 30 is equipped with the vertical deburring cutter 31 in a downward-opening angular U-shape, the hydraulic cylinder 32 to drive the vertical deburring cutter 31 in the vertical directions, the horizontal deburring cutter 33 in a side-opening angular U-shape, and the hydraulic cylinder 34 to drive the horizontal deburring cutter 33 in the horizontal directions.
[0038] As illustrated in FIG. 3A and FIG. 3B , the trimming machine 50 has trimming cutters (cutting bite) 51 , each of which is located at a position facing each of the four corners of cross section of the billet 1 , has left and right frames 52 a and 52 b , each of which is provided with two trimming cutters, as of total four trimming cutters, in vertical row, and has hydraulic cylinders 53 a and 53 b , each of which drives the left frame 52 a and the right frame 52 b , respectively, forward and rearward in relation to the billet 1 .
[0039] The position of the welded part of the billet 1 is tracked by a measuring roll (not shown) positioned in the rolling line. As shown in FIG. 3A , the left and the right frames 52 a and 52 b wait at a retracted position until the welded part of the billet 1 comes close to the trimming machine 50 . As shown in FIG. 3B , once the welded part of the billet 1 comes close to the trimming machine 50 , the left and the right frames 52 a and 52 b move forward to let the trimming cutters 51 trim (chamfer) the corners of cross section of the welded part to a specified degree. After completing the trimming to the specified degree, the left and the right frames 52 a and 52 b retract to the original waiting position.
[0040] The rolling line structured as described above conducts: welding a leading end of succeeding billet 1 b delivered from the heating furnace 10 and a trailing end of preceding billet 1 a to join them together while they are traveling using the traveling flash welding machine 20 , thus forming an endless billet; deburring the welding burrs 2 formed on the welded part using the deburring machine 30 ; trimming the corners of cross section of the deburred welded part using the trimming machine 50 ; and rolling thus formed endless billet using the rolling mill 60 .
[0041] In FIG. 2 , the “H” position is the home position of the traveling flash welding machine 20 . The welding by the traveling flash welding machine 20 begins from the home position, and the welding terminates at the “A” position in the figure. After that, deburring by the deburring machine 30 begins from the “A” position, and the deburring terminates at the “B” position. The corners of cross section of the welded part are trimmed while the billet 1 passes through the trimming machine 50 .
[0042] FIG. 4 shows the state of deburring and trimming using the deburring machine 30 and the trimming machine 50 , respectively. As illustrated in FIG. 4A , the vertical deburring cutter 31 descends toward the welded part, driven by the hydraulic cylinder 32 , thus removing the welding burrs on left and right sides of the welded part. Then, as illustrated in FIG. 4B , the horizontal deburring cutter 33 moves horizontally toward the welded part, driven by the hydraulic cylinder 34 , thus removing the welding burrs top and bottom sides of the welded part. After that, as illustrated in FIG. 4C , the hydraulic cylinders 53 a and 53 b drive the trimming cutters 51 forward to the corners of cross section of the welded part, thereby trimming the corners of cross section of the welded part to remove the fins 3 .
[0043] The amount of trimming may be adequately determined based on the magnitude of the existing fins 3 . For example, the trimming is conducted in a range of longitudinal direction of the billet from about 100 to about 200 mm including the welded part, to depths from about 5 to about 10 mm at the corners of cross section of the welded part. By the trimming, the welded part before rolling shows a good cross sectional shape free of welding burrs and fins, as shown in FIG. 4D .
[0044] Accordingly, the above apparatus accurately removes the fins 3 existing at the corners of the cross section of the welded part after deburring, and prevents the generation of rolling flaws caused by the fins, thereby assuring good product quality and product yield.
[0045] As illustrated in FIG. 5A and FIG. 5B , the trimming machine 50 may, alternatively, have each two trimming cutters 51 to each of the top and the bottom frames 52 c and 52 d , thereby letting each of the top frame 52 c and the bottom frame 52 d move forward and rearward in relation to the billet 1 using hydraulic cylinders 53 c and 53 d , respectively.
[0046] Furthermore, as illustrated in FIG. 6A and FIG. 6B , the trimming machine 50 may have each four trimming cutters 51 , thereby letting each four set thereof move forward and rearward in relation to the billet 1 using a hydraulic cylinder 53 e.
[0047] Although the above description conducts trimming by cutting using a trimming cutter, the trimming cutter may be substituted by a grinder to conduct trimming by grinding. In this case, as illustrated in FIG. 7 , four grinders 56 are located allotting each one thereof to each corner of the cross section of the billet 1 , each of which grinders 56 can move forward and rearward in relation to the billet 1 using the respective hydraulic cylinders (not shown). Then, as illustrated in FIG. 8 , when the welded part comes, each grinder 56 is made to move forward to the billet 1 using the relating hydraulic cylinder, and the grinders 56 are driven by respective motors 57 , thus conducting trimming at the corners of cross section of the welded part.
[0048] Alternatively, the trimming cutter may be replaced by a gas scarfing nozzle to conduct trimming by scarfing. In this case, as illustrated in FIG. 9A , four gas scarfing nozzles are located allotting each one thereof to each corner of the cross section of the billet 1 , each of which gas scarfing nozzles 58 can move forward and rearward in relation to the billet 1 using the respective hydraulic cylinders (not shown). Then, as illustrated in FIG. 9B , when the welded part comes, each gas scarfing nozzle 58 is made to move forward to the billet 1 using the relating hydraulic cylinder, thus conducting trimming at the corners of cross section of the welded part by gas scarfing.
[0049] In the above description, if the use of billets heated in the heating furnace is changed to the direct feed of billets after the continuous casting, it is preferable that an induction heating unit is located at upstream side of the flash welding machine or between the flash welding machine and the rolling mill to heat the billets to ensure the rolling temperature.
[0050] FIG. 10 illustrates the structure of another selected apparatus. As illustrated in the figure, the rolling line of the second embodiment has: the heating furnace 10 , the traveling flash welding machine 20 , the deburring machine 40 , the trimming machine 50 , and the rolling mill 60 , in this sequential order.
[0051] Although the first described apparatus has the deburring machine built in the traveling flash welding machine, the second described apparatus locates the deburring machine at downstream side of the traveling flash welding machine. Other configurations are, of course, possible.
[0052] As illustrated in FIG. 16 , the deburring machine 40 has cutting blades 41 a and 41 b , each having a rotating circular cutting edge. With the cutting blades 41 a and 41 b , the welding burrs 2 formed on the welded part are removed.
[0053] The rolling line structured as described above conducts: welding a leading end of a succeeding billet 1 b delivered from the heating furnace 10 and a trailing end of a preceding billet 1 a to join them together while they are traveling using the traveling flash welding machine 20 ; deburring the welding burrs 2 formed on the welded part using the deburring machine 40 ; trimming the corners of the cross section of the deburred welded part using the trimming machine 50 ; and continuously rolling thus prepared endless billet using the rolling mill 60 .
[0054] In FIG. 10 , the “H” position is the home position of the traveling flash welding machine 20 . The welding by the traveling flash welding machine 20 begins from the home position, and the welding completes at the “A” position in the figure. Then, the welding burrs 2 at the welded part are removed while the billet 1 passes through the deburring machine 40 . The corners of the cross section of welded part are trimmed while the billet 1 passes through the trimming machine 50 .
[0055] With the use of the deburring machine 40 , the generation of fins can be avoided. In addition, use of the trimming machine 50 removes the defect caused by misalignment.
[0056] As described before, if the cross sections of the billets 1 a and 1 b , deformed in their cross sectional shape by cutting after continuous casting, are butted against each other, a significant misalignment 4 appears particularly at corners (edges) of the cross sections. As illustrated in FIG. 11 , if flash welding is applied to these billets 1 a and 1 b , having that misalignment 4 , ( FIG. 11A ), the portions near the misalignment 4 are not fully welded to give a defect 6 caused by the misalignment 4 left behind at the welded part, ( FIG. 11B ). Although that type of defect 6 caused by the misalignment 4 cannot be removed by deburring (hatched part 5 ) by the deburring machine 40 , ( FIG. 11C ), the defect 6 can be removed by the trimming of corners of the cross section of the welded part, (hatched part 7 ) using the succeeding trimming machine 50 , ( FIG. 11D ), thereby providing the billet 1 free from the defect 6 caused by the misalignment 4 , ( FIG. 11E ).
[0057] The amount of trimming may be adequately determined based on the magnitude of the existing misalignment 4 . For example, the trimming is conducted in a range of longitudinal direction of the billet from about 100 to about 200 mm including the welded part, to depths from about 5 to about 10 mm at the corners of cross section of the welded part. By the trimming, the welded part of the billet before rolling shows a good cross sectional shape free of welding burrs and of defect caused by misalignment.
[0058] Accordingly, the apparatus removes accurately the defect, caused by misalignment, left behind at the corners of the cross section of the welded part after deburring, and prevents the generation of rolling flaws caused by misalignment, thereby assuring good product quality and product yield. | The continuous rolling method and the continuous rolling apparatus provide good product quality and product yield by successively joining pluralities of traveling hot steel pieces by flash welding, and by rolling thus prepared endless steel piece, thus preventing generation of flaws in the rolling step, thereby manufacture steel rods, wires, and the like by the continuous rolling technology. The method has: a heating step for heating billet to a specified temperature; a flash welding step for joining the trailing end of preceding billet with the leading end of succeeding billet while they are traveling using flash welding; a deburring step for removing burrs from the welded part; a trimming step for trimming corners of cross section of the deburred welded part; and a rolling step for rolling the joined billets. | 1 |
BACKGROUND OF THE INVENTION
[0001] The subject invention relates to asphalt-based waterproof roofing membranes used in multi-ply asphalt-based commercial roofing systems and, in particular, to a prefabricated asphalt-based waterproof roofing membrane for use in a multi-ply asphalt-based commercial roofing system, e.g. a cap sheet that forms the exposed layer of a multi-ply built-up roofing system, that is manufactured at a factory to have a highly reflective upper surface that meets EPA Energy Star requirements.
[0002] Asphalt-based waterproof roofing membranes, such as cap sheets, are currently manufactured in a process that includes several major process steps. The process steps for producing these black asphalt-based waterproof roofing membranes include: saturating a reinforcing substrate with asphalt (bitumen), typically an oxidized or modified asphalt (bitumen); building up layers of asphalt on both major surfaces of the reinforcing substrate until the asphalt saturated and coated reinforcing substrate formed attains a desired thickness; applying granules, release agents or release films, or a combination of granules and release agents or release films to at least one major surface of the asphalt-based waterproof roofing membrane; winding the finished asphalt-based waterproof roofing membrane into a roll; and packaging the roll of asphalt-based waterproof roofing membrane for storage and shipment to a job site. The process steps of saturating the reinforcing substrate with black asphalt, e.g. an oxidized or modified asphalt, and building up layers of asphalt on both major surfaces of the reinforcing substrate may occur simultaneously. Typically, the reinforcing substrate used in the asphalt-based waterproof roofing membrane is a non-woven fiberglass mat, a reinforced fiberglass mat, a non-woven polyester mat, a reinforced polyester mat, a veiled scrim of various fiber combinations, or a laminated composite of two or more of the preceding reinforcing substrates that provide the asphalt-based waterproof roofing membrane with the necessary strength and flexibility.
[0003] In a typical manufacturing process, the reinforcing substrate is passed through a saturator/coater where the reinforcing substrate is saturated and coated with asphalt at temperatures from 300 to 425° F. The asphalt typically contains asphalt and mineral fillers and may contain modifiers, such as thermoplastics [Amorphous Polypropylene (APP)], rubbers [Styrene-Butadiene-Styrene (SBS)], and other polymers, antioxidants, resins, oils, etc. Where the saturator and coater units are separate, the asphalts used in the saturator unit to saturate the reinforcing substrate and in the coater unit to coat the reinforcing substrate and build up the thickness of the asphalt saturated and coated reinforcing substrate may have the same composition or different compositions.
[0004] The reinforcing substrate is typically saturated and coated with asphalt by dipping the reinforcing substrate into a tank of the asphalt or by spreading asphalt over the top surface of the substrate as it passes through a coater. Squeeze rollers and other rollers in the saturator/coater apply the asphalt to the bottom surface of the sheet and distribute the asphalt evenly over the top and bottom surfaces of the reinforcing substrate to form built up layers of asphalt on the top and bottom surfaces of the reinforcing substrate.
[0005] After passing through the saturator/coater unit or the separate saturator and coater units, surfacing materials are typically adhered to both the top and bottom surfaces of the asphalt saturated and coated reinforcing substrate. In some processes, the asphalt saturated and coated reinforcing substrate may pass through a cooling unit where the asphalt saturated and coated reinforcing substrate is cooled prior to applying surfacing materials to the asphalt saturated and coated reinforcing substrate. Typically, the surfacing materials are applied to the asphalt saturated and coated reinforcing substrate by first passing the asphalt saturated and coated reinforcing substrate through a top surfacing unit. In the top surfacing unit, granules or other surfacing material(s) are applied to the top surface of the asphalt saturated and coated reinforcing substrate. With the desired surfacing material(s) applied to the top surface of the asphalt saturated and coated reinforcing substrate, the asphalt saturated and coated reinforcing substrate passes over a first press drum where the surfacing materials applied to the top surface of the asphalt saturated and coated reinforcing substrate are pressed into the asphalt layer on the top surface of the asphalt saturated and coated reinforcing substrate to assure good adhesion between the surfacing materials and the asphalt layer. As the asphalt saturated and coated reinforcing substrate passes over the first press drum, the asphalt saturated and coated reinforcing substrate is normally flipped simultaneously with the pressing operation so that the bottom surface of the asphalt saturated and coated reinforcing substrate is facing upward. This permits the application of surfacing materials (such as sand, other minerals (e.g. mica, talc, etc.), chemical release agents, and/or polymeric films) to the bottom surface of the asphalt saturated and coated reinforcing substrate by a bottom-surfacing unit. The asphalt saturated and coated reinforcing substrate then passes over a second press drum where the surfacing materials applied to the bottom surface of the asphalt saturated and coated reinforcing substrate are pressed into the asphalt layer on the bottom surface of the asphalt saturated and coated reinforcing substrate to assure good adhesion between the surfacing materials and the asphalt layer. The second turnover press drum returns the asphalt saturated and coated reinforcing substrate to its normal orientation.
[0006] After the application of the surfacing materials to the top and bottom surfaces of the asphalt saturated and coated reinforcing substrate, the surfaced asphalt saturated and coated reinforcing substrate is cooled rapidly by water-cooled rolls and/or water sprays. The surfaced asphalt saturated and coated reinforcing substrate is then passed through a drying section where the surfaced asphalt saturated and coated reinforcing substrate is typically air dried to finish the manufacture of the asphalt-based waterproof roofing membrane. The finished asphalt-based waterproof roofing membrane is then fed through a looper or accumulator section to permit the continuous movement of the finished asphalt-based waterproof roofing membrane during the cutting and winding operation where the finished asphalt-based waterproof roofing membrane is cut into selected lengths and wound into rolls for packaging, storage, and shipment to a job site.
[0007] The ever increasing consumption of energy to cool buildings, coupled with global and regional environmental warming issues, has caused a conversion in contemporary roofing technologies to roofing with more reflective top surfaces so that the roofing better reflects solar radiation to thereby reduce the amount of solar radiation absorbed by the roofing and the amount of energy required to cool buildings. Contemporary roofing technologies typically increase the reflectivity of the top surface of the roofing by making the top surface (the exposed surface) of the roofing system white.
[0008] Due to their irregular granular top surfaces and the intergranule spaces that reveal the black light-absorbing asphalt surfaces to which the granules are adhered, asphalt-based waterproof roofing membranes, such as cap sheets, currently on the market do not meet current EPA Energy Star reflective requirements as measured by ASTM standard E 903—Standard Test Method for Solar Absorptance, Reflectance, and Transmission of Materials Using Integrating Spheres. The current technology used at the job site to upgrade asphalt-based waterproof roofing membranes and provide these roofing membranes with more reflective top surfaces involves covering the exposed surfaces of the roofing membranes with a reflective white coating at the job site. This procedure leads to several problems: a waiting period of up to 30 days before the coating can be applied to the top surface of the membrane; the cost of and time required to clean the top surface of the membrane before applying the coating to the top surface of the membrane; the cost of and time involved in the labor intensive application of the coating to the top surface of the membrane; the quality and/or consistency of the application of the coating to the top surface of the membrane which is dependent on the skill and conscientiousness of the laborer; the limited service life of such coatings on the top surface of the membrane; and the requirement for the periodic maintenance and reapplication of the coating to the top surface of the membrane. The problems associated with applying white coatings at the job site to the top surfaces of asphalt-based waterproof roofing membranes, plus the ease with which single-ply roofing membranes, such as polyvinyl chloride and thermoplastic olefin single-ply roofing membranes, can be made from white compounds, have contributed to market shifts away from multi-ply asphalt-based commercial roofing systems to single-ply membrane roofing systems.
SUMMARY OF THE INVENTION
[0009] The method of prefabricating the asphalt-based waterproof roofing membrane and the prefabricated asphalt-based waterproof roofing membrane of the subject invention solve the problems associated with asphalt-based waterproof roofing membranes discussed in the background of the invention by providing an asphalt-based waterproof roofing membrane that is manufactured in a factory with a standardized reflective top surface that meets current EPA Energy Star reflective requirements as measured by ASTM standard E 903—Standard Test Method for Solar Absorptance, Reflectance, and Transmission of Materials Using Integrating Spheres. The standardized, prefabricated asphalt-based waterproof roofing membrane of the subject invention can be easily applied at a job site with no need to coat the asphalt-based roofing membrane at the job site to improve the reflectivity of the top surface of the membrane to meet EPA Energy Star requirements as measured by ASTM standard E 903. In the method of manufacturing the prefabricated asphalt-based waterproof roofing membrane of the subject invention, a highly reflective non-asphalt based elastomeric coating, in liquid or powder form, is applied to the top surface of a black asphalt saturated and coated reinforcing substrate of the membrane during the manufacture of the asphalt-based waterproof roofing membrane at the factory to provide the asphalt-based waterproof roofing membrane with a highly reflective top surface that meets current EPA Energy Star requirements as measured by ASTM standard E 903. Preferably, the highly reflective top surface of the asphalt-based waterproof roofing membrane is white. The highly reflective top surface of the asphalt-based waterproof roofing membrane may be smooth or may be embossed to enhance the appearance of the top surface and to provide a slip-resistant roofing surface on which the workers can walk.
[0010] The highly reflective elastomeric coating used in the prefabricated asphalt-based waterproof roofing membrane of the subject invention is opaque to protect the underlying asphalt layer of the asphalt saturated and coated reinforcing substrate of the membrane from the deleterious effects of ultraviolet radiation and may have various additives to improve the performance of the composite, e.g. fungi growth-inhibiting agents, fire retardants, etc.
[0011] The highly reflective coating of the subject invention is a polymer material binder that is preferably colored with a white pigment, such as titanium dioxide, zinc oxide, aluminum oxide. The polymer material binder used in the highly reflective coating to carry and bind the highly reflective pigments of the coating to the top surface of the asphalt layer of the asphalt saturated and coated reinforcing substrate of the membrane includes several families of binders. Preferably, the polymer binders are made up of amine-terminated polymer resins and/or amine-terminated chain extenders. Acrylic and isocyanate-based elastomers are particularly well suited for use as the coatings with the isocyanate elastomers being preferred. Preferably, a polymer primer, which is impermeable to the oils and other components of the asphalt, is applied between the highly reflective coating layer and the top surface of the top asphalt layer of the asphalt saturated and coated reinforcing substrate to prevent the exuding of oils and other components from the asphalt into the highly reflective coating and to thereby prevent the oils and other components of the asphalt from staining and otherwise discoloring or adversely affecting the highly reflective coating layer.
[0012] The highly reflective coating may be applied to the top surface of the asphalt saturated and coated reinforcing substrate, typically after the temperature of the asphalt saturated and coated reinforcing substrate has fallen to about 300° F. or less, by a number of techniques including: dip coating, spread coating, roll coating, spray coating and powder coating. The coatings are dried to maintain the cleanliness of the reflective surfaces of the asphalt-based waterproof roofing membranes thus formed and release films or agents are applied to the highly reflective top surfaces of the asphalt-based waterproof roofing membranes prior to winding the membranes into rolls.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a schematic perspective view of a first embodiment of the asphalt-based waterproof roofing membrane of the subject invention.
[0014] FIG. 2 is a partial schematic cross section taken substantially along lines 2 - 2 of FIG. 1 , on a larger scale than FIG. 1 , to illustrate the layers of the asphalt-based waterproof roofing membrane of FIG. 1 plus the release sheets.
[0015] FIG. 3 is a schematic perspective view of a second embodiment of the asphalt-based waterproof roofing membrane of the subject invention.
[0016] FIG. 4 is a partial schematic cross section taken substantially along lines 4 - 4 of FIG. 3 , on a larger scale than FIG. 3 , to illustrate the layers of the asphalt-based waterproof roofing membrane of FIG. 3 plus the release sheets.
[0017] FIG. 5 is a schematic side view of a production line that may be used to practice the method of the subject invention for prefabricating the asphalt-based waterproof roofing membrane of the subject invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] The prefabricated asphalt-based waterproof roofing membrane 10 of the subject invention, shown in FIGS. 1 and 2 , has a top major surface 12 and a bottom major surface 14 that are each defined by the length and width of the membrane 10 . The prefabricated asphalt-based waterproof roofing membrane 10 has a lateral edge portion 16 , typically called the selvage edge portion of the roofing membrane, that extends for the length of the prefabricated asphalt-based waterproof roofing membrane. The lateral edge portion 16 of prefabricated asphalt-based waterproof roofing membrane 10 is typically about four inches in width and when the prefabricated asphalt-based waterproof roofing membrane 10 is installed on a roof, the top surface of this lateral edge portion 16 is overlapped and sealed to the underside of a lateral edge portion 18 of an adjacent prefabricated asphalt-based waterproof roofing membrane to form a watertight seam. The edge portion 18 has substantially the same width as the lateral edge portion 16 and also extends for the length of the prefabricated asphalt-based waterproof roofing membrane 10 . Thus, when the prefabricated asphalt-based waterproof roofing membrane 10 is installed on a roof, the top surface of the lateral edge portion 16 is covered by the lateral edge portion 18 of the adjacent prefabricated asphalt-based waterproof roofing membrane while the remainder of the top major surface 12 of the prefabricated asphalt-based waterproof roofing membrane 10 is exposed to the weather. The prefabricated asphalt-based waterproof roofing membrane 10 is typically between 36 and 40 inches in width and comes in 1 square (108 square foot) rolls.
[0019] The prefabricated asphalt-based waterproof roofing membrane 10 includes: a reinforcing substrate 20 ; asphalt with which the reinforcing substrate 20 is saturated and which forms top and bottom layers 22 and 24 encapsulating the reinforcing substrate; and a top coating layer 26 with a highly reflective top surface 28 that is coextensive with or substantially coextensive with the top major surface 12 of the prefabricated asphalt-based waterproof roofing membrane 10 . Preferably, the prefabricated asphalt-based waterproof roofing membrane 10 has a polymer primer layer 30 , which is impermeable to the oils and other components of the asphalt. The impermeable polymer primer layer 30 is located between the highly reflective coating layer 26 and the top surface of the top asphalt layer 22 to prevent the exuding of oils and other components from the asphalt into the highly reflective coating layer 26 and to thereby prevent the oils and other components of the asphalt from staining and otherwise discoloring or adversely affecting the highly reflective top surface 28 of the coating layer 26 . In addition, the prefabricated asphalt-based waterproof roofing membrane 10 normally includes a bottom surface layer 32 formed of conventional mineral surfacing materials, such as but not limited to such as mica, talc, sand, etc., chemical release agents, and/or polymeric film.
[0020] A release film or sheet 34 may overlie the bottom surface layer 32 of the membrane to keep the bottom major surface 14 of the prefabricated asphalt-based waterproof roofing membrane 10 from adhering to or discoloring the highly reflective coating layer 26 of top major surface 12 of the prefabricated asphalt-based waterproof roofing membrane 10 when the prefabricated asphalt-based waterproof roofing membrane is wound into a roll for packaging, storage, shipment and handling prior to installation. A release film or sheet 36 may overlie the top surface 28 of the highly reflective coating layer 26 and thus the top major surface 12 of the prefabricated asphalt-based waterproof roofing membrane 10 to maintain the cleanliness of the top surface 28 of the highly reflective coating layer 26 . Where a release film or sheet 34 is not used on the bottom major surface of the prefabricated asphalt-based waterproof roofing membrane 10 , the release film or sheet 36 also functions to keep the bottom major surface 14 of the prefabricated asphalt-based waterproof roofing membrane 10 from adhering to or discoloring the top major surface 12 of the prefabricated asphalt-based waterproof roofing membrane 10 when the prefabricated asphalt-based waterproof roofing membrane is wound into a roll for packaging, storage, shipment and handling prior to installation. The surfaces of the release sheets 34 and 36 in contact with the bottom and top major surfaces of the prefabricated asphalt-based waterproof roofing membrane 10 are treated with conventional release agents, e.g. silicone or some other conventional release agent, so that the sheets 34 and 36 may be easily peeled off of the major surfaces of the prefabricated asphalt-based waterproof roofing membrane 10 during installation.
[0021] The prefabricated asphalt-based waterproof roofing membrane 110 of the subject invention, shown in FIGS. 3 and 4 , has a top major surface 112 and a bottom major surface 114 that are each defined by the length and width of the membrane 110 . The prefabricated asphalt-based waterproof roofing membrane 110 has a lateral edge portion 116 , typically called the selvage edge portion of the roofing membrane, which extends for the length of the prefabricated asphalt-based waterproof roofing membrane. The lateral edge portion 116 of prefabricated asphalt-based waterproof roofing membrane 110 is typically about four inches in width and when the prefabricated asphalt-based waterproof roofing membrane 110 is installed on a roof, the top surface of this lateral edge portion 116 is overlapped and sealed to the underside of a lateral edge portion 118 of an adjacent prefabricated asphalt-based waterproof roofing membrane to form a watertight seam. The edge portion 118 has substantially the same width as the lateral edge portion 116 and also extends for the length of the prefabricated asphalt-based waterproof roofing membrane 110 . Thus, when the prefabricated asphalt-based waterproof roofing membrane 110 is installed on a roof, the top surface of the lateral edge portion 116 is covered by and sealed to the bottom surface of the lateral edge portion 118 of the adjacent prefabricated asphalt-based waterproof roofing membrane while the remainder of the top major surface 112 of the prefabricated asphalt-based waterproof roofing membrane 110 is exposed to the weather. The prefabricated asphalt-based waterproof roofing membrane 110 is typically between 36 and 40 inches in width and comes in 1 square (108 square foot) rolls.
[0022] The prefabricated asphalt-based waterproof roofing membrane 110 includes: a reinforcing substrate 120 ; asphalt with which the reinforcing substrate 120 is saturated and which forms top and bottom layers 122 and 124 encapsulating the reinforcing substrate; and a top coating layer 126 with a highly reflective top surface 128 that, except for the lateral edge portion 116 which remains uncoated by the top coating layer 126 , is coextensive with or substantially coextensive with the remainder of top major surface 112 of the prefabricated asphalt-based waterproof roofing membrane 110 . Preferably, the prefabricated asphalt-based waterproof roofing membrane 110 has a polymer primer layer 130 , which is impermeable to the oils and other components of the asphalt. The impermeable polymer primer layer 130 is located between the highly reflective coating layer 126 and the top surface of the top asphalt layer 122 to prevent the exuding of oils and other components from the asphalt into the highly reflective coating layer 126 and to thereby prevent the oils and other components of the asphalt from staining and otherwise discoloring or adversely affecting the highly reflective top surface 128 of the coating layer 126 . In addition, the prefabricated asphalt-based waterproof roofing membrane 110 includes a bottom surface layer 132 formed of conventional mineral surfacing materials, such as but not limited to such as mica, talc, sand, etc., chemical release agents, and/or polymeric film.
[0023] Preferably, the bottom surface layer 132 , except for the lateral edge portion 118 , which remains uncoated by the bottom surface layer 132 , is coextensive with or substantially coextensive with the remainder of bottom major surface 114 of the prefabricated asphalt-based waterproof roofing membrane 110 . This structure is especially well suited for prefabricated asphalt-based waterproof roofing membranes 110 that are to be used in cold-applied roof installations. With this structure, a SBS (Styrene-Butadiene-Styrene) rubber modified bitumen that is a pressure sensitive adhesive may be used to form the top and bottom asphalt layers 122 and 124 to thereby enable the overlapping lateral edge portions 116 and 118 of adjacent prefabricated asphalt-based waterproof membranes 110 to be bonded together with a watertight weather secure seal. Preferably, a release film or sheet 134 overlies the bottom surface layer 132 and lateral edge portion 118 of the bottom major surface of the membrane to keep the bottom major surface 114 of the prefabricated asphalt-based waterproof roofing membrane 110 from adhering to or discoloring the highly reflective coating layer 126 of top major surface 112 of the prefabricated asphalt-based waterproof roofing membrane 110 when the prefabricated asphalt-based waterproof roofing membrane is wound into a roll for packaging, storage, shipment and handling prior to installation. Preferably, a release film or sheet 136 overlies the top surface 128 of the highly reflective coating layer 126 and the lateral edge portion 116 of the top major surface 112 of the prefabricated asphalt-based waterproof roofing membrane 110 to maintain the cleanliness of the top surface 128 of the highly reflective coating layer 126 and keep the lateral edge portion 116 from adhering to the bottom major surface 114 of the membrane when the prefabricated asphalt-based waterproof roofing membrane is wound into a roll for packaging, storage, shipment and handling prior to installation. Where a release film or sheet 134 is not used on the bottom major surface of the prefabricated asphalt-based waterproof roofing membrane 110 , the release film or sheet 136 functions to keep the bottom major surface 114 of the prefabricated asphalt-based waterproof roofing membrane 110 from adhering to or discoloring the top major surface 112 of the prefabricated asphalt-based waterproof roofing membrane 110 when the prefabricated asphalt-based waterproof roofing membrane is wound into a roll for packaging, storage, shipment and handling prior to installation. The surfaces of the release sheets 134 and 136 in contact with the bottom and top major surfaces of the prefabricated asphalt-based waterproof roofing membrane 110 are treated with conventional release agents, e.g. silicone or some other conventional release agent, so that the sheets 134 and 136 may be easily peeled off of the major surfaces of the prefabricated asphalt-based waterproof roofing membrane 110 for installation on a roof.
[0024] While the prefabricated asphalt-based waterproof roofing membranes 10 and 110 may include a layer of top surfacing materials, such as granules, mica, talc, etc. intermediate the top surfaces of the top asphalt layers 22 and 122 and the highly reflective coating layers 26 and 126 or on the highly reflective coating layers 26 and 126 , the preferred embodiments of the prefabricated asphalt-based waterproof roofing membranes 10 and 110 do not include any such layer of traditional top surfacing materials. The presence of such a layer of traditional top surfacing materials could adversely affect the adhesion between the highly reflective coating layers 26 and 126 and the top asphalt layers 22 and 122 and/or could reduce the reflectivity of the top surfaces 28 and 128 of the highly reflective coatings 26 and 126 .
[0025] The reinforcing substrates 20 and 120 of the prefabricated asphalt-based waterproof roofing membranes 10 and 110 may be any of the conventional reinforcing substrates commonly used in asphalt-based waterproof roofing membranes to provide the membranes with the necessary strength and flexibility, such as, but not limited to: a non-woven fiberglass mat, a reinforced fiberglass mat, a non-woven polyester mat, a reinforced polyester mat, a veiled scrim of various fiber combinations, or a laminated composite of two or more of the preceding reinforcing substrates.
[0026] The compositions of the asphalt saturating the reinforcing substrates 20 and 120 and forming the top and bottom layers 22 , 24 and 122 , 124 on the reinforcing substrates 20 and 120 may be any of the asphalt compositions discussed above and/or commonly used in asphalt-based waterproof roofing membranes. These asphalt compositions may include fire retardant chemicals, and typically, range from mineral filled oxidized asphalts to polymer-modified asphalts that are modified with modifiers, such as thermoplastics [Amorphous Polypropylene (APP)], rubbers [Styrene-Butadiene-Styrene (SBS)], and other polymers, antioxidants, resins, oils, etc. The polymer-modified asphalts may also include mineral fillers.
[0027] The highly reflective coating layers 26 and 126 are composed of a polymer binder material or materials and a reflective pigment or pigments, preferably a white pigment, such as but not limited to titanium dioxide, zinc oxide, aluminum oxide, other mineral pigments, or a combination of these pigments in quantities sufficient to make the coating layers 26 and 126 both opaque to solar radiation and highly reflective. The pigments in the highly reflective coating layers 26 and 126 protect: the impermeable polymer primer layers 30 and 130 (when used); the polymer binder materials of the coating layers 26 and 126 ; and the underlying asphalt layers 22 and 122 of the asphalt saturated and coated reinforcing substrate 20 and 120 from the deleterious effects of ultraviolet radiation. The highly reflective coating layer 26 and 126 may also include additional additives that: aid in limiting the growth of fungi during service; improve fire resistance; enhance heat, light and impact stability; improve the application and flow characteristics of the coating (slip agents, surfactants, thickeners, viscosity depressants, etc.); and reduce the aging rate, discoloration, and dirt adherence of the coating during service. While the highest reflectance values require the highly reflective coating layers 26 and 126 to have smooth top surfaces 28 and 128 , it may be feasible to emboss the top surfaces 28 and 128 of the highly reflective coating layers 26 and 126 to enhance the appearance of the top major surfaces 12 and 112 of the prefabricated asphalt-based waterproof roofing membranes 10 and 110 and make the top major surfaces 12 and 112 of the prefabricated asphalt-based waterproof roofing membranes 10 and 110 more slip resistant.
[0028] There are several families of polymer binders that are well suited for use as the polymer binder materials in the highly reflective coating layers 26 and 126 to carry the highly reflective pigments of the highly reflective coating layers 26 and 126 and bind the highly reflective pigments of the highly reflective coating layers 26 and 126 to the top asphalt layers 22 and 122 or the impermeable polymer primer layers 30 and 130 (when used). Acrylic and isocyanate-based elastomers are particularly well suited for use as the polymer binder materials in the highly reflective coating layers 26 and 126 . Due to their fast curing times; their durability when subjected to weathering forces, chemical contaminants, and solar radiation while in service on rooftops; their low glass transition temperatures (the property of remaining flexible at low temperatures); their low or nonexistent volatile organic compound emissions (voc emissions) during application; and their ability to be reapplied at the job site should the highly reflective top surfaces 28 and 128 of the membrane be damaged; isocyanate elastomers are currently preferred.
[0029] The currently preferred isocyanate elastomers are formed by reacting polyisocyantes with polyester or polyester resins (urethanes) or with polyamines (polyurea). Due to their extremely fast reaction kinetics and cure and their durability, polyurea elastomers are most preferred. Polyurea elastomers may be derived from condensing an isocyanate component and a resin blend component. The isocyanate component may be aromatic or aliphatic in nature and may be a monomer, polymer, or any variant reaction of isocyanates, quasi-prepolymer, or a prepolymer. The prepolymer, quasi-prepolymer may be made of an amine-terminated polymer resin, or a hydroxyl-terminated polymer resin. However, the aliphatic variant is most preferred because the aliphatic variant exhibits the best resistance to yellowing (it does not yellow) with exposure to ultraviolet radiation. Preferably, the resin blend is made up of amine-terminated polymer resins and/or amine-terminated chain extenders. The amine-terminated polymer resins in the preferred blend will not have any intentional hydroxyl moieties. Any hydroxyls are a result of an incomplete conversion to the amine-terminated polymer resins. The preferred resin blend may also contain additives or non-primary components. These additives may contain hydroxyls, such as pre-dispersed pigments in a polyol carrier. Normally, the resin blend will not contain a catalyst. Polyurea coatings may also be comprised of aspartic esters, which provide amine functionality.
[0030] In the application of the highly reflective coating layers 26 and 126 to the top asphalt layers 22 and 122 of the membranes 10 and 110 , incompatibility between the acrylic or isocyanate elastomers of the coating layers 26 and 126 and the asphalt (e.g. oxidized or polymer modified asphalt) of the asphalt layers 22 and 122 is a primary concern. This interaction can result in the exudation of oils and other colored components out of the asphalt into the pores or structure of the highly reflective coating layers 26 and 126 . The exudation of such oils and other colored components into the highly reflective coating layers 26 and 126 can cause permanent staining and discoloration of the highly reflective top surfaces 28 and 128 of the coating layers 26 and 126 . In addition, the exudation of such oils into the elastomers of the coating layers 26 and 126 may also exacerbate the aging rate of or otherwise adversely affect the coating layers. To prevent any significant exudation of oils and other colored components from the asphalt layers 22 and 122 into the coating layers 26 and 126 , the polymer primer layers 30 and 130 that are impermeable or substantially impermeable to the oils and other colored components of the asphalt in the asphalt layers 22 and 122 may be located intermediate the top surface of the asphalt layers 22 and 122 and the bottom surfaces of the highly reflective coating layers 26 and 126 . Suitable polymer primers for the layers 30 and 130 include those containing polyvinyl acetate, polyvinylidene chloride, cured polyacrylonitrile, cellulose polymers, and others such as disclosed in U.S. Pat. No. 4,442,148, issued Apr. 10, 1984. The disclosure of U.S. Pat. No. 4,442,148, is hereby incorporated herein in its entirety by reference. Other polymer primers than those set forth above that will block or substantially block the exudation of oils and other colored components from the asphalt may also be used.
[0031] The reflectance of the top major surfaces 12 and 112 of the prefabricated asphalt-based waterproof roofing membranes 10 and 110 formed by the top highly reflective surfaces 28 and 128 of the top coating layers 26 and 126 , as measured by ASTM standard E 903—Standard Test Method for Solar Absorptance, Reflectance, and Transmission of Materials Using Integrating Spheres, will meet current EPA Energy Star reflective requirements for low-slope roof products. The current EPA Energy Star reflectance requirements are an Initial Solar Reflectance greater than or equal to 0.65 and a Maintenance of Solar Reflectance greater or equal to 0.50 three years after installation under normal conditions. The current test criteria for determining the Initial Solar Reflectance requires the testing of a 3 inch by 3 inch sample of the product in accordance with ASTM E 903 (values for solar absorptance and transmission need not be obtained) using a black background. The current test criteria for determining the Maintenance of Solar Reflectance three years after installation under normal conditions may use any of three test methods set forth in the current EPA Energy Star guidelines including the following test method. A minimum of three (3) samples from three existing roofs on which the product has been installed for a minimum of three years with one of the existing roofs being located within a major metropolitan area such as Atlanta, Boston, Chicago, Dallas, Houston, Los Angles, Miami, Minneapolis, New York, Philadelphia, San Francisco, St. Louis, Washington D.C., etc. At least three (3) measurements of solar reflectance are to be taken from different areas on each sample in accordance with ASTM E 903. The average of all solar reflectance values obtained from the samples will be used to determine the solar reflectance of the weathered roof product. ASTM standard E 903 test method measures solar reflectance by using spectrophotometers that are equipped with integrating spheres. The test method is set forth in the ASTM test Designation E 903-96, approved Apr. 10, 1996 and published May 1996. ASTM test Designation E 903-96 is hereby incorporated herein by reference in its entirety.
[0032] FIG. 5 schematically illustrates a typical manufacturing line 220 that could be used for making the prefabricated asphalt-based waterproof roofing membranes 10 and 110 . As shown in FIG. 5 , in the manufacturing process of the subject invention, the reinforcing substrate 20 or 120 may be passed through a standard saturator/coater unit 222 or a standard saturator unit and a standard coater unit (not shown) where the reinforcing substrate 20 or 120 is saturated and coated with asphalt 224 at temperatures typically between 300 to 425° F. The saturator/coater unit 222 of FIG. 5 includes a tank 226 that contains the asphalt 224 and squeeze rollers 228 . The asphalt 224 may be any of the asphalt compositions discussed above and/or commonly used in the industry to make asphalt-based waterproof roofing membranes and typically contains asphalt and mineral fillers and may contain modifiers, such as thermoplastics [Amorphous Polypropylene (APP)], rubbers [Styrene-Butadiene-Styrene (SBS)], and other polymers, antioxidants, resins, oils, etc. Where the saturator and coater units are separate, the asphalts used in the saturator unit to saturate the reinforcing substrate 20 or 120 and in the coater unit to coat the reinforcing substrate 20 or 120 and build up the thickness of the saturated and coated reinforcing substrate 20 or 120 may have the same composition or different compositions.
[0033] As shown in FIG. 5 , the reinforcing substrate 20 or 120 is saturated and coated with the asphalt 224 by passing the reinforcing substrate 20 or 120 through a pool of asphalt 224 in the tank 226 . The thicknesses of the top and bottom asphalt layers 22 , 24 or 122 , 124 of the asphalt saturated and coated reinforcing substrate 20 or 120 and the overall thickness of the asphalt saturated and coated reinforcing substrate 20 or 120 are then set by passing the saturated and coated reinforcing substrate between the spaced apart squeeze rollers 228 . The spaced apart squeeze rollers 228 distribute the asphalt 224 evenly throughout the reinforcing substrate and over the top and bottom surfaces of the reinforcing substrate to form the built up layers of asphalt 22 , 24 or 122 , 124 on the top and bottom surfaces of the reinforcing substrate 20 or 120 .
[0034] In the preferred method of the subject invention, a polymer primer layer 30 or 130 that is impermeable or substantially impermeable to the oils and other colored components of the asphalt 224 is then applied to the top surface of the top asphalt layer 22 or 122 . The polymer primer material 230 that forms the polymer primer layer 30 or 130 would typically be applied to the top surface of the top asphalt layer 22 or 122 after the top asphalt layer 22 or 122 has been cooled to a temperature below 300° F. To form the polymer primer layer 30 of the roofing membrane 10 , the polymer primer material 230 would be applied (e.g. poured or sprayed) across the entire width of the top surface of the top asphalt layer 22 by an applicator 232 . To form the polymer primer layer 130 of the roofing membrane 110 , the polymer primer material 230 would not be applied to the lateral edge portion 116 , but would be applied (e.g. poured or sprayed) across the remaining width of the top surface of the top asphalt layer 122 by an applicator 232 with a barrier preventing the primer material from flowing onto the lateral edge portion 116 . The pool of polymer primer material 230 thus formed then passes beneath a doctor blade 234 that smoothes the top surface of the polymer primer material and forms the pool of polymer primer material into the polymer primer layer 30 or 130 . The polymer primer layer 30 , 130 is then typically air dried or cured prior to applying the pigment filled polymer binder material 236 that is formed into the highly reflective coating layer 26 , 126 . While the technique shown for applying the polymer primer material 230 to the top surface of the top asphalt layer 22 or 122 is a spread coating technique, it is contemplated that the polymer primer material 230 could be applied to the top surface of the top asphalt layer 22 or 122 by other techniques commonly used in the industry, such as but not limited to, dip coating, roll coating, spray coating, and powder coating techniques.
[0035] Where the polymer primer material 230 is utilized to provide the membrane 10 , 110 with the polymer primer layer 30 or 130 , after the polymer primer layer 30 or 130 is dried, the pigment filled polymer binder material 236 that is formed into the highly reflective coating layer 26 or 126 may be poured or sprayed in liquid form onto the top surface the polymer primer layer 30 or 130 by an applicator 238 . Where the polymer primer material 230 is not utilized to form the polymer primer layer 30 between the asphalt layer 22 and the highly reflective coating layer 26 of the roofing membrane 10 , the pigment filled polymer binder material 236 that is formed into the highly reflective coating layer 26 could be poured or sprayed in liquid form across the entire width of and directly onto the top surface of the top asphalt layer 22 by the applicator 238 . Where the polymer primer material 230 is not utilized to form the polymer primer layer 130 between the asphalt layer 122 and the highly reflective coating layer 126 of the roofing membrane 110 , the pigment filled polymer binder material 236 that is formed into the highly reflective coating layer 126 would not be poured or sprayed onto the lateral edge portion 116 , but would be poured or sprayed in liquid form across the remaining width of and directly onto the top surface of the top asphalt layer 122 by the applicator 238 with a barrier preventing the pigment filled polymer binder material from flowing onto the lateral edge portion 116 . The pool of pigment filled polymer binder material 236 thus formed then passes beneath a doctor blade 240 that smoothes the top surface of the pigment filled polymer binder material 236 and forms the pool of pigment filled polymer binder material 236 into the highly reflective coating layer 26 or 126 . The highly reflective coating layer 26 or 126 is formed by the doctor blade 240 to a desired thickness and smoothness that is sufficient to provide the highly reflective coating layer 26 or 126 and the prefabricated asphalt-based waterproof roofing membrane 10 or 110 with the necessary reflectance.
[0036] While the technique shown for applying the pigment filled polymer binder material 236 to the top surface of the polymer primer layer 30 or 130 or the top surface of the top asphalt layer 22 or 122 is a spread coating technique, it is contemplated that the pigment filled polymer binder material 236 could be applied to the top surface of the polymer primer layer 30 , 130 or the top surface of the top asphalt layer 22 , 122 by other techniques commonly used in the industry, such as but not limited to, dip coating, roll coating, spray coating, and powder coating techniques. Where the pigment filled polymer binder material 236 is in powder form, preferably, the pigment filled polymer binder material 236 is heated by a heater (not shown) to melt the powder or the surface temperature of the polymer primer layer 30 , 130 or the top asphalt layer 22 , 122 is hot enough to melt the pigment filled polymer binder material 236 to form a pool of the pigment filled polymer binder material 236 .
[0037] With the highly reflective coating layer 26 or 126 applied to the top surface of the asphalt layer 22 or 122 or the top surface of the polymer primer layer 30 or 130 , the laminate 242 thus formed by the asphalt saturated and coated reinforcing substrate 20 or 120 with the highly reflective coating layer 26 or 126 or the polymer primer layer 30 or 130 and the highly reflective coating layer 26 or 126 may be passed around a first press drum 244 . As the laminate 242 passes around the first turnover press drum 244 , the layers 22 , 26 or 22 , 30 , 26 of the roofing membrane 10 or the layers 122 , 126 or 122 , 130 , 126 of the roofing membrane 110 are pressed together to assure good adhesion between the layers. As or after the laminate 242 passes over the first press drum 244 , the laminate is flipped (represented schematically by 245 in FIG. 5 ) so that the bottom surface of the bottom asphalt layer 24 or 124 of the laminate is facing upward. This permits the application of surfacing materials (such as sand, other minerals (e.g. mica, talc, etc.), chemical release agents, and/or polymeric films) to the bottom surface of the laminate 242 .
[0038] In FIG. 5 , bottom surfacing material(s) 246 that form the bottom surface layer 32 or 132 of the roofing membrane 10 or 110 are shown being poured or sprayed onto the bottom surface of the bottom asphalt layer 24 or 124 by an applicator 248 . To form the bottom surface layer 32 of the roofing membrane 10 , the surfacing materials 246 would be poured, sprayed or otherwise applied across the entire width of the bottom surface of the bottom asphalt layer 24 by an applicator 248 . To form the bottom surface layer 132 of the roofing membrane 110 , the surfacing materials 246 would not be poured, sprayed or applied onto the lateral edge portion 118 , but would be poured, sprayed or otherwise applied across the remaining width of the bottom surface of the bottom asphalt layer 124 by an applicator 248 with a barrier preventing the surfacing materials from flowing onto the lateral edge portion 118 . The layer of surfacing material(s) thus formed then passes beneath a doctor blade 250 that smoothes the normally bottom surface of the surfacing material(s) and forms the layer of surfacing material(s) into a bottom surface layer 32 or 132 having a desired thickness and smoothness.
[0039] The laminate 252 thus formed is then passed around a second press drum 254 where the surfacing materials 246 applied to the normally bottom surface of the asphalt layer 24 or 124 of the laminate 252 are pressed into the bottom surface of the asphalt layer 24 or 124 to assure good adhesion between the surfacing material(s) 246 and the asphalt layer 24 or 124 . After the laminate 252 passes over the second turnover press drum 254 , the laminate 252 is then flipped (represented schematically by 255 in FIG. 5 ) and returned to its normal orientation.
[0040] After the application of the top layers 22 , 26 and the bottom layers 24 , 32 or the top layers 22 , 30 , 26 and bottom layers 24 , 32 to the top and bottom surfaces of the asphalt saturated and coated reinforcing substrate 20 or the application of the top layers 122 , 126 and the bottom layers 124 , 132 or the top layers 122 , 130 , 126 and bottom layers 124 , 132 to the top and bottom surfaces of the asphalt saturated and coated reinforcing substrate 120 , the laminate 252 formed is rapidly cooled by water-cooled rolls and/or water sprays. The laminate 252 is then passed through a drying section where the composite is air dried/cured to solidify the highly reflective top coating layer 26 or 126 and the bottom layer 32 or 132 and complete the manufacture of the prefabricated asphalt-based waterproof roofing membrane 10 or 110 . A bottom release sheet 34 or 134 is applied to the bottom surface layer 32 or 132 and a top release sheet 36 or 136 is applied to the top surface of the highly reflective coating layer 26 or 126 of the prefabricated asphalt-based waterproof roofing membrane 10 or 110 from rolls 256 and 258 .
[0041] The prefabricated asphalt-based waterproof roofing membrane 10 or 110 is then fed through a looper or accumulator section 260 to permit the continuous movement of the prefabricated asphalt-based waterproof roofing membrane 10 or 110 during the cutting and winding operation. In the cutting and winding operation, the prefabricated asphalt-based waterproof roofing membrane 10 or 110 is periodically cut to a desired length or lengths by a cutting unit 262 and wound into rolls 264 for packaging, storage, and shipment to a job site.
[0042] Preferably, additional surfacing materials are not applied to the top surface of the highly reflective coating layer 26 or 126 . However, after the highly reflective top layer 26 or 126 is applied to the top asphalt layer 22 or 122 or the polymer primer layer 30 or 130 and prior to passing the asphalt saturated and coated reinforcing substrate 20 or 120 over the first press drum 244 , surfacing materials (such as roofing granules, sand, other minerals (e.g. mica, talc, etc.), chemical release agents, and/or release films) may be applied to the top surface 28 or 128 of the highly reflective coating layer 26 or 126 . While it is preferred to prefabricate the prefabricated asphalt-based waterproof roofing membrane 10 or 110 in line, as described above, it is contemplated that the application of the highly reflective coating layer 26 or 126 could be effected on a separate process line. However, this would appear to be relatively impractical in that it would add to the number of process steps and the costs of manufacture.
[0043] In describing the invention, certain embodiments have been used to illustrate the invention and the practices thereof. However, the invention is not limited to these specific embodiments as other embodiments and modifications within the spirit of the invention will readily occur to those skilled in the art on reading this specification. Thus, the invention is not intended to be limited to the specific embodiments disclosed, but is to be limited only by the claims appended hereto. | A prefabricated asphalt-based waterproof roofing membrane for use in a multi-ply asphalt-based commercial roofing system, e.g. a cap sheet that forms the exposed layer of a multi-ply built-up roofing system, is manufactured at a factory to have a highly reflective non-asphalt based elastomeric top coating layer with an upper surface that meets current EPA Energy Star requirements. Preferably, a polymer primer layer is interposed between the highly reflective coating layer and an asphalt saturated and coated reinforcing substrate to keep oils and other colored components in the asphalt from exuding into the highly reflective coating layer. | 1 |
RELATED APPLICATION
This application claims the benefit of U.S. provisional application Serial No. 60/294,845 filed May 31, 2001, the disclosure of which is incorporated in its entirety herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to compositions useful for and methods of treating ocular hypertension. More particularly, the invention relates to such compositions and methods which effectively treat ocular hypertension, for example, reduce or at least maintain intraocular pressure and preferably provide enhanced benefits and/or have reduced side effects relative to other compositions and methods.
Ocular hypotensive agents are useful in the treatment of a number of various ocular hypertensive conditions, such as post-surgical and post-laser trabeculectomy ocular hypertensive episodes, glaucoma, and as presurgical adjuncts.
Glaucoma is a disease of the eye characterized by increased intraocular pressure. On the basis of its etiology, glaucoma has been classified as primary or secondary. For example, primary glaucoma in adults (congenital glaucoma) may be either open-angle or acute or chronic angle-closure. Secondary glaucoma results from pre-existing ocular diseases such as uveitis, intraocular tumor or an enlarged cataract.
The underlying causes of primary glaucoma are not yet known. The increased intraocular tension is due to the obstruction of aqueous humor outflow. In chronic open-angle glaucoma, the anterior chamber and its anatomic structures appear normal, but drainage of the aqueous humor is impeded. In acute or chronic angle-closure glaucoma, the anterior chamber is shallow, the filtration angle is narrowed, and the iris may obstruct the trabecular meshwork at the entrance of the canal of Schlemm. Dilation of the pupil may push the root of the iris forward against the angle, and may produce pupillary block and thus precipitate an acute attack. Eyes with narrow anterior chamber angles are predisposed to acute angle-closure glaucoma attacks of various degrees of severity.
Secondary glaucoma is caused by any interference with the flow of aqueous humor from the posterior chamber into the anterior chamber and subsequently, into the canal of Schlemm. Inflammatory disease of the anterior segment may prevent aqueous escape by causing complete posterior synechia in iris bombe and may plug the drainage channel with exudates. Other common causes are intraocular tumors, enlarged cataracts, central retinal vein occlusion, trauma to the eye, operative procedures and intraocular hemorrhage.
Considering all types together, glaucoma occurs in about 2% of all persons over the age of 40 and may be asymptotic for years before progressing to rapid loss of vision. In cases where surgery is not indicated, topical b-adrenoreceptor antagonists have traditionally been the drugs of choice for treating glaucoma.
Prostaglandins were earlier regarded as potent ocular hypertensives; however, evidence accumulated in the last two decades shows that some prostaglandins are highly effective ocular hypotensive agents and are ideally suited for the long-term medical management of glaucoma. (See, for example, Starr, M. S. Exp. Eye Res. 1971, 11, pp. 170-177; Bito, L. Z. Biological Protection with Prostaglandins Cohen, M. M., ed., Boca Raton, Fla., CRC Press Inc., 1985, pp. 231-252; and Bito, L. Z., Applied Pharmacology in the Medical Treatment of Glaucomas Drance, S. M. and Neufeld, A. H. eds., New York, Grune & Stratton, 1984, pp. 477-505). Such prostaglandins include PGF 2a , PGF 1a , PGE 2 , and certain lipid-soluble esters, such as C 1 to C 5 alkyl esters, e.g. 1-isopropyl ester, of such compounds.
In the U.S. Pat. No. 4,599,353 certain prostaglandins, in particular PGE 2 and PGF2a and the C 1 to C 5 alkyl esters of the latter compound, were reported to possess ocular hypotensive activity and were recommended for use in glaucoma management.
Although the precise mechanism is not yet known, recent experimental results indicate that the prostaglandin-induced reduction in intraocular pressure results from increased uveoscleral outflow [Nilsson et al., Invest. Ophthalmol. Vis. Sci. 28(suppl), 284 (1987)].
The isopropyl ester of PGF 2a has been shown to have significantly greater hypotensive potency than the parent compound, which was attributed to its more effective penetration through the cornea. In 1987 this compound was described as “the most potent ocular hypotensive agent ever reported.” [See, for example, Bito, L. Z., Arch. Ophthalmol. 105, 1036 (1987), and Siebold et al., Prodrug 5, 3 (1989)].
Whereas prostaglandins appear to be devoid of significant intraocular side effects, ocular surface (conjunctival) hyperemia and foreign-body sensation have been consistently associated with the topical ocular use of such compounds, in particular PGF 2a and its prodrugs, e.g. its 1-isopropyl ester, in humans. The clinical potential of prostaglandins in the management of conditions associated with increased ocular pressure, e.g. glaucoma, is greatly limited by these side effects.
Certain phenyl and phenoxy mono, tri and tetra nor prostaglandins and their 1-esters are disclosed in European Patent Application 0,364,417 as useful in the treatment of glaucoma or ocular hypertension.
In a series of United States patent applications assigned to Allergan, Inc. prostaglandin esters with increased ocular hypotensive activity accompanied with no or substantially reduced side-effects are disclosed. U.S. Pat. application Ser. No. (USSN) 386,835 (filed Jul. 27, 1989), relates to certain 11-acyl-prostaglandins, such as 11-pivaloyl, 11-acetyl, 11-isobutyryl, 11-valeryl, and 11-isovaleryl PGF 2a . Intraocular pressure reducing 15-acyl prostaglandins are disclosed in 3U.S. Ser. No. 357,394 (filed May 25, 1989). Similarly, 11,15-9,15- and 9,11-diesters of prostaglandins, for example 11,15-dipivaloyl PGF 2a are known to have ocular hypotensive activity. See U.S. Ser. No. 385,645 filed Jul. 27, 1990, now U.S. Pat. No. 4,494,274; 584,370 which is a continuation of U.S. Ser. No. 386,312, and U.S. Ser. No. 585,284, now U.S. Pat. No. 5,034,413 which is a continuation of U.S. Ser. No. 386,834, where the parent applications were filed on Jul. 27, 1989. The disclosures of these patent applications are hereby expressly incorporated by reference.
Woodward et al U.S. Pat. No. 5,688,819 discloses certain cyclopentane heptanoic acid, 2-cycloalkyl or arylalkyl compounds as ocular hypotensives. These compounds, which can properly be characterized as hypotensive lipids, are effective in treating ocular hypertension. The disclosure of this U.S. Patent is hereby expressly incorporated by reference.
Timolol maleate ophthalmic solution, for example, sold under the trademark TIMOPTIC® by Merck, is a non-selective beta-adrenergic receptor blocking agent which is indicated in the treatment of elevated intraocular pressure in patients with ocular hypertension or open-angle glaucoma.
The hypotensive lipids and timolol maleate, when used alone, are effective in treating ocular hypertension. Timolol maleate, when used to control ocular hypertension, may produce one or more disadvantageous side effects, such as headache, fatigue and chest pain, and can have disadvantageous effects on the cardiovascular, digestive, immunologic and nervous systems.
It would be advantageous to provide for effective, preferably enhanced, treatment of ocular hypertension, preferably with reduced side effects from the treatment employed.
SUMMARY OF THE INVENTION
New compositions for and methods of treating ocular hypertension have been discovered. The present invention provides for effective treatment of ocular hypertension often using compositions including reduced concentrations of active components. Such compositions and methods have advantageously been found to be surprisingly effective in treating ocular hypertension and/or to reduce the number and/or frequency and/or severity of unwanted side effects caused by timolol components, e.g., timolol maleate, relative to prior art compositions and methods. The present compositions and methods are relatively straightforward, can be easily produced, for example, using conventional manufacturing techniques, and can be easily and conveniently practiced, for example, using application or administration techniques or methodologies which are substantially similar to those employed with prior compositions used to treat ocular hypertension.
The present methods of treating ocular hypertension comprise applying to an eye an amount sufficient to treat ocular hypertension of a composition comprising a timolol component and a hypotensive lipid component. Each of the timolol component and the hypotensive lipid component is present in the composition in an amount effective to reduce ocular hypertension when applied to a hypertensive eye, that is an eye which has ocular hypertension. The present applying step is effective to treat ocular hypertension, for example, to substantially maintain intraocular pressure or to provide a reduction in intraocular pressure. The present methods preferably provide enhanced treatment of ocular hypertension, for example, enhanced reduction in intraocular pressure, relative to applying a similar composition including either the timolol component or the hypotensive lipid component, but not both, at twice the concentration as in the compositions used in present methods. The present applying step preferably is effective to provide at least one reduced side effect relative to applying a similar composition including the timolol component, but not the hypotensive lipid component, to provide the same treatment of ocular hypertension, e.g., the same reduction in intraocular pressure.
Without wishing to limit the invention to any particular theory or mode of operation, it is believed that the present compositions and methods take advantage of the different modes of action of the timolol component and the hypotensive lipid component. For example, the timolol component alone is effective, when administered to the eye, to decrease the rate of aqueous humor production. On the other hand, the hypotensive lipid component alone is effective, when administered to the eye, to increase the out flow of aqueous humor from the eye. The combination of a timolol component and a hypotensive lipid component is believed to provide both a decreased rate of aqueous humor production and an increased aqueous humor outflow. This combination of active materials is particularly effective in treating ocular hypotension in one or more specific groups of patients, for example, patients with ocular hypotension which effectively responds to both a reduced rate of aqueous humor production and an increase in aqueous humor outflow.
The present timolol component/hypotensive lipid component-containing compositions advantageously provide the same or better reduction in intraocular pressure with reduced concentrations of each of these active materials relative to similar compositions including only the timolol component or the hypotensive component. The reduced concentrations of the active materials in the present compositions also reduce the number and/or severity of side effects, in particular side effects caused by the timolol component.
The timolol component preferably comprises an acid salt of timolol, more preferably comprises timolol maleate. The timolol component is present in the present compositions in an amount effective to reduce intraocular pressure when the composition is applied to a hypertensive eye. The preferred amount of timolol component employed is in a range of about 0.001% to about 1.0% (w/v), more preferably about 0.01% to about 0.2% or about 0.25% or about 0.5% (w/v).
In one embodiment, the hypotensive lipid component has the following formula (I)
wherein the dashed bonds represent a single or double bond which can be in the cis or trans configuration, A is an alkylene or alkenylene radical having from two to six carbon atoms, which radical may be interrupted by one or more oxide radicals and substituted with one or more hydroxy, oxo, alkyloxy or akylcarboxy groups wherein said alkyl radical comprises from one to six carbon atoms; B is a cycloalkyl radical having from three to seven carbon atoms, or an aryl radical, selected from the group consisting of hydrocarbyl aryl and heteroaryl radicals having from four to ten carbon atoms wherein the heteroatom is selected from the group consisting of nitrogen, oxygen and sulfur atoms; X is a radical selected from the group consisting of —OR 4 and —N(R 4 ) 2 wherein R 4 is selected from the group consisting of hydrogen, a lower alkyl radical having from one to six carbon atoms,
wherein R 5 is a lower alkyl radical having from one to six carbon atoms; Z is ═O or represents 2 hydrogen radicals; one of R1 and R2 is =O, —OH or a —O(CO)R6 group, and the other one is —OH or —O(CO)R6, or R1 is ═O and R2 is H, wherein R6 is a saturated or unsaturated acyclic hydrocarbon group having from 1 to about 20 carbon atoms, or —(CH2)mR7 wherein m is 0 or an integer of from 1 to 10, and R7 is cycloalkyl radical, having from three to seven carbon atoms, or a hydrocarbyl aryl or heteroaryl radical, as defined above, or a pharmaceutically-acceptable salt thereof, provided, however, that when B is not substituted with a pendant heteroatom-containing radical, and Z is ═O, then X is not —OR 4 . (That is, the cycloalkyl or hydrocarbyl aryl or heteroaryl radical is not substituted with a pendant radical having an atom other than carbon or hydrogen.)
More preferably the hypotensive lipid component has the following formula II:
wherein y is 0 or 1, x is 0 or 1 and x and y are not both 1, Y is a radical selected from the group consisting of alkyl, halo, e.g. fluoro, chloro, etc., nitro, amino, thiol, hydroxy, alkyloxy, alkylcarboxy, halo substituted alkyl wherein said alkyl radical comprises from one to six carbon atoms, etc. and n is 0 or an integer of from 1 to about 3 and R3 is ═O, —OH or —O(CO)R6 wherein R6 is as defined above. Preferably, n is 1 or 2.
Preferably the hypotensive lipid component has the following formula (III).
wherein hatched lines indicate a configuration, solid triangles are used to indicate β configuration.
In one embodiment, the hypotensive lipid component has the following formula (IV)
wherein y 1 is C1 or trifluoromethyl and the other symbols and substituents are as defined above, in combination with a pharmaceutical carrier.
In a useful embodiment, the hypotensive lipid component has the following Formula (V)
and the 9- and/or 11- and/or 15 esters thereof.
The hypotensive lipid component is present in the present compositions in an amount effective to reduce intraocular pressure when the composition is applied to a hypertensive eye. The preferred amount of hypotensive lipid component employed is in a range of about 0.00001% to about 0.1% (w/v), more preferably about 0.0001% to about 0.01% (w/v).
In a further aspect, the present invention relates to pharmaceutical compositions comprising a therapeutically effective amount of a timolol component, and a therapeutically effective amount of a hypotensive lipid component of formulae (I), (II), (III), (IV) or (V) wherein the symbols have the above meanings, or a pharmaceutically acceptable salt thereof, in admixture with a non-toxic, pharmaceutically acceptable liquid vehicle.
Each and every feature described herein, and each and every combination of two or more of such features, is included within the scope of the present invention provided that the features included in such a combination are not mutually inconsistent.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphical representation of certain effects of a hypotensive lipid/timolol maleate combination on intraocular pressure of laser induced ocular hypertensive cynomolgus monkeys.
FIG. 2 is a graphical representation of certain other effects of a hypotensive lipid/timolol maleate combination on intraocular pressure of laser induced ocular hypertensive cynomolgus monkeys.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the use of combinations of timolol components and lipid hypotensive components as ocular hypotensives in the treatment of ocular hypertension.
The timolol component is classified as a non-selective beta-adrenergic receptor blocking agent. The chemical name of timolol maleate, a highly preferred timolol component in the present invention, is (−)-1-tert-butylamino)-3-[(4-morpholino-1,2,5-thiodiazol-3 yl)oxyl-2-propanol maleate (1:1) (salt). Other pharmacologically acceptable acid salts may be employed alone or in combination with or without timolol maleate. However, because of its ready availability and its past, known usefulness as an ocular hypotensive, timolol maleate is preferred for use in the present invention. Timolol maleate possesses an asymmetric carbon atom in its structure and preferably is provided as the levo-isomer.
The preferred amount of timolol component employed is in the range of about 0.001% to about 1.0% (w/v); more preferably about 0.0005% or about 0.01% to about 0.2% or about 0.25% or about 0.5% (w/v), based on the amount of timolol present. To illustrate, each mL of a solution containing 0.25% (w/v) contains 2.5 mg of timolol (3.4 mg of timolol maleate).
Currently, Merck sells ophthalmic solutions of timolol maleate (under trademark TIMOPTIC® in concentrations of 0.25% (w/v) and 0.5% (w/v). The present compositions and methods preferably employ concentrations of timolol component which are reduced relative to these commercially available materials. It has been surprisingly found that fully acceptable levels of ocular hypertension treatment are achieved with these reduced concentrations of timolol component in combination with the presently useful hypotensive lipid components, also preferably present at relatively reduced concentrations. The reduced amounts of both timolol component and hypotensive lipid component have surprisingly been found to provide enhanced reduction in intraocular pressure when applied to a hypertensive eye relative to applying a similar composition containing twice as much of one, but not both, of the timolol component and the hypotensive lipid component to the hypertensive eye. The relatively reduced amounts of timolol component and hypertensive lipid component advantageously provide at least one reduced side effect when applied to an eye relative to applying a similar composition including one, but not both, of the timolol component and the hypotensive lipid component to an eye to get the same degree of ocular hypotension treatment, for example, the same degree of reduction of intraocular pressure.
The hypotensive lipid components useful in the present invention are cyclopentane heptanoic acid, 2-cycloalkyl or arylalkyl compounds. These hypotensive lipid components are represented by compounds having the formula I,
as defined above. The preferred nonacidic hypotensive lipid components used in accordance with the present invention have the following formula (II)
wherein the substituents and symbols are as hereinabove defined.
More preferably the hypotensive lipid components have the following formula (III)
wherein the substituents and symbols are as defined above.
More preferably, the hypotensive lipid components utilized in the present invention have the following formula (IV)
wherein the substituents and the symbols are as defined above.
Still more preferably the present invention utilizes the hypotensive lipid compounds having the following formula (V)
and their 9- and/or 11- and/or 15-esters.
In all of the above formulae (I) to (V) for the hypotensive lipid components, as well as in those provided hereinafter, the dotted lines on bonds between carbons 5 and 6 (C-5), between carbons 13 and 14 (C-13), between carbons 8 and 12 (C-8), and between carbons 10 and 11 (C-10) indicate a single or a double bond which can be in the cis or trans configuration. If two solid lines are used that indicates a specific configuration for that double bond. Hatched lines at positions C-9, C-11 and C-15 indicate the α configuration. If one were to draw the β configuration, a solid triangular line would be used.
In the hypotensive lipid components used in accordance with the present invention, compounds having the C-9 or C-11 or C-15 substituents in the α or β configuration are contemplated. As hereinabove mentioned, in all formulas provided herein broken line attachments to the cyclopentane ring indicate substituents in the a configuration. Thickened solid line attachments to the cyclopentane ring indicate substituents in the β configuration. Also, the broken line attachment of the hydroxyl group or other substituent to the C-11 and C-15 carbon atoms signifies the α configuration.
For the purpose of this invention, unless further limited, the term “alkyl” refers to alkyl groups having from one to about ten carbon atoms, the term “cycloalkyl” refers to cycloalkyl groups having from three to about seven carbon atoms, the term “aryl” refers to aryl groups having from four to about ten carbon atoms. The term “saturated or unsaturated acyclic hydrocarbon group” is used to refer to straight or branched chain, saturated or unsaturated hydrocarbon groups having from one to about 6, preferably one to about 4 carbon atoms. Such groups include alkyl, alkenyl and alkynyl groups of appropriate lengths, and preferably are alkyl, e.g. methyl, ethyl, propyl, butyl, pentyl, or hexyl, or an isomeric form thereof.
The definition of R 6 may include a cyclic component, —(CH 2 ) m R 7 , wherein m is 0 or an integer of from 1 to 10, R 7 is an aliphatic ring from about 3 to about 7 carbon atoms, or an aromatic or heteroaromatic ring. The “aliphatic ring” may be saturated or unsaturated, and preferably is a saturated ring having 3-7 carbon atoms, inclusive. As an aromatic ring, R 7 preferably is phenyl, and the heteroaromatic rings have oxygen, nitrogen or sulfur as a heteroatom, i.e. R 7 may be thienyl, furanyl, pyridyl, etc. Preferably m is 0 or an integer of from 1 to 4.
Z is ═O or represents two hydrogen atoms.
X may be selected from the group consisting of —OR 4 and —N(R 4 ) 2 wherein R 4 is selected from the group consisting of hydrogen, a lower alkyl radical having from one to six carbon atoms,
wherein R 5 is a lower alkyl radical having from one to six carbon atoms.
Preferred representatives of the hypotensive lipid components within the scope of the present invention are the compounds of formula V wherein X is —OH, i.e. cyclopentane heptenoic acid, 5-cis-2-(3-αhydroxy-4-m-chlorophenoxy-1-trans-butenyl)-3,5-dihydroxy, [1α, 2β, 3α, 5α] and cyclopentane methylheptenoate-5-cis-2(3-αhydroxy-4-m-chlorophenoxy-1-trans-butenyl)-3,5 dihydroxy, [1α, 2α, 3α, 5α] and the 9- and/or 11- and/or 15-esters of this compound. (The numbered designations in brackets refer to the positions on the cyclopentane ring.)
The following hypotensive lipid components may be used in the pharmaceutical compositions and the methods of the present invention.
(1) cyclopentane heptenol-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(2) cyclopentane heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(3) cyclopentane N,N-dimethylheptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(4) cyclopentane heptenyl methoxide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, (1α, 2β, 3α, 5α]
(5) cyclopentane heptenyl ethoxide-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(6) cyclopentane heptenylamide-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(7) cyclopentane heptenylamide-5-cis-2-(3α-hydroxy-4-trifluoromethylphenoxy-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(8) cyclopentane N-isopropyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(9) cyclopentane N-ethyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5 dihydroxy, [1α, 2β, 3α, 5α]
(10) cyclopentane N-methyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(11) cyclopentane heptenol-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-1-trans-butenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(12) cyclopentane heptenamide-5-cis-2-(3α-hydroxy-4-meta-chlorophenoxy-1-trans-butenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α]
(13) cyclopentane heptenol-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)3, 5-dihydroxy, [1α, 2β, 3α, 5α]
A pharmaceutically acceptable salt is any salt which retains the activity of the parent compound and does not impart any deleterious or undesirable effect on the subject to whom it is administered and in the context in which it is administered. With regard to the hypotensive lipid components, such salts are those formed with pharmaceutically acceptable cations, e.g., alkali metals, alkali earth metals, etc.
The hypotensive lipid components are present in the present compositions in amounts effective to reduce the intraocular pressure of a hypertensive eye to which the composition is applied. Because of the presence of the active timolol component, the amount of hypotensive lipid component employed preferably is relatively reduced, for example, relative to a composition in which the hypotensive lipid component is the only ocular hypotensive with the same intraocular pressure reduction being achieved. Such reduced amounts of hypotensive lipid components utilized in accordance with the present invention preferably provide a reduction in at least one side effect caused by the presence of the hypotensive lipid component. The preferred amount hypotensive lipid component employed is in the range of about 0.00005% to about 1.0% (w/v), more preferably about 0.0001% to about 0.01% or about 0.1% or about 0.5% (w/v).
Pharmaceutical compositions may be prepared by combining an effective amount of each of a timolol component and a hypotensive lipid component, as active ingredients, with conventional ophthalmically acceptable pharmaceutical excipients, and by preparation of unit dosage forms suitable for topical ocular use.
For ophthalmic application, preferably solutions are prepared using a physiological saline solution as a major vehicle. The pH of such ophthalmic solutions preferably is maintained between about 4.5 and about 8.0 with an appropriate buffer system, a substantially neutral pH being more preferred but not essential. The formulations may also contain conventional, pharmaceutically acceptable preservatives, stabilizers, surfactants and one or more other conventionally used components.
Preferred preservatives that may be used in the pharmaceutical compositions of the present invention include, but are not limited to, benzalkonium chloride, chlorobutanol, thimerosal, phenylmercuric acetate phenylmercuric nitrate, chlorite components, such as stabilized chlorine dioxide, and the like and mixture thereof. A preferred surfactant is, for example, Tween 80. Likewise, various preferred vehicles may be used in the ophthalmic preparations of the present invention. These vehicles include, but are not limited to, polyvinyl alcohol, povidone (polyvinyl pyrrolidone), hydroxypropyl methyl cellulose, poloxamers, carboxymethyl cellulose, hydroxyethyl cellulose, cyclodextrin and purified water and combinations or mixtures thereof.
Tonicity adjustors may be added as needed or convenient. They include, but are not limited to, salts, particularly sodium chloride, potassium chloride, mannitol and glycerin, or any other suitable ophthalmically acceptable tonicity adjustor.
Various buffers and means for adjusting pH may be used so long as the resulting preparation is ophthalmically acceptable. Accordingly, buffers include acetate buffers, citrate buffers, phosphate buffers, borate buffers and the like and mixtures thereof. Acids or bases may be used to adjust the pH of these formulations as needed.
In a similar vein, an ophthalmically acceptable antioxidant component may be included in the present composition. Such antioxidant components include, but are not limited to, sodium metabisulfite, sodium thiosulfate, acetylcysteine, butylated hydroxyanisole, butylated hydroxytoluene, and the like and mixtures thereof.
Other excipient components which may be included in the ophthalmic preparations include, without limitation, chelating agents. The preferred chelating agent is EDTA disodium, although other chelating agents may be used in place of or in conjunction with it.
The ingredients are usually in the following amounts:
Ingredients
Amount (w/%)
Timolol Component
about 0.001–1
Hypotensive Lipid Component
about 0.00005–1
Preservative
0–0.10
Vehicle
0–40
Tonicity adjustor
0–10
Buffer
0.01–10
pH adjustor
q.s. pH
4.5–7.5
antioxidant
as needed
surfactant
as needed
purified water
as needed to make 100%
The actual doses of the timolol component and hypotensive lipid component used depends on the specific compounds, being employed on the specific condition resulting in the ocular hypertension being treated, on the severity and duration of the ocular hypertension being treated, and the like factors. In general, the selection of the appropriate doses is well within the knowledge of the skilled artisan.
The ophthalmic formulations of the present invention are conveniently packaged in forms suitable for metered application, such as in containers equipped with a dropper, to facilitate application to the eye. Containers suitable for dropwise application are usually made of suitable inert, non-toxic plastic material, and generally contain between about 0.5 and about 15 ml solution. One package may contain one or more unit doses.
Especially preservative-free solutions are often formulated in non-resealable containers containing up to about ten, preferably up to about five units doses, where a typical unit dose is in the range of one to about 8 drops, preferably one to about 3 drops. The volume of one drop usually is about 20-35 ul (microliters).
The invention is further illustrated by the following non-limiting Examples.
EXAMPLES
Intraocular pressure studies were performed in conscious cynomolgus monkeys, trained to accept pneumatonometry. The animals were restrained for pneumatonometry in custom-designed chairs and given fruit during the experiment.
A series of four (4) compositions were prepared, by blending the ingredients together. These compositions were as follows:
Compositions (A)
Ingredient
1
2
3
4
Hypotensive
0.001%
—
0.001%
—
lipid (B)
(w/v)
(w/v)
Timolol Maleate
—
0.05%
0.005%
—
w/v
(w/v)
Polysorbate 80
0.01
0.1%
0.1%
0.1%
(w/v)
(w/v)
(w/v)
(w/v)
Tris Hcl
10 mM
10 mM
10 mM
10 mM
A. Each composition had a pH of about 7.4 and was an aqueous solution including 0.9% (w/v) of sodium chloride.
B. The hypotensive lipid was: cyclopentane N-ethyl heptenamide-5-cis-2-(3α-hydroxy-5-phenyl-1-trans-pentenyl)-3, 5-dihydroxy, [1α, 2β, 3α, 5α].
The treatments, coded to the experimenter, were applied topically to the glaucomatous eye as a single 25 μl volume drop, and the normotensive fellow eye received 25 μl of normal saline. The solutions were administered at time 0. Proaracaine (0.1%) was used to provide corneal anesthesia for the intraocular pressure measurements that were performed at one hour before dosing, just before dosing, and then 1, 2, 4 and 6 hours thereafter.
The mean intraocular pressure (IOP) values for the glaucomatuous eyes at time 0 were 40.5 mm Hg for the Composition 1 group, 38.8 mm Hg for the Composition 2 group, 40.6 mm Hg for the Composition 3 group and 39.5 mm Hg for the Composition 4 group.
IOP mean differences from baseline (DFB) for treated eyes (test DFB) and fellow eyes (fellow DFB) are depicted in FIG. 1 . Test DFB values were statistically significant for the following groups (Student's t-test for paired samples):
Compositions
Range (mm Hg), p < 0.05
1
−2.0 to −10.3
2
+2.1 to −13.4
3
+2.0 to −19.0
4
+1.0 to −2.3
The effects of combination treatment with the hypotensive lipid and the timolol component (Composition 3) on IOP of glaucomatous monkeys were compared to each of the other treatments alone (Student's t-test for unpaired samples, p<0.05). The delta-delta values (test DFB—fellow DFB) for the combination treatment (Composition 3) group were significantly lower than those for the hypotensive lipid alone (composition 1) (time =1, 2, 4, 6 hr). The delta-delta values are depicted in FIG. 2 .
The combination treatment (Composition 3) using relatively low doses of hypotensive lipid and timolol maleate was surprisingly found to be more efficacious in reducing IOP than treatments with either only one of these materials (Compositions 1 and 2) or none of these materials (Composition 4).
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims. | New compositions for and methods of treating ocular hypertension provide for effective treatment of ocular hypertension often using reduced concentrations of active components. Such compositions include a timolol component and a hypotensive lipid component. The present compositions and methods are relatively straightforward, can be easily produced, for example, using conventional manufacturing techniques, and can be easily and conveniently practiced, for example, using application or administration techniques or methodologies which are substantially similar to those employed with prior compositions used to treat ocular hypertension. | 0 |
RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/857,863, filed on Nov. 10, 2006. The entire teachings of the above application are incorporated herein by reference.
BACKGROUND
Strong winds from hurricanes or tropical storms carry debris, which can cause heavy damage to windows and glass doors. Building owners typically cover windows and doors when a hurricane or tropical storm approaches with a barrier to prevent debris from hitting the glass surfaces. In the past, these barriers have either been disposable (e.g., plywood) or unsightly (e.g., a rollaway or slideaway screen permanently mounted to the door or window).
SUMMARY
Embodiments of the invention feature a portable, quick mounting, easily removable, and convenient-to-store security barrier that can protect an opening to a building, such as a window or sliding glass door, from breakage due to the hazard of flying debris caused by powerful winds generated by hurricanes and tornadoes. In conjunction with these catastrophes, an advantage of the invention is that is also offers a security benefit as a deterrent to home invasion by restricting breaking and entering through windows or sliding glass doors.
An embodiment of the invention comprises multiple panels that can be nested together when stacked for storage. The panels are easily and quickly installed and removed from a building window or other opening. In some embodiments, the panels are installed by inserting one end into slots attached to the building and installing the other end via anchoring bolts to a surface of the building. The panels may install in the slots via pins attached to the panels and the anchoring bolts may pass through the flanges on an opposite side of each panel. In some embodiments, the panels may be connected together via flanges and pins, such as clevis pins.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.
FIG. 1 illustrates an embodiment in which three panels are installed in front of a sliding door of a building;
FIG. 2A shows two panels of the embodiment of FIG. 1 in a perspective view;
FIG. 2B shows an enlarged view of a panel foot of the embodiment of FIG. 2A ;
FIGS. 3A-3B show the top portion of a panel and a side view of a pin of the embodiment of FIG. 1 ;
FIGS. 4A-4C illustrate a slotted rail according to the embodiment of FIG. 1 ;
FIG. 5 illustrates the panels of the embodiment of FIG. 1 in an uninstalled and nested configuration for storage;
FIG. 6A illustrates an optional variation of the embodiment of FIG. 1 wherein one of the panels incorporates an escape door;
FIG. 6B shows an enlarged view of a panel foot of the embodiment of FIG. 6A ;
FIG. 6C shows an enlarged side view of a triangular wedge pin of the embodiment of FIG. 6A ;
FIG. 7 illustrates a side view of the optional door shown in FIG. 6 ;
FIG. 8 illustrates a second embodiment in which three panels of equal width are installed in front of an opening of a building;
FIG. 9 illustrates the panels of the embodiment of FIG. 8 in an uninstalled and nested configuration for storage;
FIGS. 10A-10B illustrate a bracket plate of a third embodiment configured to be mounted to the side of a building; and
FIGS. 11A-11B illustrate a bracket of the embodiment of FIGS. 10A-10B that interfaces with the bracket plate.
DETAILED DESCRIPTION
FIG. 1 illustrates one embodiment of the present invention 100 in an installed configuration. In this embodiment, three panels 102 , 104 , 106 cover a sliding glass door 108 when installed. Each panel 102 , 104 , 106 includes a rectangular frame with a screen 122 covering the open area inside the frame. Each panel has a pair of pins 110 at the ends of a top side and a pair of anchoring flanges 112 at the ends of a bottom side. The pins 110 interface with a rail 118 installed in the wall 120 above the sliding door 108 and the anchoring feet interface with the ground 116 via bolts 114 . Note that the panels 102 , 104 , 106 may alternatively be installed with the pins 110 (and rail 118 ) at the bottom and the anchoring flanges 112 and bolts 114 at the top being installed in the wall 120 of the building. While the embodiment shown in FIG. 1 has three panels, other embodiments may have a fewer or greater number of panels.
Each of the panels may be constructed from a number of materials, such as high-impact plastic, aluminum, steel or stainless steel, or a combination of materials. Materials that offer high strength and relatively low weight are preferable, but not required.
FIG. 2A illustrates panels 104 , 106 in accordance with an embodiment of the present invention in perspective view. As can be seen, the pins 110 extend directly above each panel 104 , 106 on frame elements 202 and 210 . The anchoring feet 112 , enlarged in FIG. 2B , extend from each panel 104 , 106 on the opposite frame elements 206 and 214 . The anchoring feet 112 , however, extend out to the side of each panel 104 , 106 . In this embodiment, the anchoring feet 112 extend from each panel 102 , 104 , 106 . Panels 104 and 106 in this embodiment also have optionally included locking flanges 218 on frame elements 204 , 208 , and 216 . The locking flanges 218 are connected via pins, such as clevis pins, or bolts (not shown) after the panel pins 110 and anchoring flanges 112 have been installed. Two locking flanges 218 between each panel are shown in this embodiment, but more or fewer flanges may be used.
FIG. 3A illustrates pins 110 of panel 102 in accordance with an embodiment of the present invention. FIG. 3B shows that each pin 110 of the embodiment has a triangular cross-section with angled faces 302 and 304 . The angled faces 302 and 304 converge at an apex 312 .
FIGS. 4A-4C illustrate the rail 118 with slots 402 in accordance with an embodiment of the present invention. The rail 118 has slots 402 , which have angled faces 404 and 406 , which match the angled faces 304 and 306 of the pins 110 . The angled faces 302 , 304 , 404 , and 406 firmly hold the pins 110 in the slots 402 when the pins 110 are fully inserted in the slots 402 . However, the angled faces 302 , 304 , 404 , and 406 also allow the panels 102 , 104 , 106 to be pivoted about the apex 312 of each pin 110 when the pins 110 are partially inserted in the slots 402 .
FIGS. 4B and 4C illustrate a rail 118 made of solid material, wherein the slots 402 are formed by cutting out portions of the solid material. Alternatively, the rail 118 could be formed of a tubular material, such as a stainless steel or aluminum tube wherein the tube wall has a square cross-section. The slots 402 would be formed by cutting out portions of tube wall. The pins 110 , in this alternative embodiment, would be inserted through the slots 402 and be contained within the hollow space of the tubular rail 118 .
Returning to FIG. 2 , since the anchoring flanges 112 and the locking flanges 218 extend from each panel 104 and 106 , neatly stacking the panels would be difficult if the panels were all the same size because certain features that protrude from each panel 102 , 104 , 106 , such as anchoring flanges 112 , would interfere with each other, preventing the panels 102 , 104 , 106 from resting flat against each other. However, the three panels illustrated in the embodiment in FIG. 1 are each a different width. The top frame element 306 and bottom frame element 312 of the first panel 102 (as shown in FIG. 6 ) are longer than the top frame element 202 and bottom frame element 206 of the second panel 104 (as shown in FIG. 2 ), which are longer than the top frame element 210 and bottom frame element 214 of the third panel 106 (as shown in FIG. 2 ).
FIG. 5 illustrates the three panels 102 , 104 , 106 of the described embodiment stacked together in a nested configuration 500 for storage. Because panel 104 is narrower than panel 102 , the anchoring flanges 112 of panel 104 are completely within the span between the anchoring flanges 112 of panel 102 . Likewise, because panel 106 is narrower than panel 104 , the anchoring flanges 112 of panel 106 are completely within the span between the anchoring flanges 112 of panel 104 . Note that the panels' screens 122 (not shown in FIG. 5 ) must be set within each panel so that they do not interfere with the interlocking flanges 218 when the panels are nesting.
FIGS. 6A-C and 7 illustrate an escape door 602 that may be optionally installed in the above-described embodiment. The escape door 602 is best located in the largest panel 102 , but may be located on any panel 102 , 104 , 106 . The escape door 602 comprises its own frame with hinges 606 on one side and a locking latch 604 on the other side. The panel is illustrated as being located completely on the screen 122 , but may also extend to the frame elements of the panel 102 , 104 , or 106 on which it is mounted. For example, the hinges 606 can be mounted to frame element 308 of panel 102 and the latch may interface with frame element 310 .
FIG. 7 also illustrates the anchoring flanges 112 attached to the bottom frame element of panel 102 in this embodiment. Bolts 114 extend through the portion of the anchoring flanges 112 extending from the panel. Optionally, the bolts may incorporate a security interface that requires a unique tool, such as a keyed wrench or screwdriver, to remove the bolts, thereby increasing the security provided by the screen.
Typically, the anchoring flanges 112 would rest on a floor surface, such as a concrete slab, and the bolts would interface with corresponding holes in the floor surface. FIGS. 10A-B and 11 A-B illustrate an alternative embodiment in which the anchoring flanges mount to a bracket. FIGS. 10A and 10B illustrate a bracket plate 1000 that would be permanently mounted above or below a window or a door. The bracket plate 1000 is mounted to the wall with screws or bolts (not shown) through holes 1004 . The bracket plate has two flanges 1006 , 1008 . In the illustrated embodiment, flange 1008 is longer than flange 1006 . However, flanges 1006 , 1008 may be equal in size.
FIGS. 11A and 11B illustrate a bracket 1100 that interfaces with the bracket 1000 via slider plate 1102 and tabs 1104 , 1106 . Tab 1104 interfaces with flange 1006 and tab 1106 interfaces with flange 1008 . The brackets 1100 slide in bracket plate 1000 to be positioned beneath anchoring flanges 112 of a panel. The flat surface of an anchoring flange 112 is then adjacent to plate 1108 of bracket 1100 . Bolts 114 are passed through the anchoring flange 112 and into holes 1110 of bracket 1100 . Such a bracket system, or an equivalent, allows a panel to be mounted at some height above the ground.
The embodiment described above with respect to FIGS. 10 and 11 illustrates a panel system in which the pins 110 are mounted above the opening to be protected and the anchoring flanges 112 are mounted below the opening. As mentioned earlier, the panels optionally can be mounted upside-down, wherein the pins 110 are mounted beneath the opening to be protected and the anchoring flanges 112 are mounted above the opening. In such an alternative embodiment, rail 118 is mounted below the opening. Pins 110 are located at the bottom of panels 102 , 104 , 106 and are lowered into slots 402 . The panels 102 , 104 , 106 are then pivoted about the pins 110 to bring the anchoring flanges 112 into position for fastening to the building. In conjunction with the embodiment shown in FIGS. 10 and 11 , the bracket plate 1000 and brackets 1100 can be located above the building opening to be protected and anchoring flanges 112 would bolt to the brackets 1100 , which are located above. Alternatively, the anchoring flanges, in this embodiment, can be oriented such that they rest against the side of the building and bolt directly to an interface (not shown) mounted to the side of the building.
FIGS. 8 and 9 illustrate an alternative embodiment 800 of the present invention. Like the first embodiment described above, this embodiment utilizes three separate panels 802 , 804 , and 806 . However, the three panels include identical dimensions of height and width. In this embodiment, the pins 110 are positioned in the ends of top frame elements 804 and the anchoring flanges 810 , 812 , and 814 are located on the opposite bottom frame elements 816 , 818 , and 820 . However, the anchoring flanges 810 , 812 , and 814 are located at different positions on each panel 802 , 804 , and 806 . On panel 802 , the anchoring feet 810 are located at the ends of frame element 816 . On panel 804 , the anchoring feet 812 are located a distance inboard from the ends of frame element 818 . On panel 806 , the anchoring feet 814 are located a further distance inboard from the ends of frame element 820 .
FIGS. 8 and 9 also show optionally-included locking flanges 806 and 808 which differ from the first embodiment in two ways. First, the flanges sit completely outside the perimeter of each panel 802 , 804 , and 806 . Second, the locking flanges 806 and 808 vary in location between each panel. FIG. 8 shows locking flanges 806 between panels 802 and 804 and locking flanges 808 between panels 804 and 806 . There are two locking flange pairs between each pair of panels. The locking flanges 806 between panels 802 and 804 are each higher than the respective locking flanges 808 between panels 804 and 806 .
FIG. 9 shows that when panels 802 , 804 , and 806 are in a stacked configuration 900 , they nest with the anchoring flanges 812 within anchoring flanges 810 and anchoring flanges 814 within anchoring flanges 812 . The locking flanges 806 and 808 rest outside the perimeter of each panel 802 , 804 , 806 . Also, because the locking flanges 806 and 808 are located on panels 802 , 804 , 806 at different heights, they do not interfere with each other when the panels 802 , 804 , and 806 are in the nested configuration 900 .
While this invention has been particularly shown and described with references to example embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims. | An apparatus for covering an opening of a building comprising a plurality of rectangular panels. The panels are sized such that when they are stacked for storage, the panels nest together. | 4 |
FIELD OF THE INVENTION
The present invention relates to a novel catalyst for bulk polymerization and a polymerization method using the bulk polymerization catalyst.
BACKGROUND OF THE INVENTION
Polymerizable compounds having polymerizable double bonds such as acrylic acid, methacrylic acid, styrene and derivatives thereof can be polymerized, in the presence of an initiator of a radical polymerization, by the conventional emulsion polymerization process, suspension polymerization process, solution polymerization process or bulk polymerization process. The thus obtained polymers find application in various uses such as moldings, pressure sensitive adhesives, paints and fibers. Of these polymers, polymers produced by the emulsion polymerization process, suspension polymerization process and solution polymerization process have advantages in that, because the polymerization is carried out in a reaction solvent or dispersion medium, the polymerization temperature can be easily controlled, and the reaction solution has fluidity even if the rate of polymerization is high.
However, the polymers produced by the emulsion polymerization process, suspension polymerization process and solution polymerization process, according to uses, must be subjected to operations such as precipitation, filtration, washing and drying for separating the produced polymer from the reaction solvent or dispersion medium. This causes the process to be laborious and time-consuming.
By contrast, the bulk polymerization process is a process in which the polymerization is carried out in the absence of a solvent or a dispersion medium. Therefore, in the bulk polymerization process, it is not needed to add an organic solvent, a dispersant, an emulsifier and the like. The reaction system of the bulk polymerization can be simple because no impurities such as an organic solvent which participates in the polymerization are contained therein, and the obtained polymer is free from the contaminating of an emulsifier, a dispersant and other impurities therein. Furthermore, it is not needed to remove a solvent or dispersion medium for the purpose of obtaining the desired polymer. From these viewpoints, the bulk polymerization process is an industrially advantageous process.
However, the velocity of polymerization reaction is generally extremely high in the bulk polymerization process, and practically it is extremely difficult to control the bulk polymerization process. In polymers formed at high temperatures with the failure to control the polymerization velocity, it is likely that molecular terminals become unstable due to disproportionation termination, that the molecular weight is lowered, and that branching or gelation of the polymer occurs by, for example, hydrogen abstraction from the previously formed polymer. Therefore, it becomes difficult to implement not only a molecular design regarding the molecular weight, molecular weight distribution, etc. of polymer but also a definite design of molecular structure because of the polymer branching and formation of disproportionation termination terminals. Furthermore, in polymers formed at high temperatures with the failure to control the polymerization velocity, gels may be formed rapidly in a large amount, so that, in the worst case, there is even the danger of explosion attributed to runaway reaction.
Nevertheless, the velocity of polymerization of, for example, styrene and methyl methacrylate is relatively low, so that, even in the bulk polymerization, the reaction control thereof can be managed. Thus, the controlling method has been investigated for long. In the bulk polymerization of styrene, methyl methacrylate or the like, mercaptans may be used for controlling the molecular weight and molecular weight distribution thereof.
However, in the bulk polymerization reaction using mercaptans, it is often difficult to effect a homogeneous reaction control and the types of monomers subjected to the bulk polymerization are limited.
Apart from the above, in the polymerization reaction, the catalyst is varied depending on the type of employed monomer. For example, metallocene compounds such as titanocene are used as the catalyst for polymerization of ethylene or the like. However, the use of metallocene compounds as the catalyst for polymerization of monomers other than α-olefins is little known except for the use thereof together with a sensitizer in photopolymerization. Japanese Patent Laid-open Publication No. 9(1997)-5996 discloses an invention of photopolymerizable composition containing a compound having at least one ethylenically unsaturated double bond capable of addition polymerization, a titanocene compound as a photopolymerization initiator, a sensitizer capable of sensitizing the titanocene compound, the photopolymerization composition further containing a heterocyclic thiol compound. In the invention disclosed in the publication, the titanocene compound is used as a photopolymerization catalyst, and, in the publication, there is no description regarding the use of titanocene compounds as a catalyst for bulk polymerization. Further, the heterocyclic thiol compound described in the publication is a visible radiation sensitizer.
Generally, in the reaction used in metallocene compounds such as titanocene compounds as a catalyst, a sulfurous or sulfuric compound is a compound which lowers the catalytic activity of metallocene compounds. The above-mentioned use of a sulfurous or sulfuric compound as a compound capable of exerting specified function and effect like the above visible radiation sensitizer signifies a highly exceptional usage in metallocene compounds employed as a catalyst. That is, generally, a sulfurous or sulfuric compound is a catalyst poison to metallocene compounds used as a catalyst. Therefore, the addition of a sulfurous or sulfuric compound to a reaction system containing a metallocene compound as a catalyst constitutes a regularly inconceivable combination.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a novel catalyst for use in bulk polymerization. It is a particular object of the present invention to provide a novel catalyst capable of performing a bulk polymerization of a monomer having a polymerizable unsaturated bond, such as an acrylic monomer, without runaway of reaction.
It is another object of the present invention to provide a novel method of bulk polymerization in which use is made of the above novel catalyst.
SUMMARY OF THE INVENTION
The catalyst for bulk polymerization according to the present invention comprises an organometallic compound, which is represented by the formula (I), and a thiol:
wherein
M represents a metal selected from the group consisting of metals of Groups 4A, 4B, 5A and 5B of the periodic table, chromium, ruthenium and palladium; each of R 1 and R 2 independently represents at least one group selected from the group consisting of an unsubstituted or substituted aliphatic hydrocarbon group, an unsubstituted or substituted alicyclic hydrocarbon group, an unsubstituted or substituted aromatic hydrocarbon group and an unsubstituted or substituted silicon containing group, a hydrogen atom or a single bond, provided that R 1 and R 2 may cooperate with each other to bond the two 5-membered rings shown in the formula and provided that neighboring groups of R 1 or R 2 may cooperate with each other to form a cyclic structure;
each of a and b independently is an integer of 1 to 4; X represents a halogen atom or a hydrocarbon group optionally having at least one hydrogen atom thereof substituted with a halogen atom; and n is 0 or an integer substracting 2 from valence of metal M.
The polymerization method of the present invention comprises conducting a bulk polymerization of a monomer having a polymerizable unsaturated bond in the presence of the above catalyst for bulk polymerization comprising an organometallic compound represented by the above formula (I) and a thiol.
The inventors have conducted investigations into the bulk polymerization of acrylic monomers. As a result, it has been found that a catalyst comprising a combination of a metallocene compound and a thiol exerts a surprisingly high catalytic activity in the bulk polymerization of acrylic monomers, which has been difficult in the prior art. The present invention has been completed on the basis of this finding.
The use of the bulk polymerization catalyst comprising an organometallic compound represented by the above formula (I) and a thiol according to the present invention enables conducting a stable bulk polymerization of a monomer having a polymerizable unsaturated bond, such as an acrylic monomer.
DETAILED DESCRIPTION OF THE INVENTION
The bulk polymerization catalyst of the present invention and polymerization method in which use is made of this bulk polymerization catalyst will be described in detail below.
The catalyst of the present invention can subject a compound having a polymerizable unsaturated bond to conduct a stable bulk polymerization.
The organometallic compound for use in the bulk polymerization catalyst of the present invention is represented by the formula (I):
In the formula (I), M represents a metal selected from the group consisting of metals of Groups 4A, 4B, 5A and 5B of the periodic table, chromium, ruthenium and palladium. The metal M is, for example, titanium, zirconium, chromium, ruthenium, vanadium, palladium or tin.
In the formula (I), each of R 1 and R 2 independently represents at least one group selected from the group consisting of:
an unsubstituted or substituted aliphatic hydrocarbon group,
an unsubstituted or substituted alicyclic hydrocarbon group,
an unsubstituted or substituted aromatic hydrocarbon group, and
an unsubstituted or substituted silicon containing group, or
a hydrogen atom or a single bond.
Provided, however, that R 1 and R 2 may cooperate with each other to bond the two 5-membered rings shown in the formula and that neighboring groups of R 1 or R 2 may cooperate with each other to form a cyclic structure.
Further, in the formula (I), each of a and b independently is an integer of 1 to 4.
X represents a halogen atom such as chlorine, bromine or iodine, or a hydrocarbon group optionally having at least one hydrogen atom thereof substituted with a halogen atom.
n is 0 or an integer subtracting 2 from valence of metal M.
Examples of the above organometallic compounds include:
titanocene compounds such as dichloro(dicyclopentadienyl)titanium, bisphenyl(dicyclopentadienyl)titanium, bis-2,3,4,5,6-pentafluorophen-1-yl(dicyclopentadienyl)titanium, bis-2,3,5,6-tetrafluorophen-1-yl(dicyclopentadienyl)titanium, bis-2,5,6-trifluorophen-1-yl(dicyclopentadienyl)titanium, bis-2,6-difluorophen-1-yl(dicyclopentadienyl)titanium, bis-2,4-difluorophen-1-yl(dicyclopentadienyl)titanium, bis-2,3,4,5,6-pentafluorophen-1-yl(dimethylcyclopentadienyl)titanium, bis-2,3,5,6-tetrafluorophen-1-yl(dimethylcyclopentadienyl)titanium, bis-2,6-difluorophen-1-yl(dimethylcyclopentadienyl)titanium and bis-2,6-difluoro-3-(pyr-1-yl)phen-1-yl(dimethylcyclopentadienyl)titanium;
zirconocene compounds such as dichloro(dicyclopentadienyl)zirconium, bisphenyl(dicyclopentadienyl)zirconium, bis-2,3,4,5,6-pentafluorophen-1-yl(dicyclopentadienyl)zirconium, bis-2,3,5,6-tetrafluorophen-1-yl(dicyclopentadienyl)zirconium, bis-2,5,6-trifluorophen-1-yl(dicyclopentadienyl)zirconium, bis-2,6-difluorophen-1-yl(dicyclopentadienyl)zirconium, bis-2,4-difluorophen-1-yl(dicyclopentadienyl)zirconium, bis-2,3,4,5,6-pentafluorophen-1-yl(dimethylcyclopentadienyl)zirconium, bis-2,3,5,6-tetrafluorophen-1-yl(dimethylcyclopentadienyl)zirconium, bis-2,6-difluorophen-1-yl(dimethylcyclopentadienyl)zirconium and bis-2,6-difluoro-3-(pyr-1-yl)phen-1-yl(dimethylcyclopentadienyl)zirconium;
choro(dicyclopentadienyl)vanadium, chloro(bismethylcyclopentadienyl)vanadium, chloro(bispentamethylcyclopentadienyl)vanadium, chloro(dicyclopentadienyl)ruthenium and chloro (dicyclopentadienyl) chromium. These organometallic compounds can be used either individually or in combination.
These organometallic compounds can be used in a regularly employed catalyst amount. These organometallic compounds are generally used in an amount of, for example, 1 to 0.001 part by weight, preferably 0.01 to 0.005 part by weight, per 100 parts by weight of polymerizable unsaturated compound to be polymerized.
Examples of the thiols for use in the present invention include:
alkylthiols having no functional group other than a thiol group, such as ethylmercaptan, butylmercaptan, hexylmercaptan, tert-dodecylmercaptan, n-dodecylmercaptan and octylmercaptan,
aromatic thiols having no functional group other than a thiol group, such as phenylmercaptan and benzylmercaptan,
thiols having a functional group other than a thiol group, such as β-mercaptopropionic acid, mercaptoethanol, 3-mercaptopropyl(trimethoxy)silane and thiophenol,
polyfunctional thiol compounds obtained by esterifying trithioglycerol or pentaerythritol with β-mercaptopropionic acid, and
polymeric thiols having an active thiol group, such as polysulfide polymers.
The addition amount (use amount) of the above thiols can appropriately be determined. taking the properties of polymer intended to obtain into account. That is, when the thiol concentration in a reaction system is increased, not only the conversion of monomers per time but also the final (reached) conversion (ratio of polymer converted from monomer to monomer) becomes high. On the other hand, the increase of the organometallic compound leads to an increase of the conversion per time but does not exert any marked influence on the final conversion. Although the addition amount of organometallic compound does not exert any significant influence on the molecular weight of obtained polymer, the reaction does not advance when the organometallic compound is not used. Further, when the addition amount of the thiol is increased, the polymerization velocity becomes higher. From these trends, it is assumed that, in the catalyst of the present invention, the organometallic compound exerts an activating catalytic function while the thiol exerts a polymerization initiating function (namely, functions as a polymerization initiating species) throughout the reaction. Thus, in the catalyst of the present invention, the addition amount of thiol is considered to exert a large influence on the molecular weight and the conversion.
Therefore, although the addition amount of thiols can appropriately be determined taking into account the molecular weight of polymer intended to obtain, the polymerization velocity, etc., the organometallic compound and the thiol are generally used in a molar ratio of 100:1 to 1:50,000, preferably 10:1 to 1:10,000, for realizing a smooth reaction advance without runaway of reaction.
The whole amount of thiol can be added to the reaction system at the initiation of the reaction. Also, the thiol can be added in such a manner that part of the thiol is added at the initiation of the reaction, the reaction is conducted for a desirable period of time and thereafter the rest of thiol is further added optionally together with a polymerizable unsaturated compound. The conversion is increased by the above further addition of thiol, or thiol together with a polymerizable unsaturated compound.
In the bulk polymerization catalyst of the present invention, disulfide, trisulfide and tetrasulfide compounds can be used in addition to the above organometallic compound and thiol as a polymerization initiating catalyst for the purpose of regulating the polymerization velocity and polymerization degree.
Examples of the disulfide, trisulfide and tetrasulfide compounds as a polymerization regulator usable in the present invention include diethyl trisulfide, dibutyl tetrasulfide, diphenyl disulfide, bis(2-hydroxyethyl) disulfide, bis(4-hydroxybutyl) tetrasulfide, bis(3-hydroxypropyl) trisulfide, bis(3-carboxypropyl) trisulfide, bis(3-carboxypropyl) tetrasulfide, bis(3-propyltrimethoxysilane) disulfide and bis(3-propyltriethoxysilane) trisulfide. These sulfide compounds can be used either individually or in combination. These sulfide compounds can be used in such an amount that the polymerization catalyst is not deactivated in the bulk polymerization of the present invention. For example, the sulfide compounds are generally used in an amount of 50 to 0 part by weight, preferably 20 to 0.005 part by weight, per 100 parts by weight of polymerizable unsaturated compound to be polymerized.
The bulk polymerization of a polymerizable unsaturated compound can be carried out with the use of the bulk polymerization catalyst comprising the organometal and the thiol according to the present invention.
For example, polymerizable unsaturated compounds represented by the following formulae (B), (B-1) and (B-2) are preferably used as the polymerizable unsaturated compound subjected to the bulk polymerization using the catalyst of the present invention.
In the formula (B), each of R 7 to R 9 independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. R 10 represents a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 22 carbon atoms (the hydrocarbon group may be linear or may have side chains; the hydrogen atoms of the hydrocarbon group or group constituting the side chains may partially be substituted with at least one polar group, halogen atom or reactive functional group selected from the group consisting of —OH, —S, —COOH, —Cl, —NH 2 , —Si(OH 3 ) 3 , —Si(OCH 3 ) 2 (CH 3 ) and —Si(CH 3 ) 2 (OCH 3 ); and the hydrocarbon group may have a double bond or may have a cyclic structure). Specifically, R 10 can be, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, an alkoxy group or an alkyl ether group. The hydrogen atoms of the group R 10 may partially be substituted with a halogen atom, a sulfonic acid residue, a glycidyl group or the like.
In the formula (B-1), R 11 to R 13 have the same meaning as the above R 7 to R 9 . R 14 represents any of hydroxyl, —CO—NH 2 , —CN, glycidyl, alkyl, alkoxy, alkenyl, cycloalkenyl, aryl, allyl ether, alkyl ether, alkoxysilyl, silanol and halogenated silyl groups. The hydrogen atoms of the group R 14 may at least partially be substituted with a halogen atom, etc. Moreover, the group R 14 may be a group which contains a structural unit derived from an alkylene glycol, an alkoxysilyl group, an alkylalkoxysilyl group, a methylol group or an alkoxyamido group.
In the formula (B-2), R 15 and R 17 have the same meaning as the above R 7 to R 9 . Each of R 16 and R 18 independently represents any of carboxyl, hydroxyl, —CO—NH 2 , —CN, glycidyl, alkyl, alkoxy, alkenyl, cycloalkenyl and aryl groups. The hydrogen atoms of the groups R 16 and R 18 may at least partially be substituted with a halogen atom, etc. Moreover, these groups R 16 and R 18 may cooperate with two carbon atoms bonded with groups R 15 and R 17 to form a cyclic structure. The cyclic structure may have a double bond.
Furthermore, particular examples of these polymerizable unsaturated compounds include:
acrylic acid and salts thereof such as alkali metal acrylates;
methacrylic acid and salts thereof such as alkali metal methacrylates;
alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate and dodecyl acrylate;
aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
alkoxyalkyl acrylates such as methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate and ethoxypropyl acrylate;
alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate and dodecyl methacrylate;
aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
alkoxyalkyl methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate and ethoxypropyl methacrylate;
(poly)alkylene glycol diacrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate and tripropylene glycol diacrylate;
(poly)alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate and tripropylene glycol dimethacrylate;
polyacrylates such as trimethylolpropane triacrylate;
polymethacrylates such as trimethylolpropane trimethacrylate;
acrylonitrile, methacrylonitrile and vinyl acetate;
vinyl halide compounds such as vinylidene chloride, 2-chloroethyl acrylate and 2-chloroethyl methacrylate;
acrylic acid esters of alicyclic alcohol such as cyclohexyl acrylate;
methacrylic acid esters of alicyclic alcohol such as cyclohexyl methacrylate;
polymerizable compounds containing an oxazoline group such as 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline and 2-isopropenyl-2-oxazoline;
polymerizable compounds containing an aziridine group such as acryloylaziridine, methacryloylaziridine, 2-aziridinylethyl acrylate and 2-aziridinylethyl methacrylate;
vinyl monomers containing an epoxy group such as allyl glycidyl ether, glycidyl ether acrylate, glycidyl ether methacrylate, 2-ethylglycidyl ether acrylate and 2-ethylglycidyl ether methacrylate;
vinyl compounds containing a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, monoesters of acrylic acid or methacrylic acid and polypropylene glycol or polyethylene glycol and adducts of lactons and 2-hydroxyethyl (meth)acrylate;
fluorinated vinyl monomers such as fluorinated alkyl methacrylates and fluorinated alkyl acrylates;
unsaturated carboxylic acids other than (meth)acrylic acid such as itaconic acid, crotonic acid, maleic acid and fumaric acid, and salts, (partial) ester compounds and anhydrides of such unsaturated carboxylic acids;
vinyl monomers containing a reactive halogen such as 2-chloroethyl vinyl ether and vinyl monochloroacetate;
vinyl monomers containing an amido group such as methacrylamide, N-methylolmethacrylamide, N-methoxyethylmethacrylamide and N-butoxymethacrylamide;
vinyl compound monomers containing an organosilicon group such as vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine and 2-methoxyethoxytrimethoxysilane; and
diene compounds such as ethylidenenorbornene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclobutadiene and methylbutadiene.
Moreover, macromonomers (e.g., fluoromonomers, silicon containing monomers, macromonomers, styrene, silicone, etc.) having a radical polymerizable vinyl group at an end of vinyl-polymerized monomer can be mentioned as further examples of the polymerizable unsaturated compounds.
These polymerizable unsaturated compounds can be used either individually or in combination. Although these polymerizable unsaturated compounds may be liquid, or solid, or gaseous, it is preferred from the easiness of operation that a liquid monomer be used at the reaction depending on reaction conditions.
Stable bulk polymerization of these polymerizable unsaturated compounds can be accomplished by the use of the catalyst for bulk polymerization according to the present invention comprising the organometallic compound of the formula [I] and the thiol.
The term of “bulk polymerization” used herein means a reaction in which a polymerizable unsaturated compound is polymerized substantially in the absence of any solvent. Thus, generally, the reaction system of bulk polymerization does not contain any reaction solvent. The expression “substantially in the absence of any solvent” means that any reaction solvent is not used and should hot be construed as excluding an extremely small amount of solvent for dissolution or for dispersion employed to homogeneously disperse the catalyst for the bulk polymerization according to the present invention comprising the organometallic compound of the formula (I) and the thiol in the entirety of monomer, solvents remaining in raw materials, etc.
This bulk polymerization reaction is generally carried out in an atmosphere of inert gas. Thus, active gases such as oxygen are not present in the reaction system of bulk polymerization. Nitrogen, argon, helium and carbon dioxide gases can be mentioned as the inert gas for use in bulk polymerization.
Although the bulk polymerization catalyst of the present invention comprising the organometallic compound of the formula (I) and the thiol can be used in a regularly employed catalyst amount in this bulk polymerization, the organometallic compound of the formula (I) is generally added in an amount of 0.0000001 to 0.0001 mol per mol of unsaturated group of the polymerizable unsaturated compound, and preferably in such an amount that the molar ratio of organometallic compound to thiol is in the range of 10:1 to 1:10,000 in accordance with the molar amount of added thiol. The thiol is generally used in an amount of 0.00001 to 0.7 mol, preferably 0.0001 to 0.5 mol.
Although the bulk polymerization reaction using the catalyst of the present invention can be performed in heated or warm atmosphere or while cooling the reaction system, depending on the type of polymerizable unsaturated compound, it is preferred that the reaction temperature for bulk polymerization be set at 0 to 150° C., especially 25 to 120° C. The bulk polymerization reaction can be stably advanced without runaway by setting the reaction temperature for bulk polymerization so as to fall within the above range. Even if an acrylic-ester-type polymerizable unsaturated compound of relatively high polymerizability is employed, although depending on the activity of the unsaturated group of the employed polymerizable unsaturated compound, setting the reaction temperature at 0° C. or below causes lowering of the catalytic activities of the organometallic compound of the formula (I) and thiol and therefore the time required for attaining a satisfactory conversion is prolonged and not efficient. Further, even if a compound of low polymerization activity such as a styrene-type unsaturated compound is employed, a satisfactory polymerization rate can be attained by setting the reaction temperature at 25° C. or higher.
Setting the reaction temperature at 150° C. or higher may invite the danger of runaway of reaction attributed to extreme heat generation during the polymerization reaction. The smooth advance of reaction can be maintained without runaway of reaction by setting the polymerization temperature at 120° C. or below.
Although the reaction time can be appropriately set taking into account the conversion, molecular weight, etc. in the bulk polymerization of the present invention, it is generally preferred, for example, under the above conditions, that the reaction time be set at 2 to 12 hr, especially 2 to 8 hr.
This bulk polymerization reaction can be terminated by lowering the temperature of the reaction mixture or preferably by adding a polymerization inhibitor such as benzoquinone.
Polymers of a polymerization rate of generally at least 40%, preferably at least 60%, can be obtained by performing the bulk polymerization in the above described manner. Unreacted monomers, residual thiol and other low-boiling-point compounds remaining in the reaction system can be removed with the use of, for example, an evaporator in vacuum. The heating residue at 150° C. of the thus obtained polymer is generally at least 90%, preferably at least 95%.
With respect to the thus obtained polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is generally in the range of 500 to 1,000,000, preferably 1000 to 300,000, while the number average molecular weight (Mn) is generally in the range of 500 to 1,000,000, preferably 1000 to 100,000. The dispersion index thereof (Mw/Mn) is generally in the range of 1.02 to 9.0, preferably 1.2 to 3.0.
The thus obtained polymer is mostly a generally viscous liquid. The viscosity measured at 23° C. is generally in the range of 100 to 1,000,000 centipoises (cps), preferably 1000 to 100,000 centipoises (cps).
Unless a deliming treatment which removes the deactivated catalyst from the obtained polymer is conducted, the organometallic compound is mixed in the polymer obtained by polymerization with the use of the catalyst for bulk polymerization according to the present invention. Further, sulfurous or sulfuric groups derived from the added thiol are bonded to at least a part of molecular terminals of the obtained polymer. In this connection, although the compound having a thiol group is used as a polymerization initiating species in the bulk polymerization with the catalyst according to the present invention, commonly such a thiol compound alone exhibits no activity as polymerization initiating species. When an organometallic compound is used in accordance with the present invention, however, a thiol group derivable from the thiol compound is converted to an active species capable of initiating polymerization by the organometallic catalyst to thereby become an initiating species for the monomer. Therefore, in this reaction, the conversion per time is enhanced by an increase of the amount of thiol relative to the amount of monomer. Accordingly, sulfurous or sulfuric groups derived from the added thiol are bonded to polymerization initiation terminals of the obtained polymer. However, the added thiol functions not only as a polymerization initiating species but also as a chain transfer agent, so that the molecular weight (degree of polymerization) and conversion of monomer are greatly influenced by the amount of thiol. It can be presumed from these phenomena that the advance and termination of polymerization in this reaction are those of radical polymerization. The thio-radical (.S) of the thiol having undergone a hydrogen abstraction by the chain transfer once more attacks the monomer as a polymerization initiating species. Therefore, sulfurous or sulfuric groups derived from the added thiol are bonded to terminals of the polymer produced by this polymerization method, irrespective of the addition amount of thiol.
With respect to the reaction system of the present invention, the same reaction as in the above bulk polymerization can be effected in a polar organic solvent such as an alcohol or a dispersion medium such as water. Therefore, it is conceivable that a radical reaction is predominant in the polymerization of the present invention. Accordingly, it can be presumed that the reaction termination ends of obtained polymer consist of hydrogen attributed to the chain transfer from the thiol, or the thiol having thio-radicals due to the conversion to radical, and sulfurous or sulfuric groups derived from the thiol by radical coupling with growing polymer radicals.
In the obtained polymer, the organometallic compound remains in its original form (that is, the organometallic compound), or in the form of being bonded with another organic group, or in the form of a metal. The thiol directly contributes to the polymer forming reaction and the reaction is advanced while the thiol itself is being decomposed, so that terminal groups derived from the thiol are introduced in the polymer ends.
The above presumption and advance of reaction are believed to be the most rational by the inventor on the basis of various phenomena experienced in the reaction of the present invention, which naturally in no way limit the scope of the present invention.
The polymer obtained by the method of the present invention is generally a viscous liquid, which is however cured by reaction in the presence of compounded curing agent or the like. The resultant curing product has elasticity.
The polymer obtained by the method of the present invention can be applied to uses in which the curability thereof is utilized, uses in which the elasticity of the cured product is utilized, uses in which the polymer being a viscous liquid is utilized and other uses. For example, the polymer obtained by the method of the present invention can be used in coating materials (paint), sealing materials, coating film waterproofers, pressure sensitive adhesives, adhesives, sheeted items (gas permeable sheets, protective sheets, water barrier sheets, damping sheets, transfer sheets, light controlling sheets, antistatic sheets, conductive sheets, curing sheets, noise insulating sheets, shade sheets, decorative sheets, marking sheets and flame retardant sheets) and raw materials thereof, film moldings (marking films, protective films, ink fixing films and laminate films) and raw materials thereof, foams (hard, soft, semirigid and flame retardant) and raw materials thereof, ink vehicles, reactive plasticizers, plasticizers, diluents, compatibilizers, intermediate materials for resins such as polyester resins, polyurethane resins, polycarbonate resins and various block polymers, reforming materials, additives, fiber modifiers, fiber surface treatments, paper processing agents, paper modifiers, surfactants, dispersion stabilizers, dispersion mediums, solvents, viscosity regulators, adsorbents, hair treatments, toner additives, electrification controlling agents, antistatic agents, low-shrinkage agents, antifogging agents, stainproofing agents, hydrophilicity imparting agents, lipophilicity imparting agents, medicine carriers, carriers for agricultural chemicals, cosmetic compounding agents, lubricants, polymer alloy additives, gel coating agents, FRP resins, FRP resin additives, resins for artificial marble, resin additives for artificial marble, casting resins, raw materials for UV/EV cured resins, tackifiers, various binders (magnetic recording medium, for molding, for burned products and glass fiber sizing material), RIM urethane modifiers, resins for glass laminate, damping materials, noise insulating materials, resins for separating membranes, soundproofing materials, sound absorbing materials, artificial leathers, artificial skins, synthetic leathers, various industrial parts, daily needs, molded items for toiletry, acrylic urethane rubbers, acrylic urethane rubber modifiers, acrylic urethane foam modifiers, urethane rubber modifiers, urethane foam plasticizers, urethane foam modifiers and acrylic rubber modifiers.
EFFECT OF THE INVENTION
The use of the catalyst of the present invention enables performing a stable bulk polymerization, without runaway of reaction, even if polymerizable unsaturated compounds such as acrylic monomers have experienced relative difficulty in controlling the polymerization reaction.
Further, the properties of obtained polymer and polymerization condition therefor, such as polymerization rate, molecular weight and polymerization velocity, can be controlled mainly by regulating the addition amount of thiol with the use of the catalyst of the present invention.
Moreover, groups derived from the thiol are introduced in molecular terminals of the polymer produced with the use of the catalyst of the present invention, so that the employed thiol compound can securely be introduced in at least one end of each polymer molecule. When the employed thiol has a functional group other than the thiol group, the functional group can be introduced in at least one end of each obtained polymer molecule. A curing reaction and various other reactions can be performed by utilizing the introduced functional group.
EXAMPLES
The present invention will further be illustrated below with reference to the following Examples which in no way limit the scope of the invention.
Example 1
100 parts by weight of ethyl acrylate and 0.05 part by weight of ruthenocene as a metal catalyst were charged into a flask equipped with an agitator, a nitrogen gas introduction tube, a thermometer and a reflux cooling tube. The flask contents were heated to 70° C. while introducing nitrogen gas into the flask.
Subsequently, 6 parts by weight of β-mercaptopropionic acid satisfactorily purged with nitrogen gas was added to the flask contents under agitation. Cooling and heating were performed for two hours after the addition of the β-mercaptopropionic acid so that the temperature of the flask contents under agitation was maintained at 70° C. Further, another 6 parts by weight of β-mercaptopropionic acid satisfactorily purged with nitrogen gas was added to the flask contents under agitation. Reaction was carried out for four hours after the further addition of the β-mercaptopropionic acid with further cooling and heating so that the temperature of the flask contents under agitation was maintained at 70 ° C.
After the above reaction performed for 6 hr in total, the reaction product was cooled to room temperature. Then, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to the reaction product to thereby terminate polymerization.
With respect to the thus obtained THE solution of reaction product, the ratio of monomer residue was measured by gas chromatography, thereby determining the polymerization rate thereof.
As a result, it was found that a reaction product whose conversion was 78% was obtained. No runaway of polymerization reaction was observed at all during the polymerization.
Thereafter, the obtained reaction product was transferred into an evaporator and slowly heated up to 80° C. in vacuum to thereby remove THF, monomer residue and thiol compound residue.
The 150° C. heating residue of the thus obtained polymer was 99.2%.
With respect to the obtained polymer, the molecular weight measured by gel permeation chromatography (GPC) was 4400 in terms of Mw and 2800 in terms of Mn. The dispersion index was 1.6, and the viscosity at 23° C. was 48,500 centipoises (cps).
Example 2
100 parts by weight of methyl acrylate, 10 parts by weight of trimethylolpropane triacrylate and 0.02 part by weight of zirconocene dichloride as a metal catalyst were charged into a flask equipped with an agitator, a nitrogen gas introduction tube, a thermometer and a reflux cooling tube. The flask contents were gently heated to 80° C. while introducing nitrogen gas into the flask.
Subsequently, 50 parts by weight of 3-mercaptopropyl(trimethoxy)silane satisfactorily purged with nitrogen gas was added to the flask contents under agitation. Reaction was carried out for eight hours after the addition of the 3-mercaptopropyl(trimethoxy)silane while cooling and heating so that the temperature of the flask contents under agitation was maintained at 80° C.
After the above reaction, the reaction product was cooled to room temperature. Then, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to the reaction product to thereby terminate polymerization.
With respect to the thus obtained THF solution of reaction product, the ratio of monomer residue was measured by gas chromatography, thereby determining the polymerization rate thereof.
As a result, it was found that the conversion was 82%. No runaway of polymerization reaction was observed at all during the above polymerization.
Thereafter, the obtained reaction product was transferred into an evaporator and slowly heated up to 80° C. in vacuum to thereby remove THF, monomer residue and thiol compound residue.
The 150° C. heating residue of the thus obtained polymer was 98.7%.
With respect to the obtained polymer, the molecular weight measured by gel permeation chromatography (GPC) was 1400 in terms of Mw and 800 in terms of Mn. The dispersion index was 1.8, and the viscosity at 23° C. was 1300 centipoises (cps).
Example 3
80 parts by weight of styrene, 20 parts by weight of perfluorooctylethylene and 0.1 part by weight of titanocene dichloride as a metal catalyst were charged into a flask equipped with an agitator, a nitrogen gas introduction tube, a thermometer and a reflux cooling tube. The flask contents were heated to 80° C. while introducing nitrogen gas into the flask.
Subsequently, 10 parts by weight of 2-mercaptoethanol satisfactorily purged with nitrogen gas was added to the flask contents under agitation. Reaction was carried out for two hours after the addition of the 2-mercaptoethanol while cooling and heating so that the temperature of the flask contents under agitation was maintained at 80° C.
Thereafter, 10 parts by weight of 2-mercaptoethanol was added to the flask contents under agitation, and further reaction was performed for two hours. Moreover, 20 parts by weight of 2-mercaptoethanol was added to the flask contents under agitation, and still further reaction was performed for four hours.
Upon the passage of 8 hr in total, the reaction product was cooled to room temperature. Then, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to the reaction product to thereby terminate polymerization.
With respect to the thus obtained THF solution of reaction product, the ratio of monomer residue was measured by gas chromatography, thereby determining the polymerization rate thereof.
As a result, it was found that the conversion was 68%. No runaway of polymerization reaction was observed at all during the above polymerization.
Comparative Example 1
Reaction was performed in the same manner as in Example 1, except that the metal catalyst ruthenocene was not added. With respect to the thus obtained polymer, the conversion was 9%.
Comparative Example 2
Reaction was performed in the same manner as in Example 1, except that the thiol compound β-mercaptopropionic acid was not added. With respect to the thus obtained polymer, the conversion was 1%. | A catalyst for bulk polymerization comprising an organometallic compound represented by specified formula and a thiol is provided. The specified organometallic compound is a metallocene compound such as titanocene or zirconocene. The use of this bulk polymerization catalyst comprising a metallocene compound and a thiol enables stable bulk polymerization of a polymerizable unsaturated compound such as an acrylic monomer, the reaction control of which has been difficult in the bulk polymerization of the prior art. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to the following co-pending and commonly assigned patent application(s), all of which applications are incorporated by reference herein:
application Ser. No. 09/212,454, entitled “AUTONOMOUS GYRO SCALE FACTOR AND MISALIGNMENT CALIBRATION,” filed on Dec. 16, 1998, by Rongsheng Li, Yeong-Wei Wu and Garry Didinsky, now U.S. Pat. No. 6,298,288.
STATEMENT OF RIGHTS OWNED
This invention was made with Government support. The Government has certain rights in this invention.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to systems and methods for spacecraft navigation, and in particular to a spacecraft attitude determination system for correcting gyro scale factor non-linearity.
2. Description of the Related Art
Satellite navigation systems typically include an attitude determination system. Attitude determination systems typically comprises one or more rate sensors (which provide measurements of the rotation rate of the spacecraft) and one or more attitude sensors (which measure the attitude of the spacecraft). Rate sensors may include mechanical gyros, ring laser gyros (RLGs), or similar devices. Attitude sensors include, for example, sun sensors, earth sensors, and/or star trackers. Typically, sun and earth sensors are used to provide a rough spacecraft attitude estimate (useful, for example in recovering from large spacecraft motions), while the star trackers provide a more accurate attitude estimates.
For agile spacecraft, gyro scale factor and misalignment errors contribute significantly to spacecraft attitude determination errors. To ameliorate this problem, a Kalman filter can be used to generate estimates of the spacecraft attitude, gyro scale factors and gyro misalignments. Using such estimates, substantial performance improvements can be obtained. However, the Kalman filters used in such designs typically assume that the gyro scale factors are constant across different measured angular rates. What is needed is an attitude control system that compensates for rate sensor scale factor errors, without rendering the Kalman filter algorithms unnecessarily complex. The present invention satisfies that need.
SUMMARY OF THE INVENTION
To address the requirements described above, the present invention discloses a method and apparatus for calibrating rate sensor measurements to compensate for rate sensor scale factor non-linearities. The method comprises the steps of generating a current rate sensor scale factor estimate; generating a deviation of the scale factor estimate from a current scale factor non-linearity correction mapping; generating an updated scale factor non-linearity correction mapping from the deviation of the scale factor estimate from the current scale factor non-linearity correction mapping; and mapping the rate sensor measurement according to the current scale factor non-linearity correction mapping. The apparatus comprises a plurality of modules that can be implemented in hardware or in software by one or more processors. The modules include a first module for estimating a gyro scale factor; a second module, communicatively coupled to the first module, for generating a deviation of the scale factor estimate from a current scale factor non-linearity correction mapping; a third module, communicatively coupled to the second module for generating an updated scale factor non-linearity correction mapping from the deviation of the scale factor estimate from the current scale factor non-linearity correction mapping; and a fourth module, communicatively coupled to the third module, for mapping the rate sensor measurement according to the current scale factor non-linearity correction mapping.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring now to the drawings in which like reference numbers represent corresponding parts throughout:
FIG. 1 illustrates a three-axis stabilized satellite or spacecraft;
FIG. 2 is a diagram depicting the functional architecture of a representative attitude control system;
FIG. 3 is a block diagram of an attitude determination system;
FIG. 4 is a graph illustrating typical gyro scale factor non-linearity errors;
FIG. 5 is a diagram illustrating an attitude determination system having an outer loop compensator for gyro scale factor non-linearity errors;
FIG. 6 is a diagram presenting a further illustration of how the gyro scale factor non-linearity correction can be generated; and
FIG. 7 is a flow chart presenting illustrative process steps that could be used to practice one embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In the following description, reference is made to the accompanying drawings which form a part hereof, and which is shown, by way of illustration, several embodiments of the present invention. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present invention.
Attitude Control Systems
FIG. 1 illustrates a three-axis stabilized satellite or spacecraft 100 . The spacecraft 100 is preferably situated in a stationary orbit about the Earth. The satellite 100 has a main body 102 , a pair of solar panels 104 , a pair of high gain narrow beam antennas 106 , and a telemetry and command omni-directional antenna 108 which is aimed at a control ground station. The satellite 100 may also include one or more sensors 110 to measure the attitude of the satellite 100 . These sensors may include sun sensors, earth sensors, and star sensors. Since the solar panels are often referred to by the designations “North” and “South”, the solar panels in FIG. 1 are referred to by the numerals 104 N and 104 S for the “North” and “South” solar panels, respectively.
The three axes of the spacecraft 10 are shown in FIG. 1 . The pitch axis P lies along the plane of the solar panels 140 N and 140 S. The roll axis R and yaw axis Y are perpendicular to the pitch axis P and lie in the directions and planes shown. The antenna 108 points to the Earth along the yaw axis Y.
FIG. 2 is a diagram depicting the functional architecture of a representative attitude control system. Control of the spacecraft is provided by a computer or spacecraft control processor (SCP) 202 . The SCP performs a number of functions which may include post ejection sequencing, transfer orbit processing, acquisition control, stationkeeping control, normal mode control, mechanisms control, fault protection, and spacecraft systems support, among others. The post ejection sequencing could include initializing to assent mode and thruster active nutation control (TANC). The transfer orbit processing could include attitude data processing, thruster pulse firing, perigee assist maneuvers, and liquid apogee motor (LAM) thruster firing. The acquisition control could include idle mode sequencing, sun search/acquisition, and Earth search/acquisition. The stationkeeping control could include auto mode sequencing, gyro calibration, stationkeeping attitude control and transition to normal. The normal mode control could include attitude estimation, attitude and solar array steering, momentum bias control, magnetic torquing, and thruster momentum dumping (H-dumping). The mechanisms mode control could include solar panel control and reflector positioning control. The spacecraft control systems support could include tracking and command processing, battery charge management and pressure transducer processing.
Input to the spacecraft control processor 202 may come from a any combination of a number of spacecraft components and subsystems, such as a transfer orbit sun sensor 204 , an acquisition sun sensor 206 , an inertial reference unit 208 , a transfer orbit Earth sensor 210 , an operational orbit Earth sensor 212 , a normal mode wide angle sun sensor 214 , a magnetometer 216 , and one or more star sensors 218 .
The SCP 202 generates control signal commands 220 which are directed to a command decoder unit 222 . The command decoder unit operates the load shedding and battery charging systems 224 . The command decoder unit also sends signals to the magnetic torque control unit (MTCU) 226 and the torque coil 228 .
The SCP 202 also sends control commands 230 to the thruster valve driver unit 232 which in turn controls the liquid apogee motor (LAM) thrusters 234 and the attitude control thrusters 236 .
Wheel torque commands 262 are generated by the SCP 202 and are communicated to the wheel speed electronics 238 and 240 . These effect changes in the wheel speeds for wheels in momentum wheel assemblies 242 and 244 , respectively. The speed of the wheels is also measured and fed back to the SCP 202 by feedback control signal 264 .
The spacecraft control processor also sends jackscrew drive signals 266 to the momentum wheel assemblies 243 and 244 . These signals control the operation of the jackscrews individually and thus the amount of tilt of the momentum wheels. The position of the jackscrews is then fed back through command signal 268 to the spacecraft control processor. The signals 268 are also sent to the telemetry encoder unit 258 and in turn to the ground station 260 .
The spacecraft control processor also sends command signals 254 to the telemetry encoder unit 258 which in turn sends feedback signals 256 to the SCP 202 . This feedback loop, as with the other feedback loops to the SCP 202 described earlier, assist in the overall control of the spacecraft. The SCP 202 communicates with the telemetry encoder unit 258 , which receives the signals from various spacecraft components and subsystems indicating current operating conditions, and then relays them to the ground station 260 .
The wheel drive electronics 238 , 240 receive signals from the SCP 202 and control the rotational speed of the momentum wheels. The jackscrew drive signals 266 adjust the orientation of the angular momentum vector of the momentum wheels. This accommodates varying degrees of attitude steering agility and accommodates movement of the spacecraft as required.
The use of reaction wheels or equivalent internal torquers to control a momentum bias stabilized spacecraft allows inversion about yaw of the attitude at will without change to the attitude control. In this sense, the canting of the momentum wheel is entirely equivalent to the use of reaction wheels.
Other spacecraft employing external torquers, chemical or electric thrusters, magnetic torquers, solar pressure, etc. cannot be inverted without changing the control or reversing the wheel spin direction. This includes momentum bias spacecraft that attempt to maintain the spacecraft body fixed and steer payload elements with payload gimbals.
The SCP 202 may include or have access to memory 270 , such as a random access memory (RAM). Generally, the SCP 202 operates under control of an operating system 272 stored in the memory 270 , and interfaces with the other system components to accept inputs and generate outputs, including commands. Applications running in the SCP 202 access and manipulate data stored in the memory 270 . The spacecraft 10 may also comprise an external communication device supporting a satellite command link for communicating with other computers at, for example, a ground station. If necessary, operation instructions for new applications can be uploaded from ground stations.
In one embodiment, instructions implementing the operating system 272 , application programs, and other modules are tangibly embodied in a computer-readable medium, e.g., data storage device, which could include a RAM, EEPROM, or other memory device. Further, the operating system 272 and the computer program are comprised of instructions which, when read and executed by the SCP 202 , causes the spacecraft processor 202 to perform the steps necessary to implement and/or use the present invention. Computer program and/or operating instructions may also be tangibly embodied in memory 270 and/or data communications devices (e.g. other devices in the spacecraft 10 or on the ground), thereby making a computer program product or article of manufacture according to the invention. As such, the terms “program storage device,” “article of manufacture” and “computer program product” as used herein are intended to encompass a computer program accessible from any computer readable device or media.
Attitude Determination System
FIG. 3 is a block diagram of an attitude determination system 300 . The attitude determination system 300 is communicatively coupled to the rate sensors (e.g. gyros) 320 and star trackers 218 . The gyros (which are typically part of the inertial reference unit 208 ) provide measurements of the rotation rate of the satellite, 100 . Typically, such measurements are taken in three separate orthogonal axes by three different instruments. Often, the gyros are integrated with accelerometers to comprise the inertial reference unit 208 .
The attitude determination system 300 includes a gyro data processor 302 communicatively coupled to the gyro(s) 320 to receive satellite rotation rate data. The gyro data processor processes the raw spacecraft rotation rate measurement data to provide processed rate data or changes in spacecraft attitude (delta angles). This data is provided to a gyro data correction module 304 . The gyro data correction module 304 further processes the spacecraft rotation rate data to account for gyro biases, gyro scale factors, and gyro misalignments. The estimates of the gyro biases, gyro scale factors, and gyro misalignments are provided by a Kalman filter 306 .
The attitude determination system 300 also includes an attitude propagation module 308 communicatively coupled to the gyro data correction module 304 . The attitude propagation module 308 accepts corrected gyro data (spacecraft 100 rotation rates or incremental angles) from the gyro data correction module 304 as well as estimated attitude corrections from the Kalman filter 306 , and generates an attitude estimate.
The Kalman filter generates the foregoing estimates from information provided by the attitude propagation module 308 (which provides data ultimately derived primarily from the gyro 320 data) and a star identification module 312 (which provides attitude data derived from the star trackers 218 ). The star identification module 312 provides the attitude information by comparing measured star positions from the star trackers 218 and star tracker data processor 310 with information in the star catalog 314 .
The foregoing elements create an inner loop 316 compensator which can provide reasonably good estimates of spacecraft 100 attitude, changes in scale factor linearity are not adequately accounted for in highly agile spacecraft applications. In some cases, the errors in spacecraft attitude determination induced by such errors exceed the minimum performance requirements.
FIG. 4 is a graph illustrating typical gyro scale factor non-linearity errors. The horizontal axis represents the rotation rate input into the gyro, and the vertical axis represents the scale factor error in parts per million (PPM). As shown in FIG. 4, gyro scale factor errors (in terms of parts per million) are largest for small angular rate inputs. FIG. 4 also shows that scale factor error is a function of the input rate.
FIG. 5 is a diagram illustrating an attitude determination system 500 having an outer loop 506 compensator for gyro scale factor non-linearity errors. In addition to the elements described in FIG. 3, the attitude determination system 500 includes a gyro scale factor non-linearity correction module 502 in communication with the gyro data processing module 302 and the gyro data correction module 304 . The gyro data correction module 502 accepts updated gyro non-linearity correction information and provides the current gyro non-linearity correction to a deviation module 504 . The deviation module 504 accepts the estimated gyro scale factor information from the Kalman filter 306 and the current gyro non-linearity correction, and computes an estimate of the deviation between the estimated gyro scale factor and the currently implemented correction.
An updated scale factor non-linearity correction is then created, as represented in block 506 , and provided to the gyro scale factor non-linearity correction module 502 . In one embodiment, the updated scale factor non-linearity correction is a lookup table relating the rate input measurement with the required correction (or compensated rate measurement), and an interpolator in block 502 generates the precise value for rate inputs between data points. In another embodiment, the correction is a curve fitted to the data points, and the value is determined by evaluating the fitted curve.
Preferably, the estimated gyro scale factor information is obtained at a plurality of different spacecraft 100 rotation rates using the inner loop 316 . The estimated scale factors are associated with the corresponding spacecraft 100 rates and collected. From time to time, the estimated scale factors and rotation rates can then be sorted and used to generate an updated scale factor that is a function of input rate. These operations can be performed periodically (e.g. weekly, monthly), or as the need arises. For example, temporal variations in the rate sensor scale factor estimates can be examined to determine if they are converging, and the updated scale factor and/or scale factor linearity mapping determined only if the estimates are sufficiently converged. Further, the foregoing operations can be performed in a processor on-board the satellite 100 or on the ground, or a combination of both.
FIG. 6 is a diagram presenting a further illustration of how the gyro scale factor non-linearity correction is generated. The Kalman filter 306 generates an estimate of the gyro scale factor, and that estimate is provided to the derivation module 504 . The gyro scale factor 600 A is indicated in FIG. 6 as a plot of a relationship between the measured angular rate ω meas and the actual rate ω(since the Kalman filter does not provide an estimate of gyro scale factor non-linearity, the plot is a straight line, indicating that there is a linear relationship between the input rate ω and the measured angular rate ω meas ). The gyro scale factor non-linearity scale factor correction module 502 provides the current scale factor correction 600 B to the derivation module as well. The current scale factor correction is illustrated in FIG. 6 as a plot showing a relationship between the measured spacecraft angular rotation rates (perhaps after pre-processing) and the measured rate. This data is provided to differencer 602 . The difference between these two data sets represents the difference between the current scale factor non-linearity correction and the currently estimated scale factor, and is shown in plot 600 C. The sorter 604 sorts the data according to the input rate ω, resulting in the plot 600 D, and an updated non-linearity correction is formed in block 506 , resulting in plot 600 E.
FIG. 7 is a flow chart presenting illustrative process steps that could be used to practice one embodiment of the present invention. A rate sensor scale factor estimate is generated, as illustrated in block 702 . In one embodiment, this is accomplished by a Kalman filter 306 , however, other optimal estimation techniques can be used. A deviation of the scale factor estimate from a current scale factor non-linearity correction mapping is then determined, as shown in block 704 . In one embodiment this is accomplished by determining a difference between the scale factor estimate and a current scale factor non-linearity correction mapping and associating the difference with an estimated rate sensor measurement.
An updated scale factor non-linearity correction mapping is then generated from the deviation of the scale factor estimate from the current scale factor non-linearity correction mapping, as shown in block 706 . The mapping can take one or more of several forms, including a set of discrete data points relating the rate measurements and the non-linearity correction, or a continuous curve. In the case of the discrete mapping, corrections for data falling between representative values for rate measurements can be obtained by interpolation or extrapolation as required. In the case of curve fitting, a curve can be fit to the data points (e.g. exponential, power curve, or polynomial curve fitting routines using minimum mean squared error criteria).
Then, as depicted in block 708 , the rate sensor measurements are mapped according to the current scale factor non-linearity correction mapping.
In one embodiment, all of the foregoing operations are performed on a single spacecraft control processor 202 on the spacecraft 100 itself, however, this need not be the case. Any of the foregoing operations can be implemented in a special purpose processor with an associated memory (or shared memory with any of the other processors), or may be completely or partially implemented by a processor on the ground and by transmitting data between the satellite 100 and the ground station.
Conclusion
This concludes the description of the preferred embodiments of the present invention. The foregoing description of the preferred embodiment of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of the above teaching. It is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto. The above specification, examples and data provide a complete description of the manufacture and use of the composition of the invention. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended. | A method and apparatus for calibrating rate sensor measurements to compensate for rate sensor scale factor non-linearities. An outer loop compensator compares current rate sensor scale factor estimates with the current scale factor non-linearity compensation, and deviations from the current non-linearity compensation are corrected in an updated compensation. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS AND PRIORITY CLAIM
[0001] This application is a Continuation of International Application No. PCT/JP2012/071384 filed on Aug. 24, 2012, which was published under PCT Article 21(2) in Japanese, which is based upon and claims the benefit of priority from Japanese Patent Application No. 2011-183513 filed on Aug. 25, 2011, the contents all of which are incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a radiographic image capturing system (radiography system) and a radiographic image capturing method (radiography method) for obtaining a radiographic moving image by performing a radiographic image capturing process at a specified frame rate using a radiographic image capturing apparatus.
BACKGROUND ART
[0003] Recently, it has become necessary in surgery, contrast-enhanced radiography, and in treatments for bone fractures, etc., to read radiographic image information of a patient from a radiation detector, and to display the radiographic image information immediately after the radiographic image information has been captured for the purpose of quickly and adequately treating the patient. One radiation detector, which has been developed to meet such a demand, is known as a flat panel detector (FPD) having solid-state detecting elements (hereinafter referred to as “pixels”) for converting radiation directly into electric signals, or alternatively, for converting radiation into visible light with a scintillator and then converting the visible light into electric signals to read radiographic image information represented by the radiation.
[0004] There has been proposed an X-ray image diagnosing apparatus, which displays a radiographic moving image on a monitor by performing a radiographic image capturing process at a specified frame rate, so that an observer can grasp in real time how a catheter, for example, enters into a subject (see, for example, Japanese Laid-Open Patent Publication No. 2005-087633).
[0005] Heretofore, there also has been proposed an X-ray image diagnosing apparatus, which makes it unnecessary to perform an image capturing process again on a patient, and hence prevents the patient from being exposed to excessive X-rays, even in a case where an image processing circuit and an image data storage device suffer from an error while a captured image is being displayed in real time (see Japanese Laid-Open Patent Publication No. 2008-284090). Further, an X-ray image diagnosing apparatus is known, which controls a subsequent X-ray image capturing process depending on the purpose thereof, even in the event of a transmission failure of operational instruction information from a control portion (see Japanese Laid-Open Patent Publication No. 2009-297304).
SUMMARY OF INVENTION
[0006] According to Japanese Laid-Open Patent Publication No. 2008-284090 and Japanese Laid-Open Patent Publication No. 2009-297304, radiographic image information is secured upon the occurrence of an error in an X-ray image diagnosing apparatus, and a radiographic image capturing process is continued in a preset operation mode in the event that transmission of operational instruction information from a control portion is interrupted. However, these publications are silent concerning what type of processing sequence should be carried out for recovering from an error, and take nothing whatsoever into account concerning performance of a recovery process while reducing the risk of suffering from a reoccurring error and minimizing the burden on a subject, e.g., a patient.
[0007] The present invention has been made in view of the aforementioned difficulties. It is an object of the present invention to provide a radiographic image capturing system and a radiographic image capturing method for performing a process to handle errors, and to perform a recovery process while reducing the risk of suffering from a reoccurring error and minimizing the burden on a subject, e.g., a patient, due to recovery from the error.
[0008] [1] A radiographic image capturing system according to a first aspect of the invention comprises a radiographic image capturing apparatus having a radiation device including a radiation source and a radiation detecting device for converting radiation, which is emitted from the radiation source and transmitted through a subject, into radiographic image information, and a system control portion for controlling the radiographic image capturing apparatus to carry out a radiographic image capturing process at a set frame rate, wherein the system control portion includes a radiation emission disabling portion for stopping the radiation source from emitting radiation in a case where an error has occurred in at least the radiographic image capturing apparatus, and a recovery processing portion for carrying out a radiographic image capturing process while setting an irradiation energy level of the radiation source to a preset low irradiation energy level upon recovery of the radiographic image capturing apparatus from the error.
[0009] According to the present invention, in a case where an error has occurred in at least the radiographic image capturing apparatus, the radiation source is stopped from emitting radiation. In a case where the radiographic image capturing apparatus recovers from the error, the radiographic image capturing apparatus continues to capture radiographic images (a radiographic moving image) at the set frame rate. This differs significantly from the technology disclosed in Japanese Laid-Open Patent publication No. 2009-297304, i.e., a technology in which, in a case where a control signal fails to be transmitted from the console, exposure to radiation is continued in a predetermined way. This is because the technology disclosed in Japanese Laid-Open Patent Publication No. 2009-297304 does not assume that an error has occurred in the control system for the radiation source.
[0010] According to the present invention, in a case where the radiographic image capturing apparatus recovers from the error, the recovery processing portion sets the irradiation energy level of the radiation source to the preset low irradiation energy level, and thereafter, the radiographic image capturing process is carried out. Even in a case where the radiographic image capturing apparatus is judged as having recovered from an error, the radiographic image capturing apparatus actually may not have fully recovered from the error, i.e., the error may still remain unremoved. In a case where the irradiation energy level of the radiation source is set to an ordinary energy level or a high energy level prior to the occurrence of the error during a time that the radiographic image capturing apparatus has not yet fully recovered from the error, then the radiographic image capturing apparatus runs the risk of suffering from a reoccurring error. According to the present invention, as described above, since the irradiation energy level of the radiation source is set to the preset low energy level, the risk of suffering from a reoccurring error is reduced, and the radiographic image capturing system can quickly be brought back to a state for capturing a radiographic moving image. In addition, the burden posed on the subject due to undue exposure to radiation is reduced.
[0011] [2] In the first aspect of the present invention, the recovery processing portion may set a radiation dose per irradiation event from the radiation source to a level lower than a radiation dose per irradiation event immediately prior to occurrence of the error.
[0012] [3] In the first aspect of the present invention, the recovery processing portion may set a number of irradiation events per unit time performed by the radiation source to a value lower than a number of irradiation events per unit time prior to occurrence of the error.
[0013] [4] In the first aspect of the present invention, the recovery processing portion may set the total irradiation energy level per unit time of the radiation source to a low level.
[0014] [5] In the first aspect of the present invention, the recovery processing portion may set a radiation dose per irradiation event from the radiation source to a level lower than a radiation dose per irradiation event prior to the occurrence of the error, and may set a number of irradiation events per unit time performed by the radiation source to a value lower than a number of irradiation events per unit time prior to the occurrence of the error.
[0015] [6] In the first aspect of the present invention, the recovery processing portion may set the irradiation energy level of the radiation source to a lowest irradiation energy level from among a plurality of irradiation energy levels set within a predetermined period in past.
[0016] [7] In the first aspect of the present invention, the radiographic image capturing apparatus may further include a radiation source control portion for controlling the radiation source based on a command from the system control portion, wherein the radiation emission disabling portion may supply a disable signal for disabling emission of radiation to the radiation source control portion, and the radiation source control portion may stop the radiation source from emitting radiation based on the disable signal supplied from the radiation emission disabling portion.
[0017] [8] In [7], the radiographic image capturing apparatus may further include a detecting device control portion for controlling the radiation detecting device based on a command from the system control portion, wherein the system control portion may send an error notification to the detecting device control portion after the disable signal has been supplied from the radiation emission disabling portion, and the detecting device control portion may stop controlling at least the radiation detecting device based on the error notification sent from the system control portion.
[0018] [9] In the first aspect of the present invention, the radiographic image capturing apparatus may further include a radiation source control portion for controlling the radiation source based on a command from the system control portion, wherein the radiation emission disabling portion may stop supply of an exposure start signal for emitting radiation to the radiation source control portion.
[0019] [10] In [9], the radiographic image capturing apparatus may further include a detecting device control portion for controlling the radiation detecting device based on a command from the system control portion, wherein the system control portion may send an error notification to the detecting device control portion after the radiation emission disabling portion has stopped supply of the exposure start signal, and the detecting device control portion may stop controlling the radiation detecting device based on the error notification sent from the system control portion.
[0020] [11] In [7] through [10], based on the recovery from the error, the recovery processing portion may supply information concerning setting of the irradiation energy level of the radiation source to the low irradiation energy level to the radiation device, and may supply parameter information concerning the recovery from the error to the detecting device control portion, and the system control portion may resume operation of the radiation device and the radiation detecting device.
[0021] [12] In the first aspect of the present invention, the radiographic image capturing system may further comprise a display device for displaying radiographic image information captured by the radiographic image capturing process that is carried out at the set frame rate, wherein in the case where the error has occurred, the system control portion controls the display device to display radiographic image information captured immediately prior to occurrence of the error at the set frame rate, during a period from the occurrence of the error to the recovery from the error.
[0022] [13] According to a second aspect of the invention, there also is provided a radiographic image capturing method for carrying out a radiographic image capturing process at a set frame rate with a radiographic image capturing apparatus including a radiation source and a radiation detecting device for converting radiation, which is emitted from the radiation source and transmitted through a subject, into radiographic image information, comprising the steps of stopping the radiation source from emitting radiation in a case where an error has occurred in at least the radiographic image capturing apparatus, and carrying out a radiographic image capturing process while setting an irradiation energy level of the radiation source to a preset low irradiation energy level upon recovery of the radiographic image capturing apparatus from the error.
[0023] With the radiographic image capturing system and the radiographic image capturing method according to the present invention, as described above, in addition to the process performed upon occurrence of an error, a recovery process is performed to recover the radiographic image capturing apparatus from the error, while at the same time reducing the risk of reoccurring errors as well as reducing the burden on the subject, e.g., a patient.
BRIEF DESCRIPTION OF DRAWINGS
[0024] FIG. 1 is a schematic view of a radiographic image capturing system according to a first embodiment of the present invention (first radiographic image capturing system);
[0025] FIG. 2 is a block diagram of a radiation device and a radiation detecting device of the first radiographic image capturing system;
[0026] FIG. 3 is a circuit diagram showing a configuration of the radiation detecting device, and in particular, a configuration of a radiation detector;
[0027] FIG. 4 is a block diagram showing a configuration primarily of a system control portion of the first radiographic image capturing system;
[0028] FIG. 5 is a flowchart (part 1 ) of a processing sequence of the first radiographic image capturing system;
[0029] FIG. 6 is a flowchart (part 2 ) of the processing sequence of the first radiographic image capturing system;
[0030] FIG. 7 is a timing chart of the processing sequence of the first radiographic image capturing system;
[0031] FIG. 8 is a block diagram showing a configuration primarily of a system control portion of a radiographic image capturing system according to a second embodiment of the present invention (second radiographic image capturing system);
[0032] FIG. 9 is a flowchart of selected steps of a processing sequence of the second first radiographic image capturing system;
[0033] FIG. 10 is a timing chart of a processing sequence of the second radiographic image capturing system;
[0034] FIG. 11 is a block diagram showing a configuration primarily of a system control portion of a radiographic image capturing system according to a third embodiment of the present invention (third radiographic image capturing system);
[0035] FIG. 12 is a block diagram showing a configuration primarily of a system control portion of a radiographic image capturing system according to a fourth embodiment of the present invention (fourth radiographic image capturing system);
[0036] FIG. 13 is a timing chart of a processing sequence of the fourth radiographic image capturing system;
[0037] FIG. 14 is a cross-sectional view of a configuration made up of three pixels of a radiation detector according to a modification of the present invention; and
[0038] FIG. 15 is a cross-sectional view of a thin-film transistor (TFT) and an electric charge accumulator shown in FIG. 14 .
DESCRIPTION OF EMBODIMENTS
[0039] Radiographic image capturing systems and radiographic image capturing methods according to preferred embodiments of the present invention will be described below with reference to FIGS. 1 through 15 .
[0040] As shown in FIG. 1 , a radiographic image capturing system according to a first embodiment of the present invention (hereinafter referred to as a “first radiographic image capturing system 10 A”) includes a radiographic image capturing apparatus 12 and a system control portion 14 for controlling the radiographic image capturing apparatus 12 to perform a radiographic image capturing process at a specific frame rate in a range from 15 frames/second to 60 frames/second, for example. The system control portion 14 is connected to a console 16 for carrying out data communications therewith. The console 16 is connected to a monitor 18 (display device) for enabling observation of images and image diagnosis, and an input device 20 , e.g., a keyboard, a mouse, etc., for entering control inputs. Using the input device 20 , the operator, e.g., a doctor or a radiological technician, specifies a dose of radiation to be applied and the frame rate of a radiographic image capturing process, which are suitable for the present situation, for a surgical operation and a catheter insertion process to be carried out while observing a moving image being displayed. Data that have been entered using the input device 20 and data that have been generated and edited on the console 16 are supplied to the system control portion 14 . Radiographic image information, etc., from the system control portion 14 is supplied to the console 16 and displayed on the monitor 18 .
[0041] The radiographic image capturing apparatus 12 includes a radiation device 28 for applying radiation 26 to a subject 24 on an image capturing base 22 , a radiation detecting device 30 for converting radiation 26 that has passed through the subject 24 into radiographic image information, and a detecting device control portion 32 for sending and receiving data including radiographic image information between the radiation detecting device 30 and the system control portion 14 , and for controlling, e.g., moving, the radiation detecting device 30 based on commands from the system control portion 14 .
[0042] The radiation detecting device 30 may be moved in a case where it is necessary to capture a radiographic image of a relatively wide range of the subject 24 , e.g., to capture a radiographic moving image of the spine of the subject 24 , or to capture a radiographic moving image of a region where a catheter enters into the body of the subject 24 . For capturing such a radiographic image, the system control portion 14 supplies the detecting device control portion 32 with a movement control signal based on a control input entered by the operator (the doctor or the radiological technician). In response to the movement control signal from the system control portion 14 , the detecting device control portion 32 controls a moving mechanism, not shown, in order to move the radiation detecting device 30 .
[0043] As shown in FIG. 2 , the radiation device 28 has a radiation source 34 , a radiation source control portion 36 for controlling the radiation source 34 based on a command from the system control portion 14 , and an automatic collimating portion 38 for increasing or reducing the area to be irradiated with radiation 26 based on a command from the system control portion 14 .
[0044] The radiation detecting device 30 has a radiation detector 40 , a battery 42 serving as a power supply, a cassette control portion 44 for energizing the radiation detector 40 , and a transceiver 46 for sending and receiving signals including radiographic image information from the radiation detector 40 to and from an external device. The radiographic image information sent from the transceiver 46 is supplied through the detecting device control portion 32 to the system control portion 14 and the console 16 , and the radiographic image information is displayed on the monitor 18 . In a case where a radiographic image capturing process is carried out at a specified frame rate, the system control portion 14 is supplied with successive items of radiographic image information from the detecting device control portion 32 , and the system control portion 14 controls the monitor 18 to display a radiographic moving image in real time.
[0045] In order to prevent the cassette control portion 44 and the transceiver 46 from becoming damaged due to radiation 26 , a lead plate or the like preferably is provided on irradiated surfaces of the cassette control portion 44 and the transceiver 46 .
[0046] The radiation detector 40 may comprise an indirect-conversion-type radiation detector (a face-side readout type or a reverse-side readout type of radiation detector) for converting radiation 26 that has passed through the subject 24 into visible light with a scintillator, and then converting the visible light into electric signals with solid-state detecting elements (hereinafter referred to as “pixels”) made of a material such as amorphous silicon (a-Si) or the like. A radiation detector, which is of an ISS (Irradiation Side Sampling) type as a face-side readout type, includes solid-state detecting elements and a scintillator, which are arranged successively along a direction in which radiation 26 is applied. A radiation detector, which is of a PSS (Penetration Side Sampling) type as a reverse-side readout type, includes a scintillator and solid-state detecting elements, which are arranged successively along a direction in which radiation 26 is applied. The radiation detector 40 may alternatively comprise, rather than an indirect-conversion-type radiation detector, a direct-conversion-type radiation detector for converting a dose of radiation 26 directly into electric signals using solid-state detecting elements made of a material such as amorphous selenium (a-Se) or the like.
[0047] A circuit arrangement of the radiation detecting device 30 , which includes an indirect-conversion-type radiation detector 40 , for example, will be described in detail below with reference to FIG. 3 .
[0048] The radiation detector 40 comprises an array of thin-film transistors (hereinafter referred to as “TFTs 54 ”) arranged in rows and columns, and a photoelectric transducer layer 52 including pixels 50 and made of a material such as a-Si or the like for converting visible light into electric signals. The photoelectric transducer layer 52 is disposed on the array of TFTs 54 . The pixels 50 store electric charges, which are generated in a case where the pixels 50 convert visible light into electric signals (analog signals). The TFTs 54 are turned on successively along each row at a time, whereby the stored electric charges are read from the pixels 50 as image signals.
[0049] The TFTs 54 are connected respectively to the pixels 50 . Gate lines 56 , which extend in parallel with the rows, and signal lines 58 , which extend in parallel with the columns, are connected to the TFTs 54 . The gate lines 56 are connected to a line scanning drive portion 60 , and the signal lines 58 are connected to a multiplexer 62 . The gate lines 56 are supplied with control signals Von, Voff from the line scanning drive portion 60 for turning on and off the TFTs 54 along the rows. The line scanning drive portion 60 includes a plurality of switches SW 1 for switching between the gate lines 56 , and a first address decoder 64 for supplying a selection signal for selecting one of the switches SW 1 at a time. The first address decoder 64 is supplied with an address signal from the cassette control portion 44 .
[0050] The signal lines 58 are supplied with electric charges stored in the pixels 50 through the TFTs 54 , which are arranged in columns. The electric charges supplied to the signal lines 58 are amplified by charge amplifiers 66 . The charge amplifiers 66 are connected through respective sample and hold circuits 68 to the multiplexer 62 .
[0051] The electric charges read from the columns are supplied respectively through the signal lines 58 to the charge amplifiers 66 in the columns. Each of the charge amplifiers 66 comprises an operational amplifier 70 , a capacitor 72 , and a switch 74 . In a case where the switch 74 is turned off, the charge amplifier 66 converts a charge signal supplied to an input terminal of the operational amplifier 70 into a voltage signal, and supplies the voltage signal to the sample and hold circuit 68 . The charge amplifier 66 amplifies the electric signal by a predetermined gain set in the cassette control portion 44 and supplies an amplified electric signal. Information concerning the gain of the charge amplifier 66 , i.e., gain setting information, is supplied from the system control portion 14 through the detecting device control portion 32 to the cassette control portion 44 . Based on the supplied gain setting information, the cassette control portion 44 sets the gain of the charge amplifier 66 .
[0052] The operational amplifier 70 has another input terminal connected to GND (ground potential). In a case where the switch 74 is turned on, the electric charge stored in the capacitor 72 is discharged by a closed circuit of the capacitor 72 and the switch 74 , and the electric charges stored in the pixels 50 are drained to GND (ground potential) through the closed switch 74 and the operational amplifier 70 . The process of turning on the switch 74 of the charge amplifier 66 in order to discharge the electric charge stored in the capacitor 72 and to drain the electric charges stored in the pixels 50 to GND (ground potential) is referred to as a resetting process (blank reading). In the resetting process, voltage signals, which are representative of the electric charges stored in the pixels 50 , are not supplied to the multiplexer 62 , but rather are drained from the pixels 50 .
[0053] The multiplexer 62 includes a plurality of switches SW 2 for switching successively between the signal lines 58 and a second address decoder 76 , for thereby outputting a selection signal for selecting one of the switches SW 2 at a time. The second address decoder 76 is supplied with an address signal from the cassette control portion 44 . The multiplexer 62 has an output terminal connected to an A/D converter 78 . The A/D converter 78 converts radiographic image information into digital image signals, which are supplied to the cassette control portion 44 .
[0054] The TFTs 54 , which operate as switching devices, may be combined with another image capturing device such as a CMOS (Complementary Metal-Oxide Semiconductor) image sensor or the like. Alternatively, the TFTs 54 may be replaced with a CCD (Charge-Coupled Device) image sensor for shifting and transferring electric charges with shift pulses that correspond to gate signals in the TFTs.
[0055] As shown in FIG. 2 , the cassette control portion 44 of the radiation detecting device 30 includes an address signal generating portion 80 , an image memory 82 , and a cassette ID memory 84 .
[0056] Based on readout control information from the system control portion 14 , for example, the address signal generating portion 80 supplies address signals to the first address decoder 64 of the line scanning drive portion 60 , and to the second address decoder 76 of the multiplexer 62 shown in FIG. 3 . The readout control information includes information representing a progressive mode, an interlace mode (an odd-numbered row readout mode, an even-numbered row readout mode, an every third row readout mode, an every fourth row readout mode, etc.), and a binning mode (a 4-pixels-into-1 readout mode, a 6-pixels-into-1 readout mode, a 9-pixels-into-1 readout mode, etc.). In a 4-pixels-into-1 readout mode, for example, two adjacent gate lines are energized simultaneously, i.e., supplied with the control signal Von, and two adjacent signal lines are energized simultaneously, thereby mixing the electric charges, which are contained in four adjacent pixels in two rows and two columns, into a single superpixel electric charge to be read. The address signal generating portion 80 generates address signals depending on the mode represented by the readout control information, and supplies the generated address signals to the first address decoder 64 of the line scanning drive portion 60 and to the second address decoder 76 of the multiplexer 62 . The readout control information is generated by the system control portion 14 based on a control input entered by the operator, for example, and the readout control information is supplied to the cassette control portion 44 of the radiation detecting device 30 .
[0057] The image memory 82 stores radiographic image information detected by the radiation detector 40 . The cassette ID memory 84 stores cassette ID information for identifying the radiation detecting device 30 . The transceiver 46 sends cassette ID information stored in the cassette ID memory 84 and radiographic image information stored in the image memory 82 through the detecting device control portion 32 to the system control portion 14 via a wired or wireless communication link.
[0058] In addition, the system control portion 14 of the first radiographic image capturing system 10 A has a parameter setting portion 100 , a parameter history storage portion 102 , an error watching portion 104 , a radiation emission disabling portion 106 , an error notifying portion 108 , and a recovery processing portion 110 .
[0059] In the case that new parameters (dose of radiation to be applied, frame rate, etc.) are set by a control input made by the operator, the parameter setting portion 100 stores the new radiation dose, the frame rate, etc., which have been set, as latest parameters in the parameter history storage portion 102 . In particular, in a case where the dose of radiation to be applied is newly set, the parameter setting portion 100 supplies first dose setting information Sa 1 , including information (tube voltage, tube current, image capturing time, etc.) concerning the newly set radiation dose, to the radiation device 28 . In a case where a gain and a readout mode are newly set for the charge amplifiers 66 , the parameter setting portion 100 supplies first readout control information Sb 1 , including information concerning the newly set gain and the newly set readout mode, to the detecting device control portion 32 .
[0060] The parameter history storage portion 102 stores radiation doses and frame rates, which were applied over a predetermined period of time in the past from the present time, from among the radiation doses and frame rates that have been set thus far.
[0061] Based on detected signals from various non-illustrated sensors, the error watching portion 104 judges whether or not an error has occurred in at least the radiographic image capturing apparatus 12 , as well as whether the radiographic image capturing apparatus 12 has recovered from the error.
[0062] In a case where the error watching portion 104 judges that an error has occurred, then the radiation emission disabling portion 106 stops the radiation source 34 from emitting radiation. More specifically, the radiation emission disabling portion 106 supplies a disable signal Sc (see FIG. 7 ) for disabling emission of radiation to the radiation device 28 . Alternatively, the radiation emission disabling portion 106 stops supplying an exposure start signal Sd (see FIG. 7 ) for initiating emission of radiation to the radiation device 28 . The radiation source control portion 36 of the radiation device 28 stops the radiation source 34 from emitting radiation based on the disable signal Sc from the radiation emission disabling portion 106 .
[0063] After the disable signal Sc has been supplied from the radiation emission disabling portion 106 , or after the exposure start signal Sd has stopped being supplied from the radiation emission disabling portion 106 , the error notifying portion 108 sends an error notification Se (see FIG. 7 ) to the detecting device control portion 32 . In response to the error notification Se, the detecting device control portion 32 stops control of at least the radiation detecting device 30 . At this time, all of the pixels may be reset.
[0064] In a case where the error watching portion 104 judges that the radiographic image capturing apparatus 12 has recovered from the error, then the recovery processing portion 110 controls the radiation device 28 to perform a radiographic image capturing process. At this time, the radiation source 34 is set to a preset low irradiation energy level.
[0065] The recovery processing portion 110 has a low radiation dose setting portion 112 for setting the dose of radiation from the radiation source 34 per irradiation event to a level lower than the dose of radiation from the radiation source 34 per irradiation event prior to the occurrence of the error. The low radiation dose setting portion 112 sets the dose of radiation from the radiation source 34 per irradiation event to a level that is in a range from ⅓ to ⅔ of the dose of radiation from the radiation source 34 per irradiation event prior to the occurrence of the error, e.g., the latest radiation dose stored in the parameter history storage portion 102 . Alternatively, the low radiation dose setting portion 112 may set the radiation dose to a lower ratio, e.g., in a range from ⅕ to ⅘.
[0066] The recovery processing portion 110 supplies second dose setting information Sa 2 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the low radiation dose set by the low radiation dose setting portion 112 , to the radiation device 28 , and supplies second readout control information Sb 2 (parameter information), which includes information concerning a gain and a readout mode for the charge amplifiers 66 to enable recovery, to the detecting device control portion 32 .
[0067] Upon elapse of a predetermined recovery watch period (5 to 10 seconds from the time that recovery from an error is judged to have occurred), the recovery processing portion 110 supplies third dose setting information Sa 3 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the radiation dose (the latest radiation dose stored in the parameter history storage portion 102 ) immediately prior to the occurrence of the error, to the radiation device 28 . The recovery processing portion 110 also supplies third readout control information Sb 3 , which includes information (the latest gain setting information and readout mode information stored in the parameter history storage portion 102 ) concerning a gain and a readout mode for the charge amplifiers 66 immediately prior to the occurrence of the error, to the detecting device control portion 32 . Then, the recovery processing portion 110 returns control to the control system in order to perform an ordinary radiographic image capturing process. As a result, a radiographic image capturing process is performed at the irradiation energy level immediately prior to the occurrence of the error. Thereafter, a radiographic image capturing process is performed at an irradiation energy level (a radiation dose and a frame rate) which is newly set by the operator.
[0068] In a case where the error watching portion 104 judges that an error has occurred, the system control portion 14 controls the console 16 to display on the monitor 18 the radiographic image information that was acquired immediately prior to the occurrence of the error. The image information is displayed at the frame rate immediately prior to the occurrence of the error, during a period from the time at which the error was judged to have occurred until the time at which the radiographic image capturing apparatus 12 recovers from the error.
[0069] A processing sequence of the first radiographic image capturing system 10 A will be described below with reference to the flowcharts shown in FIGS. 5 and 6 and the timing chart shown in FIG. 7 .
[0070] In step S 1 of FIG. 5 , the system control portion 14 stores an initial value (=1) in an image capturing counter k.
[0071] In step S 2 , the system control portion 14 judges whether or not parameters (dose of radiation to be applied, frame rate, gain, readout mode, etc.) have been newly set. In a case where the operator has newly set such parameters, then control proceeds to step S 3 , in which the newly set dose, frame rate, etc., are stored as latest parameters in the parameter history storage portion 102 .
[0072] In a case where the radiation dose has been newly set, then in step S 4 , the system control portion 14 supplies first dose setting information Sa 1 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the newly set dose, to the radiation device 28 . Based on the first dose setting information Sa 1 from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 sets the radiation dose emitted from the radiation source 34 as a new radiation dose.
[0073] In a case where the gain and the readout mode have been newly set, then in step S 5 , the system control portion 14 supplies first readout control information Sb 1 , which includes information concerning the newly set gain and the newly set readout mode, through the detecting device control portion 32 to the radiation detecting device 30 . Based on the supplied readout control information Sb 1 , the radiation detecting device 30 sets a gain for the charge amplifiers 66 , and sets the type of address signal and the output timing thereof for the address signal generating portion 80 .
[0074] In step S 6 , the system control portion 14 judges whether or not the period corresponding to the latest frame rate has elapsed from the start time of the previous radiographic image capturing process. In a case where the value of the counter k is the initial value, or In a case where the period corresponding to the latest frame rate has elapsed from the starting time of the previous radiographic image capturing process, then control proceeds to step S 7 , in which the error watching portion 104 judges whether or not an error has occurred.
[0075] In a case where the error watching portion 104 judges that an error has not occurred, then control proceeds to step S 8 , in which the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 at the start time of a kth radiographic image capturing process. Based on the exposure start signal Sd supplied from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 controls the radiation source 34 to emit radiation 26 at the set radiation dose.
[0076] In step S 9 , the system control portion 14 sends an exposure notification Sf (see FIG. 7 ) to the detecting device control portion 32 , which indicates the start of exposure by the radiation device 28 .
[0077] In step S 10 , based on the supplied exposure notification Sf, the detecting device control portion 32 supplies an operation start signal Sg (see FIG. 7 ) representing the storage of electric charges and the readout of electric charges to the radiation detecting device 30 .
[0078] In step S 11 , the radiation detecting device 30 stores electric charges and reads out electric charges based on the operation start signal Sg supplied from the detecting device control portion 32 . More specifically, radiation 26 that has passed through the subject 24 initially is converted into visible light by the scintillator. Then, depending on the amount, the visible light is photoelectrically converted into electric charges by the pixels 50 , and the electric charges are stored in the pixels 50 . At the start of the readout period, the radiation detecting device 30 supplies a synchronizing signal Sh (e.g., a vertical synchronizing signal, see FIG. 7 ) to the detecting device control portion 32 . Based on the supplied synchronizing signal Sh, the detecting device control portion 32 synchronizes the timing at which the radiographic image information is received with the timing at which the radiographic image information is received from the radiation detecting device 30 .
[0079] During the readout period, the radiation detecting device 30 reads electric charges according to the set readout control information, i.e., information indicating a progressive mode, an interlace mode, or a binning mode, and supplies radiographic image information Da (see FIG. 7 ) in a FIFO mode, for example, from the memory 82 . Radiographic image information Da from the radiation detecting device 30 is supplied through the detecting device control portion 32 to the system control portion 14 .
[0080] In step S 12 , the system control portion 14 transfers the supplied radiographic image information Da to the console 16 . The console 16 stores the transferred radiographic image information Da in a frame memory, and displays the radiographic image information Da as a radiographic image captured by a kth radiographic image capturing process, i.e., as a radiographic image in a kth frame, on the monitor 18 .
[0081] In step S 13 , the value of the counter k is updated by +1.
[0082] In step S 14 , the system control portion 14 judges whether or not there is a system shutdown request. In a case where there is not a system shutdown request, then processing from step S 2 is repeated. In this case, insofar as no error has occurred, the operation sequence from step S 2 through step S 14 is repeated, and the monitor 18 displays a radiographic moving image at the set frame rate.
[0083] According to the example shown in FIG. 7 , in a case where the radiation dose and the readout mode are changed by a control input from the operator, for example, prior to the starting time to −1 of an (N−1)th (N=2, 3, . . . ) radiographic image capturing process, then the system control portion 14 supplies first dose setting information Sa 1 , which includes information concerning the newly set radiation dose, to the radiation device 28 , and supplies first readout control information Sb 1 , which includes information concerning the newly set readout mode, through the detecting device control portion 32 to the radiation detecting device 30 . In this manner, the radiation device 28 and the radiation detecting device 30 are set to the new radiation dose and the new readout mode.
[0084] Thereafter, at the start time tn−1 of the (N−1)th radiographic image capturing process, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while sending an exposure notification Sf to the detecting device control portion 32 . The system control portion 14 then is supplied with radiographic image information Da that was acquired by the (N−1)th radiographic image capturing process. The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays a radiographic image in an (N−1)th frame on the monitor 18 . Similarly, at the start time tn of an Nth radiographic image capturing process, after elapse of the latest frame rate Fr from the start time tn−1, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while sending an exposure notification Sf to the detecting device control portion 32 . The system control portion 14 then is supplied with radiographic image information Da that was acquired by the Nth radiographic image capturing process. The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays a radiographic image in an Nth frame on the monitor 18 . The above process is repeated to display a radiographic moving image on the monitor 18 .
[0085] In step S 7 , in a case where the error watching portion 104 judges that an error has occurred, then control proceeds to step S 15 of FIG. 6 , during which the radiation emission disabling portion 106 supplies a disable signal Sc for disabling emission of radiation to the radiation device 28 . Alternatively, the radiation emission disabling portion 106 may stop supplying the exposure start signal Sd for initiating application of radiation to the radiation device 28 . The radiation source control portion 36 of the radiation device 28 stops the radiation source 34 from emitting radiation based on the disable signal Sc from the radiation emission disabling portion 106 . In a case where the exposure start signal Sd is not supplied, emission of radiation is disabled.
[0086] In step S 16 , after the disable signal Sc has been supplied from the radiation emission disabling portion 106 , or after the exposure start signal Sd has stopped being supplied from the radiation emission disabling portion 106 , the error notifying portion 108 sends an error notification Se to the detecting device control portion 32 . In response to the error notification Se, the detecting device control portion 32 stops controlling at least the radiation detecting device 30 . At this time, all of the pixels may be reset.
[0087] In step S 17 , the system control portion 14 controls the console 16 to display the radiographic image immediately prior to the occurrence of the error at the latest frame rate Fr on the monitor 18 .
[0088] In step S 18 , the error watching portion 104 judges whether or not the radiographic image capturing apparatus 12 has recovered from the error. In a case where the error watching portion 104 judges that the radiographic image capturing apparatus 12 has not recovered from the error, control returns to step S 17 , thus repeating the process of displaying the radiographic image immediately prior to the occurrence of the error on the monitor 18 . Accordingly, as shown in FIG. 7 , for example, the radiographic image immediately prior to the occurrence of the error is displayed at the latest frame rate Fr on the monitor 18 , during a period Ta from the time to at which the error was judged to have occurred until the start time tn+1 of the first radiographic image capturing process after recovery from the error.
[0089] In a case where the error watching portion 104 judges that the radiographic image capturing apparatus 12 has recovered from the error, then control proceeds to step S 19 , during which time the low radiation dose setting portion 112 of the recovery processing portion 110 sets the radiation dose per irradiation event from the radiation source 34 to a predetermined level, which is lower than the radiation dose per irradiation event immediately prior to the occurrence of the error (latest radiation dose).
[0090] In step S 20 , the recovery processing portion 110 supplies second dose setting information Sa 2 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the low radiation dose set by the low radiation dose setting portion 112 , to the radiation device 28 . Based on the second dose setting information Sa 2 from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 sets the radiation dose emitted from the radiation source 34 to a low radiation dose.
[0091] In step S 21 , the recovery processing portion 110 supplies second readout control information Sb 2 , which includes information concerning a gain and a readout mode for recovery, through the detecting device control portion 32 to the radiation detecting device 30 . Based on the supplied second readout control information Sb 2 , the radiation detecting device 30 sets the gain for the charge amplifiers 66 , and sets the type of address signal and the output timing for the address signal generating portion 80 .
[0092] The signal processing system tends to become unduly burdened in a case where an ordinary readout process (e.g., a progressive readout process) is carried out after recovery from the error. In view of this drawback, the second readout control information Sb 2 includes information for enabling selection of an interlace mode (an odd-numbered row readout mode, an even-numbered row readout mode, an every third row readout mode, etc.), for example. Therefore, any undue burden imposed on the signal processing system of the radiation detecting device 30 is reduced upon recovery from the error. The gain setting information also includes information for enabling setting of the gain of the charge amplifiers 66 to a higher than normal gain.
[0093] In step S 22 , the system control portion 14 judges whether or not the period corresponding to the latest frame rate Fr has elapsed from the start time of the previous radiographic image capturing process. Operations of the radiation device 28 and the radiation detecting device 30 are resumed during a time period corresponding to the latest frame rate Fr, which is elapsing or has elapsed from the start time of the previous radiographic image capturing process.
[0094] More specifically, in step S 23 , the recovery processing portion 110 supplies an exposure start signal Sd to the radiation device 28 at the start time of the kth radiographic image capturing process. Based on the exposure start signal Sd supplied from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 controls the radiation source 34 to emit radiation 26 at the previously set low radiation dose.
[0095] In step S 24 , the system control portion 14 sends an exposure notification Sf, which indicates the start of exposure by the radiation device 28 , to the detecting device control portion 32 .
[0096] In step S 25 , based on the supplied exposure notification Sf, the detecting device control portion 32 supplies an operation start signal Sg, which represents the storage of electric charges and the readout of electric charges, to the radiation detecting device 30 .
[0097] In step S 26 , based on the operation start signal Sg supplied from the detecting device control portion 32 , the radiation detecting device 30 stores electric charges and reads out electric charges. This operation of the radiation detecting device 30 is the same as the operation carried out in step S 11 . According to the first embodiment, as described above, since the irradiation energy is set to a low level upon recovery from the error, the radiographic image information, which is read, exhibits a reduced grayscale range. In step S 21 , for increasing sensitivity, the gain of the charge amplifiers 66 is set to a high level. Consequently, even though the irradiation energy is set to a low level, it is possible to obtain radiographic image information having the same grayscale range as during normal operation thereof.
[0098] At the readout period start time, the radiation detecting device 30 supplies a synchronizing signal Sh (e.g., a vertical synchronizing signal) to the detecting device control portion 32 . During the readout period, the radiation detecting device 30 reads electric charges according to the set readout control information, i.e., information concerning an interlace mode or the like, and supplies radiographic image information Da in a FIFO mode, for example, from the memory 82 . Radiographic image information Da from the radiation detecting device 30 is supplied through the detecting device control portion 32 to the system control portion 14 .
[0099] In step S 27 , the system control portion 14 transfers the supplied radiographic image information Da to the console 16 . The console 16 stores the transferred radiographic image information Da in the frame memory, and displays the radiographic image information Da as a radiographic image captured by a kth radiographic image capturing process, i.e., as a radiographic image in a kth frame, on the monitor 18 .
[0100] According to the example shown in FIG. 7 , at time tr at which the radiographic image capturing apparatus 12 is judged as having recovered from the error, the system control portion 14 supplies the second dose setting information Sa 2 , which includes information concerning the low radiation dose, to the radiation device 28 . The system control portion 14 also supplies the second readout control information Sb 2 , which includes the gain setting information and the readout mode information set for recovery, through the detecting device control portion 32 to the radiation detecting device 30 . At this time, the radiation device 28 and the radiation detecting device 30 are not set to the low radiation dose, the higher gain, and the readout mode (e.g., an interlace mode).
[0101] Thereafter, at the start time tn+1 of an (N+1)th radiographic image capturing process, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while also supplying an exposure notification Sf to the detecting device control portion 32 . Thereafter, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+1)th radiographic image capturing process (which is carried out at a low irradiation energy). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+1)th frame on the monitor 18 . Similarly, at the start time tn+2 of the (N+2)th radiographic image capturing process, after elapse of the latest frame rate Fr from the start time tn+1, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while also supplying an exposure notification Sf to the detecting device control portion 32 . Thereafter, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+2)th radiographic image capturing process (which is carried out at a low irradiation energy). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+2)th frame on the monitor 18 . The above process is repeated to display a radiographic moving image on the monitor 18 after recovery from the error.
[0102] In step S 28 , the value of the counter k is updated by +1.
[0103] In step S 29 , the system control portion 14 judges whether or not a predetermined recovery watching period Tb (see FIG. 7 ) has elapsed from recovery from the error. In a case where the predetermined recovery watching period Tb has not elapsed, control returns to step S 22 , and processing from step S 22 is repeated.
[0104] In a case where the predetermined recovery watching period Tb has elapsed, then control proceeds to step S 30 , in which the system control portion 14 supplies third dose setting information Sa 3 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the radiation dose immediately prior to the occurrence of the error, to the radiation device 28 . Based on the third dose setting information Sa 3 from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 sets the radiation dose emitted from the radiation source 34 to the radiation dose immediately prior to the occurrence of the error.
[0105] In step S 31 , the system control portion 14 supplies third readout control information Sb 3 , which includes the gain setting information and the readout mode information immediately prior to the occurrence of the error, through the detecting device control portion 32 to the radiation detecting device 30 . Based on the supplied third readout control information Sb 3 , the radiation detecting device 30 sets the gain for the charge amplifiers 66 , and the type of address signal and the output timing for the address signal generating portion 80 .
[0106] Thereafter, control returns to the process from step S 6 shown in FIG. 5 , and the system control portion 14 controls the radiographic image capturing apparatus 12 to perform an ordinary radiographic image capturing process.
[0107] According to the example shown in FIG. 7 , at time ta, upon elapse of the recovery watching period Tb from time tr at which the radiographic image capturing apparatus 12 was judged to have recovered from the error, the system control portion 14 supplies the third dose setting information Sa 3 , which includes information concerning the radiation dose immediately prior to the occurrence of the error, to the radiation device 28 . The system control portion 14 also supplies the third readout control information Sb 3 , which includes the gain setting information and the readout mode information immediately prior to the occurrence of the error, through the detecting device control portion 32 to the radiation detecting device 30 . In this manner, the radiation device 28 and the radiation detecting device 30 are set to parameters immediately prior to the occurrence of the error.
[0108] Thereafter, at the start time tn+j of an (N+j)th radiographic image capturing process, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 , and also supplies an exposure notification Sf to the detecting device control portion 32 . Then, the system control portion 14 is supplied with radiographic image information Da acquired by an (N+j)th radiographic image capturing process. The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+j)th frame on the monitor 18 . Similarly, at the start time tn+j+1 of an (N+j+1)th radiographic image capturing process, after elapse of the latest frame rate Fr from the start time tn+j, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 , and also supplies an exposure notification Sf to the detecting device control portion 32 . Then, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+j+1)th radiographic image capturing process. The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+j+1)th frame on the monitor 18 . The above process is repeated to display a radiographic moving image on the monitor 18 after recovery from the error.
[0109] In a case where the system control portion 14 judges that a system shutdown request has occurred in step S 14 , the processing sequence of the first radiographic image capturing system 10 A is brought to an end.
[0110] According to the first radiographic image capturing system 10 A, as described above, in a case where an error occurs in the radiographic image capturing apparatus 12 , emission of radiation from the radiation source 34 is stopped. However, in a case where the radiographic image capturing apparatus 12 recovers from the error, the radiographic image capturing apparatus 12 can continue carrying out the radiographic image capturing process at a set frame rate in order to capture a radiographic moving image.
[0111] Even in a case where the radiographic image capturing apparatus 12 is judged as having recovered from the error, the radiographic image capturing apparatus 12 actually may not have fully recovered from the error, i.e., the error may still remain unremoved. In this case, in a case where the irradiation energy level of the radiation source 34 is set to an ordinary energy level or a high energy level prior to the occurrence of the error while the radiographic image capturing apparatus 12 has not yet fully recovered from the error, then the radiographic image capturing apparatus 12 runs the risk of suffering from a reoccurring error. According to the first radiographic image capturing system 10 A, as described above, since the irradiation energy level of the radiation source 34 is set to a preset low energy level, the risk of suffering from a reoccurring error is reduced, and the first radiographic image capturing system 10 A can quickly be brought back to a state that enables capturing of a radiographic moving image. In addition, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced.
[0112] According to the first radiographic image capturing system 10 A, furthermore, the gain of the charge amplifiers 66 of the radiation detecting device 30 is set to a higher level for increasing sensitivity during the recovery watching period Tb. Consequently, even though the irradiation energy is set to a low level, it is possible to obtain radiographic image information having the same grayscale range as during normal operation thereof. Consequently, a radiographic moving image acquired even at the low irradiation energy level, which is displayed during the recovery watching period Tb, can effectively be used for observation or diagnosis. During the recovery watching period Tb, the readout mode of the radiation detecting device 30 is set to an interlace mode, for example. Therefore, the burden imposed on the signal processing system of the radiation detecting device 30 for reading stored electric charges is reduced, thereby reducing the risk of suffering from a reoccurring error.
[0113] At the time that the radiographic image capturing apparatus 12 is judged as having recovered from an error, the system control portion 14 may supply a command to the automatic collimating portion 38 for reducing the area irradiated with radiation 26 , so that the area irradiated with radiation 26 can be reduced during the recovery watching period Tb. In this manner, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced.
[0114] A radiographic image capturing system according to a second embodiment of the present invention (hereinafter referred to as a “second radiographic image capturing system 10 B”) will be described below with reference to FIGS. 8 through 10 .
[0115] The second radiographic image capturing system 10 B essentially is of the same configuration as the first radiographic image capturing system 10 A, but differs therefrom in that, instead of the low radiation dose setting portion 112 , the second radiographic image capturing system 10 B has a low frame rate setting portion 120 for setting a low frame rate during the recovery watching period Tb. The low frame rate setting portion 120 sets a frame rate to a level that is in a range from ⅓ to ⅔ of the latest frame rate Fr stored in the parameter history storage portion 102 . The low frame rate setting portion 120 may alternatively set a frame rate to a lower ratio, e.g., ⅕ to ⅘. In order to distinguish from the latest frame rate Fr, the frame rate set by the low frame rate setting portion 120 will be referred to as a “low frame rate Fra”.
[0116] The processing sequence of the second radiographic image capturing system 10 B also differs as to the processes carried out in steps S 22 through S 29 of FIG. 6 , which have been described above.
[0117] More specifically, in step S 101 of FIG. 9 , the low frame rate setting portion 120 of the recovery processing portion 110 sets a low frame rate as described above.
[0118] In step S 102 , the recovery processing portion 110 supplies second dose setting information Sa 2 , which includes information (tube voltage, tube current, image capturing time, etc.) concerning the latest radiation dose stored in the parameter history storage portion 102 and information concerning the low radiation dose that has been set, to the radiation device 28 . Based on the second dose setting information Sa 2 from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 sets a radiation dose, a frame rate, etc.
[0119] In step S 103 , the recovery processing portion 110 supplies second readout control information Sb 2 , which includes information concerning the gain setting information and the readout mode information upon recovery, through the detecting device control portion 32 to the radiation detecting device 30 . Based on the supplied second readout control information Sb 2 , the radiation detecting device 30 sets the gain for the charge amplifiers 66 , and the type of address signal and the output timing for the address signal generating portion 80 .
[0120] In step S 104 , the system control portion 14 judges whether or not the period corresponding to the low frame rate Fra has elapsed from the start time of the previous radiographic image capturing process. During a time period corresponding to the low frame rate Fra, which is elapsing or has elapsed from the start time of the previous radiographic image capturing process, control proceeds to the next step S 105 , in which the recovery processing portion 110 supplies an exposure start signal Sd to the radiation device 28 .
[0121] In step S 106 , based on the exposure start signal Sd supplied from the system control portion 14 , the radiation source control portion 36 of the radiation device 28 controls the automatic collimating portion 38 in order to reduce the area irradiated with the radiation 26 , so as to lie within a range from ¼ to 1/10 of the area irradiated with the radiation 26 immediately prior to the occurrence of the error. The reduction ratio is set in advance by way of simulation or experimentation depending on the body region to be imaged.
[0122] In step S 107 , based on the supplied exposure start signal Sd, the radiation source control portion 36 of the radiation device 28 controls the radiation source 34 to emit radiation 26 at the set radiation dose in a kth radiographic image capturing process.
[0123] In step S 108 , the system control portion 14 sends an exposure notification Sf to the detecting device control portion 32 , which indicates the start of exposure by the radiation device 28 .
[0124] In step S 109 , based on the supplied exposure notification Sf, the detecting device control portion 32 supplies an operation start signal Sg, which represents the storage of electric charges and the readout of electric charges, to the radiation detecting device 30 .
[0125] In step S 110 , the radiation detecting device 30 stores electric charges and reads out electric charges based on the operation start signal Sg supplied from the detecting device control portion 32 . This operation of the radiation detecting device 30 is the same as the operation thereof in step S 26 of FIG. 6 . According to the second embodiment, the gain of the charge amplifiers 66 is not changed, but remains the same as the gain immediately prior to the occurrence of the error.
[0126] At the start time of the readout period, the radiation detecting device 30 supplies a synchronizing signal Sh (e.g., a vertical synchronizing signal). In the readout period, the radiation detecting device 30 reads the electric charges according to the instructed readout control information, i.e., an interlace mode or the like, and supplies radiographic image information Da in a FIFO mode, for example, from the memory 82 . The radiographic image information Da from the radiation detecting device 30 is supplied through the detecting device control portion 32 to the system control portion 14 .
[0127] In step S 111 , the system control portion 14 transfers the supplied radiographic image information Da to the console 16 . The console 16 stores the transferred radiographic image information Da in the frame memory, and displays the radiographic image information Da as a radiographic image captured by a kth radiographic image capturing process, i.e., as a radiographic image in a kth frame, on the monitor 18 .
[0128] According to the example shown in FIG. 10 , at the start time tn+1 of the (N+1)th radiographic image capturing process, for example, after recovery from the error, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while also supplying an exposure notification Sf to the detecting device control portion 32 . Then, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+1)th radiographic image capturing process (carried out with the latest radiation dose). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+1)th frame on the monitor 18 . Upon elapse of a period corresponding to a low frame rate Fra from the start time tn+1 of the (N+1)th radiographic image capturing process, i.e., at the start time tn+2 of the (N+2)th radiographic image capturing process, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 while also supplying an exposure notification Sf to the detecting device control portion 32 . The system control portion 14 is then supplied with radiographic image information Da acquired by the (N+2)th radiographic image capturing process (carried out with the latest radiation dose). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays the radiographic image information Da as a radiographic image in an (N+2)th frame on the monitor 18 . The above process is repeated to display a radiographic moving image on the monitor 18 after recovery from the error.
[0129] In step S 112 , the value of the counter k is updated by +1.
[0130] In step S 113 , the system control portion 14 judges whether or not a predetermined recovery watching period Tb has elapsed from recovery from the error. In a case where the predetermined recovery watching period Tb has not elapsed, control returns to step S 104 , and the process from step S 104 is repeated. In a case where the predetermined recovery watching period Tb has elapsed, control proceeds to step S 30 , in which the system control portion 14 controls the radiographic image capturing apparatus 12 to perform an ordinary radiographic image capturing process. For example, the radiographic image capturing apparatus 12 performs a radiographic image capturing process at the irradiation energy (radiation dose, frame rate) set by the operator, or at the irradiation energy set immediately prior to the occurrence of an error.
[0131] With the second radiographic image capturing system 10 B, similar to the first radiographic image capturing system 10 A, in a case where an error has occurred in at least the radiographic image capturing apparatus 12 , the radiation source 34 is controlled to stop emission of radiation. In a case where the radiographic image capturing apparatus 12 has recovered from the error, the radiographic image capturing apparatus 12 continues to perform a radiographic image capturing process at the set low frame rate Fra. In addition, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced.
[0132] In particular, according to the second radiographic image capturing system 10 B, upon recovery from an error, the radiation source 34 applies radiation having the latest radiation dose during normal operation. Therefore, the sensitivity of the radiation detecting device 30 is prevented from being lowered, and the radiation detecting device 30 can acquire radiographic image information having the same grayscale range as during normal operation. Consequently, a radiographic moving image, which is displayed during the recovery watching period Tb, can effectively be used for observation or diagnosis.
[0133] Furthermore, during the period (recovery watching period Tb) from recovery from the error to restoration of the ordinary radiographic image capturing process, since the area to be irradiated with radiation 26 is reduced, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced.
[0134] A radiographic image capturing system according to a third embodiment of the present invention (hereinafter referred to as a “third radiographic image capturing system 100 ”) will be described below with reference to FIG. 11 .
[0135] The third radiographic image capturing system 100 has a configuration, which combines features from the first radiographic image capturing system 10 A and the second radiographic image capturing system 10 B.
[0136] More specifically, as shown in FIG. 11 , a system control portion 14 includes a low radiation dose setting portion 112 and a low frame rate setting portion 120 .
[0137] The processing sequence of the third radiographic image capturing system′ 100 is similar to the processing sequence of the second radiographic image capturing system 10 B, but differs therefrom in the following ways.
[0138] The processing sequence of the third radiographic image capturing system 100 differs from the processing sequence of the second radiographic image capturing system 10 B, in that in step S 19 of FIG. 6 , the low radiation dose setting portion 112 sets the dose of a radiation per irradiation event from the radiation source 34 to a level lower than the radiation dose per irradiation event immediately prior to the occurrence of the error (latest radiation dose), and the low frame rate setting portion 120 sets a low frame rate during the recovery watching period Tb. In addition, in step S 22 , the system control portion 14 judges whether or not the period corresponding to the low frame rate Fra has elapsed from the start time of the previous radiographic image capturing process.
[0139] The third radiographic image capturing system 100 offers the same advantages as those of the first radiographic image capturing system 10 A and the second radiographic image capturing system 10 B.
[0140] In particular, since the radiation dose is set to a preset low radiation dose and the frame rate is set to a preset low frame rate Fra for carrying out the radiographic image capturing process upon recovery from the error, the risk of suffering from a reoccurring error is reduced, and the third radiographic image capturing system 100 can quickly be brought back to a state that enables capturing of a radiographic moving image. In addition, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced. At the time that the radiographic image capturing apparatus 12 is judged as having recovered from an error, the system control portion 14 may supply a command to the automatic collimating portion 38 in order to reduce the area irradiated with radiation 26 , so that the area irradiated with radiation 26 can be reduced during the recovery watching period Tb.
[0141] A radiographic image capturing system according to a fourth embodiment of the present invention (hereinafter referred to as a “fourth radiographic image capturing system 10 D”) will be described below with reference to FIGS. 12 and 13 .
[0142] The fourth radiographic image capturing system 10 D essentially is of the same configuration as the third radiographic image capturing system 100 , but differs therefrom in that the recovery processing portion 110 sets the irradiation energy level to a lowest irradiation energy level from among a plurality of irradiation energy levels set within a predetermined period in the past.
[0143] Specifically, the fourth radiographic image capturing system 10 D differs in that the fourth radiographic image capturing system 10 D has a second low radiation dose setting portion 112 B and a second low frame rate setting portion 120 B.
[0144] The second low radiation dose setting portion 112 B reads the lowest radiation dose from among a plurality of radiation doses during a predetermined period in the past, which are stored in the parameter history storage portion 102 , and sets the read lowest radiation dose as a low radiation dose during the recovery watching period Tb.
[0145] The second low frame rate setting portion 120 B reads the lowest frame rate from among a plurality of frame rates during a predetermined period in the past, which are stored in the parameter history storage portion 102 , and sets the read lowest frame rate as a low frame rate during the recovery watching period Tb.
[0146] The processing sequence of the fourth radiographic image capturing system 10 D essentially is the same as the processing sequence of the third radiographic image capturing system 10 C described above, and hence redundant descriptions will be omitted. As shown in FIG. 13 , in a case where from among the radiographic image capturing processes carried out in a predetermined period in the past, an (N−i−1)th radiographic image capturing process, for example, has a lowest radiation dose and a lowest frame rate Frb, then at the start time tn+1 of an (N+1)th radiographic image capturing process after recovery from the error, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 , and supplies an exposure notification Sf to the detecting device control portion 32 . Then, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+1)th radiographic image capturing process (the radiographic image capturing process carried out with the radiation dose in the (N−i−1)th radiographic image capturing process). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays a radiographic image in an (N+1)th frame on the monitor 18 . At the time (start time tn+2 of a next (N+2)th radiographic image capturing process) that a period corresponding to the lowest frame rate Frb in the (N−i−1)th radiographic image capturing process has elapsed from the start time of the (N+1)th radiographic image capturing process, the system control portion 14 supplies an exposure start signal Sd to the radiation device 28 , and supplies an exposure notification Sf to the detecting device control portion 32 . Then, the system control portion 14 is supplied with radiographic image information Da acquired by the (N+2)th radiographic image capturing process (the radiographic image capturing process carried out with the radiation dose in the (N−i−1)th radiographic image capturing process). The system control portion 14 transfers the supplied radiographic image information Da to the console 16 , which displays a radiographic image in an (N+2)th frame on the monitor 18 . The above process is repeated to display a radiographic moving image on the monitor 18 .
[0147] Similar to the third radiographic image capturing system 10 C, the fourth radiographic image capturing system 10 D offers the same advantages as those of the first radiographic image capturing system 10 A and the second radiographic image capturing system 10 B.
[0148] In particular, the radiation dose is set to a lowest radiation dose from among the radiation doses of the radiographic image capturing processes carried out during a predetermined period in the past from the time that an error has occurred. In addition, the frame rate is set to the lowest frame rate Frb from among the frame rates of the radiographic image capturing processes carried out in the predetermined period in the past from the time at which an error has occurred. Thereafter, radiographic image capturing processes are carried out with the lowest radiation dose and the lowest frame rate Frb. Consequently, it is possible to use radiation doses and frame rates, which have proven to be effective. Therefore, the risk of suffering from a reoccurring error is reduced, and the fourth radiographic image capturing system 10 D can quickly be brought back to a state for capturing a radiographic moving image. In addition, the burden posed on the subject 24 due to undue exposure to radiation 26 is reduced.
[0149] In the fourth radiographic image capturing system 10 D, the recovery processing portion 110 includes the second low radiation dose setting portion 112 B and the second low frame rate setting portion 120 B. However, either one of the second low radiation dose setting portion 112 B and the second low frame rate setting portion 120 B may be dispensed with.
[0150] In a case where the second low frame rate setting portion 120 B is dispensed with, and only the second low radiation dose setting portion 112 B is used, then similar to the case of the first radiographic image capturing system 10 A, the fourth radiographic image capturing system 10 D may use the latest frame rate Fr. Alternatively, similar to the case of the second radiographic image capturing system 10 B, the fourth radiographic image capturing system 10 D may include the low frame rate setting portion 120 and use the low frame rate Fra set by the low frame rate setting portion 120 .
[0151] Similarly, in a case where the second low radiation dose setting portion 112 B is dispensed with, and only the second low frame rate setting portion 120 B is used, then similar to the case of the second radiographic image capturing system 10 B, the fourth radiographic image capturing system 10 D may use the latest radiation dose. Alternatively, similar to the case of the first radiographic image capturing system 10 A, the fourth radiographic image capturing system 10 D may include the low radiation dose setting portion 112 and use the low radiation dose set by the low radiation dose setting portion 112 .
[0152] With the first radiographic image capturing system 10 A, the second radiographic image capturing system 10 B, the third radiographic image capturing system 10 C, and the fourth radiographic image capturing system 10 D, during the recovery watching period Tb, the dose of radiation 26 from the radiation source 34 per irradiation event is set to a level that is lower than the dose of radiation 26 from the radiation source 34 per irradiation event prior to the occurrence of the error. In addition, the number of irradiation events per unit time performed by the radiation source 34 is set to a value that is lower than the number of irradiation events per unit time prior to the occurrence of the error. Accordingly, radiographic image capturing processes are performed with the radiation dose and the number of irradiation events that have been set in the foregoing manner. Alternatively, during the recovery watching period Tb, the total irradiation energy level per unit of the radiation source 34 may be set to a low level, and radiation may be emitted continuously from the radiation source 34 during the radiographic image capturing process.
[0153] The radiographic image capturing systems and the radiographic image capturing methods according to the present invention are not limited to the aforementioned embodiments. Various arrangements may be adopted without departing from the scope of the present invention.
[0154] For example, the radiation detector 40 may comprise a radiation detector 600 according to the modification shown in FIGS. 14 and 15 . FIG. 14 is a schematic cross-sectional view of three pixel portions of the radiation detector 600 according to such a modification.
[0155] As shown in FIG. 14 , the radiation detector 600 includes a signal output portion 604 , a sensor portion 606 (photoelectric transducer), and a scintillator 608 , which are deposited successively on an insulating substrate 602 . The signal output portion 604 and the sensor portion 606 jointly make up a pixel portion. The radiation detector 600 includes a matrix of pixel portions arrayed on the insulating substrate 602 . In each of the pixel portions, the signal output portion 604 is superposed on the sensor portion 606 .
[0156] The scintillator 608 is disposed over the sensor portion 606 with a transparent insulating film 610 interposed between the scintillator 608 and the sensor portion 606 . The scintillator 608 is in the form of a phosphor film, which emits light converted from radiation 26 that is applied from above (from a side opposite to the substrate 602 ). Light emitted by the scintillator 608 preferably has a visible wavelength range (from 360 nm to 830 nm). In a case where the radiation detector 600 is used to capture a monochromatic image, then the light emitted by the scintillator 608 preferably includes a green wavelength range.
[0157] In a case where X-rays are used as the radiation 26 , then the phosphor used in the scintillator 608 preferably includes cesium iodide (CsI), and more preferably, includes CsI(Tl) (thallium-added cesium iodide) which, in a case where irradiated with X-rays, emits light in a wavelength spectrum ranging from 420 nm to 700 nm. Light emitted from CsI(Tl) exhibits a peak wavelength of 565 nm in the visible range.
[0158] The scintillator 608 may be formed by depositing CsI(Tl) having a columnar crystalline structure on an evaporation base. In a case where the scintillator 608 is formed by such an evaporation process, then the evaporation base is preferably, but not necessarily, made of Al from the standpoints of X-ray transmittance and reducing cost. In a case where the scintillator 608 is made of GOS, then an evaporation base need not be used, but in this case, the surface of a TFT active matrix substrate may be coated with GOS to form the scintillator 608 . Alternatively, a resin base may be coated with GOS to form the scintillator 608 , and the scintillator 608 may then be applied to the surface of a TFT active matrix substrate. In this manner, the TFT active matrix substrate can be preserved in the event of a failure of the GOS coating.
[0159] The sensor portion 606 includes an upper electrode 612 , a lower electrode 614 , and a photoelectric conversion film 616 , which is disposed between the upper electrode 612 and the lower electrode 614 .
[0160] Since light emitted by the scintillator 608 must be applied to the photoelectric conversion film 616 , the upper electrode 612 preferably is made of an electrically conductive material, which is transparent at least to the wavelength of light emitted by the scintillator 608 . More specifically, the upper electrode 612 preferably is made of a transparent conducting oxide (TCO), which exhibits a high transmittance with respect to visible light and has a small resistance value. Although the upper electrode 612 may be made of a thin metal film such as Au or the like, TCO is preferable thereto, because Au tends to have an increased resistance value and exhibits a transmittance of 90% or higher. For example, ITO, IZO, AZO, FTO, SnO 2 , TiO 2 , ZnO 2 , or the like preferably is used as the material of the upper electrode 612 . Among these materials, ITO is the most preferable from the standpoints of process simplification, low resistance, and transparence. The upper electrode 612 may be a single electrode, which is shared by all of the pixel portions, or may be a plurality of electrodes, each of which are assigned to respective pixel portions.
[0161] The photoelectric conversion film 616 , which contains an organic photoconductor (OPC), absorbs light emitted from the scintillator 608 , and generates electric charges depending on the absorbed light. A photoelectric conversion film 616 that contains an organic photoconductor (organic photoelectric conversion material), exhibits a sharp absorption spectrum in the range of visible light and does not absorb electromagnetic waves other than light emitted from the scintillator 608 . Therefore, any noise produced upon absorption of radiation 26 by the photoelectric conversion film 616 is effectively minimized. The photoelectric conversion film 616 may contain amorphous silicon instead of an organic photoconductor. A photoelectric conversion film 616 that contains amorphous silicon exhibits a wide absorption spectrum for efficiently absorbing light emitted from the scintillator 608 .
[0162] In order for the organic photoconductor of the photoelectric conversion film 616 to absorb light emitted by the scintillator 608 most efficiently, the absorption peak wavelength thereof should be as close as possible to the light emission peak wavelength of the scintillator 608 . Although ideally the absorption peak wavelength of the organic photoconductor and the light emission peak wavelength of the scintillator 608 should be in agreement with each other, it is possible for the light emitted by the scintillator 608 to be absorbed efficiently in a case where the difference between the absorption peak wavelength and the light emission peak wavelength is sufficiently small. More specifically, the difference between the absorption peak wavelength of the organic photoconductor and the light emission peak wavelength of the scintillator 608 with respect to the radiation 26 preferably is 10 nm or smaller, and more preferably, is 5 nm or smaller.
[0163] Organic photoconductors that meet the above requirements include quinacridone-based organic compounds and phthalocyanine-based organic compounds. Since quinacridone has an absorption peak wavelength of 560 nm in the visible range, in a case where quinacridone is used as the organic photoelectric conversion material and CsI(Tl) is used as the material of the scintillator 608 , the difference between the aforementioned peak wavelengths can be reduced to 5 nm or smaller, thus making it possible to substantially maximize the amount of electric charges generated by the photoelectric conversion film 616 .
[0164] The sensor portion 606 includes an organic layer formed by superposition or mixture of an electromagnetic wave absorption region, a photoelectric conversion region, an electron transport region, a hole transport region, an electron blocking region, a hole blocking region, a crystallization preventing region, an electrode, and an interlayer contact improving region, etc. The organic layer preferably includes an organic p-type compound (organic p-type semiconductor) or an organic n-type compound (organic n-type semiconductor).
[0165] An organic p-type semiconductor is a donor organic semiconductor (compound) mainly typified by a hole-transporting organic compound, and refers to an organic compound that tends to donate electrons. More specifically, in a case where two organic materials are placed in contact with each other, one of the organic materials, which has a lower ionization potential, is referred to as a donor organic compound. Any electron-donating organic compounds can be used as the donor organic compound.
[0166] An organic n-type semiconductor is an acceptor organic semiconductor (compound) mainly typified by an electron-transporting organic compound, and refers to an organic compound that tends to accept electrons. More specifically, in a case where two organic materials are placed in contact with each other, one of the organic materials, which has a larger electron affinity, is referred to as an acceptor organic compound. Any electron-accepting organic compounds can be used as the acceptor organic compound.
[0167] Materials capable of being used as the organic p-type semiconductor and the organic n-type semiconductor, and arrangements thereof with the photoelectric conversion film 616 are disclosed in detail in Japanese Laid-Open Patent Publication No. 2009-032854, and such features will not be described in detail below. The photoelectric conversion film 616 may contain fullerene or carbon nanotubes.
[0168] The thickness of the photoelectric conversion film 616 should be as large as possible for the purpose of absorbing light from the scintillator 608 . However, in a case where the thickness of the photoelectric conversion film 616 is greater than a certain value, the intensity of the electric field produced on the photoelectric conversion film 616 , which is formed by a bias voltage applied from opposite ends of the photoelectric conversion film 616 , becomes reduced and the photoelectric conversion film 616 is unable to collect electric charges. The thickness of the photoelectric conversion film 616 preferably is in a range from 30 nm to 300 nm, more preferably, is in a range from 50 nm to 250 nm, and particularly preferably, is in a range from 80 nm to 200 nm.
[0169] The illustrated photoelectric conversion film 616 , which is shared by all of the pixel portions, may be divided into a plurality of films assigned to respective pixel portions. The lower electrode 614 comprises a plurality of thin films assigned to respective pixel portions. However, the lower electrode 614 may be a single thin film that is shared by all of the pixel portions. The lower electrode 614 may be made of a transparent or opaque electrically conductive material, preferably aluminum, silver, or the like. The thickness of the lower electrode 614 may be in a range from 30 nm to 300 nm.
[0170] In a case where a prescribed bias voltage is applied between the upper electrode 612 and the lower electrode 614 , the sensor portion 606 moves one type of electric charges (holes or electrons) that are generated in the photoelectric conversion film 616 toward the upper electrode 612 , and moves the other type of electric charges toward the lower electrode 614 . With the radiation detector 600 according to the present modification, an interconnection is connected to the upper electrode 612 for applying the bias voltage through the interconnection to the upper electrode 612 . The bias voltage has a polarity, which is set to move the electrons generated in the photoelectric conversion film 616 toward the upper electrode 612 , and to move the holes toward the lower electrode 614 . However, the bias voltage may be of an opposite polarity.
[0171] The sensor portion 606 of each pixel portion may include at least the lower electrode 614 , the photoelectric conversion film 616 , and the upper electrode 612 . For preventing dark current from increasing, the sensor portion 606 preferably additionally includes either an electron blocking film 618 or a hole blocking film 620 , and more preferably, includes both the electron blocking film 618 and the hole blocking film 620 .
[0172] The electron blocking film 618 may be disposed between the lower electrode 614 and the photoelectric conversion film 616 . In a case where a bias voltage is applied between the lower electrode 614 and the upper electrode 612 , the electron blocking film 618 can prevent electrons from being injected from the lower electrode 614 into the photoelectric conversion film 616 , thereby preventing dark current from increasing.
[0173] The electron blocking film 618 may be made of an electron-donating organic material. The electron blocking film 618 actually is made of a material, which is selected depending on the material of the electrode and the material of the photoelectric conversion film 616 adjacent thereto. A preferable material has an electron affinity (Ea), which is at least 1.3 eV greater than the work function (Wf) of the material of the electrode adjacent thereto, and an ionization potential (Ip), which is equal to or smaller than the Ip of the material of the photoelectric conversion film 616 adjacent thereto. Materials usable as an electron-donating organic material are disclosed in detail in Japanese Laid-Open Patent Publication No. 2009-032854, and such materials will not be described in detail below.
[0174] The thickness of the electron blocking film 618 preferably is in a range from 10 nm to 200 nm, more preferably, is in a range from 30 nm to 150 nm, and particularly preferably, is in a range from 50 nm to 100 nm, in order to reliably achieve a dark current reducing capability and to prevent the photoelectric conversion efficiency of the sensor portion 606 from being lowered.
[0175] The hole blocking film 620 may be disposed between the photoelectric conversion film 616 and the upper electrode 612 . In a case where a bias voltage is applied between the lower electrode 614 and the upper electrode 612 , the hole blocking film 620 can prevent holes from being injected from the upper electrode 612 into the photoelectric conversion film 616 , thereby preventing dark current from increasing.
[0176] The hole blocking film 620 may be made of an electron-accepting organic material. The thickness of the hole blocking film 620 preferably is in a range from 10 nm to 200 nm, more preferably, is in a range from 30 nm to 150 nm, and particularly preferably, is in a range from 50 nm to 100 nm, in order to reliably achieve a dark current reducing capability and to prevent the photoelectric conversion efficiency of the sensor portion 606 from being lowered.
[0177] The hole blocking film 620 actually is made of a material, which is selected depending on the material of the electrode and the material of the photoelectric conversion film 616 adjacent thereto. A preferable material has an ionization potential (Ip), which is at least 1.3 eV greater than the work function (Wf) of the material of the electrode adjacent thereto, and an electron affinity (Ea), which is equal to or greater than the Ea of the material of the photoelectric conversion film 616 adjacent thereto. Materials usable as an electron-accepting organic material are disclosed in detail in Japanese Laid-Open Patent Publication No. 2009-032854, and such materials will not be described in detail below.
[0178] For setting a bias voltage so as to move holes, from among the electric charges generated in the photoelectric conversion film 616 , toward the upper electrode 612 , and to move electrons, from among the electric charges generated in the photoelectric conversion film 616 , toward the lower electrode 614 , the electron blocking film 618 and the hole blocking film 620 may be switched in position. It is not necessary to provide both the electron blocking film 618 and the hole blocking film 620 . Either one of the electron blocking film 618 and the hole blocking film 620 may be included in order to provide a certain dark current reducing capability.
[0179] As shown in FIG. 15 , the signal output portion 604 is disposed on the surface of the substrate 602 in alignment with the lower electrode 614 of each pixel portion. The signal output portion 604 includes a storage capacitor 622 for storing electric charges that have moved to the lower electrode 614 , and a TFT 624 for converting electric charges stored in the storage capacitor 622 into electric signals and supplying the electric signals. The storage capacitor 622 and the TFT 624 are disposed in a region that lies underneath the lower electrode 614 as viewed in plan. Such a structure arranges the signal output portion 604 and the sensor portion 606 in a superposed relation in each pixel portion in a thicknesswise direction. In a case where the signal output portion 604 is formed such that the lower electrode 614 fully covers the storage capacitor 622 and the TFT 624 , then the planar area of the radiation detector 600 (pixel portions) is minimized.
[0180] The storage capacitor 622 is connected electrically to the corresponding lower electrode 614 by an electrically conductive interconnection, which extends through an insulating film 626 that is interposed between the substrate 602 and the lower electrode 614 . The interconnection permits electric charges, which are collected by the lower electrode 614 , to move to the storage capacitor 622 .
[0181] The TFT 624 includes a stacked assembly made up of a gate electrode 628 , a gate insulating film 630 , and an active layer (channel layer) 632 . A source electrode 634 and a drain electrode 636 are disposed on the active layer 632 and are spaced from each other with a gap therebetween. The active layer 632 may be made of amorphous silicon, an amorphous oxide, an organic semiconductor material, carbon nanotubes, or the like, for example, although the active layer 632 is not limited to such materials.
[0182] The amorphous oxide that constitutes the active layer 632 preferably is an oxide (e.g., In—O oxide) including at least one of In, Ga, and Zn, more preferably, is an oxide (e.g., In—Zn—O oxide, In—Ga—O oxide, or Ga—Zn—O oxide) including at least two of In, Ga, and Zn, and particularly preferably, is an oxide including In, Ga, and Zn. An In—Ga—Zn—O amorphous oxide preferably is an amorphous oxide the crystalline composition of which is represented by InGaO 3 (ZnO) m where m represents a natural number smaller than 6, and particularly preferably, is InGaZnO 4 . However, the amorphous oxide that constitutes the active layer 632 is not limited to the aforementioned materials.
[0183] The organic semiconductor material that constitutes the active layer 632 may be made of a phthalocyanine compound, pentacene, vanadyl phthalocyanine, or the like, although the organic semiconductor material is not limited to such materials. Details concerning the phthalocyanine compound, for example, are disclosed in detail in Japanese Laid-Open Patent Publication No. 2009-212389, and such features will not be described in detail below.
[0184] In a case where the active layer 632 including the TFT 624 is made of an amorphous oxide, an organic semiconductor material, or carbon nanotubes, then since the active layer 632 does not absorb radiation 26 such as X-rays or the like, or only absorbs trace amounts of radiation 26 , it is possible to effectively reduce noise produced in the signal output portion 604 .
[0185] In a case where the active layer 632 is made of carbon nanotubes, then the switching rate of the TFT 624 is increased, and the TFT 624 absorbs light in the visible range at a low rate. However, in a case where the active layer 632 is made of carbon nanotubes, it is necessary to separate and extract highly pure carbon nanotubes by way of centrifugal separation or the like, because the performance of the TFT 624 will be greatly reduced in a case where trace metallic impurities become trapped in the active layer 632 .
[0186] The amorphous oxide, the organic semiconductor material, the carbon nanotubes, and the organic semiconductor material described above can be deposited as films at low temperatures. Therefore, the substrate 602 is not limited to being a highly heat-resistant substrate such as a semiconductor substrate, a quartz substrate, a glass substrate, or the like, but may be a flexible substrate made of plastic, a substrate of aramid fibers, or a substrate of bionanofibers. More specifically, the substrate 602 may be a flexible substrate of polyester such as polyethylene terephthalate, polybutylene phthalate, polyethylene naphthalate, or the like, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, or the like. The flexible substrate enables the radiation detector 600 to be light in weight and hence easy to carry.
[0187] By making the photoelectric conversion film 616 from an organic photoconductor and making the TFT 624 from an organic semiconductor material, it is possible to grow the photoelectric conversion film 616 and the TFT 624 at a low temperature on a flexible substrate made of plastic (substrate 602 ), as well as to make the radiation detector 600 thin and lightweight overall. The radiation detecting device 30 , which houses the radiation detector 600 therein, can also be make thin and lightweight for making the radiation detecting device 30 more convenient to use outside of hospitals. Since the base of the photoelectric transducing portion is made of a flexible material, which differs from general glass, the radiation detecting device 30 is highly resistant to damage during times that the radiation detecting device 30 is carried or is placed in use.
[0188] The substrate 602 may include an insulating layer for making the substrate 602 electrically insulative, a gas barrier layer for making the substrate 602 impermeable to water and oxygen, and an undercoat layer for making the substrate 602 flat or to improve intimate contact thereof with the electrode.
[0189] Aramid fibers for use as the substrate 602 are advantageous in that, since a high-temperature process at 200 degrees Celsius can be applied thereto, aramid fibers allow a transparent electrode material to be set at a high temperature for exhibiting lower resistance. Aramid fibers also allow driver ICs to be automatically mounted thereon by a process including a solder reflow process. Furthermore, inasmuch as aramid fibers have a coefficient of thermal expansion close to that of ITO (Indium Tin Oxide) and glass, a substrate made of aramid fibers is less likely to warp and crack after fabrication. In addition, a substrate made of aramid fibers may be made thinner than a glass substrate or the like. The substrate 602 may be in the form of a stacked assembly, which is constituted from aramid fibers and an ultrathin glass substrate.
[0190] Bionanofibers are made by compounding a bundle of cellulose microfibrils (bacteria cellulose) produced by bacteria (acetic acid bacteria, Acetobacter Xylinum ) and a transparent resin. The bundle of cellulose microfibrils has a width of 50 nm, which is 1/10 of the wavelength of visible light, is highly strong and highly resilient, and is subject to low thermal expansion. Bionanofibers that contain 60% to 70% of fibers and exhibit a light transmittance of about 90% at a wavelength of 500 nm can be produced by impregnating bacteria cellulose with a transparent resin such as an acrylic resin, an epoxy resin, or the like and setting the transparent resin. Bionanofibers have a low coefficient of thermal expansion ranging from 3 ppm to 7 ppm, which is comparable to silicon crystals, a high strength of 460 MPa that matches the strength of steel, a high resiliency of 30 GPa, and are flexible. Therefore, in a case where the substrate 602 is made of bionanofibers, the substrate 602 can be thinner than glass substrates or the like.
[0191] According to the present modification, the signal output portion 604 , the sensor portion 606 , and the transparent insulating film 610 are formed successively on the substrate 602 . Thereafter, the scintillator 608 is bonded above the substrate 602 by an adhesive resin that exhibits low light absorption, thereby completing the radiation detector 600 .
[0192] With the radiation detector 600 according to the above modification, since the photoelectric conversion film 616 is made of an organic photoconductor and the active layer 632 that includes the TFT 624 is made of an organic semiconductor material, the photoelectric conversion film 616 and the signal output portion 604 absorb almost no radiation 26 . Therefore, any reduction in sensitivity to radiation 26 is minimized.
[0193] The organic semiconductor material, which includes the active layer 632 made up of the TFT 624 , and the organic photoconductor, which includes the photoelectric conversion film 616 , can be grown as films at low temperature. Therefore, the substrate 602 can be made from plastic resin, aramid fibers, or bionanofibers, which absorb only a small amount of radiation 26 . Thus, any reduction in sensitivity to radiation 26 can be further minimized.
[0194] In a case where the radiation detector 600 is placed in the housing and is bonded to the wall that forms the irradiation surface, and in a case where the substrate 602 is made of plastic resin, aramid fibers, or bionanofibers, which are highly rigid, then since the radiation detector 600 exhibits increased rigidity, the wall of the housing that forms the irradiation surface can be made thinner. Further, in a case where the substrate 602 is made of plastic resin, aramid fibers, or bionanofibers, which are highly rigid, then since the radiation detector 600 itself is flexible, the radiation detector 600 is less likely to become damaged as a result of impacts applied to the irradiation surface.
[0195] The radiation detector 600 may be arranged in the following ways.
[0196] (1) The photoelectric conversion film 616 may be made of an organic photoconductor material, and the TFT layer 638 may be constructed to incorporate CMOS sensors therein. Since only the photoelectric conversion film 616 is made of an organic photoconductor material, the TFT layer 638 including the CMOS sensors may not be flexible.
[0197] (2) The photoelectric conversion film 616 may be made of an organic photoconductor material, and the TFT layer 638 may be made flexible by incorporating CMOS circuits having TFTs 624 made of an organic material. The CMOS circuits employ a p-type organic semiconductor material made of pentacene, and an n-type organic semiconductor material made of fluorinated copper phthalocyanine (F 16 CuPc). In a case where made in this manner, the TFT layer 638 is flexible and can be bent to a smaller radius of curvature, and the TFT layer 638 is effective to significantly reduce the thickness of the gate insulating film, thereby resulting in a lower drive voltage. Furthermore, the gate insulating film, the semiconductor, and the electrodes can be fabricated at room temperature or temperatures that are equal to or lower than 100° C. The CMOS circuits may directly be fabricated on the flexible insulative substrate 602 . The TFTs 624 , which are made of an organic material, may be microfabricated by a fabrication process according to a scaling law. The substrate 602 may be produced as a flat substrate, which is free of surface irregularities, by coating a thin polyimide substrate with a polyimide precursor, and then heating the applied polyimide precursor to convert the same into polyimide.
[0198] (3) The photoelectric conversion film 616 and the TFTs 624 , which are made of crystalline Si, may be fabricated on the substrate 602 as a resin substrate by a fluidic self-assembly process. The fluidic self-assembly process allows a plurality of device blocks on the order of microns to be placed at designated positions on the substrate 602 . More specifically, the photoelectric conversion film 616 and the TFTs 624 , which are constituted as device blocks on the order of microns, are prefabricated on another substrate and then separated from the substrate. Then, the photoelectric conversion film 616 and the TFTs 624 are dipped in a liquid and are spread onto the substrate 602 as a target substrate, so as to be statistically placed in respective positions. The substrate 602 is processed in advance to adapt itself to the device blocks, so that the device blocks can be placed selectively on the substrate 602 . Accordingly, the device blocks, i.e., the photoelectric conversion film 616 and the TFTs 624 , which are made of an optimum material, can be integrated on an optimum substrate such as a semiconductor substrate, a quartz substrate, a glass substrate, or the like. Therefore, it is possible to integrate optimum device blocks, i.e., the photoelectric conversion film 616 and the TFTs 624 , on a non-crystalline substrate such as a flexible substrate made of plastic.
[0199] The radiation detector 600 according to the above modification is constructed as a PSS (Penetration Side Sampling) type, i.e., a reverse-side readout type, of radiation detector, in which the sensor portion 606 (the photoelectric conversion film 616 ), which is positioned remotely from the radiation source 34 , converts light emitted from the scintillator 608 into electric charges in order to read a radiographic image. However, the radiation detector 600 is not limited to a PSS type of radiation detector.
[0200] A radiation detector may be constructed as an ISS (Irradiation Side Sampling) type, i.e., a face-side readout type, of radiation detector. In such an ISS type of radiation detector, the substrate 602 , the signal output portion 604 , the sensor portion 606 , and the scintillator 608 are stacked in this order along the direction in which radiation 26 is applied. Further, the sensor portion 606 , which is positioned close to the radiation source 34 , converts light emitted from the scintillator 608 into electric charges in order to read a radiographic image. Since the scintillator 608 usually emits stronger light from the irradiation surface that is irradiated with radiation 26 than from the rear surface thereof, the distance that the light emitted from the scintillator 608 travels until the light reaches the photoelectric conversion film 616 is shorter in a face-side readout type than in a reverse-side readout type of radiation detector. Therefore, the emitted light is scattered and attenuated at a lesser degree, thereby resulting in a radiographic image having higher resolution. | In a radiography system and radiography method according to the present invention, the radiography system comprises: a radiography device further comprising a radiation device further comprising a radiation source, and a radiation detection device which converts radiation which passes through a radiography subject into radiography information; and a system control portion which controls the radiography device to execute radiography at a set frame rate. The system control portion further comprises: a radiation emission disabling portion which interrupts the irradiation of radiation from the radiation source at least in a case where an error occurs with the radiography device; and a recovery processing portion which implements control so as to set the irradiation energy of the radiation source to a preset low irradiation energy and execute the radiography in a case where recovering from the error state. | 0 |
FIELD OF THE INVENTION AND RELATED ART
[0001] The present invention relates to a liquid container having an ink supply portion improved so that the liquid container can be used as an ink container or the like.
[0002] The most widely used method for forming a three dimensional object, for example, a rigid and hollow container, is a combination of a synthetic resin and injection molding. This method uses a set of male- and female-type molds. More specifically, it is a method in which melted synthetic resin is ejected into the gap between the two molds, and then, is cooled to allow the resin to solidify, in order to obtain a container having a desired shape. However, it is difficult to use injection molding to form a hollow container, more specifically, a liquid container such as an ink container, which is narrow at its opening (mouth portion) for connecting the inside and outside of the liquid container, and the internal space of the container proper (liquid storage portion) of which is substantially larger than that of the opening. Thus, in many cases, the manufacture of a container such as the above described one relied upon a complicated process; the main structure (liquid storage portion), and the cover portion were separately manufactured, and then were solidly connected to each other by adhesive or welding. Further, it was difficult to obtain a reliable container with a large capacity, because it was difficult to form a reliable seam between the main portion and cover portion.
[0003] As for a method for dealing with the above described problem, there is another method for forming a hollow container, which also has been widely used, more specifically, a molding method called blow molding. With the use of this method, a hollow container can be easily molded. According to blow molding, a piece of tube or the like formed of resin is softened, and is placed in a mold. Then, air is blown into the softened resin tube or the like to apply air pressure outward from inside the resin tube or the like to press the tube or the like against the internal surface of the mold. As a result, the internal contour of the mold is transferred onto the expanded resin tube or the like, forming a hollow container having a desired shape. In other words, this blow molding is a molding method well suited for manufacturing a hollow container, such as a PET bottle for drinking water or a ketchup tube, which is small at the opening, and the internal space of the main section of which is substantially larger than the opening portion.
[0004] However, there remained various technical problems which could not be solved even with the use of blow molding. That is, even through a hollow container is easily formed by blow molding, the air pressure applied by blow molding is in the range of no more than 5-10 kg/cm 2 . The prior art was not good enough to produce a liquid container, which is not only precise and reliable, but also is required to be rigid.
[0005] On the other hand, in the case of injection molding, melted resin is injected into the cavity between the set of molds, which is virtually sealed, except for the gap or the like provided between the molds for gas release. Thus, the pressure applied for the injection of the melted resin is greater two decimal places than the pressure applied by blow molding.
[0006] Therefore, in terms of the transferability of the internal contour of the mold to the external surface of a container to be formed, that is, the accuracy of the measurement of the external contour of the container, a hollow container formed by blow molding is similar at best in practical function, or substantially inferior in the absolute value of dimensional accuracy, to a hollow container formed by injection molding. Further, blow molding lacks a metallic mold which directly contacts the internal surface of a hollow container, being therefore a cleaner manufacturing method, that is, a method in which a product is not contaminated by releasing agent or the like. On the other hand, not only does the usage of blow molding make it impossible to directly control the internal dimension of a hollow container, but also it makes it impossible to control the wall thickness of the container. In other words, blow molding is substantially different in terms of the above described aspects from injection molding. Therefore, in order to efficiently manufacture a hollow container with the use of blow molding, a hollow container must be designed in consideration of the characteristics of blow molding.
[0007] It should be noted here that, in addition to the direct blow molding used for manufacturing the aforementioned ketchup container, there are many molding methods simply referred to as “blow molding”. For example, there is another widely used molding method called the sheet blow molding method. According to this molding method, a pair of parisons 1001 in sheet form, shown in FIG. 40( a ), or a single parison shown in FIG. 40( b ), is sandwiched between a set of metallic molds, to be molded into a hollow container. There is another blow molding method called the stretch blow molding method (which sometimes is called an injection blow molding method or injection blow molding), in combination with a preparatory process. According to this blow molding method, a parison 1003 , such as those shown in FIGS. 41 ( a ) and 41 ( b ), called preform, which has a thick wall, is formed by injection molding, and does not have an undercut portion, is formed into a hollow container with the use of blow molding.
[0008] Sheet blow molding is suitable for forming a large hollow container in the form of a flat pouch with a thin wall (pouch-like flat container with thin wall) 1004 . However, it is difficult to form by sheet blow molding, a hollow container, the mouth portion of which is satisfactory in terms of wall thickness, although the container proper of a hollow container formed by sheet blow molding is relatively uniform in wall thickness. In other words, when the sheet blow molding method is used to form a hollow container, it is difficult to precisely and solidly fix, or hold in the compressed state, the sealing member (for example, rubbery elastic members, which will be described later), which seals the mouth portion of the container, and through which the liquid in the container is drawn, to the mouth portion.
[0009] In comparison, stretch blow molding allows the mouth portion 1005 to be formed by injection molding during the formation of the preform 1003 , making it easier to form a container, the wall of which hag a predetermined thickness and is uniform in thickness. However, stretch blow molding requires two formation steps. In other words, stretch blow molding has a weakness in that it is inconvenient to use, in particular, when forming a flat container (flat and rectangular container) such as the container 1006 shown in FIG. 41( d ), the mouth portion 1007 of which is offset. More specifically, in this case, when forming the preform by blow molding, the variance in blow ratio is large across the preform. As a result, the portions with a thicker wall are insufficiently blown, or holes are created through the portions with a thinner wall. In other words, when stretch molding is used for forming a hollow container having the above described structure, there is the possibility that serious problems will occur during the formation of the container. Moreover, a hollow container formed by stretch blow molding has a relatively large variance in wall thickness, being therefore weaker. Thus, it sometimes caused problems while it was in use.
[0010] A liquid container, in particular, a liquid container for holding the liquid (ink) for an ink jet recording apparatus, is required to be capable of being precisely connected to the connective portion of a recording apparatus to prevent the ambient air from accidentally entering the container, and also, to prevent the liquid in the container from leaking or evaporating. In the past, therefore, when a liquid container (ink container) in accordance with the prior art was formed, injection molding was used in spite of the fact that the employment of injection molding made the manufacturing process complicated. Further, it was a common practice to design a liquid container in accordance with the prior art to accommodate injection molding.
[0011] There have been proposed several solutions to the above described problems of the prior art. Next, these proposals will be described. Referring to FIGS. 43 ( a ) and 43 ( b ), when a cylindrical container (container proper of which has cross section 1012 ) is formed using a cylindrical parison 1011 (having donut-shaped cross section), a parison is uniformly blown in its radius direction by compressed air. Therefore, preparing the parison so that its becomes uniform in wall thickness makes it possible to relatively easily form a hollow container excellent in terms of wall thickness. In comparison, referring to FIGS. 43 ( a ) and 43 ( c ), when a hollow container (container proper of which has cross section shown in FIG. 43( c )), which is approximately in the form of a flat, rectangular, parallelepiped, is formed using the cylindrical parison 1011 , the blow ratio is not uniform across the parison 1011 . In other words, a container having thinner portions 1013 , that is, portions having stretched more, and thicker portions 1014 , that is, portions having stretched less, is formed; a container greater in wall thickness variation is formed.
[0012] Thus, technologies for dealing with these problems have been tried. For example, in order to form a hollow container, the wall of which is uniform in blow ratio, a parison 1015 , the cross section of which is elongated (or elliptical), as shown in FIG. 43( d ), was prepared, or a parison 1016 , the wall of which was uneven in wall thickness, as shown in FIG. 43( e ), was prepared so that the wall thickness variance was inversely corrected. In either case, it was difficult to reliably prepare the above described parisons. Therefore, these technologies have not been put to practical use.
[0013] Further, there is a method called “post molding”, according to which the measurements of a liquid container being molded are controlled, in coordination with the internal contour of the main portion of the mold set, by inserting a metallic mold (internal mold formed to be fitted in only mouth portion) into the mouth portion of the container, while blowing a parison after the clamping of the mold set. The selection of this method definitely raises the level of accuracy, but requires a complicated set of molds, making it sometimes difficult to practice the process in which a desired number of (multiple) containers are continuously outputted in the parison extrusion direction, and which characterizes direct blow molding.
[0014] Moreover, as blow molding is used to form a flat liquid container, which has such a mouth portion that comprises a neck portion 1022 with the end surface 1023 , and the mouth portion of which is offset, instead of being on the center portion of the bottom surface of the liquid storage portion as shown in FIG. 44( a ), not only does the wall of the main portion of the resultant flat liquid container turn out to be nonuniform in thickness, but also the wall of the mouth portion (neck portion 1022 with end surface 1023 ) turns out to be problematically nonuniform in thickness. When it is possible to make the wall of the mouth portion of a liquid container sufficiently thick, or when the mouth portion of a liquid container is sufficiently smaller than the container itself, the wall of the mouth portion can be easily made satisfactorily uniform in thickness, whether the mouth portion is positioned in the center of the bottom wall of the liquid storage portion, or offset. However, when blow molding is used to form a flat container, the wall of which is thin, and the diameter of the mouth portion of which is approximately the same as the length of the shorter edge of the bottom wall of the flat container, it is impossible for the liquid container to be outputted as a liquid container, the thickness of the wall of which is sufficient and uniform; it is outputted as a container such as the one shown in FIG. 44( b ).
[0015] More specifically, referring to FIG. 44( b ), in which the plane horizontally halving the mouth portion 1025 of a flat liquid container 1024 in terms of the widthwise direction of the bottom wall of the container virtually coincides with the center line 1600 (parallel to the direction indicated by arrow mark X) of the bottom wall, the portion of the wall of the mouth portion, on the center line 1000 (parallel to the direction indicated by arrow mark Z, and connecting the centers of the top and bottom walls of the liquid storage portion) side, becomes thicker across the center portion 1028 than across the portions next to the corners 1029 ; the wall portion of the mouth portion, on the shorter edge (at the lengthwise end of bottom wall) of the bottom wall 1030 , also becomes thicker across the center portion 1026 than across the portions next to the corners; and the wall portions 1027 contiguous to the preceding two wall portions also become thicker across the center portion than across the portions next to the corners. Further, the wall portion 1026 , which is on the short edge side becomes thinner than the wall portion 1028 on the center line 1000 side. Further, the wall portions 1027 and 1027 become thickest at points which are offset from the center plane 1200 (parallel to the direction indicated by arrow mark Y) horizontally halving the mouth portion in terms of the lengthwise direction of the bottom wall, toward the center line 1000 .
[0016] Next, the configuration and position of the mouth portion of a liquid container based on the prior art will be described. Generally, a hollow container formed by direct blow molding is in the form of a cylinder, or flat pillar (flat, rectangular, and parallelepiped). A typical example of the former is a shampoo bottle (FIG. 40( b )), and a typical example of the latter is a blood transportation bag (FIG. 40( c )). In both cases, the container proper is virtually symmetrical, and the axial line of its mouth portion coincides with the plane halving the container proper into two virtually symmetrical portions. However, the structural arrangement in accordance with the prior art that the mouth portion is placed intentionally offset on the top or bottom wall of the container proper of a hollow container, and the technical problems resulting from such a structural arrangement, were not recognized initially.
[0017] Referring to FIG. 42, in the past, a screw plug (FIG. 42( a )), a bayonet plug, thermal welding (FIG. 42( b ), a simple sealing plug (FIG. 42( c )), etc., have been used as a means for sealing the mouth portion of a hollow container formed by direct blow molding. However, there were virtually no patents or the like disclosing a structural arrangement which ensures that the mouth portion of a hollow container is sealed with the use of ultrasonic welding, which is very simple and convenient. Further, there have been absolutely no patents or the like disclosing a means for reliably welding connective members to the end surface of the mouth portion of a hollow container formed by blow molding, more specifically, the end surface effected by the cutting or the molded precursor of a hollow container, without providing the mouth portion with a flange (flange 14 d in FIG. 45( b )). Further, reliable technologies for manufacturing a flat container having a mouth portion, which is offset and has an elongated cross section, and solidly attaching two or more components in layers by ultrasonic welding to the mouth portion, while controlling the thickness of the wall of the mouth portion, have not been disclosed. Incidentally, referential numerals 1033 , 1042 , and 1052 designate the lines along which molded precursors of a hollow container are cut.
[0018] On the other hand, technologies for welding the above described mouth portion to the above described container with the use of heat plate welding are available as alternative means for sealing the mouth portion. In the case of these technologies, it is impossible to prevent the container proper and mouth portion from being thermally deformed. Thus, they were unsuitable for forming a liquid container for an ink jet recording apparatus, from the standpoint of the accuracy regarding the position of the flat surface in terms of both the horizontal and vertical directions.
[0019] Further, a blood transportation bag or the like, the joint portion (portion connecting inside and outside of container) of which does not need to be very strictly regulated in size, does not need to be concerned with these technical problems. However, a liquid container, which needs to be compactly mounted in alignment by two or more in a device or apparatus, more specifically, an ink container, which needs to be removably mounted by the number corresponding to the number of recording liquids different in color, in the mounting portion of an ink jet recording apparatus, requires a simple, reliable, and compact joint structure (structure for connective portion).
SUMMARY OF THE INVENTION
[0020] The present invention was made in consideration of the above described technical problems. Its primary object is to provide a liquid container which comprises: a liquid storage portion, that is, a flat and hollow container proper formed of direct blow molding; and a mouth portion which is for connecting the inside and outside of the liquid storage portion, and which is superior in rigidity, precise in dimension, and is uniform in wall thickness, wherein the liquid storage portion and mouth portion can be integrally molded, and also, to provide an ink jet recording apparatus compatible with such a liquid container.
[0021] According to a first aspect of the present invention, there is provided a liquid container having a generally flat rectangular parallelepiped shape, comprising opposite major sides; an elongated bottom side connecting said opposite major sides; a port, formed adjacent a longitudinal end portion of the bottom side, for fluid communication between an inside and an outside of said liquid container, the being eleongated in a longitudinal direction of the bottom side and having a width which is larger adjacent a longitudinally central portion of the bottom side than adjacent the longitudinal end portion.
[0022] According to a second aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said port is only one port for communication between the inside and outside.
[0023] According to a third aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said port is produced by blow molding of a synthetic resin material.
[0024] According to a fourth aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said port includes a connecting portion for air venting and a connecting portion for supplying liquid out of said container.
[0025] According to a fifth aspect of the present invention, there is provided a liquid container according to aspect 4, wherein said connecting portions are arranged in a longitudinal line substantially at a widthwise center of said bottom side.
[0026] According to a sixth aspect of the present invention, there is provided a liquid container according to aspect 4, wherein said liquid supply connecting portion is disposed adjacent said one end portion and adjacent a widthwise end of said bottom side.
[0027] According to a seventh aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said port is provided with a neck portion projecting from said bottom side toward the outside and a flange extending from said neck portion in substantially parallel with said bottom side.
[0028] According to a eighth aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said port is formed by laminated structure.
[0029] According to a nineth aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said laminated structure supports an elastic member to be pierced by a connection needle.
[0030] According to a tenth aspect of the present invention, there is provided a liquid container according to aspect 8, wherein said laminated structure is welded at said port.
[0031] According to a eleventh aspect of the present invention, there is provided a liquid container according to aspect 10, wherein said laminated structure includes laminated material s having thicknesses which gradually decreases.
[0032] According to a twelfth aspect of the present invention, there is provided a liquid container according to aspect 8, further comprising a cylindrical member extended into said container to retain a shape of said port.
[0033] According to a 13th aspect of the present invention, there is provided a liquid container according to aspect 9, wherein said needle is a hollow needle.
[0034] According to a 14th aspect of the present invention, there is provided a liquid container according to aspect 1, further comprising a bottom cover for covering said port.
[0035] According to a 15th aspect of the present invention, there is provided a liquid container according to aspect 14, wherein said bottom cover is provided with a recess for engagement with a member for constituting said port.
[0036] According to a 16th aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said bottom cover is provided with an identifying portion for preventing erroneous connection.
[0037] According to a 17th aspect of the present invention, there is provided a liquid container according to aspect 14, wherein said identifying portion includes a storing member for storing a kind and/or a remaining amount of the liquid in said container by electric, magnetic or optical or memory by combination thereof.
[0038] According to a 18th aspect of the present invention, there is provided a liquid container according to aspect 1, wherein said container is disconnectably connected with an ink jet recroding apparatus for effecting recording on a recording material by ejection of the liquid.
[0039] These and other objects, features, and advantages of the present invention will become more apparent upon consideration of the following description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] [0040]FIG. 1 is a schematic perspective view of an example of a liquid container in accordance with the present invention, FIGS. 1 ( a ) and 1 ( b ) showing larger and small containers, respectively, as seen from diagonally below.
[0041] FIGS. 2 ( a ), 2 ( b ), and 2 ( c ) are top, front, side, and bottom views of the larger liquid container shown in FIG. 1( a ).
[0042] [0042]FIG. 3( a ) is a vertical sectional view of the small liquid container shown in FIG. 1( b ), at a plane parallel to the largest walls of the small container; FIG. 3( b ), bottom view of an embodiment of a small liquid container, which is in accordance with the present invention, and which employs the first ID pattern; FIG. 3( c ), bottom view of an embodiment of a small liquid container, which is in accordance with the present invention, and which employs the second ID pattern; and FIG. 3( d ) is a bottom view of an embodiment of a small liquid container, which is in accordance with the present invention, and which employs the third ID pattern.
[0043] [0043]FIG. 4 is a schematic, exploded, perspective view of an example (inclusive of both large and small liquid containers) of a liquid container in accordance with the present invention.
[0044] [0044]FIG. 5 is a schematic perspective view of the station base, into which a liquid container in accordance with the present invention is removably mountable.
[0045] [0045]FIG. 6 is a schematic vertical sectional view of an embodiment of a liquid container (inclusive of both large and small containers) in accordance with the present invention, which has been penetrated by a pair of connecting needles.
[0046] [0046]FIG. 7 is an enlarged, schematic, vertical, sectional view of the mouth portion of an embodiment of a liquid container (inclusive of both large and small containers) in accordance with the present invention, and the adjacencies of the mouth portion.
[0047] [0047]FIG. 8 is an enlarged, schematic, exploded, vertical, sectional view of the components of the mouth portion of the embodiment of the liquid container in accordance with the present invention, and the adjacencies of the mouth portion.
[0048] [0048]FIG. 9 is a schematic, vertical, sectional view of the mouth portion of the first embodiment of a liquid container in accordance with the present invention.
[0049] [0049]FIG. 10 is a schematic, vertical, sectional view of the mouth portion of the second embodiment of a liquid container in accordance with the present invention.
[0050] [0050]FIG. 11 is a schematic, vertical, sectional view of the mouth portion of the third embodiment of a liquid container in accordance with the present invention.
[0051] [0051]FIG. 12 is a schematic, vertical, sectional view of the mouth portion of the fourth embodiment of a liquid container in accordance with the present invention.
[0052] [0052]FIG. 13 is a schematic, vertical, sectional view of the mouth portion of the fifth embodiment of a liquid container in accordance with the present invention.
[0053] [0053]FIG. 14 is a schematic side view of the mouth portion of the liquid storage portion of the liquid container in accordance with the present invention, prior to the laminar attachment of the layerable members to the mouth portion.
[0054] [0054]FIG. 15 is a schematic side view of the mouth portion of the liquid storage portion shown in FIG. 14, while the housing as the first layerable member is welded to the flange of the mouth portion.
[0055] [0055]FIG. 16 is a schematic side view of the mouth portion of the liquid storage portion shown in FIG. 14, after the placement of the elastic members in the housing welded to the mouth portion.
[0056] [0056]FIG. 17 is a schematic side view of the mouth portion of the liquid storage portion, while the first retaining member is welded to the surface of the housing by ultrasonic welding after the placement of the elastic members shown in FIG. 16.
[0057] [0057]FIG. 18 is a schematic side view of the mouth portion of the liquid storage portion, while the second retaining member is welded to the surface of the first retaining member by ultrasonic welding after the fixation of the first retaining member.
[0058] [0058]FIG. 19 is a schematic plan view of the bottom cover of the liquid container shown in FIG. 2.
[0059] [0059]FIG. 20 is a schematic vertical section of the center portion of the bottom cover of the liquid container shown in FIG. 2.
[0060] [0060]FIG. 21 is a schematic side view of the bottom cover of the liquid container shown in FIG. 2.
[0061] [0061]FIG. 22 is a schematic bottom view of the bottom cover of the liquid container shown in FIG. 2.
[0062] [0062]FIG. 23 is a schematic vertical sectional view of the bottom cover of the liquid container shown in FIG. 2, at the plane represented by Line 23 - 23 in FIG. 19.
[0063] [0063]FIG. 24 is a schematic vertical sectional view of the bottom cover of the liquid container shown in FIG. 2, at the plane represented by Line 24 - 24 in FIG. 19.
[0064] [0064]FIG. 25 is a schematic plan view of the bottom cover of the liquid container shown in FIG. 3.
[0065] [0065]FIG. 26 is a schematic side view of the bottom cover of the liquid container shown in FIG. 3.
[0066] [0066]FIG. 27 is a schematic bottom view of the bottom cover of the liquid container shown in FIG. 3.
[0067] [0067]FIG. 28 is a schematic drawing for depicting the shape of the flat end surface of the mouth portion of the bottom portion of the liquid storage portion of another embodiment of a liquid container in accordance with the present invention.
[0068] [0068]FIG. 29 is a schematic drawing for depicting the shape of the flat end surface of the mouth portion of the bottom portion of the liquid storage portion of another embodiment of a liquid container in accordance with the present invention.
[0069] [0069]FIG. 30( a ) is a schematic vertical sectional view of a liquid container in accordance with the present invention, during the initial stage of the process in which the liquid container is inserted into a slot of the station base, starting from the bottom portion, and FIG. 30( b ) is the bottom portion of the same liquid container as seen from Line b-b in FIG. 30( a ).
[0070] [0070]FIG. 31( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, while the container ID portions of the liquid container are about to pass by the container ID portions on the main assembly side during the further insertion of the liquid container from the position shown in FIG. 39, and FIG. 31( b ) is a bottom view of the same liquid container as seen from Line b-b in FIG. 31( a ).
[0071] [0071]FIG. 32( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, after the passing of the container ID portions of the liquid container by the container ID portions on the main assembly side during the further insertion of the liquid container from the position shown in FIG. 31, and FIG. 32( b ) is a bottom view of the same liquid container as seen from Line b-b in FIG. 32( a ).
[0072] [0072]FIG. 33( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, when the tips of the connective needles projecting from the bottom surface of the internal space of the slot are about to enter the corresponding connective holes after the passing of the container ID portions by the positioning portions in the slot, during the further insertion of the liquid container from the position shown in FIG. 32, and FIG. 33( b ) is a bottom view of the same liquid container as seen from Line b-b in FIG. 33( a ).
[0073] [0073]FIG. 34( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, when the connective needles projecting from the bottom surface of the internal space of the slot have just begun to penetrate the corresponding elastic members as sealing members, during the further insertion of the liquid container from the position shown in FIG. 33, and FIG. 34( b ) is a bottom view of the same liquid container as seen from Line b-b in FIG. 34( a ).
[0074] [0074]FIG. 35( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, when the connective needles projecting from the bottom surface of the internal space of the slot have penetrated through the corresponding elastic members as sealing members, and the electrical connector (for transmitting electrical signals) on the internal surface of the bottom wall of the slot is about to enter the storage medium hole of the liquid container, during the further insertion of the liquid container from the position shown in FIG. 34, and FIG. 35( b ) is a bottom view of the same liquid container as seen from Line b-b in FIG. 35( a ).
[0075] [0075]FIG. 36( a ) is a schematic vertical sectional view of the liquid container shown in FIG. 30, after the completion of the insertion of the liquid container into the slot of the station base and the completion of the electrical connection between the storage medium and liquid container, and FIG. 36( b ) is the bottom view of the same liquid container as seen from Line b-b in FIG. 36( a ).
[0076] [0076]FIG. 37 is a schematic drawing for depicting an example of the structure of a liquid (ink) supply system for supplying to the ink jet recording head of an ink jet recording apparatus employing a liquid container in accordance with the present invention.
[0077] [0077]FIG. 38 is a schematic perspective view of a preferable example of an ink jet recording apparatus with which the liquid supply system shown in FIG. 37 is compatible.
[0078] [0078]FIG. 39 is a schematic perspective view of the ink ejecting portion of the ink jet recording head shown in FIG. 37 or 38 , for showing the structure thereof.
[0079] [0079]FIG. 40 is a schematic perspective drawing of the flat parison and cylindrical parison, for describing the technical problems from which a liquid container based on the prior art suffers.
[0080] [0080]FIG. 41 is a schematic perspective drawing for describing the technical problems which occur when attaching the preform of the mouth portion to the liquid storage portion.
[0081] FIGS. 42 ( a ), 42 ( b ), and 42 ( c ) are partially broken and partially sectional views of three liquid containers, one for one, for describing the technical problems which occur when processing the mouth portion of a liquid container based on the prior art.
[0082] FIGS. 43 ( a ), 43 ( b ), and 43 ( c ) are cross sectional drawings for describing the technical problems, that is, the nonuniformity in the wall thickness, of a blow molded flat liquid container in accordance with the prior art.
[0083] [0083]FIG. 44 is a schematic perspective view of two liquid containers different in the mouth portion, for describing the technical problems of a blow molded flat liquid container in accordance with the prior art.
[0084] [0084]FIG. 45 is a schematic drawing of liquid containers, for describing the difference, in the manner in which layerable members are solidly fixed in layers using ultrasonic welding or the like, between a flat liquid container, the mouth portion of which has a flange, and a flat liquid container, the mouth portion of which does not have a flange, FIGS. 45 ( a ), 45 ( b ), and 45 ( c ) being a schematic vertical sectional view of the center portion of the flat liquid container the mouth portion of which does not have a flange, a schematic perspective view of a problematic flat liquid container, and a schematic vertical sectional view of the center portion of the flat liquid container the mouth portion of which has a flange.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0085] Hereinafter, the preferred embodiments of the present invention will be concretely described with reference to the appended drawings, in which if two or more components are the same in referential numerals, they are the same or equivalent.
[0086] [0086]FIG. 1( a ) is a schematic perspective view of an embodiment of a large liquid container in * accordance with the present invention, as seen from diagonally below the container, and FIG. 1( b ) is a schematic perspective view of an embodiment of a small liquid container in accordance with the present invention, as seen from diagonally below the container. In terms of the shape (projected area) of the largest wall 14 f, the large liquid container shown in FIG. 1( a ) is the same as the small liquid container shown in FIG. 1( b ). However, in terms of the thickness (distance between two largest walls of container, which oppose each other), the former is greater than the latter, being therefore greater in liquid capacity.
[0087] FIGS. 2 ( a ), 2 ( b ), 2 ( c ), and 2 ( d ) are top, front, side, and bottom views of the larger liquid container, respectively.
[0088] [0088]FIG. 3( a ) is a vertical sectional view of the small liquid container in FIG. 1( b ), at a plane parallel to the largest walls of the liquid container; FIG. 3( b ), a bottom view of an embodiment of a small liquid container, in accordance with the present invention, having the first ID pattern; FIG. 3( c ), a bottom view of an embodiment of the small liquid container, in accordance with the present invention, having the second ID pattern; and FIG. 3( d ) is a bottom view of an embodiment of the small liquid container, in accordance with the present invention, having the third ID pattern.
[0089] [0089]FIG. 4 is an exploded schematic perspective view of an embodiment of a liquid container (inclusive of larger and smaller containers) in accordance with the present invention, and FIG. 5 is a schematic perspective view of the station base in which a liquid container in accordance with the present invention is removably mountable.
[0090] Referring to FIGS. 1 - 5 , a liquid container in accordance with the present invention (larger container 11 A, smaller container 11 B) is approximately in the form of a flat rectangular parallelepiped (which hereinafter may be referred to simply as flat container), making it possible for two or more liquid containers to be mounted side by side. The liquid storage portion 14 of the liquid container 11 A or 11 B is a molded single-piece container comprising a top wall 14 a (ceiling portion, FIG. 2), a bottom wall 14 b (FIG. 4), a mouth portion 14 k (FIG. 4), a flange portion 14 d (FIG. 4), a neck portion 14 e (FIG. 4), etc., and is manufactured by direct blow molding.
[0091] Referring to FIG. 2, the bottom portion 14 b of the larger liquid container 11 A has a connective portion through which the inside and outside of the liquid container 11 A are connectable. The structural design depicted in FIG. 2 is the same as the structural design of the corresponding portions of the small liquid container 11 B; the large and small containers 11 A and 11 B are the same in structure. Referring to FIG. 3( a ) which is a vertical sectional view of the small liquid container 11 B, at a plane which is parallel to the largest walls of the container and approximately halves the container in terms of the horizontal direction, the structural design depicted by this drawing is the same as the structural design of the corresponding portions of the large container 11 A.
[0092] The present invention is applicable to both the large liquid container 11 A and small container 11 B, and the effects of the present invention upon the former are the same as those upon the latter. Thus, in the following description of the present invention, all liquid containers will be referred to as “liquid container 11 ” unless it is necessary to specify the liquid container size. In other words, the term “liquid container 11 ” is inclusive of both the large and small containers mentioned above.
[0093] Referring to FIGS. 1 - 5 , the liquid container 11 in accordance with the present invention has a bottom cover 21 which is solidly fixed to the bottom portion 14 b of the liquid storage portion 14 . The liquid container 11 has a pair of ID portions 22 and 23 (ID patterns), which are attached one for one to the lengthwise ends of the bottom cover 21 . In this embodiment, the liquid container 11 has two ID patterns: a first container ID pattern located at one of the lengthwise ends of the bottom cover 21 , and a second container ID pattern located at the other lengthwise end of the bottom cover 21 . These two ID portions are used for identifying various liquid containers in terms of liquid type (color, etc.); several patterns are prepared to make it possible to identify the liquid in each liquid container (FIGS. 2 and 3).
[0094] Referring to FIG. 4, the liquid storage portion 14 of the liquid container 11 ( 11 A or 11 B) is flat (approximately in the form of a flat rectangular parallelepiped), and has six walls: a pair of opposing walls 14 f, the largest walls; a top wall 14 a (ceiling portion); a pair of opposing connective walls 14 g, which are connected to the largest walls 14 f and top wall 14 a; and bottom portion 14 b, which opposes the top wall 14 a and constitutes the bottom wall of the liquid container. The bottom portion 14 b has a mouth portion 14 k which leads to the interior of the liquid storage portion 14 . The mouth portion 14 k has a connective portion through which the inside and outside of the liquid storage portion 14 are connected, and which is structured as will be described later.
[0095] [0095]FIG. 6 is a schematic vertical sectional view of an embodiment of a liquid container (inclusive of large and small container) in accordance with the present invention, after the insertion of a pair of connective needles 38 and 39 into the liquid container. FIG. 7 is an enlarged schematic sectional view of the mouth portion, and its adjacencies, of the embodiment of a liquid container (inclusive of both large and small containers) in accordance with the present invention. FIG. 28 is a plan view of the mouth portion 14 k of the bottom portion 14 k of the liquid storage portion 14 of another embodiment of a liquid container in accordance with the present invention, and shows the shape of the opening of the mouth portion 14 k. FIG. 29 is a plan view of the mouth portion 14 k of another embodiment of a liquid container in accordance with the present invention, and shows the shape of the opening of the mouth portion 14 k.
[0096] Referring to FIGS. 4 - 7 , 28 , and 29 , the mouth portion 14 k is a part of the bottom wall 14 b (bottom portion). The mouth portion 14 k is offset from a vertical plane 1000 (FIG. 4) which is perpendicular to the largest walls 14 f of the liquid storage portion 14 and horizontally halves the liquid storage portion 14 , as shown in FIGS. 4, 28, and 29 ; it is located close to one end (right-hand end in this embodiment) of the bottom wall 14 b. The opening of the mouth portion 14 k is elongated in the direction parallel to the lengthwise direction of the bottom portion 14 b (direction parallel to long edges of virtually flat parallelepiped form of bottom portion 14 b ); it is long and narrow.
[0097] Referring also to FIGS. 4, 28, and 29 , the mouth portion 14 k is shaped so that its opening is narrower on the side closer to the shorter edge of the bottom wall 14 b than on the side closer to the aforementioned plane 1000 ; it is wider on the side closer to the plane 1000 . Further, the mouth portion 14 k has a flange portion 14 k, which completely surrounds the opening of the mouth portion 14 k. Because of the above described shape of the mouth portion 14 k, the portion 14 h (overhang portion) of the flange portion 14 d, that is, the portion of the flange portion 14 d on the central plane 1000 side, which is parallel to the lengthwise edges of the bottom wall, projects in the direction parallel to the short edges of the bottom wall 14 b (in the thickness direction of liquid storage portion 14 ).
[0098] Regarding the shape of the opening of the mouth portion 14 k, the opening may be optimally rounded at four corners as shown in FIG. 4, or may be rounded at both lengthwise ends as shown in FIGS. 28 and 29. Further, instead of shaping the mouth portion 14 k so that the opening will have two portions distinctively different in width (dimension in terms of direction perpendicular to largest walls of liquid storage portion), the mouth portion 14 k may be shaped so that the width of its opening gradually reduces toward the short edge of the bottom portion 14 b, as shown in FIG. 29.
[0099] [0099]FIG. 8 is an enlarged, exploded, vertical sectional view of the mouth portion, and its adjacencies, of an embodiment of a liquid container in accordance with the present invention, which is positioned upside down so that the bottom wall 14 b of the liquid storage portion 14 faces upward. It shows the various components of the mouth portion 14 k and its adjacencies. These components are assembled in layers and are solidly attached to each other. The order in which these components are layered is virtually the same as the order in which they appear layered in FIG. 7, which is a vertical sectional view of the mouth portion 14 k and its adjacencies after the assembly thereof. Next, the mouth portion 14 k will be described in more detail with reference to FIG. 8.
[0100] Referring to FIGS. 4, 7, and 8 , the problem that when a liquid container similar in design to the above described one is manufactured with the use of an ordinary blow molding method, the wall of the mouth portion 14 k becomes thinner on the side close to the lengthwise end (close to short edge of bottom portion), can be drastically reduced by designing the mouth portion 14 k so that its opening becomes narrower on the side close to the short edge of the bottom wall 14 b (bottom portion) (FIG. 4).
[0101] With the prevention of the above described problem that the portion of the mouth portion 14 k close to the short edge of the bottom wall 14 b of the liquid storage portion 14 turns out to be thinner, the portion of the mouth portion 14 k close to the short edge of the bottom wall 14 b becomes equal in thickness to the portion of the mouth portion 14 k on the plane 1000 side of the liquid storage portion 14 ; the mouth portion 14 k becomes uniform in thickness in terms of circumferential direction. Further, designing the mouth portion 14 k so that its opening becomes rounded (sufficiently large in radius) at four corners can prevent the problem that when the liquid container is manufactured with the use of an ordinary blow molding method, the mouth portion 14 k becomes nonuniform in blow ratio. The prevention of this problem can eliminates the problem that when manufacturing the liquid container with the use of an ordinary blow molding method, the mouth portion 14 k becomes constricted at the corners of its opening (for example, corner 1029 in FIG. 44( b )). Therefore, it is possible to assure that the liquid storage portion 14 of a liquid container manufactured with the use of an ordinary blow molding method has predetermined levels of strength and rigidity.
[0102] When the liquid storage portion 14 having the mouth portion 14 k was structured as described above, the positional relationship between a parison and a metallic mold, and the uniformity of the thickness of each parison, did not have much effect on liquid container quality. In other words, it was possible to use an ordinary blow molding method to successfully manufacture a liquid container, the liquid storage portion 14 of which was uniform in terms of wall thickness, and the deviation of the liquid storage portion 14 of which in terms of internal dimension was negligible. More specifically, a predetermined number of single-piece flat parallelepipedic large liquid containers 11 A, the size of which was approximately 40×70×100 mm, and a predetermined number of single-piece flat parallelepipedic small containers 11 B, the size of which was approximately 20×70×100 mm, were manufactured by blow molding. The size of the opening of the mouth portion 14 k of each liquid container was approximately 10×20 mm. The material for the liquid container was polypropylene of a blow grade (MFR=0.2 g/10 min). The molding cycle was 30 seconds, and the rate of extrusion was 20 kg/h. The resultant liquid containers were no more than 0.2 mm in terms of the variance in the wall thickness. In comparison, a liquid container in accordance with the prior art, the mouth portion of which was located in the middle of the bottom portion, was no less than 1.0 mm in terms of the wall thickness variance.
[0103] Further, this embodiment of a liquid container in accordance with the present invention (FIGS. 1 - 7 ) has the flange 14 k which perpendicularly projects outward from the edge of the opening of the mouth portion 14 . This flange 14 k was provided for the following reason: If the liquid container 14 which is to be manufactured by direct blow molding, is designed so that the neck portion 14 e (FIGS. 4 and 7) of the mouth portion 14 k extends from the bottom wall 14 b (bottom portion) to the plane of the opening of the mouth portion 14 k, the neck portion 14 e and/or bottom portion 14 b of the liquid storage portion 14 sometimes collapses (caves in) due to the load generated during ultrasonic welding. Not only does this collapsing (designated by referential numerals 335 , 337 , and 339 in FIG. 45( a ), for example) of the neck portion 14 e and/or bottom portion 14 b of the liquid storage portion 14 increases the amount by which ultrasonic energy is lost, but also, makes it impossible to precisely attach, by welding, the various components which will be described later.
[0104] As described above, according to this embodiment, it is possible to construct a compact mouth opening sealing mechanism, which does not require the container mounting portion (station base 31 in FIG. 5) to be widened in order to mount two or more liquid containers 11 side by side. More specifically, the provision of the flange 14 d, which is similar in thickness to the neck portion 14 e of the mouth portion 14 k, increases the rigidity of the neck portion 14 e, preventing therefore the problem that when attaching the members of the connective mechanism, which will be described later, to the liquid storage portion 14 and mouth portion 14 k by ultrasonic welding, the liquid storage portion 14 and/or mouth portion 14 k collapses. In other words, it is assured that these members can be easily welded by simply backing the liquid container by the back surface of the flange 14 d, and also that during the welding process, power is not wasted and the liquid container does not deform.
[0105] Further, in this embodiment, the connective portion is welded to the mouth portion 14 k in a manner of forming a butt joint, for the following reason. Even though the present invention improves the mouth portion 14 k in terms of the accuracy of its internal dimension, it still leaves a slight error in the internal dimension of the mouth portion 14 k. Therefore, in order to weld the connective portion to the mouth portion 14 k in a manner to form a share joint so that the two sides are reliably welded to each other at the internal edges, it becomes necessary to correct the shapes of the corresponding components.
[0106] It has been a common practice to secure a welding overlap by folding the mouth portion 14 k outward as the flanges 14 d in FIGS. 45 ( b ) and 45 ( c ) have been folded. However, this method increases the size of the opening of the mouth portion 14 k by the amount equal to the size of the folded portion of the mouth portion 14 k, as described before regarding the prior art. As a result, the opening portion of the mouth portion 14 k becomes too large for mounting two or more liquid containers side by side in the thickness direction of the flat liquid container (book-shaped rectangular parallelepipedic container); it becomes impossible to satisfactorily mount two or more liquid containers in an ink jet recording apparatus or the like, in a compact fashion.
[0107] Heretofore, the mouth portion 14 k of the liquid container 11 in accordance with the present invention was described in detail. Hereinafter, the portions of the liquid container 11 , other than the mouth portion 14 k, will be described in detail.
[0108] Referring to FIG. 4, the liquid container 11 comprises: the liquid storage portion 14 ; bottom cover 21 ; and various members which make up the connective portion by being placed in the mouth portion 14 k of the liquid storage portion 14 . These various members which make up the connective portion attached to the mouth portion 14 k are a housing 1107 , a pair of elastic members 16 , a first retaining member 20 , a pair of absorbent members 1104 , a second fixing member 1103 , a storage medium holder case 1502 , a storage medium holder 17 , a storage medium 18 , a two-sided adhesive tape 19 , etc. The absorbent members 1104 is a member through which connective members (hollow needles or the like) are put from the outside.
[0109] FIGS. 9 - 13 show various structures for the mouth portion 14 k, and its adjacencies, of the liquid container 11 in accordance with the present invention (connective portion attached to mouth portion 14 k ). FIG. 10 is a vertical sectional view of the mouth portion, and its adjacencies, of the first embodiment of a liquid container in accordance with the present invention, and FIG. 11 is a vertical sectional view of the mouth portion, and its adjacencies, of the second embodiment of a liquid container in accordance with the present invention. FIG. 12 is a vertical sectional view of the mouth portion, and its adjacencies, of the third embodiment of a liquid container in accordance with the present invention, and FIG. 13 is a vertical sectional view of the mouth portion, and its adjacencies, of the fourth embodiment of a liquid container in accordance with the present invention. FIG. 14 is a vertical sectional view of the mouth portion, and its adjacencies, of the fifth embodiment of a liquid container in accordance with the present invention.
[0110] Next, referring to FIGS. 9 - 13 , various examples of the structure of the adjacencies (connective portion attached to mouth portion 14 k ) of the liquid container 11 in accordance with the present invention, which connects the internal space of the liquid container 11 to the outside, will be described. The mouth portion 14 k in first embodiment shown in FIG. 9 is virtually identical in structure to the mouth portion 14 k of above described example (FIGS. 1 - 8 ) of a liquid container 11 in accordance with the present invention.
[0111] Referring to FIG. 9, the liquid storage portion 14 has a neck portion 14 e, which projects from the bottom portion 14 b of the liquid storage portion 14 . The neck portion 14 e is provided with a flange 14 d, which is attached to the end of the neck portion 14 e to make the neck portion 14 e more rigid. The flange 14 d slightly projects outward from the neck portion 14 e in parallel to the bottom wall 14 b. To this flange 14 d, various members, which make up the connective portion (which opens or shuts liquid container), are attached in layers by ultrasonic welding. More specifically, the housing 1107 as the first layer is directly fixed to the surface of the flange 14 d by ultrasonic welding. Then, a pair of elastic members 16 (rubbery elastic members) are fitted into a pair of the recesses of the housing 1107 , one for one. Then, the first retaining member 20 as the second layer is fixed to the surface of the housing 1107 by ultrasonic welding. With the fixing of the first retaining member 20 , the elastic members 16 are retained in the housing 1107 , being slightly compressed.
[0112] Next, a pair of the absorbent members 1104 (members capable of absorbing leaked liquid or adhered liquid) are placed one for one in a pair of the recesses of the first retaining member 20 . Then, the second retaining member 1103 as the third layerable member is fixed to the surface of the first retaining member 20 (second layerable layer). The second retaining member 1103 has a pair of guiding portions 14 c (portions for guiding needles to openings) for guiding a pair of hollow connective needles 38 and 39 (FIG. 6). The positions of the pair of guiding portions 14 c correspond one for one to those of the pair of absorbent members 1104 . Further, the housing 1107 has a tubular member 45 , which projects inward of the liquid storage portion 14 from the back surface of the housing 1107 .
[0113] The second embodiment of the connective portion shown in FIG. 10 is what will result as the second retaining member 1103 (third layerable member) and absorbent members 1104 are eliminated and the first retaining member 20 (second layerable member) is modified in structure (shape) (in particular, needle path location). More specifically, the first retaining member 20 has the connective needle paths with the needle guiding portion 14 c. Otherwise, the structure of the second embodiment is practically the same as that of the first embodiment. Compared to the structural arrangement in the first embodiment, the structural arrangement in this embodiment makes it possible to eliminate the absorbent members 1104 and second retaining member 1103 , which in turn makes it possible to eliminate the process for fixing the second retaining member 1103 by ultrasonic welding.
[0114] The third embodiment of the connective portion shown in FIG. 11 is a modification of the second embodiment shown in FIG. 10. More specifically, the tubular portion 45 of the housing 1107 of the second embodiment was eliminated, and the pair of elastic members 16 were replaced with a single large elastic member 16 A. Further, the connective needle insertion holes of the first retaining member 20 (second layerable member) was changed in shape. Otherwise, the structural arrangement of the third embodiment is practically the same as that of the second embodiment. The third embodiment makes it possible to further reduce component count.
[0115] The fourth embodiment of the connective portion shown in FIG. 12 is practically the same as the second embodiment shown in FIG. 10, except that there is a relatively large gap between the internal surface of the mouth portion 14 k and the peripheral surface of the tubular member of the housing 1107 . This gap was created by changing the shape of the tubular portion 45 (reducing external diameter). Otherwise, the structural arrangement of this embodiment is practically the same as that of the second embodiment.
[0116] The fifth embodiment of the connective portion shown in FIG. 13 is a modification of the first embodiment shown in FIG. 9; the elastic members 16 shown in FIG. 9 were replaced with a pair of rubbery valves.
[0117] Referring to FIG. 13, the neck portion 14 e projects from the bottom portion 14 b of the liquid storage portion 14 , and the flange 14 d perpendicularly projects outward from the lip portion of the neck portion 14 e. The connective portion has a housing 1107 b (valve box) as the first layerable member, which is fixed to the surface of the flange 14 d by ultrasonic welding. The housing 1107 b has a pair of valve chambers, each of which contains a mushroom-shaped valve 1111 , which is kept pressed by a coil spring 1112 in the opening direction. The valve chamber for drawing liquid has a liquid path 1114 (ink path), whereas the valve chamber for introducing the ambient air has an ambient air path 1115 . The connective portion further comprises a pair of absorbent members 1104 , and a first retaining member 20 A (second layerable member) having a pair of recesses for accurately positioning the pair of absorbent members 1104 . The pair of absorbent members 1104 are placed in the recesses of the first retaining member 20 A, which is fixed to the surface of the housing 1107 a by ultrasonic welding, holding the absorbent members to the surface of the housing 1107 b so that the positions of the absorbent members correspond one for one to those of the liquid and ambient air paths.
[0118] According to the structural arrangements for the connective portion described with reference to FIGS. 9 - 13 , the housing 1107 ( 1107 b ) having the pair of through holes, and the first retaining member 20 having the pair of through holes, and the second retaining member 1108 , are fixed in layers to the surface of the mouth portion 14 k to retain the elastic members 16 , which are formed of rubbery elastic substance to allow the two connective needles 38 and 39 to penetrate the elastic members 16 , as well as the absorbent members 1104 if necessary, by sandwiching them. Therefore, the internal space of the liquid container 11 can be connected to the outside (to enable liquid therein to be drawn from liquid container, and ambient air to be introduced into liquid container) simply by penetrating (stabbing through) the two elastic members 16 of the connective portion by the two connective needles 38 and 39 , one for one.
[0119] Further, the first retaining member 20 is fixed to the housing 1107 by ultrasonic welding in such a manner that the elastic members 16 are compressed by the back surface of the first retaining member. Similarly, the donut-shaped absorbent members 1104 are disposed so that their positions correspond one for one to those of the elastic members 16 , and the second retaining member 1103 is fixed to the first retaining member by ultrasonic welding so that the second retaining member 1103 functions as a retainer lid for the absorbent members 1104 . Further, the second retaining member 1103 (or first retaining member 20 ) has the pair of guiding portions 14 c (connective needle guiding portions) for guiding the connective needles 38 and 39 when the needles 38 and 39 are inserted to extract the liquid in the liquid container, and to allow the ambient air to enter the liquid container 11 .
[0120] Next, referring to FIGS. 14 - 18 , a method for fixing in layers the structural components of the connective portion by ultrasonic welding, without expanding the liquid container 11 in the direction (thickness direction) in which it is stacked, when assembling in layers (manufacturing) the components of the connective portion.
[0121] [0121]FIG. 14 is a schematic side view of the mouth portion 14 k before the fixing of the components of the connective portion to the mouth portion 14 k, and FIG. 15 is a schematic side view of the mouth portion 14 k, and the housing 1107 as the first layerable member, while the housing member 1107 is welded to the flange 14 d of the mouth portion 14 k with the use of an ultrasonic welding horn 2500 . During this ultrasonic welding process, the pressure generated by ultrasonic welding is borne through the flange 14 d of the mouth portion 14 by a flange backing jig 2501 placed in contact with the back surface of the flange 14 d.
[0122] [0122]FIG. 16 is a schematic side view of the welded housing 1107 , and the elastic member 16 , after the mounting of the elastic member 16 into the housing 1107 (recess of housing), and FIG. 17 is a schematic side view of the welded housing 1107 , elastic member 16 , and first retaining member 20 (second layerable member), while the first retaining member 20 is welded to the surface of the housing in the state shown in FIG. 16, with the use of the ultrasonic welding horn 2500 . Also during this ultrasonic welding process, the pressure from ultrasonic welding is borne by the flange backing jig 2501 , which is placed in contact with the back side of the flange 14 d of the mouth portion 14 k.
[0123] [0123]FIG. 18 is a schematic side view of the partially assembled portion of the connective portion, while the second retaining member (third layerable member) is welded to the surface of the first retaining member 20 with the use of the ultrasonic welding horn 2500 after the first retaining member 20 (second layerable member) was solidly fixed to the surface of the welded housing 1107 (first layerable member) by welding. Also during this process for attaching this second retaining member 1103 by ultrasonic welding, the pressure from ultrasonic welding is borne by the flange backing jig 2501 placed in contact with the back side of the flange 14 d of the mouth portion 14 k.
[0124] In the case of the embodiments depicted in FIGS. 14 - 18 , the height (thickness) of the first layerable member 1107 (member for housing elastic members 16 ) directly fixed to the flange 14 d integrally molded with the liquid storage portion 14 , was 4 mm. The height (thickness) of the second layerable member 20 (first retaining member) fixed to the surface of the housing 1107 solidly fixed by welding was 3 mm. This second layerable member 20 is a member which functions as a lid for encapsulating the elastic members 16 .
[0125] The height (thickness) of the second retaining member 1103 as the third layerable member to be attached last of the layers was 1 mm. This third layerable member 1103 is a member which functions as a lid for retaining the absorbent members 1104 .
[0126] The layerable members 1107 , 20 , and 1103 are directly or indirectly attached in layers to the surface of the flange 14 d of the mouth portion 14 , with the elastic members 16 placed between the first and second layerable members 1107 and 20 , and the absorbent members 1104 placed between the second and third layerable members 20 and 1103 .
[0127] More specifically, in the connective portion assembled on the surface of the flange 14 d of the liquid container 11 in accordance with the present invention, the housing 1107 as the first layerable member was rendered thicker than the flange 14 d, and the first retaining member 20 as the second layerable member was rendered thinner than the first layerable member 1107 . Further, the second retaining member 1103 as the third layerable member was rendered thinner than the second layerable member 20 . In other words, the layerable layers 1107 , 20 , and 1103 were made so that the farther from the surface of the flange 14 d, the thinner they were. With the provision of this structural arrangement, it became possible to reliably attach in layers to the flange 14 d of the mouth portion 14 , the housing 1107 as the first layerable member, the second layerable member 20 (first retaining member) to be placed straight above the welding seam between the mouth portion 14 k of the blow-molded liquid storage portion 14 and the housing 1107 , and the third layerable member 1103 (second retaining member) to be placed straight above the second layerable member 20 , by ultrasonic welding, without damaging the welding seam between the mouth portion 14 and housing 1107 .
[0128] In the case of this embodiment of a liquid container in accordance with the present invention, polypropylene was used as the material for the liquid storage portion 14 and various layerable members. Thus, the various layerable members were reliably welded with the use of 200-400 J of energy generated by an ultrasonic welding machine, which was 20 kHz in frequency and 1 kW in ultrasonic wave output. In other words, it was possible to reliably prevent the problem of the prior art, that is, the problem that the liquid storage portion of a liquid container failed to be satisfactorily sealed or remain sealed, in spite of the application of the maximum output of an ultrasonic welding machine, changes in load, changes in the ultrasonic wave duration, etc.
[0129] The studies made under various conditions revealed that as long as the various layerable members are formed of the resinous substances of the same type, all that is necessary is to assure that the distance (which hereinafter may be referred to as welding distance) from the ultrasonic welding horn 2500 to the welding seams formed during the preceding welding processes is no less than twice the distance from the ultrasonic horn 2500 to the welding seam to be formed next. According to this embodiment, the later a member is placed in the order in which the various members are solidly fixed in layers, the thinner the member, and therefore, the smaller the amount of the ultrasonic energy required to weld the member. For example, the welding distance of the second layerable member (first retaining member 20 ) is 3 mm, and the distance between the second layerable member 20 to the welding seam, which was formed during the immediately preceding welding process, and which must not be damaged by the following welding process, is: (3+4) mm>(3×2) mm, which is sufficient to prevent damage to the preceding welding seams. In other words, it is essential to divide the connective portions into such layerable components that do not damage the welding seam formed in the preceding ultrasonic welding processes while the donut-shaped retaining members (layerable components) are sequentially attached in layers by welding. With the provision of this structural arrangement, it is assured that all the layerable components of the connective portion are solidly and sequentially fixed by ultrasonic welding, by backing the partially assembled portion of the connective portion by the back side of the flange 14 d projecting slightly from the lip portion of the neck portion 14 e, no matter which layerable component is to be solidly fixed in layers by ultrasonic welding.
[0130] In other words, when the layerable members are designed so that the closer to the mouth portion 14 k the thicker the layerable members, not only is it assured that energy is concentrated to a sharp horn (which is called energy director) placed in contact with the seam at which layerable components are to be welded, but also, the ultrasonic welding energy attenuates as it propagates through the resin. Therefore, as long as the distance to the welding seams formed by the preceding welding processes is no less than twice the welding distance, the welding seams formed by the preceding welding processes are not damaged even if layerable members are attached in layers by ultrasonic welding.
[0131] If ultrasonic welding energy is applied by an amount greater than necessary, the amount of the energy unconsumed by welding propagates to the welded seams formed by the preceding welding processes, and damages them. Therefore, this problem should be considered seriously.
[0132] In other words, the layerable members can be reliably and accurately attached in layers with the use of ultrasonic welding, by designing the liquid container 11 so that the distance from the ultrasonic welding horn 2500 to the welding seam, and the distance from the ultrasonic welding horn 2500 to the welding seams formed by the preceding welding processes, fall within predetermined ranges, respectively, in consideration of the facts described with reference to FIGS. 14 - 18 .
[0133] With regard to the various structural arrangements of connective portion placed in the adjacencies of the mouth portion 14 k, which were described with reference to FIGS. 9 - 13 , the third embodiment of the liquid container 11 comprises two layerable members: the housing 1107 and a single retaining member 20 (first retaining member); the structural arrangement shown in FIG. 11 does not necessarily require the neck portion 14 e to be supported from the internal wall side.
[0134] Similarly, the fourth embodiment of the liquid container shown in FIG. 12 does not require the internal wall support for the neck portion 14 e. However, the liquid container 11 is structured so that a gap is provided between the tubular portions for detecting that the amount of the liquid remaining in the liquid storage portion 14 has become very small, and the internal wall of the neck portion 14 e. In comparison, the second embodiment shown in FIG. 10 is structured so that the tubular portion 45 of the housing 1107 supports the neck portion 14 e from inward side of the neck portion 14 e.
[0135] Further, the fifth embodiment of the liquid container shown in FIG. 13 is substantially different from the various preceding embodiments in that it has such a connective portion that comprises the valves 1111 formed of elastic substance, and the housing 1107 b, the portions of which function as valve seats.
[0136] Referring to FIGS. 4, 6, and 7 , the hollow liquid drawing connective needle 38 and hollow air introducing connective needles 39 are inserted into the liquid storage portion 14 of the thus structured liquid container, through the first connective opening 27 , the hole closer to the short edge of the bottom portion 14 b, and the second connective opening 28 , the hole closer to the center of the bottom portion 14 b, respectively, and corresponding absorbent members 1104 and elastic members 16 , one for one. The connective needles 38 and 39 have holes 38 a and 39 a, respectively, which are located close to their tips to connect the hollows of the needles 38 and 39 to the liquid storage portion 14 . With the penetration of the connective portion of the liquid container by the needles 38 and 39 , it becomes possible for the liquid (ink or the like) to be drawn out of the liquid storage portion 14 , while introducing the ambient air into the liquid storage portion 14 .
[0137] Heretofore, the adjacencies of the mouth portion 14 k of the liquid storage portion 14 were described in detail regarding their structures. In the case of the first embodiment of the present invention shown by FIGS. 1 - 7 , the bottom side (bottom portion 14 b ) of the liquid storage portion 14 has a bottom cover 21 , which is removably attached to the liquid storage portion 14 with the use of three retaining portions (coupling mechanisms) 1701 , 1702 , and 1703 (FIG. 7) in the form of a snap. More specifically, this bottom cover 21 has three retaining portions 1701 , 1702 , and 1703 in the form of a snap, which are engaged with the catches 14 P (two) of the flange 14 d of the mouth portion 14 k of the bottom portion 14 b of the liquid storage portion 14 and the catch 14 P (one) of the bottom portion 14 b, to fasten the bottom cover 21 to the liquid storage portion 14 , as shown in FIGS. 4 and 7.
[0138] The bottom cover 21 is for covering the adjacencies of the mouth portion 14 k, which make up the above described connective portion, and also, for holding a storage medium 18 for electrically storing and identifying the chemical properties, such as surface tension, of the liquid in the liquid container, the physical data, such as amount, of the liquid in the liquid container, etc.
[0139] Further, the bottom cover 21 has a pair of liquid container ID portions 22 and 23 for mechanically identifying the type of the liquid container 11 , which are at the lengthwise ends, one for one. As this bottom cover 21 is engaged with the liquid storage portion 14 , the aforementioned connective portion, and the structural members for holding the storage medium 18 , are held to the bottom portion 14 b of the liquid storage portion 14 . Referring again to FIGS. 4 and 7, the storage medium 18 is solidly fixed to an electrical wiring substrate 26 by soldering or the like, and the electrical wiring substrate 26 is solidly fixed to a storage medium holder 17 with the use of a two-sided adhesive tape 19 . The storage medium holder 17 is held within the storage medium holder case 1502 , which is held in the aforementioned bottom cover 21 .
[0140] The bottom cover 21 has capillary grooves 40 (FIG. 40), which are cut in the internal surface of the storage medium holder case 1502 , for the following reason. That is, there is a possibility that liquid travels from the bottom portion 14 b of the liquid container 11 , by way of the external surface of the liquid container, and enters the storage medium holder 17 . Thus, the storage medium holder 17 is stored in the storage medium holder case 1502 ; in other words, the means for holding the storage medium 18 is structured in two layers. With the provision of this two-layer structure, the liquid, which has traveled to the edge of the opening of the storage medium holder case 1502 , is guided by the capillary grooves 40 into the space between the storage medium holder 17 and the internal surface of the storage medium holder case 1502 , being thereby prevented from entering the storage medium holder 17 .
[0141] While liquid containers are distributed to customers after their manufacture, while they are displayed in stores, or while they are mounted in such apparatuses as ink jet recording apparatuses after being taken out of their sealed packages, they are sometimes dropped or subjected to shocks, which sometimes results in damage to the welding seams in the adjacencies of the mouth portion 14 k, and/or deformation of the adjacencies of the welding seams. This damage to the welding seams allows the ink to leak, and the deformation of the adjacencies of the welding seams makes it difficult or virtually impossible for the liquid containers to be mounted into the apparatuses. In order to prevent this kind of problem, an embodiment of a liquid container in accordance with the present invention is structured in the following fashion.
[0142] FIGS. 19 - 27 are schematic drawings of the bottom cover 21 of the liquid container 11 . FIGS. 19 - 24 show the bottom cover 21 A of the large liquid container 11 A, and FIGS. 25 - 27 show the bottom cover 21 B of the small liquid container 11 B.
[0143] [0143]FIG. 19 is a plan view of the bottom cover 21 A, and FIG. 20 is a vertical sectional view of the bottom cover 21 A, at the plane which is parallel to the largest walls of the liquid container 11 A, and which horizontally halves the bottom cover 21 A. FIG. 21 is a side view of the bottom cover 21 A, and FIG. 22 is a bottom view of the bottom cover 21 A. FIG. 23 is a vertical, cross sectional view of the bottom cover 21 A, at Line 23 - 23 in FIG. 19, and FIG. 24 is a vertical, cross sectional view of the bottom cover 21 A, at Line 24 - 24 in FIG. 19. FIG. 25 is a plan view of the bottom cover 21 B, and FIG. 26 is a side view of the bottom cover 21 B. FIG. 27 is a bottom view of the bottom cover 21 B.
[0144] Referring to FIGS. 19 - 27 , the bottom cover 21 ( 21 A, 21 B) is structured so that it covers the neck portion 14 e of the mouth portion 14 k of the liquid storage portion 14 formed by direct blow molding, the housing 1107 solidly welded to the mouth portion 14 k, and the layerable members 20 and 1103 solidly welded to the housing 1107 .
[0145] This bottom cover 21 has a snap-type fastening portions 1701 , 1702 , 1703 , 1704 a, and 1704 b. The snap-type fastening portions 1701 , 1702 , 1704 a, and 1704 b engage with the neck portion 14 e (back side of flange 14 d ) of the mouth portion 14 k in a manner to grasp the neck portion 14 e from four sides, as shown in FIG. 7, whereas the remaining snap-type fastening portion 1703 engages with the catch portion 14 p of the bottom portion 14 b.
[0146] Also referring to FIGS. 19 - 27 , the snap-type fastening portions 1701 , 1702 , 1704 a, and 1704 b of the snap-type fastening mechanism of the bottom cover 21 ( 21 A, 21 B), which engage with the neck portion 14 e of the mouth portion 14 k, are attached to the four different points Of the bottom cover 21 , one for one. However, they may be attached to three different points of the bottom cover 21 . In some cases, they may be attached to two different points of the bottom cover 21 . Further, the bottom cover 21 may be structured so that at least two snap-type fastening portions are positioned in a manner to sandwich the storage medium holder case 1502 , and so that the bottom cover 21 is held to the bottom portion 14 b by the same snap-type engaging portions.
[0147] Structuring the bottom cover 21 ( 21 A, 21 B) and snap-type fastening portions as described above makes it possible for the shock resulting from a fall of the liquid container 11 to be absorbed by the snap-type fastening portions to reduce the damages to the welding seams in the adjacencies of the mouth portion 14 k (first shock absorption).
[0148] Moreover, in the case of this structural arrangement, not only does the bottom cover 21 have a pair of recesses, into which the overhang portion 14 h of the flange 14 d, which extends in the widthwise direction (direction Y) of the liquid storage portion 14 , fits to prevent the bottom cover 21 from becoming dislodged from the liquid storage portion 14 in the lengthwise direction (direction X) and widthwise direction (direction Y) of the liquid storage portion 14 , but also, a gap is provided between each overhang portion 14 h and the wall of the corresponding recess so that the aforementioned shock is absorbed by the coordination of the recess and overhang portion 14 h (second shock absorption).
[0149] More specifically, referring to FIGS. 28 and 29, the interior (internal surface) of the bottom cover 21 is provided with a pair of recesses, the surface of which engages with the surface (peripheral surface of mouth portion 14 k ) of the overhang portion 14 h of the flange 14 d of the mouth portion 14 k extending in the widthwise direction.
[0150] Further, the liquid container 11 (bottom cover 21 in drawings) is provided with a pair of container ID portions 22 and 23 , which mechanically identify the type of a container or the type of the liquid in a container, and which also prevent mounting errors. The bottom cover 21 contains, in addition to the above described connective portion, the storage medium 18 , which is electrical, magnetic, optical, or of a combination of these properties, and which is capable of storing information regarding the amount, type, etc., of the ink in the liquid storage portion 14 .
[0151] The bottom cover 21 is structured so that it can be snap fastened to the liquid storage portion 14 . Therefore, not only can it be simply attached to the liquid storage portion 14 without requiring a special tool during one of the manufacturing processes, but also it can be easily removed to selectively remove the storage medium 18 after the expiration of the service life of the liquid container 11 .
[0152] As the liquid container 11 is subjected to an excessive shock, the layerable members attached in layers to the end surface of the flange 14 d of the mouth portion 14 k sometimes become dislodged from each other. In order to prevent this problem, the layerable members are desired to be given recesses or projections so that their recesses or projections interlock with those of the adjacent layerable members.
[0153] Extending the tubular portion 45 of the housing 1107 so that the tubular portion 45 supports the mouth portion 14 k by the internal wall of the mouth portion 14 k is particularly effective for the purpose of preventing the neck portion 14 e of the mouth portion 14 k from inwardly deforming, and/or the housing 1107 from becoming dislodged. This tubular portion 45 may be structured so that it doubles as the structure for detecting that the amount of the liquid remaining in the liquid storage portion 14 is very small. In terms of reinforcement, the tubular portion 45 as the member for supporting the neck portion 14 e by the internal surface of the neck portion 14 e when the liquid container 11 is subjected to a shock (first embodiment shown in FIGS. 6, 7, and 9 , and second embodiment shown in FIG. 10) is more effective when it is closer to the center of the short edge of the liquid storage portion 14 than when it is closer to the corner at which the internal edges of liquid storage portion 14 intersect. Therefore, it is desired that the liquid drawing portion of the connective portion attached to the mouth portion 14 k is positioned closer to the short edge (lengthwise end) of the bottom wall 14 b and the air introducing portion of the connective portion is positioned closer to the center of the bottom wall 14 b.
[0154] Referring to FIG. 3, the liquid container 11 ( 11 A, 11 B), which is made up of the above described structural components, etc., and is used as an ink container for an ink jet recording apparatus, for example, has a sealed liquid chamber 13 for storing one ink 12 (specific in terms of chromaticity, tone, saturation, composition, etc.). FIGS. 3 ( b ), 3 ( c ), and 3 ( d ) schematically show the three sets of ID portions 22 and 23 differentiated in specification for preventing the mix-up among two or more liquid containers different in the ink stored therein. The liquid container 11 is mounted into the station base 31 (FIG. 5) of an ink jet recording apparatus, in such a manner that its liquid chamber 13 is positioned on the top side of the liquid container 11 .
[0155] Referring to FIGS. 1 and 2, the liquid container 11 is approximately in the form of a flat rectangular parallelepiped, and has two pairs of opposing walls 14 f and 14 g. The walls 14 f are the largest walls of the liquid container 11 , are connected to each other by the walls 14 g. The first and second container ID portions 22 and 23 are in the adjacencies of the bottom portion 14 b and perpendicularly project outward from the bottom ends of the pair of connective walls 14 g, one for one. The connective walls 14 g extend from the bottom portion 14 b to the top portion 14 a, like the largest walls 14 f. All the projections making up the container ID portions 22 and 23 are slightly above the bottom wall 14 b of the liquid storage portion 14 ; the ID portions are slightly displaced from the bottom wall 14 b toward the top portion 14 a. The information identified by these mechanical information identifying portions is a duplication of a part of the information stored in the electrical identification storage portions, and is limited to the information regarding ink type (color, etc.).
[0156] Further, the liquid container 11 has ribs 24 , grooves 25 (recess), or the like, which make up a non-slip area to be grasped by hand when the liquid container 11 is mounted into or removed from an ink jet recording apparatus, and which are parts of the largest walls 14 f and connective walls 14 g, being close to the top wall 14 a. In the case of this embodiment, the nonslip surfaces are created by forming grooves in the external surfaces of the largest walls 14 f, and also, forming ribs on the external surfaces of the connective walls 14 g. However, the structural arrangement for providing the nonslip surfaces does not need to be limited to the above described one; the selection and positioning of the above described ribs and grooves are optional.
[0157] FIGS. 30 - 36 are drawings for sequentially describing the steps of the process for putting the liquid drawing connective needle (hollow needle) and ambient air introducing connective needle (hollow needle), through the two holes of the bottom portion 11 e (bottom portion of bottom cover 21 ) of the liquid container 11 , and the connective holes filled with elastic substances of the mouth portion 14 k. Next, referring to FIGS. 30 - 36 , the process for putting the liquid drawing connective needle and ambient air introducing connective needle through the bottom portion lie and mouth portion 14 k of the liquid container 11 will be described.
[0158] Referring to FIG. 30, the liquid container 11 is inserted into one of the slots 32 of the station base 31 (FIG. 5) from the bottom side (bottom portion lie side). The liquid drawing connective needle 38 (hollow needle) and ambient air introducing connective needle 39 (hollow needle) project from the bottom surface of the internal space of the slot 32 . The station base 31 has two or more slots 32 which are capable of accepting one liquid container 11 , and the openings of which face virtually straight upward. Thus, two or more liquid containers 11 different in the color of the ink therein (or one of other aspects of ink therein) can be mounted in the station base 31 .
[0159] The liquid drawing connective needle 38 and ambient air introducing connective needle 39 are practically identical in length and shape, and are tapered at the end in a manner to form a sharp tip so that they can penetrate the two elastic members (for example, rubber plugs) on the inward side of the bottom portion 11 e of the liquid container 11 , being positioned at approximately the same levels. The connective needles 38 and 39 are hollow, and are closed at their tips. They have holes 38 a and 39 a, respectively, which are slightly below the tapered portion, that is, the top portion of the taper-less portion (FIGS. 33, 34, 35 , and 36 ). The liquid drawing connective needle 38 and ambient air introducing connective needle 39 are solidly fixed to the bottom surface of the slot 32 so that their tips reach approximately the same heights; therefore, the heights of the holes 38 a and 39 a are approximately the same.
[0160] First, the liquid container 11 is inserted into the slot 32 . As the liquid container 11 begins to be inserted into the slot 32 , the first and second container ID portions 22 and 23 of the liquid container 11 (bottom cover 21 ) located at the short edges, one for one, of the leading end of the liquid container 11 reach the first and second container 11 portions 33 and 34 (container ID portions on main assembly side). Thus, only when the slot 32 , into which the liquid container 11 is being inserted, is the correct slot (only when container ID portions on container side match container ID portions on main assembly side), the first and second container ID portions 22 and 23 of the liquid container 11 are allowed to pass the first and second container ID portions 33 and 34 , respectively, within the slot 32 . In other words, the liquid container 11 can be mounted into the station base 31 of an apparatus such as an ink jet recording apparatus, only when the container ID portions of the liquid container 11 match the ID portions on the main assembly side in the slot 32 into which the liquid container 11 is mounted.
[0161] The first and second ID portions 22 and 23 ID of the liquid container 11 are differentiated in the mechanical identification information (ID) (structure and measurement) to make a liquid container 11 of one type uninterchangeable with a liquid container of another type (to make it impossible to mount a liquid container of one type into a slot for a liquid container of another type). Moreover, the container ID portions of the liquid container 11 are structured so that when only one apparatus (ink jet recording apparatus or the like) is involved, each container ID portion alone, that is, the first container ID portion 22 alone or second container ID portion 23 alone, is sufficient to make a liquid container 11 of one type uninterchangeable with a liquid container 11 of another type. This is for preventing the following problem. That is, even when a liquid container is inserted into the wrong slot, a user sometimes mistakenly perceives that one of the container ID portions has passed the container ID portion on the main assembly side. If this happens, the user may think that the liquid container is in the right slot and can be further inserted, and might apply more pressure to push the liquid container farther into the slot, which might result in damage to the main assembly of an apparatus such as a recording apparatus.
[0162] FIGS. 3 ( b ), 3 ( c ), and 3 ( d ) show the different structures of the above described container ID portions located at both ends. In FIG. 3, a referential sign “o” shows the location of the notch. Also for the same reason as the above described one, the container ID portions of the liquid container 11 are structured so that even when two or more apparatuses (ink jet recording apparatuses or the like), and two or more liquid containers identical in shape and ink color, are involved, each container ID portion alone, that is, the first container ID portion 22 alone or second container ID portion 23 alone, is sufficient to make a liquid container 11 of one type uninterchangeable with a liquid container 11 of another type.
[0163] As the liquid container 11 is inserted closer to the internal bottom surface of the slot 32 , the first and second container ID portions 22 and 23 of the liquid container 11 are accurately positioned by the first and second positioning portions 35 and 36 on the internal surface of the slot 32 , as shown in FIG. 33. Therefore, the liquid container 11 can be further inserted into the slot 32 without becoming horizontally (direction X and direction Y) dislodged. For example, clearances 81 and 82 in terms of the direction X and clearance 83 in terms of the direction Y, shown in FIG. 33( a ), are regulated as measurement tolerance.
[0164] Next, referring to FIG. 33( b ), as the edges of the first and second guiding portions 29 and 30 of the bottom wall of the liquid container 11 reach the tips of the connective needles 38 and 39 , respectively, the liquid drawing connective needle 38 and ambient air introducing connective needle 39 solidly fixed to the bottom wall of the slot 32 come into contact with the first guiding portion 29 of the first connective hole 27 of the bottom wall of the liquid container It, and the second guiding portion 30 of the second connective hole 28 of the bottom wall of the liquid container 11 , respectively.
[0165] Thereafter, before the elastic members ( 16 a, 16 b ) reach the connective needles 38 and 39 , the container ID portions 22 and 23 become disengaged from the positioning portions 35 and 36 , respectively; the positioning portions 35 and 36 stop regulating the position of the liquid container 11 . In other words, from this point on, the position of the liquid container 11 in terms of the directions X and Y is regulated with reference to the connective needles 38 and 39 .
[0166] Thus, after becoming disengaged from the guiding means in the slot 32 , the liquid container 11 moves so that its connective holes 27 and 28 are guided to the connective needles 38 and 39 on the main assembly side of an apparatus (for example, liquid container 11 moves so that a distance 84 , in FIG. 33( a ), that is, the amount of the displacement of the connective needle 39 from the center of the guiding portion 30 , becomes zero). Then, the connective needles 38 and 39 begin to penetrate the elastic members 16 a and 16 b in the connective holes 27 and 28 , at virtually the same time, as shown in FIG. 34. Freeing the liquid container 11 from the positional regulation placed by the slot 32 before the liquid container 11 reaches the bottom of the slot, as described above, prevents the two connective needles 38 and 39 from being damaged by the liquid container 11 ; one of the liquid container mounting errors is eliminated.
[0167] Next, referring to FIG. 35, while the connective needles 38 and 39 penetrate the elastic members 16 a and 16 b, the tip of an electrical signal transmission connector 37 solidly fixed to the bottom surface of the slot 32 begins to enter the storage means holder 17 of the liquid container 11 . The storage means holder 17 is loosely attached to the liquid container 11 to afford the storage means holder 17 some movement relative to the liquid container 11 . Therefore, even if the storage means holder 17 is not in alignment with the electrical signal transmission connector 37 (even if there is a distance 85 between the axial lines of the storage means holder 17 and electrical signal transmission connector 37 , as shown in FIG. 34), the storage means holder 17 moves while being guided by the tapered (chamfered) portion of the leading end of the electrical signal transmission connector 37 . Therefore, it is assured that the electrical signal transmission connector 37 easily enters the storage means holder 17 ; it is smoothly connected without hanging up or causing an operator to perceive any anomaly.
[0168] Thereafter, the electrical signal transmission connector 37 completely enters the storage means holder 17 , and the liquid drawing connective needle 38 and ambient air introducing connective needle 39 finish penetrating through the first and second elastic members 16 a and 16 b virtually at the same time, as shown in FIG. 36. Then, the bottom surface lie of the liquid container 11 (bottom cover 21 ) comes into contact with a container catching portion 90 , which is on the bottom surface of the slot 32 of the station base 31 and accurately positions the liquid container 11 in terms of the direction Z. This concludes the mounting of the liquid container 11 . As a result, the liquid chamber 13 in the liquid container 11 becomes connected to a device (for example, recording head of ink jet recording apparatus) which uses the liquid in the liquid chamber 13 , and also, to the ambient air, through the connective needles 38 and 39 (through holes 38 a and 39 a, and hollows of needles 38 and 39 ), respectively.
[0169] Further, for the purpose of ensuring the positional relationship between the liquid container 11 and connective needles 38 and 39 , it is desired that the station base 31 is provided with a lever for pressing down the liquid container 11 by the top surface 14 a and keeping the liquid container 11 pressured downward; the liquid container catching portion 90 for accurately positioning the liquid container 11 in terms of the direction Z is placed between the connective needles 38 and 39 ; and the point of action of the lever is directly above the liquid container catching portion 90 (coincides with vertical line 2003 ).
[0170] In the case of the embodiment shown in FIGS. 4, 7, and 8 , the housing 1107 solidly fixed to the mouth portion 14 k of the liquid storage portion 14 by ultrasonic welding or the like has the tubular portion 45 , which projects inward of the liquid chamber 13 of the liquid storage portion 14 by a predetermined length. This tubular portion 45 may be formed by molding it as an integral part of the mouth portion 14 k of the liquid storage portion 14 , as shown in FIGS. 30 - 36 . Next, this tubular portion 45 will be described.
[0171] It was described that this tubular portion 45 is effective to prevent the deformation of the neck portion 14 e of the mouth portion 14 k and the displacement of the housing 1107 , which occurs as the mouth portion 14 k of the liquid container 11 is subjected to a strong impact. However, the tubular portion 45 has other functions in addition to the above described function, and is also effective in terms of those functions. Next, these aspects of the tubular portion 45 will be described.
[0172] Referring to FIGS. 4, 7, and 30 - 36 , the tubular portion 45 extends into the liquid chamber 13 (vertically upward), entirely surrounding the opening of the second connective hole 28 for the ambient air introduction. Referring to FIG. 36, after the mounting of the liquid container 11 into a predetermined slot 32 , the ambient air introducing connective needle 39 extends through the second connective hole 28 , and the hole of the needle 39 located close to the tip of the needle 39 is below the end (top end) of the tubular portion 45 .
[0173] [0173]FIG. 37 is a drawing which depicts an example of the structure of the system for supplying liquid (ink) to the ink jet recording head of an ink jet recording apparatus employing the liquid container 11 in accordance with the present invention, and FIG. 38 is a schematic perspective view of a preferable example of an ink jet recording apparatus employing the liquid supply system shown in FIG. 37.
[0174] Referring to FIGS. 36 and 37, when a liquid (ink) supply system is structured as is the one shown in FIG. 37, the hole 39 a at the tip portion of the ambient air introducing connective needle 39 is below the liquid ejection surface 43 (surface comprising ink ejection orifices) of the ink jet recording head 43 . In FIG. 37, a referential numeral 44 designates an ambient air introduction tube connected to the ambient air introducing connective needle 39 , and a referential numeral 41 designates a liquid supply tube connecting the liquid drawing connective needle 38 and ink jet recording head 42 .
[0175] As the ambient air is introduced through the hole 39 a of the ambient air introducing connective needle 39 , the destruction and formation of meniscus is repeated across the hole 39 a by the liquid (ink). As a result, the air sometimes forms bubbles in succession in the liquid. These bubbles must be swiftly introduced into the liquid chamber 13 of the liquid storage portion 14 , without being allowed to stagnate in the tubular portion 45 . Thus, a sufficient amount of clearance is provided between the external surface of the ambient air introducing connective needle 39 and the internal surface of the tubular portion 45 . The side wall of the tubular portion 45 plays the role of a bubble blocking wall for the first connective hole 27 (liquid drawing connective hole) which is adjacent to the tubular portion 45 , preventing thereby the bubbles within the second connective hole 28 from migrating to the adjacencies of the connective hole 27 , because there is a possibility that once the bubbles reach the adjacencies of the first connective hole 27 , they will be introduced into the ink jet recording head 42 , etc., through the first connective hole 27 .
[0176] The top edges of the tubular portion 45 are chamfered, for the following reason. That is, as the liquid level falls close to, or below, the top end of the tubular portion 45 , the body of the ink within the tubular portion 45 and the body of the ink outside the tubular portion 45 must be quickly separated. With the provision of this structural arrangement, whether or not the amount of the ink remaining in the liquid container 11 is more than the threshold value can be determined with the utilization of the conductivity of the liquid (ink) provided by the ionic components in the liquid, that is, based on whether or not electric current flows between the connective needles 38 and 39 formed of electrically conductive substance.
[0177] More specifically, the liquid container 11 can be designed so that when the liquid level within the liquid container 11 is high enough for the liquid (ink) within the liquid container 11 to cover the top end of the tubular portion 45 , and therefore, allow electric current to flow between the connective needle 39 within the tubular portion 45 and the connective needle 38 outside the tubular portion 45 , no less than 10% of the initial amount of the ink in the liquid chamber 13 still remains, whereas at the point, at which electric current stops flowing between the two connective needles 38 and 39 , and thereafter, no more than 10% of the initial amount of the ink remains. Further, providing the housing 1107 with the tubular portion 45 is also effective to prevent the housing 1107 from being attached in reverse.
[0178] The tubular portion 45 also plays the role of guiding the ambient air deep into the liquid chamber 13 of the liquid storage portion 14 . Therefore, not only is the liquid smoothly drawn out through the liquid drawing connective portion (liquid drawing connective needle 38 ), but also the liquid (ink) 12 can be used in its entirety.
[0179] Normally, the tubular portion 45 remains immersed in the body of the liquid 12 . However, as the liquid level within the liquid chamber 13 falls below the top end of the tubular portion 45 , the electrical resistance between the ambient air introducing connective needle 39 and liquid drawing connective needle 38 drastically changes. Therefore, the near-end condition, that is, the condition that the liquid container is almost out of the liquid, can be detected by reading the electrical resistance between the two connective needles 38 and 39 .
[0180] In principle, the liquid within the tubular portion 45 is not drawn out and remains therein. In other words, the space within the tubular portion 45 , which contains the connective needles 39 , is always full of electrically conductive liquid. Thus, in order to detect that the liquid level outside the tubular portion 45 has just fallen below the top end of the tubular portion 45 , it is mandatory that the body of the liquid within the tubular portion 45 and the body of the ink outside the tubular portion 45 become cleanly separated in the adjacencies of the lip of the top end of the tubular portion 45 .
[0181] However, the near-end condition sometimes fails to be detected even though the ink level has dropped below the top end of the tubular portion 45 , for the following reason. That is, if a liquid container containing liquid is kept in storage, or is left unused, for a long period of time, certain ingredients of the liquid within the liquid container adhere to the peripheral surface of the top end of the tubular portion 45 , although the severity of the adhesion varies depending on ink properties. These ingredients adhering to the top end of the tubular portion 45 allow electric current to flow between the two bodies of the liquid, making it impossible to detect the nearly empty condition of the liquid chamber 13 . In order to prevent this problem, measures must be taken for more cleanly separating the two bodies of the liquid by the lip of the top end of the tubular portion 45 . Therefore, the top edges of the tubular portion 45 are chamfered, or are given surface treatment to make the lip of the top end of the tubular portion 45 liquid repellent.
[0182] Next, referring to FIG. 38, an ink jet recording apparatus equipped with a preferable liquid supply system for using a liquid container structured as described above will be described.
[0183] The ink jet recording apparatus shown in FIG. 38 has an ink jet recording head 42 as a recording means, which is removably mounted on a carriage 2 , which is supported, and reciprocally guided, by a pair of guide rails 8 and 9 . Characters, signs, images, etc., are formed on a recording sheet S as recording medium by adhering to the recording sheet S, the ink ejected from specific ejection orifices of the recording head, while reciprocally moving the recording head in synchronism with the conveyance (secondary scanning) of the recording sheet S in the direction indicated by an arrow mark A. In other words, the ink jet recording apparatus shown in FIG. 38 is a serial type ink jet recording apparatus.
[0184] As for the recording medium (recording sheet), sheet-like medium, for example, ordinary paper, special purpose paper, OHP film, etc., are used. In recent years, fabric, nonwoven fabric, metallic sheet, etc., have come to be used in addition to the preceding media.
[0185] Referring again to FIG. 38, the ink jet recording head 42 as a recording means is on the carriage 2 , on which the ink jet recording head 42 is removably mountable, and which is made to reciprocally slide on the pair of guide rails 8 and 9 , by an unshown driving means such as a motor, while being guided by the rails 8 and 9 . The recording sheet S is conveyed by a conveyance roller 3 , in the direction intersectional to the moving direction of the carriage 2 (for example, direction indicated by arrow mark A, which is perpendicular to the moving direction of carriage 2 ), in parallel to the ink ejecting surface 43 of the ink jet recording head 42 while being kept a predetermined distance away from the ink ejection surface 43 . The conveyance roller 3 is driven by an unshown driving force source (motor or the like).
[0186] The ink ejecting surface 43 of the ink jet recording head 42 has a number of orifices from which ink is ejected, and which are aligned in two or more columns different in ink color. An ink supply unit 5 for supplying ink to the ink jet recording head 42 comprises the station base 31 , shown in FIG. 5, which is capable of holding two or more ink containers (liquid containers) 11 removably mountable in the station base 31 . These liquid containers 11 are independent from each other, and the number of the liquid containers 11 corresponds to the number of inks, which are ejected from the ink jet recording head 42 , and which are different in color. The ink supply unit 5 and ink jet recording head 42 are connected by two or more ink supply tubes (liquid supply tubes) 41 , the number of which corresponds to the number of the inks different in color. Thus, as the ink containers 11 as main containers are mounted into the ink supply unit 5 , it becomes possible for the inks in the main containers 11 , different in color, to be independently supplied to the corresponding columns of orifices of the ink jet recording head 42 .
[0187] In other words, an ink jet recording apparatus in accordance with the present invention, which records images on the recording sheet S as recording medium by ejecting ink onto the recording sheet S from the ink jet recording head 42 as a recording means, is structured so that it has an ink container mounting portion, on which one or more of the liquid containers 11 structured as described above, and uses the mounted liquid containers 11 as recording ink supply sources.
[0188] The ink jet recording head 42 as a recording means is such an ink jet recording means that uses thermal energy to eject ink. Thus, it comprises electrothermal transducers for generating thermal energy. The recording means (recording head) 42 uses the thermal energy generated by the electrothermal transducers to cause the ink to boil in the film-boiling fashion, generating bubbles in the ink, and uses the pressure changes caused by the growth and contraction of the bubbles, to eject ink from the orifices to record (print) characters, signs, images, etc.
[0189] [0189]FIG. 39 is a schematic perspective view of the ink ejecting portion of the ink jet recording head 42 , for showing the structure thereof. The ink ejecting surface (surface with ink ejection orifices) 43 of the ink jet recording head 42 faces the recording medium such as recording paper, holding a predetermined gap (for example, approximately 0.2-2.0 mm) from recording medium such as recording paper. It has a number of ejection orifices 182 arranged at a predetermined pitch. The ink jet recording head 42 as a recording means also comprises a common liquid chamber 83 , liquid paths 184 , and electrothermal transducers 185 . The liquid paths 184 connect the common liquid chamber 183 to the liquid paths 184 , one for one. The electrothermal transducers are for generating the energy for ink ejection. Each electrothermal transducer is disposed within a liquid path, along its wall. The recording head 42 is mounted on the carriage 2 so that the ejection orifices 182 align in the direction intersectional to the primary scanning direction (direction in which recording head 42 and carriage 2 are moved). The electrothermal transducers 185 are selectively driven (power is supplied thereto) by the corresponding image signals or ejection signals to cause the ink within the corresponding liquid paths 184 to boil in the film-boiling fashion so that the ink is ejected from the corresponding ejection orifices 182 by the pressure generated as the ink boils.
[0190] The ink jet recording apparatus has a recovery unit 7 , which is disposed so that it opposes the ink ejecting surface of the ink jet recording head 42 , within the range in which the ink jet recording head 42 is reciprocally moved, while being in the non-recording range, that is, the range outside the path of the recording sheet S. The recovery unit 7 comprises: a capping mechanism for capping the ink ejecting surface of the ink jet recording head 42 ; a suctioning mechanism for forcefully suctioning the ink from the ink jet recording head 42 , with the ink ejecting surface capped; a cleaning mechanism comprising a blade, etc., for wiping away the contaminants on the ink ejecting surface; and the like. Normally, the operation for suctioning ink from the recording head 42 is carried out by the recovery unit 7 prior to the beginning of a recording operation.
[0191] The solvent of ink is evaporative. Thus, the ink in the ink supply tube 41 sometimes increases in density and viscosity as the solvent therein evaporates, if the ink jet recording apparatus is left unattended for a long period of time. When there is the possibility that the ink tube contains such ink that has increased in density and viscosity for the above described reason or the like, the ink can be suctioned out through the recording head 42 by the suctioning mechanism of the recovery unit 7 , to replace the old ink in the ink supply tube 41 and head 42 with a fresh supply of ink. With this procedure, only the fresh supply of ink, the density and viscosity of which has been stabilized by the stirring caused by the suction, is used for recording, making it possible to reliably produce high quality images.
[0192] The ink used for an ink jet recording apparatus contains pigments, microscopic resin particles for improving the fixation of ink to the recording sheet S, or the like. These ingredients sometimes settle at the bottom of a liquid container if the ink in the liquid container is not used for a long period of time. Thus, an ink jet recording apparatus employing a liquid container (ink container) based on the prior art sometimes recorded low quality images (inclusive of characters, etc.) as it was used after being left unused for a long period of time. In comparison, an ink jet recording apparatus employing a liquid container in accordance with the present invention eliminates the problems traceable to the sedimentation and nonuniform distribution of the aforementioned pigments, microscopic resin particles, etc., eliminating therefore the time and labor required of a user to remove a liquid container and shake it to evenly redistribute the sediments. In other words, the employment of a liquid container in accordance with the present invention makes it possible to always use such ink that is stable in terms of the density of the pigments and microscopic resin particles, making therefore it possible to form high quality images (inclusive of characters, etc.).
[0193] According to the above described embodiments, the liquid container 11 comprises: the liquid storage portion 14 which is approximately in the form of a flat rectangular parallelepiped, and is formed of a synthetic resin; mouth portion 14 k, which is a part of the bottom portion 14 b of the liquid storage portion 14 ; and the connective portion attached to the mouth portion 14 k to connect the inside and outside of the liquid storage portion 14 . The mouth portion 14 k is on the bottom wall 14 b of the liquid storage portion 14 , which is connected to the pair of opposing largest walls 14 f of the liquid storage portion 14 along their lengthwise edges. The mouth portion 14 k is offset toward one of the shorter edges (extending in the widthwise direction of the liquid storage portion 14 ), that is, the edges at lengthwise ends of the bottom walls 14 b. The opening of the mouth portion 14 k is elongated in the lengthwise direction of the bottom wall 14 b. It is wider on the side closer to the center of the bottom wall 14 b in terms of the lengthwise direction of the bottom wall 14 b than on the side closer to the aforementioned shorter edge, that is, the edge at one of the lengthwise ends of the bottom wall 14 b.
[0194] Also regarding to the structures of the above described embodiments, the mouth portion 14 k is the only opening of the liquid storage portion 14 . The liquid storage portion 14 is formed of a synthetic resin by blow molding. The mouth portion 14 k has two connective portions: liquid drawing connective portion and ambient air introducing portion, which are approximately at the center of the bottom wall 14 b in terms of the widthwise direction of the bottom wall 14 b, aligning in the lengthwise direction of the bottom wall 14 b. The liquid drawing connective portion is closer to the shorter edge of the bottom wall 14 b, that is, the edge at the lengthwise end, than the ambient air introducing portion. The mouth portion 14 k has the neck portion 14 e projecting outward from the bottom wall 14 d of the liquid storage portion 14 , and the flange 14 d projecting from the end of the neck portion 14 e in the direction perpendicular to the axial direction of the neck portion 14 e.
[0195] Further, the connective portion connecting the inside and outside of the liquid storage portion 14 comprises the layerable members 1107 , 20 , and 1103 , which are solidly attached in layers to the end surface of the mouth portion 14 k. The layerable member 1107 has the connective hole 27 and 28 . The connective portion also comprises the elastic members 16 , which are sandwiched by these layerable members, and through which the connective needles 38 and 39 are put. The layerable members 1107 , 20 , and 1103 are solidly and sequentially fixed in layers by ultrasonic welding. The closer the layerable members to the mouth portion 14 k, the thinner the layerable members in terms of the direction in which they are attached in layers. The layerable member 1107 fixed to the mouth portion 14 k has the tubular portion 45 , which is for preventing the deformation of the internal surface of the mouth portion 14 k, and which extends inward of the liquid storage portion 14 from the layerable member 1107 .
[0196] Further, the connective needles 38 and 39 are hollow needles, and have the openings 38 a and 39 a, respectively, which are near the tips of the needles 38 and 39 . The liquid container 11 has the bottom cover 21 , which is for protecting the connective portion for connecting the inside and outside of the liquid storage portion 14 , and which is removably attached to the bottom portion 14 b of the liquid storage portion 14 . The bottom cover 21 has the recesses, into which the flange 14 d of the mouth portion 14 k partially fits to prevent the displacement of the bottom cover 21 relative to the liquid storage portion 14 . The bottom cover 21 also has the container ID portions 22 and 23 for mechanically identifying a liquid container in terms of container type or the liquid therein, and also, for preventing a liquid container from being mounted into a wrong slot. Moreover, the bottom cover 21 contains the electrical, magnetic, or optical storage medium 18 , or the storage medium 18 having the combination of the preceding properties. The storage medium 18 is capable of storing the information regarding the amount, type, etc., of the ink in the liquid storage portion 14 .
[0197] The liquid container 11 is excellent as an ink container, which is removably mounted into an ink jet recording apparatus which records images on the recording sheet S by ejecting ink onto the recording sheet S as a recording medium from the ink jet recording means as a recording means.
[0198] Further, an ink jet recording apparatus compatible with the preceding embodiments of a liquid container in accordance with the present invention has a mounting portion in which the liquid container 11 is mountable.
[0199] Further, the ink jet recording head 42 as a recording means is an ink jet recording head having the electrothermal transducers for generating the thermal energy used for ejecting ink. This ink jet recording means 42 uses the film-boiling phenomenon caused in ink by the thermal energy generated by the electrothermal transducers, to eject ink from the ejection orifices 182 .
[0200] According to the preceding embodiments of the present invention regarding the structures of a liquid container and an ink jet recording apparatus employing a liquid container, not only can the liquid storage portion 14 of the liquid container 11 be formed, as a flat, hollow container proper, which is precise, rigid, and uniform in wall thickness, even by direct blow molding 11 , but also, the mouth portion 14 k having the opening for connecting the inside and outside of the liquid storage portion 14 can be formed, by blow direct blow molding, as such a mouth portion that is precise, and uniform in wall thickness, and is an integral part of the liquid storage portion 14 of the liquid container.
[0201] Further, according to the structural designs of the above described embodiments of the liquid container in accordance with the present invention, a simple, flat, hollow container formed by direct blow molding can be used as the liquid storage portion 14 , and the mouth portion 14 k (opening) of the liquid storage portion 14 k, which has the two connective portions for connecting the inside and outside of the liquid storage portion 14 , can be reliably sealed. Further, the liquid container 11 structured as described above can be aligned by two or more, leaving virtually no space between the adjacent two containers. In other words, when the liquid container 11 in accordance with the present invention is employed as an ink container for an ink jet recording apparatus or the like, it can be compactly mounted in the liquid container mounting portion of the apparatus, that is, without the need for expanding the liquid container mounting portion in the direction in which the containers are aligned. Further, the liquid container 11 structured as described above is substantially more resistant to external shocks, being therefore more reliable, than a liquid container based on the prior art.
[0202] The characteristics of the liquid container 11 structured as described above are as follows. First, the liquid container 11 can be easily formed to highly precise measurements in terms of shape and wall thickness, even by direct blow molding, which is a low pressure molding method, and which does not require an internal mold. Second, the wall of the mouth portion 14 k is made uniform in thickness by positioning the mouth portion 14 k offset, and shaping the mouth portion 14 k so that its cross section becomes elongated, and so that the mouth portion 14 k is wider on the side closer to the center of the mouth portion 14 k than on the side closer to the edge at the lengthwise end of the bottom wall 14 b.
[0203] Third, in consideration of the fact that when the liquid storage portion 14 is formed by blow molding, the corners of the mouth portion 14 k are likely to turn out to be thinner, an ultrasonic welding means can be used, which is simple, capable of preventing the mouth portion 14 k from being deformed by the welding load generated as the layerable members 1107 and 20 for retaining the sealing members (elastic members) of the connective portion are attached to the mouth portion 14 k by ultrasonic welding, and also, capable of minimizing the loss of the welding energy.
[0204] The preceding embodiments were described with reference to a case in which the apparatus which employed the liquid containers in accordance with the present invention was an ink jet recording apparatus of a serial type. However, the present invention is also applicable to a line-type ink jet recording apparatus which records images with the use of a line-type ink jet recording head, the dimension of which in terms of the widthwise direction of a recording medium matches a substantial portion, or the entirety of, the width of the recording medium, and the application of the present invention will bring forth the effects similar to those described above.
[0205] Further, the application of the present invention is not limited to the liquid container (ink container) for an ink jet recording apparatus, which is mounted in the liquid container mounting portion of the apparatus main assembly; a liquid container to which the present invention is applicable includes, for example, a liquid container, which is directly mounted on a carriage or the like, which is reciprocally moved.
[0206] Further, the application of the present invention is not limited to liquid containers removably mountable in such an apparatus as an ink jet recording apparatus; the liquid containers to which the present invention is applicable include liquid containers permanently fixed to the apparatus.
[0207] Further, the present invention is preferably applicable to liquid containers, which are to be mounted by two or more in alignment, and which have a flat, rectangular, and parallelepipedic liquid storage portion formable by direct blow molding. Moreover, the application of the present invention is not limited by the type of a liquid container in which a liquid container in accordance with the present invention is mounted. In other words, the present invention encompasses a wide range of liquid containers in terms of the apparatus in which a liquid container is mountable.
[0208] As is evident from the above descriptions, according to claim 1 of the present invention, a liquid container comprises: a liquid storage portion, approximately in the form of a flat, rectangular parallelepiped, formed of synthetic resin; and a mouth portion, which is a part of the bottom portion of the liquid storage portion, and to which the connective portion for connecting the inside and outside of the liquid storage portion is attached. The mouth portion projects from the bottom wall of the liquid storage portion, which connects, at its lengthwise edges, to the largest walls of the liquid storage portion, which oppose each other. The mouth portion is offset toward one of the short edges of the bottom wall, that is, the edges at the lengthwise ends of the bottom wall. The configuration of the mouth portion is such that the cross section of the mouth portion is elongated in the lengthwise direction of the bottom wall, and that the mouth portion is wider on the side closer to the center of the bottom wall in terms of the lengthwise direction of the bottom wall than on the side closer to the aforementioned shorter edge of the bottom wall. Therefore, even as the flat, rectangular, parallelepipedic liquid storage portion is formed by direct blow molding, it turns out to be precise, highly rigid, and uniform in wall thickness. Further, the mouth portion, which is the opening for connecting the inside and outside of the liquid storage portion can be integrally formed with the liquid storage portion so that it turns out to be precise and uniform in wall thickness.
[0209] The liquid container in accordance with the present invention is structured so that the mouth portion is the only opening of the liquid storage portion; the liquid storage portion can be formed of a synthetic resin by blow molding; the connective portion comprising two portions, that is, the liquid drawing connective portion and ambient air introducing connective portion, is attached to the mouth portion; the two portions of the connective portion are aligned in the lengthwise direction of the bottom wall of the liquid storage portion, approximately at the center line of the bottom wall of the liquid storage portion in term of the widthwise direction of the bottom wall; and the liquid drawing connective portion is positioned closer to one of the shorter edges, that is, the edges at the lengthwise ends, of the bottom walls of the liquid storage portion than the ambient air introducing connective portion. Therefore, the present invention can provide an efficient liquid container, that is, a liquid container which demonstrate the above described effects.
[0210] Further, the liquid container in accordance with the present invention is structured so that the mouth portion comprises the neck portion projecting from the bottom surface of the liquid storage portion, and the flange projecting outward from the end of the neck portion in the direction perpendicular to the side wall of the neck portion; and the connective portion for connecting the inside and outside of the liquid storage portion comprises two or more layerable members, which have connective holes, and which are attached in layers to the end surface of the mouth portion, or comprises two or more layerable members, which have connective holes, and which are attached in layers to the end surface of the mouth portion, with the elastic members penetrable by the connective needles being retained among the layerable members. Therefore, the present invention can provide a liquid container which more efficiently provides the above described effects.
[0211] Further, the liquid container in accordance with the present invention is structured so that two or more layerable members are sequentially and solidly attached by ultrasonic welding; the closer the layerable members to the mouth portion, the thinner they are; one of the layerable members solidly attached to the mouth portion has the tubular portion extending inward of the liquid storage portion to prevent the internal surface of the mouth portion from deforming; and hollow needles having an opening close to their tips are used as the connective needles. Therefore, the liquid container in accordance with the present invention easily and reliably seals the liquid storage portion, in addition to providing the above described effects.
[0212] Moreover, the liquid container in accordance with the present invention is structured so that the bottom cover for protecting the connective portion for connecting the inside and outside of the liquid storage portion can be removably attached to the bottom portion of the liquid storage portion; the internal surface of the bottom cover has the recesses into which the mouth portion fits to prevent the bottom cover from being displaced from the liquid storage portion; the liquid container has the container ID portion for mechanically identifying liquid type or container type, and for preventing erroneous mounting of the liquid container; the electrical, magnetic, or optical storage medium, or storage medium having a combination of electrical, magnetic, and optical properties, for storing the information regarding the amount, type, etc., of the ink within the liquid storage portion is held within the bottom cover; and the liquid container is removably mountable in an ink jet recording apparatus which records images on a recording medium by ejecting ink from a recording means onto the recording medium. Therefore, the liquid container in accordance with the present invention is well protected even from external shocks, in addition to providing the above described effects.
[0213] While the invention has been described with reference to the structures disclosed herein, it is not confined to the details set forth, and this application is intended to cover such modifications or changes as may come within the purposes of the improvements or the scope of the following claims. | A liquid container having a generally flat rectangular parallelepiped shape includes opposite major sides; an elongated bottom side connecting the opposite major sides; a port, formed adjacent a longitudinal end portion of the bottom side, for fluid communication between an inside and an outside of the liquid container, the port being eleongated in a longitudinal direction of the bottom side and having a width which is larger adjacent a longitudinally central portion of the bottom side than adjacent the longitudinal end portion. | 1 |
BACKGROUND AND CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] In the opinion of the inventor this device provides substantial advantages, novelty and inventive steps over prior art particularly with reference to BE 1000391, DE 3312392, U.S. Pat. No. 4,521,128, U.S. Pat. No. 5,913,632, U.S. Pat. No. 5,918,996, U.S. Pat. No. 5,842,487, U.S. Pat. No. 5,769,553, U.S. Pat. No. 5,100,252, U.S. Pat. No. 5,066,155, U.S. Pat. No. 4,291,995, U.S. Pat. No. 6,056,469, U.S. Pat. No. 6,062,233, U.S. Pat. No. 6,095,710 in a number of respects;
[0002] it is of an economic, unique and simple design, constructed with minimal assembly required, when compared to prior art,
[0003] it is disposable and is delivered to consumers fully sealed, pre-filled with dentifrice, assembled and ready for use, thus is used with ease and convenience, when compared to prior art,
[0004] provides the potential for a substantial amount of paste to last the recommended lifetime of the brush without refilling, when compared to prior art,
[0005] all parts may be manufactured out of a suitable plastic, or some other material, thus reducing costs, when compared to prior art,
[0006] Due to the inventive design the piston does not have to be wound down the length of the threaded shaft to get it into a starting position thus reducing assembly time, when compared to prior art,
[0007] The inventive design allows an assembly order such that the entire neck, head and body may be filled with dentifrice thus maximizing the devices economy, when compared to prior art,
[0008] The devices flip top cap allows the dentifrice to be sealed after each successive use, thus preventing the dentifrice from drying out or leakage, when compared to prior art.
SUMMARY
[0009] A new, disposable toothbrush and toothpaste combination unit, that allows for dentifrice or gel to be stored internally in the entire body, neck and head of the brush for dispensing dentifrice onto the toothbrush bristles by turning a knob as displayed in FIGS. 1 and 18.
[0010] After the knob is turned, the user then simply brushes their teeth with the device and rinses off the bristles with water and replace the flip top cap (if desired) and the brush is ready for use again next time, (hereafter referred to as the device).
[0011] The inventive device is constructed so that it is delivered to the user, without any required product assembly or loading of dentifrice. It also provides a tamper proof seal for the dentifrice before use and is simple and economical to manufacture, assemble and use.
[0012] The dentifrice is extruded through a central delivery nipple, on the brush head in the middle of the bristles, by the forward action of a piston along a threaded shaft. The delivery nipple does not protrude as high as the bristles from the brush head face. This nipple is surrounded by a plurality of bristles configured so they act as a funnel to ensure the dentifrice is guided up onto the top of the brush bristles and when not in use the brush head portion is covered and dentifrice is sealed from contamination and air by a removable head cap when not in use. The dentifrice delivery nipple is sealed by the flip top cap.
[0013] The flip top cap allows the device to be sealed after each successive use thus stopping the dentifrice from drying out, maintaining a hygienic seal when not in use and preventing any accidental extrusion of paste at any time.
[0014] The hand driven actuation of a knob or end cap (hereafter referred to just as “knob”, but also meaning end cap), which also acts as a sealing cap rotates the threaded shaft. The amount of dentifrice can be observed through the indicator window. The handle or body is a near isosceles shape, with rounded edges, (hereafter referred to as just “near isosceles shape”) which is ergonomic to hold and use. At the knob end of the body this moulded plastic near isosceles shape, smoothly morphs into a circle to facilitate the knob. This portion of the body also has stabilizing feet to ensure that the brush will remain bristles up when placed on a flat surface. The knob has directional arrows on it to indicate the correct knob turning direction.
[0015] The objective of the device is to provide a ready, easy, hygienic, safe, effective, ergonomic, economical, portable and atheistically pleasing toothbrush and toothpaste combination unit.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0016] To aid understanding the follow discourse will explain the individual figures that are used in my detailed description. I now refer to FIG. 1 through to FIG. 19, by complete figure references, which show the inventive device, the claims or principals contained and embodied therein.
[0017] The exterior of the device is displayed in FIG. 1, in angled side views and the bristles, body, knob, directional arrows, delivery nipple, head, neck and mating flange can be seen.
[0018] [0018]FIG. 2 shows the device exterior from a top, rear, side and front view. The delivery nipple position is noted and bristle configuration can be observed.
[0019] [0019]FIG. 3 shows the device with an exploded view of the rear assembly of the device. Here the threaded shaft, piston, knob, tapered flange, lip and seat are identified.
[0020] [0020]FIG. 4 shows the interior view regarding the order of assembly, on how the piston, threaded shaft (male) and knob (female) may be assembled and also identifies tapered male and female octagonal, the tapered threaded lead in, the internal piston thread, the piston flange and the locating lug or lip.
[0021] [0021]FIG. 5 shows various cross-sectional's of the assembled device and identifies the dentifrice reservoir and identifies the reservoir, shaft, piston, knob and cross sectional end view.
[0022] [0022]FIG. 6 shows a close up of the brush head and identifies the bristle configuration. A cross sectional of the brush head identifying the delivery nipple, the brush head portion of the dentifrice reservoir, the bristles and the extent to which the delivery nipple protrudes past the brush head face is also shown.
[0023] [0023]FIG. 7 shows a close up of the knob, piston, and threaded shaft assembled into the body in the starting position. The fastener, piston, shaft, tapered octagonal interface and knob are identified. Noteworthy here is the inventive fastening mechanism.
[0024] [0024]FIG. 8 shows various views of the knob and the knob interior and exteriors are identified. Also shown are the end and a cross sectional view of the knob.
[0025] [0025]FIG. 9 displays the fully assembled device, complete with the brush head cap. For orientations purposes the knob, brush head cover (flip top cap) and body are identified.
[0026] [0026]FIG. 10 shows a close up view of the brush stabilizing feet and displays an angled view of the external shape or profile of the invention. The brush body, cap, body end, feet and external profile are noted.
[0027] The following diagrams explain the flip top cap, which seals the delivery nipple.
[0028] [0028]FIG. 11 shows the exterior of the device, in angled side views and the hinge, ventilation holes, finger undercut and internal lip can be seen.
[0029] [0029]FIG. 12 shows the flip top cap exterior from a top, side, end and cross sectional (A-A) view. The sealing mechanism and finger-undercut positions are noted.
[0030] [0030]FIG. 13 shows the flip top cap assembled into or onto the flip top cap. Top, side and end views are noted.
[0031] [0031]FIG. 14 shows the flip top cap unassembled and in the flipped open position. The guards, lid, latch, body, lip edges and finger undercut can be seen.
[0032] [0032]FIG. 15 shows the flip top cap unassembled and in the flipped open position from a top, side, end and cross sectional view. The sealing mechanism and ventilation holes are noted.
[0033] [0033]FIG. 16 shows the flip top cap assembled onto the brush and in the flipped open position from a top, side, and cross sectional end view. Here the toothbrush head of the device is noted.
[0034] [0034]FIG. 17 shows a close up of the head section of FIG. 16. The flip top cap can be seen assembled onto the brush and in the flipped open position from a top and side view. Here the hinge and catch are noted.
[0035] [0035]FIG. 18 shows the flip top cap assembled onto the device in a side on, cross-sectional view, the device is shown here without bristles.
[0036] [0036]FIG. 19 shows a close up of the head section of FIG. 18. The flip top cap can be seen assembled onto the brush. Here the lid lip, sealing mechanism and ribs can be seen.
DETAILED DESCRIPTION OF THE INVENTION
[0037] The following statement is a full description of this invention:
[0038] This invention relates to the combining of a toothbrush and toothpaste into one combined and compact unit. This device will address the need for a convenient method of brushing your teeth that is portable and compact, particularly while away from home, but can be used as an everyday brush. This device also eliminates the need for toothpaste tubes, toothbrush and toothpaste holders or containers.
[0039] A typical embodiment of this disposable toothbrush and dentifrice combination unit is displayed and comprising of and by reference, to numerical FIGS. 1 thought to 19 (identified as figure) and the individual numerical item numbers (identified as ref. and identifying individual parts within a figure), contained herein and the device is described as follows:
[0040] A toothbrush, whose entire internal head, neck and body cavity are able to be loaded with toothpaste, dentifrice or gel for cleaning teeth. Consisting of a handle or body which is a near isosceles shape, with rounded edges (refer FIGS. 1 & 2). It has a storage section with a surrounding wall section to define the storage chamber or reservoir, within which dentifrice is contained. The body is open at one end to receive the knob. The brush delivery nipple, head, neck, body and knob receiver may be moulded in one entire section.
[0041] A toothbrush head section that has a plurality of bristles that extend from the brush head. The head section also has a dentifrice storage section, with a surrounding wall section that defines the storage chamber. This section is a seamless continuation of the body's dentifrice reservoir.
[0042] The brush head may be a continuation of the above-mentioned brush body or detachable, the head section internally and externally seamlessly morphs to the body section in one continuous piece.
[0043] The preferred embodiment for sealing the delivery nipple is via the flip top cap and is described as follows:
[0044] A typical embodiment of the flip top cap is displayed and comprising of and by reference, to numerical FIGS. 9 thought to 19 (identified as figure) and the individual numerical item numbers (identified as ref. and identifying individual parts within a figure), contained therein and the device is described as follows:
[0045] A flip top cap, which is used to cover the head of a toothbrush and seal in the dentifrice contained therein. Consisting of a body (ref 75 . & 93 .) that fits onto the hand of the brush and a lid (ref 68 ., 76 ., 81 . & 92 .)
[0046] The flip top cap is secured in place by a lip, groove and stop guide mechanism on the exterior of the brush body near the neck and a lip and stop guide on the internal face of the leading edge of the cap (ref 59 .). The internal lip and stop guide of the head cap exists around the entire interior circumference of the head cap. The groove and stop guide, exist around the entire exterior circumference of the body. The installed brush head cap (the flip top cap) is displayed in FIGS. 9, 13, 18 and 19 . In FIG. 19 the lid lip mechanism can be seen (ref 101 .).
[0047] The lid (ref 68 .) is held onto the body by way of a hinge (ref 57 . & 87 .) which allows the lid to move up or down. During the lid closing movement, the lid edges are guided into position by mating with the lip groove edges (ref 72 .) on the body. This ensures proper alignment and sealing.
[0048] In the closed position the lid is held in position by a latch (ref 69 . & 96 .) located on the lid. The latch is flexible and has a hook on the end, which interfaces with the end of the finger undercut (ref 95 .) portion of the body thus securing it in place, but still allowing the lid to be flipped open as desired by placing your finger into the finger undercut (ref 95 .) and lifting upwards.
[0049] The lid also has a sealing mechanism (ref 63 ., 78 ., 84 ., 90 ., & 98 .) which seals the dentifrice. This is achieved by placing the sealing mechanism into the internal core of the delivery nipple, guided into place by the delivery nipple tulip (ref 33 .). The sealing mechanism has a circular protrusion, which interfaces with the internal wall section of the delivery nipple creating a seal. The sealing mechanism is reinforced by ribs (ref 99 .) around its base.
[0050] The flip top cap is installed onto the brush by the following steps. The cap in the flipped open position is put onto the body of the brush so that the lid lip (ref 101 .) interfaces at its seated position. The lid portion of the flip top cap is then lowered into position so that the latch mechanism (ref 96 .) interfaces with the end portion of the undercut (ref 95 .). In this closed position the sealing mechanism is interfacing with the internal wall of the delivery nipple, thus creating a seal. The device is removed in by flipping the lid (ref 68 .) open and then pulling the flip top cap it off the brush's body.
[0051] The lid portion of the flip top lid also has guards (FIG. 14, ref 67 .). These prevent the removal of the flip top cap from the brush without opening the lid first. This prevents the sealing mechanism from being bent by improper removal. The guards, when in place, fit around the tooth brush head of the brush.
[0052] There is a round knob (ref 3 . & FIG. 8) that has an interior one way locating lug and or clip fastening (ref 25 . & 37 . & 41 .) mechanism. This mechanism enables the knob to snap onto the end of the handle thus sealing the handle end (FIG. 7), but still allowing the knob to be turned in this location. There is a threaded shaft that mate's into the knob (FIGS. 5 & 7). This occurs by way of a tapered male octagonal spigot (ref 21 .) end section on the threaded shaft. This end section, by way of interference fit, couples with the female tapered octagonal cavity (ref 20 . & 44 .) located in the centre of the knob.
[0053] The knob (FIG. 8) is located onto the body via a one-way snap on mechanism (ref 18 . & 25 . & 37 . & FIG. 7) contained in the exterior of the body and the interior of the knob. The knob has an interior leading edge that is an angled tapered one way lip that hooks itself into a groove or seat on the body. Just behind the interior leading edge, the knob has a square recess that sits on a mirror image protrusion existing on the brush body. The recess and lip exist around the entire interior circumference of the knob (FIG. 7 & ref 18 .). The protrusion and groove exist around the entire exterior circumference of the brush body (FIGS. 7 & 8).
[0054] The bodies exterior end section has a square protrusion and a square groove or seat, within which the interior face of the knob's lip and recess mates with the bodies lip and groove (ref 18 . & 19 . and FIG. 7). This method fastens the knob onto the open end of the body (ref 37 . & FIG. 3), but still allows the knob and threaded shaft to be rotated.
[0055] This rotation will cause the forward movement of the piston (ref 15 .) that is engaged via its internal female thread, on the threaded shaft, to move along the threaded shaft (ref 14 .). Thus, an internal piston may be moved from the knob end of the body, to the head end of the body, by the turning of the external knob.
[0056] The one-way snap on action of the fastening mechanism, discourages the knob from being pushed or pulled off. The knob exterior is of such an angle and has exterior grooves to aid gripping and turning during actuation but discourages the user from pulling the knob off (ref 16 . and FIGS. 7 & 8).
[0057] The threaded shaft (ref 14 . & 22 . & 29 . & 39 .) physically communicates with the knob. This is via the threaded shaft's tapered male octagonal interference fitting spigot (ref 21 . & 40 .) at one end, with the knob's female tapered octagonal receiver (ref 20 .), located in the centre of the knob. The other end of the threaded shaft is free floating, surrounded by dentifrice and not attached or fixed to any wall section. The threaded shaft self-centres as the piston travels down the shaft.
[0058] The threaded shaft and knob configuration is such that it allows the piston (ref 15 .) to be pushed over the octagonal spigot portion of the shaft, onto the tapered threaded portion, of the threaded (ref 21 . & 22 .) shaft during assembly.
[0059] The knob is pushed on thereafter (FIG. 4), onto the male octagonal spigot portion of the threaded shaft. The clearance between the internal face of the knob and the piston (ref 30 . & 31 . & FIG. 7) is such that, generally only forward motion of the piston during initial knob rotation is allowed.
[0060] The tapered male octagonal spigot end (ref 21 .) of the threaded shaft is smaller in exterior diameter than the threaded portion of same shaft (ref 14 . & 22 .). This allows the easy placement of the piston onto the threaded shaft during assembly, since the internal piston thread diameter (ref 23 .), which is located in the piston's centre, is also larger than the tapered male octagonal spigot end of the threaded shaft. After the piston is assembled over the octagonal spigot portion of the shaft, it is then located onto the tapered starting thread (ref 22 .), on the threaded shaft. This results in correct piston location, without having to wind the piston down any length of the threaded shaft to get it into the start position (FIGS. 4 & 5 & ref 38 .).
[0061] There is a piston that has an internal female thread in its centre (ref 23 .), which engages and moves along the threaded shaft. The piston thread is the mating thread for the threaded shaft. The piston has a specially angled flange (ref 24 .) that grips the internal body reservoir wall (ref 30 .). As the piston travels down through the internal brush body reservoir, the piston creates hydraulic pressure forcing the dentifrice to be extruded out of the toothbrush head's delivery nipple opening. The piston will not rotate or spin, due to the near isosceles shape, of the toothbrush handle or body. The piston shape is the same as the bodies internal near isosceles shape, with rounded edges. The piston flange angle is such so as to soak up any required draft or manufacturing variance in the interior of the body wall, and provides structural strength so the piston flange will not “lip out” or fail;
[0062] An internal tapered flange (ref 17 .) is located at the internal face of the open portion of the toothbrush body end where the knob clips on. The flange morphs smoothly from a round shape to accommodate the knob, to the main bodies near isosceles shape; thus both internal shapes are accommodated seamlessly in one continuous piece (FIGS. 1 & 2 & 3 & 9 ). This internal tapered flange allows the piston to be guided into the correct position during assembly and initial knob actuation. The circular brush body end portion is larger in external and internal diameter than the near isosceles shape portion of the brush body. This size difference provides clearance for the piston to be put in place, onto the internal tapered flange and accommodates the knob.
[0063] During the assembly process, the knob, piston and threaded shaft are assembled together into one combination unit (FIGS. 3 & 4 & 5 & 7 ). This knob, piston and threaded shaft unit are installed into the open end of the brush body cavity (FIGS. 3 & 5) and fastened by the above-mentioned one-way locking mechanism (FIG. 7). The brush reservoir is filled with dentifrice (ref 28 .) just before the knob, piston and threaded shaft unit is installed. No dentifrice comes out of the delivery nipple (ref 33 and 100 .) due to the flip top cap being in place (ref 98 .).
[0064] When in this position the knob is free to rotate but will not come off the end of the brush body. This seals the open end of the brush body, but allows the forward activation of the piston. FIG. 5 shows the assembled toothbrush and toothpaste combination unit in a cross sectional view, without the head cap.
[0065] The knob (FIG. 8) is of such construction that it allows the device to stand on its knob end for display, storage or after use purposes. The knob also has directional arrows (ref 4 . & FIG. 8) to designate the required direction of rotation to activate the forward motion of the piston.
[0066] The brush body at the circular end, near the mating flange (ref 8 .) has small stabilising feet, located on the exterior bottom surface of the brush body. The feet enable the brush to lie on its back with bristles in the air, without the brush rolling onto its side during storage, display or after use. Thus the feet provide brush stability, while at rest.
[0067] This device has a simple and inventive assembly progression as per claim two (see FIGS. 3 & 4) due to the internal construction and design of this device. This assembly progression results in the device being entirely sealed, fully loaded with dentifrice and fully assembled ready for use in a simple manner.
[0068] The delivery nipple is not as high as the bristles but does protrude above the brush head face section (FIGS. 6 & 12). The delivery nipple is soft and flexible, not hard and stiff to protect the user's teeth.
[0069] A toothbrush head that has pre-moulded bristle holes, which means such holes do not need to be formed by drilling to allow tufting, thus eliminating a manufacturing process. A special bristle hole configuration and layout that forms a bristle tube around the delivery nipple to guide the dentifrice upward onto the top of the bristles (ref 10 . & 32 .)
[0070] The installed brush head cap is displayed in FIGS. 9, 13 and 18 .
[0071] An indicator window is provided on the side of the toothbrush body so one can observe the amount of dentifrice remaining, this may but put in place by moulding, translucency, printing or labelling.
[0072] All the parts of the device can be made from suitable food grade plastics or suitable substitute material thus increasing economic viability of such a device. | A new, disposable toothbrush and toothpaste combination unit, that allows for dentifrice or gel to be stored internally in the entire body, neck and head of the brush for dispensing dentifrice onto the toothbrush bristles via a delivery nipple by turning a knob as displayed in FIGS. 1 and 18. This is accomplished by the inventive construction, assembly order and design of the device. The device will stand up on the flat face of the knob and the device will sit on it's back due to feet located on two sides of the brush body thus stopping it from rolling onto its side when placed down after use, the devices shape is a near isosceles triangle which is an ergonomic size and shape which makes using and gripping the device easy and comfortable. The device has a flip top cap comprising of hollow cylindrical push on cover for the brush head with a plastic hinged movable flap that has a centrally located tapered shaft that inserts into the interior of the delivery nipple, thus creating an air tight seal in the dentifrice delivery nipple when moved into a closed position after each use. The device is assembled by snapping, interfacing or pushing the components together, and resulting in an assembly is easy and economic to assemble but that cannot be pulled apart easily, and increasing the devices safety and economy. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to apparatus and methods for use in a wellbore to control the distribution of injected material in a wellbore. More particularly, the invention relates to methods and apparatus for providing a more uniform gravel pack in a wellbore.
2. Background of the Related Art
Hydrocarbon wells, especially those having horizontal wellbores, typically have sections of wellscreen comprising a perforated inner tube surrounded by a screen portion. The purpose of the screen is to block the flow of unwanted materials into the wellbore. Despite the wellscreen, some contaminants and other unwanted materials like sand, still enter the production tubing. The contaminants occur naturally and are also formed as part of the drilling process. As production fluids are recovered, the contaminants are also pumped out of the wellbore and retrieved at the surface of the well. By controlling and reducing the amount of contaminants that are pumped up to the surface, the production costs and valuable time associated with operating a hydrocarbon well will likewise be reduced.
One method of reducing the inflow of unwanted contaminants is through gravel packing. Normally, gravel packing involves the placement of gravel in an annular area formed between the screen portion of the wellscreen and the wellbore. In a gravel packing operation, a slurry of liquid, sand and gravel (“slurry”) is pumped down the wellbore where it is redirected into the annular area with a cross-over tool. As the gravel fills the annulus, it becomes tightly packed and acts as an additional filtering layer along with the wellscreen to prevent collapse of the wellbore and to prevent the contaminants from entering the streams of production fluids pumped to the surface. Ideally, the gravel will be uniformly packed around the entire length of the wellscreen, completely filling the annulus. However, during gravel packing, the slurry may become less viscous due to loss of fluid into the surrounding formations or into the wellscreen. The loss of fluid causes sand bridges to form. Sand bridges are a wall bridging the annulus and interrupting the flow of the slurry, thereby preventing the annulus from completely filling with gravel.
The problem of sand bridges is illustrated in FIG. 1, which is a side view, partially in section of a horizontal wellbore with a wellscreen therein. The wellscreen 30 is positioned in the wellbore 14 adjacent a hydrocarbon bearing formation therearound. An annulus 16 is formed between the wellscreen 30 and the wellbore 14 . The Figure illustrates the path of gravel 13 as it is pumped down the production tubing 11 in a slurry and into the annulus 16 through a crossover tool 33 .
Also illustrated in FIG. 1 is a formation including an area of highly permeable material 15 . The highly permeable area 15 can draw liquid from the slurry, thereby dehydrating the slurry. As the slurry dehydrates in the permeable area 15 of formation, the remaining solid particles form a sand bridge 20 and prevent further filling of the annulus 16 with gravel. As a result of the sand bridge, particles entering the wellbore from the formation are more likely to enter the production string and travel to the surface of the well. The particles may also travel at a high velocity, and therefore more likely to damage and abrade the wellscreen components.
In response to the sand-bridging problem, shunt tubes have been developed creating an alternative path for gravel around a sand bridge. According to this conventional solution, when a slurry of sand encounters a sand bridge, the slurry enters an apparatus and travels in a tube, thereby bypassing the sand bridge to reenter the annulus downstream. The shunt tubes may be placed on the outside of the apparatus or run along the interior thereof. However, there are problems associated with both designs. For example, by being outside of the apparatus, the shunt tubes are susceptible to breakage or deformation during construction or placement of the wellscreen in the wellbore. Additionally, since the shunt tubes are on the outside, the overall diameter of the production apparatus is increased, thereby decreasing the diameter of the annulus, and decreasing the filtering capabilities of packed gravel.
Shunt tubes located inside an apparatus are limited in their internal diameter and are generally constructed with little cross-sectional volume. Shunt tube-type devices also typically provide one location for slurry to enter and one location for slurry to exit. The entry and exit apertures cannot be easily relocated or adjusted for conditions of formations downhole because they are pre-manufactured. For example, when a sand bridge is by-passed using one of these conventional designs, the slurry reenters the annulus where the shunt tube exits the apparatus. As a result, the slurry may reenter the annulus adjacent the same highly permeable, formation causing the liquid portion of the slurry to be lost into the formation and more sand bridges to be formed as a result of the increased viscosity of the slurry.
There is a need therefore, for a wellscreen having an alternative pathway for injected material to by-pass sand bridges or other obstructions in a wellbore. There is a further need therefore, for a wellscreen that diverts the flow of a gravel slurry to the interior of the wellscreen and, thereafter, redirect the slurry to the exterior of the screen at a predetermined location along the wellbore. There is yet a further need for a wellscreen that controls the reentry of the slurry by decreasing, increasing or closing apertures formed in a wall of the wellscreen. There is a further need therefore, for a wellscreen for use with gravel packing operations that provides a bypass for slurry wherein the bypass provides a channel of greater volume than prior art devices. There is yet a further need for a wellscreen for use with a gravel packing operation wherein the openings of apertures are resistant to erosion by high velocity particles.
SUMMARY OF THE INVENTION
The present invention generally provides for an apparatus for use in a wellbore having an alternative pathway for a slurry to by-pass an obstruction such as a sand bridge during gravel packing.
In one aspect of the invention, an apparatus includes a perforated base pipe, a wire wrap around the perforated base pipe and an annular space therebetween providing an alternative pathway for a slurry to by-pass a sand bridge. At least one aperture is formed through the wire wrap to provide a path for slurry into the apparatus and at east one aperture is formed through the wire wrap to provide a path back out of the apparatus. Another aspect, an apparatus additionally includes a second wire wrap around the first wire wrap and forming a second annular space in the apparatus to provide an alternative pathway for a slurry to by-pass a sand bridge.
In another aspect, the invention provides a method to control and predetermine the optimal exit point for the slurry to reenter the annulus from the alternative pathway of the apparatus. The method comprises collecting information such as geological surveys and tests of the wellbore to determine the type of formations that would be encountered down hole during production; analyzing the information; adjusting the size and/or plugging up the apertures of the screen with inserts based upon the collected information, and adding protective inserts to the apertures if highly abrasive particles are present in the wellbore. In yet another aspect of the invention, the apparatus does not include a base-pipe but only two tubular-shaped wire wraps with an annular space formed therebetween.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features, advantages and objects of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof 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.
FIG. 1 is a side view, partially in section of a horizontal wellbore with a wellscreen therein.
FIG. 2 is a side view of the present invention disposed in a wellbore.
FIG. 3 is a cross-sectional view of the invention taken along line 3 — 3 of FIG. 2 .
FIG. 4 is a side view of an embodiment of the present invention disposed in a wellbore.
FIG. 5 is a cross-sectional view of an embodiment of the invention taken along line 5 — 5 of FIG. 4 .
FIG. 6 is a flow chart illustrating a method of the current invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 2 is a section view of an apparatus 100 according to the present invention disposed in a wellbore 14 and FIG. 3 is a cross-sectional view of the apparatus 100 taken along line 3 — 3 of FIG. 2 . Although apparatus 100 is shown in a horizontal wellbore, the present invention can be utilized in any wellbore. In FIG. 2, the apparatus 100 is shown having collars 41 disposed between sequential sections of wellscreen 30 . In this manner, the apparatus can be made up to any length by threading sections of wellscreen 30 together using collars 41 therebetween.
Wellscreen 30 includes a base pipe 31 having perforations 19 through the wall thereof. While the base pipe is perforated in the Figures shown, the base pipe may be slotted or include perforations of any shape so long as the perforations permit the passage of production fluid but inhibit the passage of particles. A first set of spacers 38 , visible in FIG. 3, separate the perforated base pipe 31 from a first wire wrap 32 to create a first annular space 35 between the base pipe 31 and the first wire wrap 32 . Additionally, the invention may be practiced without a base pipe so long as the wire wraps are arranged to provide an annular area therebetween and are resistant to collapse. A second set of spacers 47 separate the first wire wrap 32 from a second wire wrap 39 to create a second annular space 36 therebetween. The first and second wire wraps 32 , 39 each may be made up of coil wires extending circumferentially around the base pipe 31 . In the embodiment shown, the wire wraps are slightly spaced apart by spacers 38 , 47 to permit production fluid to pass into the perforated base pipe 31 , but also to prevent particles from entering the base pipe. In the embodiment of FIGS. 2 and 3, the second annular space 36 forms an alternative pathway through the apparatus. More specifically, the purpose of annulus 36 is to provide an alternative pathway for slurry through the apparatus when the annulus 16 between the apparatus 100 and the wellbore 14 is blocked by a sand bridge 20 .
When the flow of slurry in annulus 16 is blocked by the presence of a sand bridge, the slurry enters the second annular space 36 through an entry aperture 34 formed in the wall of the wellscreen or, as illustrated in FIG. 2, formed in a collar 41 . Second annular space 36 allows the slurry to by-pass the sand bridge 20 and the flow path through annular space 36 is illustrated with arrows 40 .
FIG. 2 also illustrates a feature of the invention designed to ensure that the reentry of the slurry into the wellbore occurs at an optimal location in the wellbore. In FIG. 2 for example the aperture 48 adjacent entry aperture 34 is also surrounded by highly permeable formation 15 . In order to prevent the slurry from reentering the annulus 16 in this continued area of high permeability, aperture 48 has a reduced inner diameter. In the preferred embodiment, the inner diameter of the aperture 48 is reduced with an insert 43 in order to discourage the flow of slurry back into the annulus 16 via aperture 48 . Instead, the flow of slurry is encouraged to continue to the next aperture 49 as illustrated by arrows 40 . Aperture 49 is constructed and arranged with a larger inner diameter. Consequently, as the flow of slurry reaches the next aperture 49 , the slurry will reenter the annulus 16 where the formation of a gravel pack in the annulus will continue. By utilizing other apparatus 100 in the string of wellbore, additional sand bridges can be avoided in a similar manner. Since the alternative pathway provided by the second annular space 36 is larger than conventional shunt tubes, the apparatus 100 is able to carry more slurry at a faster rate to form a gravel pack more rapidly.
While FIGS. 2 and 3 show one embodiment of the invention, the invention may also be practiced in alternative embodiments such as the one shown in FIG. 4 . FIG. 4 is a side view of an apparatus 200 of the present invention disposed in a wellbore and FIG. 5 is a cross-sectional view of the apparatus taken along line 5 — 5 of FIG. 4 . The apparatus 200 has a perforated base pipe 31 with perforations 19 , a first wire wrap 32 disposed directly around the base pipe 31 with no annular space therebetween, and a second wire wrap 39 disposed around the first wire wrap 32 , and separated therefrom by a first set of spacers 38 (FIG. 5) to form an annular space 35 . In this embodiment, annular space 35 forms an alternative pathway for slurry to travel in the apparatus. Another alternative embodiment includes a perforated base pipe 31 that is slotted or manufactured with openings that act to filter particles. A wire wrap 32 disposed around the perforated base pipe 31 and separated by first set of spacers 38 to form an annular space 35 for the alternative pathway.
FIG. 6 is a flow chart illustrating a method of utilizing the current invention. Initially, information about the formations surrounding the wellbore is collected 60 . The information is then analyzed 61 to determine the optimal entry and exit locations for slurry. The apparatus arrives at the well site with numerous apertures 34 prefabricated therein. Inserts 43 having various inner diameters are also supplied. The inserts 43 are also manufactured from erosion resistant materials such as tungsten carbide or ceramic and made to fit the apertures 34 . Before the wellscreen 30 is inserted into the wellbore, the apertures are pre-sized 62 using inserts to determine the optimum entry and exist points for the slurry based upon the location of highly permeable portions of formations surrounding the wellbore. If permeable formations exist, apertures 34 are sized by placing inserts 43 to decrease the diameter of the aperture so as to limit the amount of slurry reentering the annulus 16 . The apertures 34 can also receive insert that is blocked, thereby completely sealing the aperture to the flow of material therethrough. Further, if an abrasive sand packing procedure will be utilized or if the particles encountered will be highly abrasive, erosion resistant inserts 43 are added to minimize the erosion of the apertures 34 . The erosive resistant inserts 43 may be made of materials such as ceramic or tungsten carbide. The embodiment allows for more accurate control of when, where and how much of the slurry reenters the annulus 16 from the alternative pathway.
While foregoing is directed to the preferred embodiment 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. For example, the apparatus can be used in any wellbore where a portion of the wellbore is to be by-passed by a slurry of particulate matter. One example includes a water-bearing formation located between two hydrocarbon-bearing formations along a wellbore. By utilizing the apparatus according to the invention, the water-bearing formation can be isolated and by-passed by a slurry of gravel. | An apparatus and method for providing a more uniform gravel pack in the well bore. An alternative pathway is provided within the apparatus to by-pass a sand bridge formed in the wellbore. The reentry point of the slurry into the wellbore can be predetermined based upon the conditions of the formation. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an information signal reproducing apparatus, and more particularly, to an apparatus for reproducing information signals recorded in many recording tracks which are formed on a record bearing medium and spaced at a track pitch selected out of a plurality of different track pitches.
2. Description of the Related Art
In the following description, the apparatuses of the above-stated kind are exemplified by video tape recorders (hereinafter referred to as VTR's): The number of VTR's of the kind arranged to permit selection of a track pitch from different pitches have recently increased. The VTR of this kind is required to automatically shift the reproducing travel speed of the tape employed as a record bearing medium and/or the reproducing head according to the track pitch employed in recording. To meet this requirement, the VTR has been generally arranged to detect the track pitch from the reproduced frequency of a control (CTL) signal which is recorded at an edge part of the tape to indicate the track pitch employed. Meanwhile, in the case of the VTR arranged to perform tracking control in a manner called the four-frequency tracking control method, the track pitch is found, for example, by detecting the varying period of a tracking error signal.
In accordance with the above-stated conventional method, however, the frequency of the period of the signal used in finding the track pitch varies with the travelling speed of the tape. As a result, it has been possible for the VTR to detect the track pitch only in the case of normal reproduction. The VTR is used not only for normal speed reproduction but also for special speed reproduction such as slow motion reproduction, high speed search reproduction, etc. For the special reproducing operation, the tape travel speed is set at varied speeds. It has been, therefore, difficult to detect, at the time of special reproduction, the pitch at which the recording tracks are formed during recording. In order to make it possible, the VTR must be arranged to shift a circuit constant, a threshold value to be used for discrimination, etc., thereof every time the tape travel speed is changed. Such arrangement results in an extremely complex circuit arrangement.
Further, in the case of an arrangement for detect the track pitch on the basis of the varying period of the tracking error signal according to the four-frequency method, the varying period fluctuates according to the degree of linearity of the recording tracks. Accordingly, in case that the tracking error signal is obtained from reproduced pilot signals which are recorded at low levels and the track pitch is discriminated from the varying period of such low level signals, the track pitch tends to be erroneously detected.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide an information signal reproducing apparatus which is capable of accurately discriminating the track pitch.
It is another object of this invention to provide an information signal reproducing apparatus which is capable of accurately discriminating the track pitch irrespective of the medium tracing direction taken during reproduction, with an extremely simple circuit arrangement.
Under this object, an information signal reproducing apparatus, arranged as an embodiment of this invention to reproduce information signals from a record bearing medium having many recording tracks which are formed with the information signals on the medium and are spaced at a track pitch selected from a plurality of track pitches, comprises: head means for reproducing the information signals by tracing the record bearing medium; tracking control means for controlling the positions of the head means and the record bearing medium relative to each other by using signals reproduced by the head means; detecting means which produces two detection signals indicative of the levels of signals reproduced by the head means from two recording tracks neighboring a recording track presently controlled recording by the tracking control means on both sides of the controlled track; a pair of comparison means for respectively comparing the two detection signals with reference levels; and means for discriminating the track pitch on the basis of outputs of the pair of comparison means.
The above and further objects and features of this invention will become apparent from the following detailed description of a preferred embodiment thereof taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing a VTR arranged as an embodiment of this invention.
FIG. 2 is a schematic illustration of the allocation of the heads of the VTR.
FIG. 3 is an illustration of the states of pilot signals reproduced under varied conditions.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of this invention, in which the invention is applied to a VTR performing tracking control according to the four-frequency method, is arranged as described below with reference to the accompanying drawings:
FIG. 1 shows the arrangement of the VTR. FIG. 2 shows the allocation of the heads of the VTR. In this case, the VTR is arranged to be capable of performing recording and reproducing not only with a wide track pitch in a standard manner (hereinafter referred to as the SP mode) but also with a narrow track pitch in a long time mode (hereinafter referred to as the LP mode).
Referring to FIG. 2, heads Ha and Hb are for the SP mode and are mounted on a rotary cylinder 1 at a phase difference of 180 degrees between them. Other heads Hc and Hd are for the LP mode and are likewise mounted on the rotary cylinder 1 at a phase difference of 180 degrees between them. A magnetic tape 2 is wrapped 180+θ degrees around the rotary cylinder 1. Recording and reproduction are thus arranged to be accomplished according to the known two-head helical scanning method.
Referring to FIG. 1, a detector 6 is arranged to detect the rotation of the rotary head cylinder 1 and produces a rectangular wave signal (hereinafter referred to as PG signal) in synchronism with the rotation of the cylinder 1. The phase of the PG signal is shifted by a phase shifting circuit 7 to a given degree determined for each of the SP and LP modes according to the rotation phase difference of the LP mode heads Hc and Hd from the SP mode heads Ha and Hb. Head change-over switches 3 and 4 are controlled by the PG signal coming via the phase shifting circuit 7. Switch-over between the SP and LP modes is automatically accomplished by a system controller 8.
The output signal of the switch 3 is produced as a reproduced RF signal via one terminal S of a switch 5 in the SP mode. The output signal of the switch 4 is produced as the reproduced RF signal via the other terminal L of the switch 5 in the LP mode. The reproduced RF signal produced from the switch 5 is supplied to a video signal reproduction processing circuit 9. This signal undergoes a known signal processing operation. As a result, the circuit 9 produces a video output in the form similar to a television signal.
Meanwhile, pilot signal components of four different frequencies, which are superimposed on the video signal in accordance with the four-frequency method, are separated by a low-pass filter (hereinafter referred to as LPF) 10. Assuming that the four different frequencies f1, f2, f3 and f4 of the pilot signals are recorded in rotation in the sequence of f1→f2→f3→f4, they are assumed to be in a relation of f2-f1=f3-f4=fH and f4-f1=f3-f2=3fH (wherein fH represents the horizontal scanning frequency of the recorded video signal). Each of the reproduced pilot signals, which is thus separated via the LPF 10, is supplied via an automatic gain control circuit (hereinafter referred to as AGG circuit) 11 to a multiplication circuit 12. Meanwhile, a local pilot signal generating circuit 13 is arranged to generate a reference signal (or a local pilot signal) of the same frequency as that of a pilot signal superimposed and recorded in a recording track presently being scanned under a reproducing operation and hence, under tracking control. The circuit 13 thus produces the local pilot signal the frequency of which changes in the sequence of f1→f2→f3→f4 according to the PG signal. The local pilot signal thus produced from the circuit 13 is supplied to the multiplication circuit 12 to be subjected to a multiplying operation together with the reproduced pilot signal.
Band-pass filters (BPF's) 14 and 15 are arranged to separate fH and 3fH components from the output of the multiplication circuit 12, respectively. As is well known, the outputs of the BPF's 14 and 15 correspond to pilot signal components reproduced from the adjacent recording tracks located on both sides of the track being mainly traced for reproduction. The outputs of the BPF's 14 and 15 are subjected to detection processes performed by detection circuits 16 and 17. The outputs of these detection circuits 16 and 17 are compared by a comparator 19 to obtain a tracking error signal. In this instance, however, the two adjacent or neighboring tracks, from which the 3fH and fH components are obtained, become converse every time the mainly tracing track changes from one over to another. Therefore, the connections of the detection circuits 16 and 17 to the comparator 19 are changed over by a switch 18 according the PG signal.
The tracking error signal obtained from the comparator 19 is supplied to a capstan control circuit 20 to be used as a capstan phase control signal. The circuit 20 controls a capstan 21 to cause it to rotate at a speed determined by a system controller 8. A track pitch discriminating operation is performed as described below with reference to FIG. 3.
FIG. 3 schematically shows the pilot signal components reproduced under different conditions including deviation of the reproduction mode from the recording mode and deviation of the reproducing head from the track to be traced for reproduction. In the case of FIG. 3, the track pitch obtained in the SP mode is assumed to be 20 μm, the track pitch obtained in the LP mode to be 10 μm, the track width of the heads Ha and Hb to be 30 μm and that of the heads Hc and Hd to be 15 μm. In FIG. 3, a reference symbol A denotes a track under reproduction control. Symbols B and C denote the neighboring tracks on both sides of the track A. Symbols L A , L B and L C denote the levels of the pilot signal components reproduced from these tracks A, B and C.
In reproducing, in the SP mode, the record of a track which is recorded in the SP mode, if the heads Ha and Hb are adequately positioned on the reproducing track A (in an on-track state), a reproduced pilot signal is obtained with a predetermined level difference from the pilot signals obtained from the tracks B and C as shown at a part (a) in FIG. 3. If the position of the heads Ha and Hb is deviating from the track A toward the track C to an extent of one track width, the level of the pilot signal reproduced from the track C becomes higher than the pilot signal reproduced from the track A as shown at a part (b) of FIG. 3. In case that the position of the heads Ha and Hb is deviating from the track A toward the track C by as much as 1/2 track width, pilot signals are reproduced at the same level from the tracks A and C as shown at a part (c) of FIG. 3.
The fH and 3fH components are separated, respectively, by the BPF's 14 and 15 of FIG. 1 as mentioned in the foregoing. These components correspond to the pilot signals reproduced from the tracks B and C, respectively. In other words, in the case of the part (a) of FIG. 3, the outputs of the BPF's 14 and 15 are at the same amplitude. In the case of the part (b) or (c) of FIG. 3, one of the outputs of the BPF's 14 and 15 comes to have a large amplitude while the other has almost zero amplitude. In the event of the deviation of the position of the heads Ha and Hb toward the track B instead of toward the track C, the other of the outputs of the BPF's comes to have a large amplitude while the above-stated one of them has almost zero amplitude, in a manner reverse to the case of the part (b) or (c) of FIG. 3. In the event that the position of the heads Ha and Hb deviates to an extent of two track widths, the outputs of the BPF's 14 and 15 become the same as in the case of the on-track state. As apparent from the above description, in case that the record recorded in the SP mode is reproduced in the SP mode, the outputs of the BPF's 14 and 15 never come to simultaneously exceed a given amplitude, which is indicated by a symbol V H in FIG. 3. In the case of FIG. 1, the system controller 8 produces this amplitude level V H as a threshold level Vth. The outputs of the BPF's 14 and 15 are subjected to a detection process at the detecton circuits 16 and 17 and are then compared with the level V H at comparators 22 and 23. The output levels of these comparators 22 and 23 do not simultaneously become high. The level of an AND gate 24 also does not become high. The system controller 8 is arranged to supply the AND gate 24 and a NOR gate 25 with a signal S/L which is at a high level in the case of the SP mode reproduction and is at a low level in the case of the LP mode reproduction. The output level of the NOR gate 25 in this case is always low. Therefore, the output level of an OR gate 26 does not become high.
Next, in case that a record, recorded in the LP mode in the tracks, is reproduced in the SP mode, the pilot signals are reproduced from the tracks A, B and C under the on-track condition, under the 1/2 track deviated condition and under the one track deviated condition as shown at parts (d), (e) and (f) of FIG. 3 respectively. Under the condition of the part (d) of FIG. 3, the pilot signals are reproduced from the tracks A, B and C at about the same amplitude. The level V H can be set at a smaller value than the outputs of the detection circuits 16 and 17 in this instance. Then, the output levels of both the comparators 22 and 23 are high. The signal S/L is also at a high level. Following this, the output level of the OR gate 26 becomes high. The high level output of the OR gate 26 is supplied to the system controller 8. Upon receipt of the high level output of the OR gate 26, the system controller changes the SP mode reproduction over to the LP mode reproduction. More specifically, the PG signal is synchronized with the revoluation of the heads Hc and Hd by controlling the phase shifting circuit 7 in such a manner that the control target of the capstan control citcuit 20 is set at 1/2, the threshold level at a value V L and the level of the signal S/L at a low level.
Further, since the reproducing tape speed differs from the recording tape speed, the conditions shown at the parts (e) and (f) of FIG. 3 never last long. The condition shown at the part (d) of FIG. 3 is reached in a sufficiently short period of time. Then, the output level of the OR gate 26 becomes high to effect changeover to the LP mode reproducing operation.
In case that a record recorded in the SP mode in recording tracks is reproduced in the LP mode, the reproduced states of pilot signals becomes as shown at parts (g), (h) and (i) of FIG. 3. In this case, the threshold level Vth is at the value V L which is lower than the value V H . However, in the case of the condition of the part (g) of FIG. 3, no pilot signal is reproduced from the tracks B and C. Therefore, the output levels of both the comparators 22 and 23 are low. The signal S/L is also at a low level. Therefore, the output level of the NOR gate 25 becomes high. As a result, the output level of the OR gate 26 becomes high to effect changeover from the LP mode reproduction to the SP mode reproduction. Further, the conditions shown at the parts (h) and (i) never last long and the condition of the part (g) of FIG. 3 will shortly obtain. Therefore, the change-over from the LP mode reproduction to the SP mode reproduction can be promptly effected.
When a record, recorded in the LP mode, is reproduced in the LP mode, the pilot signals are reproduced from the tracks in a manner as shown at parts (j), (k) and (l) of FIG. 3. In the case of an on-track state, the pilot signals are reproduced from the tracks B and C at equal amplitudes as shown at the part (j) of FIG. 3. In this instance, the levels of the outputs of the comparators 22 and 23 never simultaneously become low with the value V L set at a value smaller than the detection level of the reproduced amplitude. Under the conditions shown at the parts (k) and (1), one of the outputs of the comparators 22 and 23 of course becomes a high level. The output levels of the NOR gate 25 and the OR gate 26, therefore, do not become high.
In the case of special reproduction, the reproducing head repetitively comes to take the on-track, one-track deviated and 1/2 track deviated positions as shown in FIG. 3 because the tracing direction of the head differs from the direction of the recording tracks. If the reproduction is performed in the same time mode as in recording, therefore, the output of the AND gate 24 and that of the NOR gate 25 remain at low levels and no high level output is obtained from the OR gate 26. If the special reproduction is performed in a manner corresponding to the LP mode on the tracks having records recorded in the SP mode, the output level of the NOR gate 25 becomes high to cause the special reproduction to be accomplished in a manner corresponding to the SP mode. Further, in case that the special reproduction is performed in a manner corresponding to the SP mode on the tracks having records recorded in the LP mode, the output level of the AND gate 24 becomes high to cause the special reproduction to be accomplished in a manner corresponding to the LP mode.
The embodiment described is capable of promptly discriminating the track pitch at any tape speed despite of the extremely simple circuit arrangement and is capable of promptly performing a switch-over action between the SP mode reproduction and the LP mode reproduction according to the result of the discrimination as necessary.
In the embodiment, the number of different track pitches is arranged to be two. However, this can be changed to three or more with some modification in the selection of the threshold level Vth and the combination of the logic gates in accordance with this invention.
While different reproducing heads are arranged for the SP and LP modes, the arrangement may be changed to use the same head for the different modes with only the conditions shown at the parts (g) to (1) in FIG. 3 taken into consideration. In that instance, the track pitch also can be discriminated by an arrangement similar to the arrangement described.
Further, in the embodiment described, the tracking control and the track pitch discrimination are arranged to be accomplished by using the pilot signals reproduced from recording tracks neighboring the controlled track on both sides thereof. However, these actions may be arranged to be accomplished by using a reproduced signal which permits discrimination of the track or tracks from which one of or both of the pilot signals are reproduced. | An information signal reproducing apparatus for reproducing information signals from a record bearing medium having many recording tracks which are formed with the information signals on the medium and are spaced at a track pitch selected from a plurality of track pitches is arranged to reproduce the information signals by head means which traces the medium; to perform tracking control by using the signals reproduced by the head means; and to detect the track pitch by comparing with a reference level each of the levels of signals reproduced by the head means from recording tracks neighboring a recording track presently controlled by a tracking control action on both sides of the controlled track. After discriminating the track pitch, the apparatus selects the rotary heads with the proper width and sets the tape speed so that the speed reproduction is at the same speed at which the tape was recorded. | 6 |
FIELD OF THE INVENTION
[0001] The invention relates in general to the technical field of rail vehicles as well as a system for analyzing the condition of the running gear of rail vehicles. The invention relates in particular to a system and a method for analysis of the condition of the running gear of rail vehicles by detecting loads which occur in wheel/rail contact with rail vehicles.
BACKGROUND OF THE INVENTION
[0002] There are already known systems in which a measurement zone is set up on a rail, e.g., from the document DE 10 2006 015 924 A1. With these known systems, a plurality of measurement devices is arranged beneath the rail in the longitudinal direction of the rail to detect the forces acting on the rail. By means of these measurement devices, the forces or torques occurring when the rail vehicle travels over the rail can be measured in the body of the track. However, such known systems are limited to measuring the forces or torques occurring in the rail, which allows only a limited diagnosis with respect to the condition of the running gear of the rail vehicle. With these systems, for example, it is thus possible to detect flat spots on wheels of rail vehicles, but this can only be done with a quality statement which is derived merely from the force measurement technique. Therefore, statements about the geometric properties of the flat spots are possible only to a limited extent.
[0003] Furthermore, there are also known systems for detecting overheated axle bearings of rail vehicles, also known as hot box detectors, in the state of the art. However, such systems have the disadvantage that they are able to detect bearing damage to the wheel or axle bearing on the rail vehicle only when the condition of the vehicle of the rail vehicle is already relatively critical.
[0004] The known hot box detectors are usually based on the principle of infrared measurement technology and can thus supply information about possible bearing damage only by way of a temperature difference measurement. For maintenance on rail vehicles as well as rail operators the hit ratio and the reliability of accurate information of diagnostic systems about the condition of the running gear of rail vehicles are of crucial importance.
SUMMARY OF THE INVENTION
[0005] The object of the present invention is therefore to create a system and a method which will allow better diagnosis with respect to the condition of the running gear of a rail vehicle.
[0006] The present invention solves this problem through a system for analysis of the condition of the running gear of rail vehicles, in which a number of force measurement devices for detecting the forces and/or torques acting on the rail measurement zone are arranged on a rail measurement zone, characterized in that the system also comprises a number of sonic measurement devices for detecting the sound waves which occur when the rail vehicle travels over the rail measurement zone.
[0007] According to another aspect of the present invention a method of analyzing the condition of the running gear of rail vehicles by means of a rail measurement zone comprising the following steps is made available:
A rail vehicle travels over a rail measurement zone; The forces and/or torques acting on the rail measurement zone, said forces and torques occurring when the rail vehicle travels over the rail measurement zone, are detected by means of a number of force measurement devices, The sound waves generated when the rail vehicle travels over the rail measurement zone are detected by means of a number of sonic measurement devices, and The electric measurement signals supplied by the force measurement devices and the sonic measurement devices are analyzed to draw conclusions regarding the condition of the running gear of the rail vehicle.
[0012] For the reliability of the diagnosis, it is advantageous in particular if the detection of the forces and/or torques in the rail measurement zone and the detection of the sound waves are performed simultaneously. Such simultaneously detected measurement signals may then be correlated with one another and superimposed so that force measurement signals and sonic measurement signals detected simultaneously when a rail vehicle travels over the rail measurement zone can be brought into a direct chronological correlation with one another and can be analyzed in parallel with one another. Then inferences about the condition of the running gear of the rail vehicle can be drawn via the analysis of the mutually correlated force measurement signals and sonic measurement signals.
[0013] The present invention thus presents a system and a method for measuring loads in wheel/rail contact of rail vehicles in which the forces occurring in the body of the track due to the rail vehicle traveling over the track as well as the resulting acoustic sound waves are detected and analyzed for whether they permit inferences about the condition of the running gear of the rail vehicle to be drawn. Consequently, a mechanical/acoustic measurement system with which bearing damage on trains can be detected at an early point in time can be provided with the present invention.
[0014] Thus the present invention offers a diagnostic system for analyzing the condition of a running gear of a rail vehicle, in particular the wheel bearing and wheel geometries with which the loads and noises occurring due to a rail vehicle traveling over the rail can be detected and analyzed, so that more reliable inferences about the condition of the running gear of the rail vehicle, for example, the wheel bearing and the wheel geometry, can be drawn.
[0015] Better information about imperfections with respect to wheel roundness or bearing damage on the running gear of a rail vehicle can be obtained with the present invention. The present invention therefore constitutes an optimization for monitoring of the functional reliability of the running gear of a rail vehicle, including its wheels and wheel bearings. Direct information about damage sites and problems with the geometry of wheels or possible bearing damage to the running gear of rail vehicles can therefore be obtained.
[0016] In addition to the force and/or torques introduced into the rails when a rail vehicle travels over the body of the track, the present invention also takes into account the resulting noise in that it detects this noise and processes it in a corresponding electronic analysis unit. In this way, the present invention is making use of acoustic measurement technology and combining it with force measurement technologies to achieve more reliable results in diagnosing the running gear of a rail vehicle with hot box detectors and/or flat spot detecting systems.
[0017] The present invention therefore comprises the following essential aspects:
Combination of acoustic measurement technology with force measurement technology (e.g., WheelScan). In the area of at least one wheel circumference inspected, these physical parameters are detected in time synchronization and their correlation is used for optimized statement with regard to imperfections. The regions monitored and/or detected acoustically may comprise in particular the region of contact geometry, i.e., in contact between rail and wheel and/or the axle bearings and/or wheel bearings.
[0021] According to one embodiment of the present invention, the processing of the acoustic signals and the force measurement signals may comprise, for example, correlation of the acoustic signals with the force measurement signals. Additionally or alternatively, the processing of the acoustic measurement signals and the force measurement signals may also comprise the correlation of various acoustic measurement signals recorded by various microphones. Furthermore, the processing of the acoustic and force measurement signals may also comprise the correlation of various force measurement signals recorded by various force measurement devices.
[0022] According to another embodiment of the present invention, a number of sonic measurement devices are embodied as directional microphones having a certain directional characteristic. The directional microphone is equipped with an interference tube, for example, which receives primarily the sound arriving frontally and thereby imparts a directional characteristic to the microphone. The sound from other directions is therefore attenuated to a greater extent and is detected to a lesser extent than the sound arriving at the front from the longitudinal direction of the interference tube.
[0023] A plurality of sonic measurement devices may advantageously be arranged in the longitudinal direction of the rail measurement zone in order to detect the development of the sound several times at different locations along the rail measurement zone as the rail vehicle travels over the rail measurement zone. The sonic measurement devices may be arranged next to the rail measurement zone at a certain angle with respect to the longitudinal direction of the rail measurement zone in order to detect the sound waves propagating at a right angle from the rail measurement zone.
[0024] Furthermore, at least one measurement device may be equipped for detecting the acoustic sound waves across the longitudinal direction of the rail measurement zone in order to detect the sound waves propagating almost parallel to the longitudinal direction of the rail measurement zone or at an oblique angle from the rail measurement zone. In this way at least one first directional microphone is oriented across the orientation of a second directional microphone.
[0025] In one embodiment according to the invention, at least one sound measuring device is arranged at the level of the wheel/rail contact and at least one sound measuring device is arranged at the height of a wheel bearing of the rail vehicle. The sound waves occurring in the wheel bearing as the rail vehicle travels over the rail can therefore be detected largely independently and separately from the sound waves occurring at the wheel/rail contact.
[0026] Accordingly, in one embodiment of the present invention, the directional microphones may be oriented so that they detect the sound waves which occur due to the rail vehicle traveling over the rail measurement zone
at the wheel/rail contact between a wheel of the rail vehicle and the rail measurement zone and/or on the wheel bearing of the rail vehicle.
[0029] This facilitates the subsequent analysis of the sound waves with regard to analysis of the condition of the wheel bearing and the wheel geometries on the running gear of the rail vehicle.
[0030] Additionally or alternatively, structure-borne sound microphones may also be used directly on the rail of the rail measurement zone for the sound emissions in the wheel/rail contact area. Furthermore, acceleration pickups may be provided to detect the accelerations occurring in one or both rails when the rail vehicle travels over the rail measurement zone.
[0031] The force measurement devices are used to detect the forces and/or torques which are introduced into the body of the track when the rail vehicle travels over the rail measurement zone. It is particularly advantageous when a number for force measurement devices are arranged beneath the base of a rail and/or between the base of the rail and the bed of the rail of the rail measurement zone because the forces and torques acting in the rail can be reliably detected at this location.
[0032] Force measurement devices for detecting the forces or torques acting on the rail in the perpendicular direction may be provided and/or force measurement devices for detecting the forces or torques acting on the rail in the horizontal direction may be provided. The accuracy of the measurement can be supported if at least one force measurement device for detecting the forces and/or torques acting on the rail is arranged at a number of neighboring railroad ties of the rail measurement zone.
[0033] The force measurement devices and sonic measurement devices convert the forces and/or torques detected and/or the sound waves detected into electric signals which are relayed to the analysis unit over appropriate lines. The analysis unit comprises electronic means, which are preferably designed so that they can correlate the electric measurement signals supplied by the force measurement devices and the sonic measurement devices with one another, superimpose them and analyze them to thereby draw inferences about the condition of the running gear of the rail vehicle. Corresponding compensation algorithms may also be implemented here to prevent false alarms. Such compensation algorithms may be applied to the electric measurement signals supplied by the force measurement devices and the sonic measurement devices so that false alarms and/or misinterpretation of the measurement signals can be prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] The present invention is explained in greater detail below on the basis of exemplary embodiments and the accompanying drawings. With regard to the drawings:
[0035] FIG. 1 shows a schematic sectional diagram of a system according to one embodiment of the present invention for analysis of the running gear of rail vehicles by measuring forces and/or sound waves generated by a rail vehicle traveling over a rail;
[0036] FIG. 2 shows a schematic diagram of the structure of a system according to another embodiment of the present invention for analysis of the running gear of rail vehicles by measuring forces and/or sound waves generated by a rail vehicle traveling over a rail; and
[0037] FIG. 3 shows a schematic diagram of a damaged rail vehicle wheel and the acoustic and force measurement signals detected by means of a measurement according to the present invention.
DETAILED DESCRIPTION
[0038] FIG. 1 shows a sectional diagram through a schematic design of a system according to one embodiment of the present invention for analysis of the condition of the running gear of rail vehicles by measuring forces and/or sound waves generated by a vehicle traveling over a rail. The system according to the invention comprises a rail measurement zone having a track body, of which a rail 1 is shown in a cross section with hatching. The wheel 3 of a rail vehicle (not shown) stands on the rail 1 and rolls over the rail 1 when the rail vehicle is traveling at a right angle to the plane of the paper. In doing so the wheel 3 rotates about its axis 4 , which at the same time represents the wheel bearing schematically.
[0039] The rail has a base 2 which is supported on a railroad tie or a rail bed 6 via a force measurement device 5 . The force measurement device 5 is thus located between the foot of rail 2 and the rail bed and/or the railroad tie 6 , so that the force measurement device 5 can transfer all the forces and torques due to loads caused by a rail vehicle traveling over the rail.
[0040] The force measurement device 5 may be, for example, a force measurement cell such as that known fundamentally from the document DE 39 37 318 A1. Deformation parts are reversibly deformed in a force measurement cell under the influence of the force to be measured so that the electric resistance of wire strain gauges mounted on the deformation parts changes, which can be detected as a measured value. This measured value can be relayed as an electric signal to a corresponding analysis unit.
[0041] In the exemplary embodiment shown in FIG. 1 , the forces and torques acting on the rail 1 and/or in the foot of rail 2 are measured by the force measurement cell 5 and converted into electric signals which are relayed via a signal line 8 to analysis unit 9 . The system according to the invention also comprises a number of sonic measurement devices 7 , which detect the sound waves occurring when the rail vehicle travels over the rail.
[0042] Directional microphones having a certain directional characteristic such as those indicated with a certain orientation 10 and through corresponding directional cones 11 in FIG. 1 may be used as the sonic measurement devices 7 which are mechanically uncoupled from the rail measurement zone. The directional microphone 7 comprises, for example, an interference tube which picks up primarily the sound arriving frontally and thus detects the sound from other directions to a lesser extent than the sound arriving from the front in the longitudinal direction of the interference tube. In the exemplary embodiment shown in FIG. 1 , two directional microphones 7 are shown, the lower directional microphone 7 of which is arranged at the height of the wheel/rail contact and the upper directional microphone 7 of which is arranged at the height of a wheel bearing 4 of the rail vehicle.
[0043] The upper directional microphone 7 is oriented so that it detects sound waves occurring in the wheel bearing 4 as represented by the orientation 10 of the upper directional microphone 7 in the direction of the wheel bearing 4 . The lower directional microphone 7 is oriented so that it detects the sound waves occurring on contact between the wheel 3 and the rail 1 , as represented by the orientation 10 of the lower directional microphone 7 in the direction of the wheel/rail contact. Additionally or alternatively, structure-borne sound microphones or acceleration pickups mounted directly on the rail may also be used here.
[0044] Therefore the sound waves occurring in the wheel bearing 4 when the rail vehicle travels on the rail are detected simultaneously and mostly separately from the sound waves occurring at the point of contact between the wheel 3 and the rail 1 .
[0045] Like the electric measurement signals generated by the force measurement devices 5 , the electric measurement signals generated by the sonic measurement devices 7 are also relayed via corresponding signal lines 8 to the analysis unit 9 . The analysis unit 9 comprises electronic means which are preferably designed so that they are able to correlate and analyze the electrical measurement signals with one another to thereby draw inferences about the condition of the running gear of the rail vehicle. Differentiated statements about the condition of the wheel bearing 4 or about the geometry of the wheel 3 can be made on the basis of the separate measurement of the sound waves occurring at the wheel/rail contact and the sound waves occurring in the wheel bearing 4 .
[0046] FIG. 2 shows a schematic diagram of the structure of a system according to another embodiment of the present invention for analysis of the condition of the running gear by measurement of forces and/or acoustic signals generated by a rail vehicle traveling over a rail 1 . As in the embodiment shown in FIG. 1 , only one rail 1 is shown in the embodiment illustrated in FIG. 2 , this time shown in a view from above, supported on a plurality of railroad ties a-g.
[0047] The accuracy of the measurement can be supported if at least one force measurement device 5 for detecting the forces and/or torques acting on the rail is arranged on a number of neighboring railroad ties a-g of the rail measurement zone. Separate force measuring devices may also be provided on the rail 1 for detecting the forces or torques acting vertically on the rail 1 and/or force measurement devices for detecting the forces or torques acting horizontally on the rail 1 .
[0048] According to the invention, the measurement signals supplied by the force measuring devices 5 are correlated with one another and/or superimposed and/or compensated with the measurement signal supplies by the sound measuring devices 7 in order to support the reliability of the analytical results to be able to make more accurate and more reliable statements about to wheel geometry, wheel roundness, imperfections, wheel damage or bearing damage to the running gear of the rail vehicle.
[0049] In the embodiment shown in FIG. 2 , two sound measuring devices and/or directional microphones 7 are also arranged side by side in the longitudinal direction of the rail measurement zone to detect acoustically the development of sound when the rail vehicle travels over the rail measurement zone from two different directions. For this purpose, the sonic measurement devices and/or directional microphones 7 are arranged next to the rail measurement zone at a certain angle with respect to the longitudinal direction of the rail measurement zone.
[0050] The directional microphone 7 shown at the right of FIG. 2 is oriented at a right angle to the longitudinal direction of the rail measurement zone in order to detect such sound waves that propagate at a right angle from the rail measurement zone. The directional microphone 7 shown in the left portion of FIG. 2 is oriented across the longitudinal direction of the rail measurement zone in order to detect the sound waves propagating almost in parallel with the longitudinal direction of the rail measurement zone or only at an oblique angle to the rail measurement zone. In this way, the one directional microphone 7 is oriented across the orientation of the other directional microphone 7 .
[0051] The electrical measurement signals generated by the force measurement devices (not shown in FIG. 2 ) and by the sonic measurement devices 7 are in turn relayed via the connected signal lines 8 to the analysis unit 9 , where the signals are correlated with one another and/or superimposed through the electronic means of the analysis unit 9 so that bearing damage or unevenness in the running area of the wheel, for example, can be detected in this way. The correlation up to acoustic measurement signals picked up from different directions may lead to further detail findings of the damage pattern detected and may be used for a more reliable differentiation between wheel damages or wheel bearing damages.
[0052] FIG. 3 shows a schematic diagram of a damaged rail vehicle wheel and a schematic diagram of the acoustic measurement signals and force measurement signals detected by means of a measurement system according to the present invention.
[0053] The left part of FIG. 3 shows the wheel 3 of a rail vehicle rolling on a rail 1 in the direction of the rotating arrow. The wheel 3 has an imperfection, i.e., a flat spot 12 on its outer radial running area which should be detected by the analysis system according to the invention. As soon as the flat spot 12 rolls over the rail 1 it generates corresponding forces and/or torques in the rail 1 which are detected by force measurement devices beneath the rail 1 . Furthermore, a noise development whose sound waves are detected by sonic measurement devices is generated as the wheel with the flat spot 12 rolls over the rail 1 .
[0054] The right part of FIG. 3 shows a signal curve of the force measurement signal 13 and a signal curve of the acoustic measurement signal 14 , each shown schematically. The signal curves 13 and 14 show that there is a rather larger deflection in the middle of the signal, which occurs when the flat spot 12 of the wheel 3 rolls over the rail 1 . Before and after this rather large deflection in time, only smaller amplitudes reflecting normal rolling of the wheel 3 on the rail 1 are detected. Through the correlation or superpositioning of the force measurement signal 13 with the acoustic measurement signal 14 according to the invention, more reliable information about the position, the type and extent of a wheel damage or wheel bearing damage can be made.
[0055] To do so, the measurement signals generated by the force measurement devices 5 and the sonic measurement devices 7 are relayed to the analysis unit, which comprises electronic means to enable correlation of the electric measurement signals with one another, superimposing them and/or compensating and analyzing them and drawing inferences from them about the condition of the running gear of the rail vehicle. Because of the separate measurement of the forces introduced into the rail 1 by means of force measurement devices 5 and the simultaneous measurement of the sound waves occurring at the wheel/rail contact as well as the sound waves occurring in the wheel bearing by means of the sonic measurement device 7 , differentiated information about the condition of the wheel bearing 4 or about the geometry of the wheel 3 can be obtained.
[0056] The system with the measurement zone according to the invention can be integrated into a real track body for rail vehicles in a particularly practical manner. In this way, running rail vehicles can be checked for the condition of their running gear during use without any negative effects or interruptions in the driving operation during operation. When an inadequate wheel or wheel bearing condition is detected, the respective rail vehicle could be sent promptly for the proper maintenance without the possibility of an accident-induced interruption in operation or even leading to a critical condition of the running gear.
[0057] Although certain exemplary embodiments are described in detail in the present description and are illustrated in the accompanying drawings, such embodiments are to be understood as being merely illustrative and are not to be interpreted restrictively for the scope of protection of the invention. It is therefore pointed out that various modifications in the embodiments of the invention described or illustrated or otherwise shown can be made without going beyond the scope of protection and the core of the invention.
LIST OF REFERENCE NOTATION
[0000]
1 Rail
2 Foot of rail
3 Wheel of a rail vehicle
4 Axis of rotation and wheel and wheel bearing
5 Force measurement device
6 Rail bed and/or railroad tie
7 Sonic measurement device and/or directional microphones
8 Signal lines
9 Electronic analysis unit
10 Orientation of the directional microphones, directional cone
11 Directional cone of the directional microphones
12 Flat spot on wheel
13 Force measurement signal curve
14 Acoustic measurement signal curve | The object to create a system and a method which allows better running gear diagnosis of rail vehicles is achieved by the present invention by arranging a number of force measurement devices on the rail measurement zone to detect the forces and/or torques acting on the rail measurement zone, such that the system also comprises a number of sonic measurement devices for detecting the sound waves which occur when the rail vehicle travels over the rail measurement zone. The present invention thus offers a diagnostic system for analysis of the condition of wheel bearings and wheel geometries in particular in which the forces and sound waves occurring when the rail vehicle travels over the rail can be detected and analyzed, so that more reliable inferences about the condition of the running gear of the rail vehicle can be drawn from them. | 6 |
SUMMARY OF THE INVENTION
This invention relates to a plug, and will have special application to a plug having flexible protrusions for use with a hollow stem auger and drill head during soil drilling operations.
Soil drilling is a long established process used by architects to determine the feasibility of certain areas for sinking a building foundation. Equipment used in soil drilling normally includes a hollow stem auger and a connected drill head having a hollow housing. After the soil has been drilled to the desired depth, accumulated soil in the hollow stem is removed and a split tube sampler is then inserted into the stem and the stem reinserted into the drilled hole to draw a soil sample from the bottom of the hole. The major problem encountered in such a process is that when drilling through sandy soil, the sand accumulates to a significant level in the stem, which requires a significant length of time to remove before the sampler is inserted.
The plug of this invention includes arcuate, inturned flexible finger projections which act as a one way valve between the stem and drill head. Soil is prevented from entering the stem by the projections during drilling. When a soil sample is required, the split tube may be pushed through the plug to obtain the sample and then removed. By eliminating the soil removal step, valuable time and money are saved.
Accordingly, it is an object of this invention to provide a flexible plug which is used for preventing soil intrusion into a hollow stem auger during soil drilling.
Another object of this invention is to provide for a flexible drill plug which permits an engineer to take soil samples during soil drilling.
Another object of this invention is to provide for a flexible drill plug which is durable and economical to produce.
Other objects of this invention will become apparent upon a reading of the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred embodiment of the invention has been depicted for purposes of illustration wherein:
FIG. 1 is a fragmentary elevational view of a soil drilling head and auger with portions cut away to illustrate the plug of this invention.
FIG. 2 is a fragmentary elevational view similar to FIG. 1 and showing a soil sampler inserted through said plug.
FIG. 3 is an exploded view of the soil drilling equipment utilizing the plug.
FIG. 4 is a perspective view of the plug.
FIG. 5 is an elevational view of the plug.
FIG. 6 is a plan view of the plug.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment herein described is not intended to be exhaustive or to limit the invention to the precise form disclosed. It is chosen and described to explain the principles of the invention and its application and practical use to enable others skilled in the art to utilize the invention.
FIGS. 1-3 depict a soil drilling apparatus 10 which generally includes a hollow stem auger 12 and a connected drill head 14. An adapter cap 16 is connected to auger 12 and transfers the torque from a motor shaft (not shown) to the auger which cause rotation and advancement of apparatus 10 into the soil. Auger 12 preferably includes a hollow stem 18 and a continuous spiral blade 20. Drill head 14 is connected to auger 12 in any conventional manner which allows simultaneous rotation of the drill head and auger, such as spline 22, keyway 24, and cross bolts (not shown). Drill head 14 includes a hollow housing 26 which houses one or more drill bits 28. Apparatus 10 as so far described is a conventionally used soil drilling apparatus.
FIGS. 4-6 depict a soil plug 30 which includes a rim 32. A plurality of flexible shape-returning projections 34 extend arcuately inwardly from rim 32 to a tapered point 36 spaced from the center axis 38 of the plug. Projections 34 form a cup like shape and are urged into edge to edge abutting contact or overlapping arrangement with one another during initial drilling to generally prevent the passing of soil. Plug 30 is preferably formed of a durable, yet resilient material, such as plastic.
FIGS. 1-2 depict plug 30 in use during drilling and sampling operations. Plug 30 is positioned as shown in FIG. 1 with rim 32 secured between a shoulder 27 of drill head housing 26 and a shoulder 19 of auger stem 18 with plug projections 34 extending towards the terminal end of drill head 14. As drill head 14 and auger 12 are rotated and advanced into soil 40, the force of the soil upon plug projections 34 causes the projections to compact and generally seal the auger stem 18 against the entry of soil. Soil 40 is removed from the resulting hole by auger blade 20 which causes the loosened soil to pass about the stem.
When an engineer wishes to take a soil sample, rotation of auger 12 is ceased and a sampling device such as a smooth split hollow tube 42 is inserted through auger stem 18 and plug 30 as shown in FIG. 2. Projections 34 allow tube 42 to pass through plug 30 into the underlying soil. Tube 42 will generally be equipped with a shoe (not shown) which allows the tube to be forced deep enough into the soil (i.e. below the terminal end of drill head 14) to allow an accurate sample to be taken. Tube 42 is then pulled up and the soil removed for analysis.
It is understood that the above description does not limit the invention to the precise form disclosed, but may be modified within the scope of the appended claims. | A flexible plug used in combination with a hollow stem auger and connected drill head which has a hollow housing. The plug includes a plurality of flexible shape-retaining arcuate projections extending towards the plug central axis. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to safety door entrances and more particularly a safety device for swinging doors which are hingedly supported from a door jamb or frame element to open and close with respect thereto. The present invention relates to a safety device for discouraging or preventing a person's fingers, toes or other implements from inadvertently being inserted into a gap created between a corner edge of the door and the door jamb while the door is opened, which gap is then closed with crushing force as the door swings closed.
2. Description of the Prior Art
Various systems have been devised for protecting against damage or injury to the fingers, toes or other implements caused from the crushing action of swinging doors or hingedly attached closure members as they swing closed. U.S. Pat. Nos. 3,319,697 and 3,941,180 disclose guards or protecting devices for hinged garage doors and the like. An extruded hinge is shown in the window construction of U.S. Pat. No. 1,925,817 and an interlocking combination door is illustrated in U.S. Pat. No. 2,960,733.
OBJECTS OF THE PRESENT INVENTION
It is an object of the present invention to provide a new and improved safety door entrance and more particularly, to provide a safety device which is highly effective to discourage insertion of fingers, toes or other objects into a gap or opening formed between the heel or corner edge of a door and the abutting door jamb whenever the door is open.
It is another object of the present invention to provide a new and improved safety door entrance of the character described which is suitable for use on doors capable of swinging from a closed position to a full open position aligned at an angle of 90° or more from the closed position.
Still another object of the present invention is to provide a new and improved safety door entrance having a detachable finger protector for continuously closing the gap formed between the heel of the door and the abutting adjacent jamb surface whenever the door is opened.
Yet another object of the present invention is to provide a new and improved safety door entrance having improved weather sealing on both faces of the door.
Still another object of the invention is to provide a new and improved safety door system wherein the hinge(s) supporting the door are covered and enclosed by a finger protecting safety shield.
Yet another object of the present invention is to provide a new and improved finger protector which is detachable and can be readily re-attached and snapped into place.
Another object of the present invention is to provide a new and improved combination of a door hingedly supported on a jamb and finger protector, wherein the jamb is readily adapted to accommodate the finger protector when the door is closed and yet is designed to support a conventional transom panel above the door.
Still another object of the present invention is to provide a new and improved safety door system suitable for use with doors having hollow tubular door stiles.
Yet another object of the present invention is to provide a new and improved safety door entrance which permits the use of simple, butt hinges and permits ready access to the hinges for servicing and maintenance thereof.
Yet another object of the present invention is to provide a new and improved safety door entrance of the character described wherein a detachable finger protector is secured to the butt edge of the door stile adjacent a jamb in a novel manner.
Yet another object of the present invention is to provide a new and improved safety door system which is neat in appearance, relatively simple in construction and operation and is relatively economical in comparison with other types of safety door entrances.
BRIEF SUMMARY OF THE INVENTION
The foregoing and other objects and advantages of the present invention are accomplished in a new and improved safety door entrance comprising, in combination, a door having opposite faces and a hinge stile element along one edge hingedly interconnected to a supporting door jamb element for swinging movement between a closed position wherein an outer door face is generally aligned with an outer face or sight line of the supporting jamb and a fully opened position wherein the outer door face is aligned at an angle of 90° or greater with respect to the outer sight line face. A novel finger protector is detachably secured on the butt edge of the hinge stile of the door and includes a curved wall section which provides for continuous bridging of the gap formed between the butt edge of the door and the adjacent door jamb whenever the door is opened. The door jamb is designed to provide a pocket for receiving the finger protector whenever the door is closed, and a pair of spaced apart weatherstrip are provided for sealing opposite faces of the door and the supporting jamb or frame while the door is both open or closed.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention, reference should be had to the following detailed description taken in conjunction with the drawings, in which:
FIG. 1 is an outside, elevational view of a new and improved safety door entrance constructed in accordance with the features of the present invention;
FIG. 2 is an enlarged, horizontal, fragmentary, cross-sectional view taken substantially along lines 2--2 of FIG. 1;
FIG. 3 is an enlarged horizontal, fragmentary, cross-sectional view taken substantially along lines 3--3 of FIG. 1;
FIG. 4 is an enlarged horizontal, fragmentary, cross-sectional view taken substantially along lines 4--4 of FIG. 1;
FIG. 5 is a horizontal, cross-sectional view similar to FIG. 2 but illustrating the door in a fully open position;
FIG. 6 is a fragmentary, vertical, cross-sectional view taken substantially along lines 6--6 of FIG. 2; and
FIG. 7 is an enlarged, fragmentary, horizontal, cross-sectional view similar to FIG. 2 but illustrating an alternative embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now more particularly to the drawings, in FIG. 1 is illustrated an outside elevational view of a new and improved safety door entrance constructed in accordance with the features of the present invention and referred to generally by the reference numeral 10. The safety door entrance includes a door 12 mounted for swinging movement by a plurality of butt type hinges 14 secured to a door jamb 16 which extends vertically upward beyond the upper edge of the door and defines a side frame member of an entrance door frame. The door frame includes a spaced apart vertical jamb 18 along an opposite stile of the door, a horizontal threshold 20 and a horizontal upper header 22.
The safety door entrance 10 is designed to be architecturally compatible within a curtain wall or store front generally represented in elevation in FIG. 1 and the curtain wall may include in addition to the vertical door jambs 16 and 18 and header 22, one or more intermediate horizontals 24 and lower sills 26 which along with upper headers (not shown) and other verticals parallel of the jambs 16 and 18 (not shown). These members define a plurality of generally rectangular, openings for accommodating large or small panels such as rectangular glazing panels 28.
The door 12 itself includes a pair of vertically extending, hollow, tubular, stiles 30 and 32 which are structurally interconnected adjacent upper and lower end portions by an upper rail 34 and a lower rail 36. The stiles and rails of the door may define one or more rectangular openings in which is mounted a glazing panel 38 and the panel is supported in the structural frame work of the door by suitable glazing stops or strips 40 which may be of a generally triangular-shaped transverse, cross-section having a base portion seated in a groove provided in the tubular stiles and rails as shown in the sectional views.
The door 12 is mounted for outward swinging movement from a closed position (FIG. 2) to a fully open position (FIG. 5) about a vertical hinge axis "A--A" and in the closed position, an outer face 42 of the door is generally parallel with the plane of an outer face 44 of the sight line of the door jambs 16, 18 and the header 22 which provide the surrounding door frame in the curtain wall structure. In the fully open position, as shown in FIG. 5, the outer door face 42 is aligned at an angle of 90° or more with respect to the outer face 44 of the sight line of the surrounding door opening in the curtain wall structure.
The hinge axis "A--A" is aligned to lie on or closely adjacent the outer door face 42 and is generally closely adjacent to the plane 44 of the sight line of the door jambs 16 and 18 and the header 22. Accordingly, only a relatively narrow gap G-1 is formed between adjacent corner edges of the hinge stile 30 and door jamb 16 at the sight line when the door is closed (FIGS. 2 and 7). The gap may be even narrower as illustrated by the spacing gap G-2 of FIG. 5 when the door is fully opened. Consequently, there is a minimal chance of a human finger, toe or other implement being accidentally inserted into the relatively narrow gap at the outer corner edge of the hinge stile of the door.
The same is not true with respect to a relatively narrow gap G-3 between a butt edge corner on an inside door face 46 and an outwardly facing corner of a door stop 48 on the door jamb 16. The narrow gap G-3 which obtains when the door is closed is rapidly enlarged to a much wider opening or gap G-4 (FIG. 5) generally large enough that a person's arm, elbow, finger, hand, toes or other implement could accidentally be inserted into the gap and thereafter suffer damage when the door swings closed.
In accordance with the present invention, a detachable finger protector 50 is detachably secured to the butt edge of the hinge stile 30 of the door which faces the jamb 16 and the finger protector includes a relatively large area, curved wall segment 52 having a rounded outer free edge 52a. The wall segment continually spans and closes the large gap G-4 formed whenever the door is open and thereby provides protection against injury. As illustrated in FIG. 5, when the door is fully opened, the rounded outer surface of the curved wall segment 52 on the finger protector provides a protective wall so that only a relatively narrow gap G-5 is permitted between the protector edge 52a and the door stop 48. Accordingly, with the protector 50 attached on the edge of the door 12 as illustrated, the chances of "pinching" a finger, tow or nose are minimized as the gaps illustrated as G-3 and G-5 are small enough to prevent even a child's finger from being cut, pinched or bruised as the door swings closed.
In accordance with the present invention, the finger protector 50 includes a planar wall segment 54 integral with the curved wall segment 52 and extending tangent to the surface of the curved wall segment which comprises a portion of a cylindrical surface having an axis common with the hinge axis "A--A". The planar wall segment is sloped away from the door stop 48 and an inside weatherstrip 56 mounted in a slot thereof so that when the door 12 is initially opened, the surface of the planar wall segment of the protector moves outwardly away from the weatherstrip thereby reducing the amount of sealing compression therewith.
The weatherstrip 56 is preferably of the type shown and described in U.S. Pat. No. 4,157,634 issued June 12, 1979, which patent is assigned to the same Assignee as the present application, and includes a deflectable outer sealing element formed of flexible material and adapted to bear and seal tightly against the inside door surface 46 and a portion of the planar wall segment 54 of the finger protector when the door is closed as shown in FIG. 2. As the door is pivoted from the closed position toward the open position, the outer surface of the planar wall segment 54 moves in front of, but outwardly away from the weatherstrip 56 and thus, friction between the surface of the finger protector and weatherstrip is reduced so as not to inhibit opening of the door in any appreciable degree. After the door is opened far enough so that the curved wall segment 52 is positioned in front of the weatherstrip 56 only a very light pressure contact is provided between the surface of the curved wall segment and the flexible sealing element of the weatherstrip as shown in FIG. 5.
The finger protector 50 includes an integral inwardly extending web or base 58 aligned in parallel with a facing wall segment 60 of the hinge stile 30 of the door. The wall segment 60 forms the bottom wall of a channel or groove facing the web 58 and a pair of opposite sidewalls of the groove are formed by a pair of opposite spaced apart ribs 62 and 64, respectively, which project beyond the wall segment 60 to engage ribs 66 and 68, respectively, of the finger protector 50. The rib 62 adjacent the outer face 42 of the door stile 30 is provided with a groove 63 on an inside face in order to receive a hook-like end portion or ridge 66a along the free edge of a rib 66 on the finger protector. The outer ridge 66a seats in the groove 63 to provide interlocking engagement between the finger protector and the door stile 30 so that the finger protector can be snapped into place as shown by subsequent rocking action. The inside surface of the inside rib 64 of the door stile is formed with a relatively large V-shaped groove 65 in order to provide engagement with the rib 68 of the finger protector which is flexible to snap into the groove and which is provided with a cross-sectional profile as illustrated. Urging finger protector 50 toward the door edge is effective to snap the ribs into interlocking engagement with the door stile as illustrated.
The finger protector may be readily detached when desired while the door is open (FIG. 5) by pulling the finger protector 50 away from the edge of the door stile 30 generally in the direction indicated by the arrow "B" (FIG. 5). When this occurs, the rib 68 is deflected inwardly until it clears the groove 65 on the rib 64 of the door stile and then the finger protector is moved so that the ridge 66a can be disengaged from the opposite groove 63 on the rib 62 of the door stile. To reassemble the finger protector 50 onto the door stile 30, the finger protector is aligned so that the ridge 66a is first engaged in the groove 63 and then is pivoted inwardly as indicated by the arrow "C" about the axis of this engagement line until the rib 68 is deflected inwardly momentarily and then snaps back or deflects outwardly again to seat against the surface of the groove 65 in the rib 64. In this manner, the finger protector 50 can be easily snapped into place and is retained in place by the engaging pairs of ribs 62 and 66 adjacent the outer surface of the door and the engaging pair of ribs 64 and 68 adjacent the inside surface of the door.
The rib 66 is also provided with a thickened body portion 66b having an outwardly facing groove therein to accommodate an outside weatherstrip 70 of the same configuration as the inside weatherstrip 56 and the outer weatherstrip provides a seal adjacent the outside face 42 of the door when the door is closed as shown in FIG. 2. The deflectable outer sealing element of the outside weatherstrip 70 is adapted to bear against an inwardly facing grooved surface on the inside face of the sight line wall segment 44 of the door jamb 16.
In accordance with the invention, the door jamb 16 is formed with an inwardly extending, relatively thick, integrally formed internal rib 72 which defines along a free edge 72a thereof, the outside edge of an elongated opening 73 providing access to a relatively large, internal jamb pocket 74 provided for accommodating the curved wall segment 52 of the finger protector 50 when the door 12 is in a closed position as shown in FIGS. 2 and 3. The internal rib 72 also provides support for hinge leaves 14a of the butt hinges 14 which are secured thereto by relatively short cap screws 76 having countersink heads. Opposite hinge leaves 14b are similarly secured to the wall segment 60 of the hinge stile 30 of the door with cap screws. Additionally, the integral rib 72 is strengthened by a hinge support strip 78 formed of steel and provided with drilled and tapped openings for accommodating the shanks of the cap screws 76. It should be noted from FIGS. 2 and 3, that the web 58 of the finger protector 50 is aligned to lie on a common plane with the leaves 14a of the hinges 14 and the web is notched out at appropriate locations designated as 59 in FIG. 6, to accommodate the hinge leaves. This notched engagement provides a means for securing the finger protector 50 against relative longitudinal movement with respect to the door jamb 16 and in particular, the internal rib 72 thereof.
The door jamb or frame member 16 is of a generally rectangular, transverse, cross-section and includes a hollow, tubular, square shaped, inside section 80 with a pair of opposite, jamb surfaces defining sidewalls 82 and 84, an inside sight line wall 86 and an intermediate web or transverse mid wall 88. The web 88 is integrally joined by a relatively thick web 90 extending transverse thereto, to an intermediate wall segment or web 92 of a generally square shaped, hollow, outer wall section 94 which provides the internal jamb pocket 74. The outer wall section of the jamb 16 is substantially tubular in transverse cross-section except for the pocket opening 73 and includes a jamb surface side wall 96 on one side aligned in parallel with the jamb side wall 84. The outside sight line, wall 44 is parallel of the wall 86 and the internal web 72 is parallel but offset from the wall 82. Transverse walls 88 and 92 and the web 90 form a pair of back-to-back glazing pockets 98 and 100 (FIG. 4) and these pockets are adapted to receive marginal edge portions of respective glazing panels 28 which are secured in place between the opposite side walls of the pockets by glazing wedges 102.
An opposite edge of the jamb pocket opening 73 formed in the outer sectional portion 94 of the jamb 16 is provided by a relatively thinner rib portion 92a along the web or wall 92 and the rib portion projects beyond the main body of the web 90 that forms the bottom wall between the back-to-back, glazing pockets 98 and 100. The thin rib portion 92a is formed with a longitudinally extending groove 93 adapted to accommodate an interlocking rib 104a along a free edge of one leg of the door stop 48. The stop includes another leg 106 provided with a rib 106a adapted to snap fit in a groove provided for the glazing wedge in the wall of the glazing pocket 98. The door stop is detachably secured to the jamb 16 and may be readily snapped into the position as shown along with the inside weatherstrip element 56 carried thereby.
In accordance with the present invention, above the door 12, a transom may be provided in the curtain wall or store front and an upwardly continuing portion of the door jamb 16 serving as a side frame member thereof, as illustrated in FIGS. 1 and 4. In order to form a jamb surface aligned with the inside jamb wall 82 of the inside tubular section of the jamb, a cover element 108 is adapted to snap in place and cover over the pocket opening 73. The cover also forms one side wall for the glazing pocket 98 for supporting the outside glazing wedge 102. The cover has an angle-shaped transverse cross-section and includes a jamb leg 110 having an offset rib 110a along the free edge thereof adapted to seat in the groove 44a provided on the inside surface of the outside, sight line wall 44. The cover includes another leg 112 at right angles to the leg 110 having a rib 112a adapted to snap into the groove 93 on the intermediate wall portion or web 92a to provide a side wall for the glazing pocket 98 to support the glazing wedge 102 against the outside surface of the glazing panel 28.
From the foregoing it will be seen that the door 12, the jamb 16 and finger protector 50 provide a novel safety door entrance 10 which is compatible with most curtain wall and store front framing systems in appearance. The door and curtain wall frame members are preferably formed of extruded aluminum sections and are especially designed for easy and rapid fabrication. The finger protector 50 is snap fitted into the edge of the door and when in place, eliminates or greatly reduces the hazard or danger of a finger, toe or other elements being pinched, bruised, or cut during swinging movement of the door. A pair of inside and outside weatherstrip 56 and 70 provide for excellent weather sealing against air infiltration or water leakage. The finger protector is detachable to provide access to the hinges 14 for service as necessary, yet overall, the safety door entrance provides good security against unauthorized entrance from the outside when locked.
Referring now to FIG. 7, an alternate embodiment is shown and identical reference numerals are used to describe parts or components similar or identical to those of the previously described embodiment. Those elements differing significally in the alternate embodiment are provided with reference numbers having a suffix "A" to distinguish them from the prior counterparts.
The embodiment of the invention shown in FIG. 7 is generally similar in operation and function to the embodiment of FIGS. 1 through 6 except that a modified finger protector 50A does not include a planar wall segment and the outer surface of the large curved segment 52 thereof conforms entirely to a segment of cylindrical surface having an axis of generation coincident with the hinge axis "A--A". A modified web 58A is provided with an angularly offset portion 61 integrally joined with the inside of the curved segment 52 and a wall 60A of the hinge stile 30A of the door 12A is formed with a recessed offset portion 67 facing the offset portion 61 in order to accommodate a rib 68 of the protector. A rib section 66A along the opposite edge of the web 58A extends toward the internal rib 72 of the jamb 16A and has an outwardly facing groove, provided therein for supporting the outside weatherstrip 70. The outside weatherstrip bears against and seals between the inside surface of the outer sight line wall 44 and the adjacent inside surface of a rib portion 62 on the door stile 30A across the gap G-1 as illustrated.
A modified form of door stop 48A is provided in a glazing pocket 98A and the pocket includes an angularly offset side wall portion 89 for receiving a self-tapping fastener 105 for holding the door stop in place. One leg 104 of the modified door stop includes a rib 104a at the outer free edge which is seated within a pocket formed by a rib 91 on the modified web 90A of the jamb member 16A. The modified finger protector 50A thus presents a slightly larger diameter, continuous cylindrical surface segment 52 which bears against the deflectable sealing element of the inside weatherstrip 56 with a substantially even or constant amount of sealing force throughout the entire opening or swinging movement of the door between its closed and open positions.
Although the present invention has been described with reference to several illustrated embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this invention. | A safety door entrance includes a door mounted for swinging movement on hinges connected to a door jamb and a finger protector for continuously bridging a gap formed between the door heel and adjacent jamb as the door swings open and closed. The protector prevents a person's fingers, toes or other objects from accidentally being inserted in the gap and subject to damage when the door swings closed. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. patent application Ser. No. 11/951,223, filed Dec. 5, 2007, entitled CONDUCTIVE NANOPARTICLE SUBSTRATE AND METHOD OF MANUFACTURE, the entire contents of which are incorporated herein by this reference.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The inventions disclosed herein relate generally to electrically conductive metal coatings on substrates for the electronics and optics industries.
[0004] 2. Related Art
[0005] On the market today there exist many conductive inks/pastes of metals such as silver or copper which can be coated onto glass to form an electrically conductive surface. These metal coated glass substrates are used in a variety of applications, in particular chips in many electronic components. While these commercial ink/paste adhesives have utility in certain applications, durability issues exist when used in applications such as integrated circuits.
[0006] Firstly, commercially available ink or paste adhesives cannot be used in applications that require a sealed environment and further processing which involves heat. The epoxy in these commercially available adhesive outgases when heated, which can result in pressure build up and catastrophic failure of a chip. Secondly, because these commercial ink/paste adhesives use larger silver particles, the resulting silver layer is less even and more prone to surface defects and conductivity gaps. Furthermore, the conductive surface must be adherent and robust enough to permit solder reflow for the attachment of circuitry components.
SUMMARY OF THE INVENTION
[0007] In the preferred embodiments, a device is described which comprises a substrate with an electrically conductive surface having first and second layers. The first layer comprises cellulosic material and the second layer comprises silver nanoparticles. The substrate comprises a material that is available to react with cellulosic material, for example a silicate material such as glass. Alternatively, polyimide, an acrylic, or a metal may also function as the substrate.
[0008] In some of the preferred embodiments, nitrocellulose is utilized as the first layer on the substrate. When nitrocellulose is heated, nitrogen is off-gassed such that a thin film of cellulose remains. This film may chemically interact with the substrate such that the film is not easily removed by scratching or with adhesive. The first layer serves as a contact substrate for the silver nanoparticles.
[0009] In other preferred embodiments, the device may serve as the primary support of an integrated circuit. Electronic components such as resistors and capacitors may be soldered directly to the device without destruction of the first and second layers. Additionally, the second layer does not contain a solvent which may potentially outgas and destroy the integrity of the circuit.
[0010] Some of the preferred embodiments describe a method of preparing an electrically conductive device. Nitrocellulose is dissolved into a solvent such as acetone and applied to a clean substrate surface, such as glass. After drying at about 50° C. to eliminate solvent and heating to about 225° C. to eliminate nitrogen, a thin layer of cellulose remains. The cellulose layer is highly adherent to the substrate. A dispersion of about 25 wt % silver nanoparticles in ethylene glycol or other volatile solvent may then be applied to the surface and heated at about 250° C. to form an electrically conductive surface that is highly adherent to the primary layer.
[0011] In other aspects of the preferred embodiments, the primary layer may be formed using other cellulosic materials other than nitrocellulose. In addition, these cellulosic materials may be dissolved in other volatile solvents. This may increase or decrease the temperature required for the heating and drying steps of the primary layer. Also, the dispersion of conductive nanoparticles used in the method of preparing the device is not limited to about 25 wt % silver in ethylene glycol. For example, copper nanoparticles compatabilized in a different solvent may also form the conductive second layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a schematic of the electrically conductive device, comprising a substrate, first, and second layer.
DETAILED DESCRIPTION
[0013] The inventive device described herein comprises an electrically conductive substrate for the fabrication of integrated circuitry, having a substrate, first, and second layers. This device should have specific qualities that permit the reflow of solder across the surface for the attachment of electrical components, namely high electrical conductivity, good adhesion, scratch resistance. Additionally, the device should not off-gas solvent during or after the placement of electrical components, as this may lead to non-uniformity of the conductive surface and ultimate failure of the circuit.
[0014] Referring to FIG. 1 , device substrate 101 is comprised of a material which can chemically interact with cellulose-based primary layer 102 upon which a secondary layer of silver 103 is applied. Substrate materials may be but are not limited to glass, polyimide, acrylic, or a metal. For example, when nitrocellulose is dissolved in a solvent such as acetone, a thin film may be cast on the substrate. Upon heating, the nitrocellulose chemically condenses and eliminates nitrogen. The resulting cellulose material may then chemically bond to the substrate.
[0015] After the first layer is established, functional groups on the cellulose can chemically bind to silver nanoparticles, thus forming good chemical and physical contact. Because the silver particles are nano-sized, a more uniform layer is formed during the sintering process. Silver nanoparticles may be dispersed in a solvent, such as ethylene glycol and directly applied to the first layer. Upon heating to remove the solvent, the resulting silver layer is uniform, conducting, and adherent. Solvents that have a boiling point below 225° C. are preferred, such that all of the solvent can be eliminated at low temperature heating. Due to the sensitivity of many substrates, heating of the device during fabrication should not exceed 300° C.
[0016] We experienced significant difficulty in providing good adhesion between the substrate and the silver nanoparticles, especially if the particles have a high melting point or do not have affinity for the substrate. Silver nanoparticles do not contain oxide material, which limits their direct bonding to a substrate such as glass. If a dispersion of silver nanoparticles are directly applied to glass and then heated, the resulting layer is conductive but is easily removed by scratching or tape test. To achieve our goal of a robust, high conductivity device that does not off-gas after preparation, a new method was invented to overcome this challenge.
[0017] The method used herein describes a dual-layer approach to promote adhesion of nanoparticles to a substrate to form a durable device for integrated circuitry. In this method, a base layer of nitrocellulose is applied to the glass. Upon heating, the nitrocellulose gives off nitrogen gas to form a thin film of cellulose. The functionalities on the cellulose bind well to glass. After this layer is established, other end groups on the cellulose film can chemically interact to the silver nanoparticles, thus forming good chemical and physical contact. Because the silver particles are nano-sized, a more uniform layer is formed during the sintering process.
[0018] In the first step, the substrate is cleaned well with acetone to remove any residual dust or other impurities. The solvents used in this method must be carefully selected such that they do not leave residues on the substrate and are removed at temperatures below 225° C. A solution of nitrocellulose in acetone is then cast onto the surface of the substrate. To ensure that all of the acetone is removed from the film, a first heating step at 50° C. for one hour is used. This is then followed by a heating step at 225° C. to remove nitrogen and chemically bond cellulose to glass. Next, a dispersion of silver nanoparticles is cast onto the first layer. Nanoparticles referenced herein have high electrical conductivity. Although larger sizes are contemplated, the metal nanoparticles desirably have a diameter of less than 100 nm. The smaller the nanoparticles size, the more likely they are to efficiently provide a uniform layer on surfaces. Metal nanoparticles may be produced by a variety of methods. One such method is detailed in U.S. Pat. No. 7,282,167, Ser. No. 10/840,409, which is incorporated herein in its entirety by reference.
[0019] In another aspect of the invention, the silver nanoparticles are then heated to 250° C. to both remove the solvent and sinter the metal particles. A heating process is commonly used in known sintering techniques. For example, if the silver nanoparticles and are heated to cause grain growth, the particles combine to form larger particles. One of ordinary skill in the art should recognize that any sintering process is likely to produce some grain growth and, thus, it is anticipated that the resulting electrodes will include grains that have grown larger than the original silver particles, including grain sizes that are larger than “nano-scale”.
[0020] Alternative solvents and nanoparticles may be used in the described method. For example, other conductive metal nanoparticles such as copper, nickel, iron, and cobalt will also provide significant electrical contact and adhere well to the substrate and first layers. Other solvents that evaporate at relatively low temperatures such as water, and many alcohols, aldehydes, ketones, ethers, and esters may also serve as dispersion solvents for the nanoparticles.
[0021] The foregoing description is that of preferred embodiments having certain features, aspects, and advantages in accordance with the present inventions. Various changes and modifications also may be made to the above-described embodiments without departing from the spirit and scope of the inventions.
EXAMPLE 1
Preparation of Aconductive Substrate
[0022] A glass surface was cleaned with acetone and allowed to dry. About 1 gram of nitrocellulose was dissolved in acetone, and the resulting solution was coated onto the glass. This coating was dried at 50° C. for one hour followed by a second heating at 225° C. for 30 minutes. Finally, the substrate plus cellulose coating was coated with a 25 wt % solution of silver nanoparticles in ethylene glycol. The resulting layer was dried at 250° C. for 30 minutes to remove residual ethylene glycol. | A device comprising a substrate with first and second layers is prepared by applying a cellulosic base layer on the substrate followed by a silver nanoparticle coating. The nanoparticle coating is durable and highly electrically conductive. This conductive substrate maybe used for the application of integrated circuitry components, and does not outgas upon application of reflow solder. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
FIELD OF THE INVENTION
[0003] The present invention relates to a device for leveling and spacing tiles.
BACKGROUND OF THE INVENTION
[0004] It is a problem in the art, when laying tiles on a surface, to equally level the tiles to be coplanar and space the tiles. This is applicable to laying tiles on surfaces in general, including floors, walls, ceilings, and on other surfaces which can support tiles. The term tiles should be understood as including panels, sheets, boards, paving stones, and other materials capable of being laid out in a pattern.
SUMMARY OF THE INVENTION
[0005] From the foregoing, it is seen that it is a problem in the art to provide a device meeting the above requirements. According to the present invention, a device is provided which meets the aforementioned requirements and needs in the prior art. Specifically, the device according to the present invention provides a device for leveling and spacing tiles.
[0006] The present invention provides a two part device for use in leveling and spacing tiles. The device includes two parts, a rotatable portion and a fixed portion. The rotatable portion referred to hereinafter as a knob-cam includes two helical diametral opposed frontal action cams, a domed knob portion, a central opening, a knurled or ribbed portion and an annular surface portion. The fixed portion referred to hereinafter as a hook-base includes a base with flat surfaces for seating the tiles and ribs for spacing and separating tiles, a neck portion extending through a slot in the knob-cam and double blades which will engage with the double cam. The installation does not require tools.
[0007] In use, the base portion is inserted from the side underneath the tiles and spaced by the ribs in between the tiles. After insertion of the base portion will be installed all surrounding tiles, and then the knob-cam will be inserted. The neck portion extends upwardly above the tiles, and is adapted to be broken away after the adhesive sets upon application of sufficient upward force or sideways force. The knob-cam is placed against the tiles such that the neck extends through the key opening. The knob-cam includes two diametral opposed frontal action cam surfaces that engage the blades when the knob-cam is rotated. The knob-cam is rotated until the tiles are temporarily secured between the knob-cam and the base. Adhesive is used to permanently secure the tiles on the surface. The device evenly holds the tiles in correct position during the curing process. When the adhesive is set, the neck and hook portions can be removed by breaking them away from the base portion. Clamping is provided from opposite directions, fastening the tiles in such a way that the upper surface of the tiles will be coplanar, having correct reciprocal positions. Optionally the device may be used in conjunction with regular spacers, wider than the ribs and the device is providing just clamping force.
[0008] Other objects and advantages of the present invention will be more readily apparent from the following detailed description when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a perspective view of a device for use in leveling and spacing tiles, the device having a knob-cam portion and a hook-base portion shown separated prior to assembly, and with some tiles in place with the hook-base portion.
[0010] FIG. 2 a is a perspective view of the device of FIG. 1 , showing an assembly step.
[0011] FIG. 2 b is a perspective view of the device of FIG. 1 , showing another assembly step.
[0012] FIG. 2 c is a perspective view of the device of FIG. 1 , showing an assembled configuration.
[0013] FIG. 3 a is a perspective section view of the device in the position shown in FIG. 2 b wherein the hook from the hook-base portion is inserted through a key opening of the knob-cam portion.
[0014] FIG. 3 b is a view similar to FIG. 3 a , and wherein the knob-cam portion has been rotated and locked into place with the hook-base portion, consequently clamping tiles.
[0015] FIG. 4 a is a perspective view of the knob-cam portion and the hook-base portion of FIG. 1 , prior to assembly, and with the tiles omitted for the sake of clarity.
[0016] FIG. 4 b is a perspective view of the device having the knob-cam portion and the hook-base portion of FIG. 4 a , following assembly and tightening, and with the tiles omitted for the sake of clarity.
[0017] FIG. 5 a is a front elevational view of the hook-base portion.
[0018] FIG. 5 b is a top elevational view of the hook-base portion shown in FIG. 5 a.
[0019] FIG. 5 c is a right side elevational view of the hook-base portion of FIG. 5 a.
[0020] FIG. 6 a is a perspective view of the hook-base portion of FIG. 5 a , for use with four tiles.
[0021] FIG. 6 b is a perspective view of a second embodiment of the hook-base portion, for use with three tiles.
[0022] FIG. 6 c is a perspective view of a third embodiment of the hook-base portion, for use with two tiles.
[0023] FIG. 7 a is a front elevational view of the knob-cam portion of FIG. 1 . The radial valleys have been omitted for the sake of clarity
[0024] FIG. 7 b is a top elevational view of the knob-cam portion of FIG. 7 a . The radial valleys have been omitted for the sake of clarity
[0025] FIG. 7 c is a side elevational view of the knob-cam portion of FIG. 7 a as viewed from the right of FIG. 7 a . The radial valleys have been omitted for the sake of clarity
[0026] FIG. 8 a is a perspective view of the knob-cam portion of FIG. 1 showing a knurled portion. The radial valleys have been omitted for the sake of clarity
[0027] FIG. 8 b is a perspective view of another embodiment of the knob-cam portion, having a plurality of separated rib portions for manual gripping and turning. The radial valleys have been omitted for the sake of clarity
[0028] FIG. 9 a is a side elevational view of a further embodiment of a knob-cam portion, having a pair of cams, and pairs of radial valleys.
[0029] FIG. 9 b is a top elevational view of the knob-cam portion of FIG. 9A , showing the pair of cams, together with the pairs of radial valleys.
[0030] FIG. 9 c is an enlarged section of a portion of one of the cams, showing a close-up view of the radial valleys and teethed stepped profile.
[0031] FIG. 9 d is an enlarged section view of an assembly formed by a blade and a cam, showing a close-up view of a blade engaging with one of the radial valleys.
[0032] FIG. 10 is a perspective view of a further embodiment of a knob-cam portion which can be used in the device of FIG. 1 , wherein the cams have textured or smooth surfaces instead of teethed stepped surfaces.
[0033] FIG. 11 is a perspective view of a further embodiment of a knob-cam portion which can be used in the device of FIG. 1 , wherein the cams are shown, as well as a plurality of spaced ribs for facilitating manual gripping and turning.
[0034] FIG. 12 a is a side sectional view showing a hook-base portion shown sliding under the tile which is previously disposed on adhesive, and a floor which is covered by the adhesive.
[0035] FIG. 12 b is an enlarged sectional view of the downward oriented chamfer of the hook-base, wherein for the sake of clarity the hatching has been removed.
DETAILED DESCRIPTION OF THE INVENTION
[0036] A device 1000 according to the present invention is shown in FIG. 1 , depicting a knob-cam portion 2000 and a hook-base portion 3000 . The hook-base portion 3000 includes a hook 3100 and a base 3200 . Three tiles 4100 are shown mounted against the base 3200 of the base portion 3000 , and the tiles 4100 are shown as having side walls 4130 . There is room for a fourth tile 4100 against the base portion 3200 , which has been omitted for the sake of illustration. The device 1000 is provided for use in leveling and spacing tiles. The knob-cam portion 2000 is shown separated from the hook-base portion 3000 , prior to assembly.
[0037] As shown in FIG. 1 and in FIGS. 4-6 , the knob-cam portion 2000 has a domed knob shape 2300 and includes a pair of frontal cams 2100 (including a left cam 2110 and a right cam 2120 , the left cam 2110 having an engaging edge 2111 , a helical teethed and stepped cam profile 2112 , an uppermost edge 2117 , and an outer wall 2118 . The right frontal cam 2120 has an engaging edge 2121 , a helical teethed and stepped cam profile 2122 , an uppermost edge 2127 , a central opening 2200 , a central key hole 2210 , a central key slot 2220 , an outer wall 2128 , a knurling 2330 formed by alternating raised portions 2331 and recesses 2332 , a surface 2310 , a surface 2320 , and an annular seating bottom surface 2350 .
[0038] The hook-base portion 3000 is formed by a hook 3100 and a base 3200 . The hook 3100 has a rounded key 3130 formed by a tongue 3133 which has a central hole 3131 with a chamfer 3132 , a pair of engaging blades 3110 and 3120 , and a neck 3140 which has two side surfaces 3141 and 3142 . The neck 3140 is connected to the base 3200 by breakable portions 3150 , consisting in the edge 3151 and the corners 3152 which are disposed at a bottom region of the neck 3140 . The base 3200 has a supporting flat wall 3210 , a plurality of ribs 3220 , each of the ribs 3220 respectively including a slanted portion 3222 and a top portion 3221 , and a plurality of flat portions 3211 . The plurality of flat portions 3211 respectively receive bottom corner portions of the tiles 4100 which are to be separated by the ribs 3220 . The flat portions 3211 are provided between adjacent ones of the ribs 3220 .
[0039] FIG. 2 a is a perspective view of the device of FIG. 1 , showing an assembly step in which the knob-cam portion 2000 is brought toward the upper surfaces 4110 of the tiles 4100 in the direction shown by the dashed arrow Dl.
[0040] FIG. 2 b is a perspective view of the device of FIG. 1 , showing the next assembly step in which the hook 3100 of the hook-base portion 3000 extends through the key opening 2200 of the knob-cam portion 2000 and the blades 3110 and 3120 extend above the cams 2110 and 2120 such that the engaging edges 2111 and 2121 of the cams are below the blades portions 3110 and 3120 . The annular surface 2350 is touching the upper portion of tiles 4110 . The knob-cam portion 2000 is about to be rotated in the direction shown by the dashed arrow R 1 , the shown mechanism is unlocked and does not provide residual force.
[0041] FIG. 2 c is a perspective view of the device of FIG. 1 , the shown assembly mechanism is locked. By rotating the knob-cam 2000 , the frontal cams act as circular wedges and will provide the clamping residual force between the knob-cam 2000 and the tiles 4100 . When the knob-cam is rotated beyond the first engaging position, the blades 3110 and 3120 will start climbing on the cams' teethed and stepped profiles 2112 and 2122 , generating click sounds which can quantify the residual force necessary for proper clamping. It is important that the rotation is stopped after few clicks, to prevent breakage of the neck 3140 along the breakable portions 3151 and 3152 . The clamping effect will self level the upper surfaces of the tiles 4110 until they all touch the annular surface 2350 which creates a datum plane for leveling. The clamping effect is similar to the force provided by the jaws from a vice. The self-leveling effect propagates to all adjacent tiles found under the knob-cam 2000 . When the adhesive securing the tiles 4100 has been sufficiently set, the hook 3100 is adapted to be broken by fracture and can be removed, either by further rotation of the knob-cam portion 2000 or by striking of the hook 3100 in a sideways direction. The breaking edges 3152 and 3151 will be below the upper surface of tiles 4110 and will be covered later with grout and hidden. The hook portion 3100 can then be removed and the knob-cam portion 2000 can be reused.
[0042] FIG. 3 a is a perspective section view of the device 1000 in the position shown in FIG. 2 b wherein the hook 3100 of the hook-base portion 3000 is inserted through the key opening 2200 of the knob-cam portion 2000 . The mechanism is shown unlocked. Also in this view, the base portion 3200 has a bottom seating wall 3210 . The remaining parts are as numbered and described in the foregoing.
[0043] FIG. 3 b is a view similar to FIG. 3 a , and wherein the knob-cam portion 2000 has been rotated and locked into place between the blades portion 3110 and 3120 and radial valleys 2115 and 2125 , consequently clamping surrounding tiles 4100 in place. The mechanism is shown locked.
[0044] FIG. 4 a is a perspective view of the device 1000 with the knob-cam portion 2000 and the hook-base portion 3000 of FIG. 1 , prior to assembly, and with the tiles 4100 omitted for the sake of clarity. The mechanism is shown unlocked. The remaining parts are as numbered and described in the foregoing.
[0045] FIG. 4 b is a perspective view of the device 1000 having the knob-cam portion 2000 and the hook-base portion 3000 of FIG. 4 a , following assembly and tightening. The mechanism is shown locked. Here the tiles 4100 have been omitted for the sake of clarity.
[0046] FIG. 5 a is a front elevational view of the hook-base portion 3000 , showing the hook 3100 , the neck 3140 , and the base 3200 . Here, the base 3200 is shown having a chamfer 3212 and a seating surface 3211 . The central neck 3140 is perpendicular to the base's flat seating surfaces 3211 . The tongue portion 3130 from the key 3100 is suitable for gripping by the user during the rotation of knob-cam 2000 . The ribs 3220 from the base 3200 have continuous material with no gaps in between. The ribs 3220 provide equidistant spacing between adjacent tiles and can be made in a plurality of colors, each color representing a different spacing distance between tiles. The remaining parts are as numbered and described in the foregoing.
[0047] FIG. 5 b is a top elevational view of the hook-base portion 3000 having the seatings surfaces 3211 of the base 3200 as shown in FIG. 5 a . The remaining parts are as numbered and described in the foregoing.
[0048] FIG. 5 c is a right side elevational view of the hook-base portion 3000 having the base 3200 shown in FIG. 5 a . The remaining parts are as numbered and described in the foregoing.
[0049] FIG. 6 a is a perspective view of the hook-base portion 3000 having the base 3200 shown in FIG. 5 a , for use with four tiles.
[0050] FIG. 6 b is a perspective view of a second embodiment of the hook-base portion 3000 having the base 3200 , for use with three tiles.
[0051] FIG. 6 c is a perspective view of a third embodiment of the hook-base portion 3000 having the base 3200 , for use with two tiles.
[0052] FIG. 7 a is a front elevational view of the knob-cam portion 2000 of FIG. 1 , having an annular bottom surface 2350 . Here, the cam 2120 is shown having respective engaging edge 2121 and uppermost edge 2127 . In this view, the cams are shown with smooth surfaces, for the sake of clarity. By providing clamping force, the tiles will self level guided by the datum plane created by the bottom annular portion 2350 of the knob-cam. The knob-cam 2000 can be reused .The remaining parts are as numbered and described in the foregoing.
[0053] FIG. 7 b is a top elevational view of the knob-cam portion 2000 of FIG. 7 a . In this view, the cams are shown with smooth surfaces, for the sake of clarity. Here, the central key opening 2200 is shown having a central key hole 2210 , a central key slot 2220 and two wing-shaped key slot ends 2221 and 2222 . The central key hole 2210 has a diameter sufficient to accommodate and guide during rotation the neck portions 3141 and 3142 of hook-base 3000 . The two wing-shaped slot ends 2221 and 2222 are sufficiently wide to accommodate passage of the entire width of the hook 3100 of the hook-base portion 3000 .
[0054] FIG. 7 c is a side elevational view of the knob-cam portion of FIG. 7 a as viewed from the right of FIG. 7 a . In this view, the cams are shown with smooth surfaces, for the sake of clarity.
[0055] FIG. 8 a is a perspective view of the knob-cam portion 2000 of FIG. 1 showing a knurled portion 2330 . The remaining parts are as described in the foregoing.
[0056] FIG. 8 b is a perspective view of another embodiment of the knob-cam portion 2000 , having a plurality of separated rib portions 2340 for ease of gripping and rotating. The remaining parts are as described in the foregoing.
[0057] FIG. 9 a is a side elevational view of a further embodiment of a knob-cam portion 2000 of FIG. 1 , having an annular bottom surface 2350 . Here, the cam 2120 is shown having respective engaging edge 2121 and uppermost edge 2127 . By providing clamping force, the tiles will self level guided by the datum plane created by the bottom annular portion 2350 of the knob-cam. The knob-cam 2000 can be reused .The remaining parts are as numbered and described in the foregoing.
[0058] FIG. 9 b is a top elevational view of the knob-cam portion 2000 of FIG. 9A , showing the cam 2110 and the cam 2120 , together with the pairs of radial valleys 2115 and 2125 . The pairs of radial valleys facilitate seating and locking of the blade portions 3110 and 3120 during operation.
[0059] FIG. 9 c is an enlarged frontal section of a portion of the cam 2120 , showing a close-up view of the teethed stepped radial valleys 2125 . Each of the radial valleys 2125 has a generally scalloped shape, and includes the edges 2121 which prevents the blade portion 3110 and blade portion 3120 from unlocking itself; a valley portion 2124 which cooperates with the edge 2121 to prevent the blade portion 3110 and blade portion 3120 from unlocking itself; and a hill portion 2126 which allows a smooth transition to the next edge 2121 and provide residual force. Each of the radial valleys 2125 has an axial pitch h 1 , measured vertically between two consecutive edges 2121 , and a depth h 1 a of the valley (which determines the key's sound pitch intensity during turning). Each of the radial valleys 2125 also has a total blade travel h 1 b from the bottom of a valley to the next edge 2121 . Each of the radial valleys 2125 has a perimeter pitch p 1 (e.g., a length p 1 ), a distance p 1 a between and edge 2121 and the bottom of a valley, and a hill p 1 b which is a distance between the bottom of the valley to the next edge 2121 , measured transversely. As seen in FIG. 9 c , the radial valley 2125 has a concave portion 2124 where the locking ramp of the valley is located and a convex portion 2126 which leads smoothly to the next edge 2121 . The cams have axial and frontal action, and the orientation of the edges 2121 from the teethed and stepped profile is in opposite direction from the tiles.
[0060] FIG. 9 d is an enlarged section view of an assembly formed by a blade 3120 which looks like a V-Notch and the cam teethed and stepped profile 2122 . The tip edge 3122 and two adjacent sidewalls 3121 seats and engages with the locking valley portions 2124 wherein the edge 2121 and the locking ramp 2124 prevent the tip blades 3122 from unlocking themselves. Upon further urging of the blade portion 3110 during rotation of the knob-cam portion 2000 , the tip 3122 slides upwardly along the hill portion 2126 which forms a smooth transition to the next edge 2121 whereupon the tip 3122 can slide into the next radial valley portion 2125 . In this preferred embodiment, this sharp and central V shape is very effective in engaging with the teethed stepped profile on cams. Because the teeth have a radial pattern, i.e. are radially disposed, the blades 3110 , 3120 have to engage in a substantially exactly radial manner, and this determines that the sharp blades tips 3122 will be substantially exactly in the middle of the radial valleys 2125 and 2115 .
[0061] FIG. 10 is a perspective view of a further embodiment of a knob-cam portion 2000 which can be used in the device of FIG. 1 , wherein the cams 2110 and 2120 have smooth or textured surfaces instead of teethed and stepped surfaces.
[0062] FIG. 11 is a perspective view of a further embodiment of a knob-cam portion 2000 which can be used in the device of FIG. 1 , wherein the cams 2110 and 2120 have smooth or textured surfaces instead of teethed and stepped surfaces as well as a plurality of ribs 2340 for facilitating manual gripping and turning.
[0063] In the foregoing description, the frontal cams have specified surfaces. It is contemplated as being within the scope of the present invention that the frontal surfaces of helical cams can have any of: teethed and stepped surfaces; textured surfaces; or smooth surfaces. This includes teethed stepped surfaces as described above.
[0064] FIG. 12 a is a frontal sectional view showing a base portion 3200 , shown sliding into is engagement from the side under the tile 4100 in the direction indicated by an arrow D 2 . The tile 4100 is disposed on the adhesive 4200 which is covering the floor 4300 .
[0065] FIG. 12 b is an enlarged view of the chamfer 3212 portion. In this view the seating wall 3210 through the seating surface 3211 of the base 3200 is supporting a tile 4100 . The leading edge of the wall 3100 has the downward oriented chamfer 3212 , wherein the chamfer 3212 assists in penetrating the adhesive A along with an arrow labeled D 2 showing a direction of insertion or movement. That is, the chamfer 3212 in this process will push down the adhesive 4200 so as to help rub and clean the lower seating surface 4120 of tile 4100 from the adhesive 4200 in the location adjacent to the base 3200 . In this view, an arrow labeled D 3 shows a direction in which the adhesive A is pushed down by the chamfer 3212 , such that adhesive is cleaned from underneath the tile 4100 , providing a clean supporting surface.
[0066] The invention being thus described, it will be evident that the same may be varied in many ways by a routineer in the applicable arts. 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 claims.
[0067] The invention has several preferred embodiments but they are not exclusive. The invention is susceptible of many embodiments, all of which are within the scope of the appended claims. All the details may be substituted by other equivalent elements. | A two part device is used in leveling and spacing tiles. The device includes two parts, a rotatable portion called a knob-cam and a fixed portion called hook-base. The hook-base includes ribs for spacing and separating tiles, and a neck portion extending through a slot opening in the knob-cam. In use, the hook-base portion is set down and tiles are laid down and spaced by the ribs of the base portion. The neck portion extends upwardly above the tiles, and is adapted to be broken away upon application of sufficient upward force or sideways force. The knob-cam includes two diametral opposed frontal action cam surfaces that engage portions of the hook when the knob-cam is rotated. The knob-cam is rotated until the tiles are secured between the knob-cam and the hook-base. This clamps the corners or edges of the tiles, making coplanar upper surfaces. | 4 |
RELATED APPLICATION
[0001] This application is a divisional of U.S. patent application Ser. No. 11/208,801, which was filed Aug. 22, 2005.
BACKGROUND
[0002] This application relates to a method of repairing a full hoop structure with a welding process, wherein heat treating is performed both at the location of the weld, and at a diametrically opposed location.
[0003] Welding methods are sometimes necessary to repair metallic structures. As an example, a cast part may have a defect such as shrinkage that may have occurred in a cast mold. Alternatively, small cracks may form in the part.
[0004] Such operations are often used in components for gas turbine engines. Structures that could be called “full hoop,” or structures that surround a central axis for 360°, often require such welding procedures. Examples of such parts in a gas turbine engine would be a diffuser case and a turbine exhaust case.
[0005] The weld being performed at a location on the part may cause an unacceptably high residual stress. In the prior art, this stress has been relieved by some post-weld heat treatment.
[0006] In one prior art method, the entire structure has been heated isothermally to heat-treat temperatures. Heating isothermally does not induce additional thermal stress at the weld, so the residual stress remains constant until actual heat treatment takes place. This “global” heating can affect dimensions that have been “machined” into the part by causing their residual stresses to also relax. In many cases, it has not been found practical due to cost and complexity to fixture the part during heat treatment to hold these dimensions constant.
[0007] Thus, localized heat treatment has also been utilized to avoid loss of dimensions. Local heat treatment can have unforeseen and potentially detrimental effects on the intended stress relaxation. The region being heated locally will expand due to its temperature change. The surrounding non-heated material will resist this expansion causing the heated area to become more compressively loaded. Since the residual stress due to weld is tensile, the net effect of local heating is to temporarily reduce the value of the tensile stress in the weld. If sufficient care is not exercised, it is possible to reduce the value of the tensile stress so much so as to eliminate it completely. In this case, subsequent heat treatment for stress relaxation would be ineffective since the stress would already be reduced to zero. Note that the full value of the residual stress in this case would return when the locally applied temperature was removed.
[0008] Also of concern, would be a situation in which the weld stress was reduced by local heating through zero and into a state of compression. This stress would relax during subsequent heat treatment, but this is far from the original intent of the heat treatment process, which was to reduce the tensile residual stress associated with the weld.
SUMMARY
[0009] In the disclosed embodiment of this invention, a weld repair is made on a part with a full hoop structure. After the weld has been completed, heat-treating is performed at the location of the weld, and at the same time, at a second opposed location. In a disclosed embodiment, the second location is diametrically opposed to the weld location. This heat-treating is preferably confined to as narrow a band as possible through the weld and its heat affected zone, and in a similar manner, at an opposed position to it. Furthermore, the heat-treating preferably occurs along an entire axial length of the part.
[0010] The opposed bands of heat-treating eliminate the compressive stresses mentioned above from forming. This allows the modified local heat treatment to mimic the beneficial effect of a global heat treatment as mentioned above while avoiding the inherent problems.
[0011] While in the disclosed embodiment the part is a full hoop part, the present invention is more powerful, and extends beyond any particular shape of part. In fact, an arbitrarily shaped part could benefit from this present invention. In an arbitrarily shaped part, an area of material on the part would be identified about which the part would thermally expand while not creating additional stress in the part at a weld treatment location. The weld treatment would be provided, and simultaneously, a local heat treatment would be provided at an area of the weld treatment, and at the identified area.
[0012] In other optional embodiments, the second band could be a plurality of bands, which are displaced from the diametrically opposed location. As an example, two separate bands spaced equally about a location spaced 180° from the weld treatment area could be utilized rather than a single second band.
[0013] In yet another embodiment, the second band can extend for a greater circumferential extent than the band about the weld treatment. In this manner, the heat treating on the second band can be at a lower temperature. By utilizing a lower temperature, the potential resultant dimensional changes in that second region can be reduced. Such dimensional changes are related to temperature, and thus being able to utilize a lower temperature, albeit over a larger area, might prove beneficial under certain applications.
[0014] These and other features of the present invention can be best understood from the following specification and drawings, the following of which is a brief description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 schematically shows a gas turbine engine.
[0016] FIG. 2 is a schematic view of a full hoop part.
[0017] FIG. 3 is a cross-sectional view of a heat treatment occurring on the mentioned part.
[0018] FIG. 4 shows yet another embodiment.
[0019] FIG. 5 shows yet another embodiment.
DETAILED DESCRIPTION
[0020] A gas turbine engine 10 is illustrated in FIG. 1 extending along an axial center line 12 . A fan section 14 is upstream of a compressor section 16 , a combustion section 18 , and a turbine section 11 . As is known, many components of a gas turbine engine 10 could be said to have a “full hoop” structure. The full hoop is defined as a structure that surrounds the axial center line 12 for 360°. An example of such full hoop structures found in the gas turbine engine 10 would include a diffuser case located downstream of the compressor, or a turbine exhaust case located downstream of the turbine section 11 . The term “full hoop” should not be taken as requiring that the component would be cylindrical. In fact, the disclosed components could be better described as somewhat conical. Even that shape is not a limitation on the definition of “full hoop” which could extend to non-symmetrical structures, or structures with complex surfaces and multi-faceted shapes at their outer surfaces.
[0021] As shown in FIG. 2 , such a part 50 can have defects such as a crack shown at 52 . Other type defects may be a casting defect such as may be caused by shrinkage. A worker of ordinary skill in the art would recognize many of the known defects, which could require welding repair treatment.
[0022] As shown in FIG. 3 , a weld treatment 53 is being applied schematically by welding tool 60 at the crack 52 . With the present invention, and after completion of the welding treatment, two narrow bands of heat treatment are applied at diametrically opposed locations 54 and 56 . Preferably the circumferential extent of the bands is selected to only be wide enough to provide the stress relief at the weld joint 53 along the defect 52 . Thus, the bands may well have the same circumferential width. As shown, heating structures 58 create these two heat treat locations. The heating structures may be induction coils, radiant lamps, gas burners, etc. The heat treatment can be on the order of 1500° F., although the heat treat temperatures may be as known in the art. The bands 54 and 56 extend along the entire length of the part 50 , as shown in FIG. 2 . Of course, it may also be that the bands do not extend for the entire length of the part.
[0023] The present invention, by utilizing the two diametrically opposed bands, achieves the benefits provided by the global heating of the prior art, but also avoids the problems of global heating as encountered in the prior art.
[0024] Also, while the present invention is disclosed as being directed to full hoop parts, it would have benefits in certain parts that do not have the full hoop structure as defined above. Arbitrarily shaped parts could benefit from the present invention by heat treating two distinct zones, to allow the numerical value of weld residual stress to be heat treated, while greatly reducing or eliminating the liability of resultant dimensional changes. For non-full hoop structures, a line or plane of material to be locally heat treated as the second band, is the line or plane about which the structure would thermally expand without creating additional stress in the component at the weld. A worker of ordinary skill in this art can determine this line or plane with structural analysis.
[0025] FIG. 4 shows another embodiment wherein the “second band” is actually provided by two separate bands 202 and 204 . As can be appreciated, the two separate bands are disclosed as being spaced equally about the point P spaced 180° from the weld treatment area T. By positioning these separate bands about the point P, the beneficial effects provided by the above-disclosed embodiment can be achieved.
[0026] FIG. 5 shows yet another embodiment wherein the circumferential extent of the second band 300 is wider than the circumferential extent of the weld band 302 . The temperature provided at the second band 300 can be lower, such that potential resultant dimensional changes in this second band are reduced.
[0027] Again, a worker of ordinary skill in the art would recognize how to incorporate the optional embodiments of FIGS. 4 and 5 to best effect.
[0028] Although an embodiment of this invention has been disclosed, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of this invention. | A unique heat treat method for relieving stresses caused by a repairing weld joint in a full hoop part heat treats locally, at the location of the weld joint, and at a diametrically opposed location. By providing the diametrically opposed heat treat location, the present invention relieves stresses caused by the weld joint, without creating any additional residual stress in the weld joint. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims priority from copending provisional patent application entitled “BLOW GUN WITH EXTENSIBLE WAND”, Ser. No. 60/443,055 filed Jan. 28, 2003. The disclosure of provisional patent application Ser. No. 60/443,055 is hereby incorporated in its entirety.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable
BACKGROUND OF THE INVENTION
The present invention pertains to compressed air blow guns. A blow gun to direct compressed air is a common tool used in factories, workshops and around trucks and other vehicles. Blow guns are frequently used around large truck tractors for the occasional need to use compressed air to expel debris and dust from a truck trailer or truck cab or sleeper and for other uses, as well as to inflate tires when the blow gun is equipped with an inflation chuck. The blow gun is coupled to an air hose coupled to a supply of compressed air which may be connected to the compressed air system of the truck tractor.
Adjustability of the length of the wand is a desirable feature in order to make the blow gun more versatile. An improvement for the standard fixed wand blow gun is shown in U.S. Pat. No. 5,832,974 to Jou which shows a blow gun with an adjustable wand. The prior art blow gun allows the wand to be adjusted by use of a threaded sleeve which urges clamping fingers into abutment with the outside of the wand of the blow gun. Adjustment of the extension of the wand requires the loosening of the threaded sleeve to a point which releases the clamping fingers and the retightening of the sleeve when the desired wand extension is made.
SUMMARY OF THE INVENTION
The present invention provides a blow gun with an extensible wand. Extension or retraction of the wand of the blow gun is accomplished by releasing the wand by rotation of a collar less than one half turn in either direction. The invention includes a handle having a trigger lever which opens a valve to permit compressed air from a source hose coupled to the handle to pass through the handle into an elongate wand on the end of which a nozzle may be mounted or alternatively a tire inflation chuck member may be mounted. The handle includes a barrel which serves as a storage housing for the wand when it is retracted. The wand through which compressed air may pass is adjustable in length by sliding it inwardly or outwardly longitudinally from the barrel of the handle. The wand may be extended to a desired length and locked into the particular extension position by use of an outer collar which is eccentrically rotatable upon an inner collar. The inner collar has a first section and an externally threaded extension which extends longitudinally from the first section. The extension is not coaxial with the first section but a longitudinal bore through the inner collar is coaxial with the first section and therefore is offset from the axis of the extension. The bore through the first section is internally threaded and sized to mount to the threads on the end of the barrel while the bore through the extension is smooth and is sized to permit the wand to be slid through it. The outer collar includes a threaded bore to receive the external threads of the extension of the inner collar. The threaded bore does not extend through the outer collar but rather longitudinally joins a smaller bore which is sized larger than the outer diameter of the wand. The axis of the smaller bore is slightly displaced from but parallel to the axis of the threaded bore of the outer collar. A ridge is formed longitudinally on the exterior of the outer collar to provide a lever to easily rotate the outer collar on the inner collar and to provide an indexing means.
Rotation of the outer collar less than one half of a turn will cause the bore of the outer collar to move such that the bore of the inner collar is no longer in registry with the small bore of the outer collar. Hence the outer collar forces the wand against the bore in the extension of the inner collar and thereby locks the wand in its then longitudinal position.
It is an object of the invention to provide a versatile blow gun which includes a wand which can quickly and simply be extended or retracted when released by less than a half turn of a collar surrounding the wand.
It is a further object of the invention to provide a blow gun with a variable length wand which may be extended or retracted without removing the wand from the handle of the blowgun.
It is also an object of the invention to provide an improved blow gun which allows for extension or retraction of the wand thereof without the use of numerous clamping parts mounted to the handle of the blow gun.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
FIG. 1 is a front elevation of the invention with the wand in a retracted position.
FIG. 2 is an exploded view in perspective of the barrel and wand assembly of the blow gun invention.
FIG. 3 is a cross section of the barrel assembly of the invention taken along its longitudinal axis.
FIG. 4 is a cross section of the inner collar of the barrel assembly of the invention.
FIG. 5 is a top plan view of the inner collar of FIG. 3 .
FIG. 6 is a cross section of the outer collar of the barrel assembly of FIG. 1 .
FIG. 7 is a top plan view of the outer collar of the barrel assembly of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The assembled blow gun invention is illustrated in FIG. 1 with wand 18 in a retracted, released position so that wand 18 may be extended. Blow gun 8 comprises a handle 14 which includes intake port 50 and contains an internal actuable valve to selectively allow compressed air to pass through handle 14 and through barrel 12 and wand 18 and to be expressed from nozzle 58 . The internal valve of the handle is opened by movement of trigger 52 towards handle 14 in a conventional manner. A hook 54 is formed on handle 14 to provide a structure for suspending handle 14 . Barrel 12 has inner collar 16 mounted thereto with outer collar 20 mounted to inner collar 16 . The ridge 84 of outer collar 20 is aligned with protrusion 72 of inner collar 16 indicating that outer collar 20 is positioned such that wand 18 is free to be adjusted.
Now referring also to FIG. 2, barrel assembly 10 is shown in exploded view. Elongate hollow barrel 12 is mountable at its first end 22 to the handle 14 by conventional screw thread means or by other means such as bayonet mounting. Opposing second end 24 of barrel 12 includes external screw threads 26 for receiving inner collar 16 . Wand 18 is selectively slidably receivable within barrel 12 in a longitudinal fashion. Outer collar 20 is receivable upon externally threaded distal end 30 of inner collar 16 . Inner collar 16 is receivable at its proximal end 32 upon threads 26 of barrel 12 . Inner collar 16 is securely mounted to barrel 12 while outer collar 20 is manually rotatable over a limited range relative to inner collar 16 .
Large O-ring 34 is receivable within bore 36 of inner collar 16 to provide a seal between barrel 12 and inner collar 16 . Ring seals 40 , 42 are slidably received around wand 18 to provide a seal around it. Wand 18 is provided with enlarged shoulder 44 at its proximal end 38 . Shoulder 44 functions as a stop against ring seals 40 , 42 when wand 18 is maximally extended from barrel 12 . Wand 18 is provided with longitudinal bore 56 therethrough terminating with nozzle 58 .
Referring now additionally to FIG. 3, the assembled barrel assembly 10 is shown in longitudinal cross section with wand 18 at an intermediate extension from barrel 12 . Barrel 12 comprises longitudinal bore 47 which includes enlarged counter bore 48 adjacent second end 24 thereof. Large elastomeric O-ring 34 is positioned at the proximal end 28 of threads 26 such that inner collar 16 is sealed to barrel 12 . Semi-rigid ring seal 40 and elastomeric ring seal 42 surround wand 18 and are retained in a gap 46 formed by enlarged counter bore 48 of barrel 12 . Semi-rigid ring seal 40 is preferably made from nylon. Inner collar 16 is mounted securely upon screw threads of barrel 12 and outer collar 20 is in place on extension 60 of inner collar 16 .
Referring now also to FIGS. 4 and 5, it can be observed that inner collar 16 comprises first section 60 and includes extension 62 joined integrally to first section 60 . Preferably inner collar 16 will be formed from nylon or another rigid polymer or of metal. Inner collar 16 comprises internal threaded bore 64 in first section 60 thereof which is communicative with tapered passageway 68 which interconnects smooth bore 70 of extension 62 to threaded bore 64 . Smooth bore 70 is sized to allow wand 18 to slide snugly yet easily therealong and is coaxial with threaded bore 64 which is sized to receive second end 24 of barrel 12 . It can be seen in FIGS. 4 and 5 that smooth bore 70 is coaxial with first section 60 of inner collar 16 while extension 62 is offset on first section 60 such that it is not centered on first section 60 . In the preferred embodiment, the offset of axis A—A of extension 62 from the centerline D—D of first section 60 is approximately 0.040 inches.
Extension 62 is provided with external screw threads 66 therealong. A protrusion 72 is formed on the periphery of first section 60 of inner collar 16 to allow indexing of the outer collar 20 therewith. First section 60 is preferably textured on its outer surfaces.
Referring now to FIGS. 6 and 7, details of outer collar 20 may be visualized. Outer collar 20 is preferably constructed of nylon of another rigid polymer or of metal, and comprises internal threaded bore 78 opening at proximal end 74 of outer collar 20 , and smooth bore 80 opening at distal end 76 of outer collar 20 . The exterior of outer collar 20 is multi-sided, comprising segments 82 which facilitate manual rotation of outer collar 20 relative to inner collar 16 . The periphery of outer collar 20 also includes longitudinal ridge 84 which is formed on outer collar 20 to provide indexing means and is oriented on outer collar 20 such that when ridge 84 is aligned with protrusion 72 of inner collar 16 , the smooth bore 80 of outer collar is in registry with smooth bore 70 of inner collar 16 . Specifically, the entire area of smooth bore 70 of inner collar 16 is within, but not centered in, the area of smooth bore 80 when ridge 84 is aligned with protrusion 72 . When outer collar 20 is rotated such that ridge 84 is not aligned with protrusion 72 , at least some portion of smooth bore 70 is not in registry with smooth bore 80 of outer collar 20 . It should be understood that the centerline B—B of smooth bore 80 of outer collar 20 is parallel to but slightly offset from the centerline C—C of outer collar 20 . In the preferred embodiment, the offset is in the approximate range of 0.012 to 0.016 inches, preferably about 0.014 inches. Therefore, when outer collar 20 is rotated such that ridge 84 is out of longitudinal alignment with protrusion 72 of inner collar 16 , smooth bore 80 of outer collar 20 is offset by an increasing distance from smooth bore 70 of inner collar 16 . As outer collar 20 is rotated, smooth bore 80 thereof applies side force to wand 18 and forces it against a side of smooth bore 70 of inner collar 16 .
In the preferred embodiment, the smooth bore 80 of outer collar 20 is slightly larger than the smooth bore 70 of the inner collar 16 . Preferably, the diameter of smooth bore 80 is 0.290±0.002 inches and the diameter of smooth bore 70 is 0.243±0.002 inches. The diameter of the wand 18 is preferably approximately 0.236 inches and wand 18 therefore slides snugly but without interference within inner collar 16 .
When outer collar 20 is rotated to a position where ridge 84 thereof is aligned with protrusion 72 of inner collar 16 , smooth bore 70 is in registry with but not centered on smooth bore 80 of outer collar 20 . When outer collar 20 is rotated away from the position in which ridge 84 is aligned with protrusion 72 , shear force is applied to wand 18 from misalignment of smooth bore 70 with smooth bore 80 .
The amount of rotation of outer collar 20 needed to sufficiently offset smooth bore 80 from smooth bore 70 is approximately one quarter turn, in order for adequate shear force to be applied along wand 18 to bind it and thereby to restrain longitudinal movement of wand 18 in relation to barrel 12 . By rotating outer collar 20 into alignment of ridge 84 thereof with protrusion 72 of inner collar 16 , the axis of smooth bore 80 of outer collar 20 is oriented such that its axis B—B is in closest proximity with the axis of smooth bore 70 of inner collar 16 and smooth bore 70 is in registry with smooth bore 80 of outer collar 20 . In that disposition, wand 18 may be moved longitudinally into a desired position, whereupon outer collar 20 may then be rotated to sufficiently bind wand 18 into a temporarily fixed extended position. | A blow gun with an extensible wand includes a barrel for receiving and storing the wand. The wand passes through an inner collar and an outer collar, the inner collar mounted to the barrel and the outer collar eccentrically rotatable upon the inner collar. Rotation of the outer collar affects alignment of the bore of the outer collar with the bore of the inner collar. When the misalignment of the bores is increased, the wand is locked in a selected extension from the barrel. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the field of fossil fuels and in particular to methods and compounds for increasing the viscosity and reducing the dispersion of bitumen-in-water emulsions following spills or leaks, and specifically with regard to a bitumen-in-water emulsion known as ORIMULSION, produced by and a trademark of Petroleos di Venezuela.
2. Description of the Related Art
ORIMULSION is a well-known alternative fossil fuel that can be combusted by industrial power plants which have been modified for the fuel. See, for example, Makansi, J., "Manatee Lays Groundwork for Commercial Use of Orimulsion," Power, September 1994, pp. 57-60; Makansi, J., "New Fuel Could Find Niche Between Oil, Coal," Power, December 1991, pp. 51-56. ORIMULSION consists of approximately 70% bitumen droplets dispersed in about 30% water, with a small amount of surfactant added to stabilize the emulsion. Bitumen is an extra heavy crude oil with an API gravity density of less than 8°. ORIMULSION is much less viscous than bitumen, and as a result, ORIMULSION may be transported by conventional pipelines and in tankers. For a particular sample tested, the pH of ORIMULSION is about 8.09, the density is about 0.995 and the wt % moisture of ORIMULSION is about 32.65.
A significant concern with the use and transport of ORIMULSION is that it is readily dispersable in water. Thus, if spills occur on land or at sea, the ORIMULSION can quickly spread over a large area in a short time, rapidly causing greater environmental damage.
It has been reported that when the ORIMULSION dispersion is reversed, that is, to a water-in-bitumen mixture (water droplets dispersed in bitumen), it has a viscosity near to that of bitumen. The following conditions may cause this inversion, or reversal, in ORIMULSION:
1) exposure to temperatures exceeding 176° F.; 2) sudden pressure drop exceeding 100 psi; 3) centrifugal pump shearing at greater than 1800 rpm; and 4) mixing with greater than 1% #6 oil, which can occur during fuel switching.
Since ORIMULSION is a multi-component, two-phase system, this type of emulsion and its physical properties can be changed by changing the composition of the components, adding other chemicals, or changing the conditions surrounding the system.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method (or methods) for reducing the dispersion of bitumen-in-water emulsions, and in particular of ORIMULSION.
It is a further object of the present invention to provide compounds for modifying the physical properties of bitumen-in-water emulsions, and in particular ORIMULSION, such that the emulsion is less prone to dispersion in water.
Accordingly, methods and compounds for lessening the dispersion in water of ORIMULSION are provided herein. Methods for retarding ORIMULSION dispersion in water include applied mixing, and decreasing the pH. Adding one or more compounds, including oil, solvents, surfactants, salts and flocculants. Additive compounds include CaCl 2 and FeCl 3 inorganic salts, and BETZ (a registered trademark of Betz Laboratories) 3395, 3367L and 3317L flocculants.
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 descriptive matter in which a preferred embodiment of the invention is illustrated.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Several methods for retarding the dispersion of a specific bitumen-in-water emulsion, ORIMULSION, were tested using shear viscosity measurements. A Haake Rotovisco viscometer was used to determine the shear viscosity of the ORIMULSION following application of the method under test. In each case, the shear rate was raised from 0 to 100 sec -1 in a fixed time period, then held constant for a second fixed time period, and then reduced to zero again in a third fixed time period. Except for tests on the effect of temperature, the temperature of the ORIMULSION was maintained at 25° C.
A reference sample of ORIMULSION was tested first according to the test method described. The viscosity of the reference sample was found to be 293 centipoise at a shear rate of 100 sec -1 and temperature of 25° C. It was discovered that ORIMULSION is thixotropic in nature. That is, the shear stress decreases at a constant shear rate. And, it has a pseudo-plastic characteristic as well, as the shear stress increased in a less than linear manner as the shear rate was increased.
The methods tested for retarding the dispersion of ORIMULSION by increasing the viscosity included shearing, or mixing the emulsion at 300 rpm for 4 hours, lowering the pH of the emulsion and adding one of several additive compounds. Additive compounds and the approximate weight percent added to the ORIMULSION which were tested included Kerosene (1.4 wt % to 4.2 wt %), TRITON RW-20, a registered trademark of Rohm and Haas, cationic surfactant (1.4 wt %), calcium chloride (CaCl 2 ) (0.2 wt % to 2.8 wt %), iron chloride (FeCl 3 ) (1.4 wt %), and three Betz flocculants--Betz 3395, Betz 3367L and Betz 3317L (all 1.4 wt %). The following table summarizes the test results.
TABLE 1______________________________________ Viscosity @ shear rateMethod or Additive applied to of 100 sec.sup.-1ORIMULSION and conditions (centipoise)______________________________________Applied 300 rpm for 4 hours 669MixingDecrease pH pH 1.67 564Add Solvent 4.2 wt % Kerosene 399Add 1.4 wt % TRITON RW-20 cationic 346SurfactantAdd Salt 2.8 wt % CaCl.sub.2 790 1.4 wt % FeCl.sub.3Add 1.4 wt % Betz 3395 3800Flocculent 1.4 wt % Betz 3367L 940 1.4 wt % Betz 3317L 1185______________________________________
As can be seen from the results summarized above, the Betz flocculants were most effective in increasing the viscosity of the ORIMULSION, thereby greatly reducing the ability of the emulsion to flow or disperse. The kerosene and TRITON RW-20 surfactant only slightly increased the viscosity and did not cause any phase separation in the emulsion.
The two inorganic salts, however, caused a significant separation of the water phase from the bitumen, which increased the viscosity. It is uncertain at this time whether the increased viscosity was caused by a phase inversion, or merely a phase separation.
Applied mixing had the effect of thickening the emulsion, thereby increasing the viscosity. Lowering the pH also caused an increase in the viscosity of the ORIMULSION.
The methods and additives tested are useful, since only small quantities of each additive need be used to produce the increased viscosity, and the resulting retardation of flowability and dispersibility of the ORIMULSION emulsion. Further, each of the additives is non-toxic, and the methods do not adversely affect the environment either. This can help keep financial and environmental costs of cleaning spills of this fuel lower.
Each of these methods can be applied to spills immediately after a spill occurs. The amounts added can be adjusted for effectiveness on site, depending on the exact composition of the ORIMULSION spilled. Once the phases of the emulsion are cleaned up as much as possible, the recovered material can be reformulated by appropriate processes including applying additives or adjusting conditions for reuse.
While a specific embodiment of the invention has been 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. | Methods and additive compounds for retarding the dispersion in water of bitumen-in-water emulsions, and in particular ORIMULSION, are disclosed. Methods include applied mixing at high speed and changing the pH of the emulsion. Additives include salts and flocculants. | 8 |
This application is a continuation-in-part of application Ser. No. 09/757,611 filed Jan. 11, 2001 now abandoned, and claims priority from U.S. Provisional Application Serial No. 60/380,817 filed May 15, 2002 and U.S. Provisional Application Serial No. 60/380,818 filed May 15, 2002. The entire contents of said three applications are hereby incorporated herein by reference.
This invention was made with United States Government support under Cooperative Agreement No. DE-FC26-00NT40756 awarded by the Department of Energy. The United States Government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention relates to combustion of carbonaceous and hydrocarbonaceous fuels, such as coal.
BACKGROUND OF THE INVENTION
One of the methods to reduce NOx and other emissions from coal fired utility boilers is to switch to a less polluting coal, e.g., from an Eastern bituminous coal to a Western sub-bituminous coal. (According to ASTM D 388, classification of coals by rank, the fixed carbon content and the calorific values are used as the basic criteria for classification of coals. Lignite is defined as having calorific values less than 8,300 Btu/lb on a moist and mineral matter free basis. Sub-bituminous coals are defined as having calorific values between 8,300 and 11,500 Btu/lb. High volatile bituminous coals are defined as having calorific values between 11,500 and 14,000 Btu/lb. These definitions apply when the foregoing terms are used herein. Medium and low volatile bituminous coals and anthracites are classified based on their fixed carbon contents.)
Western sub-bituminous coals and lignites typically have much lower sulfur contents and lower nitrogen contents than Eastern bituminous coals. Furthermore, sub-bituminous coals and lignites are more reactive than bituminous coals and produce lower unburned carbon (UBC) in ash. Emissions of SOx and NOx and UBC in ash can be substantially reduced by switching to less polluting coals.
There are, however, several technical issues in switching to a lower rank coal as all or even a portion of the fuel fed to a boiler designed for firing bituminous coals. For example, the existing coal pulverizer designed for a bituminous coal may not be able to handle the greater volume of sub-bituminous coal to provide the same heat input to the boiler. Also, the heating value of a sub-bituminous coal or lignite is much lower and the moisture content is higher than those of a bituminous coal. As a result, the flame temperature is reduced and a larger flue gas volume is produced per unit amount of heat released. The lower flame temperature and higher flue gas volume associated with a subbituminous coal typically cause a problem in heat absorption and distribution: reduced heat absorption in the radiant section and too much heat passing through the radiant section and being absorbed in the convective section. This sometimes results in a derating of the boiler, unless major modifications are made to the boiler.
To overcome capacity limitations of the existing coal pulverizer designed for a bituminous coal design modifications that increase air flow, duct heaters and mechanical capacity upgrades may be required. In-duct heaters are used to reduce the moisture content of pulverized coal so as to improve the flame ignition characteristics and to increase the flame temperature with lower rank coals. A careful analysis of boiler heat transfer conditions is required to assess the impact of reduced heat transfer to the plant steam and power outputs. Modification of the steam circuits may be required to properly balance the radiative and convective sections of the boiler. For example, economizer tubes may be added for additional heat recovery from flue gas. Furthermore, the spacing of the superheat and reheat sections and gas temperature need to be reviewed for potential fouling and plugging issues. Additional soot blower coverage or water cleaning devices for the furnace walls may need to be used. (Robert Lewis, Gary Camody, and Patrick Jennings, “Summary of Recent Low NOx achievements with Low NOx Firing Systems and High Reactivity PRB and Lignite Coal: As low as 0.1 Lb/MMBtu,” also James Topper, et al, “Maximizing PRB Coal Usage in Conjunction with In-Furnace NOx Solutions to Minimize Cost of NOx Compliance,” both papers presented at 27 th International Conference on Coal Utilization & Fuel Systems, Mar. 4-7, 2002, Clearwater, Fla.).
Although these boiler modifications have been successfully implemented to enable coal switching from bituminous coal to sub-bituminous coal, significant capital and opportunity costs are typically incurred due to the equipment and labor costs of the modification and due to the boiler down time while the modifications are being made. There is accordingly a need to provide a method to obtain the reduced NOx emissions from an existing coal fired boiler that can be realized by switching the type of coal in the fuel, without requiring major modifications to the existing boiler. A further object of the present invention is to enhance the reduction of NOx emissions by improved combustion modifications.
BRIEF SUMMARY OF THE INVENTION
The present invention is a method for modifying operation of a furnace, comprising
to a furnace that comprises a combustion chamber, burner means for combusting hydrocarbonaceous fuel containing bound nitrogen and having a given minimum calorific value in said combustion chamber to generate heat of combustion and gaseous combustion products, feed means for feeding said fuel and combustion air to said burner means, flue means for enabling said combustion products to leave said combustion chamber, and heating means for using said heat of combustion to produce steam, wherein said furnace is being operated to combust a first fuel containing bound nitrogen and having said minimum calorific value to produce steam at a defined minimum rate of energy content per unit of time,
providing replacement fuel by replacing some or all of said first fuel with a second hydrocarbonaceous fuel whose calorific value is below that of the first fuel, at a replacement ratio such that the feed rate of said second fuel to said furnace divided by the feed rate of said first fuel to said furnace in units of energy per unit time is between 1.0 to 1.3, and feeding said replacement fuel to said burner means,
feeding gaseous oxygen into said replacement fuel as the replacement fuel emerges from said burner into said combustion chamber or by adding it to the air fed through said burner, in an amount which is less than 25% of the stoichiometric amount required for complete combustion of said replacement fuel while reducing the amount of air fed through said burner by an amount containing sufficient oxygen that the overall stoichiometric ratio in said furnace varies by not more than 10% compared to the stoichiometric ratio without said addition of oxygen, and combusting said replacement fuel with said combustion air and said oxygen,.
In a preferred embodiment, the calorific values of said first fuel and said second fuel are related such that the available heat above 2000 F. generated by combusting said first fuel with air at a given stoichiometric ratio and temperature is 103% or more of the available heat above 2000 F. generated by combusting said second fuel with air at said given stoichiometric ratio and temperature.
In another preferred embodiment, said oxygen is fed to said burner at a sufficient rate that said furnace produces steam at a rate of energy content per unit of time at least equal to said defined minimum rate.
In yet another preferred embodiment, said first fuel is bituminous coal and said second fuel optionally comprises bituminous coal and further comprises coal selected from the group consisting of subbituminous coal, lignite and mixtures thereof.
In preferred embodiments of the combustion, said combustion is staged with over fire air and the primary combustion zone stoichiometric ratio is between 0.6 and 1.0.
In a preferred embodiment of operation, a stream of fuel is fed through said burner and oxygen is fed into said fuel by injecting it through a hollow lance, positioned in said stream, into the fuel as the fuel emerges from the burner. In another preferred embodiment of operation, a stream of fuel is fed through an annular fuel passage of said burner, and oxygen is fed into said fuel by injecting it through an annular passage surrounding or surrounded by said annular fuel passage.
In the present invention a small amount of oxygen is used in conjunction with switching at least some, or all, of the fuel to a lower rank (lower energy content per unit mass) fuel to reduce pollution emissions, in a manner which eliminates the needs for costly boiler modifications. A preferred embodiment is to switch some or all of the feed from bituminous coal to sub-bituminous coal or lignite. For ease of reference, the term “replacement fuel” is sometimes used herein, to refer to the fuel that is fed to the combustion chamber. When a portion of the combustion air is replaced by oxygen the flame temperature is increased and the flue gas volume is reduced because the reduced flow rate of air reduces the amount of nitrogen flowing through the combustion chamber. The oxygen addition effectively offsets the reduction in flame temperature and increased flue gas volume caused by switching the feed coal to a lower rank coal and restores the heat transfer conditions in the boiler. Furthermore, oxygen addition can be conducted under staged combustion conditions so as to enhance NOx reduction kinetics in the fuel rich combustion stage, as described herein.
As used herein, “stoichiometric ratio” means the ratio of oxygen fed, to the total amount of oxygen that would be necessary to convert fully all carbon, sulfur and hydrogen present in the substances comprising the feed to carbon dioxide, sulfur dioxide, and water.
As used herein, “NOx” means oxides of nitrogen such as but not limited to NO, NO 2 , NO 3 , N 2 O, N 2 O 3 , N 2 O 4 , N 3 O 4 , and mixtures thereof.
As used herein, “SOx” means oxides of sulfur such as but not limited to SO 2 , SO 3 , and mixtures thereof.
As used herein, “bound nitrogen” means nitrogen that is part of a molecule that also contains carbon and hydrogen and optionally also oxygen.
As used herein, “staged combustion with low NOx burners” means combustion in a furnace wherein mixing with fuel of a portion of the combustion air required for complete combustion of the fuel is delayed to produce a flame with a relatively large fuel rich flame zone
As used herein, “globally staged combustion or staged combustion with over fire air” means combustion in a furnace wherein a portion of the combustion air (the “over fire air”) required for complete combustion of the fuel is fed to the furnace not through or immediately adjacent any burner but instead through one or more inlets situated between the burner(s) and the furnace flue means, and is fed without an associated feed of fuel.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a cross-sectional representation of one embodiment of apparatus for carrying out the present invention.
FIG. 2 is a cross-sectional representation of a burner useful for carrying out the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The invention will be described with reference to the Figures, although a description that refers to the Figures is not intended to limit the scope of that which is considered to be the present invention.
FIG. 1 shows combustion device 1 , which can be any apparatus wherein combustion is carried out in the interior 2 of the device. Preferred combustion devices include furnaces and boilers which are used to generate electric power by conventional means, not shown.
Each burner 3 in a sidewall or end wall of combustion device 1 feeds fuel, air and oxygen from sources thereof outside the combustion device 1 into the interior 2 of combustion device 1 . Suitable fuels include hydrocarbon liquids, such as fuel oil, and also include pulverulent hydrocarbon solids, a preferred example of which is pulverized coal or petroleum coke.
As seen in FIG. 1 and more closely in FIG. 2, burner 3 is preferably comprised of several concentrically arranged passages, although other constructions to the same effect can be used. The fuel is fed into combustion device 1 through annular passage 4 , disposed concentrically around lance 5 through which oxygen is fed as described herein. Preferably, the fuel is transported from a supply source 20 to one or more burners 3 and propelled through burner 3 into the interior 2 of combustion device 1 , by suitable pump means in the case of liquids such as fuel oil, and by blowers and impellers of conventional design in the case of hydrocarbon solids such as pulverized coal, which are conventionally fed into the combustion device with the aid of transport air or primary air. Liquid hydrocarbon fuels are preferably fed through one or more atomizing nozzles of conventional design, to feed the liquid fuel into the combustion chamber as discrete, dispersed droplets with atomizing air. An effective amount typically about 1.5 to 2.0 lb of primary air is used to transport 1 lb of coal, which corresponds to about 20% of the stoichiometric combustion air required for complete combustion of bituminous coal. For combustion of heavy oil about 0.5 to 1.0 lb of primary air is typically used to atomize 1 lb of oil.
Combustion air 22 is supplied by a forced draft (“FD”) fan to one or more windboxes 21 and fed to air passages of one or more burners 3 . Secondary combustion air 15 is fed through burner 3 into combustion device 1 , preferably through concentrically arranged annular passages 11 surrounding the annular space 4 through which the hydrocarbon fuel is fed. Preferably tertiary combustion air 16 is fed through burner 3 into combustion device 1 , preferably through concentrically arranged annular passages 12 surrounding the secondary air passage. Preferably combustion air is also fed through over fire air port 7 (seen in FIG. 1) into combustion device 1 . Preferably, the oxygen is fed into the interior 2 of the device apart from the secondary and tertiary combustion air. That is, the oxygen that is fed through burner 3 in accordance with this invention is preferably not commingled with the secondary and tertiary combustion air before or after it is fed into combustion device 1 , especially when no over fire air is used.
Preferred low NOx burners have primary (fuel), secondary and tertiary air passages for good aerodynamic adjustability. However, other low NOx burner designs using only primary and secondary air feeds can be used. Once the optimum settings with the three passages have been determined, the secondary air swirl vanes and passage can be designed to create about the same aerodynamic mixing characteristics as with the three-passage design. Alternatively, burners with an additional (quaternary) passage can be used (such as the RSFC™ burner described in U.S. Pat. No. 5,960,724).
Before a combustion device is retrofitted in accordance with the present invention to reduce the formation of NOx formed in the operation of the combustion device, lance 5 for feeding oxygen is not yet present. Combustion is carried out between the hydrocarbon fuel and the oxygen in the combustion air, resulting in formation of a flame 6 . The region 8 of the flame closest to the end of burner 3 , that is, where the hydrocarbon fuel emerges from the burner, is a fuel-rich zone. The area of the flame 6 around its periphery, is relatively lean, as secondary and tertiary combustion air has not been fully reacted with fuel. When a sufficient amount of air is fed from over fire air port 7 for global combustion staging, the entire lower zone of the furnace, or primary combustion zone (PCZ) 10 , below over fire air port 7 becomes fuel rich, except the areas near burners 3 where air is injected and not yet fully reacted with fuel.
Then, lance 5 is added. Alternatively, a burner that feeds fuel and combustion air is replaced with a burner that performs as shown in the Figures and described herein.
Preferably, air is also fed through over fire air port opening 7 into the interior of combustion device 1 , to make the primary combustion zone 10 more fuel rich and to provide additional oxygen helping to achieve complete combustion of the fuel in the burnout zone 9 . The oxygen in the combustion air fed through burner 3 , combined with the oxygen fed at opening 7 , are sufficient to enable complete combustion of the fuel, and typically contain 10 to 15 volume percent excess oxygen over the amount required for the complete combustion of the fuel.
Preferably, the secondary and tertiary combustion air are fed at the burner 3 so as to swirl about a longitudinal axis, thereby creating a recirculation zone near each burner and improving commingling of air and fuel. Swirl can be achieved by known techniques, such as providing deflectors, 13 and 14 , in the annular passages for secondary and tertiary air flow of the burner which direct the flow of the streams in the desired swirling direction. It is preferred to provide a high degree of swirl, preferably a swirl number, as defined in “Combustion Aerodynamics”, J. M. Beer and N. A. Chigier, Robert E. Krieger Publishing Company, Inc., 1983, of 0.6 to 2.0.
Preferably the total amount of air fed through burner 3 , i.e., the sum of primary, secondary and tertiary air, is between 60 and 95% of the stoichiometric air requirement for complete combustion. Most preferably the total amount of air fed through burner 3 is about 70 to 85% of the stoichiometric air requirement for complete combustion.
The velocity of each stream of combustion air is preferably 50 to 200 feet per second. The velocity of the oxygen injected through lance 5 is preferably within 50% to 200% of the velocity of the primary air.
Tests have suggested that a preferred approach is to expose at least some of the fuel particles or droplets to a high concentration of oxygen as opposed to uniformly enriching the overall combustion air. The simple approach of injecting oxygen into the windbox 21 of a low NOx burner such that the enriched air is fed to the entire burner, including the critical primary stage air, is not considered effective.
When oxygen is premixed or mixed rapidly into the coal transport stream using 20% of stoichiometric air and the overall combustion stoichiometric ratio is 1.15, the following average concentrations of oxygen in the transport air stream and in the overall combustion air are calculated.
% SR air
O 2 concentration
Avg. O 2 concentration
replaced
in transport air
in total combustion air
with O 2 (*)
(vol. %)
(vol. %)
0
21.0
21.0
5
24.9
21.7
10
28.5
22.5
15
31.7
23.4
20
34.7
24.3
25
37.4
25.4
(* e.g. 5 cf of air replaced with 1.05 cf of pure O 2 to give the same amount of O 2)
Due to the small amount of oxygen used, only modest increases in the oxygen concentration of air are achieved when mixed uniformly even when oxygen is mixed only with the transport air. A preferred method is to inject oxygen into the coal/air transport stream at the tip of the nozzle. In this case some of the coal particles are mixed with oxygen jets and locally create zones of coal high O 2 mixture. Such conditions may provide zones of rapid ignition sources and facilitate early ignition and devolatilization as compared to the case oxygen is premixed with the transport air stream.
Another preferred method is to inject oxygen from the inner or outer annular space adjacent to the coal stream. In this case the favorable oxygen rich combustion condition is provided at the boundary of the coal and oxygen streams.
When oxygen is injected separately at high velocity parallel to the fuel stream, as was the case for Farmayan, et al., (“NOx and Carbon Emission Control in Coal-Water Slurry Combustion”, Sixth International Symposium on Coal Slurry Combustion and Technology, Orlando, Fla., Jun. 25-27, 1984), the oxygen jet(s) may be diluted quickly with surrounding gases and its effectiveness may be retarded. Thus, the method of oxygen injection has to be carefully designed.
The present invention improves, that is, lessens, the formation of NOx in the combustion device by feeding oxygen into the entering hydrocarbon fuel stream as described herein. More specifically, the oxygen (by which is meant a gaseous stream comprising at least 50 vol. % O 2 , preferably at least 80 vol. % O 2 , most preferably at least 90 vol. % O 2 ), is fed directly into the hydrocarbon fuel as it emerges from the burner and enters the interior 2 of combustion device 1 . Thus, at least some of the particles of solid fuel, or the droplets of liquid fuel, as the case may be, enter the combustion device and the fuel-rich portion of flame 6 , in a gaseous atmosphere containing a high concentration of oxygen.
When over fire air is used for global combustion staging, preferably with air burners equipped with four separate air passages, oxygen may be premixed with the primary or secondary air or both, using suitable spargers within the gas passages in burner 3 .
The oxygen is preferably fed through a lance 5 or similar feed line that can be open at the end that opens into combustion device 1 , or that is closed at the end and has numerous openings in its periphery adjacent that closed end, such that oxygen flows out through those openings directly into the hydrocarbon fuel entering the combustion device from the burner.
The amount of oxygen fed in this manner should be sufficient to establish a stoichiometric ratio in the fuel-rich zone of flame 6 which is less than about 0.85. The amount of oxygen fed through line 5 should be less than 25% of the stoichiometric amount required for the complete combustion of the fuel. More preferably, the amount corresponds to less than 15% of the stoichiometric amount required for complete combustion of the fuel.
At the same time, the amount of secondary and tertiary combustion air fed through burner 3 into combustion device 1 , need to be decreased by an amount corresponding to the amount of oxygen fed via lance 5 . More specifically, the amount of secondary and tertiary combustion, and quaternary, if used, air fed through burner 3 should be reduced by an amount containing within 10% of the amount of oxygen fed via line 5 into the fuel.
NOx emission strongly depends on the local stoichiometric conditions. As injection of oxygen makes the local stoichiometric condition leaner, one has to consider the change in the local stoichiometric conditions after the oxygen injection. For example, injection of oxygen, equivalent to 10% of the stoichiometric air, into a locally rich zone at a stoichiometric ratio of 0.4 (SR=0.4), without changing the combustion air, would alter the local stoichiometric conditions to SR=0.5 and would be expected to decrease NOx emissions substantially. Such an effect is much greater than that from “replacing 10% air with oxygen” while keeping the local stoichiometric condition constant at SR=0.4. If the same amount of oxygen is injected into the flame zone, without changing the combustion air, where the local stoichiometric condition is SR=0.95, NOx emission is expected to increase sharply if the local stoichiometric condition is increased to SR=1.05.
Thus, it is generally preferred to inject oxygen into the richest area of the flame.
Injection or mixing of oxygen into the tertiary air and quaternary, if used, should be avoided in an aerodynamically staged burner without OFA. In theory the optimization of local stoichiometric condition can be done with any oxidants including air. However, oxygen is more effective because only a small volume is required and local stoichiometric condition can be changed without a large impact on the overall aerodynamic mixing conditions of the flame.
Another important requirement is that oxygen enrichment has to be done in such a way as to preserve or enhance the physical size of the fuel rich zone (the “N 2 forming zone”) of an aerodynamically staged flame. The method of oxygen injection and the consequent reduction of air flows in certain air passages of a burner would influence the aerodynamic staging conditions of the burner, and hence the physical size and the local stoichiometric conditions. If the size of the fuel rich zone is reduced and the average gas residence time in the fuel rich zone is reduced as a result of oxygen injection, such a change could cause NOx increases. For example, high velocity injection of oxygen through an axial lance such as the one shown in FIG. 3 a would effectively increase the axial momentum of the surrounding coal/air stream, which in turn may enhance the mixing with secondary and tertiary air. As a result the size of the fuel rich NOx reduction zone of the flame may be reduced and NOx may increase. On the other hand when the oxygen flow is injected radially from an axially located oxygen lance such as the one shown in FIG. 3 b near the tip of the burner, it may effectively increase the recirculation zone near the burner and hence increase the size of the fuel rich zone and further promote NOx reduction by oxygen enrichment. Complex impacts of oxygen injection on the burner aerodynamic conditions have to be evaluated carefully for a specific burner to achieve NOx reduction.
Without intending to be bound by any particular explanation of the unexpected performance of this invention, the performance of the combustion device operated in accordance with this invention is consistent with a mechanism in which the injected oxygen causes an increase in the temperature of that portion of the flame closest to the burner, which in turn causes relatively volatile components present in the hydrocarbon fuel to enter the gas phase from the fuel and undergo partial reaction with the ambient oxygen, thereby creating a relatively reducing atmosphere that enables nitrogen-containing species released from the combusting fuel to be converted to molecular nitrogen, that is, N 2 , rather that converted to NOx compounds.
Typically, the temperature of the fuel-rich zone into which the fuel and the oxygen enter is on the order of 2500° F. or higher. Feeding the oxygen in this manner can cause the base of flame 6 to draw nearer to the opening of burner 3 , or even to become attached to burner 3 . However, feeding the oxygen in the manner described herein into the hydrocarbon fuel as it emerges from the burner proceeds in the same manner, even if the flame becomes attached to the burner. In steady state operation, for instance after a combustion device has been retrofitted in accordance with the teachings herein, operation of the combustion device continues on the basis that less than 25%, preferably less than 15%, of the stoichiometric amount of oxygen required for the complete combustion of the fuel is fed into the fuel, while combustion air is fed through the burnerin an amount less than otherwise would be the case, so that the total amount of oxygen fed into the device is at least the stoichiometric amount needed for complete combustion of the fuel.
Although the invention has been described with reference to FIGS. 1, 2 and 3 for a wall fired boiler with multiple burners, it is also applicable to other type of boilers, including, but not limited to, tangentially fired boilers and cyclone fired boilers.
In the present invention a small amount of oxygen is used, as described above, in conjunction with switching at least some, or all, of the fuel to a lower rank (lower energy content per unit mass) fuel to reduce pollution emissions, in a manner which eliminates the needs for costly boiler modifications. It is well known that emissions of NOx, SOx and other emissions from coal fired utility boilers are strongly dependent on the type of coal fired. Thus, switching to a less polluting coal, e.g., from an Eastern bituminous coal to a Western sub-bituminous coal, preferably in combination with aforementioned methods of oxygen injection, provides synergistic reduction of emissions from coal fired boilers and furnaces. Western sub-bituminous coals and lignites typically have much lower sulfur contents and lower nitrogen contents than Eastern bituminous coals. Furthermore, sub-bituminous coals and lignites are more reactive than bituminous coals and produce lower unburned carbon (UBC) in ash. Emissions of SOx and NOx and UBC in ash can be substantially reduced by switching to less polluting coals.
A preferred embodiment is to switch some or all of the feed from bituminous coal to sub-bituminous coal or lignite. When a portion of the combustion air is replaced by oxygen, the flame temperature is increased and the flue gas volume is reduced because the reduced flow rate of air reduces the amount of nitrogen flowing through the combustion chamber. The oxygen addition effectively offsets the reduction in flame temperature and increased flue gas volume caused by switching the feed coal to a lower rank coal and restores the heat transfer conditions in the boiler. Furthermore, oxygen addition can be conducted under staged combustion conditions so as to enhance NOx reduction kinetics in the fuel rich combustion stage, as described herein.
The invention is described in detail using the following example of coal switching simulated by a computer model of boiler combustion and heat transfer.
EXAMPLE 1
A 220 MW, based on thermal input, tangentially fired boiler is fired with a bituminous coal from Pittsburgh #8 (Pit #8) coal seam as the baseline (Case 1). The feed coal is switched to a lower rank sub-bituminous coal from Powder River Basin (PRB) in Wyoming. The coal properties are summarized in Table 1.
TABLE 1
Pit #8
PRB
Proximate Analysis (%,
wet)
moisture
5.2
28.7
V.M
38.1
32.0
F.C
48.1
33.7
Ash
8.6
5.6
Total
100
100
Ultimate Anaysis (%, dry)
C
74.0
68.30
H
5.1
4.91
N
1.6
1.00
O
7.9
17.25
S
2.3
0.70
ASH
9.1
7.84
Total
100
100
HHV (btu/lb, wet)
12540
8650
In Table 2, operating characteristics of the boiler are summarized for the following six cases.
Case 1. Baseline operation with Bituminous coal (Pit #8) with air
Case 2. Operation with Sub-bituminous coal (PRB) with air at same fuel input
Case 3. Operation with Sub-bituminous coal (PRB) with air at increased fuel input
Case 4 Operation with Sub-bituminous coal (PRB) with oxygen enriched air at same fuel input
Case 5 Operation with Sub-bituminous coal (PRB) with oxygen enriched air at increased fuel input
Case 6 Operation with Sub-bituminous coal (PRB) with oxygen enriched air at increased fuel input, in-line duct burner turned off
In the baseline operation, Case 1, 60,372 lb/hr of bituminous coal was fired with 9,144,000 SCFH of combustion air. The total heat input corresponds to 756.6 MMBtu/hr based on higher heating value (HHV) and the overall stoichiometric ratio was set at 1.18 to the provide 3% excess O2 in the flue gas. 50% of the moisture in the coal was vaporized in the pulverizer and the transport line to the burner. About 20% of stoichiometric combustion air was used to transport the pulverized coal as primary air and the temperature was 153 F. The balance of the air was used as secondary air for combustion and preheated to 522° F. in the air heater. No over fire air ports were used to stage the combustion. In the radiant furnace section, 342.5 MMBtu/hr of heat was absorbed to the boiler waterwalls, generating steam. Furnace exist gas temperature (FEGT) was 2144 F. 71.6 and 85.2 MMbtu/hr of heat was transferred to the finishing superheater section and the reheater section respectively and the flue gas temperature was reduced to 1520° F. Then, flue gas passed through the primary superheater/economizer section and the air heater and was exhausted from a stack. The boiler efficiency was 83.5% based on HHV of the fuel input.
TABLE 2
Boiler Operations
Case 1
Case 2
Case 3
Case 4
Case 5
Case 6
Case Definition:
Coal type
Pit. #8
PRB
PRB
PRB
PRB
PRB
% of moisture vaporized in mill
50
50
50
50
50
6
In-duct burner (Y/N)
N
Y
Y
Y
Y
N
O2% in oxidant
20.67
20.67
20.67
22.26
22.02
22.02
Furnace Operation:
Coal flow (lb/hr)
60372
87522
92160
87522
90147
91367
Firing rate (MMBtu/hr, HHV)
756.6
756.6
796.7
756.6
779.3
789.8
In-duct burner(MMBtu/hr,HHV)
0
13.2
13.2
13.2
13.2
0
Oxidant flow (SCFH)
9144000
9054000
9532800
8312400
8668800
8643600
Flue Gas Temperatures (F.):
Furnace exit (FEGT)
2144
2092
2122
2102
2122
2115
Leaving reheater
1520
1506
1536
1491
1514
1511
Leaving economizer
850
851
895
821
854
850
Heat Absorptions (MMBtu/hr):
Waterwalls
342.5
320.3
329.4
341.9
342.9
342.9
Finishing Superheater
71.6
70.0
73.1
69.2
72.2
71.7
Reheater
85.2
84.0
89.9
81.7
85.0
84.4
Primary Superheater + Economizer
132.2
136.3
140.6
130.0
133.3
133.1
Total
631.5
610.6
633.0
622.8
633.4
632.1
Boiler Efficiency:
Gross (% of HHV coal input)
83.5
80.7
79.5
82.3
81.3
80.0
Net (% of HHV coal + NG input)
83.5
79.3
78.2
80.9
79.9
80.0
In Cases 2 to 6, coal was switched to the sub-bituminous PRB coal. In Case 2, 87,522 lb/hr of sub-bituminous coal was fired with 9,054,000 SCFH of combustion air to maintain the same total heat input of 756.6 MMBtu/hr as the baseline. The overall stoichiometric ratio was adjusted at 1.19 to provide 3% excess O2 in the flue gas. About 20% of stoichiometric combustion air was used to transport the pulverized coal as primary air and the temperature was maintained at 153 F. In order to vaporize about 50% of the moisture contained in the as received coal in the coal pulverizer and the transport lines, in-duct burners were used and 13.2 MMBtu/hr of natural gas was consumed. The balance of the air was used as secondary air for combustion and preheated to 522° F. in the air heater. No other changes were made to the boiler operation. In the radiant furnace section, 320.3 MMBtu/hr of heat was absorbed to the boiler waterwalls, generating steam. Furnace exist gas temperature (FEGT) was reduced to 2,092° F. and 70.0 and 84.0 MMBtu/hr of heat was transferred to the finishing superheater section and the reheater section respectively and the flue gas temperature was reduced to 1506° F. Although the same heat input was maintained, Heat aborption by water walls, superheater and reheater sections were reduced by 6.5%, 2.2%, and 1.4% respectively, caused by the reduced flame temperature. On the other hand heat fluxes to the primary superheater/economizer section increased due to the greater flue gas volume and higher flue gas velocity. In this case the total heat absorption and hence the steam production was reduced by 3.3% as compared with the baseline case fired with the bituminous coal. The flue gas volume was increased by 5.04% with a corresponding increase in the flue gas velocity. The boiler efficiency was reduced by 2.8% to 80.7% based on HHV of the coal input. The net boiler efficiency including the HHV of the natural gas used to dry the coal was 79.3%, which represents 4.2% reduction as compared with the baseline case with bituminous coal.
In order to overcome the shortfall in steam output in Case 2, the fuel input was increased to 796.7 MMBtu/hr in Case 3, while maintaining other combustion parameters such as stoichiometric ratio and air preheat temperature. The total boiler heat absorption was 633.0 MMBtu/hr, which closely matched the baseline condition. Furnace exist gas temperature (FEGT) was increased to 2122° F. and 73.1 and 89.9 MMBtu/hr of heat was transferred to the super heater section and the reheater section respectively and the flue gas temperature was increased to 1536° F. Although the same total heat absorption was achieved as compared to the baseline Case 1, substantial increases in heat absorption to superheater and reheater sections resulted. Although the steam temperature increase caused by the higher superheater and reheater heat absorption were controlled by feed water injection in the attemperator in this boiler, the high temperature limitation at the superheater may cause a capacity limitation in some other boilers. A significant efficiency loss was observed due to higher gas temperature after the economizer. The boiler efficiency was reduced by 4.0% to 79.5% based on HHV of the coal input. The net boiler efficiency including the HHV of the natural gas used to dry the coal was 78.2%, which represents 5.3% reduction as compared with the baseline case with bituminous coal.
In Case 4, oxygen enrichment of air was used to increase the the heat absorption at waterwalls while maintaining the same fuel input and other combustion parameters in Case 1 except the fuel type. By enriching the oxygen concentration of the combustion air to 22.26%, 341.9 MMBtu/hr of heat was absorbed by the boiler waterwalls, which closely matched the baseline condition. Furnace exist gas temperature (FEGT) was 2102° F. and 69.2 and 81.7 MMBtu/hr of heat was transferred to the superheater section and the reheater section respectively and the flue gas temperature was reduced to 1491° F. A significant efficiency gain, compared to Case 2, was observed due to lower gas temperature after the economizer. Although the same total heat absorption was achieved in the waterwalls as compared to the baseline Case 1, heat absorptions to the finishing superheater, the reheater and the primary superheater/economizer sections were substantially decreased due to the smaller flue gas volume. The boiler efficiency was decreased by 1.2% to 82.3% based on HHV of the coal input. The net boiler efficiency including the HHV of the natural gas used to dry the coal was 80.9%, which represents 2.6% reduction as compared with the baseline case with bituminous coal.
In Case 5, fuel input was increase in combination with oxygen enrichment of air to match the heat transfer conditions of baseline Case 1. By increasing the fuel input to 779.3 MMBtu/hr and enriching the oxygen concentration of the combustion air to 22.02%, all heat fluxes are closely matched to those of Case 1. This example shows that it is possible to restore the original heat transfer conditions of bituminous coal and air combustion by switching fuel to sub-bituminous coal and enriching air with oxygen.
In Case 6, the natural gas fired in-duct burners were turned off and fuel input was increased in combination with oxygen enrichment of air to match the heat transfer conditions of baseline Case 1. By increasing the fuel input to 789.8 MMBtu/hr and enriching the oxygen concentration of the combustion air to 22.02%, individual and total heat fluxes to the boiler heat transfer surfaces are closely matched to those of Case 1 without requiring the in-duct burners. There is a significant economic benefits in eliminating the needs for in-duct burner fired by natural gas which is a more expensive fuel than coal.
Although the foregoing examples illustrate the invention based on switching the type of coal from bituminous to sub-bituminous coal, the invention is applicable to general fuel switching from a fuel or mixture of fuels with a given adiabatic flame temperature to another fuel or mixture of fuels containing at least a fuel which is different from the original fuels which possesses a lower adiabatic flame temperature and a greater flue gas volume For example, co-firing of biomass such as sludge, animal wastes in a coal fired boiler by partially replacing coal with biomass would be considered as part of the present invention In general, oxygen enrichment increases the flame temperature and the available heat at high temperatures. Since the boiler furnace exit gas temperature is typically in a range between 2000 F. and 2400 F., the available heat of combustion for a fuel with air under stoichiometric condition would be the best parameter to compare different fuels and the amount of oxygen required, although higher flame temperature always correlates with higher available heat. The heat flux to boiler waterwalls is closely coupled with the available heat above 2000 F., although the heat transfer properties such as flame and gas emissivities have secondary impacts on heat absorption by waterwalls. | A furnace that combusts fuel, such as coal, of a given minimum energy content to obtain a stated minimum amount of energy per unit of time is enabled to combust fuel having a lower energy content, while still obtaining at least the stated minimum energy generation rate, by replacing a small amount of the combustion air fed to the furnace by oxygen. The replacement of oxygen for combustion air also provides reduction in the generation of NOx. | 5 |
BACKGROUND
[0001] A. Technical Field
[0002] The present invention relates to a method for computer signal processing, and more particularly, to a method for providing data communication between a firmware controller and a host processor or Basic Input/Output System (BIOS) on a Peripheral Component Interconnect (PCI) Bus.
[0003] B. Background of the Invention
[0004] A host processor communicates with various peripheral devices to control the operation of these devices within the processor's system. One such example is a processor communicating with a memory device, such as a redundant array of independent disks (“RAID”), via a PCI Bus. Typically, this communication between the host processor and memory device occurs in fixed frame length command blocks on the PCI Bus. For example, communication between a firmware controller and a host processor may occur in fixed eight frame length command blocks. The command blocks communicate instructions from the host processor to an agent device's controller. This controller may operate within the device firmware and operate as an input/output processor for the device.
[0005] As the number of peripherals increases and/or the size of commands from the host processor increases, the PCI Bus may become overburdened. This stress on the PCI Bus may reduce the overall performance of the host system as well as peripherals communicating on the PCI Bus. One potential cause for stressing a PCI Bus is communication between a host processor and RAID firmware.
[0006] Communication commands may operate over various different mechanisms. For example, these mechanisms may include message registers, doorbell registers, circular queues, and index registers that allow a host processor or external PCI agent and the firmware controller to communicate through message passing and interrupt generation.
[0007] One implementation of an interface between RAID firmware and a host processor is a serialized mailbox, where the driver waits for a “BusyByte” to free before it sends any command to the firmware. The mailbox is basically a fixed length array. Usually, the mailbox is adequate for single-processor systems. However, when a multi-processor system is used, the mailbox may become inadequate and stress the PCI Bus as well as introduce various timing problems between various processors within the system. The message registers generally have four 32-bit registers. Any message, which is a 32-bit data value, is passed in one of the four 32-bit registers. Each written word generates an interrupt, whose flag is cleared before writing another word, thereby passing only single words. This protocol makes the message registers unsuitable for use as head and tail pointer registers.
[0008] Circular queues support a message-passing scheme that may use four circular queues. Once again, the message passed in a circular qeue is in a fixed length format. A result of the circular queue is that the host processor can only read or write one word at a time. Additionally, the host processor cannot see the head and tail pointers so it is unable to determine how much space remains. Further, the circular queue is typically used for passing identifiers (addresses or indices) of message buffers with the message bodies being stored elsewhere.
[0009] The length of commands, and corresponding required number of frames, changes relative to which commands are communicated. If this communication is between the host processor and a RAID memory device, these frames are fixed in length which may result in empty frames on the PCI bus if a command does not require the total number of frames in the fixed length command block. These wasted empty frames may congest the PCI bus potentially reducing the performance of peripherals attached to the bus.
[0010] Accordingly it is desirable to provide a device and method that addresses the above-described problems.
SUMMARY OF THE INVENTION
[0011] The present invention discloses a device and method for providing command blocks of variable length frames for communicating between a host processor and a peripheral device processor or firmware controller. According to one embodiment of the invention, a command block is used that integrates data, in a frame within the command block, to provide the number of frames within the particular command block. This variable length command block may be transmitted on a PCI bus to communicate between a host processor and a peripheral IO processor or firmware controller. According to this embodiment, the IO processor or firmware controller identifies the length of the command block by analyzing frame length data within a first frame of the command block. This frame length data, for example, may be provided in a three bit word found in the first frame. This three bit word may be found in numerous positions within the first frame including the least significant bits.
[0012] In yet another embodiment, an IO processor or firmware controller may receive commands from multiple processors or hosts using a hardware queue. An entry in a host-defined completion queue may be placed and an interrupt signaled. A command block, having a variable frame length, is constructed with message frames and all the message frames are aligned for a particular command block contiguous in memory. Addresses to the message frames are assigned which allows the firmware to read the address of a particular frame from a register. Thereafter, the frame length data is analyzed and the number of message frames in a command block is identified. The identified number of frames is read and a command in the command block is determined.
[0013] One skilled in the art will recognize that data describing the length of a command block may be integrated within the command block and provided to a receiving device using multiple embodiments of the present invention.
BREIF DESCRIPTION OF THE DRAWINGS
[0014] Reference will be made to embodiments of the invention, examples of which may be illustrated in the accompanying figures. These figures are intended to be illustrative, not limiting. Although the invention is generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the invention to these particular embodiments.
[0015] FIG. 1 is diagrammatic view of an interface between a firmware controller and a system processor over a PCI Bus according to one embodiment of the invention.
[0016] FIG. 2 is flowchart showing a method for determining a command in the command block according to one embodiment of the invention.
[0017] FIG. 3 is an illustration of a host based reply queue containing a driver/agent modify producer pointer and a firmware modify consumer pointer according to one embodiment of the present invention.
[0018] FIG. 4A is an illustration of format of firmware state register according to one embodiment of the present invention.
[0019] FIG. 4B is an illustration of table listing the pre-defined firmware states and their description according to one embodiment of the invention.
[0020] FIG. 5A is an illustration of table for maximum concurrent commands and SG Entries according to one embodiment of the invention.
[0021] FIG. 5B is an illustration of format of firmware command reset register according to one embodiment of the invention.
[0022] FIG. 5C is an illustration of table listing the operations performed on firmware to reset to original state according to one embodiment of the invention.
[0023] FIG. 6A illustrates a command block having 8 frames of which only 3 frames are used to communicate a command.
[0024] FIG. 6B illustrates a command block, according to one embodiment of the invention, in which command block length data is inserted into the first frame of the command block.
[0025] FIG. 6C illustrates a data block, according to one embodiment of the invention, in which multiple commands are provided.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] An apparatus and method for providing variable length command interface between a host processor and peripheral IO processor or firmware controller is described. In one embodiment of the present invention, a variable length command block includes data that provides the number of total frames within the particular command block. Thus, the actual length of command blocks that are used to communicate between a host processor and a peripheral may vary depending on the size of the command and are not fixed to a predefined number of frames.
[0027] In the following description, for purpose of explanation, specific details are set forth in order to provide an understanding of the invention. It will be apparent, however, to one skilled in the art that the invention may be practiced without these details. One skilled in the art will recognize that embodiments of the present invention, some of which are described below, may be incorporated into a number of different devices including personal computers, storage devices and network servers. The embodiments of the present invention may also be present in software, hardware or firmware. Structures and devices shown below in block diagram are illustrative of exemplary embodiments of the invention and are meant to avoid obscuring the invention.
[0028] Reference in the specification to “one embodiment” or “an embodiment” means that a particular feature, structure, characteristic, or function described in connection with the embodiment is included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
[0000] A. Overview
[0029] The present invention describes a device and method for communicating data between a host processor and an input/output (“IO”) processor or firmware controller for a peripheral. In one embodiment of the invention, a host processor communicates with a peripheral device, such as an IO processor or firmware controller, using a variable length command block that is transmitted on a PCI Bus. The number of frames within the command block may vary depending on the length of a command or data sent between the host processor and peripheral device.
[0030] FIG. 1 is a diagrammatic view of an interface between firmware 103 associated with a peripheral memory device, such as a RAID, and a host or system processor 100 . The system processor 100 is connected to the controller 102 of the memory device firmware 103 through PCI Bus 101 .
[0031] According to one embodiment of the invention, communication between the processor 100 and controller 102 occurs in a variable length command block that is transmitted on the PCI Bus 101 . The controller 102 is able to identify and read the command block because data describing the number of frames within the block may be included within a particular frame. For example, a three bit word may be included in the first frame that identifies a command block length between one frame and eight frames.
[0032] FIG. 2 is a general flowchart showing a method for determining a command in a command block according to one embodiment of the invention. The command block is constructed of at least one data frame but may also include multiple frames. At the receiving side of a command communication, a first frame of the command block is identified 205 . This first frame may be identified using a number of different methods including through its relative position within a signal or through an identifier integrated within the first frame itself.
[0033] After the first frame is identified, a processor or controller, such as the firmware controller 102 discussed above, analyzes 210 the first frame for data describing the number of frames within the command block. For example, as mentioned above, a three bit word may be included within the first frame that discloses the number of frames within the particular command block. This three bit word may be positioned anywhere within the first frame including the least significant three bits. One skilled in the art will recognize that this information disclosing the number of frames within a particular command block may be provided the firmware controller 102 using a number of different mechanisms.
[0034] Once the number of frames in the command block is identified, the corresponding number of frames, comprising a complete command block, is read 215 . Thus, if the three bit word discloses a five frame command block, the firmware controller 102 reads the first frame and next four sequential frames in order to complete the command block. Thereafter, the command in the command block is determined 220 and the controller or processor acts accordingly.
[0000] B. Variable Length Command Block for Dual Addressing Scheme
[0035] Communication between the host processor 100 and controller 102 may include the use of one or more registers. These registers may include message registers, doorbell registers, and interrupt registers. The processor 100 may put a command in an inbound post queue (e.g., circular qeue) after preparing a message frame in the host memory. If a physical address allotted to this message frame is greater than a particular value (e.g. 32 GB) then two address cycles are needed to send this frame to firmware 103 . The use of two address cycles for a single command is called as Dual Addressing Scheme (“DAS”).
[0036] A switch between DAS and single address scheme may be performed at runtime provided there is no pending command in firmware 103 . According to one embodiment of the invention, once DAS is enabled, a driver writes a particular bit in an inbound queue port for switching back to a single address scheme. According to this embodiment, a single address scheme is set as a default when the firmware 103 boots up. If the physical address of the message frame is less than a particular value (e.g., 32 GB), then it may be right shifted a certain number of bits, such as 3 bits for making the driver/agent specify the number of frames to be read. If the physical address of the message frame is greater than a particular value (e.g., 32 GB), then the number of frames to be read is specified in a lower address.
[0037] FIG. 3 is an illustration of a host based reply queue 302 comprising a driver/agent modify producer pointer 301 and a firmware modify consumer pointer 300 . According to one embodiment of the invention, firmware 103 completes processing the command, and places the content of a message frame request in the reply queue 302 . The firmware 103 also places addresses of all completed IO requests in this queue 302 . The reply queue 302 my be an array of 4-bytes or 8-bytes pointers depending on a number of different factor included in a firmware initialize frame. The size of the reply queue 302 is generally kept more than the maximum number of command that can be issued to the adapter at any one time. According to one embodiment of the invention, the size of the reply queue 302 is set by the firmware 103 and is limited to 1024 . Accordingly, in this particular embodiment, a maximum of 1024 commands may be issued at any one time.
[0038] According to one embodiment of the invention, a command may be posted in the reply queue 302 by the firmware 103 along with incrementing the producer pointer 301 and issuing an interrupt. After receiving the interrupt, the driver may check an outbound interrupt status register for the status of its second bit. If the second bit is found to be set, the firmware controller 102 raises the interrupt. Firmware 103 may clear the interrupt by writing back the same value. The driver now checks the difference between the producer pointer 301 and consumer pointer 300 . If there is a difference, the driver may find more commands in the reply queue 302 to be completed. The driver picks the remaining commands, completes them and sends to the host processor 100 , along with updating the consumer pointer 300 . If the producer pointer 301 and consumer pointer 300 are same, it indicates that there is no command pending for completion in the reply queue 302 . The interrupt may be generated by the firmware 103 depending on the number of computed commands.
[0039] FIG. 4A is an illustration of a format for a firmware state register according to one embodiment of the invention. As described above, the status of the firmware 103 may be posted to an outbound message register and a device driver checks this register, before sending any commands. A driver may reset the modes in firmware 103 by writing to an inbound message register. According to one embodiment of the invention, the firmware state register is a 32-bit register containing the firmware state in its four Most Significant Bits (MSB) and state specific data in its remaining 28 bits.
[0040] FIG. 4B is an exemplary table listing pre-defined firmware states and their description according to one embodiment of the invention. As shown in this table, if the firmware state is in MFI_STATE_READY ( 11 ) or MFI_STATE_OPERATIONAL ( 12 ) the driver may send commands. In one particular embodiment of the invention, the firmware state is determined by reading the above-described four MSB of an outbound message register. If the state is less than MFI_STATE_READY ( 11 ), the driver waits until the firmware state becomes MFI_STATE_READY ( 11 ) before sending any commands.
[0041] If firmware state is MFI_STATE_FAULT ( 15 ), then it indicates that an internal firmware/hardware fault has occurred and the driver should not load any further commands. Further, whenever any fault occurs, the driver posts an operating system event indicating the fault condition of the controller 102 . If firmware state is MFI_STATE_READY ( 11 ) or MFI_STATE_OPERATIONAL ( 12 ), then firmware 103 posts the maximum possible number of outstanding commands, and the maximum possible number of scatter/gather elements (“SGE”) for any one command in the MFI_STATE register.
[0042] FIG. 5A is an illustration of table, according to one embodiment of the invention, listing the maximum concurrent commands and SG Entries as explained in relation to FIG. 4B . According to one embodiment of the invention, an “M64” field 510 indicates that a 64-bit mode is currently enabled by setting the bit within the field as 1 or disabled by setting the “M64” field as 0. Once enabled, all incoming firmware addresses (FAs) are issued as 64-bit frame pointer, and all contexts are returned as 64-bits, else, all FAs are issued as 32-bit and contexts are returned as 32-bits. During firmware initialization, a driver may clear all pending commands and set a new state using an inbound message register. The lower two bytes 512 may contain the maximum concurrent commands supported. Bits 16 - 23 513 indicate the maximum SGE supported and the four MSB contain the Firmware state as explained in relation to FIG. 4A .
[0043] FIG. 5B is an illustration of a format for a firmware command reset register according to one embodiment of the invention. According to this embodiment, the firmware 103 may reset to an original state whenever it receives Abort 515 , Ready 520 or MegaRAID Firmware Initialize (“MFI”) Mode 525 commands. In one embodiment, the firmware command reset register contains the reset states in its lower most byte. All other bytes of this register may be reserved for other applications.
[0044] FIG. 5C is an illustration of table listing the operations performed on firmware 103 to reset to original state according to one embodiment of the invention. In this embodiment, the state of the Abort operation is set as 0 and Ready Mode is set as 1, in which the firmware 103 transits from OPERATIONAL state ( 12 ) to Ready State ( 11 ) and the queue information is discarded. The MFI mode may be set as 2, the low MFA posted in 64-bit mode is discarded. All states from 3 - 7 may be reserved for future use.
[0045] a) Variable Length Command Block Structure
[0046] One skilled in the art will recognize that the above-described dual addressing scheme may potentially overburden a PCI Bus with commands between the host processor 100 and firmware 102 . FIG. 6A illustrates a typical command block structure that may be used in such a DAS. This command block structure includes a fixed number of frames, within the command block, in which command data may be communicated. This particular structure may require unused frames to be communicated on the PCI Bus 101 resulting in wasted bandwidth on the Bus 101 .
[0047] FIG. 6B illustrates a.command block, according to one embodiment of the invention, having frame number data integrated in a first frame. In this particular embodiment, the first frame of the command block includes a three bit word that discloses the number of frames within the command block. In this particular example, the three bit word 610 “ 010 ” is inserted at the end of the first frame and indicates that the command block has three total frames (or two frames following the first frame). Accordingly, communication of this particular command block between the processor 100 and firmware 102 may occur in a three frame command block as opposed to the eight fixed frame command block in FIG. 6A . Thus, frames four through 8 may be discarded in this instance and not transmitted onto the PCI Bus 101 .
[0048] FIG. 6C illustrates a command block, according to one embodiment of the invention, in which multiple commands are integrated into a particular number of frames, such as 8 frames as illustrated. As described above, the insertion of frame length data into a command block may allow the size of a command block to be reduced. This ability to vary the length of command blocks relative to particular commands allows for data commands to be sequenced together without any empty or filler frames. Thus, as shown in this figure, a first command block having three frames is provided within the command sequence. This first command block provides the number of frames in the command block by inserting the above-described three bit word in the first frame. In this particular instance, a “ 010 ” word 620 is inserted into the end of the first frame indicating that the command block is a three frame block.
[0049] Immediately following the first command block, a second command block having five frames is provided. The second command block provides the number of frames in the command block by inserting a “ 100 ” word 630 into the end of the first frame. This three-bit word identifies the second command block as a five frame block.
[0050] This variable length command block structure allows for a more optimized use of PCI Bus bandwidth because it reduces the number of empty or filler frames that are communicated between the host processor and a peripheral, such as the memory firmware 103 . Furthermore, this variable length command block structure allows for various types of command to be communicated. These commands may include an initialize frame command, a read/write frame command, a direct command descriptor block frame command, a direct command frame command and an abort frame command.
[0051] According to one embodiment of the invention, a command requiring more than eight frames may also be supported. In this particular instance, if a three bit word identifies a command block length of eight frames (i.e., “ 111 ”), then the command block is checked to identify the actual number of frames containing the particular command.
[0052] The above description is included to illustrate the operation of the preferred embodiments and is not meant to limit the scope of the invention. From the above description, many variations will be apparent to one skilled in the art that would yet be encompassed in the spirit and scope of the invention. Accordingly, the scope of the invention is to be limited only by the following claims. | The invention relates to a method for computer signal processing data and command transfer over an interface and more particularly to a communication between peripheral firmware and a host processor or Basic Input/Output System (BIOS) on a Peripheral Component Interconnect (PCI) bus. In one embodiment, a device and method for reducing the load on the PCI Bus is described. In yet another embodiment, a device and method is described for constructing a variable length command block comprising message frames and aligning all message frames for a particular command block that are contiguous in memory. | 6 |
BACKGROUND
This invention relates to a method and apparatus for incorporating feature substances into a paper web and to a paper machine having such an apparatus.
It is known to incorporate feature substances into documents of value made of paper, in particular bank notes, as security features, for example luminescent particles fluorescing in a characteristic color under suitable excitation radiation such as UV light. Feature substances refer here in general to substances with certain physical properties whose presence and/or arrangement can be checked due to these properties by measurement technology, for example by suitable sensors. Such features are usually placed at defined positions in the paper as characters, patterns or lines.
It is known for example from DE-A-197 54 776 to spray colored patterns with sharp contours onto finished paper in linear form so as to produce graphic security features recognizable to the naked eye. Said security features are deposited on the surface of the paper and are therefore not only visible but also tangible. In particular when using luminescent substances whose color effects are only recognizable under certain excitation conditions, however, it is desirable that their place of incorporation is inconspicuous to the casual viewer and in particular to possible forgers.
UK-A-696 673 proposes for example injecting coloring pigments in a suspension liquid immiscible with water into the center of the sheet from a jet or nozzle during sheet formation to produce dotted lines or continuous pipes, for example of material fluorescent in UV light. However, since the fluorescent suspension spreads at least partially and uncontrollably in the not yet fully dipped paper material, the contours of such lines are blurred and the pigment concentration is uneven across the line width.
DE-C-497 037, in contrast, proposes applying, for example spraying, a suspension with fluorescent substances onto the fully dipped, still moist paper web in such a way that the paper structure itself does not undergo any appreciable change. However, spraying also leads to patterns whose contour acuity is difficult to control and whose feature concentration is inconstant across the surface of the pattern.
These disadvantages are partly overcome by the method described in UK-C 643 430 wherein an endless metal band with stencil-like gaps is moved together with the arising paper web and the colored feature substances are sprayed on diffusely so as to penetrate into the paper web in the area of the stencil-like gaps. However, this also fails to obtain a sufficiently homogeneous distribution of feature substances, as EP-A0 659 935 criticizes.
EP-A-0 659 935 instead proposes dispersing feature substances not in suspension but in gas, so that agglomerates of feature particles readily break down and are present in the gas in a defined, homogeneous concentration, to then be sprayed onto the still wet paper web by a nozzle. This is said to achieve a homogeneous distribution in paper at the same time as relatively sharp contours even at low feature concentrations.
The disadvantage of this aerosol application of the particles is that only few feature substances are suitable for application in aerosol form since the pipes and nozzles are easily clogged. This applies in particular to fine-grained feature substances which tend to agglomerate. Furthermore, test results have shown relatively high fluctuations in concentration so that a high feature concentration is necessary for obtaining reliably measurable features.
SUMMARY
The problem of the present invention is therefore to propose a method and apparatus as well as a corresponding paper machine which make it possible to incorporate feature substances into paper in patterns or tracks with sharp contours and concentrations as uniform as possible across the pattern surface, even if they are low, without this resulting in changes of the fiber structure of the paper which are visible to the eye.
This problem is solved by a method and apparatus as well as a paper machine having the features stated in the independent claims. Preferred developments and embodiments of the invention are stated in claims dependent thereon.
As in DE-C 497 037, the feature substances are, according to the present invention, incorporated into the paper web during the papermaking process at a time when the bulk of the liquid is already withdrawn from the original paper pulp, i.e. the paper web is still moist but already consolidated, by applying a feature substance suspension to the still moist paper web in such a way that the paper web does not undergo any change in fiber structure. In order to achieve this, the feature substance suspension is directed onto the surface of the paper web as a laminar jet with low jet pressure. The feature substance suspension flows onto the paper web at low pressure.
The low jet pressure, this referring to the pressure on the inlet side of a nozzle, prevents the fiber structure of the paper web from changing upon application of the feature substance suspension. Accordingly, the place where the feature substance suspension is applied is invisible to the naked eye on the finished paper, even in transmitted light. Therefore, the method can also be used for incorporating feature substances in the watermark area.
A jet pressure on the nozzle inlet side in the range of about 30 to 200 millibars, preferably 50 to 100 millibars, has proved especially suitable. A nozzle inlet pressure therebelow leads to uneven and unstable jet formation and to deposits of feature substance in the feed pipes, while a higher nozzle inlet pressure from about 250 millibars upward leads to structural changes in the fibrous web of the paper web. The outlet nozzles themselves can be designed very simply, for example as metal or ceramic tubes. However, it is especially suitable to use so-called solid jet nozzles or flat jet nozzles which discharge the feature substance suspension as a solid jet with a circular or flat cross section.
The extension of width of the feature track is empirically determinable, and almost constant if the quantity of suspension is supplied constantly. The patterns produced thereby therefore have sharp contours. Since the suspension jet directed onto the paper web penetrates the wet and still soft paper layer uniformly, the quantity of suspension applied is roughly constant across the surface. As a result, the feature concentration is almost homogeneous across the width of the produced pattern, regardless of how high the feature concentration in the suspension is. This makes it possible to produce patterns even with the lowest feature concentrations distributed homogeneously over the pattern surface. The feature concentration of the produced patterns can be so low that the features are invisible to the naked eye and only detectable by machine using suitable sensors.
Since the feature substances are incorporated on a liquid basis, one can use almost any type of feature substances which are dispersible or soluble in a suitable suspending medium. Even high-density pigments can thus be incorporated uniformly into the paper web. Incorporating the feature substances by means of solid jets has the further advantage over spraying methods that no mist occurs. Thus the equipment used does not soil as easily and there are fewer problems with the deposit of particles on the nozzles.
The feature substances are preferably dispersed in water since water is available anytime, inexpensive, safe and chemically neutral. This does not exclude the use of other liquids such as alcohol. Especially suitable feature substances are luminescent pigments which are only recognizable under special excitation conditions such as UV light, so that the feature patterns incorporated into the paper are not readily visible in daylight. However, magnetic feature substances or ones absorbent in certain wave ranges can also be processed with the inventive method and apparatus.
The laminar feature substance suspension jet is preferably directed onto the paper web directly after sheet formation and removal of the still soft paper web from the mold, since at this point the paper web is sufficiently consolidated but still so moist that the suspension with the feature substances can penetrate into the paper web without leaving any traces. A special embodiment provides that a suction device in the form of a separate suction box is disposed at a following place in the paper machine in the direction of transport of the paper web for sucking the suspending medium through the paper web. This promotes the feature substances being present not only in near-surface areas of the paper but distributed throughout the paper thickness.
The volume should have a certain size since it serves as a buffer volume which compensates for fluctuations in the concentration of the feature substance in the volume which are caused by the supply of further feature substance concentrate and suspending medium into the volume. Said volume must not be too great, on the other hand, since otherwise any changes to be made in the set point of the feature substance concentration last too long. It has proved expedient to select the size of the volume so that an exchange or the throughput of the volume through the nozzles lasts about 15 minutes.
A further important aspect, which is to be heeded in particular when producing paper webs with multiple-copy sheets whereby several identical feature patterns are regularly incorporated simultaneously, is that the pressure at which the feature substance suspension is directed onto the paper web in different places is identical in each case. For this purpose it is provided that a great number of up to several hundred connecting pipes branch off from the closed, continuously conveyed feature substance suspension circuit to nozzles from which feature substance suspension is directed onto the paper sheet in laminar jets. This necessarily involves a pressure loss in the closed circuit. Like the pressure loss through the flow resistance of the circuit, it means that an individual suspension pressure or connecting pipe inlet pressure is present depending on the place where the connecting pipe leading to the nozzle branches off from the circuit, said pressure having to be reduced up to the nozzle just so far that the same outlet pressure is present at all nozzles used for producing similar patterns. This can be realized for example by a special control device in each connecting pipe. A simpler and therefore preferred solution, however, is to select the length and/or diameter of the connecting pipes so that the pressure loss in the connecting pipes is just so high that the nozzle outlet pressure is identical in each case.
The connecting pipe inlet pressure depends, on the one hand, on how high the maximum suspension pressure in the closed circuit is and, on the other hand, on how high the pressure loss in the circuit is up to the branching-off of the connecting pipe in question. Said pressure loss in turn depends directly on the rate at which the feature substance suspension is conveyed within the circuit. Preferably, the feed or circulating pump is operated at high and constant delivery to produce a circulation rate as high as possible and thus a turbulent flow which prevents sedimentation of the feature particles while simultaneously achieving uniform intermixture of the suspension. Maintaining the circulating pump delivery constant ensures constant conditions in the pipes and nozzles during operation. The operability and effect of the pump is monitored by monitored by measurement of a pressure difference. For this purpose the pressure in the circuit can be measured before and after the connecting pipe branches and the delivery of the circulating pump inferred from the differential pressure measured. Both wear of the circulating pump due to abrasive properties of the suspended particles and a reduction in cross-sectional area or clogging due for example to deposits in the pipes or filters of the circuit lead to a decrease in the pressure difference measured in the circuit. Monitoring of the pressure difference thus permits countermeasures to be taken in time.
A control device is preferably provided for maintaining the maximum or absolute suspension pressure in the circuit constant. For this purpose the absolute pressure is measured at a suitable place in the volume and the quantity of suspending medium supplied to the volume controlled by a feed pump. Although feature suspension is continuously removed from the volume via the nozzles, the essential parameters remain constant in the volume and thus also on the nozzles.
Alternatively, the conveyed or circulated quantity can be monitored and maintained constant, instead of the pressure in the removing volume. In this case, suspension fractions withdrawn from the volume are also compensated for and constant conditions ensured. Pressure control has the advantage, however, that it ensures that the same quantity of suspension leaves each nozzle if the nozzles are the same, regardless of the number of open nozzles. This is of advantage in particular when a fast change is to be made in the coding produced in the paper with the suspension jets while paper web production is underway.
It is important for the operability of the apparatus for applying feature substance suspension to the paper web that there are no deposits, in particular of feature substances, in individual elements of the apparatus since this can have an adverse effect on the pressure relations in the apparatus and thus on the uniformity of the produced feature patterns. Therefore it is provided that the feature substance suspension is produced in the desired concentration substantially only in the volume from which the connecting pipes branch off to the jet outlet nozzles, i.e. only in the closed circuit system in the case of the specific preferred embodiment. A feature substance concentrate and the suspending medium are therefore supplied to the circuit separately, preferably locally before the pump for circulating feature substance suspension in the closed cirsuspension in the closed circuit, so that said circulating pump performs the function of mixing the feature substance concentrate with the suspending medium.
In addition it is advantageous to provide a degassing device for degassing the suspending medium before it is supplied to the volume. This ensures, among other things, that the suspension does not emit gas and form bubbles, in particular upon a drop in pressure. In the degassed medium, air bubbles already present in the feature substance suspension can also dissolve again. If such air bubbles were discharged from the nozzles with the feature substance suspension, this would have an adverse effect on the contour and concentration distribution of feature substance at this place in the finished paper. For similar reasons the connecting pipes are preferably connected to the volume from above and protrude into the volume so that any air bubbles contained in the volume cannot pass into the connecting pipes and in addition no feature substances sedimented in the volume can pass into the connecting pipes and block them. In particular with especially high-density feature substances there is the danger of some larger particles being deposited on the bottom of the volume.
In preferred embodiments, shut-off devices are provided between the discharge points of the suspension from the buffer volume and the nozzles to permit each individual nozzle to be switched on and off individually. The shut-off devices can be for example stopcocks or valves which are controlled manually or automatically and actuated manually, electrically or pneumatically. This makes it possible to produce in a paper web an individual or regularly recurring feature pattern, which can also consist of interrupted tracks and also render coded information. In particular with automatically controlled switching apparatuses one can produce feature patterns whose application or incorporation in the paper web is synchronized with marks located thereon. In a preferred embodiment, said marks are formed by watermarks present in the paper.
BRIEF DESCRIPTION OF THE DRAWING
In the following, the invention will be explained by way of example with reference to a diagrammatic drawing showing an inventive apparatus in a paper machine.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Only a tiny detail of the paper machine is shown, namely the end of mold 1 . Paper web 2 , shown by dash lines, leaves mold 1 in the direction of the arrow. In this state, paper web 2 is already largely consolidated but still moist. Paper web 2 leaving mold 1 is transported further and guided under nozzle rail 10 . Through nozzles 11 a feature substance suspension is directed onto the moist paper web from above in order to produce linear feature patterns in the paper web parallel to the outside edge of the paper web. Several hundred nozzles 11 can be provided side by side which are individually activable and deactivable via associated stopcocks 12 . Following nozzles 11 in the transport direction of the paper web is suction device 3 which is provided under paper web 2 to suck feature substance suspension applied to paper web 2 by nozzles 11 through paper web 2 so that only the feature substances are left in the paper. As indicated by the Figure, said suction device can already begin before nozzles 11 in the transport direction of the paper web. Paper web 2 is then supplied optionally to following processing stations (not shown) for drying, coating, printing and the like.
The apparatus for incorporating feature substances into paper web is composed substantially of four subsystems. The core element of the apparatus is a volume preferably defined as a closed circuit 13 of nozzle rail 10 formed as a pipe system and having centrifugal pump 14 as a circulating pump for continuously conveying feature substance suspension within the pipe system. The second subsystem is formed by water preparation and supply unit 20 , and the third subsystem by feature substance concentrate preparation and supply unit 30 . The fourth subsystem is formed by nozzles 11 and their connecting pipes 15 to closed circuit 13 of nozzle rail 10 . The various subsystems will be described in detail below.
Feature substances are held ready as feature substance concentrate in a storage vessel. Through cover opening 32 feature substances are supplied to vessel 31 in pulverized form. Water is supplied via blockable feed pipe 33 . Water and feature substances are mixed by agitator 34 , and the feature substance concentration is preferably in the range of 10 to 30 wt %, in particular 0.4 kg of feature substance for 1 liter of water. The exact concentration value in the storage vessel is relatively uncritical since the final concentration of the feature substance suspension directed onto paper web 2 by nozzles 11 is only adjusted in closed circuit 13 by admixture of water. The higher the concentration in the storage vessel, the greater the feature supply and thus the time period until the storage vessel is refilled. The fill level of the storage vessel is monitored with level gage 35 . However, the concentration in the storage vessel must not exceed a predetermined viscosity limit of the feature concentrate since this otherwise this otherwise impairs the feed of feature concentrate by means of metering pump 36 preferably formed as a diaphragm pump. At the abovementioned concentration values the feature substance suspension is still very liquid, almost like water, for most feature substances. Via feed pipe 38 , metering pump 36 finally pumps feature substance concentrate out of storage vessel 31 into closed circuit 13 of nozzle rail 10 .
Prepared water is in addition supplied to closed circuit 13 via feed pipe 28 . The water is previously degassed in vacuum vessel 21 holding for example 20 liters at a negative pressure of approximately 0.3 bars relative to ambient pressure, so that any air bubbles passing into closed circuit 13 with the feature substance concentrate for example can dissolve in the feature substance suspension of closed circuit 13 . The vacuum vessel is equipped with vacuum pump 27 and level gage 25 which ensures that the fill level is maintained at about 90% of capacity for safety reasons. A feed pump executed for example as gear pump 26 conveys prepared water out of vacuum vessel 21 via feed pipe 28 to closed circuit 13 . The maximum delivery of gear pump 26 is for example about 550 liters an hour, which suffices for supplying about 300 nozzles simultaneously with a throughput of about 1.7 liters an hour per nozzle. Water treatment and supply unit 20 preferably has a water deliming device additionally integrated therein, which is not shown in the Figure.
Closed circuit 13 is formed substantially by a closed pipe system with integrated centrifugal pump 14 for circulating feature substance suspension conveyed in closed circuit 13 . Feature substance concentrate and prepared water are supplied to closed circuit 13 via feed pipes 38 , 28 shortly before centrifugal pump 14 . Centrifugal pump 14 thus performs the function of intermixing supplied feature substance concentrate with supplied prepared water. This guarantees that the concentration distribution of feature substances in the feature substance suspension is homogeneous to a very large extent before feature substance suspension fractions are branched off from circuit 13 via connecting pipes 15 to nozzles 11 . Strainer 16 with a 100 micron steel screen is provided shortly after the centrifugal pump and retains particles which could lead to clogging of nozzles 11 . Stopcock 17 is provided for example on the strainer screen for ventilating the apparatus after it is switched on.
Closed circuit 13 has two control circuits, a pressure control circuit and a density control circuit.
The pressure control circuit includes two pressure sensors P 1 and P 2 at different places in closed circuit 13 , preferably at a place before the branchings-off of connecting pipes 15 to nozzles 11 and at a following place in the direction of circuit flow. Pressure p 1 can be for example between 500 and 800 millibars depending on the pipe lengths and cross sections. Deviations from this set point are measured and used for controlling gear pump 26 for conveying the prepared water so that set point p 1 is maintained. Pressure value p 2 is preferably measured after the branching-off of last connecting pipe 15 to last nozzle 11 to determine the drop in pressure arising due to the branched-off feature substance suspension fractions and the flow resistance of the pipes in closed circuit 13 . Said drop in pressure should always be constant to ensure that roughly the same pressure relations always prevail at all nozzles 11 regardless of the number of nozzles activated. Since pressure difference p 2 −p 1 is directly dependent on the flow rate of feature substance suspension in closed circuit 13 , differential pressure measured value p 2 −p 1 is used to monitor the delivery of centrifugal pump 14 .
The density control circuit includes density sensor ρ. The inlet of density sensor ρ is connected directly to closed circuit 13 directly after strainer 16 . The outlet of density sensor ρ is located on the opposite side shortly before the inlet to centrifugal pump 14 . The pressure drop between inlet and outlet ensures sufficient flow through density sensor ρ which prevents deposits from forming in density sensor ρ. Density sensor ρ is used to determine the actual density of feature substance suspension in closed circuit 13 . This is a measure of the concentration of feature substances in the feature substance suspension of closed circuit 13 . According to the information on the actual density of feature substance suspension provided by density sensor ρ, metering pump 36 on storage vessel 31 is controlled to adjust a predetermined set point of suspension density corresponding to a concentration of a feature substance. A typical density adjustment for metering feature substances in feature substance suspension is e.g. 0.1 to 0.5 wt %.
The aforementioned measures ensure that not only the same feature substance concentration is present in the feature substance suspension at every branching-off of connecting pipe 15 , but also a time-constant connecting pipe inlet pressure, although it varies from connecting pipe to connecting pipe. On these premises the same connecting pipe outlet pressure can be adjusted for all pipes by simple constructional design of design of the connecting pipes, by producing a defined pressure loss in each connecting pipe 15 by suitable choice of the diameter and/or preferably the length of connecting pipes 15 , so that the same pressure is present at the end of each connecting pipe, that is, at nozzles 11 . To achieve the same outlet pressure for all nozzles 11 for example at pressure p 1 in the range of 500 to 800 millibars and an accordingly lower value for p 2 in closed circuit 13 , connecting pipes 15 with a length of typically a few decimeters have proved suitable, the connecting pipes consisting for example of tubes with an inside diameter of about 1 millimeter.
Each connecting pipe 15 has individual stopcock 12 . However, the blockage of individual stopcocks 12 has no effect on throughput and nozzle outlet pressure, since the connecting pipe inlet pressure is maintained roughly constant by the above-described pressure control regardless of the number of active nozzles.
Stopcocks 12 can be replaced by shut-off valves. An electric or pneumatic drive (not shown in the Figure) of the shut-off devices is advantageous in particular for frequent or fast change of the produced coding patterns. Altogether several hundred nozzles can be disposed side by side, also offset, at a distance of about 3 to 15 millimeters.
It should also be mentioned that connecting pipes 15 are connected to closed circuit 13 from above to prevent larger feature substance particles deposited on the bottom of closed circuit 13 from being sucked in, which could lead to clogging of the components such as stopcocks, nozzles, etc. In addition, connecting pipes 15 protrude from above about 10 millimeters into closed circuit 13 to prevent any air bubbles from being discharged through nozzles 11 with feature substance suspension, which would have an adverse effect on the quality of the stripe pattern produced.
The above-described apparatus for incorporating feature substances into a paper web permits a great variety of line codings by activating and deactivating individual nozzles 11 using respective associated stopcocks 12 without this having an effect on the feature substance concentration of the individual lines ultimately present in the finished paper. This is essentially due to the special pressure control circuit wherein the absolute pressure in the volume, e.g. pressure p 1 , is measured in closed circuit 13 before the branching-off of connecting pipes 15 and pressure p 2 after branching-off of connecting pipes 15 , each being maintained at a constant value by control of the deliv-delivery of gear pump 26 . The advantages achieved by said pressure control circuit are also achieved when the feature substance suspension is directed onto the surface of the paper web not as a laminar jet with low jet pressure but for example with high jet pressure or as a turbulent jet or sprayed jet. | A method and apparatus for incorporating feature substances into a still moist but already sufficiently consolidated paper web provides for directing a feature substance suspension onto the surface of the paper web as a laminar jet with low jet pressure. A special pressure control circuit ensures that the jet pressure is always constant regardless of the number of parallel feature substance suspension jets directed onto the paper web. This makes it possible to incorporate a great variety of line codings in paper under the same process conditions without any visible changes in fiber structure occurring in the paper. | 3 |
BACKGROUND OF THE INVENTION
The conventional timers are mostly mechanical type, which can not set the correct time and are easy to be out of order. Although some of conventional timers are electronic type, those timers can only be presetted several daily ON/OFF times within several specified days. There is no way for a conventional electronic timer to operate repeat-cycle timing or to control more than one load concurrently. Traditional electronic timer device can be improved to meet the special timing requirements.
SUMMARY OF THE INVENTION
The major objective of present invention is to offer a repeat-cycle timing device which can continuously operate ON and OFF actions after the cycling interval has been presetted. Therefore the timer device can be applied to air-conditioner control, electrical home appliance control and other industrial control.
The second objective of present invention is to offer a timer device which can concurrently control two loads.
In brief, in accordance with this invention there is provided two cascaded digital counters with the input of the first digital counter connected to a time-base pulse generator and the digital output of the second digital counter connected to a timing interval composition unit. Two switches can select either one of the presetted timing intervals under the repeat-cycle timing mode or one-time timing mode through the timing interval selection unit which is connected to the timing interval composition unit. A bistable circuit will change state when one of the switches sends a pulse and another switch is prevented from sending a pulse. Thereafter a resetted pulse generator will generate a positive pulse to reset two digital counters so as to complete one cycle under the repeat-cycle timing mode. The bistable circuit will only change state one time to reset the digital counters one time under the one-time timing mode.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic diagram of one embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Both IC 1 and IC 2 are the same digital counters. The present invention adopts CD 4020 as an example to describe in the following:
CD 4020 is a 16-pinned digital counter with 14-stage digital outputs. Pin 1 is for Q 12 , pin 2 for Q 13 , pin 3 for Q 14 , pin 4 for Q 6 , pin 5 for Q 5 , pin 6 for Q 7 , pin 7 for Q 4 , pin 8 for Vss, pin 9 for Q 1 , pin 10 for pulse input, pin 11 for reset, pin 12 for Q 9 , pin 13 for Q 8 , pin 14 for Q 10 , pin 15 for Q 11 , and pin 16 for V DD . Wherein Q 1 , Q 4 , Q 5 , . . . and Q 14 represent its 14-stage digital output. The inventor herein announced that the adoption of CD 4020 in the embodiment of the present invention is not for confining the scope of the present invention but only for describing the example. Regarding other IC or electronic circuits with a similar function of CD 4020, these are also included in the present invention.
Block 1 is a time-base pulse generator. Time-base pulses are applied to pin 10 (pulse input pin) of IC 1 to activate the counting function of IC 1 . Pin 3 (Q 14 ) of IC 1 connects to pin 10 (pulse input pin) of IC 2 , thus the Q 14 of IC 1 is the pulse input of IC 2 . The frequency of time-base pulse input of IC 1 can be changed by adjusting variable resistor VR 1 of Block 1 so as to change the frequency of the output pulse in pin 3 of IC 1 . Therefore the frequency of the time-base pulse input of IC 2 can be changed accordingly, so as to change the presetted interval of a repeat-cycle timer which is controlled by IC 2 . IC1 along with block 1 is incorporated as a time-base pulse generator, with adjustable time-base interval for IC2
Pins 7, 5, 4, 6, 13, 12, 14, 15, 1, 2, and 3 of IC2 are respectively digital outputs of Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 Q 11 , Q 12 , Q 13 , and Q 14 . The above-mentioned digital outputs are connected to a timing interval composition unit as shown in Block 2. The said timing interval composition unit is composed of several AND Gates and diodes to result in ten different interval outputs. This timing interval composition unit is only used for example description. The same timing interval composition unit can also be achieved by incorporating other similar logic circuit. Any minor modifications which cannot be illustrated herein one by one should also be included in the scope of the present invention.
Block 3 is a timing interval selection unit with SW 1 which represents switch 1 and SW 2 which represents switch 2. Either SW 1 or SW 2 can be connected to one of the above-mentioned ten different interval outputs to select one of the ten different presetted intervals, for example, 5 minutes, 10 minutes, 30 minutes, 1 hour, 2 hours, 5 hours, . . . and 24 hours etc. Pin 11 of the timing interval selection unit is a null pin which is specially designed for one-time timing mode whose operation will be described in the later paragraph. Therefore both SW 1 and SW 2 have eleven different selectable positions, ten timing intervals and one null pin.
To facilitate the description of the embodiment of the present invention, SW 1 is assumed to be presetted in timing interval T 1 and SW 2 is assumed to be presetted in timing interval T 2 and T 1 is less than T 2 . After timing initiates and time arrives at T 1 , output of SW 1 will turn to HIGH but output of SW 2 still remain as LOW, which accordingly make input of NOT Gate NOT 2 in Block 4 (SW 1 bistable circuit trigger) HIGH and output of NOT 2 LOW, therefore diode D 7 will be ON, and input point 1, IP 1 , of the bistable circuit as shown in Block 6 will be LOW accordingly. Input of NOT gate NOT 6 in Block 5 (SW 2 bistable circuit trigger) will be LOW due to the LOW output of SW 2 , therefore output of NOT 6 will be HIGH, which will make diode D 11 OFF and input point 2, IP 2 , of the bistable circuit will be HIGH accordingly. According to the theory of a bistable circuit, output point 1, OP 1 , of the bistable circuit will be HIGH and output point 2, OP 2 , will be LOW. This bi-output state, designated as STATE 1, will remain unchanged until IP 1 turns to HIGH and concurrently IP 2 turns to LOW next time, which will make the bi-state output change, with OP 1 changed to LOW and OP 2 changed to HIGH so as to designate as STATE 2.
When OP 2 remains LOW in STATE 1, the Base of transistor Q 2 is also LOW which will make Q 2 OFF and accordingly deactivate relay RL 1 . Therefore reed switch of RL 1 will be connected to contact point 1 so as to turn on the Load 1 connected to power receptacle 1, REC 1 controlled by contact point 1 of reed switch of RL 1 . On the hand, Load 2 connected to power receptacle 2, REC 2 will be turned off.
As soon, as the bistable circuit turns to STATE 1, OP 1 will produce a square wave which thereafter be applied to a capacitor C 4 , diode D 10 in reset pulse generator, which is shown in Block 7, to generate a positive pulse. The positive pulse will then be applied to the pin 11 of IC 1 and IC 2 so as to reset two digital counters IC 1 , and IC 2 simultaneously.
When time arrives at T 1 again after resetting, OP 2 still remain as LOW to make diode D 5 ON. Therefore input of NOT 2 will be LOW in spite of output of SW 1 being HIGH. Output of NOT 2 will be HIGH accordingly to make D 7 OFF and thereafter IP 1 will be HIGH. In the mean time, output of SW 2 remains LOW that will keep the IP 2 HIGH just as the same operation described in the former paragraph. Therefore the bistable circuit can not be changed to STATE 2. Diode D 5 will prevent SW 1 from sending a pulse to Block 4 before SW 2 has sent a pulse to Block 5.
When time arrives at T 2 after resetting, output of SW 2 will turn to HIGH. Therefore input of NOT 6 will be HIGH and output of NOT 6 will be LOW to make D 11 ON. IP 2 will change to LOW accordingly but IP 1 still remains HIGH, that will change the bistable circuit to STATE 2, OP 1 to LOW and OP 2 to HIGH just as the description in the former paragraph. Then the base of Q 1 will be HIGH to make Q 2 ON, which will activate the relay RL 1 . Reed switch will hereby disconnect to a contact point 1 but connect to contact point 2, thereafter to turn off Load 1 which is connected to REC 1 and turn on Load 2 which is connected to REC 2 .
As soon as a bistable circuit turns to STATE 2, OP 2 will produce a square wave which thereafter is applied to a capacitor C 3 and diode D 9 to generate a positive pulse. The said positive pulse will then be applied to the pin 11 of IC 1 and IC 2 so as to reset two digital counters IC 1 and IC 2 simultaneously. According to the same operation described in the former paragraph, a diode D 13 will prevent SW 2 from sending a pulse to Block 5 before SW 1 has sent a pulse to Block 4.
SW 1 and SW 2 will send a pulse in turn to a trigger bistable circuit due to the operation of D 5 and D 13 , thereafter the repeat-cycle timing mode will be activated. If the SW 2 is connected to the null pin, pin 11, of timing interval selection unit, SW 2 will be incapable of sending a pulse forever. Therefore the bistable circuit will remain as STATE 1 once the STATE 1 is achieved in the first time, thereafter the one-time timing mode will be activated.
The operation of a switching indicator and timing indicator, as shown in Block 8, will be described as follows: In the STATE 1, during Load 1 turning-on and Load 2 turning-off, OP 2 will be LOW, which will make the negative terminal of diode D 6 LOW. If the output of pin 2 of IC 1 is LOW, the base of transistor Q 1 will be LOW. If the output of pin 2 of IC 1 is HIGH, hereby the D 6 will be ON to keep the base of Q 1 still being LOW. No matter what is output status of pin 2 of IC 1 , the base of Q 1 will always remain LOW only if the bistable circuit remains in STATE 1, so as to make Q 1 OFF and inactivate LED 2 , and OP 1 will be HIGH, which will make diode D 12 OFF. Therefore the output pulse of pin 2 of IC 1 will continuously apply to the base of Q 3 to make Q 3 ON and OFF continuously. Hereby LED 1 will blink so as to indicate STATE 1. In the STATE 2, during Load 1 turning-off and Load 2 turning-on, will deactivate LED 1 and make LED 2 blink according to the same operation described above.
A timer inactivating circuit is showed in Block 9. When switch SW 3 is ON, a permanent HIGH voltage will be applied to pin 11, reset pin, of IC 1 and IC 1 to inactivate the timer device.
A power supply circuit is shown in Block 10, the points A and B will output 10 V DC voltage to power on the timer device. When AC power is temporarily turned off, the back-up battery will offer 9 V DC voltage to support the timer device. | An improved timer device which incorporates an electronic circuit to offer the user two selectable timer modes, either one-time timing mode or repeat-cycle timing mode. The cycle interval under the a repeat-cycle timing mode can be presetted by the user. The timer device comprises two AC power control circuits to control two loads concurrently. | 6 |
BACKGROUND OF THE INVENTION
The present invention concerns a device for cutting sheets of material. It includes a counter for the material to rest on, a blade to cut the material, and a holdfast. The holdfast can be lowered onto the material by a mechanism and raised off it by a spring.
A device for cutting sheets of material with a counter for the material to rest on, a blade to cut the material, and a holdfast that can be lowered onto the material is known for example from European Patent 0 056 874 A1 for example. Such holdfasts are lowered onto the material by a mechanism and raised off it by a spring with the lowering mechanism out of action.
In practice, it is possible with such cutting devices to position the particular cut. The operator lowers the device slowly toward the material, and the proximity of the holdfast to the surface of the material plus the parallelism between the lower forward edge of the of the holdfast and the blade allows ideal orientation of the material in relation to the plane of the cut. It is generally impossible to prevent the operator from shifting the material between the holdfast. To prevent injury to the operator, especially to prevent his finger from getting caught, the pressure applied by the holdfast is decreased while the cut is being positioned. It is of course still possible for the operator to injure himself while the holdfast is being raised, when the mechanism is inactive and the spring that raises the holdfast is broken, allowing it to drop back onto the stack subject to its own weight. Serious injury to the operator in this event cannot be ruled out.
SUMMARY OF THE INVENTION
The object of the present invention is to improve the generic device to the extent that the operator cannot be injured when the holdfast-raising spring is broken.
This object is attained in accordance with the present invention in a device of the aforesaid genus by an interceptor that brakes the holdfast when the spring that raises it is broken. "Brake" is to be understood comprehensively in the present context. The braking is intended to ensure that the holdfast comes to rest either immediately or after only a short descent once the spring is broken, effectively preventing the holdfast from striking either the material or the operator's fingers. The holdfast is preferably braked by notching, which is a very simple mechanical procedure for braking it after only a short descent. It is in particular intended for the holdfast to notch indirectly. It is on the other hand conceivable to brake the holdfast directly, hydraulically for example. Such holdfasts are generally lowered hydraulically and the hydraulic system depressurized to allow the holdfast to rise. A broken holdfast-raising spring can be represented by increased pressure in the hydraulics, immediately actuating a valve that hydraulically prevents the holdfast from descending farther.
It is particularly simple from the engineering aspect to brake the holdfast when the spring that raises it is broken if the interceptor accommodates a detente component in the power train that leads to the holdfast, whereby a stationary stop extends into the path of the holdfast when the spring is broken. As long as the spring is intact, the detente component, which accompanies the holdfast, does not come into contact with the stop, whereas a broken spring leads to a variation in the adjustment of the detente component that leads in turn to the stop extending into the component's path. Once the detente component comes into contact with the stop, the holdfast stops descending and is accordingly intercepted in that position.
The detente component in one advantageous embodiment pivots in the power train and between two stops, whereby the holdfast-raising spring engages a stationary component on the device and the detente component while a weaker release spring exerts force on the detente component in opposition to the force exerted by the holdfast-raising spring. As long as the holdfast-raising spring is intact, it will tension the detente component against one stop, whereby the path traveled by the detente component will always be remote from the stationary stop. If the holdfast-raising spring is broken and accordingly fails, the release spring will pivot the detente component against the other stop, and the stationary stop will again extend into the path of the detente component.
The interceptor can be at any position in the power train that terminates in the holdfast. It could basically be immediately next to the holdfast. The holdfast in one preferred embodiment, however, is accommodated in a frame, and the holdfast power train essentially comprises rods that engage each end of the holdfast, angled levers that pivot on the frame and engage the other end of the rods, a rod system that connects the levers, and a mechanism that operates in conjunction with one of the levers, whereby the holdfast raising spring engages the frame and the detente component, which is mounted in the connecting-rod system. In this event the detente component is associated with the lever-connecting rod that ensures simultaneity of the holdfast and rods.
The detente component in one particularly simple embodiment is angled and pivots at its vertex on the connecting-rod system, whereby the holdfast-raising spring engages one arm of the detente component and the free end of the other arm can operate in conjunction with the stationary stop. If the arms of the detente component are at a right angle, the holdfast-raising spring will be able to intervene very powerfully, and the other arm will be exposed essentially only to compressive forces when the holdfast-raising spring is broken, leading to impact against the stationary stop. It is practical for the release spring to be a leg spring accommodated in the connecting-rod system with one leg resting against the connecting-rod system and the other against the detente component between the component's pivot and the holdfast-raising spring's point of intervention. The detente component's two stops can for example be pins extending remote from the pivot through a slot in the component that extends along the direction it pivots in.
The stationary stop in one particular embodiment has a sliding detente that allows engagement of the detente component in accordance with the interception position of the holdfast. The background here is that the connecting-rod system mounted in the two angled levers moves along the arc of a circle in accordance with the position of the holdfast, with the consequence that the detente lever will complete a similar motion as long as the holdfast-raising spring is intact. To ensure rapid braking of the holdfast no matter what position it is in when the holdfast-raising spring is broken, the sliding detente, with its large number of notches for the detente component, is at almost the same distance from any position of the detente lever.
Further characteristics of the present invention will be evident from the subsidiary claims, the description of the figures, and the figures themselves. All characteristic and combinations thereof are essential to the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
One embodiment of the present invention will now be specified without limiting its scope in any way with reference to the accompanying drawing, wherein
FIG. 1 is a schematic representation of a device for cutting sheets of material,
FIG. 2 is a larger-scale illustration of the detail x in FIG. 1, and
FIG. 3 is a section along the line A--A in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 represents the basic design of a device for cutting sheets of material along a plane perpendicular to the direction the material is being advanced in and parallel to the direction traveled by the holdfast and blade 25. Only the essential parts of the device are illustrated.
As will be evident from FIG. 1, a counter 12 with a horizontal top 13 that supports the sheets 2 of material is accommodated in a frame 1. A holdfast 11 ascends and descends in the direction indicated by double-headed arrow Z in two parallel and perpendicular tracks 14. FIG. 1 illustrates holdfast 11 in its uppermost position. The distance separating the upper surface of sheets 2 from the lower edge 15 of holdfast 11 will be evident.
Two parallel rods 3 engage the sides of holdfast 11. Rods 3 pivot on angled levers 4. Levers 4 pivot in turn in frame 1. The other end of each angled lever 4 pivots on a connecting-rod system 5, which accordingly mechanically couples rods 3, creating a ganged track for holdfast 11. One angled lever 4 has a third arm 4a that functions as an actuating arm. The free end of arm 4a extends into the positioning path of the piston 10a. Piston 10a operates in conjunction with a hydraulic cylinder 10. Cylinder 10 is accommodated in frame 1. As piston 10a travels out, the activating arm 4a, which rests against it, of the angled lever 4 next to cylinder 10 will pivot along with the rigidly integrated lever 4. The lever will accordingly not only draw its associated rod 3 down but transmit its motion to the other angled lever 4 by way of connecting-rod system 5. Rod system 5 will then draw its associated rod 3 down. The synchronized motion of both rods 3 will draw holdfast 11 down, in order to position the cut for example. Holdfast 11 is raised by depressurizing cylinder 10, whereupon a holdfast-raising spring 6 that engages both frame 1 and, indirectly, connecting-rod system 5 will apply force to the connecting-rod system, pivoting angled lever 4 against the direction the force is applied in when the hydraulics are in action. Holdfast-raising spring 6 is a spiral tension spring.
The design of the interceptor in accordance with the present invention will be evident from FIGS. 2 and 3 in particular. Connecting-rod system 5 comprises two parallel rods 5a and 5b. Rods 5a and 5b pivot, accommodating between them not only the free arms of angled levers 4 but also an angled detente component 8. A bolt 16 extends snugly through concentric bores in rods 5a and 5b and loosely through a bore at the vertex of angled detente component 8. Another bolt 17, remote from bolt 16, extends snugly through rods 5a and 5b and loosely through a slot 18 that is concentric with secured bolt 16 in the essentially perpendicular arm 8a of angled detente component 8. The end 6a of holdfast-raising spring 6 is suspended in a hole in the vicinity of the free end, which faces away in bolt 16, of arm 8a. Another bolt 19 (FIG. 1) extends snugly through concentric bores in rods 5a and 5b on the side facing holdfast-raising spring 6. Bolt 19 also extends through a leg spring 7. One leg 7a of leg spring 7 rests against the end of connecting-rod system 5 facing holdfast-raising spring 6. The other leg 7b rests against the arm 8a of angled detente component 8. Angled detente component 8 has another arm 8b perpendicular to arm 8a and to the length of its bearing bolt 16a.
As holdfast 11 moves, connecting-rod system 5 describes, due to its pivoting on both angled levers 4, a motion along the circumference of a circle with a radius equal to the lifting arm of levers 4 between the bearing axis 23 and the point of intervention against connecting-rod system 5. While holdfast 11 is up, holdfast-raising spring 6 is less powerfully tensioned and, when it is farther down, more powerfully tensioned. Holdfast-raising spring 6 draws angled detente component 8 into the position represented by the solid lines in FIG. 2, where bolt 17 rests against one end of slot 18. Without holdfast-raising spring 6, which means when it is broken and is out of action, it is leg spring 7 that ensures angled detente component 8 is pivoted into the position represented by the broken lines in FIG. 2. In this event the bolt 17 at the other end of slot 18 will rest against arm 8a.
The figures reveal how a stop 9 mounted in frame 1 and accordingly stationary operates in conjunction with the arm 8b of angled detente component 8. The end of stop 9 facing arm 8b constitutes a sliding detente 20. The contour 21 of sliding detente 20, which is not actually illustrated in the vicinity of the detente itself, slants, ensuring that, as long as holdfast-raising spring 6 acts on angled detente component 8, free end 8c will remain at the same slight distance away from contour 21 no matter what the position of holdfast 11. If holdfast-raising spring 6 is broken, leg spring 7 will pivot angled detente component 8 into the position represented by the broken line. The free end 8c of arm 8b will come to rest in one of the notches 22 in sliding detente 20, preventing connecting-rod system 5 from moving any farther in the direction indicated by arrow Y. The braking of connecting-rod system 5 will, by way of the kinematic coupling associated with holdfast 11, stop the holdfast when holdfast-raising spring 6 is broken. Which notch 22 in sliding detente 20 angled detente component 8 will encounter depends on what position holdfast 11 is in when holdfast-raising spring 6 is broken. The broken line in FIG. 2 illustrates the braking action in the event that holdfast-raising spring 6 is broken while holdfast 11 is almost all the way up. If the spring is broken with the holdfast farther down, connecting-rod system 5 would travel farther in the direction indicated by arrow Y, and the free end 8c of arm 8 would come into contact with on of the rear notches 22. The invisible notches 22 are included in FIG. 3 to facilitate comprehension. | Device for cutting sheets of material, with a counter (12) for the material to rest on, a blade to cut the material, and a holdfast (11) that can be lowered onto the material by a mechanism (10) and raised off it by a spring (6). When the spring in such a device breaks, the holdfast can drop and injure the operator. The object is to prevent such injuries. An interceptor (7, 8, & 9) accordingly brakes the holdfast when the spring that raises it is broken. | 8 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This application is a continuation-in-part of applicants' copending patent application U.S. Ser. No. 09/416,291, filed on Oct. 14, 1999, which was a continuation-in-part of patent application U.S. Ser. No. 09/396,034, filed on Sep. 15, 1999, which in turn was a continuation-in-part of patent application U.S. Ser. No. 09/181,307, filed on Oct. 28, 1998, now abandoned.
FIELD OF THE INVENTION
A process for controlling a system for generating electricity in which a multiplicity of compressors which are connected to a microturbine are selectively turned on and off in response to the level of gas pressure.
BACKGROUND OF THE INVENTION
Microturbines, also known as turbogenerators and turboalternators, are gaining increasing popularity and acceptance. These microturbines are often used in conjunction with one or more compressors which supply gaseous fuel to them at a desired pressure, generally from about 40 to about 500 pounds per square inch.
The microturbines are often employed in a system comprising two or more microturbines. These systems could be supplied by only one compressor, but such operation often results in too much compressor capacity when less than all of the microturbines are operating.
It is an object of this invention to provide a process for controlling the output of a multiplicity of compressors connected to one or more microturbines.
SUMMARY OF THE INVENTION
A process for controlling a system for generating electricity, which system is comprised of a first compressor, a second compressor, a first microturbine, and a second microturbine, comprising the steps of supplying a first compressed gas at a pressure of from about 40 to about 500 pounds per square inch from a first gas source to said first microturbine, making a first measurement of the pressure of gas within said first gas source, supplying gas from a second gas source to a first compressor, compressing said gas from said second gas source in said first compressor to a pressure of from about 40 to about 500 pounds per square inch, thereby producing a second compressed gas, supplying said second compressed gas to said first gas source, supplying said second compressed gas from said first gas source to said first microturbine, making a second measurement of the pressure of gas within said first gas source, supplying gas from a second gas source to a second compressor, compressing said gas from said second gas source in said second compressor to a pressure of from about 40 to about 500 pounds per square inch, thereby producing a third compressed gas, supplying said third compressed gas to said first gas source, and supplying said third compressed gas from said first gas source to said second microturbine.
BRIEF DESCRIPTION OF THE DRAWINGS
The claimed invention will be described by reference to the specification and the following drawings, in which:
FIG. 1 is a perspective view of one preferred rotary mechanism claimed in U.S. Pat. No. 5,431,551;
FIG. 2 is an axial, cross-sectional view of the mechanism of FIG. 1;
FIG. 3 is a perspective view of the eccentric crank of the mechanism of FIG. 1;
FIG. 4A is a transverse, cross-sectional view of the eccentric crank of FIG. 3;
FIG. 5 is a perspective view of the rotor of the device of FIG. 1;
FIG. 6 is an axial, cross-sectional view of the rotor of FIG. 5;
FIG. 7 is a transverse, cross-sectional view of the rotor of FIG. 5;
FIG. 8 is an exploded, perspective view of the device of FIG. 1;
FIG. 9 is a sectional view of one hollow roller which can be used in the rotary positive displacement device of this invention;
FIG. 10 is a sectional view of another hollow roller which can be used in the rotary positive displacement device of this invention;
FIG. 11 is a schematic view of a modified rotor which can be used in the positive displacement device of this invention;
FIG. 12 is a block diagram of a preferred electrical generation system;
FIG. 13 is a block diagram of the gas booster system of FIG. 12;
FIG. 14 is a schematic representation of an apparatus comprised of a guided rotor device and a reciprocating compressor;
FIG. 15 is a schematic representation of another apparatus comprised of a guided rotor device and a reciprocating compressor;
FIG. 16 is a schematic representation of another guided rotor apparatus; and
FIG. 17 is a schematic representation of yet another guided rotor apparatus;
FIG. 18 is a sectional view of a multi-stage guided rotor assembly;
FIG. 19 is a sectional view of a guided rotor assembly with its drive motor enclosed within a hermetic system;
FIG. 20 is a schematic illustration of a microturbine electric generation and waste heat recovery system;
FIG. 21 is a schematic diagram of one preferred process of the invention, illustrating one preferred means for measuring gas pressure within the electrical generating system;
FIG. 22 is a schematic diagram of the process depicted in FIG. 21, illustrating a preferred a preferred pressure relief system;
FIG. 23 is graph illustrating the a typical history of gas pressure versus time for the system of FIG. 21 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the first part of this specification, applicants will describe a system for generating electricity. In the second part of this specification, applicants will describe a system for controlling the amount of gas delivered in an electrical generating system comprised of two or more microturbines.
FIGS. 1, 2 , 3 , 4 , 4 A, 5 , 6 , 7 , and 8 are identical to the FIGS. 1, 2 , 3 , 4 , 4 A, 5 , 6 , 7 , and 8 appearing in U.S. Pat. No. 5,431,551; and they are presented in this case to illustrate the similarities and differences between the rotary positive displacement device of such patent and the rotary positive displacement device of the instant application. The entire disclosure, the drawings, the claims, and the abstract of U.S. Pat. No. 5,431,551 are hereby incorporated by reference into this specification.
Referring to FIGS. 1 through 8, and to the embodiment depicted therein, it will be noted that rollers 18 , 20 , 22 , and 24 (see FIGS. 1 and 8) are solid. In the rotary positive displacement device of the instant invention, however, the rollers used are hollow.
FIG. 9 is a sectional view of a hollow roller 100 which may be used to replace the rollers 18 , 20 , 22 , and 24 of the device of FIGS. 1 through 8. In the preferred embodiment depicted, it will be seen that roller 100 is a hollow cylindricral tube 102 with ends 104 and 106 .
Tube 102 may consist of metallic and/or non-metallic material, such as aluminum, bronze, polyethyletherketone, reinforced plastic, and the like. The hollow portion 108 of tube 102 has a diameter 110 which is at least about 50 percent of the outer diameter 112 of tube 102 .
The presence of ends 106 and 108 prevents the passage of gas from a low pressure region (not shown) to a high pressure region (not shown). These ends may be attached to tube 102 by conventional means, such as adhesive means, friction means, fasteners, threading, etc.
In the preferred embodiment depicted, the ends 106 and 108 are aligned with the ends 114 and 116 of tube 102 . In another embodiment, either or both of such ends 106 and 108 are not so aligned.
In one embodiment, the ends 106 and 108 consist essentially of the same material from which tube 102 is made. In another embodiment, different materials are present in either or both of ends 106 and 108 , and tube 102 .
In one embodiment, one of ends 106 and/or 108 is more resistant to wear than another one of such ends, and/or is more elastic.
FIG. 10 is sectional view of another preferred hollow roller 130 , which is comprised of a hollow cylindrical tube 132 , end 134 , end 136 , resilient means 138 , and O-rings 140 and 142 . In this embodiment, a spring 138 is disposed between and contiguous with ends 134 and 136 , urging such ends in the directions of arrows 1444 and 146 , respectively. It will be appreciated that these spring-loaded ends tend to minimize the clearance between roller 130 and the housing in which it is disposed; and the O-rings 140 and 142 tend to prevent gas and/or liquid from entering the hollow center section 150 .
In the preferred embodiment depicted, the ends 144 and 146 are aligned with the ends 152 and 154 of tube 132 . In another embodiment, not shown, one or both of ends 144 and/or 146 are not so aligned.
The resilient means 138 may be, e.g., a coil spring, a flat spring, and/or any other suitable resilient biasing means.
FIG. 11 is a schematic view of a rotor 200 which may be used in place of the rotor 16 depicted in FIGS. 1, 5 , 6 , 7 , and 8 . Referring to FIG. 11, partial bores 202 , 204 , 206 , and 208 are similar in function, to at least some extent, the partial bores 61 , 63 , 65 , and 67 depicted in FIGS. 5, 6 , 7 , and 8 . Although, in FIG. 11, a different partial bore has been depicted for elements 202 , 204 , 206 , and 208 , it will be appreciated that this has been done primarily for the sake of simplicity of representation and that, in most instances, each of partial bores 61 , 63 , 65 , and 67 will be substantially identical to each other.
It will also be appreciated that the partial bores 202 , 204 , 206 , and 208 are adapted to be substantially compliant to the forces and loads exerted upon the rollers (not shown) disposed within said partial bores and, additionally, to exert an outwardly extending force upon each of said rollers (not shown) to reduce the clearances between them and the housing (not shown).
Referring to FIG. 11, partial bore 202 is comprised of a ribbon spring 210 removably attached to rotor 16 at points 212 and 214 . Because of such attachment, ribbon spring 210 neither rotates nor slips during use. The ribbon spring 210 may be metallic or non-metallic.
In one embodiment, depicted in FIG. 11, the ribbon spring 210 extends over an arc greater than 90 degrees, thereby allowing it to accept loads at points which are far from centerline 216 .
Partial bore 204 is comprised of a bent spring 220 which is affixed at ends 222 and 224 and provides substantially the same function as ribbon spring 210 . However, because bent spring extends over an arc less than 90 degrees, it accepts loads primarily at our around centerline 226 .
Partial bore 206 is comprised of a cavity 230 in which is disposed bent spring 232 and insert 234 which contains partial bore 206 . It will be apparent that the roller disposed within bore 206 (and also within bores 202 and 204 ) are trapped by the shape of the bore and, thus, in spite of any outwardly extending resilient forces, cannot be forced out of the partial bore. In another embodiment, not shown, the partial bores 202 , 204 , 206 , and 208 do not extend beyond the point that rollers are entrapped, and thus the rollers are free to partially or completely extend beyond the partial bores.
Referring again to FIG. 11, it will be seen that partial bore 208 is comprised of a ribbon spring 250 which is similar to ribbon spring 210 but has a slightly different shape in that it is disposed within a cavity 252 behind a removable cradle 254 . As will be apparent, the spring 250 urges the cradle 254 outwardly along axis 226 . Inasmuch as the spring 250 extends more than about 90 degrees, it also allows force vectors near ends 256 and 258 , which, in the embodiment depicted, are also attachment points for the spring 250 .
Figure is 12 is a block diagram of one preferred apparatus of the invention. Referring to FIG. 12, it will be seen that gas (not shown) is preferably passed via gas line 310 to gas booster 312 in which it is compressed to pressure required by micro turbine generator 314 . In general, the gas must be compressed to a pressure in excess of 30 p.s.i.g., although pressures as low as about 20 p.s.i.g. and as high as 360 p.s.i.g. or more also may be used.
In FIGS. 12 and 13, a micro turbine generator 314 is shown as the preferred receiver of the gas via line 313 . In other embodiments, not shown, a larger gas turbine and/or a fuel cell may be substituted for the micro turbine generator 314 .
In one embodiment, in addition to increasing the pressure of the natural gas, the gas booster 312 also generally increases its temperature to a temperature within the range of from about 100 to about 150 degrees Fahrenheit. In one embodiment, the gas booster 312 increases the temperature of the natural gas from pipeline temperature to a temperature of from about 100 to about 120 degrees Fahrenheit.
The compressed gas from gas booster 312 is then fed via line 313 to micro turbine generator 314 . The components used in gas booster 312 and in micro turbine generator 314 will now be described.
FIG. 13 is a schematic diagram of the gas booster system 312 of FIG. 12 . Referring to FIG. 12, it will be seen that gas booster system 312 preferably is comprised of a guided rotor compressor 316 .
The guided rotor compressor 316 depicted in FIG. 13 is substantially identical to the guided rotor compressor 10 disclosed in U.S. Pat. No. 5,431,551, the entire disclosure of which is hereby incorporated by reference into this patent application. This guided rotor compressor is preferably comprised of a housing comprising a curved inner surface with a profile equidistant from a trochoidal curve, an eccentric mounted on a shaft disposed within said housing, a first rotor mounted on said eccentric shaft which is comprised of a first side, a second side, and a third side, a first partial bore disposed at the intersection of said first side and said second side, a second partial bore disposed at the intersection of said second side and said third side, a third partial bore disposed at the intersection of said third side and said first side, a first solid roller disposed and rotatably mounted within said first partial bore, a second solid roller disposed and rotatably mounted within said second partial bore, and a third solid roller disposed and rotatably mounted within said third partial bore.
The rotor is comprised of a front face, a back face, said first side, said second side, and said third side. A first opening is formed between and communicates between said front face and said first side, a second opening is formed between and communicates between said back face and said first side, wherein each of said first opening and said second opening is substantially equidistant and symmetrical between said first partial bore and said second partial bore. A third opening is formed between and communicates between said front face and said second side. A fourth opening is formed between and communicates between said back face and said second side, wherein each of said third opening and said fourth opening is substantially equidistant and symmetrical between said second partial bore and said third partial bore. A fifth opening is formed between and communicates between said front face and said third side. A sixth opening is formed between and communicates between said back face and said third side, wherein each of said fifth opening and said sixth opening is substantially equidistant and symmetrical between said third partial bore and said first partial bore.
Each of said first partial bore, said second partial bore, and said third partial bore is comprised of a centerpoint which, as said rotary device rotates, moves along said trochoidal curve.
Each of said first opening, said second opening, said third opening, said fourth opening, said fifth opening, and said sixth opening has a substantially U-shaped cross-sectional shape defined by a first linear side, a second linear side, and an arcuate section joining said first linear side and said second linear side. The first linear side and the second linear side are disposed with respect to each other at an angle of less than ninety degrees; and said substantially U-shaped cross-sectional shape has a depth which is at least equal to its width.
The diameter of said first roller is equal to the diameter of said second solid roller, and the diameter of said second solid roller is equal to the diameter of said third solid roller.
The widths of each of said first opening, said second opening, said third opening, said fourth opening, said fifth opening, and said sixth opening are substantially the same, and the width of each of said openings is less than the diameter of said first solid roller.
Each of said first side, said second side, and said third side has substantially the same geometry and size and is a composite shape comprised of a first section and a second section, where in said first section has a shape which is different from that of said second section.
The aforementioned compressor is a very preferred embodiment of the rotary positive displacement compressor which may be used as compressor 316 ; it is substantially smaller, more reliable, more durable, and quieter than prior art compressors. However, one may use other rotary positive displacement compressors such as, e.g., one or more of the compressors described in U.S. Pat. Nos. 5,605,124, 5,597,287, 5,537,974, 5,522,356, 5,489,199, 5,459,358, 5,410,998, 5,063,750, 4,531,899, and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
In one preferred embodiment, the rotary positive displacement compressor used as compressor 316 is a Guided Rotor Compressor which is sold by the Phoenix Engine and Compressor Corporation of 210 Pennsylvania Avenue, East Aurora, N.Y.
Referring again to FIG. 13, it will be seen that the compressed gas from compressor 316 is fed via line 313 to micro turbine generator 314 . As is disclosed in U.S. Pat. No. 5,810,524 (see, e.g., claim 1 thereof), such micro turbine generator 314 is a turbogenerator set including a turbogenerator power controller, wherein said turbogenerator also includes a compressor, a turbine, a combustor with a plurality of gaseous fuel nozzles and a plurality of air inlets, and a permanent magnet motor generator; see, e.g., FIGS. 1 and 2 of such patent and the description associated with such Figures.
The assignee of U.S. Pat. No. 5,819,524 manufactures and sells micro turbine generators, such as those described in its patent.
Similar micro turbine generators 314 are also manufactured and sold by Elliott Energy Systems company of 2901 S.E. Monroe Street, Stuart, Fla. 34997 as “The TA Series Turbo Alternator.”
Such micro turbines are also manufactured by the Northern Research and Engineering Corporation (NREC), of Boston, Mass., which is a wholly-owned subsidiary of Ingersoll-Rand Company; see, e.g., page 64 of the June, 1998 issue of “Diesel & Gas Turbine Worldwide.” These micro turbines are adapted to be used with either generators (to produce micro turbine generators) or, alternatively, without such generators in mechanical drive applications. It will be apparent to those skilled in the art that applicants' rotary positive displacement device may be used with either of these applications.
In general, and as is known to those skilled in the art, the micro turbine generator 314 is comprised of a radial, mixed flow or axial, turbine and compressor and a generator rotor and stator. The system also contains a combustor, bearings and bearings lubrication system. The micro turbine generator 314 operates on a Brayton cycle of the open type; see, e.g., page 48 of the June, 1998 issue of “Diesel & Gas Turbine Worldwide.”
Referring again to FIG. 13, and in the preferred embodiment depicted therein, it will be seen that natural gas is fed via line 310 to manual ball valve 318 and thence to Y-strainer 320 , which removes any heavy, solid particles entrained within the gas stream. The gas is then passed to check valve 322 , which prevents backflow of the natural gas. Relief valve 324 prevents overpressurization of the system.
The natural gas is then fed via line 326 to the compressor 316 , which is described elsewhere in this specification in detail. Referring to FIG. 13, it will be seen that compressor 316 is operatively connected via distance piece 328 , housing a coupling (not shown) which connects the shafts (not shown) of compressor 316 and electric motor 330 . The compressor 316 , distance piece 328 , and electric motor 330 are mounted on or near a receiving tank, which receives and separates a substantial portion of the oil used in compressor 316 .
Referring again to FIG. 13, when the compressor 316 has compressed a portion of natural gas, such natural gas also contains some oil. The gas/oil mixture is then fed via line 334 to check valve 336 (which prevents backflow), and thence to relief valve 338 (which prevents overpressurization), and then via line 340 to radiator/heat exchanger 342 .
Referring again to FIG. 13, it will be seen that oil is charged into the system via line 344 through plug 346 . Any conventional oil or lubricating fluid may be used; in one embodiment, automatic transmission fluid sold as “ATF” by automotive supply houses is used.
A portion of the oil which was introduced via line 344 resides in the bottom of tank 332 . This portion of the oil is pressurized by the natural gas in the tank, and the pressurized oil is then pushed by pressurized gas through line 348 , through check valve (to eliminate back flow), and then past needle valve 352 , into radiator 354 ; a similar needle valve 352 may be used after the radiator 354 . The oil flowing into radiator 354 is then cooled to a temperature which generally is from about 10 to about 30 degrees Fahrenheit above the ambient air temperature. The cooled oil then exits radiator 354 via line 356 , passes through oil filter 358 , and then is returned to compressor 316 where it is injected; the injection is controlled by solenoid valve 360 .
In the preferred embodiment depicted in FIG. 13, a fan 362 is shown as the cooling means; this fan is preferably driven by motor 364 ; in the preferred embodiment depicted in FIG. 13, air is drawn through radiators 342 and 354 in the direction of arrows 363 . As will be apparent to those skilled in the art, other cooling means (such as water cooling) also and/or alternatively may be used.
Referring again to FIG. 13, the cooled oil and gas mixture from radiator 342 is passed via line 366 through ball valve 368 and then introduced into tank 332 at point 370 .
In the operation of the system depicted in FIG. 13, a sight gauge 380 provides visual indication of how much oil is in receiving tank 332 . When an excess of such oil is present, it may be drained via manual valve 384 . In general, it is preferred to have from about 20 to about 30 volume percent of the tank be comprised of oil.
Referring again to FIG. 13, compressed gas may be delivered to turbogenerator 314 through port 386 , which is preferably located on receiving tank 332 but above the oil level (not shown) in such tank. Bypass line 388 and pressure relief valve 390 allows excess gas flow to be diverted back into inlet line 326 . That gas which is not in bypass line 388 flows via line 313 through check valve 392 (to prevent backflow), manual valve 394 and thence to turbogenerator 314 .
Thus, and again referring to FIG. 13, it will be seen that, in this preferred embodiment, there is a turbo alternator 314 , an oil lubricated rotary displacement compressor 316 , a receiving tank 332 , a means 310 for feeding gas to the rotary positive displacement compressor, a means 346 for feeding oil to the receiving tank, a means 342 for cooling a mixture of gas and oil, a means 332 for separating a mixture of gas and oil, and a means 356 for feeding oil to the rotary positive displacement compressor.
In the preferred embodiment depicted in FIG. 13, there are two separate means for controlling the flow capacity of compressor 316 . One such means, discussed elsewhere in this specification as a bypass loop, is the combination of port 386 , line 388 , relief valve 390 , and line 391 . Another such means is to control the inlet flow of the natural gas by means of control valve 396 . As will be apparent, both such means, singly or in combination, exert their control in response to the gas needs of turbogenerator 314 .
FIG. 14 is a schematic representation of a hybrid booster system 420 which is comprised of a rotary positive displacement device assembly 422 operatively connected via line 424 to a reciprocating compressor 426 .
Rotary positive displacement device assembly 422 may be comprised of one or more of the rotary positive displacement devices depicted in either FIGS. 1-8 (with solid rollers) and/or 9 - 11 (hollow rollers). Alternatively, or additionally, the displacement device 422 may be comprised of one or more of the rotary compressors claimed in U.S. Pat. No. 5,769,619, the entire disclosure of which is hereby incorporated by reference into this specification.
U.S. Pat. No. 5,769,619 claims a rotary device comprised of a housing comprising a curved inner surface in the shape of a trochoid and an interior wall, an eccentric mounted on a shaft disposed within said housing, a first rotor mounted on said eccentric shaft which is comprised of a first side and a seocnd side, a first pin attached to said rotor and extending from said rotor to said interior wall of said housing, and a second pin attached to said rotor and extending from said rotor to said interior wall of said housing, and a third pin attached to said rotor and extending from said rotor to said interior wall of said housing. A continuously arcuate track is disposed within said interior wall of said housing, wherein said continuously arcuate track is in the shape of an envoluted trochoid. Each of said first pin, said second pin, and said third pin has a distal end which is disposed within said continuously arcuate track. Each of said first pin, said second pin, and said third pin has a distal end comprised of a shaft disposed within a rotatable sleeve. The rotor is comprised of a multiplicity of apices, wherein each such apex forms a compliant seal with said curved inner surface, and wherein each said apex is comprised of a separate curved surface which is formed from a strip of material pressed into a recess. The curved inner surface of the housing is generated from an ideal epictrochoidal curve and is outwardly recessed from said ideal epitrochoidal curve by a distance of from about 0.05 to about 5 times as great as the eccentricity of said eccentric. The diameter of the distal end of each of said first pin and said second pin is from about 2 to about 4 times as great as the eccentricity of the eccentric. Each of the first pin, the second pin, and the third pin extends from beyond the interior wall of the housing by from about 2 to about 2 times the diameter of each of said pins.
Referring again to FIG. 14, it is preferred that several rotary positive displacement devices 10 and 10 ′ be used to compress the gas ultimately fed via line 424 to reciprocating positive compressor 426 . As is disclosed in U.S. Pat. No. 5,431,551, the devices 10 and 10 ′ are staged to provide a multiplicity of fluid compression means in series.
Thus, as was disclosed in U.S. Pat. No. 5,431,551 (see lines 62 et seq. of column 9), “In one embodiment, not shown, a series of four rotors are used to compress natural gas. The first two stacked rotors are substantially identical and relatively large; they are 180 degrees out of phase with each other; and they are used to compress natural gas to an intermediate pressure level of from about 150 to about 200 p.s.i.g. The third stacked rotor, which comprises the second stage of the device, is substantially smaller than the first two and compresses the natural gas to a higher pressure of from about 800 to about 1,000 p.s.i.g. The last stacked compressor, which is yet smaller, is the third stage of the device and compresses the natural gas to a pressure of from about 3,600 to about 4,500 p.s.i.g.”
Many other staged compressor circuits will be apparent to those skilled in the art. What is common to all of them, however, is the presence of at least one rotary positive displacement device 10 whose output is directly or indirectly operatively connected to at least one cylinder of a reciprocating positive displacement compressor 426 .
One may use any of the reciprocating positive displacement compressor designs well known to the art. Thus, by way of illustration and not limitation, one may use one or more of the reciprocating positive compressor designs disclosed in U.S. Pat. Nos. 5,811,669, 5,457,964, 5,411,054, 5,311,902, 4,345,880, 4332,144, 3,965,253, 3,719,749, 3,656,905, 3,585,451, and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
Referring again to FIG. 14, it will be apparent that reciprocating positive displacement compressor 426 may be comprised of one or more stages. In the preferred embodiment depicted, compressor 426 is comprised of stages 428 and 430 .
Referring again to FIG. 14, an electric motor 432 connected by shafts 434 and 436 is operatively connected to compressors 428 / 430 and 10 / 10 ′. It will be apparent that many other such drive assemblies may be used.
In one embodiment, not shown, the gas from one stage of either the 10 / 10 ′ assembly and/or the 428 / 430 assembly is cooled prior to the time it is passed to the next stage. In this embodiment, it is preferred to cool the gas exiting each stage at least about 10 degrees Fahrenheit prior to the time it is introduced to the next compressor stage.
FIG. 15 depicts an assembly 450 similar to the assembly 420 depicted in FIG. 14 . Referring to FIG. 15, it will be seen that gas is fed to compressor assembly 10 / 10 ′ by line 452 . In this embodiment, some pressurized gas at an intermediate pressure is fed from compressor 10 via line 454 to turbine or micro-turbine or fuel cell 456 . Alternatively, or additionally, gas is fed to electrical generation assembly 456 by a separate compressor (not shown).
The electrical output from electrical generation assembly 456 is used, at least in part, to power electrical motor 432 . Additionally, electrical power is fed via lines 458 and/or 460 to an electrical vehicle recharging station 462 and/or to an electrical load 464 .
Referring again to FIG. 15, and in the preferred embodiment depicted therein, waste heat produced in turbine/microturbine/fuel cell 456 is fed via line 466 to a heat load 468 , where the heat can be advantageously utilized, such as, e.g., heating means, cooling means, industrial processes, etc. Additionally, the high pressure discharge from compressor 430 is fed via line 470 to a compressed natural gas refueling system 472 .
In one embodiment, not shown, guided rotor assembly 10 / 10 ′ is replaced is conventional compressor means such as reciprocating compressor, or other positive displacement compressor. Alternatively, or additionally, the reciprocating compressor assembly may be replaced by one or more rotary positive displacement devices which, preferably, are adapted to produce a more highly pressurized gas output the either compressor 10 or compressor 10 ′. Such an arrangement is illustrated in FIG. 16, wherein rotary positive displacement devices 11 / 11 ′ are higher pressure compressors used. In one embodiment, not shown, separate electrical motors are used to power one or more different compressors.
FIG. 17 is a schematic representation of an assembly 500 in which electrical generation assembly 456 is used to power a motor 502 which is turn provides power to rotary positive displacement device 504 . Gas from well head 506 is passed via line 508 , and pressurized gas from rotary positive displacement device 504 is fed via line 510 to electrical generation assembly 456 , wherein it is converted to electrical energy. Some of this energy is fed via line 512 to electric motor 432 , which provides motive power to a single or multi-compressor guided rotary compressor 514 ; this “well head booster” may be similar in design to the compressor assembly illustrated in FIGS. 1-8, or to the compressor assembly illustrated in FIGS. 9-12, and it may contain one more compressor stages. The output from rotary positive displacement assembly 514 may be sent via line 516 to gas processing and/or gas transmission lines. The input to rotary positive displacement assembly 514 may come from well head 518 , which may be (but need not be) the same well head as well head 516 , via line 520 .
Multistage Rotor Assembly
FIG. 18 is a sectional view of a multistage rotor assembly 600 which is comprised of a shaft 602 integrally connected to eccentric 604 and eccentric 606 . The rotating shaft 600 /eccentric 604 /eccentric 606 assembly is supported by main bearings 608 and 610 ; eccentrics 604 and 606 are disposed within bearings 612 and 614 ; and the eccentrics 604 / 606 and bearings 612 / 614 assemblies are disposed within guided rotors 616 and 618 . This arrangement is somewhat similar to that depicted in FIG. 1, wherein eccentric 52 is disposed within guided rotor 60 .
As will be apparent to those skilled in the art, one shaft 602 is being used to translate two rotors 616 and 618 . The gas to be compressed is introduced into port 620 and then introduced into the volume created by the rotor 616 and the housing 622 . The compressed gas from the volume created by the rotor 616 and the housing 622 is then introduced within an annulus 624 within intermediate plate 626 via port 628 and then sent into the volume created by rotor 618 and housing 630 through port 632 . After being further compressed in this second rotor system, it is then sent to discharge annulus 632 within discharge housing 634 by port 636 .
Referring to FIG. 1, it will be seen that guided rotor assembly 10 has a housing 12 with a thickness 640 which is slightly larger than the thickness of the rotor 16 disposed within such housing (see FIG. 1 ). Similarly, the thickness 642 of rotor assembly 616 , and the thickness 644 of rotor assembly 618 are also slightly smaller than the thicknesses of the housings in which the guided rotors are disposed.
It is preferred that the thickness 644 be less than the thickness 642 . In one embodiment, thickness 642 is at least 1.1 times as great as the thickness 644 and, preferably, at least 1.5 times as great as the thickness 644 .
It will be apparent that, with the assembly 600 of FIG. 18, one can achieve higher pressures with lower operating costs.
A Hermetically Sealed Guided Rotor Apparatus
FIG. 19 illustrates an guided rotor assembly 670 comprised of a multiplicity of guided rotors 672 and 674 . Shaft 676 is rotated by electric motor 678 which, in the embodiment depicted, is comprised of motor shaft 680 , motor rotor 682 , and stator 684 supported by bearings 686 and 688 . The motor shaft 680 is directly coupled to compressor shaft 676 by means a coupling 690 .
The compressor shaft 676 rotates one or more of rotors 672 and 674 , which may be of the same size, a different size, of the same function, and/or of a different function.
The motor 678 is cooled by incoming gas (not shown), and such incoming gas is then passed to compressor 692 , wherein it is distributed equally to the rotor assemblies 672 and 674 , which are disposed within housings 694 and 696 , respectively.
In the embodiment depicted in FIG. 19, the rotor assemblies 674 and 676 have substantially the same geometry and capacity. In another embodiment, not shown, the rotor assemblies 674 and 674 have different geometries and/or capacities.
Referring again to FIG. 19, it will be seen that the entire compressor and drive assembly is disposed within hermetic enclosure 698 . The end flange 700 is form an interface 702 with enclosure 698 which is a hermetic seal.
FIG. 20 is a schematic of an assembly 750 for generating electric power and recovering thermal energy for other useful work. Referring to FIG. 20, it will be seen that a multiplicity of micro turbines 752 , 754 , 756 , and 758 are used to generate electricity which, in the embodiment depicted, is fed from the unit at outlet 760 .
In one embodiment, a micro turbine such as those sold by the Capstone Turbine Corporation of Woodland Hills, Calif. may be used. Thus, e.g., the Model 330 Capstone Micro Turbine may be used. Thus, e.g., one may use one or more of the micro turbines disclosed in U.S. Pat. Nos. 5,903,116, 5,899,673, 5,850,733, 5,819,524, and the like. The disclosure of each of these United States patents is hereby incorporated by reference into this specification.
Referring again to FIG. 20, the heat, discharged from one or more of micro turbines 752 , 754 , 756 , and/or 758 is passed to waste heat boilers 760 and/or 762 , wherein the waste heat is used to heat fluid, such as water, and to preferably generate either hot water or steam. The hot fluid from waste heat boilers 760 and/or 762 is then passed via lines 764 and 766 to industrial processes 768 and 770 . Any industrial or commercial processes which utilize heat energy may be used in the process. Thus, the waste heat may be used to heat or cool working space, inventory space, etc.; it may be used to heat chemical reagents; it may, in fact, be used in any process which requires heat. Conventional means, such as pipes, heat exchangers, and the like (see, e.g., heat exchanger 771 ) may be used to extract heat from the heated fluid.
In one embodiment, not shown, the exhaust gases from micro turbines 752 , 754 , 756 , and/or 758 into the air inlet of a combustion boiler, or into any other device which can profitably utilize such hot gasses.
Referring again to FIG. 20, it will be seen that a multiplicity of guided rotor compressors 772 and 774 supply compressed natural gas to the micro turbines 752 , 754 , 756 , and/or 758 . Accumulator 776 accumulates compressed gas produced by compressors 772 and/or 774 ; and, as needed, it also may supply compressed gas to micro turbines 752 , 754 , 756 , and 758 .
A Process for Controlling Compressors
FIG. 21 is a schematic diagram of a system 800 for generating electricity which is comprised of a multiplicity of microturbines 752 , 754 , 756 , and 758 which are described elsewhere in this specification. The system 800 also is comprised of a multiplicity of compressors 802 , 804 , and 806 .
Although four microturbines 752 et seq. are shown in the system depicted in FIG. 21, fewer or more microturbines can be used. It is preferred to use at least two such microturbines in the system 800 , but one can use many more in such system such as, e.g., 60 microturbines.
Although three compressors 802 et seq. are shown in the system depicted in FIG. 21, fewer or more such compressors may be used. It is preferred to use at least two such compressors in the system 800 , but one can use many more such compressors such as, e.g., 60 compressors.
One may use the guided rotor compressor, described and claimed in U.S. Pat. No. 5,431,551, as one or more of the compressors in system 800 . Alternatively, or additionally, one may use one or more of the “hollow roller compressors,” described elsewhere in this specification, as one or more of the compressors in system 800 . Alternatively, or additionally, one may use other types of compressors such as, e.g., scroll compressors, vane compressors, twin screw compressors, reciprocating compressors, continuous flow compressors, and the like.
Regardless of the compressor, it should be capable of compressing gas to a pressure of from about 40 to about 500 pounds per square inch and of delivering such compressed gas at a flow rate of from about 5 to about 200 standard cubic feet per minute (“scfm”). The term “scfm” is well known to those skilled in the art, and means for measuring it are also well known. See, e.g. U.S. Pat. Nos. 5,672,827, 4,977,921, 5,695,641, 5,664,426, 5,597,491, and the like. The disclosure of each of these United States patents is hereby incorporated by reference into this specification.
Referring to FIG. 21, when system 800 has been shut down and is in the process of just starting up, compressed gas at a pressure of from about 40 to about 500 pounds per square inch is first delivered to microturbine 752 .
In the embodiment depicted in FIG. 21, it is preferred to use a pressure regulator 836 in line 313 to insure that gas delivered to microturbine(s) 752 and/or 754 and/or 756 and/or 758 is stable and remains within a specified range of gas pressure.
In the embodiment shown in Figure, reservoir 808 generally will contain a source of compressed gas at a pressure of from about 40 to about 500 pounds per square inch, and this compressed gas may be fed via lines 313 and 810 to microturbine 752 .
Reservoir 808 can be any container sufficient for storing and/or dispensing gas at a pressure of from about 40 to about 500 pounds per square inch. Thus, by way of illustration and not limitation, one may use any of the gas storage vessels disclosed in U.S. Pat. Nos. 5,908,134, 5,901,758, 5,826,632, 5,798,156, 5,997,611, and the like. The entire disclosure of each of these United States patents is hereby incorporated by reference into this specification.
In the embodiment depicted in FIG. 21, gas storage vessel 808 acts as the initial supply of compressed gas to microturbine 752 . In another embodiment, not shown, gas storage vessel 808 is not used in the system and compressed gas is fed to microturbine 752 from another initial gas source such as, e.g., gas delivery line 810 .
Referring again to FIG. 21, after the compressed gas has been delivered to microturbine 752 from either storage vessel 808 and/or line 810 , the microturbine starts operation. In the embodiment depicted in FIG. 21, each of microturbines 752 , 754 , 756 , and 758 is comprised of its own controller which, in response to the introduction of gas to such microturbine, starts it in operation. In another embodiment, a central controller operatively connected to each of microturbines 752 , 754 , 756 , and 758 , and to each of compressors 802 , 804 , and 806 , is utilized.
Referring again to FIG. 21, each of compressors 802 , 804 , and 806 is operatively connected to a controller 812 , 814 , and 816 , respectively. In another embodiment, not shown, one controller (not shown) is connected to each of the compressors; this controller might be a computer, a programmable logic controller, etc. In one aspect of this latter embodiment, one controller is operatively connected to each of the compressors, but such unitary controller includes a separate gas pressure sensor device for each such compressor. It is preferred, regardless whether one uses one or more controllers, that each such controller contain a separate gas sensing device for each compressor.
Regardless of which controller or controllers are connected to the compressors 802 , 04 , and 806 , it is preferred that such controllers(s) be comprised of pressure sensing means (not shown) for measuring the pressure of gas. Thus, for example, the pressure sensing means may be pressure switches which combine the function of pressure sensing and electrical switching. Thus, e.g., the pressure sensing means may be pressure transducers adapted to provide a signal to a programmable logic controller.
Regardless of the pressure sensing means used, such means is adapted to determine the pressure within either vessel 808 and/or line 810 . When such pressure is outside of a specified desired range of a pressure, but is within the broad pressure range of from about 40 to about 500 pounds per square inch, the pressure sensing means acts as a switch to turn one or more of compressors 802 , 804 , and/or 806 on or off, depending upon the pressure sensed.
Referring again to FIG. 21, the controllers 812 , 814 , and 816 are operatively connected to compressors 806 , 804 , and 802 , respectively, by lines 818 and 820 , 822 and 824 , and 826 and 828 , respectively. It should be noted that lines 820 , 824 , and 828 , in one embodiment, preferably comprise a manual switch 830 , 832 , and 834 , respectively to allow one to manually control each of the compressors.
As will be apparent to those skilled in the art, one or more of the manual switches 830 , 832 , and/or 834 may be used in conjunction with the controllers 812 , 814 , and 816 . When one or more of the controllers 812 , 814 , and/or 816 are connected in the system 800 , the manual switches may be used to disconnect the compressors and negate the effects of the controllers. If the controllers 812 , 814 , and/or 816 are omitted from system 800 , one may manually perform the operations of such controllers by using such switches in response to gas pressure readings may be manual means.
In one embodiment, the controllers 812 , 814 , and 816 are programmed to turn compressors 802 , 804 , and 806 on sequentially, in response to the presence of different gas pressure levels within either vessel 808 or line 810 . This feature will be illustrated later in the specification by reference to FIG. 23 .
Thus, in one typical embodiment, compressor 802 will be turned on when the gas pressure in vessel 808 and/or line 810 is less than, e.g., 60 pounds per square inch; compressors 802 , 804 , and 806 may be fed gas from gas lines 310 , 311 , 313 , and 315 . When this condition occurs, compressor 802 will be switched on and will cause compressed gas to flow to microturbine 752 at a flow rate of, e.g., 7 standard cubic feet per minute.
During the operation of compressor 802 , and as long as the gas flow from compressor 802 is sufficient to meet the needs of whichever of microturbines 752 , 754 , 756 , and/or 758 is running, the gas pressure within vessel 808 and line 810 preferably remains at a specified value such as, e.g., 60 pounds per square inch.
After controller 816 has activated compressor 802 , when one or more of the sensors in controller 814 senses that the gas pressure within vessel 808 and line 810 has dropped below a desired value, such as, e.g., 55 pounds per square inch, it will then turn on compressor 804 so that it is operating in addition to compressor 802 .
Similarly, when compressors 802 and 804 are running, and the sensor in, e.g., controller 812 senses that the gas pressure within vessel 808 and/or line 810 has dropped below a desired value such as, e.g., 50 pounds per square inch, it will turn on compressor 806 .
The same process may be used in the reverse order, when one or more of the controllers 812 , 814 , and 816 sense that the pressure within vessel 808 and/or line 810 exceeds a certain predetermined value. Thus, e.g., compressor 806 may be turned off when the pressure sensed is greater than about, e.g., 65 pounds per square inch, compressor 804 may be turned off when the pressure sensed is greater than about, e.g., 66 pounds per square inch, and compressor 802 may be turned off when the pressure sensed is greater than about 67 pounds per square inch.
As will be apparent to those skilled in the art, other conditions and sequences may be used. What is common to all of the processes, however, is the sequential turning on and/or turning off of a multiplicity of compressors.
FIG. 22 illustrates one preferred means of providing pressure relief in an electricity generating system 800 .
Referring to FIG. 22, when the pressure within pressure vessel 808 exceeds a specified value, pressure relief valve 850 allows such pressure to vent via line 852 to atmosphere. Thus, e.g., valve 850 can be set to open when, e.g., the pressure within vessel 808 exceeds, e.g., 150 pounds per square inch.
A bypass relief valve 854 is set to open whenever the pressure within vessel 808 exceeds a specified value. In one embodiment, the pressure required to actuate valve 850 is greater than the pressure required to actuate valve 854 ; if the former pressure, e.g., may 150 pounds per square inch and the latter pressure may be, e.g., 70 pounds per square inch. As will be apparent to those skilled in the art, the actual actuation points for valves 850 and 854 will vary depending upon factors such as the rating of the vessel 808 , the power ratings of compressors 802 , 804 , and 806 , the pressures required in the system, etc.
Referring again to FIG. 22, when valve 854 is actuated, gas flows from vessel 808 through line 856 and then through check valve 858 back into line 310 at point 860 . Check valve 862 prevents gas recycled into the system at point 860 from flowing back to the original gas supply 864 .
Referring again to FIG. 22, and in the preferred embodiment depicted therein, it will be seen that each of compressors 802 , 804 , and 806 is comprised of a pressure relief valve 866 , 868 , and 870 which, when the pressure within the compressor discharge 872 , 874 , and 876 exceeds a certain specified value, gas is vented to the atmosphere 878 . Thus, e.g., pressure relief valves 866 , 868 , and 870 may be designed to actuate at a pressure of, e.g., 150 pounds per square inch.
When the gas pressure at compressor discharge 872 , 874 , and 876 is less than the pressure required to actuate valves 866 , 868 and 870 but is more than another specified value (such as, e.g., 80 pounds per square inch), bypass relief valves 880 , 882 , and 884 open and flow gas through lines 886 , 888 , and 890 through check valves 892 , 894 , and 896 and thence back into lines 311 , 313 , and 315 . In one embodiment, the relief valves 880 , 882 , and 884 are set to be actuated at levels somewhat lower than the settings in controllers 816 , 814 , and 812 for turning the compressors off (see FIG. 21 ).
Referring again to FIG. 22, it will be seen that the gas exiting from compressors 802 , 804 , and 806 via lines 898 , 900 , and 902 pass through check valves 904 , 906 , and 908 which can be used to prevent backflow.
FIG. 23 is a graph of pressure versus the number of compressors operating, in the system depicted in FIG. 21 .
As is illustrated in FIG. 23, the pressure PI, which is within the range defined by points 910 and 912 , exists when each of compressors 802 , 804 , and 806 are operating. The pressure P 2 , which is within the range defined by points 914 and 916 , exists when only compressors 802 and 804 are operating. The pressure P 3 , which is defined by the points 918 and 920 , exists when only compressor 802 is operating. The pressure P 4 , which is defined by a pressure in excess of the pressure at point 920 , exists when the pressure vessel 808 has a pressure outside of the desired range and at least one compressor is operating and producing pressure outside of the desired range, which causes bypass relief valve 854 (see FIG. 21) to open and reduce the pressure at or below level 920 .
It is to be understood that the aforementioned description is illustrative only and that changes can be made in the apparatus, in the ingredients and their proportions, and in the sequence of combinations and process steps, as well as in other aspects of the invention discussed herein, without departing from the scope of the invention as defined in the following claims. | A process for controlling a system for generating electricity which contains at least two compressors and two microturbines. Compressed gas from a pressure vessel is supplied to the first microturbine, and thereafter the pressure within the pressure vessel is measured. If the pressure is below a specified value, a first compressor is caused to operate to feed compressed gas to the pressure vessel. Thereafter, as the system needs require, a second compressor and, optionally, a third compressor is caused to furnish compressed gas to the pressure vessel. If the system pressure within the pressure vessel is too high, the third compressor is shut down and, if necessary, the second compressor and the first compressor are then sequentially shut down. | 8 |
FIELD OF THE INVENTION
The present invention relates generally to fluid handling apparatus and, in particular, to such apparatus permitting fluid movement through a passageway in one direction and having means for preventing the back-flow of fluid therethrough.
BACKGROUND OF THE INVENTION
In this century, machines have come to be widely used for washing articles of clothing. These machines typically run through an automatic sequence of washing, rinsing, and spin-drying steps alternatingly receiving and discharging water with each step. The discharged "grey" water, including contaminating detergents and suspended particulate matter, is most often conveyed through the drainage system of a building structure into a public sewer line for ultimate disposal. In some instances, however, blockages in such drainage systems have lead to large volumes of grey water being discharged onto the floor of a building structure and causing considerable damage thereto.
In my prior patent, U.S. Pat. No. 4,069,837, issued Jan. 24, 1978, a device for detecting a blockage in a drainage system and preventing a damaging overflow condition by disabling a washing machine was disclosed. In order to function as intended, the device illustrated in my patent required a readily-achieved, fluid-tight seal with the stand-pipe or inlet to the drainage system of a building structure. While my original device was fully effective in accomplishing its principal intended purpose, i.e., preventing unintended spillage, the pressurized back-flow of fluid through the stand-pipe or drainage system inlet was found not to be substantially deterred from reentering a washing machine after its initial discharge.
In highrise apartments and washaterias, where multiple clothes washing machines discharge grey water into a common drainage system, the potential for fluid back-flow is especially acute. As a single washing machine is discharging its liquid contents under pressure, a downstream blockage can lead to the undesired entry of the just pumped grey water into several other machines and contamination of the contents thereof.
SUMMARY OF THE INVENTION
In view of the problems associated with the prior devices for detecting a blockage in a drainage system and preventing a damaging overflow condition by disabling a washing machine, a novel valve has been developed for permitting fluid movement through its main flow passageway in one direction and having means for preventing the back-flow of fluid therethrough. The novel valve includes a rigid body having a tubular valve member of flexible, elastomeric material secured thereto. The tubular valve member has upstream and downstream ends in fluid communication with one another and is normally open for fluid flow therebetween. In response to downstream pressure increases, however, the tubular valve member is yieldingly collapsible so as to prevent fluid from passing therethrough. A ring, dimensioned to prevent the passage of said downstream end through the inlet opening of the rigid valve body in the event of a downstream pressure increase, is secured about said tubular valve member.
Such a valve construction is a significant improvement over prior check valves incorporating an elastomeric element in that no rigid element projecting into, or across, the fluid flow stream is required for the support thereof. Thus, frictional resistance to fluid flow, formerly caused by screens or props of various configurations, is eliminated. Furthermore, when the instant valve is used to control the flow of a liquid which contains suspended impurities such as lint or hair, there will be absolutely no tendency for such filamentary matter to build up within the valve as often happens when a projection into the flow stream is provided.
In order to optimally utilize the waste or "grey" water discharged from clothes washing machine, a novel manifold is proposed for use with a valve of the type hereinabove described. The manifold includes a connection to a municipal, potable water source for flushing such after use. Of course, the need for preventing the back-flow of contaminated liquids into a supply of potable water has long been recognized. For public health reasons, local plumbing codes often include provisions mandating the use of certain apparatus for preventing the suction of contaminants into potable water conduits in the event of a system failure. In this regard, the manifold is provided with a tubular valve member of flexible, elastomeric material which is yieldingly collapsible and adapted to prevent fluid from passing into the municipal water source in the event of a back pressure condition.
It is an object of the invention to provide improved elements and arrangements thereof in an apparatus for the purposes described which is inexpensive, dependable and fully effective in accomplishing its intended purposes.
These and other objects of the present invention will become readily apparent upon further review of the following specification and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more readily described with reference to the accompanying drawings, in which:
FIG. 1 is a side elevational view, partially in cross section, illustrating a drain control valve in accordance with the present invention.
FIG. 2 is a cross-sectional view of a portion of the drain control valve showing the installation of the cylindrical tap therein.
FIG. 3 is a cross-sectional view of the drain control valve of FIG. 1 installed upon the stand-pipe of a fluid drainage system and employed in combination with a pressure sensing alarm unit, the elastomeric tubular body being collapsed to prevent the back-flow of fluid through the valve.
FIG. 4 is an electric circuit diagram of a pressure sensing alarm unit for use with the drain control valve of the present invention.
FIG. 5 is an alternative embodiment of the drain control valve shown threadably fastened within a portion of a side wall outlet box.
FIG. 6 is a schematic view of a building structure piped to utilize the drain control valve and manifold system of the present invention for irrigation purposes.
FIG. 7 is cross-sectional view of the fluid distribution manifold of FIG. 6 showing details thereof.
Similar reference characters denote corresponding features consistently throughout the accompanying drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1 of the drawings, there is shown a drain control valve 10 in accordance with the present invention. Broadly, the drain control valve 10 includes a body 12 having a central, axially-extending passageway 14 for the main flow of fluid through the body 12. Disposed within the passageway 14 is an elastomeric valve member 16 adapted for preventing the back-flow of fluids through the passageway 14. A secondary passageway or aperture 18, in the valve body 12, having a ball valve element 20 disposed therein interconnects the passageway 14 with the atmosphere and acts as an anti-siphon feature. Thus, it is to be understood that the drain control valve 10 checks the unintended flow of fluid through the passageway in both directions.
The preferred valve body 12 is of three-part construction and comprises: inlet member 22, outlet member 24, and cup member 26. As may be seen, the inlet member 22 is a hollow tube having, at its lower end, threads 28 about the exterior thereof. Likewise, the outlet member 24 is a hollow tube, albeit with a larger relative diameter than that of the inlet member 22, having threads 30 about its interior which are adapted for fluid-tight engagement with threads 28. When threadably engaged, the tubular inlet and outlet members 22 and 24 define the passageway 14 which is the principal fluid conveyance channel through the drain control valve 10. Secured about the periphery of the inlet and outlet members 22 and 24 is the cup member 26. The cup member 26 includes an upper cylindrical portion 32 and a lower cylindrical portion 34, of relatively smaller diameter, joined together by an integral, conical intermediate portion 36. The lower cylindrical portion 34 of the cup member 26 is placed in fluid-tight engagement with the outlet member 24 by sliding the close-fitting outlet member into the lower cylindrical portion thereby snugly contacting the exterior surface of the outlet member with the interior surface of the lower cylindrical portion. An inwardly directed flange 38, provided in the cup member 26 at the junction between the conical intermediate portion 36 and lower cylindrical portion 34, supplies a stop to the continued axial movement of the outlet member 24 into the lower cylindrical portion when such are being engaged.
The inlet member 22 includes a plurality of laterally-spaced, peripheral ridges 40 at its upper end provided principally for gripping a resilient drain hose so as to connect the valve 10 to a fluid source such as a clothes washing machine for use. A peripheral flange 42 is disposed adjacent the lowermost one of the ridges 40 and extends outwardly beyond such so as to provide a stop capable of exactly positioning the drain hose upon the inlet member 22.
Positioned between the peripheral flange 42 and the threads 28 is a bore 44 which traverses a side wall of the inlet member 22, intersecting the passageway 14 and providing fluid communication therebetween. With reference to FIG. 2, however, it may be seen that the bore 44 is initially fully obstructed by an integrally formed knock-out plug 46. The bore 44, then, is first opened by the application of an external force to the plug 46 sufficient to detach the plug 46 from the inlet member 22 and discharge the plug 46 from the bore 44. After removal of the plug 46, a tubular tap 48 is secured within bore 44 so that the external end portion of the tap 48 is in fluid communication with the passageway 14.
An aperture 18, positioned within a side wall of the outlet member 24, interconnects the passageway 14 with the atmosphere. The aperture 18 is provided with a lower section 50 and an upper section 52, in fluid communication therewith, having a relatively smaller diameter. As shown, the aperture 18 is positioned substantially parallel to the passageway 14, and has a single entrance at each of its opposed ends. A lower entrance 54, in an upwardly sloping and conically-shaped wall 56 extending from the threads 30 to the bottom of the outlet member 24, provides direct access to the lower section 50. An upper entrance 58, on the other hand, in the top of the outlet member 24, provides direct access to the upper section 52.
A longitudinally-movable ball valve element 20, having a diameter somewhat greater than that provided to the upper section 52, is positioned within the lower section 50. In applications where the valve 10 is utilized in controlling the flow of liquids, the ball valve element 20 is preferably formed of a material having a density somewhat less than that of a liquid so that such may float thereon. (When water is the liquid being controlled, neoprene has been found to be a suitable material for forming element 20.) Thus, a valve seat 60 is formed at the junction of the lower and upper sections 50 and 52. An integral projection 62 partially traverses the lower entrance 54 to maintain ball valve element 20 within the lower section 50. Thus, the movement of the ball valve element 20 within the lower section 50 is limited by the projection 62 when the aperture 18 is open for fluid flow and by the valve seat 60 when the aperture 18 is in a closed position due to pressure build-up within the passageway 14.
With continuing reference to FIG. 1, it may be seen that portions of the cup member 26 project upwardly from the outlet member 24 to a predetermined height above the outlet member and that the upper entrance 58 is at an elevation lower than that of the top of the cup member 26. Thus, small amounts of liquid which inadvertently leak past the valve seat 60 under conditions of excessive fluid pressure in the passageway 14 will be collected within the open space formed within the cup member 26 and will not spill onto a floor or other surface. When the conditions of excessive pressure within the passageway 14 are relieved, the collected liquid will drain under the force of gravity through the aperture 18 and into the passageway 14 for ultimate disposal.
Fixed substantially within the passageway 14 of the valve body 12 is an elastomeric valve member 16. The elastomeric valve member may be formed of any suitable elastomeric material such as natural or synthetic rubber or any appropriate type of plastic. In this regard, ethylene-propylene terpolymer, more commonly known as EPT rubber, may be advantageous. EPT rubber has the desirable characteristics of being resistant to degradation by: ozone, hot water, detergent and bleach. Further, EPT rubber is resistant to compression set and retains its flexibility after long periods of exposure to either high or low temperatures. EPT rubber thus imparts several ideal qualities to the elastomeric valve member 16 which, in one of its foreseeable uses involving clothes washing machines, would be exposed to hot and cold detergent solutions while being under varying degrees of physical deformation.
The elastomeric valve member 16 is molded or otherwise manufactured to have a tubular form of substantially constant diameter and wall thickness throughout its length. Preferably, the outer diameter of the elastomeric valve member 16 is not larger than the inner diameter of the inlet member 22 so that the collapse of the elastomeric valve member, under conditions of back-pressure in the passageway 14, will not be encumbered. As illustrated, the upper end of the elastomeric valve member 16 is fixed to the upper end of the inlet member 22 by having a portion thereof turned back as indicated at 64 over the upper end of the inlet member 22 so that such turned back portion will engage at least one of the plurality of peripheral ridges 40. Thus, when a drain hose 66 is fitted onto the upper end of the inlet member 22, as is shown in FIG. 3, the inner wall of the drain hose 66 will press against the turned back portion 64 of the elastomeric valve member 16 and compress it into at least one of the peripheral ridges 40 thereby forming a water-tight seal between the upper end of the elastomeric valve member 16 and the valve body 12.
A ring 68 is secured to the lower, free end of the elastomeric valve member 16 for keeping the free end of the elastomeric valve member open and retaining the elastomeric valve member in slight tension. As may seen in FIG. 1, the ring 68 is secured in place by turning back a portion of the elastomeric valve member 16, as indicated at 70, over the ring 68 so that such turned back portion 70 will engage the peripheral surface of the ring 68 and completely isolate such from potential contact with fluids passing through the drain control valve 10. As shown, the ring 68 comprises a pipe nipple, formed from a corrosion-resistant material such as brass, having threads 72 about its external periphery which assist in retaining the turned back portion 70 in position. As an alternative to the threads 72, ribs or serrations may be applied to the peripheral surface of the ring. Preferably, the ring 68 has an outer diameter greater than that of the inner diameter of the inlet member 22 so as to prevent the complete passage of the ring 68 and elastomeric valve member 16 through the passageway 14 under extreme back-pressure conditions. Further, the preferred ring 68 has an inner diameter sufficient to receive the elastomeric valve member 16 without substantially restricting the cross-sectional area available for fluid flow through the elastomeric valve member.
The mass of the ring 68 may be varied at installation in response to differences in the thickness and composition of the material comprising the elastomeric valve member 16. Generally, however, a mass which is too great would stretch the elastomeric valve member 16, creating considerable stress in the material throughout the stretched area, so that the elastomeric valve member would strongly resist being collapsed or closed by fluid in a back-pressure condition. On the other hand, insufficient mass may undesirably permit portions of the elastomeric valve member 16 to be expelled from the top of the inlet member 22 of the valve body 12 in a back-pressure condition. Thus, in determining an appropriate mass for the ring 68, the physical characteristics of the elastomeric valve member 16 as well as the intended environment of use must be taken into account.
Referring now to FIGS. 3 and 4, the installation of the drain control valve 10 upon a stand-pipe 74 of a fluid drainage system is illustrated. As may be seen, a rubber sleeve 76 is fitted about both the stand-pipe 74 and the outlet member 24. Secured about the sleeve 76, proximate each of its ends, are a pair of hose clamps 78 of well known construction for providing a fluid-tight seal between the drain control valve 10 and the stand-pipe 74. The upper end of the inlet member 22 is connected, in a fluid-tight relationship, with the drain hose 66 so that liquid can be passed through the drain hose 66, elastomeric valve member 16, and stand-pipe 74 into the usual drainage system (not shown) of an associated building structure.
The drain control valve 10 is operatively connected to a pressure sensitive control unit 80. The pressure sensitive control unit 80 can be any apparatus which is known in the art, such as that disclosed in U.S. Pat. Nos. 3,091,111 and 3,133,917 hereby incorporated by reference for all purposes. Preferably, however, the control unit 80 is provided with a housing 82 and an electrical control circuit 84 positioned within the housing. The pressure sensitive control unit 80 may be provided with an internal source of electrical current such as a 9-volt battery 86. Alternatively, electrical current may be supplied to the control circuit 84 of the control unit 80 via a well-known 110-volt transformer and power cord arrangement (not shown).
Pressure sensitive control unit 80 includes a pressure responsive electric switch 88 having a diaphragm 90 which may be slightly deformed to actuate the switch 88 in response to changes in fluid pressure within the drain control valve 10. Fluid pressure changes may be transmitted to the diaphragm 90 through any suitable means including a conduit 92 having its opposed ends in fluid communication with both the tubular tap 48 and an inlet tube 94 mounted on the housing 82 which, itself, is in fluid communication with the diaphragm 90. When fluid pressure within the inlet tube 94 exceeds a predetermined level, the pair of normally open electrical contacts comprising the switch 88 are placed into electrical contact with one another. Electric alarm units, such as a light 96 and a buzzer 98 may be connected in series with the switch 88 so that upon fluid pressure exceeding a predetermined limit a visual or audible alarm is activated by the closing of the contacts to alert a user of the event.
If a blockage in the drainage system induces a back-flow situation in stand pipe 74, the valve 10 will function to prevent the back flow of contaminated fluids from the outlet member 24 toward the inlet member 22 thereof. Where there tends to be a backward flow, that is, from bottom to top as viewed in FIG. 3, the pressure on the outside of the elastomeric valve member 16 tends to collapse the tubular wall thereof and snugly press its opposite sides together along a substantially planar surface thereby closing the member 16 to fluid flow. Simultaneously, the back-flow of fluid into the aperture 18 presses the ball valve element 20 into the valve seat 60 thereby sealing the aperture 18. If the back-flow condition creates a significant rise in pressure in the conduit 92, the pressure sensitive control unit 80 may sound an alarm. This is, in essence, the condition shown in FIG. 3.
When, however, there is pressure upstream of the valve 10, that is, there is to be flow through the valve from top to bottom, the upstream pressure causes the elastomeric valve member 16 to return to an open condition as shown in FIG. 1. It is to be noted that the elastomeric valve member 16, when open, provides a substantially straight passage to the flow of fluid therethrough without friction-inducing impedances caused by projections into the fluid flow path. In addition to the open elastomeric valve member 16, however, open aperture 18 maintains atmospheric pressure within the passageway 14 and stand pipe 74 when substantial pressure is not present in same so as to prevent a suction from being created across the valve 10. Thus, the aperture 18, prevents the siphoning of fluid through the drain control valve 10.
Although the valve 10 may be mounted in essentially any orientation, a vertical position is preferred. A vertical position permits the elastomeric valve member 20 to be suspended in the center of the passageway 14 without, otherwise, partially collapsing under the influence of gravity and increasing drag forces associated with fluid flow through the valve.
Although operation of the drain valve of the instant invention was described with reference to the embodiment of FIGS. 1-3, it is to be understood that the embodiment of FIG. 5, described fully hereinbelow, functions in essentially the same manner in preventing the back-flow of fluid therethrough.
Referring now to FIG. 5, another embodiment of the drain control valve is depicted for use in conjunction with a side wall outlet box 100. As such a box has been fully described in my U.S. Pat. No. 4,069,837, hereby incorporated by reference for all purposes, a detailed description will not be provided herein. Nevertheless, FIG. 5 shows that the bottom of the side wall outlet box 100 is provided with a downwardly extending cup member 102 into which the drain control valve 104 may positioned. The cup member 102 allows water dripping from faucets (not shown) positioned within the box 100 to be collected therein and disposed into the stand-pipe 106 through the valve 104. The cup member 102 is provided with a tubular extension 108, adapted for connection with the top of the stand-pipe 106 and for supporting the valve 104.
Fixed within the tubular extension 108 of the cup member 102, and in fluid-tight engagement therewith, is an adaptor socket 110 for threadably receiving the drain control valve 104. The adaptor socket 110 includes an outwardly-extending peripheral flange 112 about its top for limiting the downward movement of the adaptor socket into the tubular extension 108 upon association of the two elements. Preferably, the adaptor socket 110 also includes a peripheral groove 114 about its top for the flush receipt and similar support of an outwardly-extending peripheral flange 116 from the valve 104. Also, provided about the interior surface of the adaptor socket 110 are threads 118 for engagement with the drain control valve 104.
The drain control valve 104 includes a body indicated generally at 120 having a central, axially-extending passageway 122 within which is disposed an elastomeric valve member 124 adapted for preventing the back-flow of fluids through the passageway 122. A secondary passageway or aperture 126, in the body 120, having a ball valve element 128 disposed therein interconnects the passageway 122 with the atmosphere and acts as an anti-siphon feature. Thus, it is to be understood that the drain control valve 104 checks the unintended flow of fluid through the passageway in both directions.
The preferred valve body 120 is of three-part construction and comprises: inlet member 130, outlet member 132, and threaded adaptor sleeve 134. As may be seen, the inlet member 130 is a hollow tube having, at its lower end, threads 136 about the exterior thereof. Likewise, the outlet member 132 is a hollow tube, albeit with a larger relative diameter than that of the inlet member 130, having threads 138 about its interior which are adapted for fluid-tight engagement with threads 136. When threadably engaged, the tubular inlet and outlet members 130 and 132 define the passageway 122 which is the principal fluid conveyance channel through the valve 104. Secured in fluid-tight engagement to the periphery of the outlet member 132 is the threaded adaptor sleeve 134 for threaded engagement with the adaptor socket 110 fixed within the cup member 102.
Like the adaptor socket 110, the threaded adaptor sleeve 134 includes both a peripheral flange 116 and a laterally-disposed peripheral groove 140 about its top. The peripheral flange 116 is adapted for flush engagement with the peripheral groove 114 of the adaptor socket 110. The peripheral groove 140, on the other hand, is provided to closely receive a peripheral flange 142 extending outwardly from the top of the outlet member 132. Threads 144 about the exterior periphery of the adaptor sleeve 134 permit threaded engagement with the threads 118 of the adaptor socket 110 for fluid-tight attachment of the valve 104 to the cup member 102.
The inlet member 130 includes a plurality of laterally-spaced, peripheral ridges 146 at its upper end for securely gripping a resilient drain hose 148. A peripheral flange 150 is disposed adjacent the lowermost one of the ridges 146 and extends outwardly beyond such so as to provide a stop capable of exactly positioning the drain hose 148 upon the inlet member 130. Positioned between the peripheral flange 150 and the threads 136 is a bore 152 which traverses a side wall of the inlet member 130, intersecting the passageway 122 and providing fluid communication therebetween. A tubular tap 154 is secured within bore 152 so that the external end portion of the tap 152 is in fluid communication with the passageway 122.
An aperture 126, positioned within a side wall of the outlet member 132, interconnects the passageway 122 with the atmosphere. The aperture 126 is provided with an upper section 156 and an lower section 158, in fluid communication therewith, having a relatively smaller diameter. As shown, the aperture 126 is positioned substantially parallel to the passageway 122, and has a single entrance at each of its opposed ends. A lower entrance 160, in an upwardly sloping and conically-shaped wall 162 extending from the threads 138 to the bottom of the outlet member 132, provides direct access to the lower section 158. An upper entrance 164, on the other hand, in the top of the outlet member 132, provides direct access to the upper section 156.
A longitudinally movable ball valve element 128, having a diameter somewhat greater than that provided to the upper section 156, is positioned within the lower section 158. Thus, a valve seat 166 is formed at the junction of the upper and lower sections 156 and 158. An integral projection 168 partially traverses the lower entrance 160 to maintain ball valve element 128 within the lower section 158. Thus, the movement of the ball valve element 128 within the lower section 158 is limited by the projection 168 when the aperture 126 is open for fluid flow and by the valve seat 166 when the aperture 126 is in a closed position due to pressure build-up within the passageway 122.
With continuing reference to FIG. 5, it may be seen that portions of the cup member 102 of the side wall outlet box 100 project above the outlet member 132 to a predetermined height and that the aperture entrance 164 is at an elevation lower than that of the top of the cup member 102. Thus, small amounts of liquid which inadvertently leak around the valve seat 166 under conditions of excessive fluid pressure in the passageway 122 will be collected within the open space formed within the cup member 102 and will not spill onto a floor or other surface. When the conditions of excessive pressure within the passageway 122 are relieved, the collected liquid will drain under the force of gravity through the aperture 126 and into the passageway 122 for ultimate disposal.
Fixed substantially within the central, axially-extending passageway 122 of the valve body 120 is an elastomeric valve member 124. The elastomeric valve member 124 may be formed of any suitable elastomeric material such as natural or synthetic rubber or any appropriate type of plastic. The elastomeric valve member 124 is molded or otherwise manufactured to have a tubular form of substantially constant diameter and wall thickness throughout its length. Preferably, the outer diameter of the elastomeric valve member 124 is not larger than the inner diameter of the inlet member 130 so that the collapse of the elastomeric valve member, under conditions of back-pressure in the passageway 122, will not be encumbered. As illustrated, the upper end of the elastomeric valve member 124 is fixed to the upper end of the inlet member 130 by having a portion thereof turned back as indicated at 170 over the upper end of the inlet member 130 so that such turned back portion will engage at least one of the plurality of peripheral ridges 146. Thus, the inner wall of the drain hose 148 will press against the turned back portion 170 of the elastomeric valve member 124 and compress it into at least one of the peripheral ridges 146, thereby forming a water-tight seal between the upper end of the elastomeric valve member 124 and the valve body 120.
A ring 172 is secured to the lower, free end of the elastomeric valve member 124 for retaining such in an open configuration and under slight tension. The ring 172 is secured in place by turning back a portion of the elastomeric valve member, as indicated at 174, over the ring 172 so that such turned back portion 174 will engage the peripheral surface of the ring 172 and fully isolate such from potential contact with fluids passing through the valve 104. As shown, the ring 172 comprises a pipe nipple, formed from a corrosion-resistant material such as brass, having threads 176 about its external periphery. Preferably, the ring 172 has an outer diameter greater than that of the inner diameter of the inlet member 130 so as to prevent the complete passage of the ring 172 and the elastomeric valve member 124 through the passageway 122 under extreme back-pressure conditions. Further, the preferred ring 172 has an inner diameter sufficient to receive the elastomeric valve member 124 without substantially restricting the cross-sectional area available for fluid flow through the elastomeric valve member.
Preferably, the valve body of each embodiment of the invention is made of polyvinyl chloride (PVC) or similar plastic material but may be made wholly of metal or ceramic to suit user needs. PVC, because of its great durability and resistance to detergent solutions, is ideal for applications wherein the invention is used with clothes washing machines. Of course, to firmly secure the various elements comprising each of the valve bodies together in watertight fashion, a suitable adhesive cement may be employed at the joints therebetween.
While the above-described valve embodiments are especially adapted for use with machines such as clothes washers, dish washers and the like, it is believed that such are also well suited for use in other environments. For instance, such valves may be of particular utility in an oilfield or industrial settings as a check valve capable of alerting users of excessive back-pressure in flowlines carrying liquid chemical compositions. Additionally, with the provision of a suitable electrical control circuit, the instant valves may be of use in the computer-controlled "smart" homes now being developed wherein a back-pressure situation in a drain line may be responded to by a preprogrammed digital device. Further, as described hereinbelow, the inventive valves may be used in the distribution of water through an irrigation system.
Referring to FIG. 6, a building structure 178 containing a clothes washing machine 180 is piped to utilize the waste or "grey" water generated by the clothes washing machine for lawn and garden irrigation purposes. By utilizing such a system, the grey water may be advantageously employed and need not be flushed into a municipal sewage system for costly treatment and disposal. As shown, the washing machine 180 is provided with inlets 182 and 184 from which it receives hot and cold water, respectively, for washing purposes. After use within the washing machine 180, the grey water discharged therefrom, which contains relatively small amounts of soap or detergent residues, is conveyed through the drain hose 186 into the drain control valve 10 (shown by way of example only as any of the valve embodiments of the instant invention may be employed herein) secured atop the stand-pipe 188. A conduit 190, in fluid communication with the stand-pipe 188, passes through the building wall to the outdoors and there is connected to a manifold 192 which, in turn, supplies grey water to a plurality of feeder hoses 194. Although a plurality of feeder hoses 194 are shown, it should be apparent that their number may be varied from a great multiplicity down to a single hose 194 according to grey water supply volumes, surrounding terrain, and user needs.
Grey water may be distributed to the ground surface from a sprinkler 196 at the remote terminus of each feeder hose 194 or along the length thereof through perforations as at 198 if the hose terminus is plugged for a more even distribution of the grey water. Of course, the perforations 198 may be either individually formed in an otherwise impermeable hose material or formed "in mass" in the manner associated with well-known soaker hoses.
Additional water volumes may be delivered to the manifold 192 from a spigot 200 in fluid communication with a municipal water source (not shown) for flushing the feeder hoses 194 and soaking the irrigated ground surface. Preferably, an ordinary garden hose 202 is used to place the spigot 200 and manifold 192 in fluid communication with one another. To prevent grey water from inadvertently entering the garden hose 202 and upstream municipal water supply, back-flow prevention means are provided within the manifold 192.
With reference to FIG. 7, an elastomeric valve member 204 can be seen secured within the manifold 192 for preventing the back-flow of fluids into the hose 202. The elastomeric valve member 204 may be formed of any suitable elastomeric material such as natural or synthetic rubber or any appropriate type of plastic. The elastomeric valve member 204 is preferably molded or otherwise manufactured to have a tubular form of substantially constant diameter and wall thickness throughout its length which may be any suitable fraction of the manifold length. Regardless of length, the outer diameter of the elastomeric valve member 204 is, preferably, sufficiently smaller than the inner diameter of the manifold 192 so that the flow of grey water from the manifold into the feeder hoses 194 will not be significantly impeded by the presence of the elastomeric valve member 204 within the manifold.
As illustrated, the elastomeric valve member 204 is joined to the inwardly projecting, threaded portion 206 of the female hose fitting 208 by a suitably sized locking ring 210. The free end of the elastomeric valve member 204 is provided with a ring 212 for retaining such in an open configuration and preventing movement of the free end of the elastomeric valve member 204 into the hose fitting 208 under back-flow conditions. The ring 212 is secured in place by turning back a portion of the elastomeric valve member 204, as indicated at 214, over the ring 212 so that such turned back portion 214 will engage the peripheral surface of the ring 212 and completely isolate such from contact with grey water passing through the manifold 192. As shown, the ring 212 comprises a pipe nipple, formed from a corrosion-resistant material such as brass, having threads 216 about its external periphery. Preferably, the ring 212 has an outer diameter greater than that of the inner diameter of the threaded portion 206 so as to prevent the passage of the ring 212 and the elastomeric valve member 204 through the female hose fitting 208 under back-pressure conditions. Further, the preferred ring 212 has an inner diameter sufficient to receive the elastomeric valve member 204 without substantially restricting the cross-sectional area available for water flow through the elastomeric valve member 204.
The mass of the ring 212 may be varied at installation in response to differences in the thickness and composition of the material comprising the elastomeric valve member 204 as well as conditions of use. As the manifold 192 would normally be installed with its longitudinal axis parallel to the ground surface, stretching of the elastomeric valve member 204 and the internal stresses caused thereby would ordinarily be minimal and not a problem. However, the preferred mass would, under conditions of normal fluid flow through the manifold 192, act as a sinker to retain the free end of the elastomeric valve member 204 at the bottom of the manifold and, simultaneously, space the valve member 204 from the manifold outlets 218 positioned in the sides thereof.
From the foregoing description, it will be apparent that there is provided by the present invention a drain control valve, which, when installed in a fluid carrying conduit, will function to prevent the back-flow of fluid therethrough. This operation is continuous and automatic at all times that the drain control valve is installed. Even if the drain control valve should fail because of a rupture or deterioration of the elastomeric valve member, the valve will continue to alert the user to a back-pressure situation through the activation of the pressure sensitive control unit. Of course, when fluid is passing through the drain control valve in a desired direction, the elastomeric valve member will remain open and not impede in any way the flow of fluid therethrough.
While the invention has been described with a high degree of particularity, it will be appreciated by those skilled in the art that numerous modifications and substitutions may be made to the valve bodies of the several embodiments of the invention. For example, the valve bodies may be integrally formed rather than assembled from a plurality of separate components. Therefore, it is to be understood that the present invention is not limited to the embodiments described above, but encompasses any and all embodiments within the scope of the following claims. | A valve for permitting fluid flow in a first desired direction and preventing fluid flow in a reverse direction. The valve includes a valve body having a rigid wall defining inlet and outlet openings at opposite ends thereof and a main flow passageway between the inlet and outlet openings. Secured to the rigid wall, so as to receive fluid entering the passageway through the inlet opening, is a tubular valve member of elastomeric material having upstream and downstream ends in fluid communication with one another. The tubular valve member is normally open to fluid flow but is yieldingly collapsible in response to downstream pressure increases to prevent fluid from passing therethrough. A ring is secured about the tubular valve member and is dimensioned to prevent the passage of the downstream end through the inlet opening in the event of a downstream pressure increase. The drain control valve may be employed in conjunction with a novel manifold for irrigation purposes. | 3 |
BACKGROUND OF THE INVENTION
[0001] This invention relates generally to a magnetic sensing probe assembly and method for detecting and marking the location of an implanted medical device. Particularly, this invention relates to a magnetic sensing probe assembly and method for locating the source of a magnetic field emitted from an implanted medical device. The assembly and method provide for easily and conveniently locating the magnetic source in an implanted medical device and marking its location for purposes of conducting a medical procedure.
[0002] Related art devices have been found to be difficult to operate because of their physical dimensions, because they require sensory adjustments for various conditions or procedures, and/or because of their mechanical or antiquated design. The present invention overcomes the problems with the prior art and provides a convenient probe assembly for a user, for example a medical technician, practitioner, or physician, to precisely locate a magnetic material incorporated into or a magnetic field emanating from an implanted medical device and to physically mark the location of the magnetic material or field with a nonpermanent agent. Both the sensing and marking mechanisms are incorporated into the assembly.
[0003] It is an object of this invention to provide a sensing probe assembly constructed and arranged to locate magnetic material incorporated into or a magnetic field from a medical device or its components. Another object of the invention is to provide an improved sensing probe assembly which is accurate and easy to use. Another object of the invention is to incorporate a marking mechanism into the assembly so that the location of the magnetic material or field can be conveniently, physically, and nonpermanently marked. Yet another object of this invention is to provide a medical device which is compact, reliable, and economical.
SUMMARY OF THE INVENTION
[0004] This invention relates to a magnetic sensing probe assembly and method for detecting and locating an implanted medical device. The present invention is easily held in and controlled by one hand. The assembly comprises an elongated housing containing a light source or diode, a power source, a magnetic switch and a circuit for electrical connection between the light source and the magnetic switch. The housing has opposing ends, namely, a light end and a tip end.
[0005] The assembly of the present invention further has a marking means located on the tip end of the housing to mark the location of a source of a magnetic field on the tissue of a patient once the magnetic field has been detected. The magnetic source is accurately located by moving the magnetic sensing probe assembly across the area containing the medical device to establish two pairs of points above the source. The points are detected as locations where the light source illuminates as the magnetic switch detects a magnetic field. The points are marked by depressing the marking means on the patient's skin or tissue. The intersection of the line segments connecting the two pairs of points provides the precise location of the magnetic material or the magnetic field. This method can be used to locate a component of a medical device spatially aligned with the magnetic material or source, so that a medical procedure can then be performed on the medical device.
[0006] The present invention provides an assembly and method for using a magnetic sensing probe in an easy, quick, reliable and convenient manner to locate a source of a magnetic field and to mark its location, thereby marking the location of an implanted medical device, for example. Particularly the sensing probe assembly may be utilized to non-invasively locate an injection port of a tissue expander or implanted inflatable device to thereby permit the device to be filled with fluid.
[0007] These and other benefits of this invention will become clear from the following description by reference to the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] [0008]FIG. 1 is a lateral cross-sectional view of the probe housing of the magnetic sensing probe assembly of the invention;
[0009] [0009]FIG. 2 is a lateral view of the magnetic sensing probe assembly being used to locate an implanted medical device;
[0010] [0010]FIG. 3 is a lateral view of a marking cover having a circular marking tip;
[0011] [0011]FIG. 4 is a bottom end view of the marking cover of FIG. 3;
[0012] [0012]FIG. 5 is a lateral view of a marking cover having a square marking tip;
[0013] [0013]FIG. 6 is a bottom end view of the marking cover of FIG. 5;
[0014] [0014]FIG. 7 is a lateral view of a marking cover having a triangular marking tip;
[0015] [0015]FIG. 8 is a bottom end view of the marking cover of FIG. 7;
[0016] [0016]FIG. 9 is a perspective view of the magnetic sensing probe assembly of the present invention;
[0017] [0017]FIG. 10 is a perspective view of the magnetic sensing probe assembly of the present invention showing the assembly in a disassembled state;
[0018] [0018]FIG. 11 is a perspective view of the magnetic sensing probe assembly in use with a magnetic implant port assembly;
[0019] [0019]FIG. 12 is a plan view showing the probe housing of the sensing probe assembly;
[0020] [0020]FIG. 13 is a plan view showing the marking cover of the sensing probe assembly;
[0021] [0021]FIG. 14 is an end plan view of the marking cover of FIG. 13; and
[0022] [0022]FIG. 15 shows the coordinate system used to locate an implanted medical device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0023] The present invention relates to a magnetic sensing probe assembly and method which is useful for medical technicians, practitioners and physicians to locate and mark the source of a magnetic field which is incorporated into a medical device, for example. The invention provides for the quick, convenient and reliable marking of an implanted device in a non-invasive manner.
[0024] [0024]FIG. 1 shows a lateral cross-sectional view of the magnetic sensing probe assembly 10 having an elongated housing 11 that encapsulates a magnetic switch 18 , a light source or light-emitting diode (LED) 15 , and a circuit for electrical connection between the magnetic switch 18 and LED 15 . For example, the electrical circuit structure disclosed in U.S. Pat. No. 4,296,376 may be used to interconnect magnetic switch 18 and LED 15 . Other circuits may also be used in accordance with the teachings of the present invention. The housing 11 has an elongated shape so that it may be conveniently held in one hand like a pencil and is preferably made of a nonmagnetic material. The housing 11 has a tip end 12 encapsulating the magnetic switch 18 and a light end 13 encapsulating the light-emitting LED 15 , as shown in FIG. 12. The light end 13 of the housing 11 surrounding the LED 15 is transparent so that a user can clearly see when the diode or light source is illuminated. Optimally, the housing end 13 may be of a colored, transparent or translucent material, such as a polycarbonate or the like.
[0025] As shown in FIG. 2, the magnetic sensing probe assembly 10 enables a user to detect and physically mark the precise location of a magnetic material incorporated into an implant port 21 of an implanted medical device 20 , for example. The magnetic sensing probe assembly 10 includes a marking cover structure 16 for marking the magnetic location on the skin or tissue 22 of a patient. The marking cover 16 , further shown in FIGS. 13 and 14, is generally tubular in configuration and is constructed and arranged to fit over and hold onto the tip end 12 of the housing 11 encapsulating the magnetic switch 18 . The marking cover 16 is preferably made of any nonmagnetic material, such as an acetal homo-polymer composition or the like. The cover structure 16 has a marking tip 17 for physically marking the location of the magnetic implant port 21 . The marking tip 17 is constructed so that it is held on the tip end 12 of the housing 11 , and so that it can be depressed upon a patient's skin or tissue 22 to leave a nonpermanent physical mark thereon. The marking tip 17 is shown to have a peripheral indented portion which defines a geometric shape. While the marking tip may be of any shape or dimension, as shown in FIGS. 3 - 8 , the cover tip is shown to have a geometric shape such as a circle 24 , a square 26 , or a triangle 28 which are shown on covers 23 , 25 and 27 , respectively. The physical mark may be created by the tip or by a marking agent, such as nonpermanent ink, that coats the marking tip 17 before it is pressed upon the patient. The marking cover 16 can be removed and reattached to the housing 11 as desired by the user or it may be permanently affixed to or incorporated into the housing 11 . Both the housing 11 and marking cover 16 are of a material, as discussed above, which can be sterilized as required before using the sensing probe assembly 10 in a medical procedure.
[0026] [0026]FIG. 9 shows a perspective view of the magnetic sensing probe assembly 10 , having light end 13 , housing 11 and marking cover 16 with marking tip 17 . FIG. 10 shows the marking cover 16 with marking tip 17 removed from magnetic sensing probe assembly 10 , thereby showing the tip end 12 of housing 11 . FIG. 11 shows the magnetic sensing probe assembly 10 in use with a magnetic implant port 21 . Housing 11 is shown having light end 13 which illuminates when a magnetic material or field is sensed. Marking cover 16 with marking tip 17 can then be used to mark the location of the magnetic material.
[0027] An advantage of this invention is that a user can use the magnetic sensing probe assembly 10 with one hand to easily and quickly locate the precise location of the magnetic material or field. A medical device or component spatially aligned with the magnetic material, for example, an implant port may be located in a non-invasive manner. The location procedure is accomplished by using the assembly to detect and mark the periphery of the associated magnetic field, since both the sensing and the marking mechanisms are incorporated into a single, convenient design.
[0028] The method of the present invention uses the magnetic sensing probe assembly 10 to mark a coordinate system 30 on a patent's skin or tissue, as shown in FIG. 15. The probe assembly is scanned or moved across an area of the patient's skin or tissue under which the medical device is implanted. The magnetic material incorporated into the medical device produces a magnetic field which is detectable outside the patient's body. The magnetic switch activates and causes the light tip of the probe assembly to illuminate when it senses a magnetic field. When scanning the probe assembly across the area of skin the magnetic switch will activate when it senses a magnetic field and cause the light tip to illuminate, and will deactivate when it no longer senses the field, causing the light tip to darken. One sweep across the area will establish one point 36 where the light tip illuminates and another point 37 where the light tip illuminates. The marking tip can mark these two points 36 and 37 which establish a horizontal line segment 32 . Upon sweeping the probe assembly perpendicular to the horizontal line segment 32 two more points 34 and 35 will become apparent where the light tip illuminates due to the magnetic switch sensing the magnetic field. These points 34 and 35 can be marked and establish vertical line segment 31 . The intersection 33 of these two line segments 31 and 32 can also be marked and represents the location of the implanted medical device which is spatially aligned with a magnetic material or field. This location is where the medical procedure can be performed. More than two line segments and four reference points may also be detected and marked.
[0029] As many changes are possible to the embodiments of this invention, utilizing the teachings thereof, the description above and the accompanying drawings should be interpreted in the illustrative and not the limited sense. | A sensing probe assembly and method for locating a magnetic field emitted by an implanted medical device. The assembly has a housing containing a magnetic field sensor circuit having an indicator light and a magnetic switch. The assembly further has a structure for marking the location of the magnetic field. The method utilizes a marking system whereby at least four points forming at least two perpendicularly intersecting line segments are located and marked above the magnetic field. The intersection is then used as a reference point for performing a medical procedure on the implanted medical device. | 0 |
FIELD OF THE INVENTION
The present invention relates to the field of ink jet inks and ink-jet printing. More specifically, the present invention describes water based ink-jet inks compositions, which contain metal nanoparticles and polymeric additives dispersed within the liquid vehicle comprising mainly water, and methods for the formation of stable, concentrated dispersions of metallic nanoparticles, and inks containing such dispersions. After printing a pattern on a substrate with the use of ink-jet printer, which is either DOD (drop on demand piezo or bubble), or continuous, a layer of the metal nanoparticles is formed. The thickness of the layer can be increased by printing the specific pattern several times, while drying the ink by means such as hot air, in between printing cycles. After the pattern is printed, the substrate with the printed pattern can be transferred into an oven, in which the nanoparticles can be sintered, thus forming a continuous metal pattern, namely, a conductive pattern. The invention also teaches methods to prepare concentrated, stable dispersions of metal particles, and also methods for the stabilization of metallic nanoparticles by various polymers, including conductive polymers. Using the present invention, decorative and conductive patterns can be obtained without the need for sintering at very high temperatures.
BACKGROUND OF THE INVENTION
Metallic nanoparticles are particles having a diameter in the submicron size range, and are either crystalline or amorphous materials. They are composed of pure metal, such as silver, gold, copper etc., or mixture of metals such as alloys, or core of copper covered by a shell of gold or silver.
Currently, nanoscale metal particles draw intense scientific and practical interest due to their unique properties, which differ from those of bulk and atomic species. The unique properties of metal nanoparticles result from their distinct electronic structure and from their the extremely large surface area and high percentage of surface atoms. Metal nanoparticles are characterized by enhanced reactivity of the surface atoms, high electric conductivity, and unique optical properties. Virtually, nanosized materials are well-known materials with novel properties and promising applications in electrochemistry, microelectronics, optical, electronic and magnetic devices and sensors as well as in new types of active and selective catalysts. Creation of stable concentrated nanocolloids of metals with low resistivity may offer new prospects in computer-defined direct-write noncontact technologies, such as ink-jet printing, for deposition of metallic structures on various substrates. Microfabrication of such structures by lithographic technique is a time-consuming and expensive process. Techniques based on expelling small droplets of molten metals onto substrate have met several problems, such as difficulty of adhering droplets onto a substrate, oxidation of the liquid metal, and the difficulty of fabrication a droplet-expulsion mechanism compatible with high temperatures.
Conventional ink-jet inks may contain two types of colored material, dye or pigment, and are characterized by their main liquid, which is the vehicle for the ink. The main liquid may be water (water-based inks), or an organic solvent (solvent-based inks).
The dye or pigment based inks differ with respect to the physical nature of the colored material. Pigment is a colored material that is insoluble in the liquid, while the dye is soluble in the liquid. Each system has drawbacks: pigments tend to aggregate, and therefore clog the nozzles in the orifice plate, or the narrow tubings in the printhead, thus preventing the jetting of the ink while printing. Dyes tend to dry, and form a crust on the orifice plate, thus causing failure in jetting and misdirection of jets.
It is clear that the term “dye” or “pigment” is a general wording for materials, which are soluble or insoluble, respectively, in the solvents comprising the ink. Therefore, metal nanoparticles may be considered, in this context, if introduced into an ink, as pigments of metal, having a size in the nanometer range.
Conventional pigments in ink-jet inks contain particles in the size range of 100-400 nm. In theory, reducing the particle size to 50 nm or less should show improved image quality and improved printhead reliability when compared to inks containing significantly larger particles.
The majority of inks in ink-jet printers are water-based inks. The use of metal nanoparticles as pigments requires the elaboration of ink formulations containing stable concentrated aqueous metal colloid. The synthesis of stable colloidal systems with high metal concentration is a serious problem. A variety of substances have been used to stabilize silver colloids: amphiphilic nonionic polymers and polyelectrolytes, ionic and nonionic surfactants, polyphosphates, nitrilotriacetate, 3-aminopropyltrimethoxysilane, and CS 2 . Stable water-soluble silver nanoparticles were also obtained by reduction of a silver ions in the presence of amino- and carboxilate-terminated poly(amido amine) dendrimers, and crown ethers. However, the preparations of stable silver colloids, described up to now in the literature, in procedures based on reduction of metal from solution, have low metal concentrations, which amount only to 10 −5 -10 −2 M (about 0.0005-0.1%) even in the presence of stabilizers (it is almost impossible to obtain a stable aqueous silver colloid with the metal concentrations higher then 10 −3 M without an additional stabilizer, due to immediate particle aggregation).
Since ink-jet ink compositions contain, in addition to dyes or pigments, other additives, such as humectants, bactericides and fungicides and binders (polymeric additives, which improve the dye or pigment binding to substrate), the stabilizers should be compatible with these substances and should not change noticeably the physicochemical and rheological characteristics of inks (the most important characteristics are viscosity and surface tension).
Several methods of the metallic image generation with the use of ink-jet technology have been described.
One known method is based on an ink containing a reducing agent and receiving material containing the reducible silver compound (AgNO 3 or silver di(2-ethylhexyl)-sulphosuccinate), and, on the contrary, an ink and a receiving support containing a silver compound and reducer, respectively. Heating the receiving support during or after the ink deposition resulted in an image formed by silver metal (U.S. Pat. No. 5,501,150 to Leenders, et al; U.S. Pat. No. 5,621,449 to Leenders, et al).
Another approach for the deposition of metal structures is based on ink-jet printing of organometallic precursors dissolved in organic solvent with subsequent conversion of the precursor to metal at elevated temperatures (˜300° C.). To increase the metal (silver) loading of ink and to obtain higher decomposition rates, silver or other metal nanoparticles may be added to the ink along with the organometallic precursor. Near-bulk conductivity of printed silver films has been achieved with such compositions (Vest, R. W.; Tweedell, E. P.; Buchanan, R. C. Int. J. Hybrid Microelectron. 1983, 6, 261; Teng, K. F.; Vest, R. W. IEEE Trans. Indust. Electron. 1988, 35, 407; Teng, K. F.; Vest, R. W. IEEE Electron. Device Lett. 1988, 9, 591, Curtis, C.; Rivkin, T.; Miedaner, A.; Alleman, J.; Perkins, J.; Smith, L.; Ginley, D. Proc. of the NCPV Program Review Meeting . Lakewood, Colo., USA, Oct. 14-17, 2001, p. 249).
Fuller et al. demonstrated ink-jet printing with the use of colloidal inks containing 5-7 nm particles of gold and silver in an organic solvent, α-terpineol, in order to build electrically and mechanically functional metallic structures. When sintered at 300° C., the resistivity of printed silver structures was found to be 3 μΩ·cm, about twice of that for bulk silver (Fuller, S. B.; Wilhelm, E. J.; Jacobson, J. M. J. Microelectromech. Syst. 2002, 11, 54).
SUMMARY OF THE INVENTION
The present invention provides compositions and methods for the preparation of water-based ink-jet inks, in which the pigments are nanoparticles of metal, and composition and methods for preparing stable, concentrated metallic nanoparticles dispersions. The ink composition of the present invention overcomes a common problem in pigment containing ink-jet inks, namely sedimentation, since the particle size is very small, below 100 nanometers, preferably in the range 20-60 nanometers, thus the sedimentation rate is very slow, and is hindered by the Brownian motion. Another aspect of the invention is that the stable dispersions of nanoparticles are prepared in the presence of suitable polymeric stabilizers, which prevent the particles from growing during the aggregation process, even if the nanoparticles are present at a high concentration in the liquid. The stabilizer is a water-soluble polymer or a surfactant, or a combination of the two. It was found that the best stabilizer is carboxymethyl cellulose sodium salt (CMC), low or medium viscosity grade. It was found that the CMC can also function as the binder in the ink-jet ink formulations, namely, as the component which provides the adhesion of the ink droplets onto the substrate, while the substrate can be made of various materials, such as plastics, paper, glass, etc. . . . CMC also allows for the modification of the viscosity of the ink for the viscosity range required for the ink-jet printing.
In another aspect of the invention, we found, surprisingly, that a conductive polymer, polypyrrole (PP), can be used as the stabilizing polymer, thus forming new, and previously unknown, metallic dispersions and inks. The use of π-electron conjugated polymers, in addition to their stabilizing and adhesive effects, is determined by their electric conductivity. Such polymers can serve as binder, providing for the formation of continuous electroconducting layers on the substrate surface after ink-jet printing.
In a different embodiment of the invention, in order to increase the conductivity of printed circuits without sintering at elevated temperature we also used a new approach, based on flocculation of the metallic particles, after printing. Using this approach, first the metallic dispersion is printed, followed by printing a second layer of aqueous solution of a flocculant. The flocculant causes aggregation of the metallic nanoparticles, after they have been printed, thus bringing them into close contact, and improving the possibility for obtaining electrical conductivity. We describe here the use of two flocculants, representing two classes of flocculation agents, but the process may be obtained with a large variety of flocculants. The flocculants used are either an electrolyte having high valency ions, or polymer whicj is has electrical charge opposite to that of the metallic nanoparticles, such as: aluminum sulfate, poly(diallyldimethylammonium chloride (PDAC) or a charged, water soluble conductive polymer. Addition of Al 2 (SO 4 ) 3 induces the compression of the electrical double layer around colloidal particles that leads to overcoming the energy barrier caused by repulsive forces. As a result, attractive Van der Waals forces pull the nanoparticles into contact following aggregation. It is generally accepted that polymeric flocculants act by adsorption and “bridging”, resulting in the formation of tough flocs of colloidal particles, such that a low-temperature “sintering”-like process takes place. Obviously, if the bridging polymer is conductive by itself, a better electrically conductive layer can be obtained.
The present invention focuses mainly on the formation and printing of silver nanoparticles by ink jet printers, but may include, as clear for those skilled in the art of nanoparticles, nanoparticles of metals other then silver, such as gold, copper, etc. . . . . In addition, it is clear that the metallic patterns can be used for decoration purposes, even if the resulting pattern is not electrically conductive. Another aspect of the invention is that the resulting pattern of the silver nanoparticles has an antimicrobial effect, due to the presence of silver nanoparticles, thus eliminating the need for antimicrobial agents which are often introduced into water based ink jet inks.
It should be mentioned that the nanoparticles, due to their very small size, will behave differently, when compared to large particles. For example, nanoparticles have a lower melting point than bulk metal, and a lower sintering temperature than that of bulk metal. This property is of particular importance when sintering is needed in order to obtain electrical conductivity.
Prior art search did not show any report on formation of water-based ink-jet ink, which contain silver nanoparticles. The only attempt to make a silver printed layer by direct ink-jet printing, as has been already mentioned, was performed with the use of gold and silver nanoparticles dispersed in a solvent, α-terpineol (Fuller, S. B.; Wilhelm, E. J.; Jacobson, J. M. J. Microelectromech. Syst. 2002, 11, 54). The benefits of using water based inks over solvent based inks are clear, to those familiar with the field of printing. Furthermore, there are no reports on the formation of stable, concentrated dispersions of metallic nanoparticles, and there are no reports on the formation and stabilization of metallic nanoparticles in presnce of conductive polymers.
The present invention relates to an ink jet composition for use in ink jet printing onto a substrate comprising a water-based dispersion comprised of metal nanoparticles and at least one stabilizer.
According to preferred embodiments of the present invention, the metal nanoparticles have a particle size below 100 nanometers. Preferably, the metal particles have a particle size between 20-60 nanometers.
Further according to preferred embodiments of the present invention, the water-based dispersion further comprises at least one of the group consisting of humectants, antimicrobial agents, surfactants, fungicides, and rheology modifiers.
Additionally according to preferred embodiments of the present invention, the stabilizer comprises a surfactant.
Still further according to preferred embodiments of the present invention, the stabilizer comprises a water-soluble polymer.
Moreover according to preferred embodiments of the present invention, the polymer is carboxymethyl cellulose sodium salt.
Further according to preferred embodiments of the present invention, the polymer is a conductive polymer.
Additionally according to preferred embodiments of the present invention, the polymer is polypyrrole.
Still further according to preferred embodiments of the present invention, the metal nanoparticles are of metal having high electric conductivity. The metal nanoparticles may be, for example, silver, gold, or copper nanoparticles.
Moreover according to preferred embodiments of the present invention, the composition comprises at least one wetting agent. Preferably, the wetting agent is selected from one or more of group consisting of BYK-154, BYK-348, Disperbyl-181, Disperbyk-184 and LABS.
Further according to preferred embodiments of the present invention, the substrate is glass, PVC, or paper. Other appropriate substrates could also be used.
The present invention also relates to method for obtaining a metallic decorative pattern, comprising ink jet printing the ink jet composition as described above onto a suitable substrate.
The present invention also relates to a method for obtaining a conductive pattern, comprising ink jet printing the ink jet composition as described above onto a suitable substrate.
Further according to preferred embodiments of the present invention, the method for obtaining a decorative or a conductive pattern also comprises repeating ink jet printing any number of times to form additional conductive layers on the substrate.
Additionally according to preferred embodiments of the present invention, the method further comprises printing a flocculant solution onto the substrate.
Still further according to preferred embodiments of the present invention, the method further comprises drying the substrate.
Moreover according to preferred embodiments of the present invention, the method further comprises heating the substrate in an oven to allow sintering.
Further according to preferred embodiments of the present invention, the method also comprises dipping at least a portion of the substrate into an electroless bath.
The present invention also relates to a method for ink jet printing onto a substrate comprising printing an ink containing a water based dispersion comprising metal nanoparticles and at least one stabilizer onto a substrate and printing a liquid containing a flocculant onto said substrate on top of said ink containing said water based dispersion.
According to preferred embodiments of the present invention, the flocculant comprises a conductive polymer. Preferably, the flocculant comprises aluminum sulfate. Alternatively, the flocculant comprises poly(diallyldimethylammonium chloride).
Further according to preferred embodiments of the present invention, the flocculant is in a solution in an amount of 0.01%.
The present invention also relates to a method for ink jet printing onto a substrate using an ink jet comprising printing an ink containing at least one flocculant onto a substrate, and printing an ink containing a water based dispersion comprising metal nanoparticles and at least one stabilizer onto said substrate on top of said ink containing said flocculant.
According to preferred embodiments of the present invention, the flocculant comprises a conductive polymer. Preferably, the flocculant comprises aluminum sulfate. Alternatively, the flocculant comprises poly(diallyldimethylammonium chloride).
Further according to preferred embodiments of the present invention, the flocculant is in a solution in an amount of 0.01%.
The present invention also relates to a method for the preparation of an ink jet composition for use in ink jet printing onto a substrate, said ink jet composition comprising a water based dispersion comprised of metal nanoparticles and at least one stabilizer, comprising reducing a metal salt in the presence of an appropriate reducing agent and a water-soluble polymer to obtain a metal colloid.
According to preferred embodiments of the present invention, the polymer is carboxymethyl cellulose sodium salt. Preferably, the carboxymethyl cellulose sodium salt is at a concentration of 0.2% by weight.
Further according to preferred embodiments of the present invention, the polymer is a conductive polymer. Preferably, the polymer is polypyrrole. More preferably, the polypyrrole is at a concentration of 0.03% by weight.
Still further according to preferred embodiments of the present invention, the metal nanoparticles are silver nanoparticles.
Additionally according to preferred embodiments of the present invention, the reducing agent is selected from the group consisting of sodium borohydride, trisodium citrate, hydrazine, ascorbic acid, ribose, and gaseous hydrogen. Other suitable reducing agents may be used, depending on the type of metal nanoparticles that are used.
Moreover according to preferred embodiments of the present invention, the method also comprises removing water so as to obtain highly concentrated metal nanoparticles. Preferably, said removing of water is accomplished through a method selected from the group consisting of lyophilization, treating in a vacuum oven, evaporating, and spray drying. Other suitable method may also be employed.
The present invention also relates to a composition comprising a water based dispersion of metal nanoparticles and at least one water soluble polymer.
According to preferred embodiments of the present invention, the metal nanoparticles have a particle size below 100 nanometers. Preferably, the metal particles have a particle size between 20-60 nanometers.
Further according to preferred embodiments of the present invention, the metal nanoparticles are silver nanoparticles.
Additionally according to preferred embodiments of the present invention, the polymer is carboxymethyl cellulose sodium salt.
Still further according to preferred embodiments of the present invention, the water soluble polymer is a conductive polymer. Preferably, the polymer is polypyrrole.
The present invention also relates to a method for obtaining a film having high electromagnetic radiation absorption capability, comprising printing or coating a water based dispersion of metal nanoparticles and at least one water soluble polymer onto a substrate. The film is useful for absorbing electromagnetic radiation such as that produced by radar for determining the location of airplanes, or for other applications as well.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph illustrating the effect of increasing Ag 0 concentration on colloidal silver particle size prepared in the absence of a stabilizer. Measurements were carried out one hour after preparation with the use of Dynamic Light Scattering.
FIG. 2 is a graph illustrating the average particle size of colloidal silver as a function of CMC concentration. Measurements were carried out with the use of Dynamic Light Scattering.
FIG. 3 is a graph illustrating the average particle size of colloidal silver as a function of PP concentration. Measurements were carried out with the use of Dynamic Light Scattering.
FIG. 4 is a graph illustrating the average size of CMC-stabilized Ag 0 nanoparticles as a function of Ag 0 concentration and time (by Dynamic Light Scattering).
FIG. 5 is a graph illustrating the average size of polypyrrole (PP)-stabilized Ag 0 nanoparticles as a function of Ag 0 concentration and time (by Dynamic Light Scattering). [PP]=0.03 wt %.
FIG. 6 is a graph illustrating the average particle size as a function of Ag 0 concentration in lyophilizing nanocolloid ([CMC]0=0.1 wt %) by Dynamic Light Scattering.
FIG. 7 is a graph illustrating the average size of redispersed Ag 0 nanoparticles as a function of Ag 0 concentration and time (by Dynamic Light Scattering).
FIG. 8 is a chart illustrating CCC of a flocculant (black bars represent Al2(SO4)3; open bars represent PDAC) as a function of polymeric stabilizer (CMC) concentration for a colloid with [Ag 0 ]=0.1 wt %.
FIG. 9 is a printed image formed with the use of Ag-containing ink-jet ink (Formulation 3) on inkjet transparency.
FIG. 10 is a SEM (Scanning Electron Microscopy) image of printed Ag-containing formulation on ink-jet transparency.
DETAILED DESCRIPTION OF THE INVENTION
1. Preparation of Silver Nanoparticles
Fine metal particles from micrometer to nanometer size can be synthesized by both physical methods (formation in gas phase, laser ablation) and chemical methods (sonochemical or photochemical reduction, electrochemical synthesis, chemical reduction), as are known in the art. The former methods provide fine metal particles by decreasing the size by applying energy to the bulk metal, while in the latter methods, fine particles are produced by increasing the size from metal atoms obtained by reduction of metal ions in solution.
In the present invention, the chemical method for the preparation of silver nanoparticles is preferably employed, namely, fine particles were produced by a proper silver nitrate reduction in aqueous solution with the use of a proper reducing agent according to the following scheme:
Silver nanoparticles can be prepared with the use of various reducing agents, such as sodium borohydride, trisodium citrate, hydrazine, ascorbic acid, ribose and gaseous hydrogen.
A number of samples with different concentrations were prepared.
Silver colloids with nanosized particles were prepared by reduction of AgNO 3 by trisodium citrate at various concentrations of reagents according to the procedure described by Lee and Meisel (Lee, P. C.; Meisel, D. J. Phys. Chem. 1982, 86, 3391.) (the AgNO 3 :citrate molar ratio was kept constant and equal to 1.56).
1.1. Preparation without a Polymer
Solution of trisodium citrate dihydrate (1-10 wt % in 2 ml of double distilled water) was added dropwise to a hot (94-95° C.) solution of silver nitrate (18-180 mg in 100 ml of double distilled water), while stirring. The reaction mixture was kept hot for 10 minutes and then cooled at room temperature. The resulting colloid had a yellow-brownish color and has nanosized particles, as seen from FIG. 1 , only at silver concentrations lower than ˜0.07 wt % (˜6.7·10-3 M). At higher Ag 0 concentrations, which are the aim of this invention, the average particle size increases rapidly and is followed by precipitation of microparticulate silver within a few hours. Obviously, such preparation is not suitable for use as a component in an ink jet ink.
1.2. Preparation of Polymer-Stabilized Nanoparticles
Two milliliters of trisodium citrate solution (1-10%) in aqueous CMC or PP (0.025-0.2%) was added dropwise to heated (94-95° C.) solution of AgNO 3 (18-180 mg in 100 ml of aqueous CMC (carboxy methyl cellulose sodium) or PP (polypyrrole) with concentration 0.025-0.2%), while stirring. The reaction mixture was kept hot for 10 min, and then cooled at room temperature. The resulting CMC-stabilized colloid had a brownish color, and PP-stabilized colloid had blue-black color (black color is observed by the color of PP solution).
As seen from FIGS. 2 and 3 , an increase in polymer concentration results in increase in the average particle size (Z ave ). The optimal concentrations of CMC and PP, which allow obtaining stable Ag 0 nanocolloids with average particle size (Z ave ) up to 100 nm, was found to be 0.2% and 0.03%, respectively.
2. Stability of Polymer-Stabilized Ag 0 Nanoparticles
The stability of the Ag 0 nanoparticles prepared in the presence of stabilizers was evaluated by the changes in the average particle's size with time.
As seen from FIG. 4 , the silver nanocolloid prepared in the presence of 0.2 wt % CMC is stable at least 2 months, as indicated by the relative constancy of the average particle size (25-60 nm). PP-stabilized Ag 0 nanoparticles ( FIG. 5 ) are stable in the presence of 0.03 wt % of this conductive polymer for at least 4 month (Zave in the range of 60-80 nm). It was found that films of PP-stabilized Ag nanoparticles (0.3-1% of Ag and 0.3-1% of PP), which were deposited onto glass and let dry, display electrical conductivity of 0.13-0.17 S/m.
3. Preparation of Highly Concentrated Silver Nanocolloids
Highly concentrated silver nanocolloids were prepared by partial or total removal of the water present in the dispersion of polymer-stabilized nanocolloids (by means of lyophilization, spray drying etc. . . . ), followed by redispersion in a proper (smaller volume) amount of water.
3.1. Preparation by Partial Lyophilization
FIG. 6 presents Z ave of colloidal particles as a function of increasing Ag 0 concentration during lyophilization. The maximum concentration in FIG. 6 , 0.37 wt %, corresponds to 3·10 −2 M. The Z ave values are in the range of 50-60 nm.
3.2. Preparation by Exhausted Lyophilization and Redispersion
The Ag 0 powder obtained after exhausted lyophilization of polymer-stabilized nanocolloid was redispersed in a proper amount of water. As seen from FIG. 7 , the average size of redispersed particles is in the range of 50-60 nm one day after preparation and increases only up to about 100 mm 205 days (˜7 months) after preparation. Thus, the water-based Ag 0 nanocolloids with very high concentration (compared to reported concentrations) of 1.1 wt % (˜0.1 M) display excellent long-term stability, while being non viscous (viscosity below 8 cps) and can be used in ink-jet ink formulations. Also clear is that the final concentration of the particles can be even much higher, up to about 60-74% by volume, limited only by the viscosity of the final dispersion, yielding liquids having low viscosity, or pastes. The use as ink jet ink will be limited to a specific viscosity range required for jetting, depending on the printhead type and temperature of jetting. Obviously, such metallic dispersions (or dried powder) can be used in applications other then ink jet printing.
4. Nanoparticles Flocculation
In order to study the “non-thermal sintering” of Ag 0 nanoparticles by flocculants, one milliliter of Al 2 (SO 4 ) 3 or PDAC solutions with different concentrations were added to 1 ml of Ag 0 nanocolloid, and the concentrations inducing formation of Ag 0 precipitate (Critical Coagulation Concentration, or “CCC”) were evaluated. It has been found that at any concentration of Ag 0 in nanocolloid, CCC strongly depends on the concentration of polymeric stabilized. This is obvious from the bar diagram in FIG. 8 for the nanocolloid with Ag 0 concentration of 0.1 wt %.
Because of bridging effect of PDAC, its CCC is noticeably lower compared to Al 2 (SO 4 ) 3 . It is clear that the flocculated metall nanoparticles can be achieved by printing by ink jet two layers: first printing the metallic ink, followed by printing, on the same pattern, the solution of the flocculant (“flocculation ink”), or vise versa. In addition, the printing can be performed on a substrate which was pre-treated with the flocculant, at appropriate concentrations, thus yielding fixation and flocculation of the metal particles in the printed pattern. It should be noted that the pattern may be printed on various types of substrates, such as paper, plastics and polymeric compositions, glass etc.
5. Preparation of Ink Jet Inks Containing Silver Nanoparticles
The suitability of formulations for printing was evaluated with the use of Epson Stylus-460 ink-jet printer, which requires very low viscosity inks, below 10 cps. Several ink jet formulations are described in the following examples. Obviously, the additives such as wetting agents, humectants, can be selected from a wide range of possibilities. Each formulation was capable of printing, even after prolonged time.
Example 1
Silver nanoparticles (0.18%) in 0.2% CMC solution
99.75%, w/w
BYK-154
0.25%, w/w
Example 2
Silver nanoparticles (0.18%) in 0.2% CMC solution
94.95%, w/w
BYK-348
0.1%, w/w
DPnB (dipropyleneglycol butyl ether)
5%, w/w
Example 3
Silver nanoparticles (1.44%) in 0.1% CMC of solution
98.9%, w/w
Disperbyk-181
0.1%, w/w
Disperbyk-184
1.00%, w/w
Example 4
Polypyrrol solution (1%)
98.9%, w/w
Disperbyk-184
1%, w/w
Disperbyk-181
0.1%, w/w
Example 5
Silver nanoparticles (0.112%) in 0.03% of PP solution
98.9%, w/w
Disperbyk-184
1%, w/w
Disperbyk-181
0.1%, w/w
Example 6
This example presents the possibility to print the metallic pattern, followed by printing of a flocculating agent on said metallic pattern, in order to obtain close contact of the metallic particles, due to the flocculation.
Step 1. Printing the ink containing 0.112% dispersion of silver nanoparticles stabilized by 0.03% CMC (98.9%, w/w), Disperbyk 184 (1%, w/w) and Disperbyk 181 (0.1%, w/w) onto proper support.
Step 2. Printing the 0.01% PDAC solution (99.23%, w/w) containing Disperbyk 184 (0.7%, w/w) and Disperbyk 181 (0.07%, w/w) onto the image printed in Step 1.
Printing was performed on various substrates, such as paper, transparency, glass and PVC. In general, the suitable surface tension could be achieved by selecting a proper surfactant or co-solvent, and the proper viscosity could be achieved by adjusting the concentration of the CMC.
In general, the new ink jet ink contains the silver nanoparticles, and aqueous solution which may contain surfactants, additional polymers, humectants, cosolvents, buffering agent, antimicrobial agent and defoamers in order to ensure proper jetting and adhesion of the ink to specific substrates.
The conductive pattern can be achieved either by the direct printing repeated for several times, with or without heating and drying cycles, or/and by using the first metal pattern to induce formation of additional metal layers, such as encountered in “electroless process”. For example, the printing may be followed by additional dipping in electroless bath, or by printing the electroless solution onto the printed pattern. Actually, the printed nanoparticles can be used as templates for further crystallization and precipitation of other materials.
FIG. 9 represents an example of printed image formed with the use of Ag-containing ink-jet ink on ink-jet transparency. FIG. 10 represents SEM (Scanning Electron Microscopy) image of printed Ag-containing formulation on the same substrate. | Compositions for use in ink jet printing onto a substrate comprising a water based dispersion including metallic nanoparticles and appropriate stabilizers. Also disclosed are methods for the production of said compositions and methods for their use in ink jet printing onto suitable substrates. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to the deodorizing of noxious fumes in a toilet. More specifically, it relates to a self-contained, air-filtration system fully contained in a toilet seat.
BACKGROUND OF THE INVENTION
[0002] There have been various attempts to provide odor control systems in toilet seats to deodorize the foul air in toilets created during their use. Some of these systems have included specially designed toilet seats that include air filtration systems. It is known, for example, to provide a toilet seat with a hollow body which includes air intake, ducting and exhaust with the filtering system, such that air is drawn in from the toilet bowl into the toilet seat duct and deodorized, thereafter being exhausted through a rear portion of the seat. Such a device is disclosed, for example, in U.S. Pat. 6,823,532 issued to Anderson entitled “Malodor Control Systems for Toilets” which relies on a water spray to treat the foul air. This is a complicated device comprising a pressurized water feed line and provides only limited air handling capacity. Another system is disclosed in U.S. Patent Publication 2007/0163033 by Kelly entitled “Toilet Seat” This document discloses a toilet seat which is a fully self-contained air filtration system that includes batteries for powering fan units to move air through internal ducting. The toilet seat of this invention is provided with a microswitch which is switched by force applied to the seat by the weight of a person sitting down. Thus, the fan units are energized only when needed.
[0003] Despite these attempts in the art to provide an effective deodorizing self-contained battery-powered toilet seat, deficiencies still remain. Most importantly, prior art toilet seat deodorizing systems lack the sufficient volume of air flow to adequately deodorize foul toilet vapors. There is therefore still a need in the art for an effective deodorizing toilet seat.
SUMMARY OF THE INVENTION
[0004] In order to solve the problems in the art, the present deodorizing toilet seat has been devised. In accordance with the present invention, a toilet seat includes a large-capacity internal ducting connected between a very large intake opening and a large exhaust opening. Efficient, high-capacity fans are utilized to move a large volume of air through a filtering system providing a flow capacity not heretofore achievable by the prior art. An air handling system located within the apparatus simultaneously filters and scents foul air emanating from the toilet bowl. The unit is activated as the user sits on the seat and is programmed to continue its function for a controlled length of time after toilet use. Upon actuation, as the user is seated, the fan(s) draw foul air through the air inlet and filter(s) and then expels the treated air toward the rear and sides of the toilet via the exhaust vents. The invention is composed of a seat assembly comprising upward and lower halves joined along a horizontal seam. Contained within the seat assembly is the ventilation system. The components of the ventilation system are an air inlet, at least one filter, at least one fan, a circuit board, a battery pack connected to the circuit board, and at least one exhaust vent. The seat assembly shell forms the passageways to process the foul air. Contained within the seat assembly are mechanisms to provide the user with easy access to clean and maintain the device.
[0005] The seat assembly includes an outer shell composed of two mating halves, an upper case half and a lower case half. Both the upper case and lower case pivot on the axle, allowing the upper case to swing away from the lower case. The upper case and lower case snap together at a latch point at the front of the seat. The cases are joined by snap-fit and can be snapped apart to facilitate access to the internal duct for cleaning purposes. Further, due to a spring action, the latch allows the upper case to pivot a controlled distance. This resulting vertical displacement, or movement downward of the upper case as the user is seated, actuates a micro switch connected to the circuit board which initiates the ventilation cycle. Upon release of pressure on the upper case, as the user stands, the ventilation flow continues for a prescribed amount of time, after which power to the fan is interrupted and the ventilation cycle is complete.
[0006] More specifically, the invention comprises a air filtering toilet seat being an annular seat having mounting means for hingably connecting the seat to a top opening of the toilet bowl. An internal compartment lies between an upper seat case and a lower case which are joined along overlapping sidewalls. An air duct within the compartment conducts a flow of air from an inlet opening at the front of the seat to an exit duct at the rear of the seat. The inlet opening lies along an inside wall of the seat and spans a substantial portion of the seat between overlapping sidewalls along a seam between the seat halves. Filters for deodorizing foul air from the toilet bowl are arranged in the duct such that all of the flow of air passes through the filters. Fans downstream of the filters is arranged in the duct creating the flow of air along the duct and through the filters. Process control circuitry on a circuit board within the compartment at the rear of the seat controls operation of the fan which is powered by a battery which is also within the compartment but located within a section isolated from the duct. The filters are removably arranged in the duct by way of flanges at the downstream ends of the filters having opposing side edges which are slidably engaged slots in the inside wall of the duct. The bodies of the filters are substantially tubular and lie longitudinally along channels of the duct. Operation of the seat is activated by sensing the presence of a human body on the seat which can be supplied by a microswitch activatable by movement by the upper seat half with respect to the lower seat half caused by the weight of the human body.
[0007] The invention provides several advantages over the prior art. It is easy to install and as simple as changing a normal toilet seat. The usual mounting bolts are located at the rear. The invention requires no exhaust to the outdoors and is particularly suitable to enclosed environments. The invention is exceedingly simple and easy to maintain without harboring foul-smelling contaminants within the seat. Because the odors are filtered at the source, the device requires a minimum amount of energy, which contributes to long battery life. Other objects and advantages of the invention will be apparent to those of skill in the art from the following drawings and description of the preferred embodiment.
[0008] 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.
[0009] As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods, and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a top-left isometric view of the invention installed on a toilet which is shown in phantom.
[0011] FIG. 2 is a left-rear isometric assembly view.
[0012] FIG. 3 is a top-plan partial sectional view.
[0013] FIG. 4 is a left-side elevation sectional view taken from FIG. 1 as shown in that Figure.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] Referring now to FIG. 1 , the toilet seat of the invention 11 is seen mounted on a typical toilet 10 in the usual position of a normal toilet seat, having the same general shape and configuration and approximate size. As will be more fully described herein, the seat comprises an upper seat case half 13 and a lower seat case half 15 separated by a substantially horizontal overlapping seam 17 .
[0015] Referring now to FIG. 2 , basic elements of the invention are shown. The upper seat half 13 is hingably connected to the lower seat half 15 by way of hinge means 22 . The lower seat half includes a channel 23 which when mated with a similar channel in the top seat half forms an internal compartment between them. Spring 24 biases the case halves apart from a fully collapsed position to an extended position. This provides a resilient movement of the seat which in turn operates a microswitch (not-shown) to detect the presence of a user on the seat. The seat halves include cutouts along the front of their inner walls 16 which form a large inlet opening 14 at the front of the seat as more clearly shown in FIGS. 3 and 4 . Identical components of the ducting and air filtration system are symmetrical about a front-to-rear center line. A forward portion of the compartment encloses filters 19 which are releasably held in the compartment by way of flanges 17 that slideably engage cooperating slots in the duct. Similarly, fans 20 and 21 are releasably held at the rear of the ducts by slideable fitment with slots in the duct. In an isolated portion of the compartment at the rear of the seat, a circuit board 25 which controls operation of the fans is secured. The circuit board is electrically connected to the fans and further includes a microswitch which is operative to indicate movement to the upper seat half 13 with respect to the lower seat half 15 . The circuit board assembly is attached to the lower half of the seat assembly, and is sealed within the lower case by a cover plate. The circuit board is composed of the electronic devices that control the ventilation system. This includes a switch, timing devices, battery holder, and other electronic elements.
[0016] Referring now to FIG. 3 , fans 20 and 21 create the air flow from the inlet duct 14 in the front of the seat's inside wall 26 into channel 23 and through filter 19 . The filtering chambers contained within the seat assembly use activated charcoal 30 to treat the air as it passes through filter layers. The filtering system is composed of at least one filter. The filters have an outer porous membrane through which air passes. The filters are self-contained, coming in contact with the seat assembly via the flanges. Activated charcoal is located within the filter chambers in such a manner as to allow air to be drawn through, but to come in contact with the activated charcoal as it passes through the filtering chambers. The filters are disposable. They are replaceable by the user, once said filters are exhausted. Contained within the filtering chambers described above, are porous membranes that contain agents to scent the air that passes through the filtering chamber.
[0017] Foul air is drawn in through inlet opening 14 and the filtered air is then exhausted at the rear of the seat through outlet duct 27 . Since components of the seat are symmetrically arranged on opposite sides, the duplicate arrangement of components and flow of air just described will be understood to apply to the opposite side of the seat as well. The location of the exhaust vents, to the rear and sides, helps to direct air away from the user. Urine over-spray is not allowed to collect in the vents. Regardless, any unusual contamination of the vents is easily cleaned by wiping down, and thoroughly accomplished by disengaging the upper case from the lower case. Here again, there are no small apertures to collect and harbor urine or other matter. The generous size of the outlet ducts 27 and 29 helps to keep any reduction in airflow to a minimum, further increasing the efficiency of the unit.
[0018] Referring now to FIG. 4 , the unusually large size of inlet duct 14 as well as its shape and location will be better appreciated. Emphasis is placed upon the size of the intake, calculated at approximately 19 square inches, so that a minimal amount of restriction is imparted to the flow of the foul air emanating from within the toilet bowl, and through filter 19 . A tight seal of the seat assembly to the toilet bowl 31 is not necessary with this design, due to the large air intake, eliminating fitting problems with most toilet bowl configurations. The resulting smooth and unencumbered surface, therefore, allows for easy cleaning and maintenance of the underside of the unit. The location of the intake 14 , to the front of the unit, helps prevent foul air from rising where it would be most easily detected. Additionally, and as previously mentioned, the location away from the rear of the unit, helps to ensure that urine over-spray from a standing user, with the seat in the upright position, is not allowed to be collected by the ventilation system. Spring means 24 biases the case halves 13 and 15 slightly biased apart so that there will be movement between the two caused by the weight of the user which can be detected by sensing means on the circuit board 25 comprises a microswitch. The fans will then be provided power from battery means located in the circuit board compartment by control circuitry on the circuit board to operate the fans for a prescribed period of time after the sensing means has signaled that the user has left the seat.
[0019] From the foregoing description of the preferred embodiment, the advantages of the invention will be apparent. The large open nature of the air intake is such that cleaning is simple and convenient. All interior surfaces of the air intake are accessible and easily wiped clean. Normal cleaning of the seat assembly is accomplished as easily as for a conventional toilet seat. There are no small apertures to trap urine or other matter. The shape is such that foul elements are allowed to be shed rather than collected and harbored, as a series of small apertures would do. The flanges formed along the inner edges of the upper and lower cases of the seat assembly direct urine spray down and into the toilet bowl. This is especially important in guarding against the collection of miss-directed urine spray by a standing user when the seat is in an upright position. Wherein small apertures, especially if located to the rear of the toilet seat, collect and harbor urine over-spray. Under these circumstances, this design with the built-in flanges, helps to shed over-spray. Further, and due to the ease of the separation of the upper case from the lower case of the seat assembly, any urine that does manage to seep beyond the flanges is easily wiped clean upon disengagement of the upper and lower cases. In addition, urine over-spray and splash from a seated user is also easily cleaned, being accomplished simply by wiping down the accessible surfaces. Disengagement of the upper and lower cases, exposes the interior, and allows for easy clean up.
[0020] It should be understood that there may be other modifications and changes to the present invention that will be obvious to those of skill in the art from the foregoing description, however, the present invention should be limited only by the following claims and their legal equivalents.
[0021] 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 toilet seat for filtering foul air includes large capacity internal ducting connected between a very large intake opening and a large exhaust for efficient, high capacity air filtration. The seat comprises an assembly including upper and lower halves joined along a horizontal seam. The seat halves pivot on an axle and are biased apart to sense use of the device to control its on/off timing. The device is activated as the user sits on the seat and is programmed by a controller to continue for a length of time after toilet use. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/691,790 filed Jun. 17, 2005, and U.S. Non-Provisional application Ser. No. 11/370,414 filed Mar. 8, 2006, each hereby incorporated by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention is drawn to a load bearing panel member formed by a method of injection molding.
BACKGROUND
[0003] There are numerous known systems for plastic injection molding. In conventional plastic injection molding systems, plastic pellets are melted in an injection molding machine and advanced by a screw ram through an injection nozzle and into a mold cavity. The mold cavity is preferably formed between two mold halves. The molten plastic material in the cavity is allowed to cool and harden in the cavity. When the plastic material has cooled and sufficiently hardened, the two halves of the mold are separated or opened and the part is removed, typically by one or more ejector pins.
[0004] Some injection molding systems utilize a gas in the injection molding process and are commonly known as “gas-assisted injection molding” systems. In these systems, the gas is injected into the molten plastic material through the plastic injection nozzle itself, or through one or more pin mechanisms strategically positioned in the mold. It is also possible to inject the gas directly into the molten plastic in the barrel of the injection molding machine. The gas, which typically is an inert gas such as nitrogen, is injected under pressure and forms one or more hollow cavities or channels in the molded part.
[0005] Gas-assisted injected molding produces a structure having a hollow interior portion which results in saving weight and material, thereby reducing costs. The pressurized gas applies an outward pressure to force the plastic against the mold surfaces while the article solidifies. This helps provide a better surface on the molded article and reduces or eliminates sink marks and other surface defects. The use of pressurized gas also reduces the cycle time as the gas is introduced and/or migrates to the most fluent inner volume of the plastic and replaces the plastic in those areas which would otherwise require an extended cooling cycle. The pressure of the gas pushing the plastic against the mold surfaces further increases the cooling effect of the mold on the part, thus solidifying the part in a faster manner and reducing the overall cycle time.
SUMMARY
[0006] The present invention provides a method for producing a structural or load bearing injection molded panel member. According to a preferred embodiment, the panel member is a floor panel for a van having retractable rear seats wherein the panel member is adapted to cover the rear seats when fully retracted and act as a load floor. The panel member preferably includes a first portion, a second portion and an interior surface portion. The present invention will hereinafter be described according to the preferred embodiment wherein the interior surface portion is a carpet material; however, it should be appreciated that according to alternate embodiments the interior surface portion could also include, for example, a vinyl material or a textile material.
[0007] The preferred method of the present invention includes placing the carpet material into a mold cavity configured to produce the panel member. The mold cavity preferably includes a first chamber adapted to form the first portion of the panel member, and a second chamber adapted to form the second portion of the panel member. After the carpet material is inserted into the mold, molten plastic material and pressurized gas are injected into the first chamber of the mold cavity. After the molten plastic material is injected into the first chamber of the mold, molten plastic material is injected into the second chamber of the mold cavity. A sequential gating process is used to achieve this sequence of operations. The molten plastic is then cooled until it solidifies. After the molten plastic is sufficiently cooled, the pressurized gas is vented and the panel member is removed from the mold.
[0008] It should be appreciated that the order in which the steps of the preferred embodiment are performed may be varied according to alternate embodiments. For example, according to one alternate embodiment of the present invention, the molten plastic material may be injected into the second chamber of the mold cavity before molten plastic material is injected into the first chamber of the mold cavity. According to yet another alternate embodiment, molten plastic may be injected into the first and second chambers of the mold cavity simultaneously.
[0009] The present invention also provides a structural or load bearing panel member and a product by process. The load bearing panel member preferably includes a generally rectangular first portion, a generally rectangular second portion, and a carpet material. The carpet material is attached to the first portion and the second portion such that the carpet material forms an integral or living hinge at a gap therebetween. The first portion of the panel member defines a plurality of solid horizontally disposed ribs and a plurality of solid vertically disposed ribs. The first portion of the load bearing panel member also includes a plurality of hollow ribs formed by the gas assisted injection molding process. The hollow ribs are generally located around the periphery of the first portion of the load bearing panel member as well as in an X-shape originating at the center of the first portion and extending toward the corners thereof. The solid ribs and hollow ribs are adapted to increase strength and rigidity and provide substantial structural or load-bearing capability
[0010] The above features and advantages and other features and advantages of the present invention are readily apparent from the following detailed description of the best modes for carrying out the invention when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a bottom view of a load bearing panel member in accordance with the present invention;
[0012] FIG. 2 is a block diagram illustrating a method of the present invention;
[0013] FIG. 3 is a sectional view of the panel member taken along line A-A of FIG. 1 ;
[0014] FIG. 4 a is a schematic sectional view of an injection molding nozzle and a plurality of valves; and
[0015] FIG. 4 b is a schematic plan view of a mold cavity.
DESCRIPTION
[0016] Referring to the drawings, wherein like reference numbers refer to like components, FIG. 1 shows a panel member 10 produced according to a method of the present invention. The panel member 10 will hereinafter be described as a floor panel for a van having retractable rear seats (not shown), wherein the panel member 10 is adapted to cover the rear seats when the seats are fully retracted and also to act as a load floor. It should be appreciated, however, that the method of the present invention may be implemented to produce other conventional panel members as well.
[0017] The panel member 10 includes a generally rectangular first portion 12 , a generally rectangular second portion 14 , and an interior or appearance surface portion 16 (shown in FIG. 3 ). The present invention will hereinafter be described according to the preferred embodiment wherein the interior surface portion 16 is carpet material; however, it should be appreciated that according to alternate embodiments the interior surface portion 16 could also include, for example, a vinyl material or a textile material. According to a preferred embodiment, the carpet material 16 is a polypropylene material with a polyester backing. The carpet material 16 is attached to the first portion 12 and the second portion 14 such that the carpet material 16 forms an integral or living hinge 18 at a gap 19 between the first portion 12 and the second portion 14 . The first portion 12 of the panel member 10 defines a plurality of solid horizontally disposed ribs 20 and solid vertically disposed ribs 21 . The solid ribs 20 and 21 are normal to each other so as to increase strength and rigidity and provide substantial load-bearing capability. According to a preferred embodiment of the present invention, the second portion 14 of the panel member 10 includes a plurality of up-standing clip attach members 22 .
[0018] The clip attach members 22 preferably each retain a metallic attachment clip (not shown) configured to mount the second portion 14 of the panel member 10 to a seat assembly (not shown). When the seat assembly is in an upright position, the hinge 18 allows the second portion 14 of the panel member 10 to fold underneath the first portion 12 and below the seat.
[0019] When the seat assembly (not shown) is fully retracted, the first portion 12 of panel member 10 is rotatable about the integral hinge 18 from an open position exposing the seat assembly to a closed position at which the seat assembly is covered. When the seat assembly is fully retracted and the first portion 12 of panel member 10 is in the closed position, the carpet material 16 (shown in FIG. 3 ) is exposed and the seat assembly is completely hidden. In this manner, the panel member 10 is adapted to provide an aesthetically pleasing carpeted interior when the seat assembly is retracted, and also provide substantial floor-strength.
[0020] Referring to FIG. 2 , a method for manufacturing the panel member 10 according to the present invention is shown. At step 50 , the carpet material 16 is placed into a mold cavity 70 (shown in FIG. 4 b ) configured to produce the panel member 10 . Optionally, at step 50 , metal inserts such as bars and/or tubes (not shown) can also be placed into the mold cavity 70 with the carpet material 16 to produce a panel member 10 with increased strength and rigidity. The mold cavity 70 of the present invention preferably includes a first chamber 72 (shown in FIG. 4 b ) adapted to form the first portion 12 of the panel member 10 , and a second chamber 74 (shown in FIG. 4 b ) adapted to form the second portion 14 of the panel member 10 . The first and second chambers 72 , 74 are preferably separated by an insert or feature 75 (shown in FIG. 4 b ) configured to produce the integral hinge 18 (shown in FIG. 3 ). At step 52 , molten plastic material 76 (shown in FIG. 4 a ) is injected into the first chamber 72 of the mold cavity 70 . The molten plastic material 76 is preferably injected in a conventional manner, such as, for example, by a reciprocating screw type injection device (not shown), through an injector nozzle 40 (shown in FIG. 4 a ), through a valve gate 42 a (shown in FIG. 4 a ), and into the first chamber 72 of the mold cavity 70 .
[0021] At step 54 , an inert gas 80 (shown in FIG. 4 b ) such as nitrogen is injected into the first chamber 72 of the mold cavity 70 (shown in FIG. 4 b ) through a plurality of gas pins 82 (shown in FIG. 4 b ) positioned at locations predefined by the desired locations of the hollow ribs 30 . The gas 80 preferably does not mix with the molten plastic material 76 , but takes the path of least resistance through the less viscous portions of the plastic melt. The molten plastic 76 is therefore pushed against the wall portions of the mold cavity 70 , which forms channels 31 and produces the hollow ribs 30 (shown in FIGS. 1 and 3 ).
[0022] Referring to FIG. 3 , a sectional view taken through section A-A of FIG. 1 is shown. It can be seen in FIG. 3 that the hollow ribs 30 define an internal Channel 31 through which the gas is injected. Referring again to FIG. 1 , the gas 80 (shown in FIG. 4 b ) is preferably injected through the gas pins 82 (shown in FIG. 4 b ) into the first portion 12 of the panel member 10 at the gas injection locations 32 . According to a preferred embodiment, the hollow ribs 30 are generally located around the periphery of the first portion 12 of the panel member 10 as well as in an X-shape originating at the center of the first portion 12 and extending toward the corners thereof. It has been observed that the hollow ribs 30 formed in the manner described increase the rigidity and strength of the first portion 12 of the panel member 10 . The increased strength and rigidity is particularly advantageous for the preferred embodiment wherein the panel member 10 is implemented as a load bearing floor panel.
[0023] Referring again to FIG. 2 , at step 56 molten plastic material 76 (shown in FIG. 4 a ) is injected into the second chamber 74 of the mold 70 (shown in FIG. 4 b ). The molten plastic material 76 is preferably injected through the injector nozzle 40 (shown in FIG. 4 a ), through a valve gate 42 b (shown in FIG. 4 a ), and into the second mold chamber 74 .
[0024] A sequential gating process is preferably implemented to perform previously described steps 52 and 56 . Referring to FIGS. 4 a - 4 b , the valve gates 42 a and 42 b , which are adapted to feed the first and second mold chambers 72 , 74 , respectively, are opened using the sequential gating process. In other words, the sequential gating process is implemented to control the timing of the gates 42 a , 42 b and to coordinate the operation of valve gate 42 b with the operation of valve gate 42 a . According to a preferred embodiment, the valve gates 42 a and 42 b are configured to open and close at a predetermined time. The predetermined time at which the valve gates 42 a and 42 b open and close is generally based on the needs of the specific part to be molded and type of material being used. Alternatively, the valve gates 42 a and 42 b may be opened and closed based on the position of a screw type injection device (not shown).
[0025] Referring again to FIG. 2 , at step 58 the molten plastic material 76 (shown in FIG. 4 a ) that was injected into the first and second chambers 72 , 74 of the mold cavity 70 (shown in FIG. 4 b ) at steps 52 and 56 is allowed to cool and solidify. Thereafter, at step 60 , the pressurized gas 80 (shown in FIG. 4 b ) that was injected in to the first chamber 72 of the mold cavity 70 at step 54 is allowed to vent through the gas pins 82 (shown in FIG. 4 b ). At step 62 , the finished panel member 10 is removed from the mold cavity 70 .
[0026] It should be appreciated that the order in which the steps 50 - 62 of the preferred embodiment are performed may be varied according to alternate embodiments. For example, according to one alternate embodiment of the present invention, step 56 at which the molten plastic material 76 (shown in FIG. 4 a ) is be injected into the second chamber 74 (shown in FIG. 4 b ) of the mold cavity 70 (shown in FIG. 4 b ) may be performed before step 52 at which molten plastic material 76 is injected into the first chamber 72 (shown in FIG. 4 b ) of the mold cavity 70 . According to yet another alternate embodiment, steps 52 and 56 may be performed simultaneously such that molten plastic 76 is injected into the first and second chambers 72 , 74 of the mold cavity 70 simultaneously.
[0027] 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 invention within the scope of the appended claims. | A load bearing panel member having a first portion, a second portion, and an appearance surface portion is formed by injection molding such that the first portion includes a plurality of rib members forming a grid pattern on the first portion and another plurality of rib members extending toward the periphery of the first portion which may be non-orthogonal to each other and to the rib members forming the grid pattern. A tubular cavity may be formed within each of the non-orthogonal rib members by injecting a gas into the rib member during the molding process forming the panel. An appearance surface portion attached to the first portion and second portion of the panel member forms an integral hinge between the first and second portions of the panel member. The panel member may be configured as a floor panel of a vehicle. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is the first application filed for the present invention.
MICROFICHE APPENDIX
[0002] Not Applicable.
TECHNICAL FIELD
[0003] The present invention relates to management of traffic forwarding in packet networks, and in particular to methods of preventing loops in multicast routes mapped through a packet network.
BACKGROUND OF THE INVENTION
[0004] Network operators and carriers are deploying packet-switched communications networks in place of circuit-switched networks. In packet-switched networks such as Internet Protocol (IP) networks, IP packets are routed according to routing state stored at each IP router in the network. Similarly, in Ethernet networks, Ethernet frames are forwarded according to forwarding state stored at each Ethernet switch in the network. The present invention applies to communications networks employing any Protocol Data Unit (PDU) based network and in this document, the terms “packet” and “packet-switched network”, “routing”, “frame” and “frame-based network”, “forwarding” and cognate terms are intended to cover any PDUs, communications networks using PDUs and the selective transmission of PDUs from network node to network node.
[0005] Multicast forwarding of data packets (where packets are sent from a source node to multiple destination nodes more or less simultaneously) is of increasing importance as demand for services such as PTV and Video on Demand (VoD) grows.
[0006] Protocols such as Intermediate System—Intermediate System (IS-IS) and Open Shortest Path First (OSPF) and Multicast OSPF are used to distribute topology information to permit distributed calculation of paths that interconnect multiple nodes, resulting in the installation the forwarding state required to implement those paths. OSPF and IS-IS are run in a distributed manner across nodes of the network so that, for example, when a topology change occurs in the network such as a node or link failure, this information is flooded to all nodes by the protocol's operation, and each node will locally recompute paths to circumvent the failure based on a consistent view of network topology.
[0007] In Ethernet networks, Provider Backbone Transport (PBT), also known as Provider Backbone Bridging-Traffic Engineering (PBB-TE), as described in Applicant's British patent number GB 2422508 is used to provide a unicast Ethernet transport technology. Provider Link State Bridging (PLSB) as described in Applicant's co-pending U.S. patent application Ser. No. 11/537,775 will be used to provide a multicast transport capability for Ethernet networks using IS-IS to set up both unicast paths and multicast trees in the network. Both above patent documents are hereby incorporated by reference.
[0008] While the present invention is not limited to the application of a routing system to Ethernet bridging, Ethernet terminology is used in this disclosure where possible. So, for example, the term filtering database (FDB) can be considered interchangeable with any term for an information repository of packet forwarding information, such as forwarding information base or label information base.
[0009] FIG. 1 is a flowchart illustrating the principle steps in an all-pairs shortest path multicast route computation algorithm (known, for example, from Applicant's co-pending U.S. Patent Application Publication No. 20070165657), which is normally implemented in each node. In this example it is assumed that included in routing system advertisements is multicast group membership information, although it is easy to envision that multiple systems may be combined to achieve the same result.
[0010] As shown in FIG. 1 , upon receipt of either a multicast group membership change or a network topology change (for example via a Link State Packet—LSP) the node employs algorithms such as Dijkstra's algorithm to compute both unicast connectivity (at S 2 ) and the set of pairs of network nodes where the computing node lies on the shortest path between the pair. For that set of node pairs, the node determines where intersections of multicast group membership occur, which define the required FDB entries to instantiate it's portion of multicast paths accordingly. Both Unicast and Multicast forwarding state implementing the computed forwarding is then installed in the node's filtering database (FDB), at S 4 , so that received packets can be forwarded to the appropriate output port(s) of the node, based on the destination address in the frame.
[0011] As is known in the art, network nodes can be implemented with either a single common FDB which is used to control forwarding of traffic received through all input ports (interfaces), or a respective different FDB for each input port or subsystem. In the case of a node having a respective different FDB associated with each input port, multicast forwarding state can be installed in the respective FDB of the appropriate input port, which may be identified using the computed unicast path to the root node of the multicast tree.
[0012] Typically, changes in the network topology, whether detected directly by a node (e.g. a failure of a physical link connected directly to the node) or indirectly (e.g. via receipt of a Link State Advertisement, LSA) will be reflected in changes in a Network Topology Database. Accordingly, recomputation of forwarding state in response to changes in network topology may be triggered by a change in the network topology database. In any event, following a network topology change, the (old) forwarding state will remain in effect until new forwarding state is installed in the FDB.
[0013] In a network where path computation is distributed, there is always the danger of the loose synchronization of the routing databases that the local FDB is derived from, and other variations in individual node implementation such as compute capacity, speed with which the internals can be synchronized etc. This loose synchronization can result in transient loops. A high level summary is that transient loops can occur due to the physical impossibility of instantaneously distributing and acting upon state change information across multiple nodes of the network. Looping of packets is at best wasteful of network resources, and at worst may result in congestive network failure. Looping is significantly more serious for multicast forwarding than for unicast forwarding because packets may be replicated outside of and forwarded around, such a loop, resulting in an explosion of packet creation and forwarding.
[0014] There are various approaches to mitigating the problems of loops appearing in a network. In IP networks, IP packets have a Time To Live (TTL) counter which is decremented at each hop and will eventually cause looping packets to be discarded. Routers will not forward packets where the TTL counter has been decremented to zero. However, this merely “limits the size of the blast crater” created by the loop. Spanning Tree Protocol is used in Ethernet networks to block ports during periods of network instability, which shuts down all traffic, not simply the traffic whose forwarding paths were directly impacted by the network change, and unblocks the ports only when the network has converged in a new loop free solution. This prevents loops, but is wasteful of network resources in reasonably sized networks, disrupts traffic out of proportion to the topology change, and is incompatible with technologies that exploit Ethernet mesh connectivity such as PBT and PLSB. Other mitigating approaches include ordering the installation of forwarding state in a controlled manner as described in a paper “Avoiding Transient Loops During the Convergence of Link-State Routing Protocols” Pierre Francois and Olivier Bonaventure, IEEE/ACM TRANSACTIONS ON NETWORKING 15(6):1280-1932, December 2007. However, this slows down fault recovery times which is unattractive to network operators.
[0015] The application of a Reverse Path Forwarding Check (RPFC) to packets is a well known technique that reduces the probability of packet looping by eliminating promiscuous packet receipt at intermediate nodes (i.e. arrival on any port is not acceptable), converting the forwarding to what is known as a directed tree. This is accomplished by ensuring that any packet received from a given source arrives on an expected port for that source at each intermediate node. In the case of an Ethernet bridge, there will be only one expected port. When a packet sent from a given source node arrives at an intermediate node on a particular port or interface, a check is performed to see if there is a matching entry for the source address of the packet in the intermediate nodes filtering database for that port or interface. If there is, the packet is forwarded as normal. If not, the packet is dropped. In other words, a check is performed to see if the packet came in on a port or interface that the intermediate node would itself use for forwarding a packet on the “reverse” unicast path to the source node. For some packet forwarding paradigms, there may be more than one valid port that can be used to reach a given source (e.g. equal cost multipath), in which case the degree of robustness provided by RPFC is diminished. For PLSB there is a one-to-one correspondence between the partial multicast tree from the source node to the intermediate node, and the reverse unicast path from the intermediate node back to the source node, in any given Backbone VLAN Identifier (B-VID). Accordingly, if a packet is received from the source node via any port other than the one port that corresponds to the reverse unicast path, then an inference can be made that a loop may exist.
[0016] When constructing multicast trees, it may be necessary or desirable to construct individual source-specific point-to-multipoint trees (known as (S, G) trees). In such trees, the source is encoded as part of the destination address. As a result, an explicit Reverse Path Forwarding Check (RPFC) is not required if the (S, G) tree multicast address is only installed on ports facing the tree root, because an implicit RPFC is performed by the presence of the multicast address on the port. Throughout this description, the term “RPFC” is used to cover both explicit and implicit versions of the technique.
[0017] RPFC eliminates most circumstances in which looping may occur. However, there remain circumstances in which a transient loop may occur. Specifically, it can be shown that, even when using RPFC, a transient loop may occur when two or more topology changes occur more or less simultaneously. It is possible to consider a number of permutations of two simultaneous topology changes and the partial dissemination of knowledge of each which could achieve the same result, the example considered being of interest as both changes are not immediately adjacent to the nodes that will ultimately break the loop when they have completed computation and installation of their forwarding tables.
[0018] FIGS. 2 a - d illustrate a simple scenario in which a transient loop may occur. In these figures, a network fragment is shown, which comprises nodes B, C, D, E and R, where R is the source or root node for a multicast tree considered in this example. In the illustrated network, physical links are shown by lines between respective nodes, along with the respective cost of each link (indicated by the value of c). The route followed by packets being forwarded through the multicast tree is shown by arrows, which traces the least cost routing through the network. Thus, in the network state illustrated in FIG. 2 a , forwarding state is installed in node R for forwarding packets to node B; and in nodes B, C and D for forwarding packets to nodes C, D and E, respectively. FIGS. 2 b - d illustrate state transitions that occur in the network as a result of two topology changes in the network; in this example, the physical link between nodes R and B is broken, and a new, low-cost, link becomes available between nodes E and B, so that this new link is part of the lowest cost route between nodes D and C.
[0019] Referring to FIGS. 2 b and 2 c , when the physical link between nodes R and B is broken (indicated by a cross in the figures), this topology change will be propagated through the network (initially from nodes R and B), for example using a conventional Link State Advertisement (LSA) process. Consequently, nodes B, C, D and E will become aware of the topology change, and will begin re-computing the multicast tree to utilize the physical link from R to D. Similarly, when the new link between nodes E and B becomes available, this topology change will be propagated through the network (initially from nodes E and B). Consequently, nodes B, C, D and E will become aware of the topology change, and will begin re-computing the multicast tree to utilize the new link between nodes E and B. If these two topology changes occur sufficiently far apart in time, then the recomputation of the multicast tree in response to failure of the physical link between nodes R and B, and installation of new forwarding state in all of the affected nodes, will have time to finish before the recomputation of the multicast tree to utilize the new link between nodes B and E begins.
[0020] However, if both changes occur close enough in time (that is, they are approximately simultaneous), as shown in FIG. 2 b , then the two multicast tree recomputations will overlap in time. For example, in response to the topology change due to failure of link R-B, nodes R, B, C, D and E begin recomputing the multicast path to utilize the link between nodes R and D. While this recomputation is proceeding, the previous forwarding state installed in each node remains in place, so node B continues to forward queued packets to node C. Nodes C and D, in turn, continue forwarding packets to nodes D and E, respectively.
[0021] Meanwhile, nodes B and E will be the first nodes to become aware of the availability of the new link, and so will be the first nodes to begin recomputing the multicast tree to use this link. When they complete their respective path recomputations and install the new forwarding state, node E will begin forwarding packets to node B, and node B will continue forwarding packets to node C. If this occurs before nodes C or D have completed their respect path re-computations, the scenario illustrated in FIG. 2 c can occur. In this scenario, node E has installed forwarding state for forwarding packets to node B, but node C is still forwarding packets to node D (in accordance with its previous forwarding state—which has not yet been updated), resulting in a loop around nodes B, C, D and E. This loop will persist until such time as either of nodes C or D has recomputed the multicast tree and installed forwarding state to account for at least one of the two topology changes. When this latter recomputation is completed, the network will transition to the loop-free state illustrated in FIG. 2 d , in which the loop is broken. However, during the transient period while the network is in the intermediate state shown in FIG. 2 c , the loop may cause significant congestion or damage to the network.
[0022] Techniques for reducing the probability of transient loops in packet switched networks remain highly desirable.
SUMMARY OF THE INVENTION
[0023] Thus, an aspect of the present invention provides a method of coordinating the installation of forwarding state in a link state protocol controlled network node having a topology database representing a known topology of the network, and at least two ports for communication with corresponding peers of the network node. A unicast path is computed from the node to a second node in the network, using the topology database, and unicast forwarding state associated with the computed unicast path is installed in a filtering database (FDB) of the node. Detecting whether or not an unsafe condition exists, and, when an unsafe condition is detected, multicast forwarding state is removed for multicast trees originating at the second node. Subsequently, a “safe” indication signal is advertised to each of the peers of the network node. The “safe” indication signal comprises a digest of the topology database. A multicast path is then computed from the second network node to at least one destination node of a multicast tree. Finally, multicast forwarding state associated with the computed multicast path is installed in the filtering database (FDB) of the network node, when a corresponding “safe” indication signal has been received from at least one of the peers of the network node.
[0024] In some embodiments, computation of the unicast path is performed in response to a change in the topology database. This change may be indicated by either a detected change in the network itself, or receipt of a message (such as, for example, a Link State Advertisement, LSA) containing information of a change.
[0025] Computation of a unicast path may comprise computing respective unicast paths to every other node in the network. In some embodiments, computation of a unicast path may comprise computing respective distances to every other node in the network.
[0026] In some embodiments, detecting the unsafe condition comprises detecting a difference in a characteristic of the unicast path to the second node relative to a previous unicast path to the second node. In some embodiments, the characteristic is the distance to the second node. In other embodiments, the characteristic is the route traversed by each of the computed and previous unicast paths to the second node.
[0027] In some embodiments, detecting the unsafe condition comprises determining whether the computed unicast path would not have been a valid path on the previous topology (where “valid” is defined as the new path to the second node having a monotonic decrease in distance to the second node when traversed on the previous topology).
[0028] An advantage of the present invention is that, when a change occurs in the network, each node first makes itself safe (by the installation of unicast reverse path filtering information and the blocking any multicast traffic affected by the change in the network topography), and advertises that it has done so, before calculating the new multicast forwarding state. However, it cannot instantiate the changed multicast forwarding state until its neighbours (peers) have also indicated that they have made themselves “safe”. This achieves a significant degree of parallelism in the operation of synchronization, as typically upon completion of computation of multicast state, a node will have already received “safe” indication from its peers. The amount of computation to get to the “safe” state is only a fraction of that to compute the multicast FDB entries, requiring the computation of a single SPF tree only.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Further features and advantages of the present invention will become apparent from the following detailed description, taken in combination with the appended drawings, in which:
[0030] FIG. 1 is a flow-chart showing principle steps in a conventional method of computing and installing forwarding state in nodes of a multicast tree;
[0031] FIGS. 2 a - 2 d is a block diagram schematically illustrating state changes in a network subject to two topology changes, using the process of FIG. 1 ;
[0032] FIG. 3 is a flow-chart showing principle steps in a method of computing and installing forwarding state in nodes of a multicast tree, in accordance with a representative embodiment of the present invention; and
[0033] FIGS. 4 a - 4 d is a block diagram schematically illustrating state changes in a network subject to two topology changes, using the process of FIG. 3 .
[0034] It will be noted that throughout the appended drawings, like features are identified by like reference numerals.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0035] The present invention provides a method of computation and installation of multicast forwarding state in a network, in which the likelihood of transient loops is minimized, as compared to conventional methods. In a well behaved network, the likelihood of transient loops may be considered to be substantially eliminated. Embodiments of the invention are described below, by way of example only, with reference to FIGS. 3-4 d.
[0036] As described above with reference to FIG. 1 , when a node detects or is informed of a change in the network topology, it re-computes the shortest path between each node in the network such that the computing node can determine for which shortest paths it is an originating, transit or terminating node. When multicast group membership information is also advertised by the control plane, the node can then determine where intersections of multicast group membership occur for each of those pairs, inferring a multicast path accordingly. The forwarding state required to implement those paths is then installed in the node's filtering database (FDB), so that packet traffic received (directly or indirectly) from any node can be properly forwarded toward the destination node(s). Until the new forwarding state is installed, packets continue to be forwarded in accordance with the old forwarding state, that is, without regard to the changed topology of the network.
[0037] As described above, inconsistent distribution of topology change notifications combined with the delay in re-computing and installing new forwarding state creates the opportunity for transient loops to form. In general it takes a combination of elements from two or more non-looping versions of a multicast tree to produce a loop. This combination being produced by two or more topology changes, one which closes the loop, and one which changes the path to the root. Each multicast tree will have a unique component which, when combined with elements from other versions of the multicast tree, closes the loop. And, because of the RPFC performed by the network nodes, there must be at least two common components that connect the unique portions of each version of the multicast tree together.
[0038] In a network of n nodes, computation of unicast paths from any given node to all other nodes is a computational problem of order n log n, whereas computation of multicast paths is a computational problem that may reach order n 2 log n, and will always be more resource consuming than the unicast computation. As a result, for any given node in the network, re-computation of the unicast paths will normally be completed in less time than re-computation of the multicast paths. Further effects that will tend to enlarge the window within which a network is not synchronized and therefore may have transient loops, such as compute capability of individual nodes or overall network size, will also tend to extend multicast tree computation times far more than the unicast path computation times.
[0039] The inventors of the present invention have recognised that transient loops cannot form in a well behaved system if there is direct traceability of agreement on the path to the root of a given multicast tree from a given point in the network all the way to the root. At that point RPFC has ensured that the only valid source for a multicast tree is the root.
[0040] In practice such agreement can be verified by: invalidating multicast entries for a multicast tree when it has been determined that the path to the root of the tree has changed, as traceability of agreement has been lost; and only re-installing multicast entries when peers agree that they have similarly invalidated multicast state (new multicast forwarding state can be installed because all peers are safe) or for whom the path to the root has not changed (again the peer is safe, but this is because the traceability to the root was not interrupted). In both cases the agreeing nodes need to agree on what the multicast tree should be. The result is contiguous connectivity to the root will only occur when agreement is reached between nodes for which the path to the root has changed, or when a node for whom the path changed is adjacent to one for which it has not. It should be noted that since a node will only install multicast state when both it and its peers agree on the path to the root of the multicast tree, isolated looping in regions without traceability to the root cannot happen.
[0041] The inventors also acknowledge that it is possible to achieve an aggregated agreement on “safe” (that is, not specific to any individual multicast tree) by simply agreeing on the information from which any number of trees were derived. An example being a digest or checksum of the entire topology database.
[0042] In the example discussed above with reference to FIGS. 2 a - d , any possibility of looping will be broken upon the nodes detecting that, with the failure of link RB, the path to the root has changed, and therefore all multicast entries for trees originating at node R should be invalidated. More generally, the likelihood of transient loops can be minimized by implementing a path computation algorithm such that both RPFC and traceability are facilitated and inherent to the process. A representative algorithm that achieves this result is described below with reference to FIGS. 3 and 4 a - d.
[0043] In the embodiment of FIG. 3 , when a network topology change is detected (or, equivalently, when the network topology database is changed), a node first computes (at S 6 ) the shortest (unicast) path from itself to all other nodes in the network. The node then examines the computed unicast paths to identify any nodes for which the unicast path to that node has changed (at S 8 ) and traceability to the root is now suspect. For each such node, multicast forwarding state for which that node is the root of the respective multicast tree is then removed from the FDB (at S 10 ). Unicast forwarding state for each changed unicast path can then be installed in the node's Filtering Database (FDB), at S 12 . For implementations that can also perform RPFC, sufficient information will then exist in the FDB to perform this additional loop mitigation filtering.
[0044] There is a condition under which the path to the root changes, but multicast forwarding may be allowed to continue. This is when the computed distance between the node and a second node does not change. Under these circumstances, no loop can form and the multicast forwarding state for which that second node is the root of the multicast tree can be kept in the FDB and/or updated without waiting for a safe condition.
[0045] There is another condition under which the path to the root changes, but forwarding may be allowed to continue. This is when the new path to the root existed in its entirety in the topology database before the change, but was unused in that topology. Under these circumstances, no loop can form provided that each neighbour to which the node is transmitting on a multicast tree was further from the root in the topology prior to the change than the node's new next hop towards the root is in the new topology. This can be implemented as a per tree condition, so that multicast forwarding state for the entire tree is removed if any neighbour receiving from the node fails to satisfy the condition above, or it can be applied per neighbour, with filtering of the forwarding state to block transmission only to those neighbours which fail to satisfy the condition above.
[0046] As will be appreciated, removal of multicast state for multicast trees rooted at nodes to which the unicast path has changed blocks any multicast paths that were affected by the network topology change. Not restoring the multicast path until a neighbour indicates it has similarly either blocked the state, or the tree past that neighbour was unaffected by the change, and is therefore loop free extending to the root, prevents inadvertently creating a loop during installation of the new multicast forwarding state.
[0047] The node then advertises (at S 14 ) a digest of the network topology database to each of its peers in the network. This digest will normally contain information reflecting the new network topology. In some embodiments, the digest may take the form of a condensed or lossy representation of the contents of the topology database. In other embodiments, the digest may be a hash or checksum computed over the topology database. This advertisement can be interpreted, by each peer node that receives it, as a “safe” indication signal indicating that the advertising node is “safe”, at least in-so-far as it is aware of the new network topology and has removed multicast forwarding state for any multicast trees for which the path to the root has changed.
[0048] Once the digest has been advertised, the node begins re-computation of multicast paths (at S 16 ). However, installation of the new multicast forwarding state (at S 20 ) is delayed until a predetermined “go” condition is met (at S 18 ), which guarantees that installation of the new multicast forwarding state will not create a loop. In the case of a node having a single FDB common to all ports and not performing reverse-path forwarding check, the “go” condition to install the multicast forwarding state in the FDB is having received a “safe” indication signal, from all of the node's peers, with a network digest that matches that advertised by the node. In the case of a node having a respective different FDB associated with each input port or a node performing reverse-path forwarding check, the “go” condition to install multicast forwarding state for a multicast path, is receipt of a “safe” indication signal from each of the peers of the node that are on that path, with a network digest that matches that advertised by the node. The requirement for matching digests ensures that each of the involved network nodes has made itself “safe” with respect to the same version of the network topology database. This prevents a scenario in a node inadvertently creates a loop by installing multicast forwarding state in response to receipt of a “safe” indication signal which was generated on the basis of a different view of the network topology.
[0049] In the case of a node having a respective different FDB associated with each input port or a node performing reverse-path forwarding check, the “go” condition can be relaxed further. If the computed distance between the node and the second node is less than the former distance then the “go” condition to install the multicast forwarding state in the FDB is having received a “safe” indication signal, from the node's peer that is one hop toward the second node, with a network digest that matches that advertised by the node. If the computed distance between the node and the second node is greater than the former distance then the “go” condition to install the multicast forwarding state in the FDB is having received a “safe” indication signal, from all the node's peers on the multicast path that are one hop further away from the second node (that is, towards one or more destinations of the multicast tree), with a network digest that matches that advertised by the node.
[0050] It is anticipated that the foregoing process will be implemented in parallel by all nodes in a given network domain, so as to achieve distributed computation of paths across the network in response to changes in network topology. Furthermore, this process can be used, generally without modification, to install forwarding state for new paths being mapped through the network in response to customer requests. In such cases, where no actual change in the network topology has occurred, it will only be necessary to compute unicast paths to the node(s) involved in the customer requested new path, and the check at step S 8 will not identify any existing paths that are affected by the (non-existent) topology change, so it will not be necessary to remove forwarding state for any existing multicast trees (at S 10 ). However, the advertisement of “safe” indication signals, and delaying the installation of multicast forwarding state for the new path, as described above with reference to FIG. 3 , are still beneficial because they guarantee that installation of the new multicast forwarding state in each node will not inadvertently create a loop.
[0051] It will be appreciated that further network changes may occur during execution of the above-noted process; that is, prior to completion of installation of the new multicast forwarding state in the FDB. In some embodiments, the receipt of further topology database updates cause the process to reset, and begin again with computation of new unicast paths, progressing through a new “safe” indication advertisement and multicast FDB computation.
[0052] FIGS. 4 a - d illustrate operation of this process, in the network fragment and topology change scenario of FIGS. 2 a - d . FIG. 4 a corresponds with FIG. 2 a , and shows the network fragment prior to the topology changes. FIG. 4 b shows the two previously discussed simultaneous topology changes, namely: breaking of the physical link between nodes R and B; and additional of a new low-cost link between nodes D and E. These changes will be propagated across the network in a conventional manner, so that nodes B, C, D and E will begin re-computing the multicast tree to accommodate the new network topology. However, unlike in the conventional process discussed above with reference to FIGS. 2 a - d , in the embodiment of FIG. 4 , all four nodes will first compute unicast routes to other nodes in the network, and then break existing forwarding state related to the multicast tree (indicated by crosses through the arrows in FIG. 4 c ). In so doing, multicast traffic forwarding through the multicast tree is interrupted, in particular as the path to R has changed for all the nodes in the network, the multicast entries for trees rooted on R will be removed. Each node then installs new unicast forwarding state, as appropriate, and advertises respective “safe” indication signals. With specific reference to node D, this operation has the effect of completing the connection through the physical link to the source node R, and at the same time ensures that node D will discard any packets subsequently received from R via any other node (most importantly, in this example, from node C). When each node completes installation of forwarding state related to its unicast path(s), it begins its multicast computation. As each node receives “safe” indication signals from its neighbours, and completes installation of multicast forwarding state in its FDB, the network transitions to the stable state illustrated in FIG. 4 d.
[0053] As may be appreciated, the order of operations implemented in accordance with the preset invention eliminates the probability of a transient loop existing in a sane system and minimizes the period of time during which such a loop could persist in the presence of insane nodes. In particular, most transient loops in an insane system can be broken upon installation of forwarding state associated with the reverse unicast path. By performing this operation before beginning the more time-consuming process of recomputing the forward multicast path, the period of time during which transient loops can form is minimized. The step of breaking the forwarding state associated with the (old) forward multicast path interrupts the forwarding of multicast traffic from that node, and thus limits the amount of traffic that could potentially circulate in any loops that might form during the network resynchronization process.
[0054] In the embodiments described above with reference to FIG. 3 , a node first computes (at S 6 ) the shortest (unicast) path from itself to all other nodes in the network, and then examines the computed unicast paths to identify any nodes for which the unicast path to that node has changed (at S 8 ). For each such node, multicast forwarding state for which that node is the root of the respective multicast tree is removed from the FDB (at S 10 ). In an alternative embodiment, a different criterion may be applied to the removal of multicast state, with the benefit of minimising the duration of disruption to traffic. In particular, the computed unicast paths to identify any nodes for which the unicast path to that node has changed (at S 8 ) as described above. In this case, however, each identified changed unicast path is then checked to determine if that path would have been “valid” in the previous network topology. The new path cannot, by definition, be the shortest path in the previous topology (otherwise there would be no change between the old and new paths), but it may have been a valid alternate path. “Valid”, in this case, means that the new path to the root has a monotonic decrease in distance to the root when the nodes of the new path are traversed on the previous topology. This criterion is applied after a unicast path change to a root has been found, and tests whether the new unicast path to the root was a valid path to that root on the previous topology. If the new path would have been valid in the previous topology, new multicast state for that root may be computed and installed without awaiting the “go” conditions described above. If the new path would not have been valid in the previous topology, then the installation of new multicast state for that root must await receipt of “safe” indication signals from peer nodes, as described above.
[0055] The embodiment(s) of the invention described above is(are) intended to be exemplary only. The scope of the invention is therefore intended to be limited solely by the scope of the appended claims. | A method of installing forwarding state in a link state protocol controlled network node having a topology database representing a known topology of the network, and at least two ports for communication with corresponding peers of the network node. A unicast path is computed from the node to a second node in the network, using the topology database, and unicast forwarding state associated with the computed unicast path installed in a filtering database (FDB) of the node. Multicast forwarding state is removed for multicast trees originating at the second node if an unsafe condition is detected. Subsequently, a “safe” indication signal is advertised to each of the peers of the network node. The “safe” indication signal comprises a digest of the topology database. A multicast path is then computed from the network node to at least one destination node of a multicast tree originating at the second node. Finally, multicast forwarding state associated with the computed multicast path is installed in the filtering database (FDB) of the network node, when predetermined safe condition is satisfied. | 7 |
FIELD
[0001] The following discloses the use of thermosetting binder systems for use in the manufacture of composites from glass fiber. More particularly, the following pertains to thermosetting binder resins derived from renewable resources that are useful as binders in non-woven fiberglass goods.
BACKGROUND
[0002] Processes for producing glass fibers are well established and documented. In the rotary process, a stream of molten glass is delivered to an open spinning disc containing multiple orifices that causes fibers to extrude from the disc sidewall. The extruded fibers are directed downwardly toward a moving chain by pressurized air from nozzles in an annular ring positioned above the disc or by the jet blast of a gaseous combustion system. As the fibers fall from the spinning disc a rotating column of glass fiber is formed, which is sprayed with binder that is later heat cured in an oven. In the flame attenuation process, a coarse primary filament is drawn from a viscous silicate melt. Course fiber is then remelted and attenuated into many fine fibers. High velocity gases propel the fine glass fibers through a forming tube where a binder is applied. The coated fibers are deposited on a collecting chain where they entangle to produce a wool. Other glass fiber forming processes known in the art include fiber blowing processes, wheel centrifuge processes, and Downey processes. Acceptable binders coat the glass fibers in such a way as to provide strength and stiffness to the bonded glass fiber composition. The final products consist of bonded fiber glass batts, blankets and rolls employed in thermal and/or acoustical applications in residential or commercial buildings. Glass fiber based and/or reinforced products are also often found in original equipment manufacturer and other industrial applications.
[0003] In recent years the response to concerns over formaldehyde in building products has grown significantly. The Federal Environmental Protection Agency regulates the fiber glass manufacturing emissions of formaldehyde through the Maximum Achievable Control Technology Standards section of the Clean Air Act while the Occupational Safety and Health Administration and other Federal agencies regulate the workplace and product off-gassing of formaldehyde from insulation products made with traditional phenol formaldehyde binders. Formaldehyde has long been suspected as a probable human carcinogen and has been known to cause eye and throat irritations as well as respiratory aggravation. In June 2004, the International Agency for Research on Cancer, a division of the World Health Organization, classified formaldehyde as a known human carcinogen, a classification that likely will lead to further restrictions on human exposure to formaldehyde.
[0004] In response to concerns over exposure of formaldehyde in the environment, to factory workers employed in its use, and ultimately the consumers of products containing it, formaldehyde free thermoset binders have been developed and are employed to make the aforementioned products. The compositions of these developments are described in numerous patents, such as U.S. Pat. No. 5,661,213 to Arkens, U.S. Pat. No. 5,318,990 to Strauss, and U.S. Pat. No. 6,331,350 to Taylor et al. The Arkens, Strauss, and Taylor patents can be summarized as describing thermoset binder systems, free of any formaldehyde containing or generating components, and comprising a low molecular weight polycarboxylic acid, such as polyacrylic acid, and a polyol, such as triethanolamine, and phosphorus based catalyst.
[0005] While these formulations have proven successful in the production of fiber glass insulation materials, there still remains strong dependence on crude petroleum for the basic raw materials as well as a price structure highly impacted by crude oil prices. Although the reserves of crude oil appear to be plentiful in the future, the availability and price is controlled by the Organization of the Petroleum Exporting Countries. The acrylic based binders are more costly than traditional phenol formaldehyde binders and have been subjected to higher price increases. In addition, there a limited number of producers that manufacture the basic chemicals used to produce polycarboxylic acid. Therefore, a need exists for a thermosetting binder comprised of readily available, i.e. renewable, resources at a lower cost when compared to acrylic binders.
[0006] Vegetable oil derivatives have been used to supplement petroleum-based products in a variety of applications. Soy protein derived from soybeans has long been known as an additive and component in adhesive formulations, specifically wood adhesives. The high protein content of soybean makes for an excellent source of biopolymer material. While having excellent dry strength, typically biopolymer-based adhesives do not retain high strength when exposed to wet or humid conditions. For a binder to be acceptable as a fiber glass binder, it must be able to retain strength when exposed to wet or humid conditions so that compression packaged fiber glass will achieve a recovered thickness after installation and satisfy the specified thermal value.
[0007] The worldwide availability of soybeans, and thus soy protein, and the need for improved biopolymer-based adhesives has lead to the development of enhanced adhesive formulations derived from soy protein capable of achieving high strength in wet or humid conditions. Recent developments in the area of soy-based adhesives have focused on uses in the manufacture of wood-derived products. U.S. Pat. No. 6,719,882 issued to Vijayendran et al. describes a resin-binder system prepared by hydrolyzing protein to produce protein hydrosylates which are then mixed with a synthetic resin to produce a resin binder. U.S. Pat. No. 6,306,997 issued to Kuo et al., incorporated herein by reference, describes a soybean-based adhesive resin useful as a replacement for urea-formaldehyde resins in the manufacture of wood composite panel products. U.S. Pat. No. 6,790,271 issued to Thames et al., incorporated herein by reference, describes a mixture of soy protein isolate, polyol plasticizer, and vegetable oil derivative useful as an adhesive in the formation of particleboard and other wood composites. U.S. Patent Application Publication No. 2004/0089418, incorporated herein by reference, also contains further details of soy-derived adhesive technology which comprises improved thermosetting adhesives consisting of soy protein isolate or kraft lignin treated with a crosslinking agent.
[0008] The development of agriculturally based binders to replace conventional binder systems in the formation of glass fiber composites would represent a significant advancement in the art. This disclosure is directed to manufacturing methods for forming glass fiber products utilizing renewable resources in the form of agriculturally based binders in the manufacturing process. A method for forming glass fiber composites using an agriculturally based binder is disclosed and claimed herein.
SUMMARY
[0009] A method for forming a glass fiber composite by applying an agriculturally based binder to a glass fiber substrate and curing the resulting glass fiber composite to form a glass fiber article is disclosed. In one embodiment, the agriculturally based binder is derived from soy protein.
DESCRIPTION OF EMBODIMENTS
[0010] Fiberglass binders have a variety of uses, including uses in fully cured systems such as building insulation. Fibrous glass insulation products generally comprise a glass fiber substrate of matted glass fibers bonded together by a cured thermoset polymeric material. Molten streams of glass are drawn into fibers of random lengths and blown into a forming chamber where they are randomly deposited as a mat onto a traveling conveyor. The fibers, while in transit in the forming chamber and while still hot from the drawing operation, are sprayed with an aqueous binder. The residual heat from the glass fibers and the flow of air through the fibrous mat during the forming operation are generally sufficient to volatilize water from the binder, thereby leaving the remaining components of the binder on the fibers as viscous or semi-viscous high solids liquid. The coated fibrous mat is transferred to a curing oven where heated air, for example, is blown through the mat to cross-link the components, cure the binder, and rigidly bond the glass fibers together. In the flame attenuation process, a coarse primary filament is drawn from a viscous silicate melt. Course fiber is then remelted and attenuated into many fine fibers. High velocity gases propel the fine glass fibers through a forming tube where a binder is applied. The coated fibers are deposited on a collecting chain where they entangle to produce a wool-like fiber composite. Other glass fiber forming processes known in the art include fiber blowing processes, wheel centrifuge processes, and Downey processes. The resulting glass fiber composite has a variety of applications, including uses as building and industrial insulation, and glass-based substrates useful in the manufacture of wall board facing, filter stocks, reinforcement scrims, and the like.
[0011] Fiberglass binders used in the present sense should not be confused with matrix resins which are an entirely different and non-analogous field of art. While sometimes termed “binders,” matrix resins act to fill the entire interstitial space between fibers, resulting in a dense, fiber reinforced product where the matrix must translate the fiber strength properties to the composite, whereas “binder resins” as used herein are not space-filling, but rather coat only the fibers, and particularly the junctions of fibers. Fiberglass binders are not directly analogous to paper or wood product “binders” where the adhesive properties are tailored to the chemical nature of cellulosic substrates. While many such resins are not suitable for use as fiberglass binders without modification, agricultural derived wood adhesives and binder share some common constituents that can be altered and adjusted for use with the manufacture of glass fiber composites.
[0012] Binders useful in fiberglass insulation products generally require a low viscosity in the uncured state, yet possess characteristics so as to form a rigid thermoset polymeric bond of the glass fibers when cured. A low binder viscosity in the uncured state is required to allow the glass fibers to bind correctly. Also, viscous binders commonly tend to be tacky or sticky and hence they lead to the accumulation of fiber on the forming chamber walls. This accumulated fiber may later fall onto the collected fibers causing dense areas and product problems. A binder which is rigid and insoluable when cured is required so that, for example, a finished fiberglass thermal insulation product, when compressed for packaging and shipping, will recover to its as-made vertical dimension when installed in a building. Water is used as a diluent with the polymer-forming components to form a binder.
[0013] From among the many thermosetting polymers, numerous candidates for suitable hermosetting fiberglass binder resins exist. Agricultural-based derivatives, with appropriate modifications, can make suitable precursors from which binder resins can be synthesized. In one embodiment, a binder resin is synthesized by combining an agricultural isolate with an appropriate compound having curing and adhesive properties. In another embodiment, a binder resin is synthesized by combining a vegetable protein with an appropriate compound having curing and adhesive properties. In an alternate embodiment, a binder resin is synthesized by combining a vegetable protein with one or more formaldehyde-free compounds having desirable curing and adhesive properties. As used herein, “FF” means “formaldehyde-free.” Since formaldehyde exists in nature, FF as used herein means that exogenous formaldehyde is not added to the binder resin. That is not to say, however, that formaldehyde endogenous to a compound, as a reactant bi-product or otherwise, has been removed from all compounds described herein. In another embodiment, the vegetable protein is a soy protein. In an alternate embodiment, a binder resin is synthesized by combining a vegetable protein isolate with one or more curing agents, including an amine, amide, imine, imide, or nitrogen-containing heterocylic functional group that can react with at least one functional group of the soy protein isolate. In yet another embodiment, the amine is a di- or multi-functional primary or secondary amine. In another embodiment, the di- or multi-functional primary or secondary amine includes 1,2-diethylamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, piperazine, 4,4′-xylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and mixtures thereof.
[0014] Soy proteins can be prepared for use in a fiber glass binder and combined with other compounds to form adhesive compositions. Inter- and intra- molecular hydrogen bonds inherent in soy proteins can be disrupted through the use of plasticizers such as polyhydric alcohols. Numerous polyols are suitable for use as plasticizers, including, but not limited to, hexanediols, hexanols, butanediols, propanediols (such as trimethylol propane), propanetriols (such as glycerol), and ethanediols. While plasticizers improve molecular mobility at high temperatures, plasticizers reduce T g . To counteract a polyol effect on T g , other compounds can be added to soy protein-based fiber glass binder resins to improve rigidity after a fiber glass composite has been cured. Lignins, calcium arbonate, and silicates are all known adhesive stiffeners. Other compounds, such as adhesion promoters, oxygen scavengers, moisture repellants, solvents, emulsifiers, pigments, fillers, anti-migration aids, coalescents, wetting agents, biocides, plasticizers, organosilanes, anti-foaming agents, colorants, waxes, suspending agents, anti-oxidants, silanes, and crosslinking catalysts, can be added to the binder resin to improve its properties as a glass fiber resin. In one embodiment, a soy-based adhesive is synthesized with one or more compounds having desirable curing, adhesive, and stiffening properties. In another embodiment, the silane is an organosilane. As mentioned above, multiple examples of soy-based binder systems and related additives are known in the art (U.S. Pat. No. 6,719,882; U.S. Pat. No. 6,306,997; U.S. Patent No. 6,790,271; U.S. Patent Application Publication No. 2004/0089418), and such additives may be used to improve the properties of the general compositions for use as a binder system for the formation of fiber glass composites.
EXAMPLE
[0015] To form a fiber glass composite, molten streams of glass can be drawn into fibers of random lengths and blown into a forming chamber where they can be randomly deposited as a mat onto a traveling conveyor. The fibers, while in transit in the forming chamber and while still hot from the drawing operation, can be sprayed with an aqueous soy-based binder. The residual heat from the glass fibers and the flow of air through the fibrous mat during the forming operation can be generally sufficient to volatilize water from the binder, thereby leaving the remaining components of the binder on the fibers as viscous or semi-viscous high solids liquid. The coated fibrous mat can be transferred to a curing oven where heated air, for example, is blown through the mat to cure the binder and rigidly bond the glass fibers together.
[0016] Principles, embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention. | The use of thermosetting binder systems in the manufacture of glass fibers and composites manufactured from glass fiber is disclosed, and in particular, thermosetting binder resins derived from renewable resources that are useful as replacements for formaldehyde-based binders in non-woven fiberglass goods. | 3 |
This application is a continuation of application Ser. No. 08/365,616, filed on Dec. 28, 1994.
TECHNICAL FIELD
This invention relates to arrangements for informing customers of a change of service or service provider.
Problem
In an exemplary problem situation telephone customers are allowed to select a preferred in exchange carrier to serve toll calls for which the caller does not supply a specific per call selection of a carrier. The selected carrier is effectively a preferred carrier used in default of a specific indication on the call of which carrier is to carry the call. Provision of telephone toll services is a highly competitive business and the competitors try very hard to attract customers into selecting them as the preferred toll carrier. In practice, the preferred toll carrier carries a very large majority of the calls initiated by a typical customer so that the selection is equivalent to attracting most of the toll business generated by the customer. This situation has led to various types of abuse whereby callers are switched to a different toll carrier without having a true intent to make the switch. Sometimes this switch is made as a result of deliberate or good faith misunderstanding of the switched caller's intentions and sometimes the switch is made as a result of trickery. An example of the latter is a case in which callers are given vouchers for some nominal amount (perhaps 10 dollars) and in signing the endorsement of the voucher they sign a statement, frequently in small print, that they wish to be transferred to a particular toll carrier.
A specific problem of the prior art therefore is that changes in the preferred carrier for providing toll telephone service can be made without a customer having a true intention to have such a change made and frequently, the customer is not specifically informed that a change is being, or has been made. A more general problem is that a switch of type of service provider or type of service in any of a number of fields are made without the true intent and consent of the party allegedly requesting the change. Examples of service providers include local toll provider, wireless service provider, cable TV program supplier, preferred electric power or gas supplier, or appliance maintenance service supplied from a common referral service. Examples of services in the field of telephony include a service wherein a customer receives a discount based on length of service with a provider or receives a discount on all calls of a type in return for a flat fee paid every month, a different local calling plan (e.g., expanded flat rate service), custom calling features (call waiting, call forwarding, three-way calling), voice mail services, and home wire service (Ameritech's Line Backer®).
Solution
The above problem is substantially alleviated and a contribution is made to the art in accordance with applicant's invention wherein customers are notified at the time of use of a service that the provider or the type of service has been changed or is about to be changed. Advantageously, the customer receives such notification at a time when the customer is about to use the service and usually away from sources of sales pressure.
In accordance with one aspect of the invention a customer receives an announcement of the change for a definable period of time and/or a definable number of uses of the service. This ensures that the customer has ample opportunity to cancel an apparent or alleged request.
In accordance with another aspect of the invention, a new service provider or the provider of the changed service supplies the customer with a positive validation number and the service provider is not changed or the new type of service is not activated until the customer supplies the number. In accordance with one preferred embodiment, the customer supplies the number in response to a request from the telecommunication network at a time when the customer is requesting the service. Advantageously, such an arrangement gives a high degree of protection against false activation of a request to change service or to change service provider.
In accordance with another aspect of the invention the customer who receives the announcement is given an option to indicate one of a number of courses of action including validation of the proposed change, cancellation of the proposed change, deferral of a decision on the proposed change or the option of talking to a customer service representative. The customer service representative can be selectable to be a representative of the old service provider or the new service provider. Advantageously, such an arrangement gives the customer a simple way of validating or canceling a request.
In accordance with another aspect of the invention customers are simply given an announcement of a change and optionally provided with a telephone number to call in case they have any questions or wish to cancel the change.
The arrangement can be used for offering customers a trial service, and for notifying the customers of a renewal period, because the customers are informed of the service and because they have the ability to validate or cancel the service.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a block diagram illustrating the operation of applicant's invention;
FIGS. 2-4 are flow diagrams illustrating the method of applicant's invention; and
FIG. 5 is a layout of customer data in an equal access data base for implementing applicant's invention.
DETAILED DESCRIPTION
FIG. 1 is a block diagram illustrating the operation of applicant's invention. Telephone station 1 and telecommunications terminal 2 are both connected to a local access switch 3. Either of these stations may receive announcements although the announcement to station 1 is likely to be oral whereas the announcement to station 2 may be in the form of data for controlling a video display. Local access switch 3 is connected to a message processor 4 for supplying announcements and to the caller and accepting control instructions from the caller. Local access switch 3 is also connected to a local toll switch 5 which is connected to another local access switch 8 for completion of local toll calls, for example telephone station 1 and a telephone station 10 connected to local access switch 8.
Local access switch 3 is also connected to a toll switch 6 possibly via toll access switch (not shown) and the toll switch 6 is connected to another local access switch 7 (possibly via a toll access switch, not shown) which local access switch is connected to a telephone 9 for completion of interexchange area toll calls between, for example, telephones 1 and 9.
Local access switch 3 includes a processor 12 for controlling a switching network 14 and accessing an equal access data base 16. The switching network is used for connecting callers to each other or to the telecommunications network for completion of calls to telephone stations or terminals connected to other switching systems. The equal access data base contains data for identifying an interexchange toll carrier for use in completing telephone interexchange toll telephone calls when the caller does not specifically request the use of a interexchange carrier (a caller can request that a particular interexchange carrier be used on a particular call by dialing a prefix of 10 followed by a three or four digit identification of the interexchange carrier followed by the telephone number of the destination). The object of the equal access data base is to allow each customer to specify a preferred toll carrier so that calls may be completed using this prespecified toll carrier without requiring the customer to dial additional information to specify such a carrier. Note that while the preferred embodiment is described in terms of interexchange carrier selection the same principles can be used for selecting a preferred local exchange area toll carrier or a preferred supplier of video services. Note further that while the specific embodiment shows the equal access data base as being within local access switch 3, in other embodiments, a centralized equal access data base, shared by many switches is used instead.
The message processor comprises a control processor 22 and an announcement system 24, data transceiver 25, dual tone multifrequency receivers 26, speech recognition circuits 28 and a data base 29. Any of the blocks 24, 25 26 or 28 are connectable via a small switching network 30 to communications connection 34 to local access switch 3. In addition the control processor 22 is connected via data link 32 with the processor of the local access switch 12. The message processor may supply announcements to the caller through an announcement system 24, data for controlling a display through the data transceiver 25 and may detect from the caller data signals in the data transceiver 25, dual tone multifrequency signals in DTMF receivers 26 or speech signals in speech processor 28. The announcement system can be programmed to respond to user input to provide multi-lingual responses. Speech processor 28 may be used for example in communicating with dial telephones which generate signals that cannot pass through the telecommunications network; if such telephones are connected to local access switch 3 via an intermediate switching system, then dial signals cannot be received in local access switch 3. Data base 29 provides data for the types of announcements or data to be transmitted back to callers and would include any customized announcements for specific service providers or services.
FIGS. 2-4 are flow diagrams illustrating the operation of applicant's invention. The first block of FIG. 2 indicates that the customer has gone off hook (action block 202). A local access switch identifies the customer using the well-known technique of automatic number identification (ANI) (action block 204). The number of the customer is used subsequently by processor 12 of local access switch 3 to access the equal access data base 16 in order to determine which interexchange carrier should carry the call.
Next, the local access switch 3 determines that the customer has dialed an interexchange toll call (action block 205). As noted above, similar kinds of provisions can be made for local exchange toll calls.
In the future, simple local calls may be served by either the local telephone company, a cable TV service provider, or local wireless server. Selection of the preferred carrier for simple local calls may be made in customer premise equipment (e.g., the set top box used for cable TV), which is programmable externally by one of these carriers. Similar needs exist to notify the customer, if their local preferred service provider selection has changed, no matter how.
For emergency calls ("911"calls), all special announcements, including those of applicant's invention, are bypassed.
The local switch then accesses the equal access data base (action block 206). The data received from this data base is then examined to determine whether the customer's preferred toll carrier has changed (test 207). If not, then the switch and telecommunications network processes the call normally as in the prior art (action block 208).
If the preferred toll carrier has changed, then test 210 determines whether the customer has validated the choice of the changed carrier. If so then the call is processed normally as in the prior art (action block 212). If the customer has not validated the choice, then test 214 is used to determine whether the announcement period has expired and/or number of announcements specified for this customer or for this switch has been reached. If the time interval has expired and/or the number of announcements has been reached, then the call is processed normally as in the prior art (action block 216). Otherwise test 220, which appears in the beginning of FIG. 3, is entered.
The above description is for the situation in which an interchange toll carrier is being changed. Essentially, the same flow diagram may be used for other changes of telecommunications carriers or service. For other types of service provider or service changes, the same arrangement can be used, and can be triggered by any telephone service request.
Alternatively, for other changes of service provider or service, a call to the customer is initiated by the old or new service provider (action block 201). After the customer answers (action block 203), the subsequent interactions between a call processing system and the customer are essentially the same, except that no toll call is completed since the customer did not initiate such a call.
Test 220 is used to determine whether data for validation (a validation code) from the subscriber is required. This option is likely to be an option for a particular switch or, effectively, a particular local exchange carrier, or may be mandated by rules of a regulatory body. It is also possible that in a particular switch, the validation code would be required for some carriers but not for others. At any rate if such a validation code is required, then an audible or visual message or prompt is returned to the caller asking that the validation code be supplied (action block 222). Such a validation code would be given to the customer by the new interexchange carrier at the time that the customer agrees to change interexchange carriers; for other applications, the validation code can be supplied at the time that the caller agrees to make whatever other change is being considered. Test 224 checks whether the code entered by the caller matches a code previously recorded for that particular customer. If there is no match, the caller is reprompted and given another chance. If the caller consistently fails to enter the correct code the customer receives a prompt for help (action block 233). Test 234 is used to determine whether the customer wants help, if not, the call is processed normally using the old carrier (action block 238). If the customer does request help then the customer receives the help (action block 236). In the preferred embodiment the help is provided through a connection to a customer service representative. Alternatively, help may be provided through an oral or displayed menu, and visual or voice prompting, with DTMF or voice response, and, probably, an operator default.
If the code matches, then a verification message is given to the caller either through an audible announcement or through data for controlling a display at the caller's telephone (action block 226) and the system recognizes that it has a customer validated service provider change (action block 228). The equal access data base is then updated to indicate that the customer is now being served by the new interexchange carrier and the message is turned off so that the customer will not receive subsequent announcements or messages about the change of interexchange carrier (action block 230). Thereafter, normal call processing of the call that was dialed proceeds (action block 232).
If no validation code is required (negative result of test 220) then test 240 is used to determine whether customer feedback is requested. Test 240 has the same basic characteristic as test 220, namely, it is likely to be provided as an option in a particular local access switch or at the request of the new carrier. If no feedback is requested then the carrier change notification is provided in audible or visual form to the caller (action block 242). In the preferred embodiment the notification would include the date of the requested activation of the change to the new carrier, an optional advertising message, probably for the new carrier, and an indication that if the customer is unhappy about the switch, he/she should call a specified customer service number. Additionally, such an announcement might include a message from the old carrier effectively conveying some inducement to encourage the customer to cancel the change request or warning the customer of the drawbacks and/or costs of making the change. In addition, this message also has an indication that if the customer wishes to have the announcement stopped, i.e., if the customer is happy with the change and does not want to be annoyed with further announcements, the customer can stop the announcements through the act of keying a 1. Test 244 then checks whether a 1 has been keyed. If so the announcement is shut off (action block 246), the switch to a new carrier is effectively validated, and the customer will not get further announcements. Thereafter, the call is processed normally (action block 248). If the customer does not key in a 1, then the actions of block 246 are bypassed and the call is simply processed normally (action block 248).
The announcement is selected for the customers experiencing a specific change. Therefore the announcement can include such details as the fact that the customer is being given a trial service which requires acceptance in order to be continued, that the customer's service is up for renewal and requires re-validation, or that the carrier would like to receive feedback concerning the service from the customer (such an announcement would include a telephone number of an operator or automatic voice/data entry system for the feedback).
The case in which customer feedback is requested is covered in FIG. 4 which begins with decision block 260. Decision block 260 is used to determine whether the customer's service provider has already been changed. This decision block has the same characteristic as decision blocks 220 and 240, namely that it is basically at the discretion of the local exchange carrier operating the local access switch, or the keeper of the equal access data base. (In this case it would be in the interest of the changed-to carrier to change the service as quickly as possible so that if that carrier specified the outcome of decision block 260, the "yes" leg is most likely to be requested.)
If the outcome of decision block 260 is positive, then action block 262 provides an announcement indicating the change of carrier, the identity of the new carrier, and providing options to the caller. The options are summarized in action block 264 and include: 1 (accept the change); 2 (cancel the change); 3 (delay the decision); and 4 (connect to customer service because the caller is confused). The default in case the caller keys nothing is also a connection to customer service. In case the caller keys a 1, then announcements are canceled and a record is made of the customer's acceptance in billing records for that caller (action block 266). If the caller keys a 2 requesting a cancellation of the change, then the records are changed to the pre-implementation state so that the customer will subsequently be served by the previous interexchange carrier, and a record is made in the billing records to indicate that the customer has canceled the request (action block 268). If the customer keys a 3, then the call is simply sent to normal call processing (action block 270) and the caller will receive an announcement the next time that the caller dials an interexchange toll call. If the customer keys a 4 or does nothing (timeout), then the customer is automatically connected to a customer service representative (action block 272). (If the caller calls at a time when no customer service representatives are available, the customer will receive an announcement indicating the number to call when service representatives are available.) Appropriate announcements (not shown) can also be provided if the customer keys a validation or cancellation code. The announcements for the validation or cancellation code may include an advertisement and/or warning of costs and benefits lost as a result of the switch or failure to go through with the change, respectively.
In this specific embodiment, four responses, namely keyed 1, 2, 3, or 4 are shown. In alternative embodiments, a larger number of more detailed responses can be used. For example, a validation response might be a two or three character code to ensure that validation is not accidental. A feedback loop to ensure the intentional character of the customer's validation or cancellation, and to give a customer another chance if the validation response is incorrect, enhances the reliability of the procedure.
In case the result of test 260 is that the service provider has not yet been changed, in anticipation of input from the caller then the caller receives an announcement (action block 280) which is essentially the same kind of announcement received in action block 262. The customer then keys a response (action block 282). If the customer has keyed a 1 indicating an acceptance, then the records are changed to show that the new carrier is the preferred carrier and the call is established using the new carrier (action block 284) and normal call processing proceeds (action block 290). If the customer keys a 2 indicating a cancellation of the earlier request then the request for change is canceled; a record is made of the cancellation in billing records and the caller will receive no more announcements (action block 286). Thereafter, the call is established using normal call processing (action block 290). If the caller keys a 3 indicating a delay in the decision, then the call will be processed conventionally (action block 290) using the indicated interexchange carrier which in this case will be the old carrier. If the customer keys in a 4 then the customer is connected to a customer service representative (action block 288). The customer is also connected to a customer service representative (action block 288) if the customer does nothing (timeout) or keys some undefined response. If the customer is to be connected to a service representative, the customer may select, based on keyed information, either a representative of a regulatory agency (to register a complaint), a local exchange carrier, the old preferred toll carrier, or the new preferred toll carrier.
FIG. 5 illustrates some of the data maintained for customers in the equal access data base in accordance with applicant's invention. This data includes the automatic number identification of that customer, the identity of the old and the new preferred carrier, e.g., the carrier interconnect codes of the old and new preferred carriers, an indication of the number of the announcements already given to the caller, an indication of the date of change requested by the caller, an indication of the date of acceptance of the change by the caller, the status of the change (i.e., whether or not the change has in fact been made so that the customer is expected to be served by the new preferred carrier and whether the customer has already approved of such a change), and the code number supplied to that customer by the new carrier for verifying the customer's intention to make the change.
It is to be understood that the above description is only of one preferred embodiment of the invention. Numerous other arrangements may be devised by one skilled in the art without departing from the scope of the invention. The invention is thus limited only as defined in the accompanying claims. | An arrangement for routing the possibility of switching telephone users to another preferred carrier without the intent of the telephone user. When a record has been made in a data base indicating a change of preferred carrier, the telephone user is provided with an announcement indicating the change when the user makes a toll call. In accordance with one embodiment of the invention the user simply is informed and if the user wants to undo the change the user contacts the local carrier. In accordance with another embodiment the user is provided with a validation code and must enter the validation code in order to effect the change of carriers. In accordance with another embodiment the user is provided with a number of options including the keying of a request to effect the change of carrier, or cancel the change of carrier. Advantageously, users are informed of a change of carrier before they make any calls using the new carrier and before they receive any telephone bills identifying the change. | 7 |
TECHNICAL FIELD
The present invention relates to a structure for retaining a drive ring rotatable with respect to a nozzle mount in a variable displacement exhaust turbocharger, which is used for an exhaust turbocharger of an internal combustion engine and which is equipped with a variable nozzle mechanism for varying a vane angle of a plurality of nozzle vanes.
BACKGROUND ART
As one variable displacement exhaust turbocharger which is used for an exhaust turbocharger of an internal combustion engine and which is equipped with a variable nozzle mechanism for varying a vane angle of a plurality of nozzle vanes, the technique of JP 2010-19252 (Patent Document 1) is provided.
This technique of the related art is illustrated in the attached drawings. FIG. 6A is an illustration of a turbine housing 010 . FIG. 6B is a partial enlarged view of section P of FIG. 6A . FIG. 6C is an exploded view of components of FIG. 6B .
A variable nozzle mechanism 0100 is configured such that a plurality of guide vanes (nozzle vanes) 080 is positioned between a lower vane ring 020 and an upper vane ring 030 . The guide vane 080 is rotatably supported about an axis to control a flow rate of exhaust gas flowing in a turbine. The distance between the lower vane ring 020 and the upper vane ring 030 is maintained by a stepped spacer 050 which is positioned therebetween. The upper vane ring 030 and the lower vane ring 020 are attached to the turbine housing 010 by nuts 040 and metal fastening members 042 .
Further, the stepped spacer 050 has a through-hole formed in the center so that the fastening member 042 can pass through the stepped spacer 050 .
Meanwhile, another technique is disclosed in JP 4545068B (Patent Document 2). A variable displacement exhaust turbocharger of JP 4545068B is configured, as illustrated in FIG. 7 , such that a drive ring 064 is arranged on a peripheral circumferential surface of a guide part 057 of a nozzle mount 055 to be disposed between a side face of a lever plate (not shown, disposed on a left side of the drive ring 064 ) and a side face of the nozzle mount 055 so that they are next to each other in the axial direction and a stud with a flange (a nail pin) 066 is fixed to a side part of the nozzle mount 055 to be in contact with an outer surface 064 a of the drive ring 064 so as to prevent the drive ring 064 from moving in the axial direction, i.e. coming off toward the lever plate side.
In FIG. 7 , a nozzle vane 068 is provided between the nozzle mount 055 and an annular support plate 070 .
CITATION DOCUMENT
Patent Document
[Patent Document 1]
JP 2010-095252 A
[Patent Document 2]
JP 4545068 B (FIG. 3)
SUMMARY
Technical Problem
However, the stepped spacer 050 described in Patent Literature 1 has the central through-hole for the fastening member 042 to pass through. Further, this stepped space 050 is provided to maintain the distance between the lower vane ring 020 and the upper vane ring 030 where the plurality of guide vanes (nozzle vanes) 080 is arranged.
Patent Document 1 teaches to use the stepped spacer 050 for positioning. However, there is no disclosure as to the use of the stepped spacer 050 for positioning of the drive ring in a thrust direction by fitting the drive ring for varying a vane angle of the nozzle vane to the guide part of the nozzle mount.
In the fixing mechanism of Patent Document 2 using the nail pin 066 capable of abutting to the outer surface 064 a of the drive ring 064 , the guide part 057 of the nozzle mount 055 is required to have a space to accommodate a mounting width of the drive ring 064 . Correspondingly, the nozzle mount 055 is required to have a significant width in the axial direction of the nozzle mount 055 . It results in increase of the nozzle mount 055 in size and weight, and this also makes it difficult to manufacture the nozzle mount 055 by press-molding. Moreover, as the width dimension of the guide part 057 of the nozzle mount 055 needs to be machined with high precision in relation to the width dimension of the drive ring 064 , and this causes an increase in the number of the processing steps.
In view of the above issues, it is an object of the present invention to reduce the weight and production cost of a nozzle mount by pres-fitting a pin with a flange portion into a press-fitting hole formed in an end face of a guide part along a thrust direction so as to retain the drive ring to the guide part of the nozzle mount in the thrust direction and providing an adjusting member (a spacer member) between the flange portion and the end face for adjustment in the thrust direction.
Solution to Problem
To solve the above issues, the present invention provides a variable displacement exhaust turbocharger which is equipped with a variable nozzle mechanism and is driven by exhaust gas from an engine, and the variable displacement exhaust turbocharger comprises:
a plurality of nozzle vanes supported rotatably by a nozzle mount which is fixed to a case including a turbine casing of the variable displacement exhaust turbocharger;
a drive ring which is interlocked with an actuator and is fitted to an annular guide part protruding from a center part of the nozzle mount in an axial direction, the guide part having a width in a thrust direction which is smaller than a width of the drive ring;
a plurality of lever plates each of which is fitted to a groove formed in the drive ring at one end via a connection pin and is connected to the nozzle vane at the other end;
a press-fitting pin which has a flange portion facing a side face of the drive ring, the press-fitting pin being press-fitted into a press-fitting hole formed in an end face of the guide part along a thrust direction of the guide part so as to retain the drive ring in the thrust direction; and
an adjusting member arranged between the flange portion of the press-fitting pin and the end face of the guide part,
wherein the adjusting member is configured to adjust a distance between the flange portion of the press-fitting pin and a side face of the nozzle mount, the drive ring being sandwiched between the flange portion and the side face of the nozzle mount.
According to the present invention, by reducing the thrust-directional thickness of the guide part of the nozzle mount and providing the adjusting member for adjustment in the thrust direction between the guide part and the flange portion for restricting rocking of the drive ring in the thrust direction, it is possible to form an appropriate amount of clearance in the thrust direction of the drive ring.
Therefore, as the guide part can be shortened in the thrust direction by the amount equivalent to the thickness of the adjusting member (in the thrust direction of the guide part), it is possible to achieve weight reduction and cost reduction of materials.
Further, by reducing the thrust-directional thickness of the guide part of the nozzle mount, it is possible to reduce the thrust-directional thickness of the nozzle mount including the guide part in the thrust direction. This enables production by press working, thereby reducing the production cost.
In a preferred embodiment of the present invention, the adjusting member comprises the press-fitting pin formed integrally with the flange portion.
By forming the adjusting member integrally with the press-fitting pin, it is possible to simplify the mounting work and production of the adjusting member.
It is also preferable in the present invention that the adjusting member has an annular shape and is formed by a separate member from the press-fitting pin.
With this configuration, the adjusting member can be formed separately, and thus it is possible to precisely process the adjusting member to a desired thickness.
Advantageous Effects
With the configuration that the thrust-directional width of the guide part is made smaller than the width of the drive ring, the adjusting member is sandwiched between the flange portion of the press-fitting pin and the end face of the guide part, the distance between the side face of the nozzle mount supporting the drive ring and the flange portion of the press-fitting pin is adjusted by the adjusting member, an amount of clearance at the guide part in the thrust direction of the drive ring is adjustable using the adjusting member. Thus, compared to the case where the thrust-directional length of the guide part is precisely processed by end mill machining or the like, the production cost can be reduced.
Moreover, as the thrust-directional length of the nozzle mount can be reduced by the amount of the thickness of the adjusting member (in the thrust direction of the guide part), it is possible to achieve the weight reduction and cost reduction of the materials. Further, by reducing the thrust-directional thickness of the guide part of the nozzle mount, it is possible to reduce the thrust-directional thickness of the nozzle mount including the guide part. This enables production by press working, thereby reducing the production cost.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a longitudinal cross-sectional view of a main part of a variable displacement exhaust turbocharger equipped with a variable nozzle mechanism according to an embodiment of the present invention.
FIG. 2A is a front view of a variable nozzle mechanism according to a first embodiment of the present invention, which is taken from a lever plate side.
FIG. 2B is a cross-sectional view in A-A of FIG. 2A .
FIG. 3A is an enlarged cross-sectional view of a part where a nail pin is press-fitted in a nozzle mount according to a first embodiment of the present invention, which is taken in B-B of FIG. 2A .
FIG. 3B is an enlarged view of a press-fitting hole on a nozzle mount side according to the first embodiment of the present invention.
FIG. 3C is a schematic view of the nail pin according to the first embodiment of the present invention.
FIG. 4A is an enlarged cross-sectional view of a section where a nail pin according to a second embodiment of the present invention is press-fitted in the nozzle mount.
FIG. 4B is an enlarged view of a press-fitting hole on the nozzle mount side according to the second embodiment of the present invention.
FIG. 4C is a schematic view of the nail pin according to the second embodiment of the present invention.
FIG. 5 illustrates a schematic configuration of the nail pin according to a third embodiment.
FIG. 6A illustrates a turbine housing 010 of the related art.
FIG. 6B is a partial enlarged view of section P of FIG. 6A .
FIG. 6C is an exploded view of components of FIG. 6B .
FIG. 7 is an illustration of the related art.
DETAILED DESCRIPTION
Embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
It is intended, however, that unless particularly specified, dimensions, materials, shapes, relative positions and the like of components described in the embodiments shall be interpreted as illustrative only and not limitative of the scope of the present invention.
(First Embodiment)
FIG. 1 is a longitudinal cross-sectional view of a main part of a variable displacement exhaust turbocharger equipped with a variable nozzle mechanism according to an embodiment of the present invention.
FIG. 1 illustrates a turbine casing 30 , a scroll 38 of a scroll shape formed in an outer peripheral part of the turbine casing 30 , a turbine rotor of a radial flow type 34 , a compressor 35 , a turbine shaft 32 for connecting the turbine rotor 34 and the compressor 35 , a compressor housing 31 and a bearing housing 36 .
The turbine shaft 32 connecting the turbine rotor 34 and the compressor 35 is rotatably supported by the bearing housing 36 via two bearings 37 , 37 . The drawing also illustrates an exhaust gas outlet 8 and a rotation axis CL of the exhaust turbocharger.
A plurality of nozzle vanes 2 is arranged on an inner circumferential side of the scroll 38 at equal intervals in the circumferential direction of a turbine and is supported rotatably by a nozzle mount 5 . A nozzle shaft 2 a is formed on a vane end of the nozzle vane 2 and is rotatably supported by the nozzle mount 5 which is fixed to the turbine casing 30 .
On an opposite side of the nozzle shaft 2 a from the vane end, a lever plate 1 for varying a vane angle of the nozzle vane 2 by rotation of the nozzle shaft 2 a is connected to the drive ring 3 via a connecting pin 10 .
An actuator rod 33 is configured to transmit a reciprocating motion from an actuator (not shown). A drive mechanism 39 is configured to convert the reciprocating motion of the actuator rod 33 (a reciprocating motion in a direction substantially perpendicular to the drawing) into a rotational motion by a rotation shaft 15 a , and rotate the drive ring 3 by a drive pin 15 c disposed at an end of a lever 15 b fixed to the rotation shaft 15 a.
A section 100 surrounded by a dotted line is a part of a variable nozzle mechanism for varying a vane angle of the nozzle vane 2 .
In the operation of the variable displacement exhaust turbocharger equipped with the variable nozzle mechanism which is configured as illustrated in FIG. 1 , exhaust gas from an internal combustion engine (not shown) enters the scroll 38 and flows into the nozzle vanes 2 while swirling along the scroll shape of the scroll 38 . After flowing past between the nozzle vanes, the exhaust gas flows in the turbine rotor 34 from its outer peripheral side. Then, the exhaust gas flows radially toward the center to perform expansion work in the turbine rotor 34 . After performing the expansion work, the exhaust gas flows out in the axial direction and then guided toward the exhaust gas outlet 8 and sent outside of the turbine rotor 34 .
In order to control the displacement of this variable displacement turbine, a vane angle of the nozzle vanes 2 at which a flow rate of the exhaust gas through the nozzle vanes 2 a reaches a desired flow rate is set by a vane angle controller (not shown) with respect to the actuator. The reciprocal displacement of the actuator with respect to this vane angle is transmitted to the drive ring 3 via the drive mechanism 39 so as to drive and rotate the drive ring 3 .
By rotation of the drive ring 3 , the lever plate 1 is caused to rotate around the nozzle shaft 2 a via a connection pin 19 which is described later. By rotation of the nozzle shaft 2 a , the nozzle vane 2 is rotated to the vane angle which is set as to the actuator.
FIG. 2A is a front view of the variable nozzle mechanism, which is taken from the lever plate 1 side. FIG. 2B is a cross-sectional view in A-A of FIG. 2A . The drawings illustrate a variable nozzle mechanism 100 for varying the vane angle of the nozzle vanes 2 . The variable nozzle mechanism 100 is configured as described below.
The drive ring 3 formed in a disk shape is externally fitted to a guide part 5 a (see FIG. 2B ) of a cylinder shape which protrudes in the direction of the axis CL of the nozzle mount 5 (in the same direction as the rotation axis of the exhaust turbocharger) to be rotatably supported. Further, grooves 3 y , with which the connection pins 10 engage, are formed in drive ring 3 at equal intervals in the circumferential direction. The grooves 3 y are described later. The drive mechanism 39 has a drive groove 3 z where the actuator rod 33 engages.
The same number of the lever plates 1 as the grooves 3 y of the drive ring 3 is provided at equal intervals in the circumferential direction. On the outer peripheral side of each of the lever plates 1 , the connection pin 10 is formed. On the inner peripheral side of each of the lever plates 1 , the nozzle shaft 2 a of the nozzle vane 2 is fixed.
A nozzle plate 6 of an annular shape is connected to the nozzle mount 5 by a plurality of nozzle supports 61 .
In the variable nozzle mechanism, as illustrated in FIG. 2B , the lever plate 1 is arranged on an inner side in the axial direction (on the compressor housing 31 side in FIG. 1 ), and between a side face of the lever plate 1 and a side face of the nozzle mount 5 , the drive ring 3 is arranged in the state where the drive ring 3 , the lever plate 1 and the nozzle mount 5 are arranged next to one another in the axial direction.
The connection pin 10 is formed integrally with a base material by pressurizing one side face of each of the lever plates 1 by a press machine so that a rectangular depression 10 a is formed on the side face and a rectangular protrusion is formed on the other side face by extrusion.
The drive ring 3 of the variable nozzle mechanism 100 which is formed in the above manner, needs to be retained with respective appropriate clearances between the nozzle mount 5 and the flange portion 20 a of the nail pin 20 , and between the inner peripheral surface of the drive ring 3 and the outer peripheral surface of the guide part 5 a.
If the clearance is greater than a specified value, the drive ring 3 rocks in the axial direction of the nozzle mount 5 . This can result in one-side hitting of a thrust-direction end of a sliding face of the drive ring 3 against the guide part (one-side contact), which causes fixation.
On the other hand, if the clearance is smaller than the specified value, the sliding resistance of the nozzle mount 5 increases, which causes fixation of the sliding portion.
To prevent the fixation, it is desired to ensure an appropriate amount of a thrust-directional clearance L 8 (see FIG. 3B ) in the thrust direction of the nozzle mount 5 and the drive ring 3 . To maintain the appropriate amount of clearance L 8 , a nail pin 20 which is a pin with a flange portion 20 a is press-fitted in the press-fitting hole 5 b formed at an outer peripheral edge part of the end face of the guide part 5 a in the thrust direction, so as to secure an appropriate clearance by means of the flange.
FIG. 3A is an enlarged cross-sectional view of a part where a nail pin serving as the press-fitting pin is press-fitted in the nozzle mount 5 according to a first embodiment of the present invention, which is taken in B-B of FIG. 2A . FIG. 3B is an enlarged view of a press-fitting hole on the nozzle mount. FIG. 3C is a schematic view of the nail pin to be press-inserted in the press-fitting hole of FIG. 3B .
At the end face of the guide part 5 a , a nail pin 20 with a flange portion 20 a is press-fitted in a press-fitting hole 5 b . The nail pin 20 has the flange portion 20 a to prevent rocking of the drive ring 3 in the direction of the axis CL of the nozzle mount 5 during rotation of the drive ring 3 .
In FIG. 3A , the disc-shaped drive ring 3 is externally fitted to the cylindrical guide part 5 a protruding in the direction of the axis CL of the nozzle mount 5 such that there is a small clearance L 7 therebetween in the radial direction.
The length L 1 of the guide part 5 a (a protrusion amount) is set smaller than a thickness T 2 of the drive ring 3 which is externally fitted to the nozzle mount 5 such that the drive ring 3 contacts a section of the nozzle mount 5 disposed between a contact portion 5 c where the drive ring 3 contacts and the end face of the guide part 5 a.
A thickness T 1 of the nozzle mount 5 (in the thrust direction) is set to the maximum length that can be machined by press so as to reduce the process cost and weight of the nozzle mount 5 .
As for the thickness T 1 of the nozzle mount 5 , the press-machining precision is improved, whereby maintaining a fixed strength and a perpendicularity of a stopper pin (not shown) for restricting a swing amount of the lever plate 1 which swings to define a fully-closed position of the vane angle of the nozzle vane 2 and the nail pin which is press-fitted in the nozzle mount 5 .
FIG. 3B is a detailed view of the press-fitting hole 5 b . FIG. 3C is an illustration of the nail pin 20 to be press-fitted in the press-fitting hole 5 b.
The press-fitting hole 5 b is formed in the outer peripheral edge part of the end face of the guide part 5 a along the axis CL of the nozzle mount 5 , and a plurality of the press-fitting holes 5 b is arranged at equal intervals in the circumferential direction.
The press-fitting hole 5 b changes in hole diameter at two stages along an axis of the hole. Specifically, the hole diameter of the press-fitting hole 5 b is ø 1 on an opening side (L 4 area) where the nail pin 20 is inserted and changes to ø 2 on its deeper side (L 3 -L 4 area) to satisfy the relationship of ø 1 >ø 2 .
The area of the length L 4 of the section with the hole diameter ø 1 extends from a deeper side of the contact portion 5 c (a position on left side of the contact portion 5 c on the drawing) to the end face of the guide part 5 a.
The nail pin 20 includes a pin portion 20 b to be press-fitted in the press-fitting hole 5 b , the flange portion 20 a , a stepped portion 20 c which is an adjusting member for forming the appropriate clearance L 8 between the drive ring 3 and the flange portion 20 a , and a protruding portion 20 d which protrudes from the flange portion 20 a which is opposite from the flange portion 20 a.
The nail pin 20 is integrally formed with the stepped portion 20 c.
By a thrust-directional thickness L 5 of the nail pin 20 , the appropriate amount of the clearance L 8 is formed.
The hole diameter ø 2 is smaller than a diameter ø 3 of a tip part of the nail pin 20 , and the hole diameter ø 2 and the diameter ø 3 are formed according to a dimensional relationship of press-fitting. The length L 9 of the tip part of the pin 20 (a press-fit margin) which is inserted in the hole diameter ø 2 is long enough to possess a fixing strength to prevent the nail pin 20 from coming out from the press-fitting hole 5 b easily during the operation of the drive ring 3 .
Further, the outer peripheral surface of the outer diameter ø 4 of the stepped portion is set so as not to project beyond the outer peripheral surface of the guide part 5 a in the radial direction when the nail pin 20 is press-fitted in the press-fitting hole 5 b.
The protruding portion 20 d is a portion where a press-fitting tool is abutted when press-fitting the nail pin 20 into the press-fitting hole 5 b . Without the protruding portion 20 d , the pin portion 20 b deforms during insertion of the nail pin 20 due to the press-fitting pressure acting on the pin portion 20 b . The deformation of the pin portion 20 b accompanies deformation of the flange portion 20 a . Therefore, the protruding portion 20 d is provided to prevent deformation of the nail pin 20 and facilitate assembling thereof.
Further, the height L 1 of the guide part 5 a and the thickness L 5 of the stepped portion 20 c are set so that an appropriate clearance L 8 is secured between the flange portion 20 a of the nail pin 20 and the drive ring 3 when the nail pin 20 is press-fitted into the press-fitting hole 5 b.
Furthermore, in a section where the sliding face width (T 2 ) of the drive ring 3 is located, a space 5 e is formed in L 1 section of the press-fitting hole 5 b.
Thus, although a section of the press-fitting hole 5 b of the nozzle mount 5 on the drive ring 3 side is thin and has low rigidity, it is possible to prevent outward bulging of the section caused by the press-fitting of the nail pin 20 .
This is, however, not restrictive and it is not a problem in this embodiment even if the space 5 e is not provided.
A relief R is provided in a continuous portion between the contact portion 5 c and the guide part 5 a of the nozzle mount 5 so that the edge of the sliding face width (T 2 ) of the drive ring 3 reliably contacts the guide part 5 a.
By ensuring that the slide face of the drive ring 3 contacts across the guide part 5 a , it is possible to reduce rocking of the drive ring 3 in the thrust direction during rotation of the drive ring 3 , thereby preventing the fixation of the edge of the sliding face width of the drive ring and the guide part 5 a.
On an outer circumferential side of the relief R of the side face, the contact portion 5 c of a disk shape is formed so that the radial-direction side face of the drive ring 3 contacts the disk-shaped contact portion 5 c . The contact portion 5 c is provided to reduce frictional resistance between the side face of the nozzle mount 5 and the radial-direction side face of the drive ring 3 , thereby enhancing smooth rotation of the drive ring 3 .
With the above configuration, by press-machining the nozzle mount 5 , the length L 1 of the guide part 5 a of the nozzle mount 5 becomes small and the thrust-directional thickness T 1 of the entire nozzle mount 5 is reduced by an amount of the thickness L 5 of the stepped portion 20 c . Thus, it is possible to achieve the weight reduction and cost reduction of materials.
The configuration of the nozzle mount 5 (the configuration around the guide part) was conventionally complicated and it required many steps to achieve machining precision when machining the guide part 5 a in the thrust direction (end mill machining). However, with the integral configuration in which the stepped portion serving as the adjusting member is integrally provided in the nail pin 20 , high machining precision can be easily achieved by adopting lathe machining, whereby achieving significant reduction in the machining cost.
Further, as the space 5 e is formed in L 4 section of the nail pin 20 and the press-fitting hole 5 b , press-fitting of the nail pin 20 does not generate a bulging portion on the surface of the guide part 5 a in the section where the sliding face T 2 of the drive ring 3 is located. Therefore, it is possible to maintain the surface of the guide part 5 a smooth and avoid the fixation of the drive ring 3 and the guide part 5 a.
In the case where the space 5 e is not provided, the fitting dimension of the pin portion 20 b and the press-fitting hole 5 b in the L 4 section may be adjusted to avoid generation of the bulging portion.
Moreover, as the diameter of the press-fitting hole 5 b in the L 4 section is large, press-fitting work is facilitated.
(Second Embodiment)
A second embodiment will be described in reference to FIG. 4A , FIG. 4B and FIG. 4C .
The structure is the same as the first embodiment, except for press-fitting of a nail pin 21 in the nozzle mount 51 . Thus, structures such as the variable nozzle mechanism will not be described further herein.
In addition, for parts of the same shape with the same effect, are assigned the same reference numerals, and a description thereof will be omitted.
FIG. 4A is an enlarged cross-sectional view of a section where a nail pin according to the second embodiment of the present invention is press-fitted in the nozzle mount. FIG. 4B is an enlarged view of a press-fitting hole on the nozzle mount side. FIG. 4C is a schematic view of the nail pin to be inserted in the press-fitting hole of FIG. 4B .
FIG. 4A shows a nozzle mount 51 and a lever plate 1 . In FIG. 4A , the drive ring 3 is externally fitted to a guide part 51 a of the nozzle mount 51 .
FIG. 4B illustrates a press-fitting hole 51 b where a nail pin 21 is press-fitted. FIG. 4C illustrates the nail pin 21 to be fitted to the press-fitting hole 51 b.
The press-fitting hole 51 b has a diameter ø 2 and is formed in the outer peripheral edge part of the end face of the guide part 51 a along the axis CL of the nozzle mount 51 , and a plurality of the press-fitting holes 51 b is arranged in the outer peripheral edge part at equal intervals in the circumferential direction.
The area of the length L 4 of the section with the hole diameter ø 2 extends from the end face of the guide part 51 a to a deeper side of a contact portion 51 c (a position on left side of the contact portion 51 c on the drawing).
The length L 1 of the guide part 51 a (a protrusion amount) is set smaller than an amount equivalent to the thickness T 2 of the drive ring 3 which is externally fitted to the nozzle mount 5 such that the drive ring 3 contacts a section of the nozzle mount 51 disposed between the contact portion 51 c where the drive ring 3 contacts and the end face of the guide part 5 a.
The nail pin 21 comprises a pin tip portion 21 b to be press-fitted in the press-fitting hole 51 b , a reduced diameter part 21 c with smaller diameter than the pin tip portion 21 b , a stepped portion 21 f which is a disc-shape adjusting member having an outer diameter portion does not project beyond the outer peripheral surface of the guide part 51 a in the radial direction, a flange portion 21 a for maintaining an appropriate clearance L 8 (see FIG. 4B ) with respect to the side face of the drive ring 3 and restricting rocking of the side face of the drive ring 3 in the thrust direction, and a protruding portion 21 d from the flange portion 21 a to a side which is opposite from the stepped portion 21 f . The nail pin 21 is integrally formed.
The nail pin 21 to be press-fitted in the press-fitting hole 51 b is configured so that the pin tip part 21 b has diameter ø 3 and the reduced diameter part 21 c between the pin tip part 21 b and the stepped portion 21 f has diameter ø 5 , and diameter ø 3 >diameter ø 5 .
The thrust-directional length L 5 of the stepped portion 21 f is determined to secure an appropriate clearance L 8 between the side face of the drive ring 3 and the flange portion 21 a.
A length L 10 of the diameter ø 3 of the tip part 21 b (press-fit margin) has a length that achieves fixing strength so that the nail pin 21 does not come out from the press-fitting hole 51 b easily at the operation of the drive ring 3 when inserting the nail pin 21 into the press-fitting hole 51 b.
Further, each of the tip part 21 b of the nail pin 21 and the press-fitting hole 51 b is formed in interference-fitting dimension of a respective elastic deformation region so that the section (L 1 ) of the press-fitting hole 51 b opposing the drive ring 3 does not plastically deform when press-fitting the nail pin 21 into the press-fitting hole 51 b.
Thus, by press-fitting the nail pin 21 into the press-fitting hole 51 b , the stepped portion 21 b is abutted to the end face of the guide part 51 a to form the appropriate clearance L 8 .
With this configuration, the thrust-directional thickness T 1 of the nozzle mount 51 is reduced by the amount equivalent to the thickness L 5 of the stepped portion 21 f . Thus, it is possible to achieve the weight reduction and cost reduction of materials.
The configuration of the nozzle mount 51 (the configuration around the guide part) was conventionally complicated and it required many steps to achieve machining precision when machining the guide part 51 a in the thrust direction (end mill machining). However, with the integral configuration in which the stepped portion serving as the adjusting member is integrally provided in the nail pin 21 , high machining precision can be easily achieved by adopting lathe machining, whereby achieving significant reduction in the machining cost.
Further, as the space 21 e is formed in L 4 section of the nail pin 20 and the press-fitting hole 5 b , press-fitting of the nail pin 21 does not generate a bulging portion on the surface of the guide part 51 a in the section where the sliding face T 2 of the drive ring 3 is located. Therefore, it is possible to maintain the surface of the guide part 51 a smooth and avoid the fixation of the drive ring 3 and the guide part 51 a.
(Third Embodiment)
A third embodiment will be described in reference to FIG. 5 .
The structure is the same as the first embodiment, except for a shape of the nail pin. Thus, structures except for the nail pin will not be described further herein.
A nail pin 22 comprises a pin portion 22 b to be press-fitted in the press-fitting hole 5 b (see FIG. 3B ), a flange portion 22 a for restricting rocking of the drive ring 3 (see FIG. 3B ) in the thrust direction, and a press-fitting tool receiving part 22 d where a press-fitting strikes when the nail pin 22 protruding from the flange portion 22 a to a side which is opposite from the pin portion 22 b is press-fitted into the press-fitting hole 5 b . The nail pin 21 is integrally formed.
Moreover, in a section where the pin portion 22 b contacts the flange portion 22 a , a spacer 23 (corresponding to the stepped portion 20 c of the first embodiment) serving as an adjusting member is press-fitted.
The dimension of the spacer 23 is adjusted so that the outer peripheral surface of the space 23 does project beyond the outer peripheral surface of the guide part 5 a (see FIG. 3B ) when the nail pin 22 is press-fitted in the press-fitting hole 5 b.
In this embodiment, the spacer 23 is press-fitted to the nail pin 22 . Thus, by eliminating a gap between an inner peripheral surface of the spacer 23 and the pin portion 22 b and setting the outer diameter of the spacer 23 to the maximum diameter which is twice as large as the distance between the axis of the press-fitting hole 5 b and the outer peripheral surface of the guide part 5 a , it is possible to prevent the spacer 23 from projecting beyond the outer peripheral surface of the guide part 5 a to secure the clearance L 7 (see FIG. 3B ) between the inner peripheral surface of the drive ring 3 and the spacer 23 , prevent fixation of these parts and also secure the clearance L 8 in the thrust direction of the drive ring 3 .
In this embodiment, the configuration in which the spacer 23 is press-fitted to the pin portion 22 b is described. This is, however, not restrictive, and the spacer 23 may be inserted in a manner other than press-fitting to achieve the same effects as long as, with the clearance between the pin portion 22 b and the inner peripheral surface of the spacer 23 , even if the spacer 23 is disposed closer to the guide part 5 a side when the nail pin 22 is press-fitted in the press-fitting hole 5 b , the outer peripheral part of the spacer 23 is either flush with the outer peripheral surface of the guide part 5 a or slightly closer to the center of the spacer 23 without projecting beyond the outer peripheral surface of the guide part 5 a.
INDUSTRIAL APPLICABILITY
According to the present invention, it is possible to provide a variable displacement exhaust turbocharger equipped with a variable nozzle mechanism for varying a vane angle of a plurality of nozzle vanes, whereby the drive ring of the variable nozzle mechanism is easily retained to the guide part with an appropriate clearance and fixation of the inner peripheral surface of the drive ring and the outer peripheral surface of the guide part is prevented so as to achieve cost reduction and improved durable reliability. | It is intended to achieve weight reduction and production reduction of a nozzle mount for pivotably supporting a drive ring constituting a variable nozzle mechanism, and is characterized by: providing on an end face of a guide part 5 a a nail pin 20 having a flange portion and being positioned so as to hold a drive ring 3 of a variable nozzle mechanism 100 to the guide part 5 a of a nozzle mount 5 in the thrust direction, and setting the thrust-directional width of the drive ring 3 smaller than the width of the guide part 5 a , and providing an adjusting member 20 c between the flange portion of the nail pin 20 and the end face of the guide part 5 a to adjust a distance between the side face of the nozzle mount and the flange portion of the nail pin 20. | 5 |
BACKGROUND OF THE INVENTION
[0001] A wind turbine power generation systems is used to generate energy by harnessing the force of the wind generated by wind flowing over various types of rotors. Wind turbines generally work by converting kinetic energy of the wind flow into mechanical energy. The wind turns a mechanical device called a rotor that is connected to a generator, where the generator is designed to generate electricity due to the turning motion imparted to the rotor which is then transferred to the input shaft of the electrical power generator.
[0002] Wind turbines are inherently inefficient at low wind speeds as the mass of a single rotor takes substantial force to rotate from a standstill and also to overcome the friction and the inertia of the generator coupled to it. Single rotor systems can also be inefficient as the changing wind direction can cause fluctuation in rotational speed due to a drop in wind flow incident on the rotors.
[0003] At low wind speeds, the torque imparted by the wind against a single rotor may not be large enough to overcome the turbine and generator's initial resistance to rotation. However, that same wind speed may be powerful enough to maintain the rotational speed of multiple smaller turbines. As a result, a single large turbine might not start rotating at lower wind speeds that would be adequate to produce energy in a system with multiple smaller turbines. Typical wind turbines lose out on the energy that would be generated if they were able to overcome this initial resistance to rotation. Also a smaller turbine would also be more efficient when the wind packet or volume of wind incident on the rotor is less than ideal.
[0004] Accordingly, a need exists for a multiple wind turbine power generation system with improved efficiency, particularly a multiple wind turbine power generation system that operates at lower wind speeds and with a lower moment of inertia in individual rotor systems. This multiple wind turbine power generation system will include single or multiple generators arranged within a frame structure which will be used to set-up the individual turbines such that the system works as a singular unit which will produce electrical energy when the wind turbines are coupled to an electrical power generator.
[0005] In addition, typical wind turbines have exposed rotors. In case of a vertical rotor assembly, one half side of the rotor is moving in the same direction as the wind flow while the other half of the rotor is moving in the opposite direction with respect to the wind flow. The maximum efficiency of the aerodynamic forces is on the side of the rotor which is moving in the same direction as the wind while the other half of the rotor has to overcome opposing drag force which reduces the efficiency of the rotor.
[0006] Therefore, a need exists to provide a multiple wind turbine power generation system that shields the rotor from aerodynamic inefficiencies created by the incident wind pressure against the leeward side of the rotor and increase the rotational force on the windward side. The structure housing will be designed to improve the wind flow incident on the side of the rotor which is moving in the same direction as the wind and reduce the backpressure on the side that is moving against the direction of the wind which will increase the aerodynamic efficiency of the individual rotors. The frame structure will include aerodynamic devices for each rotor to increase the effect of the wind flow on the individual rotors.
[0007] In addition, the wind flow can change direction over the course of time as it occurs in a naturally occurring weather environment and there is a need to orient the entire assembly or system, in the direction of the wind in order to get the maximum wind-flow to impact the rotor at the optimum angle which will provide more rotational velocity to the turbine rotors thus increasing the power generated by the multiple wind turbine power generation system.
[0008] The multiple wind turbine power generation system will be equipped with a sensor or sensors to detect wind speed and direction and will orient the wind power system by computing the change in the orientation of the multiple wind turbine power generation system that is required and communicating the same to an electrical motor device which will turn the frame structure to face the wind in the optimum manner.
[0009] Further, exposed rotors can be a physical hazard. As a result, there is a need for improving the safety of wind turbines, particularly by reducing the danger imposed by the rotor mechanism. The frame housing and the aerodynamic devices mounted on each of the turbine rotors will reduce the exposed area of the rotating vanes thus reducing the physical hazard.
[0010] Further vertical wind turbines also suffer from mechanical failure due to inadequate mechanical support to a rotating turbine. The frame housing will provide additional rigidity to the turbines thus reducing mechanical stress on the rotor shaft and bearings.
SUMMARY OF THE INVENTION
[0011] The needs described above are met by the solutions provided herein. The present invention provides a multiple wind turbine power generation system, which converts wind energy into mechanical energy and then into electric power using one or more generators. While primarily described as a multiple wind turbine power generation system, it is understood that fluids other than wind can be used to drive the turbine. The primary embodiment of the multiple wind turbine power system is one or more vertical axis, wind turbines, but it is contemplated that the wind turbine may be oriented in other directions.
[0012] The solution provided herein is preferably provided with a multiple wind turbine power generation system with one or more vertical axis wind power turbines used to generate electricity or provide direct power to a mechanical device through a power transfer mechanism. Within the system, multiple rotor assemblies, where each rotor with multiple blades is mounted on individual shafts with bearing mounts with a power transfer mechanism consisting of a gear (or multiple gears), which drives the power generator or a mechanical and electrical power generation device. A movable frame structure houses the turbine rotors with an aerodynamically shaped device mounted coaxially about each of the turbine rotors. The aerodynamically shaped device will be fixed to the frame structure. Each of the turbine rotors will be mounted in parallel in the frame housing with bearing assemblies to allow for free rotation. The wind turbine rotors will be mounted such that there will be no interference between each of the wind turbine rotors. The shape and structure of the frame housing can be varied to allow for multiple rotors and by aesthetical considerations.
[0013] A wind-sensing device is set-up in the vicinity or within the frame structure such that the unhindered wind flow information is captured to sense wind direction and speed. This sensor transmits the wind speed and direction information to a controlling device. The controlling device will store the current orientation of the frame structure and compare it with the wind speed and direction information communicated by the sensor. If the orientation of the frame housing with respect to the wind flow is not optimum per the design of the system, the controlling device will calculate the change in orientation that is required of the frame structure. The controlling device thus includes intelligent decision-making capabilities and signals the electrical motor device to rotate the frame structure about a central pivot point on the base mount. The electrical motor device is powered by a reserve power source, which may be charged by the power generator in the system. A part of the output power of the generator will be used to charge or provide power to the reserve power source to replenish the power source when it is drained or when the reserve power level falls below a predetermined level. The control device may determine the charging schedule of the reserve power source.
[0014] The controlling device will also include decision making capabilities to stop the power flow from the generator to the output location if the power generation is above or below a certain threshold value, the power flow from the generator will be switched off to prevent overloading the system and will also include decision making capabilities to actuate a locking mechanism to prevent the frame structure from moving during strong wind gusts and when the entire system is switched off and power production has to be ceased.
[0015] The present invention, therefore, has the objective of providing a multiple wind turbine power generation system having improved starting and operating efficiency other existing turbine systems.
[0016] The invention has the further objective of providing a turbine which operates efficiently over a wide range of air or fluid flow rates including lower wind speeds and can operate at optimum efficiency with naturally occurring changes in wind direction, and which therefore is suitable for use where the incoming fluid flow varies randomly and wind direction is varied.
[0017] The invention therefore also has the objective of providing improved rotational characteristics to the individual turbine rotor thus facilitating continuous generation of power at lower wind speeds.
[0018] The invention therefore has the objective of making it more feasible to produce electricity using wind power.
[0019] The invention is an improvement to a standard turbine, particularly in improving power generating efficiency at times when the wind changes direction or the wind speed drops as it occurs naturally due to weather patterns.
[0020] The present subject matter provides a multiple wind turbine power generation system in which the individual turbine rotor will drive a coupled power generator with a reduced moment of inertia thus allowing for higher operating efficiencies.
[0021] The present disclosure also provides a wind turbine power generator system with an improved efficiency turbine by improving the aerodynamic efficiency of the individual turbine rotor system by reducing the pressure of the wind on the leeward side, or reducing the incident wind flow on the part of the turbine rotor or blades where drag is induced, which otherwise would cause the turbine to slow down or lose rotational velocity. A pressure differential will be generated between the sides of the rotor, the first side, which is exposed to the wind, and the second side, which is encased. This pressure differential will be directly incident on the blades of the rotor thus causing the rotor to spin at a higher speed than conventional turbines.
[0022] The combination of these improvements increases the operational range of the multiple wind turbine power generation system by the virtue of lower wind speeds required to start the turbine and maintain the rotational speed of the turbine at lower speeds when compared to conventional wind power generator systems. The higher rotational speed caused by the improvement of the aerodynamic efficiency of the individual turbine rotors mounted within the frame housing will mean more mechanical power, thus generating more electrical energy.
[0023] Additionally, most wind turbines need to be mounted at a height to afford clearance for the rotating blades to ensure safety and gain from the higher wind speeds at higher relative altitudes. However, with the design presented herein, the turbine assembly and generator can be mounted at a lower height, including rooftops and on other civil structures with similar elevation. Also, with respect to the preferred embodiment, the vertical axis design also allows for mounting the assembly in spaces where the side-to-side clearance required will be less than the clearance required for a horizontal axis wind turbine.
[0024] Most multiple wind turbine power generation systems also pose a risk to the flying species due to the exposed rotating vanes, but this vertical axis wind system reduces the risk, as the blades will be partially enclosed and the general layout of the blades and the rotor will reduce the dangerous exposed areas when compared to a typical wind turbine.
[0025] This system will also have a reduced noise pollution effect as the rotating vanes or blades will be encased and arranged to provide a streamlined air-flow around the blades thus reducing the interference effect on the wind flow. The multiple rotors will also be supported by a frame which will provide adequate support to both the ends of the rotor with a bearing mechanism thus facilitating reduced bending and torsional and other mechanical stress load on the shaft, which will increase the life of the rotors, reducing the potential to fail and thus increase the life of the wind turbine.
[0026] This mechanism and control process can be used for multiple rotor shafts with different layouts.
[0027] In one example, a multiple wind turbine power generation system consists of one or more rotor assembly affixed to a substantially vertical rotor shaft supported by bearings, the rotor assembly includes blades mounted where the shaft is housed in a bearing mechanism where the shaft rotates and provides mechanical rotational power by direct mechanical linkage to drive an electrical generator. The rotor assembly is partially enclosed in an aerodynamically efficient wind splitter device which is affixed to the frame structure which reduces the drag or opposing forces on the turning rotor and blade assembly and increases the rotational force on the blades due to the formation of a pressure differential.
[0028] A wind direction and speed sensing device is provided, which signals an electrical motor device to move the frame structure which houses the rotors to provide controlled wind flow to the blades of each of the rotors. The control mechanism operationally coupled to the processor, wherein the one or more sensors are further adapted to determine wind direction, further wherein the control mechanism receives a control signal from the processor to rotate the frame structure based on wind direction as determined by the one or more sensors. The processor may provide a control signal to the generator motor mechanism to restrict the rotation of the rotor shaft when the wind speed is above a predetermined speed. The wind turbine may include a reserve power supply operatively coupled to the motor mechanism. The reserve power supply may be controlled by the processor to recharge based on a charging schedule provided by the processor and the charging schedule may be based on wind speed determined by the one or more sensors.
[0029] These arrangements are especially useful in harnessing wind power when the wind speed is low.
[0030] An advantage of the wind turbine presented herein is higher efficiency at lower wind speeds.
[0031] Another advantage of the wind turbine presented herein is improved efficiencies with naturally occurring changing wind directions.
[0032] A further advantage of the wind turbine presented herein is an increased operational range of power generation with varying wind speeds.
[0033] Yet another advantage of the wind turbine presented herein is a reduced potential for causing injury to living species from exposed rotor blades.
[0034] Still another advantage of the wind turbine presented herein is a reduction in operating noise thus reducing noise pollution.
[0035] Moreover, it is an advantage of the wind turbine presented herein that the rotor shafts are adequately supported at both ends and mounted appropriate bearing assemblies thus reducing mechanical wear and tear thus increasing the life of the wind power generation system and reducing maintenance requirements over the life of the system.
[0036] Additional objects, advantages and novel features of the wind turbine 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 description and the accompanying drawings or may be learned by production or operation of the examples. The objects and advantages of the concepts and solutions provided herein may be realized and attained by means of the methodologies, instrumentalities and combinations particularly pointed out in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] The drawing figures depict one or more implementations in accord with the present concepts, by way of example only, not by way of limitations. In the figures, like reference numerals refer to the same or similar elements.
[0038] FIG. 1 is a front sectional elevation perspective view of an example of a multiple wind turbine power generation system.
[0039] FIG. 2 is another front sectional elevation perspective view of the multiple wind turbine generation from FIG. 1 .
[0040] FIG. 3 is a top perspective view of the multiple wind turbine power generation system from FIG. 1 .
[0041] FIG. 4 is a top sectional perspective view of the blades and rotor of the multiple wind turbine power generation system from FIG. 1 .
[0042] FIG. 5 is a side perspective view of the wind turbine generator system from FIG. 1 .
[0043] FIG. 6 is another perspective view of the multiple wind turbine power generation system.
[0044] FIG. 7 is a perspective view of another example of the multiple wind turbine power generation system, illustrating an alternate blade layout.
[0045] FIG. 8 is a perspective view of another example of the multiple wind turbine power generation system, illustrating an alternate frame structure design.
DETAILED DESCRIPTION OF THE INVENTION
[0046] Referring now to the drawings and particularly to FIGS. 1 and 2 , a multiple wind turbine power generation system 11 is shown. In use, the multiple wind turbine power generation system 11 is typically mounted on a surface with adequate strength to hold the weight of the multiple wind turbine power generation system 11 and withstand the mechanical loads caused by rotation of the individual turbines, the wind force on the system and the vibration forces that might be caused due to the rotation of the turbines and the system. As shown, the preferred orientation of the multiple wind turbine power generation system 11 is a vertical placement.
[0047] As shown, a base 13 supports the frame structure 15 , multiple rotor assemblies 17 , a wind flow optimization or wind splitter device 19 and a central support 21 . In the example shown, the central support 21 is mounted on the frame structure 15 and is stationary. The central support structure 21 supports an anemometer 23 . The anemometer 23 is operatively connected to a control device 25 and a reserve power source 27 . The control device 25 controls the operation of the anemometer 23 and the reserve power source 27 is used to operate electrical functionality within the multiple wind turbine power generation system 11 when the power generated by the operation of the electrical power generators 29 does not support the operation of the electrical functions. Further, the control device 25 and reserve power source 27 may be used to pass a charge to the anemometer 23 to heat the anemometer 23 to operate in weather conditions where the temperature is below a predetermined threshold level. It is contemplated that in certain embodiments, the reserve power source 27 may increase or decrease the power delivered to the control device 25 to support necessary functions. For example, the power flow level may be increased at fixed intervals as calculated by the control device 25 , when the wind speed and direction information is to be checked by the anemometer 23 .
[0048] The control device 25 , reserve electrical power source 27 and electrical motor device 45 to orient the frame structure 15 may be installed or mounted within the base 13
[0049] As further shown in FIG. 1 , each of the wind turbines 17 consist of a rotor shaft 31 and includes a top thrust bearing 33 and supported by a bottom thrust bearing 35 . The turbine rotor shaft 31 is mounted in the frame structure 15 with additional support from the thrust bearings 33 and 35 . The turbine rotor shaft 31 includes numerous blades 37 depending therefrom. The turbine blades 37 are disposed in a radial manner with a design intended to increase the aerodynamic efficiency of the turbine, capture the maximum amount of kinetic energy from the wind flow and reduce the chop generated by the rotation of the turbine rotors.
[0050] The wind turbine rotor assembly 17 is thus formed of multiple wind turbines with individual turbine rotor shafts 31 and multiple blades 37 attached to the individual rotor shaft 31 . In use, the wind will be incident on the turbine blades 37 , thus producing rotational force. The turbine rotor assembly 17 with an individual top thrust bearing 33 and bottom thrust bearing 35 for each of the turbine rotors 17 , which allows for generally free rotation. The shape and design of the turbine blades 37 may be streamlined to reduce drag and increase the rotational power provided to the turbine rotor shaft 31 , as will be understood by a person skilled in the art in light of the disclosure provided herein.
[0051] As further shown, a power transfer mechanism 39 is attached to the turbine rotor shaft 31 to transmit power to a follower mechanism by gearing or a belt and pulley mechanism. The mechanical power is transferred to a generator input shaft 41 of an electric power generator 29 . It will be clear to a person skilled in the art that the power transfer mechanism 39 may be embodied in many varied forms including, but not limited to, direct-drive gears and multiple gears arrangements.
[0052] An electrical drive motor 45 is provided to rotate the frame structure 15 around the vertical axis of the multiple wind turbine power generation system 11 , as described further herein.
[0053] Referring now to FIG. 3 , the anemometer 23 is mounted clear of any obstacles and in a location where it can measure the undisturbed wind speed and direction. The wind speed and direction information is transmitted to the control device 25 located in the base 13 . The control device 25 includes logical algorithms included in the central processing unit 47 to calculate whether the multiple wind turbine power generation system 11 is working at the optimal efficiency. The control device 25 may further transmit signals to an electrical drive motor 45 to reorient the frame structure 15 , as required. The frame structure 15 is shaped to reduce drag forces and provide for smooth airflow around the turbine blades 37 by the effective use of the wind flow optimization device or wind splitter 19 affixed to the frame structure 15 thus reducing the vortex generation around the turbine blades 37 and increasing the direct force on the exposed turbine blades 37 in FIG. 3 and FIG. 4 .
[0054] The anemometer 23 also communicates with the control device 25 to transmit the wind speed and direction in an electrical code to be deciphered by the control device 25 to accurately compute the data. The anemometer 23 data is then captured and converted by the control device 23 using logical algorithms built in to the central processing unit 47 within the control device 23 to check the wind speed to make sure any extraneous information like sudden or quick change in wind direction or wind gusts are to be included and is accounted for when calculating the required or desired orientation of the frame structure 15 and the multiple wind turbine power generation system 11 in general. The control device 23 , the electrical drive motor 45 and anemometer 23 are powered by the reserve power source 27 when required. The flow of power to the control device 23 , the electrical drive motor 45 and anemometer 23 is monitored and controlled by the control device 23 which will include logical algorithms to decide on the activation or deactivation of these devices.
[0055] Referring now to FIGS. 1 , the control device 25 compares the wind speed and the rotational speed of the turbine rotors 17 to ascertain whether the multiple wind turbine power generation system 11 is working as designed at its optimum level and will move or orient the frame structure 15 via the electrical drive motor 45 at regular intervals to the calculated optimal position. When the frame structure 15 should be moved the electrical drive motor 45 rotates the housing 15 via the power transfer mechanism 53 and then locks and holds the frame structure 15 in the desired position with an electro-mechanical locking mechanism 55 to prevent the frame structure 15 from moving or rotating due to the wind or other forces incident on it. The locking mechanism 55 is controlled by the controlling device 25 and the central processing unit based on logical algorithms and is actuated based on a signal from the controlling device 25 . The locking and unlocking process may be synchronized with the rotational movement of the frame structure 15 to ensure that it is oriented in the optimum direction with respect to the wind flow at any given time.
[0056] The control device 25 will signal the locking mechanism 55 t to allow the frame structure 15 to be rotated. The frame structure 15 can be rotated or moved only when the locking mechanism 55 is disengaged and the locking mechanism 55 will be reactivated to prevent the frame structure 15 from moving after the frame structure is oriented in the required direction. The control device 25 may be programmed to derive the wind speed and direction information at a fixed predetermined interval and store this information to be retrievable by electronic data processing aid and may be activated at fixed intervals by the central processing unit 47 .
[0057] The control device 25 may also check the reserve power source 27 to ascertain whether it has sufficient power reserve or electrical power available to power the anemometer 23 , control device 25 with the central processing unit 47 and the electrical drive motor 45 . If the power level available in the reserve electrical power source 27 falls below a certain threshold value, the control device 25 may divert power from the electrical power generator 29 via a switch or a similar device. When the power level in the reserve power source 27 is greater than a predetermined value, the flow of power to the reserve power source 27 will be cut-off and the power generated by the generator will flow to the power output circuit 57 . The control device 25 may be programmed to check the available electrical power parameters in the reserve power source 27 at a fixed predetermined interval and store this information to be retrievable by electronic data processing aid. The electrical devices and switches that may be used to charge the reserve power source 27 are also included in the multiple wind turbine power generation system 11 . These electrical switches and components are generally known to one skilled in the art and thus will not be discussed further.
[0058] The control device 25 could also monitor the wind speed and direction information transmitted by the anemometer 23 and compare the rotational speed of the individual turbine rotors 17 to determine whether the wind speed is higher than a threshold value. If the rotational speed is above the threshold, the control device 25 may decide the turbine rotors 17 should not be in motion. If the control device 25 completes the check and the turbine rotors 17 are in motion at a speed greater than the predetermined threshold, the control device 25 may close the switch for the power flow from the electrical power generator 29 to avoid damage to the generator 29 . If the speed of the wind is above a certain predetermined threshold level, then the control device 25 will also signal the reserve power source 27 to switch the power flow to the generator braking system to clamp or lock the generator shaft 41 from turning, thus preventing the turbine rotor 17 from turning. The electrical devices and components, which will switch the flow of power from the electrical power generator 29 are generally known to one skilled in the art and thus will not be discussed further.
[0059] FIG. 5 and FIG. 6 illustrates the general set-up of the multiple wind turbine power generation system where the base 13 will be mounted on a flat surface of adequate strength with the exposed rotor blades 37 directly facing the wind.
[0060] FIG. 7 illustrates an alternate embodiment of the multiple wind turbine power generation system 11 and is provided to describe an example of alternate rotor layouts with lift type rotor blades 49 . With this layout, the multiple wind turbine power generation system 11 will have the same layout and schema as the embodiment described with respect to FIGS. 1-5 , but the layout and type of turbine blades 37 used in the individual turbine rotors of the multiple wind turbine power generation system 11 will be visibly different. As shown, the turbine blades 37 will be shaped like an aerofoil that is oriented in a circumferential direction and the blades 37 are attached to the turbine rotor shaft 31 by horizontal supports 51 .
[0061] FIG. 8 illustrates an alternate embodiment of the multiple wind turbine power generation system where the shape of the frame structure is varied to be aesthetically harmonious with the installation location and requirements of the customer. The working operation and design of the multiple wind turbine power generation system will also be varied to work with the design of the frame structure but will have the same general layout and schema as the embodiment described in FIGS. 1-5 .
[0062] The above description embodies the general spirit of the invention and the schematic relationships for the parts of the invention, to include variations in size, schema, 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.
[0063] Therefore, various changes in layout, size, shape and structure and departures may be made to the invention without departing from the spirit and scope thereof. Thus it is not intended that the invention be limited to what is described in the specification and illustrated in the drawings, rather only as set forth in the claims. | A multiple wind turbine power generation system includes: multiple rotors each with a substantially vertical shaft and multiple blades extending in a radial manner from each of the rotor shafts with a generator operationally coupled to the rotor shafts; a movable structural frame housing multiple rotors and generators mounted within the frame with a design exposing at least a portion of the rotor blades for each of the rotors; an electrical motor mechanism operatively coupled to the frame; with one or more sensors mounted around the frame structure adapted to determine wind speed and direction, where the electrical motor mechanism is coupled with a processor and assists the movement of the frame structure to orient the wind turbine generator system in the direction of the incident wind flow which will provide the maximum wind force for the turning moment of the rotor shafts of each turbine. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to improvements in a valve and more particularly, but not by way of limitation to a ball-type shut off valve having improved seating means and ball actuator means to insure more effective closure and provide a valve which is easily assembled and maintained.
2. Description of the Prior Art
The improvements specified herein relate to a ball-type valve of the type disclosed in the patent to Burke, U.S. Pat. No. 3,343,803 issued Sept. 26, 1967, entitled "Ball Valve With Improved Resilient Closing Means"; the patent to Burke, U.S. Pat. No. 3,467,355, issued Sept. 16, 1969, entitled "Ball Valve With Improved Resilient Closing Means", and applicant's copending Application Ser. No. 360,654, filed May 16, 1973 and entitled "Improved Ball Valve" and now abandoned.
The pivotally mounted actuator arm of the type disclosed in the above patent and patent application is generally provided with an outwardly extending cam surface for forcing the ball against the ball seat, the ball being guided toward the seat by a ball retaining pin. The actuator arm is also provided with a pair of elongated outwardly extending parallel fingers or ball carrying means for contacting and carrying the unseated ball out of the way of fluid passage through the valve. It is necessary in this type of valve that these fingers have an opening in the center in order to straddle the ball retaining pin when moving past the said pin. Due to the required length of the said fingers, it has heretofore proven difficult to install the actuator arm within the valve body.
Further, one of the primary advantages disclosed in the prior art patents is that of a resilient pivot pin connected to the actuator arm whereby the ball is resiliently urged toward the metal seat to prevent damage to the ball or the seat if too much force is applied on the ball against the seat. However, since the ball cannot be guided directly into the seat, even with this resilient pivot pin some damage and often excessive wear is induced by the ball impacting the rim of the seat before falling into place within the seat and being urged thereagainst with the actuator arm cam.
SUMMARY OF THE INVENTION
The present invention is particularly designed and constructed to provide a valve having all of the advantageous features enumerated in the aforementioned patents and patent application and including improved ball seating means and actuator means to overcome the disadvantages inherent in said prior art valves.
The improved seating means comprises an annular seating ring having an annular seating surface for receiving the ball thereagainst. This seating ring is provided with a specially designed O-ring groove around the outer periphery of the seating surface for receiving an O-ring therein. The valve ball then makes initial contact with the O-ring and then is pressed into sealing contact against the seating surface thereby cushioning the impact of the ball against the seating surface which prevents damage to both ball and surface and at the same time provides a double leak-proof seal.
The improvements in the actuator arm lies in providing said arm with a removable U-shaped ball carrying means which allows straight in assembly of the actuator arm through the operator shaft opening and into the valve body. The actuator arm is provided with a pair of spaced apertures therethrough for receiving the legs or the pair of parallel fingers of the U-shaped carrying means therethrough. The said fingers of the carrying means are constructed having a length less than the diameter of the valve operation port.
The fingers are then partially inserted into and through the spaced apertures in the actuator arm and then centered therein with respect to the axis of rotation of the said actuator arm. The actuator arm with carrying means is then inserted straight in through the operator port. A separate tool is then inserted through one of the ports in the valve and used to drive the cross piece of the U-shaped carrying means against the actuator arm shaft so that the legs or fingers thereof are fully extended into the interior of the valve body. The fingers are then in position to contact the ball and move it from its seated position and remove it from the path of fluid flow through the valves when the actuator arm is rotated to the open position.
DESCRIPTION OF THE DRAWINGS
Other and further advantageous features of the present invention will hereinafter more fully appear in connection with a detailed description of the drawings in which:
FIG. 1 is a partial sectional view of a ball-type valve embodying the present invention and showing the ball in a seated position.
FIG. 2 is a partial sectional view taken along the broken lines 2--2 of FIG. 1.
FIG. 3 depicts the valve as shown in FIG. 2 with the ball in the unseated position.
FIG. 4 is a partial sectional view depicting the use of an auxiliary tool for extending the ball carrying means after assembly of the valve.
FIG. 5 is a partial sectional enlarged view of the valve seat broken to indicate the position of the ball upon contact with the seat O-ring and the position of the ball after seating against the seating surface.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings in detail and particularly to FIG. 1, reference character 10 generally indicates in partial cross-section a ball type valve comprising a valve body 12 with pipe connection means at each end 26 forming a longitudinal flow channel through a circular opening 22 which is sealed by means of a metal ball or sphere 18. The seal is between a metal ring insert 24 having an O-ring 25 carried thereby and the ball 18 in a manner which will hereinafter be more fully set forth.
The valve body 12 is also provided with a circular actuator arm opening 28 which is traverse to the longitudinal flow channel and opens into an enlarged interior portion 30 of the valve body 12. The opening 28 is provided with a first annular groove 32 therearound for receiving a suitable O-ring 34 therein and a second annular groove 36 for receiving a split retainer ring 38 therein for a purpose that will be hereinafter set forth.
The interior of the valve body 12 is provided with a pivot post recess 40 which is diametrically opposite the opening 28 and in concentric alignment therewith. The valve 10 is provided with an actuator arm assembly generally indicated by reference character 42 and which comprises a cylindrical portion 44 which is journalled within the opening 28 of the valve body 12. The outer end of the cylindrical portion 44 is provided with an outwardly extending operator arm 46. The opposite end of the cylindrical member 44 is provided with a shaft portion 48 which is pivotally installed in the interior 30 of the valve 12. The inner end of the shaft portion 48 is provided with a resilient pivot pin 50 which extends into the recess 40 in a manner that is well known in the art. The actuator arm assembly is held in place within the valve body 12 by means of the split retainer ring 38 within the ring groove 36.
The shaft portion 48 is provided with an outwardly extending cam arm 52 having a cradle surface 54 on one side thereof with a cam surface 56 along the outer end thereof for engaging and seating the ball 18. The actuator arm means 48 is also provided with another similar outwardly extending arm 58 which is at approximately right angle to the cam arm 52. The second arm 58 is provided with a pair of spaced parallel transverse bores 60 and 62 therethrough, said bores being on an angle somewhat less than 90° with respect to the outwardly extending cam arm 52. A substantially U-shaped carrier means 64 having a pair of outwardly extending legs or fingers 66 and 68 are frictionally inertable within the bores 60 and 62, respectively.
The arm 58 is for the sole purpose of providing space for the aperture 60 and 62. However, the said arm is considered a part of the shaft 48 and by making the said shaft 48 a little larger than is shown, the bores 60 and 62 may be made therethrough.
The interior 30 of the valve body 12 is also provided with a ball retaining pin 70 which is inserted into a bore 72 adjacent to the ring insert 24. Said retaining pin 70 extends into the interior 30 of the valve body at a small angle with respect to the longitudinal flow axis therethrough. The pin is disposed in a position so that when the actuator arm means 48 is rotated the outwardly extending ball carrier fingers 66 and 68 will stradle the said retaining pin which allows passage thereof.
Referring now to FIG. 5 the ring insert 24 is provided with an annular seating surface 74 around the interior thereof in the nature of an interior bevel and provided at a suitable angle to receive the surface of the sphere or ball 18 tangentially thereagainst. An annular groove 76 is provided in the ring insert 24 around the outer periphery of the seating surface 74, the said groove extending straight into the ring insert 24. The lower portion of the groove 76 is provided with a deeper angular groove 78 for a purpose which will be hereinafter set forth. The O-ring 25 is disposed within the groove 76 for contacting the ball 18.
Therefore, when the ball 18 encounters the seating means, it first encounters the O-ring 25 as depicted on the upper portion of FIG. 5 and is then forced into contact with the seating surface 74 thereby compressing the said O-ring 80 as shown in the lower portion of FIG. 5 into the groove extension 78. The O-ring provides a cushioning effect upon impact of the ball with the seating means and then provides a double seal of both metal-to-metal contact between the ball and the seating surface 74 and metal-to-O-ring contact adjacent thereto.
The assembly of the valve as hereinbefore described is easily accomplished by first inserting the fingers 66 and 68 of the U-shaped carrier means into and through the bores 60 and 62 of the actuator arm means to a position as shown in FIG. 4 so that the ends of the U-shaped carrier means are disposed in alignment with and not protruding beyond the cylindrical portion 44 of the actuator arm assembly 42. The ball is first inserted into the valve body. The actuator arm assembly 42 may then be inserted straight into and through the opening 28 of the valve body with the pivot pin 60 being inserted into the bore 40 provided therefore. The retainer ring 38 is then installed within the groove 36 to hold the actuator arm assembly in place.
After the actuator arm assembly has been inserted and locked in place by the retainer ring the actuator arm is then rotated to a position as shown in FIG. 4 wherein the ball is unseated and resting between the seating means and the cradle surface 54 of the actuator arm. A suitable punch or special tool 82 may be then inserted through the port 26 into the interior 30 of the valve body 12 and in contact with the crossbar of the U-shaped carrier means 64. The said carrier means is then driven further through the bores 60 and 62 until the cross bar is resting against the arm 58 of the shaft 48 so that the fingers 66 and 68 are fully extended within the interior 30 of the valve body 12 as depicted by the dashed lines in FIG. 4.
Disassembly of the valve is accomplished by rotating the actuator arm means to a position as shown in FIG. 4 and using a hook or other tool (not shown) for pulling the carrier means 64 back to the position as shown in the solid lines in FIG. 4. The retainer ring 38 may then be released and the actuator arm assembly pulled directly out of the valve body.
Where the valve is in a open position as depicted in FIG. 3 ball 18 may rest in the area adjacent to the cradle surface 54 between the actuator arm 52 and the fingers 66 and 68 of the carrier means. By rotating the shaft 48 in a clockwise direction as shown in FIG. 3 the ball 18 may be moved out of the way to substantially prevent interference with the flow of fluid through the interior 30 of the valve body 12. In order to seat the valve the actuator arm assembly 42 is rotated in a counterclockwise direction as shown in FIG. 2 and 3 and the ball is carried around to the vicinity of the valve seat assembly or ring insert 24. As the actuator arm continues to be pivoted in the counterclockwise direction the ball is prevented from passing the seat by encountering the retainer pin 70 and is deflected thereby toward the valve seat. The surface of the ball 18 then rolls up the inclined cradle surface 54 of the actuator arm means until it is encountered by the cam surface 56 of the cam arm. Further rotation then tightly presses the ball against the seat thereby deflecting the O-ring and allowing metal-to-metal contact between the ball 18 and the seating surface 74 of the ring insert 24. The tightness of the seat between the ball 18 and the ring insert 24 is determined by the amount of pressure applied by the cam surface 56 of the actuator arm means 48. This pressure is likewise cushioned by the resilient pivot pin 50 of the actuator arm means 48 as hereinbefore described.
From the foregoing, it is apparent that the present invention provides an improved seating means and improved actuator means for a ball-type valve.
Whereas, the present invention has been described in particular relation to the drawings attached hereto it is apparent that other and further modifications apart from those shown or sugested herein may be made within the spirit and scope of this invention. | Improvements in a ball-type shut off valve including a resilient seating means whereby an O-ring is included in conjunction with the seat to provide both metal-to-metal and metal-to-O-ring seating. Also included is a removable ball carrying means carried by the actuator arm, whereby straight through assembly of the actuator arm may be made directly through the valve operator opening thereby reducing the possibility of damaging seals on assembly and disassembly. | 5 |
BACKGROUND
In semiconductor processing, systems are employed that can process a number of workpieces simultaneously. The workpieces may be semiconductor wafers for fabrication of ultra large-scale integrated circuits or display panels or solar arrays, or the workpieces may be masks employed in photolithography. For semiconductor wafers, the wafers may be robotically transferred at high speed (e.g., 1.7 meters per second) through a factory interface for transfer to any one of a number of parallel processing chambers or modules. The centering of the wafer on the wafer support pedestal within each processing chamber is critical and must be consistent. For example, one of the processing chambers may be employed to deposit a film on the wafer surface, while a small annular region or zone at the wafer periphery is masked to prevent film deposition in the peripheral region. This annular peripheral region may also be referred to as the film annular exclusion region. Film deposition in the annular peripheral exclusion region may be prevented by photolithographic masking during film deposition or by other suitable techniques. For example, the film layer may be removed from the annular peripheral exclusion region following film deposition over the entire wafer surface. Any error or inconsistency in the placement of the wafer on the wafer support pedestal in the reactor chamber can cause the film layer boundary to be non-concentric with the wafer edge. Such non-concentricity may cause the radial width of the annular exclusion region at the wafer periphery to vary with azimuthal angle, so that in some cases the width of the annular exclusion region may be greater or lesser than the width required to comply with the required production specifications.
Some attempts have been made to provide early warning of variations or error in wafer placement, by detecting non-concentricity of the film layer when the wafer is transferred to or from the processing chamber in which the film layer is masked or deposited. Most of these techniques are based on measurements or detection with the wafer outside the process tool. In-situ measurements of features on the wafer (such as non-concentricity or film-free annular region width) have been sought in order to save space in the fabrication area and provide more timely results. However, accurate in-situ measurement of the width or concentricity of the film edge exclusion annular region has been hampered by the high speed at which the wafer is transferred. Such high speed (and/or acceleration or deceleration) can cause the wafer image to be distorted from the true circular shape of the wafer. In the prior art, wafer images requiring high accuracy could not be obtained while the wafer was in motion. Therefore, an approach has been to slow down or stop the wafer motion while an image of the wafer is acquired from which the film layer concentricity and width may be accurately measured. This approach reduces productivity.
What is needed is a way in which the geometry of various surface features on the wafer (e.g., film layer concentricity and width) may be accurately measured without slowing down the wafer motion from the high speed at which the robot travels (e.g., 1.7 meters per second). Another need is for accurate imaging of a wafer in order to detect and locate defects.
SUMMARY
A method is provided for obtaining an image of a workpiece in a processing system including a robot for transporting a workpiece to and from the processing chambers of the system along a workpiece transfer path. The method includes capturing successive frames of an elongate stationary field of view transverse to a transit path portion of the workpiece transit path while the workpiece is transported along the transit path portion by the robot. The method further includes illuminating the transit path portion with an elongate illumination pattern transverse to the transit path portion during the capturing of the successive frames, and defining an image of the workpiece including the successive frames. The method also includes correction of motion-induced image distortion by computing respective correct locations of respective ones of the frames along a direction of the transit path portion, and correcting the image by defining the location of each frame in the image as the corresponding one of the respective correct locations.
In one embodiment, the elongate stationary field of view has a length of at least a workpiece diameter extending transverse to the transit path portion and a width on the order of one picture element of the image.
In one embodiment, the distortion correction is carried out by computing the correct location as a function of a ratio between a width of the workpiece in the respective one of the successive frames and a known workpiece diameter.
In a further embodiment, the distortion correction is carried out by computing the correct location from robot velocity profile information corresponding to movement of the robot. In this further embodiment, the robot velocity profile information is obtained either from a robot controller memory that contains data defining a predetermined robot velocity profile or from an encoder that is responsive to movement of the robot.
In one embodiment, the capturing includes capturing a signal from an elongate array of photosensitive elements, and wherein the illuminating includes providing an array of light emitting elements in a pattern that illuminates individual ones of the photosensitive elements through a range of incident angles.
In a yet further embodiment, the transit path portion corresponds to a Y-axis parallel to the transit path portion and an X-axis normal to the Y-axis, the method further including correcting X-axis coordinates in the image for distortion attributable to a misalignment angle between the field of view and the X-axis. This latter embodiment may be carried out by determining the misalignment angle by matching a motion of a wafer center location in successive frames to a function of the misalignment angle, and correcting the X-axis coordinates by a correction factor including the function of the misalignment angle.
In a yet further embodiment, the method further includes correcting the image for distortion from vibration of the workpiece in a plane of the workpiece. This latter embodiment may be carried out by finding the motion of a center of the wafer in successive ones of the frames, defining an average motion of the center of the wafer through the successive frames, and, for each frame containing a difference between the wafer center and the average motion of the center of the wafer, shifting the image by the difference.
In yet another embodiment, the method further includes correcting the image for distortion from vibration of the workpiece in a direction transverse to the plane of the workpiece. This latter embodiment may be carried out by determining an apparent workpiece radius from the image and determining a radial correction factor as a ratio between the apparent workpiece radius and a known workpiece radius, and scaling radial locations in the image by the radial correction factor.
In another embodiment, the method further includes smoothing movement of the correct location over the successive frames by fitting predetermined velocity profile data of the robot to the movement of the correct location to produce a fitted robot velocity profile, and obtaining the correct location for each of the successive frames from the fitted robot velocity profile.
In a further embodiment, the method measures non-concentricity by determining a center of the workpiece in each one of the frames, determining a motion of the center of the workpiece over the successive frames, matching the motion of the center of the workpiece to a sinusoidal function, and deducing a sinusoidal amplitude as an amplitude of non-concentricity of the workpiece and a sinusoidal phase angle as a direction of non-concentricity of the workpiece. These results may be used by providing the amplitude of non-concentricity and the direction of non-concentricity as corrective feedback to the robot.
In a yet further embodiment, respective wavelengths of light are emitted from respective parallel rows of discrete light emitters, wherein each one of the rows emits a monochromatic spectrum corresponding to a respective one of the wavelengths. In a first related embodiment, a particular one of the parallel rows of light emitters is selected for activation during capturing of the successive frames depending upon a type of material in a layer on the workpiece to be illuminated. In a second related embodiment, different wavelengths of light are emitted during capturing of successive ones of the frames by activating successive ones of the rows of light emitters, whereby to produce a color image of the workpiece.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the exemplary embodiments of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. It is to be appreciated that certain well known processes are not discussed herein in order to not obscure the invention.
FIG. 1 depicts an exemplary wafer processing system including a wafer image capture apparatus in accordance with a first embodiment.
FIGS. 2A and 2B are plan and elevational views respectively of a portion of the system of FIG. 1 in accordance with one embodiment.
FIG. 3 is a bottom plan view corresponding to FIG. 2A .
FIG. 4 is a bottom plan view of an alternative embodiment of the image capture apparatus of FIG. 3 .
FIG. 5A is a block diagram depicting a method of operating the system in FIG. 1 , in accordance with an embodiment.
FIG. 5B depicts an apparatus for carrying out the embodiment of block 172 - 1 of the method of FIG. 5A .
FIG. 5C depicts an apparatus for carrying out the embodiment of block 172 - 2 of the method of FIG. 5A .
FIG. 6 is a block diagram of the process of block 172 - 3 of FIG. 5A .
FIG. 7 depicts the raw image of a wafer edge distorted by motion of the wafer while being transferred by the robot.
FIG. 8 is a graph of the observed wafer width in pixels as a function of camera frame number, as used in a calculation of the maximum wafer width in the raw image.
FIG. 9 illustrates the geometry employed in a method of processing the raw image to remove motion-induced distortion.
FIG. 10 is a diagram depicting the geometry of the camera misalignment in accordance with one example.
FIG. 11 depicts a method of determining a misalignment angle of the camera from the image data.
FIGS. 12A , 12 B and 12 C together depict a method of using the undistorted wafer image to measure non-concentricity of the film layer.
FIG. 13 depicts a method of correcting the image data for errors caused by wafer vibration along the X-axis.
FIG. 14 is a graph of the wafer center location along the X-axis as a function of the shifted frame number, used to perform the method of FIG. 13 .
FIG. 15 depicts a method of correcting radial measurements from the image data for errors caused by out-of-plane vibration (along the Z-axis).
FIG. 16 is a graph of the geometry employed in the method of FIG. 15 .
FIG. 17 is a simplified block flow diagram of methods of smoothing the undistorted wafer motion function.
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 and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. It is to be noted, however, that the appended drawings illustrate only exemplary 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.
DETAILED DESCRIPTION
FIG. 1 depicts a wafer processing tool that includes a vacuum transfer chamber 102 coupled to four wafer processing chambers 104 , all held at sub-atmospheric pressure. A vacuum robot 106 transfers individual wafers between any one of the processing chambers 104 and any one of two load lock chambers 108 . A factory interface 110 is at atmospheric pressure, and includes an atmospheric robot 112 for transferring a wafer between one or more cassettes 114 and the load lock chamber 108 . The load lock chamber 108 provides a transition between the atmospheric pressure of the factory interface 110 and the vacuum of the vacuum transfer chamber 102 . The vacuum robot 106 holds each wafer on a vacuum robot blade 116 , while the atmospheric robot 112 holds each wafer on an atmospheric robot blade 118 . The robots 106 , 112 move each wafer along a wafer transit path 120 through the factory interface at a high speed of over 1 meter per second, e.g., about 1.7 meters per second. The robots 106 , 112 are controlled by a robot controller 113 in accordance with stored instructions defining the velocity profile (acceleration, deceleration, direction, etc.) of each robot blade 116 , 118 along the various wafer transit paths.
Each processing chamber 104 has a wafer support pedestal 124 on which a wafer 122 is either placed (or removed) by the vacuum robot 106 . The centering of the wafer 122 on the pedestal 124 can affect the concentricity of thin film layers deposited near the wafer edge, such as a film layer. This placement is affected by the placement of the wafer on the atmospheric robot blade 118 and by the placement of the wafer on the vacuum robot blade 116 , and/or alignment or centering of the photolithographic mask on the wafer.
An image capture apparatus 130 is placed at a fixed location over a selected portion of the wafer transit path 120 . Referring to FIGS. 2A , 2 B and 3 , the image capture apparatus 130 includes a camera 132 , focusing optics 133 and a light source 134 . In one embodiment, the camera 132 is implemented as a single line or imaging array of plural photosensor elements 150 depicted in FIG. 3 . The camera 132 and the light source 134 may operate in the visible wavelength or in other wavelengths, such as UV, Infra Red or Microwave. In one embodiment, the light source may have a wavelength between 200 nm and 900 nm, for example.
The camera 132 has an elongate thin field of view (FOV) 121 having a length L (as depicted in FIG. 2A ) that is transverse to the portion of the wafer transit path 120 underlying the line camera 132 . The length L of the field of view 121 is affected by the optics 133 . The optics 133 may be designed so that the length L of the field of view 121 exceeds the length of the elongate array of photosensor elements 150 . As shown in FIG. 2A , the length L of the field of view 121 extends across the entire diameter of the wafer 122 . As depicted in FIG. 2A , the wafer transit path portion 120 beneath the camera 132 lies along a Y-axis, while the length L of the field of view 121 of the camera 132 extends along an X-axis. FIG. 2A shows that the length L of the elongate field of view 121 is transverse to the direction of wafer travel (the Y-axis) in the transit path portion 120 in that it is perpendicular to it. However, in other embodiments the elongate field of view 121 is transverse by being disposed at an acute angle with respect to the Y-axis, or any angle between about 10 and 90 degrees.
An image control processor 123 controls the camera 132 and processes the images provided by the camera 132 . The camera 132 capture successive line images (frames) of the wafer 122 , and provides these images in succession to the image control processor 123 . A raw image of the wafer 122 consists of a succession of such frames covering the entire wafer. The image control processor 123 removes velocity profile-induced distortion from the raw image of the wafer. Further, the image control processor 123 may use the undistorted (corrected) wafer image to perform measurements of various features on the wafer, such as (for example) concentricity of a film layer deposited on the wafer, or to detect some features, such as water droplets or other defects. Alternatively, the image control processor 123 may use the distorted (uncorrected) wafer image to perform the measurements. In this alternative mode, the measurement data may be extracted from the uncorrected image, and the compensation for speed-induced distortion performed for each individual point or picture element (pixel). This correction may be performed by using a look-up table. Such a look-up table may be constructed in a straight-forward manner in the image processor 123 by correlating the locations of individual pixels in the uncorrected image with locations of the corresponding pixels in the corrected image.
In the embodiment depicted in FIG. 1 , the image capture apparatus 130 is inside the factory interface 110 and overlies the portion of the wafer transit path 120 lying within the factory interface 110 . In an alternative embodiment, an image capture apparatus 130 ′ overlies a wafer transit path 120 ′ inside the load lock chamber 108 . The image capture apparatus 130 or 130 ′ may be located in any suitable location overlying a wafer transit path in the wafer processing tool of FIG. 1 .
As noted above, the length L of the field of view 121 enables the camera 132 to capture individual images or frames that extend across the diameter of the wafer 122 . Each successive image or frame captured by the camera 132 is one (or more) picture element (“pixel”) long (along the direction of the wafer transit path 120 or Y-axis) and many (e.g., thousands) of pixels wide along the X-axis. The camera 132 captures one frame at a time. A succession of many such frames provides a raw image of the entire wafer 122 . While the drawing depicts a camera having a single row of pixels, in an alternative embodiment, the camera may have multiple rows of pixels.
The raw image may consist of an identification of the location along the Y-axis of each frame captured by the camera 132 , and, for each frame, a listing of the luminance values of all the pixels in the frame. As will be described below, the raw image of the wafer is distorted by acceleration or deceleration of the wafer occurring during image capture. This distorts the Y-axis frame locations in the raw image. In embodiments described herein, the distortion is corrected by replacing the Y-axis frame locations given in the raw image with correct Y-axis frame locations.
The side view of FIG. 2B depicts the light rays emanating from the light source 134 and the light ray impinging on the camera 132 . As depicted in the bottom plan view of FIG. 3 , the camera 132 in one embodiment consists of a line array of individual image-sensing or photosensitive elements 150 , which may be individual photosensitive diodes, for example. Each photosensitive element 150 corresponds to an individual picture element or pixel in the captured image. Therefore, each photosensitive element 150 may also be referred to as a pixel. The photosensitive elements 150 are individually coupled to a transfer circuit 152 that assembles the parallel output signals of the photosensitive elements into a desired format (e.g., a serial succession of individual pixel values) and outputs the formatted signal to the image control processor 123 .
As described above with reference to FIG. 3 , the light source array 134 consists of an array (e.g., a line array) of individual light emitting devices 154 . In one embodiment, the light emitting devices 154 are light emitting diodes. A light source electrical power supply 156 is coupled to the light source array 134 to power the individual light emitting devices 154 . In one embodiment, the light emitting devices 154 are of the same type and emit the same wavelength spectrum.
The light source array 134 of FIGS. 2A and 2B may be obtained from any one of a number of suppliers. For example, the following LED arrays may be used as the light source array 134 : an LED array emitting at a wavelength of 830 nm by Opto Diode Corporation of Newbury Park, Calif.; an LED array emitting at 620 nm by Stocker Yale, Inc. of Salem, New Hampshire. The line camera 132 may be a UM8 CCD camera from e2v Technologies of Essex, England, having 12,288 photosensitive elements or pixels (corresponding to the photosensitive elements or pixels 150 of FIG. 3 ), each pixel measuring about 5 microns by 5 microns (in other words, 5 microns on each side). A CCD camera of this type may have a static resolution of 26μ/pixel, and a resolution of 70-80μ/pixel along the axis of motion (the Y-axis) where the motion of the wafer is about 1.7 meters per second. Nominally, the frame time may be about 50 μsec/frame and the exposure time may be about 35 μsec.
Generally, the camera 132 may have a static resolution in a range of 10-40 p/pixel, a pixel size in a range of 1-10 microns on each side, a frame width (along the Y-axis) in a range of one to five pixels, and a frame length (along the X-axis) in a range of 5,000-15,000 pixels. The camera 132 may be operated at a frame rate in a range of 10-100 μsec/frame and an exposure time in a range of about 5-80 μsec/frame. The light source array 134 may consist of discrete sources emitting at single wavelength lying in a range of 200-900 nanometers.
Each pixel of a high resolution camera of this type has a very narrow light cone angle through which light rays may be sensed. This angle may be as little as one tenth of a degree for each pixel. This presents a problem whenever reflections from the wafer are deflected from the intended incidence by wafer bowing, for example. Wafer bowing is common in such applications because the process chamber environment may be comparatively hot. As a result, light from the light source array 134 may not be sensed by the camera 132 .
This problem is overcome by providing an enhanced light source array 166 depicted in FIG. 4 . The enhanced light source array 166 of FIG. 4 mimics the light output of a diffused light source, providing light rays across a nearly continuous range of angles to each pixel 150 of the camera 132 . In this way, regardless of perturbation of the reflected light due to wafer bowing or the like, at least one light ray will fall within the light cone angle of each pixel 150 . In the embodiment depicted in FIG. 4 , the enhanced light source array 166 has plural rows 168 of light emitting devices 154 . The rows 168 may extend a length which is different from the length of the camera 132 . The enhanced light source array 166 may have roughly ten light emitting devices 154 for each pixel 150 of the camera 132 , providing light from a different angle with respect to a particular pixel. Each light emitting device 154 (which may be a light-emitting diode) radiates light over a wide cone of angles, as much as 20 degrees, for example. Thus, the ten light emitting devices 154 in the enhanced light source array 166 of FIG. 4 illuminating a particular pixel 150 provide light rays in a continuum of angles in a two-dimensional plane to the pixel 150 , so that wafer bowing or other perturbations do not prevent light reflection into the narrow light cone of the pixel. In this manner, the enhanced light source array 166 functions in the same way as an ideal diffuse light source.
FIG. 5A depicts a method of employing the foregoing apparatus to measure or detect features on a wafer. The image capture apparatus 130 (stationary camera 132 and light source array 134 ) is employed to capture an image of a wafer as the wafer is being transported by the robot at high speed (block 170 of FIG. 5A ) to produce a succession of frames including a raw image of the entire wafer. In one embodiment, the wafer motion continues at the high speed (over 1 meter per second) of the normal robotic transfer action during image capture. Next, an image processor processes the data of the raw image to remove distortion of the image caused by the velocity profile of the high speed motion of the robot-transported wafer (block 172 of FIG. 5A ). The location of each frame along the direction of wafer transit path 120 or Y-axis in the captured image of the wafer is distorted by acceleration or deceleration in the wafer motion profile. For example, the image of a circular wafer may be non-circular. In one embodiment, the distortion is removed in block 172 by replacing the Y-axis location of each frame given in the raw image with the actual Y-axis location of each frame. This produces an undistorted image.
The edges of various features of interest in the distorted or undistorted image are located and various feature dimensions are measured or detected in the undistorted image (block 174 of FIG. 5A ). For example, the edges of the wafer and of the film layer may be detected. The non-concentricity of a film layer edge relative to the wafer edge may be measured, and the radial width of a peripheral region lacking the film layer is measured and compared to the required width. The wafer image may be processed to search for and precisely locate features of interest, such as contamination or fiducial features.
The operation of block 172 may be performed in accordance with any one of different methods referred to in blocks 172 - 1 , 172 - 2 or 172 - 3 of FIG. 5A .
In the method of block 172 - 1 , the image processor 123 is provided information defining the motion of the robot blade 116 or 118 . The information may be stored instructions used by the robot motion controller 113 to govern the robot end effector (blade) motion. Alternatively, the information may be from a motion encoder coupled to the robot. In either case, the information is used by the image control processor 123 to deduce the true position of the robot end effector (and therefore of the wafer) and from that true position, compute the correct Y-axis position of the current image frame. The correct Y-axis position of each frame is combined with the image data of each frame to form an undistorted image.
The process of block 172 - 1 may be carried out by apparatus illustrated in FIG. 5B in accordance with one embodiment. In FIG. 5B , robot motion information is obtained from a reliable source. This source may be a memory 182 associated with the robot controller 113 that stores instructions, commands or definitions employed by the robot controller 113 to govern the motion robot 106 or 112 and/or the robot blade 116 or 118 of FIG. 1 . Alternatively, the source of the robot motion information may be an encoder 184 that may be an integral part of one of the robots 106 or 112 or it may be a separate encoder that is coupled to the robot 106 or 112 . A computational function 186 within the image control processor 123 uses the robot motion information from the memory 182 or from the encoder 184 to compute the correct Y-axis location of the wafer during the current frame, from which the Y-axis location of the current frame is inferred. An image processing function 188 within the image control processor 123 replaces the Y-axis frame location of the raw image with the correct Y-axis location determined by the computational function 186 . This operation is performed for each frame captured by the camera 132 . After all captured frames have been thus corrected, the image processor 123 outputs an undistorted image of the wafer.
In the method of block 172 - 2 of FIG. 5A , the image control processor 123 uses robot motion information to govern the camera frame rate so as to prevent distortion of the wafer image acquired by the camera 132 . The image control processor 123 accesses information or data defining the motion of the robot as in block 172 - 1 . However, the image control processor 123 uses this information to deduce the actual velocity of the wafer along the Y-axis during the time of the current frame. The image control processor then adjusts the frame rate of the camera 132 in accordance with any change in wafer velocity following the previous frame so as to maintain a constant ratio between the wafer speed along the Y-axis and the camera frame rate.
The process of block 172 - 2 of FIG. 5A may be carried out by the apparatus illustrated in FIG. 5C in accordance with one embodiment. In FIG. 5C , robot motion information is obtained from a reliable source. This source may be the memory 182 associated with the robot controller 113 . Alternatively, the source of the robot motion information may be the encoder 184 . A computational function 192 within the image control processor 123 uses the robot motion information from the memory 182 or from the encoder 184 to compute the wafer speed along the Y-axis for the next frame. A computational function 193 of the image control processor 123 computes a ratio between the camera frame rate and the wafer speed computed by the function 192 . A comparator 194 compares the frame rate-to-wafer speed ratio with the same ratio of a previous frame, and a frame rate computational function 195 determines a new frame rate for the next frame that will keep the frame rate-to-wafer speed ratio constant relative to the previous frame or frames. This new frame rate is applied as a control input to the camera 132 . The change in frame rate compensates for acceleration or deceleration of the wafer motion, so that the image acquired by the camera is free or nearly free of motion profile-induced distortion. The frame exposure time may be adjusted in proportion to the change in frame rate.
In the method of block 172 - 3 of FIG. 5A , the raw (distorted) image of the wafer is used by the image control processor 123 to actually compute the correct (undistorted) Y-axis location of each frame. This is accomplished by first observing the wafer width in the raw image frame and then using the observed wafer width and the known wafer diameter to compute the undistorted Y-axis location of the frame. The image control processor 123 constructs a corrected or undistorted image by substituting the correct Y-axis location of each frame in the image in place of the Y-axis location given by the raw (distorted) image.
In one embodiment, the process of block 172 - 3 of FIG. 5A is not applied to correct the entire image of the wafer. Instead, for example, only a selected portion of the distorted image is processed, to yield data related to an undistorted image of only the selected portion. For example, if it is desired to calculate the width of the film layer peripheral zone, then only that portion of the image near the edge of the wafer is corrected for distortion by the process of block 172 - 3 . Thus, the result may not be an undistorted image of the wafer, but rather data relating to an undistorted image of a selected portion of the wafer.
Alternatively, the analysis may be performed on the undistorted image and correct for specific frame number or angular position using a lookup table.
FIG. 6 depicts the process of block 172 - 3 of FIG. 5A in detail, in accordance with one embodiment. In this embodiment, the true Y-axis location of each frame is computed as a function of the ratio between the wafer width in each frame and the known wafer diameter. The process begins by collecting the data of the raw image of the wafer (block 200 of FIG. 6 ) frame-by-frame. As described above, each image frame produced by the camera 132 is one pixel wide and thousands of pixels long. A succession of such frames contains the image of the entire wafer. (In an alternative embodiment, the frame may be more than one pixel wide.)
The image of the wafer edge is obtained (block 202 of FIG. 6 ). The wafer edge image is obtained by conventional edge-detection image processing techniques. The first and last pixels of the wafer image are then determined for each frame, yielding the wafer edge image depicted in FIG. 7 . The graph of FIG. 7 depicts the location (by pixel number) of the first and last pixels of all frames. The first pixels are indicated by symbols and the last pixels are indicated by dots, in FIG. 7 . Distortion of the wafer shape due to acceleration/deceleration at the high robotic transfer speed during image capture is apparent in FIG. 7 .
The wafer width in each frame is obtained (block 204 of FIG. 6 ). The wafer width, w, as a function of frame number, f, may be defined as w(f), and is calculated as the distance between the first and last wafer pixels in the corresponding frame. The curve w(f), typically a parabola, is depicted in FIG. 8 .
A maximum wafer width, w(f) max , corresponds to the wafer diameter and is determined (block 206 of FIG. 6 ) from the peak of the curve, w(f), which is found using conventional techniques. The frame number in which w(f) max occurs is also noted and defined as f max (block 208 of FIG. 6 ).
A pixel-to-millimeter conversion factor σ that correlates the distance between pixels (corresponding to individual light sensing elements 150 in the camera 132 ) and actual distance in millimeters on the wafer surface is obtained (block 210 of FIG. 6 ). The conversion factor is obtained by dividing the maximum width in pixels, w(f) max , by the known wafer width, typically 300 mm.
The raw wafer outline of FIG. 7 is distorted because the wafer acceleration and deceleration distorts the apparent location of each frame along the wafer transit path 120 or Y-axis of FIG. 2A . Correction of such distortion may be performed by replacing the apparent Y-axis location of each frame with the correct Y-axis location. The correct Y-axis location corresponds to the distance of wafer movement along the Y-axis. The distance of wafer movement along the wafer transit path 120 or Y-axis is calculated for each frame from the wafer width w(f) measured in the particular frame (block 212 of FIG. 6 ). The geometry employed in this calculation is illustrated in FIG. 9 . The wafer transit path 120 of FIG. 2A , established by the robot, is the Y-axis of FIG. 9 . The general orientation of the line camera 132 corresponds to the X-axis of FIG. 1 . The distance of wafer movement along the wafer transit path (Y-axis) as a function of frame number f will be referred to herein as a Y-axis location function h(f), where h denotes the distance and f denotes the frame number. Referring to FIG. 9 , for a 300 mm wafer, the wafer width w for a given frame f is related to h as follows:
W (in mm)= w (in pixels)·σ (Eqn. 1a)
θ=2 sin −1 ( W/ 300mm) for W< 300mm (Eqn. 1b)
θ=2 sin −1 (1) for W≧ 300mm (Eqn. 1c)
d=W/[ 2 tan(θ/2)] (Eqn. 1d)
h ( f )=150mm−d for f<f max (Eqn. 1e)
h ( f )=150mm+ d for f≧f max (Eqn. 1f)
The foregoing may be summarized as follows: for values of W within the diameter of the wafer, the Y-axis location function is computed as:
h ( f )=150mm− W/[ 2 tan(sin −1 ( W/ 300)] for a first half of the wafer in which f<f max , and
h ( f )=150mm+ W/[ 2 tan(sin −1 ( W/ 300)] for a second half of the wafer in which f≧f max .
It is understood that the wafer diameter and radius values (300 mm and 150 mm) present in the foregoing definitions are applicable to a 300 mm wafer, and may be modified depending upon the diameter of the wafer being processed.
In one embodiment, the frame number f in the Y-axis location function h(f) may be defined such that the frame containing the leading edge of the wafer is frame zero, corresponding to the origin. The frame containing the leading edge of the wafer is identified (block 214 of FIG. 6 ). It may be identified in one embodiment by first plotting the line number of each first and last pixel (found in the step of block 202 of FIG. 6 ) as a function of pixel number for a group of frames near the wafer leading edge. The frame number containing the leading edge of the wafer corresponds to the minimum value of this function and is found using conventional techniques. The frame numbers of the Y-axis location function h(f) are then shifted so that the leading edge frame number is zero, in one embodiment (block 216 of FIG. 6 ).
Optionally, the Y-axis location function h(f) may be smoothed (block 218 of FIG. 6 ) in a process described below in this specification with reference to FIG. 17 .
The raw image of the wafer, obtained from the succession of frames output by the camera 132 , is corrected for motion-induced distortion (block 220 of FIG. 6 ). This correction consists of replacing the Y-axis coordinate of each frame by h(f). The foregoing correction to the Y-axis coordinate of each frame produces an image of the wafer in which distortion attributable to wafer motion profile (acceleration/deceleration) along the Y-axis has been removed, which image may be referred to as the undistorted image. This correction permits the image capture to be performed at high wafer transfer speeds without having to stop or slow down the wafer transfer during image capture.
The operation of block 220 may further include scaling and correcting the X-axis coordinate. The X-axis coordinate of any feature of interest in each frame is scaled by the pixel-to-millimeter scale factor σ, while accounting for a misalignment angle β between the major axis of the line camera 132 and the X-axis. The determination of the camera misalignment angle β is described later in this specification with reference to FIG. 11 . The X-axis coordinate, X raw image , obtained from the raw image of any feature of interest is scaled to a corrected value X′ as follows:
X′=X raw image ·σ−Y tan β (Eqn. 2)
How to determine the camera misalignment angle β used in Equation (2) above is now described. The misalignment angle β between the long axis of the camera 132 and the X-axis ( FIG. 2A ) is depicted in FIG. 10 , and may be relatively small (less than a few degrees, for example). A method in accordance with one embodiment for determining β from the undistorted wafer image is depicted in FIG. 11 . The first step in FIG. 11 is to inspect the wafer image to find a pixel location X 0 where the wafer first appears in the Wafer leading edge frame f lead (block 310 of FIG. 11 ). The pixel location of the wafer center X C is computed for each frame (block 320 of FIG. 11 ). The wafer center X C is half the difference between the first and last wafer pixels referred to with reference to block 202 of FIG. 6 :
X C =[X last pixel +X first pixel ]/2 (Eqn. 3)
Next, the motion of the wafer center attributable to the misalignment angle is defined (block 330 of FIG. 11 ) as
P=X 0 +[h ( f−f lead )tan β]/σ (Eqn. 4)
A conventional non-linear minimization algorithm is employed to calculate β by minimizing
Σ[ P−X C ] 2 (Eqn. 5)
in which the indicated sum is carried out over all frames (block 340 of FIG. 11 ). This minimization is carried out by adjusting β and X 0 . This operation corresponds to curve-fitting the motion of the wafer center X C to a function of tan β. The calculated value of β (obtained by carrying out the minimization of Equation 5) is employed in the computation of Equation (2) described above with reference to block 220 of FIG. 6 (block 350 of FIG. 14 ), to correct the X-axis coordinate.
In block 230 of FIG. 6 , the undistorted image may be corrected for errors due to in-plane vibration or perturbation of the wafer motion (along the X-axis), and corrected for out-of-plane vibration or perturbation of the wafer motion (along the Z-axis). These corrections are described later in this specification with reference to FIGS. 13 and 15 .
Various measurements may be accurately performed using the undistorted corrected wafer image produced by the foregoing. For example, the radius or diameter of a film layer may be measured (block 240 of FIG. 6 ). Also, the annular width of a peripheral exclusion zone that was masked during film deposition may be measured (block 250 ). The concentricity of the film layer outer boundary with the wafer edge may be measured (block 260 ) using a method which is now described.
Referring to FIG. 12A , a film layer 300 is deposited on the wafer 122 while being processed in one of the reactor chambers 104 of FIG. 1 . The film layer 300 is disk-shaped and is intended to be concentric with the edge of the wafer 122 . FIG. 12A depicts an instance in which the film layer 300 is nonconcentric with the wafer 122 . The film layer 300 has a radius R 1 that is smaller than the radius R 2 of the wafer 122 , leaving a peripheral annular region 302 of the wafer surface that is not covered by the film layer 300 . The width of the annular region 302 is W M =R 2 −R 1 . Because of the nonconcentricity of the film layer, W M varies with the azimuthal angle θ and is therefore a function of θ, W M (θ). W M (θ) is a sinusoidal function that is illustrated in FIG. 12B .
The non-concentricity of the film layer is measured in accordance with a suitable process. An example of such a process is depicted in FIG. 12C . First, the function W M (θ) is extracted from the undistorted image data (block 280 of FIG. 12C ). A function
W M (average)+C cos(θ+α) (Eqn. 6)
is then curve-fitted to W M (θ) (block 285 of FIG. 12C ). This curve-fitting is performed using conventional techniques. The term W M (average) is the average value of W M around the entire wafer edge. The term C is the amplitude of the non-concentricity. The angle α is the azimuthal orientation of the non-concentricity. From the results of the curve-fitting, the actual values of C and a are obtained and output as corrective error feedback to the robot controller 113 for correction of the motion of one of the robots 106 or 112 (block 290 of FIG. 12C ).
FIG. 13 depicts a method in accordance with one embodiment for carrying out the correction of distortion in the image attributable to in-plane (or X-axis) vibration in the step of block 230 of FIG. 6 . First, the motion of the wafer center X C is determined from the wafer image as a function of frame number (block 360 of FIG. 13 ), which is the same operation as block 320 of FIG. 11 . The motion of the wafer center X C as a function of frame number is illustrated in the graph of FIG. 14 . From the data defining X C as function of frame number, an average value of X C between the minima and maxima in X C is determined using conventional techniques (block 365 of FIG. 13 ). This average value is labeled X C (average) in FIG. 14 , and generally follows a straight line, as depicted in FIG. 14 . (The slope of the straight line X C average) is a function of the camera offset angle β discussed previously.) The distortion attributable to X-axis vibration is removed by determining the difference between X C (average) for that frame and X C for that frame, and shifting all X coordinates in the frame by that difference, namely the difference {X C (average)−X C } (block 370 of FIG. 13 ).
In one embodiment, the foregoing correction may be made to the image to remove in-plane vibration distortions, and the resulting image used to perform a desired calculation (such as a calculation of the film peripheral zone width). In an alternative embodiment, the foregoing corrections are not applied to the wafer image. Instead, the desired calculation is performed on the image containing the in-plane vibration distortions, and then the foregoing correction is applied to the results of that calculation.
FIG. 15 depicts a method in accordance with one embodiment for carrying out the correction of distortion in the image attributable to out-of-plane (or Z-axis) vibration in the step of block 230 of FIG. 6 . For each image of a workpiece, the apparent workpiece (wafer) radius R is determined as half the workpiece width determined in accordance with Equation 1 above (block 380 of FIG. 15 ). A magnification ratio M is then computed from R and from the known wafer radius (e.g., 150 mm) as M=150 mm/R (block 385 of FIG. 15 ). Thereafter, each measurement of a radial distance along a particular azimuthal angle 8 as depicted in FIG. 16 (such as the location of the wafer edge, the location of the film layer edge, the width of the peripheral region 302 , etc.) is scaled by a magnification correction factor M cos θ (block 390 of FIG. 15 ). This corresponds to a scaling of the image in polar coordinates by scaling the radius in accordance with the magnification ratio M.
In one embodiment, the foregoing correction may be made to the image to remove out-of-plane vibration distortions, and the resulting image used to perform a desired calculation (such as a calculation of the film peripheral zone width). In an alternative embodiment, the foregoing corrections are not applied to the wafer image. Instead, the desired calculation is performed on the image containing the out-of-plane vibration distortions, and then the foregoing correction is applied to the results of that calculation.
A process for smoothing of the Y-axis wafer motion function h(f), performed in block 218 of FIG. 6 , is depicted in FIG. 17 in accordance with an embodiment. The trajectory of the robot blade along the wafer transit path in the field of view of the image capture apparatus 130 of FIG. 1 is obtained (block 400 of FIG. 17 ). This trajectory defines a robot motion profile s(t) along the Y-axis (wafer transit path beneath the image capture apparatus 130 of FIGS. 1 and 2A ). The robot motion profile sit), a function of time, is converted to a motion profile as a function of frame number by multiplying the time t by the frame rate of the camera 132 (block 410 of FIG. 17 ) to obtain a robot frame number f r for each value of time t. The converted robot motion profile, s(f r ) is a function of the robot frame number f r , having an arbitrary origin. The robot motion profile is then fitted to the wafer motion profile obtained from the wafer image data in the step of block 216 of FIG. 6 , using either one of two different methods. Alternatively, the Y-axis wafer motion function is smoothed using conventional techniques without using the robot motion profile. One of these three methods is chosen (block 420 of FIG. 17 ). If the choice is a robot motion-based method, then one of the two robot motion-based methods is chosen (block 422 ).
A first one of the two robot motion-based methods (branch 423 of block 422 of FIG. 17 ) fits the robot motion profile by sliding the robot motion profile s(f r ) relative to the wafer motion profile h(f−f lead ) until a best fit is obtained (block 424 of FIG. 17 ). This is performed in one embodiment using a non-linear minimization algorithm. The sliding of the robot motion profile is achieved by varying a robot frame offset that shifts the frame number of the robot motion profile relative to that of the wafer image until an optimum fit is obtained. The shifted robot motion profile is then substituted for the wafer image Y-axis motion profile (block 432 of FIG. 17 ).
In an alternative robot motion-based method (branch 426 of block 422 of FIG. 17 ), the foregoing optimization is performed but a constraint is imposed that forces the distance (in frame numbers) along the Y-axis between the leading and trailing edges of the wafer to equal the known wafer diameter (e.g., 300 mm).
An advantage of substituting the shifted robot motion profile for the wafer image motion profile is that the robot motion profile is derived from a predetermined continuous (smooth) motion profile defined for the robot.
As one alternative (branch 434 of block 420 of FIG. 17 ), the wafer image motion profile is smoothed without substituting any robot motion profile, and instead conventional smoothing methods are employed using spline, averaging, interpolation and/or extrapolation techniques (block 436 ). The data may be smoothed beyond the edges of the wafer image (block 438 ) before outputting the smoothed wafer motion profile (block 432 ).
The apparatus of FIGS. 1-3 may serve a number of different applications. For example, the image capture apparatus 130 may obtain the image of the wafer prior to its introduction into a particular one of the processing chambers 104 in order to obtain measurements of previously deposited thin film features, and then obtain another image of the same wafer following deposition of another thin film feature to obtain a second set of measurements that may be compared to the first set of measurements. This comparison may yield information useful in adjusting the processing of subsequent wafers.
As another example, after measuring the non-concentricity amplitude C and phase a in the manner described above with reference to FIG. 12C , these parameters may be forwarded by the image control processor 123 to the robot controller 113 for use as error correction feedback to correct the action of a wafer placement apparatus of the robot (e.g., of the atmospheric robot 112 of FIG. 1 ), so that the initial placement of each wafer on a robot blade provides a better concentricity.
The light source has been described above as a light source array 134 overlying the wafer 122 and on the same side of the wafer 122 as the camera 132 . However, for better contrast in the image of the edge of the wafer 122 , another light source 134 ′ may be placed underneath the wafer 122 so as to illuminate the wafer backside. In this way, the camera 132 would view a clear silhouette image of the wafer edge, with enhanced contrast at the edges of the wafer in the image.
The light source has been described above as an array 134 of light emitting diodes having the same monochromatic emission spectrum. With such a monochromatic source, the interference effects in the light reflected from the wafer 122 may be analyzed using conventional interferometric techniques in order to deduce the variation in thickness of a thin film deposited on the surface of the wafer 122 . The thin film thickness may be computed from the observed interference effects using conventional techniques. Furthermore, the thin film thickness may be computed for each one of a succession of locations near the edge of the thin film, and the change in thin film thickness observed and stored to define thin film edge taper profile. This taper profile in film thickness may then be compared with a
FIG. 3 depicts the LED array 134 as a single row of discrete light emitters 154 having a monochromatic emission spectrum. However, the light source or LED array 134 may have a spectrum consisting of two (or more) predetermined discrete wavelengths. In this case, the light emitters or light emitting diodes 154 of the light source array 134 may consist of two (or more) separate arrays arranged as parallel rows of light emitters or diodes, each array or row having a monochromatic emission spectrum different from the other array or row. Each array or row may emit a monochromatic spectrum at a different wavelength, and each of the two arrays may be activated depending on the wafer type or type of material in a layer of interest on the wafer surface, to ensure optimal contrast. Optimal contrast is wavelength dependent, as different types of layers or layers of different materials will reflect differently at different wavelengths. For example, one wavelength may be about 450 nm and the other wavelength may be about 600 nm. Alternatively the LED array 134 may have three rows of light emitters, each row emitting a different wavelength. The three wavelengths may correspond for example to red, blue and green, and each may be activated in synchronism with the camera, once every third frame, to provide a color RGB image of the wafer.
The measurements of film thickness may be compared with specified or desired film thickness values (or edge taper profile) and the comparison may be used to adjust one or more process parameters of one of the processing chambers 104 of FIG. 1 (e.g., deposition time, temperature, precursor gas composition, etc.).
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. | A method is provided for imaging a workpiece by capturing successive frames of an elongate stationary field of view transverse to a workpiece transit path of a robot, while the workpiece is transported by the robot. The robot transit path is illuminated with an elongate illumination pattern transverse to the transit path to obtain a workpiece image of successive frames. Motion-induced image distortion is corrected by computing respective correct locations of respective ones of the frames along the transit path. | 6 |
BACKGROUND OF THE INVENTION
RELATED APPLICATIONS
This application is a continuation-in-part of copending patent application Ser. No. 825,672, filed Aug. 18, 1977, now abandoned.
FIELD OF THE INVENTION
This invention relates generally to the field of packages for matches, and more particularly concerns safety packages adapted to prevent children from inadvertently striking cardboard matches thereon.
DESCRIPTION OF THE PRIOR ART
The potential disasters engendered when young childern, particularly in the age group of one to four years old, play with matches are well known and feared by parents. Heretofore, however, there has not been developed a package for cardboard matches which is designed to defeat a young child's efforts to produce a flame by striking a match from a package which he has come across in his interminable searching and wandering.
The only pertinent prior art of which applicant is aware is the well-known matchbook comprising a deck of cardboard matches attached to a base along a perforated line, and a cardboard cover is folded so as to provide a back portion, an upturned lip, and front flap. The base of the match deck is interposed between the lip and back portion and secured there with a staple extending through the lip, base and back. The front flap portion is openable and closable by tucking its free end between the lip and the match deck base. In most such matchbooks, a striking strip is provided on the front, presented surface of the lip portion of the cover. The striking strip is comprised of a layer of an appropriately abrasive material affixed to the cardboard cover material, which generally has a non-abrasive, decorative finish. The striking strip is usually in a contrasting color to the remainder of the cover--usually the strip is a very dark brown--and is completely accessable.
The only "safety features" provided with such matchbooks are the fact that the cardboard matches contained therein may only be struck on the provided striking strip, and the familiar legend printed on the match cover, "Please close cover before striking".
The accessability and noticeability of the match striking strip, together with the ease with which the cover may be opened and the matches obtained, make such matchbooks hazardous in the hands of inquisitive children. After having seen an adult open the cover, pull out a match and draw the colorful head of the match across the dark, abrasive strip to produce a flame, a curious child will find it relatively easy to emulate those actions when given the opportunity to pick up such a book of matches carelessly left lying about. The potential danger goes without saying.
It is an object of the invention herein disclosed to provide means for striking matches which are not easily used by young children, and which require more than casual observance of an adult utilizing the striking means in order for a child to successfully strike a match himself.
It is a further object of the invention to combine the striking means with a standard matchbook to produce an improved, safe matchbook, which is also an inexpensive-to-produce article of manufacture.
SUMMARY OF THE INVENTION
In accordance with the present invention, the abrasive, match-striking strip is provided with a cover flap extending longitudinally thereof. By this arrangement, a two-fold safety factor is accomplished. First, the dark colored, abrasive strip is hidden from the view of a child either observing an adult's use of the invention, or playing with it himself: he cannot see what it was that the adult struck his match on, and consequently, will have difficulty striking a match himself. Second, the striking strip, being covered, is not easily accessable to a child's random poking and prodding with an unspent match, and, therefore, accidental striking of a match is much less likely than with the common matchbook presently in use. The only way a match can be struck with the present article of manufacture is by placing the unspent match end in the recess formed between the safety flap and the striking strip--a deliberate action which is likely to be beyond the dexterity of a large number of small children.
By constructing the inventive article so that the material used and the transverse dimensions of the match-covering cavity bounded by the walls of the protective "tube" are such that insufficient friction can be generated by simply placing a match head in contact with the striking strip and moving it back and forth, another safety feature is achieved. To strike a match placed in such a cavity, the match head must be pinched between the striking strip and the inside surface of the safety flap with one hand as it is drawn out of the cavity with the other. This pinching action is carried out rapidly and is virtually unnoticeable to a child observing it, thus, not only will a child have trouble emulating the action, the limits of his dexterity and strength will also deter him from efficiently copying the requisite motion.
Finally, the "tubular" striking means can be easily and cheaply manufactured simply by extending the upturned lip portion of the presently known matchbooks, and making several easy folds in the extension material to define a safety flap. The matchbook is completed by a staple extending through the lip, match deck base, and back portion of the cover. The vastly improved safety cover herein disclosed can be manufactured with little or no change in the presently used method of manufacture.
It will be appreciated that an effective safety package for matches has been disclosed which hinders a child's observation of the method of striking matches, prevents accidental striking of a match randomly contacted with the package, and which requires that several deliberate steps be taken before a match may be struck, which steps are beyond the ability of most young children to perform due to limits on their strength and dexterity.
These and other features of the invention will be discussed in more detail in the following sections.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view in perspective, indicating the proper use of a matchbook constructed in accordance with the present invention;
FIG. 2 is a view in perspective of the article of manufacture of the present invention, with the safety flap folded back so as to reveal the striking strip;
FIG. 3 is a view in end elevation of a matchbook constructed in accordance with the present invention as it appears with safety flap flattened against striking strip;
FIG. 4 is a view similar to that shown in FIG. 3 of the match cover with safety flap spaced apart from striking strip.
FIG. 5 is a view in perspective of another embodiment of the invention, showing the safety flap in its unfolded state.
FIG. 6 is a view similar to that shown in FIG. 5 with the safety flap partially folded.
FIG. 7 is a view similar to that shown in FIGS. 5 and 6 with the safety flap folded and in its normal, flattened position.
FIG. 8 is a view in perspective showing the operation of the invention.
FIG. 9 is an enlarged sectional view of the invention as seen from the line 9--9 of FIG. 7 showing its normal position in solid lines, and indicating its second, use position in dotted lines.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 2, there is shown an improved, safe matchbook 10, constructed in accordance with the present invention. As in conventionally known matchbooks, matchbook 10 comprises a cardboard cover 12, enclosing a plurality of cardboard matches 14 (shown in FIGS. 3 and 4) which are perforatedly attached to one or two cardboard base members 16. Cover 12 includes a back portion 18, a front flap 20, and an upturned lip portion 22. Affixed or coded, on the front presented surface of lip portion 22 is a match-striking strip 24. Striking strip 24 may be of sandpaper or emery paper, or some other suitable abrasive material which is well-known in the art. As opposed to the rough texture of strip 24, the remaining surfaces of cover 12 are generally smooth, and often polished and printed with decorative material, so that a match may only be struck on strip 24.
On a conventional matchbook, lip 22 terminates at the edge indicated by fold line 26, and front cover flap 20 is tucked between lip 22 and the base or bases 16 to secure the flap in a closed position. In the present invention, a safety flap 28 extends from lip 22, as shown in FIG. 2. Safety flap 28 is folded down along fold line 26 and secured to lip portion 22 by means of staple 30 which extends through flap 28, lip 22, base or bases 16 and back 18.
By folding flap 28 over and securing it to lip portion 22, a generally tubular structure is achieved, whereby striking strip 24 is situated within a longitudinally extending, match-receiving cavity 32, which is open at both ends to facilitate insertion of a match 34 therein, as indicated in FIG. 1. It will be appreciated that flap 28 could be secured to lip 22 by means other than a staple--glue, for instance, would be appropriate--or that a continuous tubular wall-something on the order of that provided by a soda straw--having a striking portion on the interior wall would be within the scope of my invention. However, the preferred form, especially for the purpose of ease of manufacture, is the flap and staple arrangement shown in the drawings.
Cavity 32 extends, in longitudinal dimension, over the length of striking strip 24. In its transverse dimensions, cavity 32 must be such that, when a match is inserted therein, with its head resting against striking strip 24, there will be no appreciable force exerted by the interior wall of flap 28 tending to press match head 36 against strip 24. In general, this means that cavity 32 is slightly larger in transverse dimension than the corresponding dimensions of the matchhead portion 36 of match 34. This dimensioning allows match 34 to be easily inserted into cavity 32; it also ensures that there is not such a tight fit of the match between the interior wall of flap 28 and striking strip 24 that sufficient striking friction can be generated by simply pulling the match out of the match receiving space.
Since cardboard matches are not very rigid in their construction, there is also no way to "lever" matchhead 36 against strip 24 by applying a moment around the shaft portion of match 34 while it is inserted in space 32--such a moment would only buckle the shaft of match 34. Consequently, the only way in which sufficient striking friction can be generated is to insert match 34 into cavity 32, and pinch matchhead 36 between flap 28 and strip 24 as it is drawn out of cavity 32. This operation is illustrated in FIG. 1. As there suggested, the requisite striking action requires use of both hands, and a level of dexterity, coordination, and timing, which, although simple for adults to master, is beyond the capabilities of most children in the age group which is the target of the invention.
To accomplish the pinching of the matchhead, safety flap 28 is flattenable against lip 22, and strip 24 and illustrated in FIGS. 3 and 4. This is primarily due to the generally non-rigid characteristic of the cardboard used in the construction of cover 12. This "flattenability" could be accomplished by other means with other materials, however--by scoring, hinging, spring-biasing, etc.
Referring to FIGS. 5-9 a second embodiment of the present invention is shown. The matchbook 10' of this embodiment includes a cardboard cover 12' enclosing a comb of matches 14', having a base member 16'. Cover 12' comprises a back cover portion 18' attached to a front cover portion 20' by means of a hinge portion 21', which not only allows front cover 20' to be opened, but also provides for a sliding motion of front cover 20' between the first and second position shown in FIG. 9. An upturned lip 22' curls around base member 16', and a staple 30' extends through lip 22', base 16' and back cover 18' to secure the match comb 14' within cover 12'.
Cover 12' further comprises a safety flap portion 40' extending from lip 22' above the staple point. Safety flap 40' is folded along fold lines 42', 44' and 46' as shown in FIGS. 5, 6 and 7 in a "reverse-S" manner to define panels 48' and 50', and second upturned lip 52'. Striking strip 24' may be mounted on the interior surface of panel 48', as shown in FIG. 5, or on the interior surface of panel 50' (not shown). Upturned lip 52' and panel 50' cooperate to define a receiving groove for front cover 20', as is best shown in FIGS. 7-9.
Safety flap 40', when folded, is normally in the flat position shown in FIG. 7, whereby there is no access to striking strip 24'. A sliding movement of front cover 20', as shown in FIG. 8 to a second position, bulges panel 50' outwardly to define a generally tubular member, thus giving access to striking strip 24'. This sliding action is best shown in FIGS. 8 and 9. With panel 48' bulged outwardly, a match 34' may be inserted in the longitudinal, flattenable cavity defined by panels 48' and 50', and struck as previously described.
It will be appreciated that the addition of a safety flap over the striking strip of a conventional matchbook--an inexpensive operation requiring no additional parts and very few modifications in the present method of manufacture-- provides several extremely beneficial safety factors. First, the striking surface of the match cover and the entire striking operation are effectively hidden from the casual observance of a young child watching an adult strike a match. Second, the striking strip is covered so that a child who picks up the book cannot accidentally strike a match on an easily accessable, exposed surface of the book. Third, the presence of the open ended tube formed by the safety flap in the lip portion requires that a match be held between thumb and forefinger and inserted longitudinally therein in order for the match head to be brought into contact with the striking strip; this step requires manual dexterity and hand-eye coordination that very young children may not have developed, thus precluding their being able to strike a match on the safety package. Finally, the dimensions of the tube formed by the safety flap--particularly the transversely measured distance between the interior surface of the safety flap and the striking surface are such that a match head once inserted into the tube, must be pinched between the flap and striking strip by exerting a force on the outside surface of the flap with the fingers of one hand, while drawing the match rapidly across the strip and from the tube with the other hand--an easily disguised motion which a child may not learn by casual observance, and a difficult-to-perform step for a young child with limited strength and dexterity.
All of their safety features previously described are present in this embodiment of the invention. In addition, a further step of bulging the safety flap by sliding the cover is required, so as to further hamper a child's attemp to strike a match, and, also, if safety flap 40' should for some reason be torn from the matchbook 10', the striking strip 24' will also be removed, thus rendering the remaining assembly strike proof. | An improved package for matches is disclosed, in which the striking surface of the package is protected by a flattenable, generally tubular enclosure. The enclosure hides the striking surface from view, and prevents a match from being struck unless it is pinched between the striking surface and the interior wall of the enclosure as it is drawn across the striking surface.
The tubular enclosure may include a front cover receiving recess, and normally be in a flattened position, whereby a sliding motion of the front cover towards the tubular enclosure while in engagement with the receiving recess expands the tubular enclosure allowing access to the striking surface. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This Application is a Section 371 National Stage Application of International Application No. PCT/KR2012/010626, filed Dec. 7, 2012 and published, not in English, as WO 2013/094904 on Jun. 27, 2013.
FIELD OF THE DISCLOSURE
[0002] The present disclosure relates to a method for manufacturing high-strength flake graphite cast iron, flake graphite cast iron manufactured by the method, and an engine body comprising the cast iron, and more particularly, to flake graphite cast iron capable of uniformalizing graphite shapes of a thin walled part and a thick walled part, reducing low possibility of the formation of chill and exhibiting high strength and excellent processibility by controlling a very small amount of sulfur (S) and a content of strontium (Sr) to be a predetermined ratio even though ferroalloy is added to achieve high strength, and a method for manufacturing the same.
BACKGROUND OF THE DISCLOSURE
[0003] In recent years, as environmental regulations are tightened, it is necessary to reduce contents of environment pollutants discharged from an engine, and in order to solve the pollutant discharge, it is necessary to increase a combustion temperature by increasing an explosion pressure of the engine. In this way, when the explosion pressure of the engine is increased, strength of engine cylinder block and head constituting the engine needs to be increased in order to stand the explosion pressure.
[0004] A material that is currently used for the engine cylinder block and head is flake graphite cast iron to which a very small amount of ferroalloy such as chrome (Cr), copper (Cu), or tin (Sn) is added. Since the flake graphite cast iron has excellent heat conductivity and excellent damping ability and a very small amount of ferroalloy is added thereto, the flake graphite cast iron is less likely to occur chill, and has excellent castability. However, since tensile strength is about 150 to 250 MPa, there is a limitation in using the flake graphite cast iron for the engine cylinder block and head requiring an explosion pressure of more than 180 bar.
[0005] Meanwhile, the material of the engine cylinder block and head for standing the explosion pressure of more than 180 bar needs to have a high strength of about 300 MPa. To achieve this, an element such as copper (Cu) or tin (Sn) for stabilizing pearlite or an element such as chrome (Cr) or molybdenum (Mo) for prompting generation of carbide needs to be added. However, since the addition of the ferroalloy may potentially cause the occurrence of the chill, there is a problem in that the chill is highly likely to be caused in thin walled parts of engine cylinder block and head having a complicated structure.
[0006] As the related art for achieving high strength of the flake graphite cast iron, there is a method of forming MnS emulsion by controlling a using ratio between manganese (Mn) and sulfur (S) added in a molten cast iron, that is, Mn/S to be a predetermined ratio. At this time, the formed Mn/S emulsion serves to prompt generation of the nucleus of graphite and to reduce the occurrence of the chill due to the addition of the ferroalloy. Since the aforementioned method can be applied to high manganese molten cast iron having a manganese (Mn) of about 1.1 to 3.0%, the content of the manganese (Mn) needs to be used two times more than a content of manganese used in manufacturing flake graphite according to the related art. Thus, material cost may be unavodiably increased. Further, the manganese (Mn) serves to prompt a pearlite structure, and allows a cementite distance within the pearlite structure to be densed to strengthen a matrix structure. However, when a large quantity of manganese (Mn) is added, since carbide is stabilized to disturb growth of the graphite. Accordingly, when the Mn/S ratio is not controlled to be a predetermined range, the occurrence of the chill is further prompted due to the large content of the manganese. Therefore, there is a limitation in applying the flake graphite cast iron to the engine cylinder block and head having a complicated structure.
[0007] CGI (compacted graphite iron) that has excellent castability, damping ability and heat conductivity of the flake graphite cast iron and satisfies a high tensile strength of 300 MPa or more is recently applied to engine cylinder block and head having a high explosion pressure. In order to manufacture the CGI of a tensile strength of 300 MPa or more, it is necessary to use a melting material and pig iron in which a content of an impurity such as sulfur (S) or phosphorus (P) is low, and it is necessary to precisely control magnesium (Mg) which is an element of spheroidizing the graphite. However, since it is difficult to control the magnesium (Mg) and the CGI is very sensitive to changes of melting and casting conditions such as a tapping temperature and a tapping speed, it is highly likely to cause material quality deterioration of the CGI and casting defect. Further, manufacturing cost may be increased.
[0008] Moreover, since the CGI has relatively poor processibility than the flake graphite cast iron, when the engine cylinder block and head are manufactured using the CGI, it is difficult to manufacture the engine cylinder block and head in an existing processing line for the flake graphite cast iron, and it is necessary to change the processing line to a processing line for the CGI. Accordingly, enormous facility investment cost may be incurred.
[0009] The discussion above is merely provided for general background information and is not intended to be used as an aid in determining the scope of the claimed subject matter.
SUMMARY
[0010] This summary and the abstract are provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. The summary and the abstract are not intended to identify key features or essential features of the claimed subject matter, nor are they intended to be used as an aid in determining the scope of the claimed subject matter.
[0011] In order to solve the aforementioned problems, an embodiment of the present disclosure is to provide flake graphite cast iron which simultaneously has high strength and excellent processibility and fluidity even though ferroalloy such as molybdenum (Mo) or copper (Cu) is added to achieve high strength by controlling a content of strontium (Sr) among a very small amount of components added in cast iron and a content ratio between sulfur (S) and strontium (Sr) to be in a predetermined range, and a method for manufacturing the same.
[0012] An embodiment of the present disclosure is to also provide cast iron having a stable property and structure by precisely controlling a using ratio between sulfur and strontium, and more particularly, to provide flake graphite cast iron capable of being applied to an engine body for an internal combustion engine having a complicated shape, preferably, an engine cylinder block and/or an engine cylinder head.
[0013] An exemplary embodiment of the present disclosure provides a method for manufacturing high-strength flake graphite cast iron. The method comprises (i) manufacturing molten cast iron that includes 3.2 to 3.5% of carbon (C), 1.9 to 2.3% of silicon (Si), 0.4 to 0.9% of manganese (Mn), 0.06 to 0.1% of sulfur (S), 0.06% or less of phosphorous (P), 0.6 to 0.8% of copper (Cu), 0.15 to 0.25% of molybdenum (Mo), and a remainder of iron (Fe) with respect to a total weight %; (ii) adding strontium (Sr) to the melted molten cast iron such that a ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) is in a range of 16 to 98; and (iii) tapping the molten cast iron in a ladle to put the tapped molten cast iron in a casting mold.
[0014] Here, an additive content of the strontium (Sr) may be preferably in a range of 0.001 to 0.005% with respect to a total weight of the molten cast iron.
[0015] According to one example of the present disclosure, the molten cast iron of the step (i) may be manufactured by adding 0.6 to 0.8% of copper (Cu) and 0.15 to 0.25% of molybdenum (Mo) to molten cast iron manufactured by melting a cast iron material that includes 3.2 to 3.5% of carbon (C), 1.9 to 2.3% of silicon (Si), 0.4 to 0.9% of manganese (Mn), 0.06 to 0.1% of sulfur (S), 0.06% or less of phosphorous (P), and a remainder of iron (Fe) with respect to a total weight % in a blast furnace.
[0016] Further, according to one example of the present disclosure, Fe—Si-based inoculant may be added in tapping the molten cast iron in the ladle.
[0017] Furthermore, another exemplary embodiment of the present disclosure provides flake graphite cast iron manufactured by the aforementioned manufacturing method, preferably, flake graphite cast iron for engine cylinder block and engine cylinder head.
[0018] Here, the flake graphite cast iron comprises 3.2 to 3.5% of carbon (C), 1.9 to 2.3% of silicon (Si), 0.4 to 0.9% of manganese (Mn), 0.06 to 0.1% of sulfur (S), 0.06% or less of phosphorous (P), 0.6 to 0.8% of copper (Cu), 0.15 to 0.25% of molybdenum (Mo), 0.001 to 0.005% of strontium (Sr), and a remainder of iron (Fe) that satisfies 100% with respect to a total weight %, and has a chemical composition such that a ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) is in a range of 16 to 98.
[0019] According to one example of the present disclosure, when carbon equivalent (CE) of the flake graphite cast iron is calculated by a method of CE=% C+% Si/3, the carbon equivalent (CE) may be in a range of 3.80 to 4.27.
[0020] Further, according to one example of the present disclosure, tensile strength of the flake graphite cast iron may be 300 to 350 MPa, and a Brinell hardness value (BHW) may be in a range of 200 to 230.
[0021] Meanwhile, according to one example of the present disclosure, in the flake graphite cast iron, a chill depth of a wedge test piece may be 3 mm or less.
[0022] Moreover, in the flake graphite cast iron, a length of a spiral of a fluidity test piece may be 730 mm or more.
[0023] Still another exemplary embodiment of the present disclosure provides an engine body for an internal combustion engine which includes an engine cylinder block or an engine cylinder head which is made of the aforementioned flake graphite cast iron, or both of the engine cylinder block and the engine cylinder head.
[0024] Here, the engine cylinder block or the engine cylinder head may have a thin walled part having a cross-section thickness of 5 mm or less and a thick walled part having a cross-section thickness of more than 10 mm, and a graphite type of the thin walled part may be a A+B type.
[0025] According to the present disclosure, the tensile strength, chill depth and fluidity may be changed depending on the ratio (S/Sr) between the additive contents of the sulfur (S) and the strontium (Sr), and the S/Sr ratio is controlled to be in the range of 16 to 98 in order to apply the flake graphite cast iron to the high-strength engine cylinder block and engine cylinder head in which a shape thereof is complicated and the thick walled part and the thin walled part simultaneously exist.
[0026] As stated above, according to the present disclosure, since the content of the strontium (Sr) and the ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) are precisely controlled, it is possible to provide flake graphite cast iron which has a high tensile strength of 300 to 350 MPa and excellent processibility and fluidity even though ferroalloy such as Cu or Mo is added and is appropriately used for engine components of an internal combustion engine, and a method for manufacturing the same.
DESCRIPTION OF THE DRAWINGS
[0027] FIG. 1 briefly illustrates an example of a process of manufacturing high-strength flake graphite cast iron for engine cylinder block and engine cylinder head according to the present disclosure.
[0028] FIG. 2 illustrates a wedge test piece for measuring a chill depth of the flake graphite cast iron according to the present disclosure.
[0029] FIG. 3 illustrates a mold for manufacturing a spiral test piece for measuring fluidity of the flake graphite cast iron according to the present disclosure.
[0030] FIG. 4 is a plane cross-sectional view illustrating a thin walled part in a cylinder block according to the present disclosure.
[0031] FIG. 5 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 1 is applied to the cylinder block.
[0032] FIG. 6 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 2 is applied to the cylinder block.
[0033] FIG. 7 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 3 is applied to the cylinder block.
[0034] FIG. 8 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 4 is applied to the cylinder block.
[0035] FIG. 9 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 5 is applied to the cylinder block.
[0036] FIG. 10 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 6 is applied to the cylinder block.
[0037] FIG. 11 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Embodiment 7 is applied to the cylinder block.
[0038] FIG. 12 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 1 is applied to the cylinder block.
[0039] FIG. 13 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 2 is applied to the cylinder block.
[0040] FIG. 14 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 3 is applied to the cylinder block.
[0041] FIG. 15 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 4 is applied to the cylinder block.
[0042] FIG. 16 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 5 is applied to the cylinder block.
[0043] FIG. 17 is a photograph illustrating a surface structure of a thin walled part to which flake graphite cast iron of Comparative Example 6 is applied to the cylinder block.
[0000]
Description of Main Reference Numerals of Drawings
1: Engine cylinder block
2: Thin walled part having
cross-section of 5 mm or less
100: Blast furnace
110: Molten Cast iron
210: Copper, Molybdenum
220: Strontium
300: Ladle
400: Mold
DETAILED DESCRIPTION
[0044] Hereinafter, the present disclosure will be described in detail in connection with concrete examples.
[0045] In the present disclosure, a very small amount of strontium (Sr) is used as a component of cast iron. When a content ratio (S/Sr) between sulfur (S) and strontium (Sr) in the cast iron is controlled to be in a predetermined range, the strontium (Sr) reacts with the sulfur (S), and sulfide is formed. The formed sulfide serves as a nucleation site of flake graphite to suppress an occurrence of a chill and to assist growth and cystallization of useful A type flake graphite, so that it is possible to achieve high-strength and excellent processibility and fluidity.
[0046] At this time, the content of the added strontium (Sr) and the content ratio (S/Sr) between the strontium (Sr) and the sulfur (S) in the cast iron are the most important factors in manufacturing high-strength flake graphite cat iron having a tensile strength of 300 MPa or more. Accordingly, it is necessary to limit the flake graphite cast iron of the present disclosure to a manufacturing method and a corresponding chemical composition exemplified herein.
[0047] Hereinafter, a method for manufacturing flake graphite cast iron and a chemical composition of the manufactured flake graphite cast iron according to the present disclosure will be described. However, the present disclosure is not limited to the following manufacturing method, and the manufacturing method may be performed by modifying steps of the respective processes or selectively combining the steps when necessary.
[0048] Here, an additive content of each element is weight %, and is simply expressed as % in the following description.
[0049] Referring to FIG. 1 , molten cast iron 110 that includes 3.2 to 3.5% of carbon (C), 1.9 to 2.3% of silicon (Si), 0.4 to 0.9% of manganese (Mn), 0.06 to 0.1% of sulfur (S), 0.06% or less of phosphorous (P), 0.6 to 0.8% of copper (Cu), 0.15 to 0.25% of molybdenum (Mo), and a remainder of iron (Fe) with respect to a total weight % is manufactured.
[0050] The method for manufacturing the molten cast iron 110 according to the present disclosure is not particularly limited. For example, a cast iron material having carbon (C), silicon (Si), manganese (Mn), sulfur (S) and phosphorous (P) which are five elements of the cast iron with the aforemention content range is melted in a blast furnace to manufacture molten cast iron, and ferroalloy 210 such as copper (Cu) or molybdenum (Mo) is added to the molten cast iron to prepare the molten cast iron 110 having the aforementioned chemical composition.
[0051] At this time, the phosphorous (P) may be included in a raw material for casting as an impurity, or may be separately added. Meanwhile, in the present disclosure, since the reason why the chemical composition of the molten cast iron is limited is the same as a reason described for a chemical composition of flake graphite cast iron to be described below, description thereof will not be presented.
[0052] Strontium (Sr) 220 is added to the molten cast iron 110 melted as described above, and the strontium is added such that a ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) is in a range of 16 to 98. At this time, the additive content of the strontium (Sr) 220 is preferably in a range of 0.001 to 0.005% with respect to the total weight % of the molten cast iron.
[0053] In the present disclosure, it is required that the chemical composition of the flake graphite cast iron is limited to the aforementioned composition and the ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) is limited to the range of 16 to 98. When the S/Sr ratio is out of the above-mentioned range, since hardness is increased, processibility may be degraded. In this way, by limiting the S/Sr ratio, even though the ferroalloy such as copper (Cu) or molybdenum (Mo) which is an element for strengthening matrix and stabilizing carbide is added in order to manufacture high-strength flake graphite cast iron, it is possible to obtain A+B type flake graphite. Further, since the occurrence of the chill is reduced, it is possible to obtain high-strength flake graphite cast iron for engine cylinder block and engine cylinder head having a tensile strength of 300 MPa or more and excellent processibility.
[0054] Component analysis of the molten cast iron 110 manufactured as described above is finished using a carbon equivalent measuring instrument, a carbon/sulfur analyzer and a spectrum analyzer.
[0055] Subsequently, the molten cast iron is tapped in a ladle 300 for tapping the molten cast iron, and Fe—Si-based inoculant is added simultaneously with the tapping in order to stabilize a material of the high-strength flake graphite cast iron. At this time, a size of the added inoculant may be a diameter in a range of 1 to 3 mm, and the added amount of the inoculant for obtaining an effect of stabilizing the material of the high-strength flake graphite cast iron is preferably limited to 0.3±0.05 weight %.
[0056] A molten temperature of the ladle in which the tapping have been finished is measured using an immersion thermometer, and after measuring the temperature, the molten cast iron 110 is put into a prepared casting mold 400 to finish the manufacturing of the high-strength flake graphite cast iron for engine cylinder block and engine cylinder head.
[0057] The high-strength flake graphite cast iron of the present disclosure manufactured as described above has a strength higher that of flake graphite cast iron having a tensile strength of about 250 MPa that is currently used for engine cylinder block and head and exhibits the same processibility as the currently used flake graphite cast iron. Further, even though the ferroalloy such as copper (Cu) or molybdenum (Mo) is added, it is less likely to cause the chill. In addition, the flake graphite cast iron of the present disclosure is applied to engine cylinder block and head having a complicated shape that simultaneously include a thick walled part having a cross-section thickness of 10 mm or more and a thin walled part having a cross-section thickness of 5 mm or less, a difference in content ratios of A+B graphites constituting the thick walled part and the thin walled part may be a cross-section ratio of less than 10%.
[0058] In the present disclosure, the high-strength flake graphite cast iron manufactured by the above-described method is provided. More specifically, the flake graphite cast iron comprises 3.2 to 3.5% of carbon (C), 1.9 to 2.3% of silicon (Si), 0.4 to 0.9% of manganese (Mn), 0.06 to 0.1% of sulfur (S), 0.06% or less of phosphorous (P), 0.6 to 0.8% of copper (Cu), 0.15 to 0.25% of molybdenum (Mo), 0.001 to 0.005% of strontium (Sr), and a remainder of iron (Fe) that satisfies 100% with respect to the total weight %, and has a chemical composition such that a ratio (S/Sr) of the content of sulfur (S) to the content of the strontium (Sr) is in a range of 16 to 98.
[0059] In the present disclosure, the reason why the respective components included in the flake graphite cast iron are added and the reaon why the ranges of the added contents are limited are as follows.
[0060] 1) 3.2 to 3.5% of Carbon (C)
[0061] The carbon is an element that crystallizes useful flake graphite. In the flake graphite cast iron according to the present disclosure, when the content of the carbon (C) is less than 3.2%, A+B type flake graphite can be crystallized in the thick walled part having a cross-section thickness of 10 mm or more in the engine cylinder block and head, whereas since D+E type graphite which is unuseful flake graphite is crystallized in the thin walled part having a cross-section thickness of 5 mm or less in which a cooling speed is fast, it may be highly likely to cause the chill, and the processibility may be degraded. Furthermore, when the content of the carbon (C) exceeds 3.5%, since the flake graphite is excessively crystallized, the tensile strength is decreased, so that it is difficult to obtain the high-strength flake graphite cast iron. Accordingly, in order to prevent the aforementioned defect in high-strength engine cylinder blocks and heads having various thickness, the content of the carbon (C) is preferably limited to 3.2 to 3.5% in the present disclosure.
[0062] 2) 1.9 to 2.3% of Silicon (Si)
[0063] When the silicon (Si) is added with an optimal ratio with respect to the carbon, it is possible to maximize the amount of crystallizing the flake graphite, the occurrence of the chill is decreased, and the strength is increased. In the flake graphite cast iron according to the present disclosure, when the content of the silicon (Si) is less than 1.9%, shirinkage defect is caused in a final solidified portion of the molten cast iron, and when the content thereof exceeds 2.3%, since the flake graphite is excessively crystallized, the tensile strength is decreased, so that it is difficult to obtain the high-strength flake graphite cast iron. Accordingly, in the present disclosure, the content of the silicon (Si) is preferably limited to 1.9 to 2.3%.
[0064] 3) 0.4 to 0.9% of Manganese (Mn)
[0065] The manganese (Mn) is an element that allows an interlayer distance within pearlite to be densed to strengthen the matrix of the flake graphite cast iron. In the flake graphite cast iron according to the present disclosure, when the content of the manganese (Mn) is less than 0.4%, since the manganese does not largely affect the strengthening of the matrix, it is difficult to obtain the high-strength flake graphite cast iron. When the content of the manganese (Mn) exceeds 0.9%, since the carbide stabilizing effect further exhibits than the matrix strengthening effect, the occurrence of the chill is increased, so that the processibility may be deteriorated. Accordingly, in the present disclosure, the content of the manganese (Mn) is preferably limited to 0.4 to 0.9%.
[0066] 4) 0.06 to 0.1% of Sulfur (S)
[0067] The sulfur (S) reacts with the very small amount of elements included in the molten cast iron to form the sulfide, and the sulfide serves as the nucleation site of the flake graphite to assist the growth of the flake graphite. In the flake graphite cast iron according to the present disclosure, in order to manufacture the high-strength flake graphite cast iron, the content of the sulfur (S) needs to be 0.06% or more. In addition, when the content of the sulfur (S) exceeds 0.1%, since brittleness of the material is increased, the content of the sulfur (S) according to the present disclosure is preferably limited to 0.06 to 0.1%.
[0068] 5) 0.06% or Less of Phorphorus (P)
[0069] The phorphorus is a kind of impurity that is naturally added in a process of manufacturing cast iron in the air. The phorphorus (P) stabilizes pearlite, and reacts with the very small amount of elements included in the molten cast iron to form phoshide (steadite). Accordingly, the phorphorus serves to strengthen the matrix and improve wear resistance. However, when the content of the phorphorus (P) exceeds 0.06%, the brittleness is rapidly increased. Accordingly, in the present disclosure, the content of the phorphorus (P) is preferably limited to 0.06% or less. At this time, a lower limit of the content of the phorphorus (P) may exceed 0%, and is not particularly limited.
[0070] 6) 0.6 to 0.8% of Copper (Cu)
[0071] The copper (Cu) is an element that strengthens the matrix of the flake graphite cast iron, and since the copper acts to prompt generation of the pearlite and to miniaturize the pearlite, the copper is a necessary element for securing the strength. In the high-strength flake graphite cast iron for engine cylinder block and head according to the present disclosure, when the content of the copper (Cu) is less than 0.6%, the tensile strength may be insufficient. Even when the content thereof exceeds 0.8%, since there is no effect obtained by an exceeding amount, material cost may be increased. Accordingly, in the present disclosure, the content of the copper (Cu) is preferably limited to 0.6 to 0.8%.
[0072] 7) 0.15 to 0.25% of Molybdenum (Mo)
[0073] The molybdenum (Mo) is an element that strengthens the matrix of the flake graphite cast iron, improves the strength of the material, and improves the high-temperature strength. In the high-strength flake graphite cast iron for engine cylinder block and head according to the present disclosure, when the content of the molybdenum (Mo) is less than 0.15%, it may be difficult to obtain the tensile strength required in the present disclosure, and the high-temperature tensile strength applied to engine cylinder block and head having a high operation temperature may be insufficient. Meanwhile, when the content of the molybdenum (Mo) exceeds 0.25%, since a matrix strengthening effect is increased, the processibility is remarkably degraded as compared to the typically used flake graphite cast iron having a tensile strength of 250 MPa. Accordingly, in the present disclosure, the content of the molybdenum (Mo) is preferably limited to 0.15 to 0.25%.
[0074] 8) 0.001 to 0.005% of Strontium (Sr)
[0075] The strontium (Sr) is a strong graphitization element that reacts with the sulfur (S) in being solidified even at a very small amount to form the sulfide, and forms a substrate on which the nucleus of the graphite can be grown to produce the useful A type graphite. In the present disclosure, in order to prevent the occurrence of the chill due to the addition of the ferroalloy such as Mo or Cu and to improve the strength by crystallizing useful flake graphite, the content of the strontium (Sr) needs to be 0.001% or more. However, since the strontuim (Sr) has a high oxidizing property, when 0.005% or more of strontium is added, the generation of the nucleus of the flake graphite is disturbed due to the oxidation to generate D+E type flake graphite and to cause the chill, so that the processibility may be degraded. Accordingly, in the present disclosure, the content of the strontium (Sr) is preferably limited to 0.001 to 0.005%.
[0076] 9) Iron (Fe)
[0077] The iron is a main material of the cast iron according to the present disclosure. The remaining component other than the aforementioned components is iron (Fe), and other unavoidable impurities may be partially included.
[0078] The flake graphite cast iron of the present disclosure is limited to the above-described chemical composition, and the ratio (S/Sr) of the content of the sulfur (S) to the content of the strontium (Sr) is limited to the range of 16 to 98. Thus, even though the ferroalloy such as copper (Cu) or molybdenum (Mo) which is an element for strengthening the matrix and stabilizing the carbide is added in order to manufacture the high-strength flake graphite cast iron, it is possible to obtain the A+B type flake graphite. Further, since the occurrence of the chill is reduced, it is possible to obtain the high-strength flake graphite cast iron for engine cylinder block and head with a tensile strength of 300 MPa or more and excellent processibility.
[0079] According to one example of the present disclosure, when carbon equivalent (CE) of the flake graphite cast iron is calculated by the method of CE=% C+% Si/3, the carbon equivalent (CE) is allowed to be in a range of 3.80 to 4.27. When the carbon equivalent is less than 3.80, D+E type flake graphite is generated in the thin walled part having a cross-section thickness of 5 mm or less and the chill is caused, so that the producing defect may be caused and the processibility may be degraded. Further, when the carbon equivalent exceeds 4.27, the tensile strength may be decreased due to the excess crystallization of the process graphite. Accordingly, in the present disclosure, the carbon equivalent is preferably limited to the range of 3.80 to 4.27, and it is possible to appropriately control the carbon equivalent within such a range in order to control a quality and a mechanical property of the engine cylinder block and the head.
[0080] According to one example of the present disclosure, the tensile strength of the flake graphite cast iron having the aforementioned chemical composition is in a range of 300 to 350 MPa, and a Brinell hardness value (BHW) is about 200 to 230.
[0081] According to an example of the present disclosure, a chill depth of a wedge test piece to which the flake graphite cast iron having the aforementioned chemical composition is applied is 3 mm or less. At this time, the wedge test piece for measuring the chill depth may be illustrated as in FIG. 2 .
[0082] Furthermore, according to one example of the present disclosure, a length of a spiral of a fluidity test piece to which the flake graphite cast iron having the aforementioned chemical composition is applied may be 730 mm or more. At this time, the fluidity test piece may be illustrated as in FIG. 3 , and an upper limit of the length of the spiral of the fluidity test piece is not particularly limited. As one example, the upper limit may be an end point of the length of the spiral of the fluidity test piece standard.
[0083] In addition, since the flake graphite cast iron of the present disclosure is a high-strength material having a tensile strength of 300 MPa or more, the flake graphite cast iron can be applied to an engine body for an internal combustion engine, particularly, an engine cylinder head or an engine cylinder block in which a shape thereof is complicated and the thick walled part and the thin walled part simultaneously exist, or both of them.
[0084] Referentially, terms to be described below are terms set in consideration of functions in the present disclosure, and may be changed depending on an intension of a manufacturer or a precedent. Thus, the terms should be defined based on contents described in the present specification. For example, the engine body in the present disclosure means a configuration of an engine including an engine cylinder block, an engine cylinder head, and a head cover.
[0085] The engine cylinder block and/or the engine cylinder head to which the flake graphite cast iron according to the present disclosure is applied as a material has a thin walled part having a cross-section thickness of 5 mm or less and a thick walled part having a cross-section thickness of 10 mm or more, and a graphite type of the thin walled part is preferably A+B type. Actually, it can be seen that all of the thin walled parts of the cylinder blocks to which the flake graphite cast iron of the present disclosure is applied are A+B type graphite (see FIGS. 5 to 11 ).
[0086] Hereinafter, the embodiments of the present disclosure will be described in more detail. However, the following embodiments are presented to help understanding of the present disclosure, and are not intended to limit the scope of the present disclosure. It is possible to change or modify the embodiments without departing from the spirit of the present disclosure.
EMBODIMENTS 1 TO 7 AND COMPARATIVE EXAMPLES 1 TO 6
[0087] Flake graphite cast irons are manufactured according to Embodiments 1 to 7 and Comparative Examples 1 to 6 on the basis of compositions of Table 1.
[0000]
TABLE 1
Other
Category
C
Si
Mn
S
P
Cu
Mo
Sr
S/Sr
components
Fe
Embodiment 1
3.24
2.17
0.62
0.085
0.030
0.68
0.18
0.0024
35
Remainder
Embodiment 2
3.38
2.07
0.62
0.086
0.028
0.63
0.19
0.003
29
Remainder
Embodiment 3
3.42
2.11
0.71
0.065
0.041
0.71
0.23
0.004
16
Remainder
Embodiment 4
3.27
1.99
0.69
0.091
0.031
0.65
0.21
0.0021
43
Remainder
Embodiment 5
3.26
2.21
0.81
0.071
0.045
0.74
0.20
0.0035
20
Remainder
Embodiment 6
3.22
2.19
0.77
0.093
0.030
0.70
0.19
0.0013
71
Remainder
Embodiment 7
3.31
2.09
0.75
0.098
0.030
0.70
0.19
0.0010
98
Remainder
Comparative
3.25
2.19
0.65
0.15
0.027
0.69
0.22
0.0014
107
Remainder
Example 1
Comparative
3.29
2.22
0.73
0.045
0.022
0.69
0.19
0.0047
9
Remainder
Example 2
Comparative
3.31
2.10
0.72
0.082
0.030
0.72
0.18
0.0008
103
Remainder
Example 3
Comparative
3.33
2.09
0.64
0.080
0.021
0.73
0.22
0.0075
10
Remainder
Example 4
Comparative
3.28
1.95
0.67
0.053
0.030
—
—
—
—
0.07% Sn
Remainder
Example 5
0.2% Cr
Comparative
3.23
2.12
0.70
0.092
0.028
0.45
—
—
—
0.07% Sn
Remainder
Example 6
0.036 Cr
[0088] Firstly, initial molten metal including carbon (C), silicon (Si), manganese (Mn), sulfur (S) and phosphorus (P) on the basis of the composition of Table 1 is prepared. The phosphorus (P) is an impurity included in a raw material for casting, and the content thereof is adjusted to be 0.06% or less without separately adding the phosphorus.
[0089] Before tapping, carbon equivalent (CE) is measured using a carbon equivalent measuring instrument, and the content of the carbon (C) is controlled to be 3.2 to 3.5%. Ferroalloy such as copper (Cu) or molybdenum (Mo) is controlled to be the same compositions as those represented in Table 1. After the strontium (Sr) is added to finish the melting, the tapping is performed. At this time, Fe—Si-based inoculant is input simultaneously with the tapping. After the tapping is finished in the ladle, a temperature of the molten cast iron is measured, and the molten cast iron is put into a prepared casting mold. Thus, flake graphite cast iron products for engine cylinder block and engine cylinder head are manufactured.
[0090] Carbon equivalent, tensile strength, Brinell hardness and chill depth of cast irons manufactured according to Embodiments 1 to 7 and Comparative Examples 1 to 6 on the basis of the compositions of Table 1 are respectively measured and represented in Table 2.
[0000]
TABLE 2
Carbon
Tensile
Chill
Equivalent
Strength
Hardness
depth
Fluidity
Category
(C.E.)
(N/mm 2 )
(HBW)
(mm)
(mm)
Embodiment 1
3.96
331
224
0
788
Embodiment 2
4.07
315
220
0
761
Embodiment 3
4.12
322
224
0
791
Embodiment 4
3.93
331
224
1
782
Embodiment 5
3.99
325
217
0
774
Embodiment 6
3.95
315
217
0
765
Embodiment 7
4.01
318
210
0
770
Comparative
3.98
290
243
6
689
Example 1
Comparative
4.03
341
241
4
711
Example 2
Comparative
4.01
287
243
5
701
Example 3
Comparative
4.02
315
243
4
722
Example 4
Comparative
3.93
270
210
0
845
Example 5
Comparative
3.93
304
234
4
759
Example 6
[0091] As can be seen from Table 2, tensile strengths of the cast irons according to
[0092] Embodiments 1 to 7 whose ratio (S/Sr) is controlled to be in the range of 16 to 98 are in a range of 300 to 350 MPa, and Brinel hardness values are in a range of 200 to 230 HBW. Moreover, it can be seen that chill depths is 3 mm or less and length of spirals of fluidity test pieces are 730 mm or more.
[0093] Further, except for Comparative Example 5 whose tensile strength is 250 MPa, Comparative Examples 1 to 4 and 6 are in D+E type graphite types, whereas thin walled parts to which the flake graphite cast irons of Embodiments 1 to 7 are applied are all in A+B type graphite types (See FIGS. 5 to 17 ).
[0094] Referentially, the cast irons of Comparative Examples 1 and 2 have the same contents as those of the compositions of Embodiments 1 to 7, and are manufactured by the same manufacturing process as that in Comparative Examples 1 and 2. However, the content of the sulfur (S) and the S/Sr ratio are out of the composition range of the present disclosure.
[0095] Comparative Examples 3 and 4 have the same contents at those of the compositions of Embodiments 1 to 7, and are manufactured by the same manufacturing process as that in Embodiments 1 to 7. However, the content of the strontium (Sr) and the S/Sr ratio are out of the composition range of the present disclosure.
[0096] Comparative Example 5 is a material having a tensile strength of 250 MPa that is commercially available as flake graphite cast iron for engine cylinder block and head according to the related art.
[0097] Comparative Example 6 is a material in which only ferroalloy is simply added to a material having a tensile strength of 250 MPa that is conventionally used to manufacture high-strength flake graphite cast iron for engine cylinder block and head.
[0098] As a result, since the high-strength flake graphite cast iron according to the present disclosure has a stable tensile strength, hardness, chill depth, and fluidity, it is possible to usefully apply the high-strength flake graphite cast iron to the engine cylinder block and engine cylinder head requiring high strength.
[0099] Although the present disclosure has been described with reference to exemplary and preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the disclosure. | The present disclosure relates to a flake graphite cast iron simultaneously having high strength, good machinability, and fluidity, to a method for manufacturing same, and to an engine body comprising the flake graphite cast iron for an internal combustion engine and, more particularly, to a method for manufacturing a flake graphite cast iron, for an engine cylinder block and head having improved castability, a low possibility of the occurrence of chill due to ferroalloy, stable tensile strength and yield strength, and good machinability by adding a trace of strontium in a cast iron including carbon (C), silicon (Si), manganese (Mn), sulfur (S), and phosphorus (P), which are five elements of the cast iron, molybdenum (Mo), a high strengthening additive, and copper (Cu) while controlling the ratio (S/Sr) of the sulfur (S) content to the strontium (Sr) content in the cast ion. | 2 |
RELATED APPLICATIONS
The present invention incorporates by reference and claims priority to U.S. Provisional Patent Application No. 62/120,472 filed on Feb. 25, 2015.
BACKGROUND
Field of the Invention
The present invention relates generally to an awareness enhancement apparatus and method for undesirable repeated behaviors, including but not limited to obsessive compulsive and related disorders, and most relevant to trichotillomania (hair pulling), onychophagia (nail biting), dermatillomania (skin picking) and thumb sucking, among others. More particularly, the invention relates to a sensing and feedback device and associated methods of use which indicates a behavior based on the user's physical gestures and positioning of the hands, these gestures and positions being related to these undesirable behaviors typical of such disorders and alerting the user so that he or she can reduce the behavior.
Background Description of the Related Art
Nervous behaviors such as trichotillomania (hair pulling), onycophagia (nail biting), dermatillomania (skin picking), thumb sucking and others might be labeled dismissively as “bad habits” and are often harmless for the majority of the affected population. There is, however, increasing focus in the medical community on the group of people for whom these behaviors have significant negative psychological or physical consequences. These specific problematic subtype of behaviors are called body focused repetitive behaviors (BFRBs), which is an umbrella term used to describe certain obsessive compulsive and related behaviors that cause damage to one's body or physical appearance. The prevalence rate of BFRBs has been difficult to determine due to being a poorly understood condition from a scientific perspective and often involving individuals who are attempting to hide their condition(s) or who are not consciously aware of when they are engaging in such behavior. Nevertheless, one study in 2002 of 454 university students reported prevalence rate of BFRBs at 13.7% of the population (Teng, Woods, et al.).
Trichotillomania is one type of BFRB and is characterized by recurrent pulling of one's hair, resulting in hair loss. Reliable trichotillomania prevalence estimates suffer from the two problems of many BFRBs: the individuals that have it may attempt to hide the condition, and there have not been a wealth of academic studies. Nevertheless, the range of reported prevalence is between 0.6-4% (Huynh, Gavino) of the population. In individuals with trichotillomania, hair is most commonly pulled from the scalp, eyebrows and eyelashes but can be pulled from anywhere on the body. The patient may pull hair while being conscious of the action (focused pulling) or the action may be a subconscious behavior (unfocused pulling). When the person engages in focused pulling, he or she may feel an urge to pull from a particular area and feels relief once the hair is pulled. In unfocused pulling, the person may be unaware while he or she is pulling hair, and only become aware once he or she sees the pulled hairs or resulting bald spot. Persons with trichotillomania may suffer from distress due to negative social interactions including bullying and harassment from having thinning or baldness on the scalp, eyebrows, eyelashes or other areas. In spite of the distress caused by this condition, the urge to pull, whether focused or unfocused, can be difficult to overcome. Additionally, patients suffering from trichotillomania, in particular, but also other BFRBs often feel a sense of shame, embarrassment, anger or guilt stemming from their condition.
Individuals with BFRBs generally find methods of hiding their condition, and some may seek treatment. Common methods of hiding trichotillomania may include wigs, hats, eyebrow pencils, false eyelashes, or similar cosmetic approaches. The primary methods of treatment of BFRBs are Cognitive Behavior Therapy (CBT), supportive counseling, support groups, hypnosis, medications and combined approaches (Franklin, Zagrabbe). However, the scientific literature supporting the efficacy of these approaches is not well developed, with fewer than 20 randomized controlled trials available to guide treatment choice and implementation (Franklin, Zagrabbe). The current leading method for addressing BFRBs is Cognitive Behavioral Therapy (CBT), whereby individuals learn how to change their thoughts, feelings, and behaviors by working alongside a therapist or professionally trained psychologist. Studies have shown that, when followed through, CBT can be useful in managing and preventing a wide variety of mental disorders (Trich.org). However, relapse rates can be high once the patient stops CBT. Additionally, CBT is not available to everyone as not all psychologists have been trained in treating BFRBs, not all psychologists practice CBT, and this form of therapy can be prohibitively expensive for many individuals.
Other methods of preventing BFRBs and similar conditions have been presented using some form of physical restraints. U.S. Pat. No. 6,093,158 for example, is directed to a system for monitoring an undesirable behavior from the set of bruxism, jaw clenching, or snoring. The invention can use a variety of sensors, including those to monitor sound from the undesirable behaviors, signals from muscles in and around the mouth, or force on the teeth. The system described involves wearing an apparatus on the head to monitor the conditions, which is undesirable from a user's perspective due to the common desire to hide the condition via the use of discreet wearable apparatuses.
Another patent, U.S. Pat. No. 4,965,553 discusses a device to alert the user when the hand is near the mouth in order to aid in calorie counting. While it may be effective in reminding the user when that person is eating, eating is an action that is necessary for survival and therefore not always undesirable. Creating a negative feedback signal for an undesirable action can be a more effective system.
Finally, in U.S. Pat. No. 6,762,687, a system of alerting the user when he or she is performing certain obsessive-compulsive spectrum disorders, is described. The specific embodiments of the system are comprised of two pieces, a sensor worn on the head, neck or chest, as well as an element associated with the arm, hand, or finger. Such a system is overly cumbersome for the application of preventing a user from a behavior, and a system eliminating one of these pieces could be preferable to users seeking to keep the purpose of the apparatus discreet.
Thus, a need exists for a method and apparatus that can monitor, provide feedback about, and ultimately assist in controlling BFRBs that substantially eliminates the problems associated with the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a drawing of an individual equipped with apparatus according to this invention.
FIG. 2 is a simplified block diagram of the electronic circuitry applicable to the invention.
FIG. 3 is a flowchart showing the action of the system when in use.
SUMMARY OF THE INVENTION
In accordance with the present invention, the problem of having a discreet device that alerts the user when performing undesirable behaviors is solved by incorporating orientation and/or gesture recognition into a single device worn on the arm, wrist or hand.
Various objects, features, aspects, and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention, along with the accompanying drawings in which like numerals represent like components.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 , a wearable repetitive behavior awareness device 100 is shown in the form of a wrist-band, which includes the components mentioned in FIG. 2 . The wearable repetitive behavior awareness device 100 includes a processor and memory 210 , sensors 220 (including an inertial measurement unit (IMU) comprised of an accelerometer, gyroscope, and optionally a magnetometer, and may include biofeedback sensors measuring heart rate, skin electrical activity, or other physiological activity), a power source 230 , a radio frequency transmitter 240 , a radio frequency receiver 250 , and a vibration motor or some other real-time tactile, auditory or visual signal 260 to indicate that the bad habit or undesirable behavior has been detected and is occurring.
FIG. 1 shows a user wearing the repetitive behavior awareness device 100 that alerts the user when he or she is performing the undesirable behavior by a tactile, auditory or visual signal. In the preferred embodiment, the alarm is a tactile sensation, such as a vibration, which will allow the device to remain discreet. The device can be trained to actuate the tactile sensation when the user performs a custom gesture or hand orientation associated with a BFRB, and can also come pre-programmed for specific pre-defined common physical gestures and orientations, such as raising the hand to the face and keeping it there.
In a preferred embodiment, the wearable repetitive behavior device is a discreet wrist-worn or hand-worn band, which may have the appearance of a common fitness band or piece of jewelry such as a bracelet or ring. The device sensor unit is an inertial measurement unit accelerometer, gyroscope, and a magnetometer, for optimal hand orientation and gesture recognition. Use of specific biofeedback sensors such as heart rate monitoring and/or skin electrical activity could further augment the accuracy of the device by corroborating biofeedback signals with the inertial measurement unit's readings of orientation and gesture.
The device could be worn on one arm, wrist or hand, and a device with similar functionality (but potentially a different form factor) could be worn on the opposing arm, wrist or hand. This way the user could monitor undesirable behaviors that occur with both hands, as most people with BFRBs and similar conditions use both hands to perform the behavior. The devices are both connected to a single mobile device (e.g. smartphone) via the radio frequency transmitter.
Example Use Case
In the case of an individual with trichotillomania who pulls from the eyebrows and eyelashes, the device worn on both wrists would help him or her become more aware of the act of pulling, whenever the algorithm on the device detects the undesired behavior. The user has the option of using the algorithms already programmed on the device (e.g. for common undesirable movements), or can train the algorithm to detect a custom behavior. If the user chooses to train the algorithm, he or she would do so by performing the behavior and giving feedback (details below) so as to minimize the occurrence of false positives (instances when the alarm is actuated but the behavior performed is benign) as well as false negatives (instances when the alarm is not actuated in spite of the undesirable behavior having been performed). Once the algorithm has been trained, the user could wear the device to alert him or her when the hands have moved to the face and are near the eyebrows/eyelashes.
The device would then work as described in the system flowchart ( FIG. 3 ). The device sensors would record the motion and orientation, and intermittently check if the motion pattern or orientation reading matches that of the trained algorithm. If the processor determines there is a match, then the processor would trigger the alarm, which would preferably be a discreet tactile vibration. The device would record the time that the behavior had occurred and store it in the memory, and transmit the data when connected to the smartphone via the RF transmitter. Finally, the data would be stored in the cloud remotely from the phone for analysis and retrieval in the future.
The primary benefit of such a device is the real-time feedback via the alarm of the undesirable behavior occurring so that the user can stop him or herself prior to pulling the hair. Additionally, the device is unobtrusive and does not interfere with the user's appearance or normal movements, which would avoid calling attention to the user and the condition so as to increase compliance. Though it may help most during cases of unfocused (subconscious) pulling, the user may derive benefit in cases of focused (conscious) pulling as well because the alert prompts the user to reexamine his or her choice. Over time, and perhaps in conjunction with existing treatments including Cognitive Behavioral Therapy, the alerts from the device could help drive awareness of the behavior, identify the situations that trigger the behavior, and help the user develop strategies for reducing the behavior.
Sensor Functionality
The device sensor contains an inertial measurement unit (IMU), consisting of an accelerometer and a gyroscope, and optionally a magnetometer. The IMU can record specific force, angular rate, and optionally magnetic field data, which can be processed to determine whether a specific motion (i.e. gesture) or hand position (i.e. orientation) is occurring. This information can help the user because in order to perform a BFRB or related behavior, a hand reaches toward another body part such as the head or face. At the end state of this motion, such as in FIG. 1 , the orientation of the arm changes and the force of gravity acts on the sensors in a specific and repeatable pattern that can be identified to trigger an alert. Finally, the addition of biofeedback sensors such as heart rate monitors and skin electrical activity sensors are useful to inform when a user is suffering from acute anxiety or stress, which can be correlated to BFRB activity. The additional biofeedback sensors improve the accuracy of the device, but are not necessary for the device to perform its basic function of gesture and orientation pattern recognition.
Actuating the Vibration
The device sensors 220 are connected to a processor 210 that is operative to generate an output signal in the event that the motion or hand orientation being performed by the user matches a particular pre-defined set of undesirable behaviors, which are determined by either the custom training process or a general set of gestures (e.g. raising the hand to the face). The apparatus further includes a device operative to alert the user in response to the output signal generated by the device sensors 220 . The device operative to alert the user in response to the output signal generated by the device sensors produces an audible, visual or tactile vibration sensation. The sensor housing itself may produce the alert directly, or circuitry may be provided to produce a wireless signal to a separate unit operative to generate an audible, visual or tactile sensation.
Additionally, further functionality is provided to minimize false alarms including appropriate hand orientation and/or gesture recognition, physiological activity, time spent performing an appropriate gesture, contextual information (e.g. if the user is currently using a mobile device) or other behaviors that do not represent any of the undesirable behaviors. The system is also equipped with a manual user-operable override (see “Feedback Mechanisms” section below) to prevent the alarm from being activated for a predetermined period of time to permit acceptable activities (e.g. in the case of hair pulling, the user may want to override the alarm while he or she is eating, which may have a similar motion and hand orientation to hair pulling).
Training Algorithms
There are a number of different gestures associated with one or more undesirable behaviors that users may want to eliminate. For example, in the case of a user who has trichotillomania, the user can pull from the eyebrows and eyelashes or different areas of the scalp, which may likely have different motion patterns and positions of the hands associated with them. To achieve these goals, the user initially calibrates the device with his or her undesirable motions. The wearable repetitive behavior awareness device will record the data associated with the motions from the device sensors 220 and use that set of data so that the alarm (e.g. vibration motor) will be actuated whenever the user performs the custom motion. The device “gesture training” will impart the advantage of personal customization to detect the undesirable repetitive behaviors.
Mobile Interface—Mobile Phone App, Snooze
In a preferred embodiment, the wearable repetitive behavior awareness device pairs with a mobile device, such as a smartphone to provide the user with additional features and functionality. The features provided with the mobile application include data logging and tracking, amongst others. The user would be able to see data pertaining to their undesirable behavior(s) including when and how often they have performed the behaviors.
Feedback Mechanisms
The user is able to deliver feedback to the device directly, via either buttons or physical gestures, or indirectly via the mobile application.
In the direct feedback case, for example, after receiving an alert from the device due to an undesirable behavior detection, the user can confirm the correct reading from the device using a button or through the accelerometer by tapping the device in a predefined way (e.g. tapping twice). Alternatively, the user can inform the device that the behavior was benign by a similar mechanism.
In the indirect feedback case, the user confirms or rejects readings from the device via the mobile app. For example, the mobile app logs each instance that it registers the undesirable behavior with a timestamp, and the user may confirm or correct the readings through the mobile app.
While the preferred embodiment of the invention has been described in reference to the Figures, the invention is not so limited. For example, the device can be used without an alarm feature. In some applications it may be desirable to simply collect information associated with a behavior to determine if a particular treatment has helped, or if the behavior has worsened or improved over time. Thus, the alarm can be turned on or off as needed to both alert the user, and/or merely allow the device to collect information.
Further, the device can be used as a positive feedback device. For example, in the case of BFRBs the device can detect periods when the behavior is absent and emit an alert (such as a pleasant tone) that may assist the user in understanding when the behavior is not occurring, or as a reward.
Further, the device can be used as a feedback mechanism for any physical bad habit that the user may want to track or reduce, which may or may not be classified as BFRBs. Some examples of such habits could be smoking, overeating, or hair twirling. Still further, the device can be used in connection with behaviors that may be repetitive but not necessarily harmful or undesirable. These could be precursor behaviors associated with the onset of BFRBs. Or, the behaviors monitored could have nothing to do with disorders but instead the device could monitor body position relationships that may be positive or negative to a user in the field of sports, ergonomics, and the like.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar to or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety to the extent allowed by applicable law and regulations. In case of conflict, the present specification, including definitions, will control.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore desired that the present embodiment be considered in all respects as illustrative and not restrictive, reference being made to the appended claims rather than to the foregoing description to indicate the scope of the invention. Those of ordinary skill in the art that have the disclosure before them will be able to make modifications and variations therein without departing from the scope of the invention. | The present invention relates generally to an awareness enhancement apparatus and method for undesirable repeated behaviors, including but not limited to obsessive compulsive and related disorders, and most relevant to trichotillomania (hair pulling), onychophagia (nail biting), dermatillomania (skin picking) and thumb sucking, among others. More particularly, the invention relates to a sensing and feedback device and associated methods of use which indicates a behavior based on the user's physical gestures and positioning of the hands, these gestures and positions being related to these undesirable behaviors typical of such disorders and alerting the user so that he or she can reduce the behavior. | 6 |
RELATED APPLICATIONS
This application claims priority from Israeli patent application No. 155545, filed on Apr. 21, 2003, entitled tert-BUTYL METHYL ETHER SOLVATE FORM OF CABERGOLINE. The disclosure of this patent application as well as the references cited therein and the references cited herein are expressly incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 schematically shows a perspective view of cabergoline and tert-butyl methyl ether molecules and the atomic numbering of non-hydrogen atoms as derived from single crystal x-ray analysis of solvate form A cabergoline. (Atomic coordinates based on Table 2).
FIG. 2 shows a characteristic x-ray powder diffraction pattern of solvate form A of cabergoline. Vertical axis: intensity (CPS); Horizontal axis: 2θ (degrees).
FIG. 3 shows calculated x-ray powder diffraction pattern of solvate form A cabergoline. Vertical axis: intensity (CPS); Horizontal axis: 2θ (degrees).
FIG. 4 shows the infrared spectrum (diffuse reflectance, DRIFTS) of solvate form A of cabergoline in potassium bromide.
FIG. 5 shows the differential scanning calorimetry (DSC) curve of solvate form A of cabergoline, showing thermal event associated with eutectic melting of cabergoline with tert-buthyl methyl ether.
FIG. 6 shows the 1 H nuclear magnetic resonance (NMR) spectrum of solvate form A of cabergoline in CDCl 3 .
FIG. 7 shows a characteristic x-ray powder diffraction pattern of amorphous physical form of cabergoline. Vertical axis: intensity (CPS); Horizontal axis: 2θ (degrees).
FIG. 8 shows the infrared spectrum (diffuse reflectance, DRIFTS) of amorphous cabergoline in potassium bromide.
FIELD OF THE INVENTION
This invention relates to a new crystalline form of cabergoline and to processes for its preparation. Uses of the novel form of cabergoline in purification of crude cabergoline, in the preparation of amorphous cabergoline and in the manufacture of a medicament are disclosed. A method for treating a prolactin disorder with the medicaments is also disclosed.
List of References
The following prior publications are considered to be pertinent for the purpose of understanding the background of the present invention:
S. F. Ashford et al., J. Org. Chem., 2002, v. 67, 7147; E. Brambilla et al., Eur. J. Med. Chem., 1989, v. 24, 421; I. Candiani et al., Synlett, 1995, 605; P. Sabatino et al., Farmaco, 1995, v. 50, 175; Federal Register, 1997, v. 62, 67377–88; The Merck Index, 12th Edition, 1637; GB 2,103,603; U.S. Pat. No. 4,526,892; U.S. Pat. No. 5,382,669; U.S. Pat. No. 6,673,806; U.S. Pat. No. 6,680,327; U.S. Pat. No. 6,696,568; US 2002/0123503 A1; US 2003/0149067 A1; WO 01/70740; WO 03/78392 A2; WO 03/78433 A1.
BACKGROUND OF THE INVENTION
Cabergoline is a long-acting oral dopamine agonist specific for the D2 receptor and is used to treat different types of medical problems that occur when too much of the hormone prolactin is produced. Cabergoline works by stopping the brain from making and releasing the prolactin hormone from the pituitary. It can be used to treat certain menstrual problems, fertility problems in men and women, and pituitary prolactinomas (tumors of the pituitary gland).
Prolactin hypersecretion, or hyperprolactinemia, is a condition characterised by an increased level of prolactin. Hyperprolactinemia may have anyone of a number of functional causes, including various neurogenic causes such as thoracic sensory nerve stimulation, stress, and psychogenic causes, various hypothalamic causes such as diffuse processes, granulomatous diseases, neoplasms, stalk section, empty sella, non-lactotropic cell pituitary tumors, and prostradiation treatment to sella, various pituitary causes such as prolactinomas and pituitary lactotropic cell hyperplasia, and various endocrine causes such as pregnancy, estrogen administration, hypothyroidism, and adrenal insufficiency.
Cabergoline, 1-(6-allylergoline-8β-carbonyl)-1-[3-(dimethylamino)propyl]-3-ethylurea, having the formula:
is one of the most potent prolactin inhibitors (Brambilla, 1989 and The Merck Index, 12th Edition, 1637).
Cabergoline may be prepared by the method described in Example 1 of U.S. Pat. No. 6,696,568. Alternatively, cabergoline may be prepared by the methods described by Ashford (2002), Brambilla (1989), Candiani (1995), GB 2,103,603, U.S. Pat. No. 4,526,892 and U.S. Pat. No. 5,382,669.
U.S. Pat. No. 6,673,806, U.S. Pat. No. 6,680,327, US 2003/0149067, WO 03/78392, WO 03/78433 and Sabatino (1995) disclose five physical forms of cabergoline, designated Form I, Form II, Form V, Form VII and Form X. These forms differ from one another in respect of their physical properties, stability, spectral data and methods of preparation. Among these forms, Forms V and X are solvate forms of cabergoline. More precisely, there are toluene solvate forms of cabergoline. Toluene is related to Class 2 solvents. According to Federal Register, 1997, v. 62, 67377–88, the use of Class 2 solvents should be limited in pharmaceutical products because of their inherent toxicity.
Citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
SUMMARY OF THE INVENTION
The present invention provides for, inter alia, new solid forms of cabergoline—amorphous cabergoline and tert-butyl methyl ether solvate form A of cabergoline, the latter is referred to as solvate form A of cabergoline. The new forms of cabergoline are relatively stable physical form of cabergoline. Preferably, each of the new forms of cabergoline is substantially free of other physical forms.
The present invention also provides a method of preparing amorphous physical form of cabergoline from crude cabergoline comprising the steps of:
a) mixing cabergoline with tert-butyl methyl ether; b) isolating the precipitated solid; c) drying the solid at 0–30° C. to obtain solvate form A of cabergoline substantially free from other physical forms; d) conversion of the solvate form A of cabergoline to the desired amorphous physical form of cabergoline.
The present invention also provides the use of amorphous physical form of cabergoline and solvate form A of cabergoline in the manufacture of a medicament. The medicament is prepared by combining the physical forms of cabergoline with pharmaceutically acceptable excipients.
The present invention also relates to the field of hyperprolactinemias, and prolactinomas. More specifically, the present invention relates to the treatment of a subject afflicted with either condition, and the lowering of prolactin levels and/or the size of the tumor by administration to the subject by the medicament prepared from solvate form A of cabergoline or amorphous physical form of cabergoline.
DETAILED DESCRIPTION
The present invention discloses, according to a first of its aspects, a new amorphous physical form of cabergoline. Preferably, the amorphous physical form of cabergoline is substantially free of other physical forms. Suitably, amorphous physical form of cabergoline contains not more than 20%, preferably not more than 10% of any crystalline form of cabergoline. Most preferably the amorphous physical form of cabergoline contains not more than 5% of any crystalline form of cabergoline.
The amorphous physical form of cabergoline has a halo x-ray powder diffraction pattern as depicted in FIG. 7 .
The amorphous physical form of cabergoline was further characterized by an infrared absorption spectrum carried out in potassium bromide as depicted in FIG. 8 .
The present invention also provides the method of preparing amorphous physical form of cabergoline, which method comprises the preparation of solvate form A of cabergoline and its conversion into amorphous physical form of cabergoline. Preferably, the method comprises the step of:
a) recrystallizing or crystallizing, or triturating or/and reslurring of cabergoline in tert-butyl methyl ether; b) isolating the precipitated solid; c) drying the solid at 0–30° C. to obtain solvate form A of cabergoline having x-ray powder diffraction pattern of FIG. 2 ; and d) conversion the solvate form of cabergoline into amorphous physical form of cabergoline.
Optionally, the conversion the solvate form of cabergoline into amorphous physical form of cabergoline comprises the steps of:
a) dissolving solvate form A of cabergoline in organic solvent; and b) evaporating the solution prepared in step (a) to obtain desired solid.
Preferably, said organic solvent is selected from the group consisting of alcohols, ethers, esters and ketones. More preferably, said organic solvent is ethanol, isopropanol, ethyl ether, isopropyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone. Most preferably, the solvent is ethanol or isopropanol.
Preferably, the method of preparing amorphous physical form of cabergoline comprises the step of:
a) dissolving solvate form A of cabergoline in organic solvent; b) mixing the solution of cabergoline with anti-solvent; c) evaporating the obtained suspension under reduced pressure at 0–40° C. to obtain desired solid.
More preferably, the method of preparing amorphous physical form of cabergoline, comprising the step of:
a) dissolving solvate form A of cabergoline in an organic solvent; b) mixing the solution of cabergoline with anti-solvent; c) isolating of the precipitated solid; d) drying the solid at 0–40° C. to obtain desired solid.
Preferably, the anti-solvent is saturated hydrocarbon. More preferably, the anti-solvent selected from the group consisting of pentane, heptane, hexane and cyclohexane.
Most preferably, the method of preparing of amorphous physical form of cabergoline comprises the steps of:
a) dissolving solvate form A of cabergoline in a solvent; and b) lyophilizing the solution prepared in step (a) to obtain desired solid.
Preferably, said solvent is selected from the group consisting of tert-butanol, aqueous tert-butanol, 1,4-dioxane, aqueous 1,4-dioxane, benzene, dimethyl carbonate and cyclohexane.
The present invention also provides the use of amorphous physical form of cabergoline or solvate form A of cabergoline in the manufacture of a medicament. The medicaments prepared from amorphous physical form of cabergoline or solvate form A of cabergoline may be used in a manner similar to that of medicament prepared from any existing forms of cabergoline. Preferably, the medicament is prepared by combining amorphous physical form of cabergoline or solvate form A of cabergoline with pharmaceutically acceptable excipients. Preferably, the excipient may be an acid, a carrier, a binder, a diluent, a lubricant, a glidant, an adjuvant or a combination thereof. More preferably, the suitable pharmaceutically acceptable excipients include the following components:
i) Acids, such as pharmaceutically acceptable organic or inorganic acids, e.g. acetic acid, stearic acid, tartaric acid, citric acid, leucine or a combination thereof;
ii) Binders, such as cellulose and its derivatives, e.g. ethyl cellulose hydroxypropylmethyl cellulose, hydroxypropylcellulose, hydroxyethyl cellulose, sodium carboxymethyl cellulose, starches, polyvinyl pyrrolidone, natural gums, corn syrup, polysaccharides (including acacia, tragacanth, guar, and alginates), gelatin, or a combination thereof;
iii) Glidants, such as talc, fumed silica, or a combination thereof;
iv) Lubricants such as magnesium stearate, calcium stearate, aluminum stearate, stearic acid, calcium oleate, talc, mineral oil, waxes, glyceryl behenate, potassium stearyl fumarate, sodium stearyl fumarate, hydrogenated vegetable oils, or a combination thereof. Such lubricants are commonly included in the final tabletted product in amounts of less than 1% by weight;
v) Diluents, such as lactose, cellulose, starch or calcium phosphate or a combination thereof.
Preferably, the medicament comprises a therapeutically effective amount of cabergoline. The medicament may be in the form of tablet, powder mixture, capsule, solution, suspension, suppository, emulsion, dispersion or food premix. Preferably, the medicament is in the form of a tablet.
As used herein the term “effective amount” refers to the amount or dose of the compound, upon single or multiple dose administration to the patient, which provides the desired effect in the patient under diagnosis or treatment.
An effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by the use of known techniques and by observing results obtained under analogous circumstances. In determining the effective amount or dose of compound administered, a number of factors are considered by the attending diagnostician, including, but not limited to: the species of mammal; its size, age, and general health; the specific disease is involved; the degree of or involvement or the severity of the disease; the response of the individual patient; the particular compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the dose regimen selected; the use of concomitant medication; and other relevant circumstances. For example, a typical daily dose may contain from about 50 micrograms to about 150 mg of the active ingredient.
The present invention also discloses a new relatively stable solvate form of cabergoline, namely solvate form A of cabergoline. Solvate form A of cabergoline is a tert-butyl methyl ether solvate. Preferably, solvate form A of cabergoline is crystalline. In one embodiment, solvate form A of cabergoline is substantially pure. Suitably, solvate forms A of cabergoline contains not more than 20%, preferably not more than 10% of any other crystalline form of cabergoline. Most preferably the solvate form A of cabergoline contains not more than 5% of any other crystalline form of cabergoline.
The crystalline state of a compound can be unambiguously described by several crystallographic parameters: unit cell dimensions, space group, and atomic position of all atoms in the compound relative to the origin of its unit cell. These parameters are experimentally determined by single crystal x-ray analysis. The crystalline solvate form A of cabergoline is characterized by the crystal parameters obtained from single crystal x-ray crystallographic analysis set forth in Table 1 below.
TABLE 1
Crystal parameters of solvate form A of cabergoline.
Formula
C 26 H 37 N 5 O 2 .C 5 H 12 O
Formula weight (amu)
539.75
Space group
P2 1 2 1 2 1
Cell dimensions
a (Å)
12.955 (3)
b (Å)
14.312 (3)
c (Å)
17.704 (4)
α = β = γ (°)
90
V (Å 3 )
3282.5 (13)
Z (molecules/units cell)
4
Density (g/cm 3 )
1.092
The unit cell dimension is defined by three parameters: length of the sides of the cell, relative angles of sides to each other and the volume of the cell. The lengths of the sides of the unit cell are defined by a, b and c. The relative angles of the cell sides are defined by α, β and γ. The volume of the cell is defined as V.
The crystalline solvate form A of cabergoline of the present invention is characterized by a single x-ray crystallographic analysis, which yields atomic positions of all atoms relative to the origin of the unit cell as shown in Tables 2 through 6, and as represented in FIG. 1 . Tables 2 through 6 list the parameters of atomic coordinates, and their isotropic thermal parameters, bond lengths, bond angles, anisotropic thermal parameters, bond lengths, bond angles, anisotropic thermal parameters, and proton atom coordinates and their isotropic thermal parameters.
TABLE 2
Atomic coordinates (×10 4 ) and equivalent isotropic
displacement parameters (Å 2 × 10 3 ). U (eq) is
defined as one third of the trace of the orthogonalized Uij tensor.
x
y
z
U (eq)
N(1)
4118(3)
7929(3)
4368(3)
63(1)
C(2)
4732(4)
7161(4)
4498(3)
64(2)
C(3)
5403(4)
7341(4)
5081(3)
55(1)
C(4)
6204(4)
6784(3)
5489(3)
54(1)
C(5)
6409(4)
7215(3)
6286(3)
48(1)
N(6)
7279(3)
6750(3)
6668(2)
49(1)
C(7)
7458(4)
7167(4)
7409(3)
57(1)
C(8)
7770(4)
8178(4)
7346(3)
52(1)
C(9)
6908(4)
8727(3)
6978(3)
55(1)
C(10)
6609(4)
8297(3)
6233(3)
47(1)
C(11)
5684(4)
8779(3)
5867(3)
49(1)
C(12)
5304(4)
9663(4)
5989(3)
67(2)
C(13)
4490(5)
10015(4)
5587(4)
77(2)
C(14)
4002(4)
9515(4)
5019(4)
75(2)
C(15)
4396(4)
8630(4)
4860(3)
55(1)
C(16)
5197(3)
8277(4)
5311(3)
51(1)
C(17)
7091(4)
5741(3)
6770(3)
61(2)
C(18)
7975(5)
5242(4)
7115(4)
76(2)
C(19)
7957(6)
4754(5)
7703(5)
102(3)
C(20)
8063(4)
8581(4)
8100(4)
63(2)
O(21)
7864(5)
8156(3)
8688(3)
101(2)
N(22)
8497(3)
9456(3)
8130(3)
64(1)
C(23)
8964(4)
9914(5)
7510(4)
67(2)
O(24)
9405(3)
9454(3)
7014(3)
90(2)
N(25)
8854(4)
10832(4)
7523(3)
78(2)
C(26)
9325(6)
11395(5)
6924(5)
103(2)
C(27)
9387(7)
12381(5)
7126(6)
130(3)
C(28)
8642(7)
9881(5)
8895(4)
95(2)
C(29)
7621(9)
10132(5)
9266(4)
118(3)
C(30)
7230(17)
10991(13)
9095(12)
460(20)
N(31)
7204(4)
11472(4)
8426(3)
92(2)
C(32)
6361(10)
11310(20)
7990(12)
450(20)
C(33)
7198(10
12430(7)
8617(10)
240(9)
C(34)
4107(10)
8272(7)
9417(7)
147(4)
C(35)
4494(13)
8563(9)
8612(7)
212(7)
C(36)
4843(13)
7794(11)
9895(9)
244(8)
C(37)
3138(17)
7644(16)
9342(10)
358(16)
O(38)
3866(12)
9146(8)
9644(9)
269(6)
C(39)
3493(13)
9134(17)
10410(8)
299(13)
TABLE 3
Bond lengths (Å).
N(1)—C(2)
1.376(7)
N(1)—C(15)
1.377(7)
N(1)—H(1)
0.8600
C(2)—C(3)
1.373(7)
C(2)—H(2)
0.9300
C(3)—C(16)
1.425(7)
C—(3)C(4)
1.494(7)
C(4)—C(5)
1.564(7)
C(4)—H(4A)
0.9700
C(4)—H(4B)
0.9700
C(5)—N(6)
1.472(6)
C(5)—C(10)
1.574(7)
C(5)—H(5)
0.93(5)
N(6)—C(7)
1.460(6)
N(6)—C(17)
1.476(6)
C(7)—C(8)
1.506(7)
C(7)—H(7A)
0.9700
C(7)—H(7B)
0.9700
C(8)—C(20)
1.503(7)
C(8)—C(9)
1.513(7)
C(8)—H(8)
0.96(5)
C(9)—C(10)
1.507(7)
C(9)—H(9A)
0.9700
C(9)—H(9B)
0.9700
N(1)—C(2)
1.376(7)
N(1)—C(15)
1.377(7)
N(1)—H(1)
0.8600
C(2)—C(3)
1.373(7)
C(10)—C(11)
1.527(7)
C(10)—H(10)
0.99(4)
C—(11)C(16)
1.372(7)
C(11)—C(12)
1.374(7)
C(12)—C(13)
1.368(8)
C(12)—H(12)
0.9300
C(13)—C(14)
1.387(8)
C(13)—H(13)
0.9300
C(14)—C(15)
1.395(8)
C(14)—H(14)
0.9300
C(15)—C(16)
1.404(7)
C(17)—C(18)
1.481(8)
C(17)—H(17A)
0.9700
C(17)—H(17B)
0.9700
C(18)—C(19)
1.253(9)
C(18)—H(18)
0.9300
C(19)—H(19A)
0.9300
C(19)—H(19B)
0.9300
C(20)—O(21)
1.233(7)
C(20)—N(22)
1.373(7)
N(22)—C(23)
1.414(7)
N(22)—C(28)
1.498(8)
C(23)—O(24)
1.238(7)
C(23)—N(25)
1.322(7)
N(25)—C(26)
1.465(9)
C(26)—C(27)
1.459(9)
C(26)—H(26A)
0.9700
C(26)—H(26B)
0.9700
C(27)—H(27A)
0.9600
C(27)—H(27B)
0.9600
C(27)—H(27C)
0.9600
C(28)—C(29)
1.520(12)
C(28)—H(28A)
0.9700
C(28)—H(28B)
0.9700
C(29)—C(30)
1.364(13)
C(29)—H(29A)
0.9700
C(29)—H(29B)
0.9700
C(30)—N(31)
1.371(14)
C(30)—H(30A)
0.9700
C(30)—H(30B)
0.9700
N(31)—C(32)
1.358(11)
N(31)—C(33)
1.413(9)
N(31)—H(31)
0.9100
C(32)—H(32A)
0.9600
C(32)—H(32B)
0.9600
C(32)—H(32C)
0.9600
C(33)—H(33A)
0.9600
C(33)—H(33B)
0.9600
C(33)—H(33C)
0.9600
C(34)—O(38)
1.350(14)
C(34)—C(36)
1.446(15)
C(34)—C(37)
1.550(17)
C(34)—C(35)
1.568(16)
C(35)—H(35A)
0.9600
C(35)—H(35B)
0.9600
C(35)—H(35C)
0.9600
C(36)—H(36A)
0.9600
TABLE 4
Bond Angles (°).
C(2)—N(1)—C(15)
109.0(4)
C(2)—N(1)—H(1)
125.5
C(15)—N(1)—H(1)
125.5
C(3)—C(2)—N(1)
109.9(5)
C(3)—C(2)—H(2)
125.0
N(1)—C(2)—H(2)
125.0
C(2)—C(3)—C(16)
105.9(4)
C(2)—C(3)—C(4)
134.6(5)
C(16)—C(3)—C(4)
119.5(5)
C(3)—C(4)—C(5)
110.1(4)
C(3)—C(4)—H(4A)
109.6
C(5)—C(4)—H(4A)
109.6
C(3)—C(4)—H(4B)
109.6
C(5)—C(4)—H(4B)
109.6
H(4A)—C(4)—H(4B)
108.1
N(6)—C(5)—C(4)
111.5(4)
N(6)—C(5)—C(10)
110.3(4)
C(4)—C(5)—C(10)
111.2(4)
N(6)—C(5)—H(5)
109(3)
C(4)—C(5)—H(5)
108(3)
C(10)—C(5)—H(5)
107(3)
C(7)—N(6)—C(5)
110.5(4)
C(7)—N(6)—C(17)
108.4(4)
C(5)—N(6)—C(17)
111.9(4)
N(6)—C(7)—C(8)
111.6(4)
N(6)—C(7)—H(7A)
109.3
C(8)—C(7)—H(7A)
109.3
N(6)—C(7)—H(7B)
109.3
C(8)—C(7)—H(7B)
109.3
H(7A)—C(7)—H(7B)
108.0
C(20)—C(8)—C(7)
111.8(5)
C(20)—C(8)—C(9)
111.7(5)
C(7)—C(8)—C(9)
109.5(4)
C(20)—C(8)—H(8)
108(2)
C(7)—C(8)—H(8)
115(2)
C(9)—C(8)—H(8)
100(2)
C(10)—C(9)—C(8)
110.8(4)
C(10)—C(9)—H(9A)
109.5
C(8)—C(9)—H(9A)
109.5
C(10)—C(9)—H(9B)
109.5
C(8)—C(9)—H(9B)
109.5
H(9A)—C(9)—H(9B)
108.1
C(9)—C(10)—C(11)
112.9(4)
C(9)—C(10)—C(5)
113.0(4)
C(11)—C(10)—C(5)
109.9(4)
C(9)—C(10)—H(10)
107(2)
C(11)—C(10)—H(10)
108(2)
C(5)—C(10)—H(10)
105(2)
C(16)—C(11)—C(12)
115.5(5)
C(16)—C(11)—C(10)
115.4(4)
C(12)—C(11)—C(10)
129.1(5)
C(13)—C(12)—C(11)
122.2(5)
C(13)—C(12)—H(12)
118.9
C(11)—C(12)—H(12)
118.9
C(12)—C(13)—C(14)
122.6(5)
C(12)—C(13)—H(13)
118.7
C(14)—C(13)—H(13)
118.7
C(13)—C(14)—C(15)
116.6(5)
C(13)—C(14)—H(14)
121.7
C(15)—C(14)—H(14)
121.7
N(1)—C(15)—C(14)
134.0(5)
N(1)—C(15)—C(16)
106.9(4)
C(14)—C(15)—C(16)
118.9(5)
C(11)—C(16)—C(15)
124.0(5)
C(11)—C(16)—C(3)
127.7(5)
C(15)—C(16)—C(3)
108.3(5)
N(6)—C(17)—C(18)
113.3(5)
N(6)—C(17)—H(17A)
108.9
C(18)—C(17)—H(17A)
108.9
N(6)—C(17)—H(17B)
108.9
C(18)—C(17)—H(17B)
108.9
H(17A)—C(17)—(17B)
107.7
C(19)—C(18)—C(17)
126.6(7)
C(19)—C(18)—H(18)
116.7
C(17)—C(18)—H(18)
116.7
C(18)—C(19)—H(19A)
120.0
C(18)—C(19)—H(19B)
120.0
H(19A)—C(19)—(19B)
120.0
O(21)—C(20)—N(22)
120.2(5)
O(21)—C(20)—C(8)
120.5(5)
N(22)—C(20)—C(8
119.2(5)
C(20)—N(22)—C(23)
124.7(5)
C(20)—N(22)—C(28)
117.1(5)
C(23)—N(22)—C(28)
117.3(5)
O(24)—C(23)—N(25)
126.2(6)
O(24)—C(23)—N(22)
120.1(6)
N(25)—C(23)—N(22)
113.7(6)
C(23)—N(25)—C(26)
119.2(6)
C(27)—C(26)—N(25)
112.1(7)
C(27)—C(26)—H(26A)
109.2
N(25)—C(26)—H(26A)
109.2
C(27)—C(26)—H(26B)
109.2
N(25)—C(26)—H(26B)
109.2
H(26A)—C(26)—H(26B)
107.9
C(26)—C(27)—H(27A)
109.5
C(26)—C(27)—H(27B)
109.5
H(27A)—C(27)—H(27B)
109.5
C(26)—C(27)—H(27C)
109.5
H(27A)—C(27)—H(27C)
109.5
H(27B)—C(27)—H(27C)
109.5
N(22)—C(28)—C(29)
112.1(6)
N(22)—C(28)—H(28A)
109.2
C(29)—C(28)—H(28A)
109.2
N(22)—C(28)—H(28B)
109.2
C(29)—C(28)—H(28B)
109.2
H(28A)—C(28)—H(28B)
107.9
C(30)—C(29)—C(28)
116.1(9)
C(30)—C(29)—H(29A)
108.2
C(28)—C(29)—H(29A)
108.2
C(30)—C(29)—H(29B)
108.2
C(28)—C(29)—H(29B)
108.2
H(29A)—C(29)—H(29B)
107.4
C(29)—C(30)—N(31)
130.8(14)
C(29)—C(30)—H(30A)
104.6
N(31)—C(30)—H(30A)
104.6
C(29)—C(30)—H(30B)
104.6
N(31)—C(30)—H(30B)
104.6
H(30A)—C(30)—H(30B)
105.7
C(32)—N(31)—C(30)
115.1(17)
C(32)—N(31)—C(33)
107.4(14)
C(30)—N(31)—C(33)
106.3(13)
C(32)—N(31)—H(31)
109.3
C(30)—N(31)—H(31)
109.3
C(33)—N(31)—H(31)
109.3
N(31)—C(32)—H(32A)
109.1
N(31)—C(32)—H(32B)
110.3
H(32A)—C(32)—H(32B)
109.5
N(31)—C(32)—H(32C)
109.0
H(32A)—C(32)—H(32C)
109.5
H(32B)—C(32)—H(32C)
109.5
N(31)—C(33)—H(33A)
109.5
N(31)—C(33)—H(33B)
109.3
H(33A)—C(33)—H(33B)
109.5
N(31)—C(33)—H(33C)
109.6
H(33A)—C(33)—H(33C)
109.5
H(33B)—C(33)—H(33C)
109.5
O(38)—C(34)—C(36)
114.6(13)
O(38)—C(34)—C(37)
112.0(15)
C(36)—C(34)—C(37)
108.1(12)
O(38)—C(34)—C(35)
95.6(10)
C(36)—C(34)—C(35)
116.6(12)
C(37)—C(34)—C(35)
109.5(12)
C(34)—C(35)—H(35A)
109.5
C(34)—C(35)—H(35B)
109.4
H(35A)—C(35)—H(35B)
109.5
C(34)—C(35)—H(35C)
109.5
H(35A)—C(35)—H(35C)
109.5
H(35B)—C(35)—H(35C)
109.5
C(34)—C(36)—H(36A)
109.5
C(34)—C(36)—H(36B)
109.4
H(36A)—C(36)—H(36B)
109.5
C(34)—C(36)—H(36C)
109.5
H(36A)—C(36)—H(36C)
109.5
H(36B)—C(36)—H(36C)
109.5
C(34)—C(37)—H(37A)
109.6
C(34)—C(37)—H(37B)
109.5
H(37A)—C(37)—H(37B)
109.5
C(34)—C(37)—H(37C)
109.4
H(37A)—C(37)—H(37C)
109.5
H(37B)—C(37)—H(37C)
109.5
C(34)—O(38)—C(39)
110.3(13)
O(38)—C(39)—H(39A)
109.5
O(38)—C(39)—H(39B)
109.5
H(39A)—C(39)—H(39B)
109.5
O(38)—C(39)—H(39C)
109.5
H(39A)—C(39)—H(39C)
109.5
H(39B)—C(39)—H(39C)
109.5
TABLE 5
Anisotropic displacement parameters (Å 2 × 10 3 ).
U 33
U 23
U 13
U 12
U 11
U 22
N(1)
45(2)
74(3)
71(3)
1(3)
−18(2)
−8(2)
C(2)
47(3)
69(3)
75(4)
−8(3)
−8(3)
−12(3)
C(3)
41(3)
60(3)
63(4)
0(3)
0(3)
−7(2)
C(4)
49(3)
53(3)
61(3)
−7(3)
−5(3)
−7(2)
C(5)
35(3)
54(3)
56(3)
0(3)
9(3)
−9(2)
N(6)
40(2)
2(2)
2(2)
−3(2)
58(3)
50(2)
C(7)
45(3)
67(4)
58(3)
−2(3)
−17(3)
−2(2)
C(8)
44(3)
63(3)
49(3)
0(3)
−4(3)
−9(3)
C(9)
52(3)
53(3)
61(4)
−10(3)
−5(3)
−4(2)
C(10)
37(3)
52(3)
53(3)
0(2)
4(3)
−6(2)
C(11)
40(3)
55(3)
53(3)
5(3)
−3(3)
−6(2)
C(12)
56(3)
67(4)
79(4)
−18(3)
−13(3)
6(3)
C(13)
84(4)
63(4)
85(5)
−2(3)
−16(4)
16(3)
C(14)
60(4)
80(4)
85(5)
3(3)
−24(4)
14(3)
C(15)
39(3)
67(3)
60(3)
2(3)
2(3)
−3(3)
C(16)
30(2)
66(3)
57(3)
−12(3)
−4(3)
−2(2)
C(17)
64(3)
48(3)
71(4)
−2(3)
−12(3)
−4(3)
C(18)
80(4)
67(4)
82(5)
2(4)
−14(4)
16(3)
C(19)
107(6)
82(5)
118(7)
20(5)
−33(5)
8(4)
C(20)
67(4)
63(4)
59(4)
0(3)
−16(3)
6(3)
O(21)
159(5)
80(3)
65(3)
3(3)
−25(3)
−19(3)
N(22)
58(3)
70(3)
64(3)
−17(3)
−12(3)
−1(2)
C(23)
37(3)
83(4)
80(4)
−3(4)
1(3)
−7(3)
O(24)
63(3)
87(3)
121(4)
−38(3)
29(3)
−11(2)
N(25)
68(3)
68(3)
99(4)
−10(3)
18(3)
−8(3)
C(26)
98(5)
87(5)
125(6)
−18(5)
−19(4)
18(5)
C(27)
138(7)
108(6)
145(8)
−8(5)
31(7)
−55(5
C(28)
121(6)
97(5)
66(4)
−1(4)
20(5)
−30(4)
C(29)
197(10)
87(5)
69(5)
−13(4)
20(6)
−16(6)
C(30)
490(30)
275(19)
620(40)
270(30)
510(40)
260(20)
N(31)
64(4)
125(5)
86(4)
−28(4)
12(3)
16(3)
C(32)
97(8)
830(50)
410(30)
−440(30)
−94(14)
163(17)
C(33)
174(11)
108(7)
440(30
−5(7)
146(14)
−104(11)
C(34)
176(10)
99(6)
167(11)
35(7)
−37(9)
23(7)
C(35)
310(20)
173(12)
154(11)
35(9)
1(12)
36(12)
C(36)
287(18)
265(16)
180(13)
36(13)
−1(14)
157(15)
C(37)
380(30)
450(30)
240(20)
150(20)
−130(20)
−270(30)
O(38)
294(14)
195(10)
318(17)
71(10)
−15(13)
79(9)
C(39)
226(16)
520(30)
150(12)
135(17)
100(13)
107(19)
TABLE 6
Hydrogen coordinates (× 10 4 ) and isotropic displacement
parameters (Å 2 × 10 3 ).
x
y
z
U(eq)
H(1)
3639
7965
4033
76
H(2)
4698
6602
4231
76
H(4A)
6839
6781
5198
65
H(4B)
5971
6144
5543
65
H(7A)
7998
6822
7667
68
H(7B)
6833
7120
7709
68
H(9A)
6313
8738
7310
66
H(9B)
7132
9366
6898
66
H(12)
5610
10034
6357
81
H(13)
4254
10613
5700
93
H(14)
3440
9758
4757
90
H(17A)
6942
5463
6282
73
H(17B)
6488
5657
7088
73
H(18)
8607
5296
6871
92
H(19A)
7342
4678
7968
123
H(19B)
8557
4468
7874
123
H(26A)
10014
11161
6822
124
H(26B)
8921
11329
6465
124
H(27A)
9579
12739
6690
196
H(27B)
9895
12464
7515
196
H(27C)
8727
12590
7307
196
H(28A)
9061
10440
8849
114
H(28B)
9011
9444
9216
114
H(29A)
7115
9664
9123
141
H(29B)
7709
10094
9809
141
H(30A)
7568
11412
9446
553
H(30B)
6515
10962
9256
553
H(31)
7785
11341
8157
110
H(32A)
6500
10789
7662
668
H(32B)
6199
11850
7693
668
H(32C)
5787
11160
8311
668
H(33A)
7251
12799
8166
361
H(33B)
7773
12563
8942
361
H(33C)
6567
12581
8874
361
H(35A)
4655
9218
8609
317
H(35B)
3963
8438
8247
317
H(35C)
5101
8211
8486
317
H(36A)
4569
7745
10398
366
H(36B)
5477
8141
9908
366
H(36C)
4971
7180
9698
366
H(37A)
2561
8016
9181
537
H(37B)
2985
7364
9821
537
H(37C)
3267
7163
8976
537
H(39A)
4068
9101
10751
448
H(39B)
3058
8599
10483
448
H(39C)
3106
9693
10507
448
H(5)
5810(40)
7130(30)
6580(30)
48(13)
H(8)
8320(30)
8300(30)
7000(30)
38(12)
H(10)
7210(30)
8360(20)
5890(20)
30(10)
Solvate form A of cabergoline also gives distinctive x-ray powder diffraction pattern, as depicted in FIG. 2 . The pattern has characteristic peaks expressed in degrees 2θ at approximately 7.9±0.2, 10.5±0.2, 16.5±0.2, 17.0±0.2, 18.1±0.2 and 23.8±0.2.
The results of a single crystal x-ray analysis are limited to, as the name implies, one crystal placed in the x-ray beam. Crystallographic data on a large group of crystals provides powder x-ray diffraction. If the powder consists of a pure crystalline compound, a simple powder diagram is obtained. To compare the results of a single crystal analysis and a powder x-ray analysis, a simple calculation can be done converting the single crystal analysis and powder x-ray diagram. This conversion is possible because the single crystal experiment routinely determines the unit cell dimensions, space group, and atomic positions. These parameters provide a basis to calculate a perfect powder pattern.
In addition, comparison of the powder pattern experimentally obtained from a large collection of crystals to the calculated powder pattern of solvate form A of cabergoline shows correlation and similarity to each other. These results are graphically displayed in FIG. 2 and FIG. 3 and in Table 7.
TABLE 7
Calculated from single crystal X-ray analysis powder diffraction
pattern (λ = 1.5418 Å radiation) where in I/I 1 represents
the relative intensity:
2θ (°)
I/I 1
h
k
l
7.943
1000
0
1
1
8.457
141
1
0
1
9.207
213
1
1
0
10.478
650
1
1
1
11.755
332
0
1
2
12.369
62
0
2
0
13.603
401
1
1
2
13.670
62
2
0
0
14.139
317
1
2
0
14.561
342
2
0
1
15.002
139
1
2
1
15.830
228
2
1
1
15.925
95
0
2
2
16.506
533
1
0
3
16.961
593
2
0
2
17.343
361
1
2
2
18.066
521
2
1
2
20.462
129
1
3
1
21.046
278
2
2
2
21.155
53
0
3
2
21.292
319
2
1
3
22.079
89
3
1
1
22.113
165
1
1
4
22.252
133
1
3
2
22.913
170
3
0
2
23.753
539
3
1
2
23.889
72
2
2
3
24.597
124
3
2
1
24.628
84
1
2
4
26.119
57
3
2
2
26.320
236
3
1
3
27.403
59
2
2
4
FIG. 2 shows an experimentally derived powder x-ray diffraction pattern of solvate form A of cabergoline and FIG. 3 corresponds to the x-ray diffraction derived from the single crystal x-ray data. The peak overlap indicates that the two techniques yield the same results. The primary powder x-ray diffraction peaks provide an unambiguous description of the crystalline state of solvate form A for cabergoline.
A pure crystalline organic compound has, in general, a definite melting point range. The melting point is defined as the point at which the sample is entirely in the liquid phase. The crystalline solvate form A of cabergoline has a characteristic melting point range determined by the capillary method from 66 to 70° C.
The crystalline solvate form A of cabergoline was further characterized by an infrared absorption spectrum carried out in potassium bromide as depicted in FIG. 4 .
The DSC thermogram of solvate form A of cabergoline is shown in FIG. 5 .
Solvate form A of cabergoline was further characterized by a 1 H magnetic resonance spectrum in CDCl 3 and shows characteristic absorption bands for the tert-butyl methyl ether moiety at approximately δ (ppm) 1.16 (singlet) and 3.18 (singlet). The 1 H NMR spectrum of solvate form A of cabergoline is shown in FIG. 6 .
Crude non-crystalline cabergoline may be prepared by the method described in U.S. Pat. No. 6,696,568. Alternatively, crude non-crystalline cabergoline may be prepared by the methods described by Ashford (2002), Brambilla (1989), Candiani (1995), GB 2,103,603, U.S. Pat. No. 4,526,892 and U.S. Pat. No. 5,382,669. The present invention provides method for purifying of the crude cabergoline from related impurities comprising recrystallizing or crystallizing, or triturating or/and reslurring of the crude cabergoline in tert-butyl methyl ether. Preferably, the method for purifying of crude cabergoline from related impurities comprises the steps of:
a) recrystallizing or crystallizing, or triturating or/and reslurring of the crude solvate form A of cabergoline; b) isolating the precipitated solid; and c) drying the solid at 0–30° C. to obtain substantially pure solvate form A of cabergoline.
Alternatively, solvate form A of cabergoline also may be prepared by recrystallizing or crystallizing, or triturating or/and reslurring of any form of cabergoline in tert-butyl methyl ether.
Preferably, solvate form A of cabergoline may be prepared by:
a) mixing any physical form of cabergoline with tert-butyl methyl ether; b) isolating the precipitated solid; and c) drying the solid at 0–30° C. to obtain desired crystals.
The solvate form A of cabergoline prepared by the method of the invention may be used in the manufacture of pharmaceutical compositions, in a similar way as amorphous physical form of cabergoline. Thus, the present invention further provides the use of solvate form A of cabergoline in the manufacture of a medicament. Preferably, the medicament will be adapted for oral administration. Particularly suitable compositions for oral administration are unit dosage forms such as tablets and capsules.
The medicament may be prepared by combining the solvate form A of cabergoline with pharmaceutically acceptable excipients. Preferably, a method for preparing a pharmaceutical composition from solvate form A of cabergoline, comprising the step of combining an amount of solvate form A of cabergoline, an amount of a granulating fluid, and an amount of pharmaceutically acceptable excipient. More preferably, the method for preparing a pharmaceutical composition from solvate form A of cabergoline comprises the step of:
a) combining an amount of solvate form A of cabergoline, an amount of a granulating fluid, and an amount of pharmaceutically acceptable excipient; b) blending to form a wet granulate; and c) drying to obtain dry granules.
Most preferably, the method for preparing a pharmaceutical composition from solvate form A of cabergoline comprises the step of dissolving the solvate form A of cabergoline in the granulating fluid.
Preferably, the granulating fluid is water, organic solvent or combinations thereof. More preferably, the granulating fluid is ethanol, isopropanol or acetone. The excipient may be an acid, a carrier, a binder, a diluent, a lubricant, a glidant, an adjuvant or a combination thereof. Preferably, the acid is pharmaceutically acceptable organic or inorganic acid. More preferably, the acid is carboxylic acid, amino acid or combination thereof.
EXAMPLES
A better understanding of the present invention and of its many advantages will be had from the following non-limiting examples, given by way of illustration.
Experimental Details:
HPLC was carried out on a Merck-Hitachi Lachrom chromatographic system with UV detector.
Single crystal x-ray crystallographic analysis was performed on a Phillips PW 11000 diffractometer, ω/2θ mode, graphite monochromator, MoK α radiation.
Powder x-ray diffraction patterns were obtained by methods known in the art using PANALYTICAL (Philips) X'Pert Pro MPD x-ray powder diffraction system (CuK α radiation, PW3050/60 goniometer, PW3011/20 proportional detector). The Bragg-Brentano scheme was used for beam focusing.
1 H spectra were recorded on a Bruker AM-200 (200 MHz) and Bruker AM-400 (400 MHz) instruments using CDCl 3 as a solvent.
Melting points were determined in open capillary tubes with Buchi B-545 capillary melting point apparatus and are uncorrected. The melting points of solvent form A of cabergoline generally depend upon their level of purity. Typically, solvent form A of cabergoline has been found to have a melting point between 66 and 70° C.
Infrared absorption spectra were obtained with a Nicolet Impact 410 FT-IR spectrophotometer equipped with Pike Technologies EasiDiff Diffuse Reflectance Accessory using a 5% dispersion of sample material in a potassium bromide over the wave number range 400 to 4000 cm −1 .
DSC graphs were recorded on a Mettler DSC 30 Differential Scanning Calorimeter.
Example 1
Solvate Form A of Cabergoline
Trimethylsilyl trifluromethanesulfonate (7.6 g, 34.2 mmol, 1.1 eq) was added dropwise during 2 hours to a stirred mixture of N-[3-(dimethylamino)propyl]-6-allylergoline-8β-carboxamide (11.9 g, 31.5 mmol, 1 eq), triethylamine (3.8 g, 37.6 mmol, 1.2 eq) and dichloromethane (280 g) at −2° C. The mixture was stirred for 14 hours at 18° C. Ethyl isocyanate (11.1 g, 156.2 mmol, 5 eq) was added in one portion to the stirred mixture at 18° C. The obtained mixture was stirred for 48 hours at the same temperature. Tetrabutylammonium fluoride, 1.0 M solution in THF (30.4 g, 34.2 mmol, 1.1 eq) was added dropwise during 2 hours to the stirred mixture at −2° C. The reaction mixture was stirred for 2 hours at the same temperature and evaporated under reduced pressure. A solution of the residue in tert-butyl methyl ether was washed with aqueous solution of sodium bicarbonate and aqueous solution of sodium chloride, dried over sodium sulfate and passed through short silica gel column. The column was washed with acetone and the acetone solution was evaporated under reduced pressure to give 9.6 g (68.2%) of cabergoline as amorphous solid with 98% purity by HPLC. A hot solution of the amorphous cabergoline in tert-butyl methyl ether was kept at 0–5° C. for 60 hours. The precipitated solid was filtered off, washed on the filter with cold tert-butyl methyl ether and dried under reduced pressure at 15–25° C. to give 8.5 g (50%) solvate form A of cabergoline as white crystals with mp 66–70° C. and 99.8% purity by HPLC.
Solvate form A of cabergoline was characterized by powder x-ray diffractometry and IR spectroscopy as set forth above and in FIGS. 2 and 4 . Single crystal of solvate form A of cabergoline was isolated and used for determination crystallographic parameters (see Tables 1–6).
Example 2
Purification of Crude Cabergoline
Crude cabergoline with 97–99% purity by HPLC, prepared according to Brambilla (1989), Candiani (1995) or Ashford (2002) was crystallized from tert-butyl methyl ether to give after drying under reduced pressure at 15–25° C. solvate form A of cabergoline as off-white crystals with purity of at least 99.5% by HPLC.
Example 3
Solvate Form A of Cabergoline
A mixture of cabergoline (2.0 g) and tert-butyl methyl ether (4.5 mL) was stirred for 3 days at 0–5° C. Precipitated crystals were filtered off, washed on the filter with cold tert-butyl methyl ether (4.5 mL) and dried under reduced pressure at 15–25° C. to give 1.8 g (88%) solvate form A of cabergoline as off-white crystals.
Example 4
Amorphous Physical Form of Cabergoline
A solution of solvate form A of cabergoline (5.0 g) in diethyl ether (67 mL) was added dropwise during 1 hour to a stirred pentane (130 mL) at −25° C. The resulted mixture was stirred for 3 hours at the same temperature. Precipitated solid were filtered off and dried under reduced pressure at 20–25° C. to give 3.5 g of amorphous physical form of cabergoline.
Example 5
Amorphous Physical Form of Cabergoline
A solution of solvate form A of cabergoline (196.6 g) in diethyl ether (2.7 L) was added dropwise during 5 hours to a stirred pentane (5.2 L) at −20° C. The resulted mixture was stirred for 3 hours at the same temperature and evaporated under reduced pressure to give 154.3 g of amorphous physical form of cabergoline.
The amorphous physical form of cabergoline was characterized by x-ray powder diffractometry and infrared spectroscopy (see FIGS. 7 and 8 ).
Example 6
Amorphous Physical Form of Cabergoline
A 6% solution of solvate form A of cabergoline in cyclohexane was lyophilized to give amorphous physical form of cabergoline.
Example 7
Amorphous Physical Form of Cabergoline
A solution of solvate form A of cabergoline in isopropanol was evaporated under reduced pressure at 45° C. to give amorphous physical form of cabergoline.
Example 8
Amorphous Physical Form of Cabergoline
A solution of solvate form A of cabergoline (1.0 g) in a mixture of acetic acid (2.5 g) and water (10 mL) was washed with heptane (5 mL) and added dropwise to a stirred 25% aqueous ammonia solution (5 mL) at 5–15° C. The resulting mixture was stirred for 0.5 hours at the same temperature. Precipitated solid was filtered off and dried under reduced pressure at 25–35° C. to give 0.6 g of amorphous physical form of cabergoline.
Example 9
Amorphous Physical Form of Cabergoline
A solution of solvate form A of cabergoline (1.0 g) in a mixture of acetic acid (2.5 g) and water (10 mL) was washed with heptane (5 mL). A 25% aqueous ammonia solution (5 mL) was added dropwise to the stirred solution of cabergoline at 5–15° C. The resulting mixture was stirred for 0.5 hours at the same temperature. Precipitated solid was filtered off and dried under reduced pressure at 25–35° C. to give 0.7 g of amorphous physical form of cab ergo line.
Example 10
Tablets Prepared from Amorphous Physical Form of Cabergoline
About one thousand tablets were compressed from the mixture of amorphous physical form of cabergoline (0.5 g), citric acid anhydrous (1.2 g), croscarmellose sodium (2.4 g), magnesium stearate (0.1 g) and microcrystalline cellulose (75.8 g).
Example 11
Tablets Prepared From Solvate Form A of Cabergoline
Granulate obtained by mixing of microcrystalline cellulose (75.1 g) and citric acid anhydrous (1.2 g) with a solution of solvate form A of cabergoline (0.6 g) in isopropanol was dried to give acceptable dry granules which were submitted to milling. The dried-milled granules were mixed with croscarmellose sodium (2.4 g) and with magnesium stearate (0.1 g). Finally, the lubricated blend was compressed to manufacture about one thousand tablets.
Although certain presently preferred embodiments of the invention have been described herein, it will be apparent to those skilled in the art to which the invention pertains that variations and modifications of the described embodiments may be made without departing from the spirit and scope of the invention. Accordingly, it is intended that the invention be limited only to the extent required by the appended claims and the applicable rules of law. | The invention provides methods for preparing amorphous physical form of cabergoline, and solvate form A of cabergoline useful in the preparation of the first mentioned physical form. A method for treating a prolactin disorder with medicaments prepared from amorphous physical form of cabergoline and solvate form A of cabergoline is also disclosed. | 2 |
This application claims benefit of Provisional Appln No. 60/030,682 filed Nov. 13, 1996.
BACKGROUND INFORMATION
1. Field of the Invention
The invention relates a process for the removal and recovery of zinc from aqueous process streams. In particular, a process of the invention is useful in the removal and recovery of zinc chloride from an aqueous process stream such as an aqueous effluent stream resulting from the manufacture of sorbic acid.
2. Description of the Related Art
Certain chemical manufacturing processes such as the process used to manufacture sorbic acid result in an aqueous effluent stream which contains one or more dissolved zinc compounds such as zinc chloride. One method of manufacturing sorbic acid is described in U.S. Pat. No. 4,736,063. Environmental constraints require substantial reduction in the concentration of zinc in such effluent streams prior to the release of the stream to the environment. Zinc compounds such as zinc chloride are extremely toxic to aquatic life and cannot be treated in conventional waste water treatment facilities.
SUMMARY OF THE INVENTION
The invention provides a process for the removal and recovery of zinc from aqueous process streams such as an aqueous effluent stream produced in the manufacture of sorbic acid. Sorbic acid and potassium sorbate are useful as anti-microbial shelf-life extenders in foods.
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the invention is a process which removes substantially all of the zinc from an aqueous, zinc chloride solution and, advantageously, permits the recovery of a relatively concentrated aqueous solution of zinc chloride.
According to the invention, a process is provided for the removal and recovery of zinc from an aqueous zinc chloride solution by the steps of:
(1) treating an aqueous zinc chloride solution having a zinc [Zn] concentration of about 10 to 10,000 parts per million (ppm) zinc with sufficient aqueous sodium hydroxide solution to produce an aqueous suspension of zinc hydroxide having a pH of about 9.5 to 11;
(2) subjecting the suspension of step (1) to filtration using a filter which is capable of filtering particles having a particle size of 0.5 micron to obtain a solid comprising zinc hydroxide and a filtrate which contains not more than 2 ppm zinc; and
(3) contacting the zinc hydroxide collected on the filter in step (2) with hydrochloric acid or aqueous acetic acid to obtain an aqueous solution of zinc chloride or acetate containing at least 10 weight percent zinc.
The process enables the zinc content of zinc chloride-containing effluent streams to be reduced sufficiently to permit the disposal of the effluent according to conventional disposal procedures. The process also permits the regeneration/recovery of zinc chloride in the form of a concentrated aqueous solution which may be reused in the same or other chemical processes. In another aspect of the present invention, the concentration of zinc in the effluent stream is reduced by about 15 fold, more preferably about 30 fold, even more preferably about 50 fold, and optimally about 100 fold.
Zinc is precipitated from the aqueous effluent stream by contacting with aqueous sodium hydroxide to precipitate the zinc as zinc hydroxide. The zinc hydroxide is filtered on a filter capable of filtering particles with a fine particle size of, for example, about 1.0 micron. Preferably, the zinc hydroxide is filtered on a filter capable of filtering particles with a particle size of about 0.5 micron. The zinc hydroxide is contacted with aqueous hydrochloric acid or aqueous acetic acid to give a concentrated solution of zinc chloride or zinc acetate which can disposed of by the normal means.
The first step may be carried out at a temperature of about 20 to 80° C., preferably about 30 to 40° C., using an aqueous sodium hydroxide solution containing from about 5 to 50 weight percent sodium hydroxide. It is preferred that the mixture obtained in step (1) has a pH of about 9.5. The zinc [Zn] concentration of the aqueous zinc chloride solution used in step (1) more typically is in the range of about 50 to 200 ppm. This aqueous zinc chloride solution also may contain other materials or compounds, e.g., dissolved or partially dissolved sorbic acid.
The filter means utilized in step (2) must be capable of removing particles having a size of 0.5 microns. Multiple pleated, polypropylene fiber filter cartridges are one type of a suitable filter means. The number of filter elements used is a function of flow rate. The temperature at which the second step may be carried out is in the range of about 20 to 80° C., preferably about 30 to 40° C.
The third step may be carried out at a temperature of about 20 to 50° C., preferably about 30 to 40° C., using either an aqueous hydrochloric acid or aqueous acetic acid solution. The hydrochloric acid solution may have a hydrogen chloride concentration of about 5 to 37 weight percent. The aqueous acetic acid solution may have an acetic acid concentration of about 10 to 25 weight percent. The concentration of the regenerated/recovered zinc chloride solution produce by step (3) corresponds to a zinc [Zn] concentration of at least 15 weight percent, preferably a zinc concentration of about 15 to 18 weight percent.
A further understanding can be obtained by reference to certain specific examples which are provided herein for purpose of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLES
Example 1
An aqueous sorbic acid process stream (1000 mL) containing 103 ppm zinc and having a pH of 2.3 was charged to a 2000 mL beaker. After adding 0.5 grams of Dicalite filter aid the pH of the stream was adjusted to 9.0 with aqueous sodium hydroxide with stirring at room temperature. After stirring for 15 minutes after the pH adjustment the suspension was vacuum filtered on a Buchner funnel. The concentration of zinc in the filtrate was 2.6 ppm as zinc.
Example 2
A procedure as in example 1 was followed except that the pH was adjusted to 10.0. The concentration of zinc in the filtrate was less than 1 ppm.
Example 3
A procedure as in example 1 was followed except that the pH was adjusted to 10.5. The concentration of zinc in the filtrate was less than 1 ppm.
Example 4
A procedure as in example 1 was followed except that the pH was adjusted to 11.0. The concentration of zinc in the filtrate was 3.4.
Example 5
An aqueous sorbic acid process stream (4998 g) containing 130 ppm zinc was charged to a 5000 mL beaker. The pH of the stream was adjusted to 9.75 with aqueous sodium hydroxide with stirring at room temperature. After stirring for 15 minutes after the pH adjustment the suspension was vacuum filtered on a Buchner funnel through Dicalite filter aid. The solids on the filter were stirred with 10 g acetic acid and 80 g water at room temperature for one hour. The mixture was vacuum filtered on a Buchner funnel. This gave 74.4 g of solution with a zinc concentration of 7109 ppm zinc. | The invention provides a process for the removal and recovery of zinc from an aqueous process stream. In particular, the process of the invention is useful in the removal and recovery of zinc compounds such as zinc chloride from an aqueous effluent stream produced in various manufacturing processes such as the manufacture of sorbic acid. | 2 |
CROSS-REFERENCED TO RELATED APPLICATIONS
This application claims the benefit of PCT/US10/49421 filed on Sep. 20, 2010 and U.S. provisional application 61/338,866 filed on Feb. 25, 2010 and 61/337,530 filed on Feb. 5, 2010 by the applicants which are both incorporated by reference herein in their entireties.
BACKGROUND
1. Field
The present application relates to improved anti-smudging, gripping and shelf-life properties of products and surfaces through the use of low-ion plasma, superheated steam and gas system surface treatments as well as system combinations thereof.
2. Prior Art
There is currently a great need for bottles made of many materials, including plastics, for the containment and storage of consumer products. Plastic bottles often have labels on them which need to appear visually sharper and not smudge with use or age. Profitability is increased to a great extent when these conditions are achieved by making products more aesthetically pleasing and attractive as well as increasing the shelf-life of the bottle and its identifying label. Longer-lasting and visually sharper product labels allow older goods to stay on the shelf and remain for sale longer before replacement with fresher items. This would be especially important with non-perishable goods that, if marked with sharp and long-lasting labels, could be left on shelves indefinitely and still remain appealing and marketable to consumers. Older items, with still fresh-appearing labels, could be placed at the front of shelves and sold first. Costs associated with inventory and replacement of goods could thereby be substantially decreased.
Improvements in the physical properties of bottles are vital as well. Surface treatments are needed that can beneficially affect properties such as hardness, fatigue, creep, stickiness, gripability and the reactivity of a bottle's material. Often the transparency of a bottle is impaired by the presence of a wax or glue coating that is applied during processing. Methods are needed to remove the wax or glue without damaging labels if present; thereby making a surface that is matte, due to the presence of glue, transparent. Alternatively, a system is needed to create a matte finish, if desired, on bottles directly or in a manner that does not disturb labels, lettering or bar codes. Bottle or container surfaces often need to be cleaned before the application of labels as well.
Surface heat treatment using an open flame as the heat source is the present solution for the meeting of many of the above goals. Flame treatment is the current industry standard for surface cleaning of bottles prior to application of items such as chemical etch/photo etch/screened nameplates, pressure sensitive labels and decals, UID and mil-spec labeling, serialization and bar-code identification, specialty engravings, large-format digital and screen printing and specialty food and packaging labels. Flame is also required for heat transferred decals which may display abstract design elements resembling, for example, henna tattoo artwork. Flame curing is needed for labels, produced by DI-NA-CAL®-brand heat transfer labels, for example, which are formulated with a protective lacquer and, sometimes, a custom-designed adhesive print coat. Examples of methods and processes using flame to prepare and alter surfaces of bottles for application and/or preservation of labels and direct printing on a surface include U.S. Pat. No. 6,991,261 by Dronzek, Jr., et al., U.S. Pat. No. 6,939,602 by McGee, et al., U.S. Pat. No. 6,616,786 by Blom, et al., U.S. Pat. No. 6,513,435 by Detzner, U.S. Pat. No. 6,086,991 by Hubbard, et al., U.S. Pat. No. 5,925,208 and U.S. Pat. No. 5,711,839 by Dronzek, Jr., et al. and U.S. Pat. No. 5,085,034 by Haas.
As an alternative to open flame as a heat source, U.S. Pat. No. 6,013,333 by Carson, et al., and U.S. Pat. No. 6,086,991 by Hubbard, et al. suggest the use of plasma. This plasma, however, is not low-ion plasma, which can be defined as plasma with an ion percentage by volume of 2% or less. Upon application, ions in the plasma have been found to have a beneficial impact on surface properties. Plasma with low-ion content may be generated by the devices of U.S. Pat. No. 5,963,709 by Staples, et al. and U.S. Pat. No. 6,816,671 by Reddy, et al. Small amounts of thermal plasma may be created in very high temperature environments employing high temperature heating elements composed of materials such as molybdenum, tungsten and molybdenum disilicide materials. Plasma can also generated by RF means, as illustrated by U.S. Pat. No. 3,648,015 by Fairbairn, which relates to cold plasma, U.S. Pat. Nos. 5,403,453, 5,387,842, 5,414,324, 5,456,972 by Roth, et al., U.S. Pat. Nos. 5,669,583, 5,938,854, 6,146,724 by Roth and U.S. Pat. No. 6,245,132 by Feldman et al. Not all techniques can produce air plasma at normal pressures and not all techniques, except for U.S. Pat. Nos. 5,963,709 and 6,816,671, can be considered to produce substantial heat delivered simultaneously with hot gas. The plasma recombination leads to heat but only generally at a recombining surface.
Superheated steam, which is often used synonymously with saturated and super-saturated steam, although there may be some differences, may be generated in a number of ways for various purposes. U.S. Pat. No. 6,900,421 by Varma is directed to a sterilizing apparatus using microwave heating for the generation of superheated steam. U.S. Pat. No. 6,880,491 by Reiner, et al. concerns the generation of superheated steam using hydrogen peroxide and a combustible fluid, wherein the combustion process decomposes the hydrogen peroxide to produce superheated steam. U.S. Pat. No. 7,115,845 by Nomura, et al. consists of a superheated steam generator that uses electromagnetic induction to produce the superheated steam. Here, in one embodiment of the present application, the superheated steam generator may be comprised of a heater such as the coil-in-coil type disclosed in U.S. Publication No. 2007/0145038 by Vissa, et al., which overcomes problems associated with the relationship of Psat and Tsat. The heater may also be of the type disclosed in U.S. Publication No. 2010/129157 by Reddy, et al. In the present patent application, the use of superheated steam, alone or in conjunction with low-ion plasma has been shown to improve surface and bulk properties of products exposed to it.
When an open flame is applied directly to a bottle to remove glue and wax or to improve surface and bulk properties, a number of disadvantages are presented including:
a) Flame treatment processes are environmentally harmful. They produce CO 2 and SO 2 soot. Typically, 20,000 BTU natural gas burners produce about 22 moles of greenhouse gasses per hour (10 25 molecules per hour). Combustion products from fuels containing carbon also often produce very toxic gasses such as carbon monoxide (CO). Such a method is not environmentally friendly or a green technology. b) Combustion gas input is used which requires plumbing for delivery and application adding to the cost of set-up and operation. c) Combustion flame has a narrow area of impact and is therefore its application is non-uniform. To attain the needed uniformity many burners may be needed, adding to the cost and complexity of the process. d) There is a high potential for explosion due to the presence of combustible gas. Combustion flame is commonly associated with combustion emissions and fire hazards. Employees must be adequately trained and be provided with protective equipment. e) Flames are inherently energy inefficient with, typically, about 10% of the energy being used in directed flame operations. Most of the energy is not applied to the product. f) There is a lack of precise control from combustion flames leading to lack of optimization of processes. g) Flame combustion produces high noise. It also requires the added cost of hearing protection for workers and possible specialized placement and sound insulation of process equipment. h) There is a continuous requirement for consumables such as reactant gasses leading to increased costs and decreases in profitability. Safety and environmental clean-up costs are incurred.
It is therefore apparent that the current technology is not meeting the above stated goals in an environmentally safe, energy efficient or cost effective manner. With the increase in potentially disastrous effects associated with global warming and the volatile economy, new devices and methods are needed to address these effects, where the present flame treatment technology does not, in regards to improvement of anti-smudging, gripping and shelf-life properties of products and surfaces.
SUMMARY
In accordance with a favored embodiment, a low-ion plasma and superheated steam (LIP™) system for surface treatment and cleaning for the improvement of anti-smudging, gripping and shelf-life of products and surfaces comprises a means to electrically generate low-ion plasma and a means to electrically generate superheated steam. Such low-ion plasma and superheated steam will be applied to the surface of a product in order to cause the enhancement and improvement of the above and other surface and physical properties of bottles and other products made of various materials to, in part, enhance the appearance and life of labels found on the bottles and products. This new method will alleviate problems associated with the current technology including toxic emissions, safety concerns, explosion hazards, pollution, noise, inefficiency, lack of optimization and high costs due to consumables, insurance and specialized training in operation and safety. These and other benefits will become apparent in the following descriptions of the embodiments of the LIP™ system.
DRAWINGS
Figures
FIG. 1 is a perspective view of the LIP™ system.
FIG. 2( a ) is an interior view of the LIP™ system revealing the low-ion plasma generator and superheated steam generation devices contained therein.
FIG. 2( b ) is a perspective view of the low-ion plasma generator contained in the LIP™ system.
FIG. 2( c ) is a perspective view of an example of a superheated steam generation device contained in the LIP™ system.
FIG. 3 is a perspective view of the LIP™ system and a product conveyor means.
FIG. 4 is a front view of two LIP™ units arranged side by side with a conveyor means.
FIG. 5 is a view of the single-hole nozzle design for the low-ion plasma generator.
FIG. 6 is a view of the slit nozzle design for the low-ion plasma generator.
FIG. 7 is a view of the multi-hole #1 nozzle design for the low-ion plasma generator.
FIG. 8 is a view of the multi-hole #2 nozzle design for the low-ion plasma generator.
FIG. 9 is a cut-away view of an embodiment of a low-ion plasma generator as employed in an embodiment of the present apparatus.
FIG. 10 is a cut-away view of an embodiment of a steam generator as employed in an embodiment of the present apparatus.
It is an object of this invention to provide a device and method for heating a gaseous flow that can impart plasma to the flow. A device for heating a gaseous flow is provided having a first materials, a second materials, and a heat source. The first materials has an inlet side for receiving the gaseous flow, an inner side for discharging the gaseous flow, and a plurality of openings, the openings providing at least one passageway for the inlet side to the inner side. The first materials preferably comprise porous ceramic materials.
The second materials has an inner side for receiving the gaseous flow, an outlet side for discharging the gaseous flow, and a plurality of openings, the openings providing at least one passageway from the inner side to the outlet side. The inner side of the first materials and the inner side of the second material define a gap for providing residence time for gases passing therethrough. Preferably, the second material comprises a porous ceramic materials. It is also preferred that the ratio of the volume of the materials to the volume of the gap is 3. The heat source is in direct or indirect contact with the gaseous flow and provides heat thereto. Preferably, the heat source is an electric heating element.
As shown in FIG. 9 , hot plasma blower 12 has a housing comprising a stainless steel shell 14 configured in a substantially cylindrical shape. The blower 12 has an inlet end 20 and an outlet end 22 . A fan 16 is disposed near the inlet end 20 for receiving a gaseous flow, depicted by the arrows 18 , so that the gaseous flow can be directed through the blower 12 from its inlet end 20 toward its outlet end 22 . Fan 18 is preferably driven by an electric motor (not shown).
The gaseous flow 18 to be heated by the blower 12 can comprise a variety of gases or combinations of gases, preferably so that the gases are not chemically reactive when heated to a temperature at which the blower will operate. For example, the gaseous flow 18 can be air that is to be heated and applied to a part or chamber. Also, the gaseous flow can be engine exhaust having particulates that are to be incinerated by the heat of the blower 12 . Moreover, although the blower 12 is depicted in its vertical position in FIG. 9 , it may be operated in a horizontal manner or at any angle to horizontal.
As shown in FIG. 9 , the blower preferably has an insulating liner 38 adjacent the interior surfaces of shell 14 for preventing loss of heat from the interior of the blower. Insulating liner 38 can comprise any insulating material that is physically and chemically stable at the temperature at which the blower is to operate, such as alumina silica fibers, micro quartz fiber and the like.
As is also shown by FIG. 9 , the representative embodiment further includes a first material 24 and a second material 26 disposed within the shell 14 . The first material 24 includes an inlet side 44 for receiving a gaseous flow (depicted by arrows 18 ), from the fan 16 and an inner side 46 for discharging the gaseous flow. The second material 26 includes an inner side 48 for receiving the gaseous flow discharged by the first material 24 , and an outlet side 50 for discharging this gaseous flow. Preferably, the outer edges of the first and second materials 24 and 26 directly abut the interior surface of the liner 38 such that there is no gap between the liner and the sides of the materials. It is also preferred that the materials 24 and 26 are spaced apart along the longitudinal axis of the blower 12 such that a gap 30 is formed between the two. Spacer 40 can be utilized to maintain the gap 30 between the inner sides 46 and 48 of the first and second materials 24 and 26 . The spacer 40 is preferably comprised of an alumina silica cylindrical refractory. Ledge 42 may be utilized to help maintain the materials 24 and 26 at a desired location within the shell 14 ; the second material 26 can be placed upon the ledge, the spacer 40 may be placed upon the second material, and the first material 24 may be placed upon the spacer. Alternatively, the materials 24 and 26 can be secured to the shell using any manner known in the art such as by bolting, clamping, or the use of high temperature adhesives.
The first material 24 contains a plurality of pores 28 (shown schematically in FIG. 9 ) that provide at least one passageway for a gaseous flow to travel from the inlet side 44 to the inner side 46 . Similarly, the second material 26 also contains a plurality of pores 28 that provide at least one passageway from the inner side 48 to the outlet side 50 of the material. Preferably, the pores 28 within the first material 24 are interconnected so as to provide a plurality of passageways through the material. Similarly, it is preferred that the pores 28 within the second material 26 are interconnected.
The heating element should be made of a resistive material such that it becomes heated as an electric current passes there through as is well known in the art. The element can comprise any number of resistive materials suitable for obtaining a high temperature when an electric current passes there through. For example, the element can comprise a metallic material such as iron or nickel based alloys, iron or nickel based alloys containing aluminum and niobium, nickel aluminide, molybdenum disilicide (or other molybdenum silicides), silicon carbide, nickel chromium alloy, and the like. Conventional U-shaped elements based on molybdenum disilicide, silicon carbide, zirconia, carbon or boron nitride can be heated up to a 1900° C. element temperature. While the heating element is shown as a U-shaped in FIG. 9 , it is to be understood that the heating element can comprise any number of shapes and types as are well known in the art. For example, the heating element can have a multiple number of connected U-shaped members or can be provided in a spiral shape or as coil shape or combinations. In one embodiment of this invention we provide for adding tungsten or tungsten bearing compounds to the heating element itself in order to obtain a convective plasma output from the product of this invention.
Furthermore, it is contemplated that hot air could be drawn directly out of the gap as it is simultaneously drawn from the outlet end of the blower or compressor or gas bottle delivering the gas. Moreover, additional fans may be utilized to aid in drawing the air from the blower. It is also contemplated that fins or baffles be utilized within the gap to aid in increasing residence time and raising the temperature of the air output from the fan. In operation, the blower, fan or compressor forces air (or other gas if desired) into the inlet. When the air reaches the first material, it travels from the inlet side, through the pores, and out the outlet side. As noted above, the pores preferably provide a plurality of passageways through which the air may travel. It is even more preferred that the passageways have several turns and twists so that the air travels a “tortuous” path, as is known in the art. As also noted above, the pores within the material are preferably interconnected so that each pore is connected to a plurality of passageways extending from the inlet side to the inner side. The first material has a preferred porosity of 10 pores per inch, each pore having a diameter of about 0.01 inches.
The tortuous path provided by the pores serves at least two functions. First, as air travels the tortuous path, it absorbs the heat retained by the first material and received from the heating element. This preheating of the air helps to prevent the heating elements from cracking, as metallic elements have been known to do when they come in contact with air that is too cool relative to the temperature of the element. The amount of preheating that occurs depends upon the thickness of the material, the porosity of the material, and the size of the pores. The greater the thickness and porosity, the more tortuous the path. The larger the pore size, the less tortuous the path.
The second function of the tortuous path is to help to prevent air from escaping the blower in the opposite direction of the intended flow. Thus, although air that becomes heated will have a tendency to rise from the inner side to the inlet side when the blower is used in the vertical position, the air will have difficulty doing so due to the complex and turbulent flow experienced within the gap upon exiting the material.
Once the air is discharged from the inner side, it enters the gap defined by the first material, the second material and the interior wall of the spacer. The gap can also be described as a cavity, space, or chamber. When air travels through the gap, it receives heat from the element by convection and radiation. The gap provides residence time for the air traveling from inner side of the first material to the inner side of the second material to become heated by the element. It is also believed that a complex combination of turbulent flow, convective flow, and recirculation zones occurring within the gap contribute to the heat imparted to the gas therein. Thus, when the air reaches the inner side of the second material, it has a higher temperature than when it first entered the gap through the inner side of the first material.
Like the first material, the second material also have a number of pores which are preferably interconnected so as to provide a tortuous path from the inner side to the outlet side of the material. It is also preferred that the second material have the same porosity of the first material. As in the first material, the pores of the second material provide a tortuous path for air traveling through the second material and cause the air to rise even higher in temperature as it travels through the material. The element in addition to being disposed within the gap, is preferably also disposed within the second material so as to provide additional heating of the air. The air is finally discharged through the outlet side of the second material and out the outlet end of the blower where is can be utilized by the user. Due to the tortuous paths provided by the materials and, the residence time provided by gap, the air exiting the blower at the outlet end is at a higher temperature than air brought into the blower through the inlet end.
A heater and steam generator 300 in accordance with another embodiment of the invention is illustrated in FIG. 10 . A pump 302 may be used to actively supply the working fluid to the heat and steam generator 300 from a fluid reservoir 304 . For example, the pump 302 may be a peristaltic pump having the necessary controls for selectively metering the flow rate of the working fluid (e.g., water) to the heater and steam generator 300 . Such peristaltic pumps are commercially available. Other arrangements for supplying the working fluid to the heater and steam generator 300 are also within the scope of the invention. By way of example, a passive arrangement (shown in phantom in FIG. 10 ) may be utilized wherein the fluid reservoir 304 (e.g., water bag, cartridge, etc.) supplies the working fluid to the heater and steam generator 300 through gravity, for example, or other passive means. In such an embodiment, the reservoir 304 may include appropriate valving 305 (e.g., drip chambers, clips, etc.) for metering the flow of the working fluid to the heater and steam generator 300 . Another modification to heat and steam generator 300 is the inclusion of an outer jacket housing 306 that defines a chamber 308 about at least a portion of the casing 210 having an inlet 310 for receiving the working fluid from pump 302 via a suitable conduit 312 , and an outlet 314 in fluid communication with delivery tube 212 . While the outer jacket housing 306 is shown adjacent the outlet side of the heater and steam generator 300 , the housing 306 may be located along other portions of the heater and steam generator.
In operation, the pump 302 or other active or passive supply device supplies the working fluid from the reservoir 304 through conduit 312 , through inlet 310 , and into the chamber 308 defined by housing 306 . The heater 10 heats the casing 210 sufficiently to preheat the working fluid contained in chamber 308 to near or at its saturation temperature (e.g., boiling point). Thus, saturated liquid, saturated vapor or both may be present in chamber 308 . Similar to the previous embodiment, the fluid in chamber 308 then flows into the delivery tube 212 where it mixes with the heated gas exiting gas heater 10 . The heat from the gas causes the working fluid introduced from chamber 308 to become superheated. In one embodiment, the working fluid is water and the heater and steam generator 300 generates superheated steam. Other working fluids, however, may be used in accordance with aspects of the invention as mentioned above. The end of the delivery tube 212 may include a threaded portion for coupling to various exit nozzles 228 that facilitate directing the superheated vapor-gas mixture (e.g., steam-air mixture) toward various items.
DESCRIPTION
FIGS. 1 , 2 ( a ), 2 ( b ), 2 ( c ), 3 and 4 —Best Mode
The embodiment of the best mode of the LIP™ system for the improvement of anti-smudging, gripping and shelf-life properties of products and surfaces is illustrated in FIG. 1 (perspective view), FIG. 2( a ) (cut-away view), FIG. 2( b ) (perspective view of low-ion plasma generator) and FIG. 2( c ) (perspective view of superheated steam generator). The LIP™ system 100 is comprised of a housing 120 configured with a vertical section 122 and a horizontal section 124 contiguous with and located above the vertical section 122 . An access panel 128 is located at the top of the housing 120 in the horizontal section 124 covering an access opening 130 . A cowling 126 is attached to the horizontal section 124 and has an open end 136 on one side and a closed end 134 on the other with the open end 136 being attached to the horizontal section 124 . The cowling 126 has a plasma nozzle aperture 138 and a steam nozzle aperture 140 cut through its closed end 134 allowing for placement of the plasma nozzle 182 of the low-ion plasma generator 180 and the steam nozzle 162 of the superheated steam generator 160 . In this embodiment the plasma nozzle aperture 138 and the steam nozzle aperture 140 are positioned to allow the plasma nozzle 182 and the steam nozzle 162 to be placed side by side. In this embodiment the low-ion plasma generator 180 is of the type disclosed in U.S. Pat. No. 5,963,709 by Staples and U.S. Pat. No. 6,816,671 by Reddy. The superheated steam generator 160 of the present embodiment is of the types disclosed in U.S. Publication No. 2007/0145038 by Vissa or U.S Publication No. 2010/129157 by Reddy, et al.
A conveyor means 1000 is positioned in a manner to move products in front of the steam nozzle 162 and the plasma nozzle 182 projecting through the closed end 134 of the cowling 126 . The speed of the conveyor means is variable can be changed to match requirements in regards to product material type and the property or feature that is in need of alteration by the low-ion plasma and/or superheated steam. The order of the operations (i.e., low-ion plasma, superheated steam) may be changed or one operation may not follow each other right away or one or the other operation may be omitted entirely to achieve desired results. The distance between the conveyor means 1000 and the steam nozzle 162 and the plasma nozzle 182 may be adjusted as well.
Operation
In the present embodiment, a bottle or other product is propelled by the conveyor means 1000 in front of the steam nozzle 162 and plasma nozzle 182 of the LIP™ system 100 . The steam nozzle 162 projects superheated steam, which contains ions, produced by the superheated steam generator 160 and the plasma nozzle 182 projects low-ion plasma produced by the low-ion plasma generator 180 on a product or surface. In this manner the bottle or product is passed through both a superheated steam and low-ion plasma stream for a predetermined optimal time for the attainment of the desired improved surface properties. The product may also be passed in front of the plasma nozzle 182 first and then passed in front of the steam nozzle 162 . A cooling cycle may also be employed between applications of steam and plasma. It is also contemplated that the product to be treated may be passed only through the plasma stream projected by the low-ion plasma generator 180 or alternatively only through the superheated steam stream of the superheated steam generator 160 . The temperature and flow rates of the plasma and steam are variable and controllable as well. The experiments and testing described below present various temperatures, environments and exposure times anticipated and evaluated for different embodiments.
ALTERNATE EMBODIMENTS
FIGS. 5-8 show alternate embodiments of the plasma nozzle 182 of the low-ion plasma generator 180 of the LIP™ system 100 . FIG. 5 displays a single-hole plasma nozzle 182 ( a ) while FIG. 6 shows a slit plasma nozzle 182 ( b ). Multiple holes are depicted in FIG. 7 for the multi-hole #1 plasma nozzle 182 ( c ) and in FIG. 8 for the multi-hole #2 plasma nozzle 182 ( d ). These and other anticipated embodiments of the plasma nozzle 182 give great versatility in the direction and intensity of the projection of the plasma stream produced by the low-ion plasma generator 180 . The plasma nozzle 182 can be designed to meet any requirement of plasma direction control in regards to the size, shape or material of a product and in accordance with the desired surface and bulk properties. The special design and materials of the nozzles 162 and 182 in some way affect the delivery of a low-ion gas or system. The shapes of the nozzles 162 and 182 can be convex, concave or a combination of the two to achieve diffuse or direct flow for specific uses. Plasma nozzles 182 with single openings found in FIGS. 5 and 6 allow for a more direct and intense plasma stream for smaller products or smaller areas on a larger product. On the other hand, plasma nozzles 182 with multiple holes, such as those in FIGS. 7 and 8 , allow for a broader area of plasma application on larger products and surface areas. The plasma nozzles 182 can particularly be adapted to take the shape of an object to be treated, especially if the object has very varying dimensions like a bottle and its mouth. Also anticipated are: plasma nozzles 182 with slits in circular shape around main large hole; steam nozzle 162 to direct steam flow into plasma stream; the use of insulating materials between product and LIP™ system 100 to reduce heat transfer to undesired areas and; the use of shrouds or opposite wall backing to retain heat in the LIP™ system 100 . The low-ion and gas can be used to treat metal, inorganic, organic, polymer, composite, solid, semi-solid or liquid surfaces.
By using an ion generation/formation system, even a slight amount of ions, as low at 0.0001%, 0.001%, 0.01%, 0.1% or 1%, as well as large amounts that may be as great as 10% to 100% by volume of a cold or hot gas, can often greatly impact the anti-smudging and/or shininess of surfaces leading to better commercially applicability. Gas, including steam, and all fluid mixtures are contemplated with a small to large concentration of ions. Plasma may be generated from any ion or chemical gas species of H 2 O, CO 2 , CO or from complex organic gasses which condense, for instance as glue. The gasses employed could be, for example, air, oxygen and ideal gasses such as helium or argon. Also, the gasses could be combustion products or other plasma gasses. Ions in a gas can result from reactions, flame, heating, plasma generation, electric potential, especially at high frequencies in the ranges of kHz, Ghz and MHz, or electrolytic methods for a gas or fluid. Ions can also be introduced through work based systems (e.g., rubbing of surfaces). Ions can be created by discharges in a gas, vacuum or low pressure gas. Ions are also produced during boiling, evaporating or phase change processes. Ions may be produced from intermediary species that have an ionic nature (for example in catalytic reactions and surface reactions). A combination technique can also be used to produce ions. The main idea is to have a fluid with some ions. All fluids including liquids, droplets, gasses and their mixtures are fully contemplated by the inventors as are fluids containing solid particles and solid ions like colloids, zeolites and other soft and hard fibers including nano-materials in relation to the production of ions.
The inventors have tested surfaces (laser surface reflection and projection) treated by the techniques below for producing ions. It has been found that ions in the fluid provide a great benefit to surfaces by rendering them smudge resistant, better gripping and visually more sharp and attractive. Also found was that the good properties are retained over time, i.e., retained over days, months and possibly years thus improving shelf-life. The shine is retained over many months proving that the technique of having a small amount of ions applied as an anti-corrosive (or anti oxidant) to materials including metals, common plastics, ceramics, nano-materials, paper, PTFE, PTE, styrene, polystyrene, textiles, polyester, ester, polycarbonates, composites and others, as well as products including bottles, storage containers, labels and plastic adhesives is effective in improving product shelf-life. It is anticipated that the surfaces of organic items including fruits, vegetables, meat or even the skin of humans may benefit from the superheated steam, low-ion surface treatment described by the present application. Applicable surface types include transparent, partially transparent, non-transparent and “speckled” surfaces. Tests further indicate that it is more difficult for droplets to fall off ion treated surfaces. This is often an indication that the surface energy is higher for ion treated surfaces. The gripping ability of ion treated surfaces was better, indicating that the coefficient of friction may have been better after such surface treatment. Again, 1% to as little as 0.0001% or less by volume of ions in the fluid seems good enough to achieve these results. Testing indicates that the LIP™ system represents a new technology which allows the use of hot air and gasses to efficiently transfer energy from just above room temperature to 1000° C. containing very low amounts of plasma.
Experiments and Testing
A typical scenario for surface processing for the elimination of flame and the attainment of a better surface that was applied to multiple embodiments is given below:
1. Particular Objective:
1.1. To replace a flame based process. The flame process suffers from: (1) environment consideration arising from emissions of the combustion products, i.e., CO 2 , SO 2 and soot; (2) has a narrow area impact; (3) possibly suffers from commonly recognized combustion and related fire hazards; (4) has the potential of causing explosions; (5) is energy inefficient; (6) cannot be precisely controlled; (7) makes combustion noise; and (8) is costly because of the requirement for constantly used consumables such as reactant gasses.
2. Specific Goal for the Test:
The specific goal is the replacement of the multiple flame processing nozzle design on a bottle conveyor line with a safer and more technologically current product.
3. Test Procedure:
3.1 The printed or labeled faces of bottles are held together by glue which is currently burnt off by the flame.
3.2 The surfaces of two bottles were treated with a low-ion plasma only and with a low-ion plasma and steam process at speeds exceeding 200 ft/min.
3.3 The bottles were attached to a linear stage (conveyor means 1000 ). Velocity and interaction time defined a Ua/2α were measured. This is a standard Fourier number or dimensionless interaction time parameter and can be used to scale a process. a is treatment area or beam size. U is the velocity of movement and α is the thermal diffusivity
4. Equipment:
4.1 6.5 kW Low-ion plasma generator 180 (For product description see www.mhi-inc.com.)
4.2 1 kW HGA-S-01 superheated steam generator 160 .
4.3 Bearing Slide (conveyor means 1000 )
4.4 Bottle samples provide from outside MHI
4.5 LIP™ system 100 of combination energy delivery sources and gasses and different nozzle orientations.
5 Results:
5.1 The flame may be easily and safely replaced. Both the overall goals and specific goals can me met.
General Test
1.1 The present application describes a new plasma use and use of steam plasma in various forms in order to obtain a better surface. A better surface is for metal ceramic or polymer (plastic) with improved surface and/or bulk properties including better transparency, hardness, fatigue, wear etc. The low-ion plasma generator 180 was run at 1260° C. at the exit.
1.2 The platform was about 2″ from the front of the low-ion plasma generator 180 .
1.3 The low-ion plasma generator 180 fan speed was set at 1.5 meters per second.
1.4 The HGA-S-01 superheated steam generator 160 was setup to inject steam diagonally into the plasma stream (steam/plasma test only). The diagonal is better than normal but both are possible.
2 Small Volumes and Large Volumes can be Treated with the New Process.
Typical Small Volume Procedure:
2.1 Low-Ion Plasma Generator Test
2.1.1 The low-ion plasma generator 180 will start and heated to the maximum recommended temperature. 2.1.2 The top half of each bottle will be covered with high temperature tape so that the before and after effects of the test can be shown. 2.1.3 The marked bottles will be installed on the bearing slide (conveyor means 1000 ). 2.1.4 For the plasma test bottle #1 will be used. 2.1.5 High temperature tape will be used to cover the non-tested area of the bottle so that further runs may be completed on the same bottle. 2.1.6 Using the bearing slide (conveyor means 1000 ) the samples will be moved in front of the plasma stream at a known (estimated) rate of speed. The length of travel will be known and the movement of the bottle will be timed for each run. 2.1.7 Data for the run time, sample, temperature, and any notes will be recorded.
2.2 Steam/Plasma Test 1
2.2.1 The HGA-S-01 superheated steam generator 160 will be heated to 400° C. while running at a flow rate of 20 mL/min. 2.2.2 The sample bottle will be passed in front of the steam flow. 2.2.3 The sample will then be run in front of the low-ion plasma generator 180 .
2.3 Steam/Plasma Test 2
2.3.1 The HGA-S-01 superheated steam generator 160 will be heated to 400° C. while running at a flow rate of 20 mL/min. 2.3.2. The sample bottle will be passed in front of the combined steam/plasma steam flow.
3. Data:
3.1. Plasma Testing Data
Run #
Sample ID
Temp
Time
Notes
1
Water
1190
n/a
Water bottle
2
1F
1260
0.840
Wax was cleared
3
1B
1260
1.10
Center strip was cleared as rest
was blanked off with tape
4
1B
1260
n/a
Wax cleared
3.2. Steam/Plasma Test 1 Data. Separately treated.
Run #
Sample ID
Temp
Time
Notes
1
2B
400/1260
n/a
Wax cleared
3.3. Steam/Plasma Test 2 Data. Concomitantly treated.
Run #
Sample ID
Temp
Time
Notes
1
2F
475/1260
n/a
Wax cleared, no deformation
2
3F
382/1260
n/a
Wax cleared, no deformation
3.4. Large Volume procedures involve combinations of power and surface speed. Use of low and large area sources. Alternating steam, plasma and other heat sources like IR, Laser (all wavelengths are considered but some may be more preferable such as excimer lasers or carbon dioxide lasers), electron beam, ion beam and even flame in all combinations and order of treatment and re-treatment etc.
LIP™ Testing Schedule
Procedure #1
LIP 6.5P with 4″ Slit Nozzle 182 b
Procedure #2
LIP 6.5P with 1″ Round Nozzle 182 a
Procedure #3
LIP 6.5P with Multihole Nozzle #1 182 c
Procedure #4
LIP 6.5P with Multihole Nozzle #1 182 c
Procedure #5
LIP 6.5P with Multihole Nozzle #1 182 c
LIP 10D with Multihole Nozzle #1 182 c
2 LIP units side-by-side spaced ˜8″ apart
Procedure #6
LIP 6.5P with Multihole Nozzle #2 182 d
LIP 10D with Multihole Nozzle #2 182 d
2 LIP units side-by-side spaced ˜ ¼″ apart
Procedure #7
LIP 6.5P with Multihole Nozzle #2+(×2) 1 kW LTA units w/4″ knife LIP 10D with Multihole Nozzle #2+(×2) 1 kW LTA units w/4″ knife 2 LIP units side-by-side spaced˜ ¼″ apart
Procedure #8
LIP 6.5P with Multihole Nozzle #2+1 kW LTA units w/4″ knife+1 kW TTA steam unit w/4″ knife LIP 10D with Multihole Nozzle #2+(×2) 1 kW LTA units w/4″ knife 2 LIP units side-by-side spaced˜ ¼″ apart
Further embodiments concerning the order of application of the superheated steam and low-ion plasma streams anticipate increased versatility. The superheated stream may be applied to a product before, after or simultaneously to the application of the low-ion plasma. In some cases the low-ion plasma or superheated steam may be applied by themselves to achieve desired results. If desired, the product may be allowed to cool after the application of the plasma or steam and before the application of the other. Typically, the low-ion can be generated with non-combustible air, but if needed, could be generated with a variety of other gasses. The type of product to be treated and the surface or bulk property to be augmented can determine which of these and other embodiments is to be employed. Units of the LIP™ system 100 may be used singly, side-by-side or facing each other and with or without a conveyor means 1000 depending on the needs of the customer. In general, the LIP™ system 100 is designed for continuous short-time exposure of forced convective heat, utilizing ions in a flowing gas. The major heat transfer mechanisms are ion recombination and forced convection while a minor heat transfer mechanism is radiative as apposed to the co-filed PCT patent application no. PCT/US10/49418 entitled “Clean Green Electric Protectors For Materials” which relies predominately on radiative heat and little on convection for heat transfer. The forced convection is of a hot gas with temperatures above 100° C., 200° C., 500° C., 750° C., 1000° C. or 1250° C. Ions are supplied by low-ion plasma and all sources and mechanisms of heat are directed with velocity. Also, the forced convection acts to enhance the affects of the low-ion plasma.
Advantages
While fully realizing there are many other advantages provided by the LIP™, from the description above, a number of advantages of the embodiments of the LIP™ system over the use of open flame become evident including:
a) No toxic emissions or greenhouse gasses are produced. Device uses only air input requiring no other gasses and, as a result, no venting is needed as only air is released into the environment. The replacement of a combustion flame with an “air flame” is more energy efficient, improves productivity and is safer, thereby improving the insurance profile of the user.
b) The LIP™ system has a very wide area flexibility which increases line speed dramatically.
c) There is no possibility of explosion from the inlet source with the LIP™ system since no combustion gasses are involved. LIP™ systems can be integrated with over-temperature controls leading to less monitoring and labor savings.
d) The LIP™ system is over 90% efficient. Energy savings depend on the user's objectives and the total power replaced, but as an example, a 30 kW flame is generally replaced by 6 kW of clean electric for select operations.
e) Precise control is available to fully optimize all processes and provides for safety controls such as over-temperature cut-off. Directional application of stream of gas and low-ion plasma is possible.
f) Quiet operation requiring no hearing protection.
g) LIP™ systems offer great savings in many ways. The system uses only air and electricity rather than costly consumables including combustible gas. Insurance premiums may be influenced in a positive many due to increases in safety provided by the LIP™ system including no flame, no combustible gas and low noise output. Allows a user to differentiate itself from the competition by allowing the user to stress its use of green technology. Depending on the application, the LIP™ system is often less expensive in general that conventional flame technology.
h) The use of low-ion plasma overcomes the problems of excessive heat generated by the recombination of high percentages of ions in plasma. Fewer ions to be recombined lead to less heat allowing for uses where too much heat created by too many ions, for example, would cause melting and be destructive.
i) The heat generated by low-ion plasma is controllable and, in effect the low percentage of ions beneficially catalyzes reactions on a surface or in a gas-ion mixture.
The LIP™ system provides even further advantages over open flame and other methods due to the great flexibility it provides. Though the preferred embodiment calls for the use of low-ion plasma, the LIP™ system can perform its function of improving anti-smudging, better grip-ability and improved shelf life with plasma with percentages of ions from 0.0001% to 100% by volume. Further flexibility is provided by the fact that meeting the stated goals of product improvement do not depend on the order in which the superheated steam and low-ion plasma are applied. Studies at MHI Inc. have revealed that the LIP™ system is effective regardless of the order in which the steam or plasma is applied and is even effective if a product is subjected to only one. The system can be employed for direct flow or at any angle required. It may be used for material heat treating in complex situations where the surface to be heated is out of sight allowing for treatment without expensive and time consuming disassembly.
It is anticipated that the improvements that the low-ion plasma and superheated steam LIP™ system provides may be employed on a wide and diverse array of applications encompassing: engine parts, printing on plastic food containers, energy-efficient window coatings, safe drinking water, voice and data communications components, waste processing, coatings and films, electronic computer chips and integrated circuits, advanced materials (e.g., ceramics), high-efficiency lighting, plasma enhanced chemistry, surface finishing and cleaning, processing of plastics, gas treatment, spraying of materials/nano crystals, glass heating and cutting, aluminum, nano-structures, chemical analysis, semiconductor production for computers, changing surface polarity or influencing transparency, modification of chemical compounds, hydrogen, melting and vaporization, boilers, energy systems (including nuclear, combustion and equipment), televisions and electronics, standard metallurgical processing at improved efficiencies and ease of use, and microbial reduction Improved surface and/or bulk properties, e.g., hardness, fatigue and wear, will be imparted to metal, ceramic and polymer (plastic) materials by the LIP™ system.
The above descriptions provide examples of specifics of possible embodiments of the application and should not be used to limit the scope of all possible embodiments. Thus the scope of the embodiments should not be limited by the examples and descriptions given, but should be determined from the claims and their legal equivalents. | A device to provide improved anti-smudging, better gripping and longer shelf-life to products and surfaces includes an electric superheated steam generator and an electric low-ion plasma generator to provide superheated steam and low-ion plasma to the surfaces of products including plastics. One embodiment envisions the superheated steam generator and the low-ion plasma generator being contained in a housing while another embodiment anticipates a conveyor means positioned in front of the superheated steam generator and the low-ion plasma generator. A method for the improving of anti-smudging, gripping and shelf-life for properties includes the application of superheated steam and low-ion plasma by means of a superheated steam generator and a low-ion plasma generator to products for specific periods of time and at specific distances to attain desired surface and bulk properties. The superheated steam and low-ion plasma may be applied individually, simultaneously or sequentially. | 7 |
This application claims the benefit of provisional application 60/436,948, filed on Dec. 30, 2002.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a slotwall panel having multiple channels forming slots in which brackets and other accessories can be mounted, and, more particularly, to a fire-retardant slotwall, the composition for making the slotwall, and the method for making the slotwall.
2. Description of the Related Art
Slotwalls are widely used to organize a room or an area of a room. A slotwall has multiple, spaced horizontal grooves forming the “slots” of the slotwall. Mounting brackets and accessories are designed to be received within the grooves. The mounting brackets are used to secure various items to the slotwall. The mounting brackets typically have hooks or other structures designed to support various items. The mounting brackets can also have specific structures designed to mount a particular item.
The accessories mounted to a slotwall include a wide variety of items. An illustrative accessory is a cabinet or other storage bin-type item that can be mounted to the wall. The accessories are typically mounted to the slotwall by an integrated or custom bracket assembly. However, one of the mounting brackets could be used depending on the configuration of the accessory.
Slotwalls can be formed from multiple sheets or from multiple slats. In either case, the sheets or slats will have one or more grooves forming the slot for mounting the bracket or accessory. The sheets or slats are typically mounted directly to a framed wall or similar structure in a building.
The grooves generally have an L or T-shape cross-section, resulting in a lip or similar structure extending over the channel. A portion of the bracket or accessory is generally received within the channel such that it can bear against the lip to hold the bracket or excess for the within the channel.
The sheets and slats are typically manufactured by an extrusion process. Currently, the sheets or slats are typically extruded from PVC (polyvinyl chloride). One disadvantage of the sheets or slats made from the PVC is that they do not satisfy current fire retardant standards. It is desirable to have a slotwall formed by either sheets or slats that had the desired fire retardant characteristics well still retaining the desired structural characteristics.
SUMMARY OF THE INVENTION
The invention addresses the shortcomings of the prior art by providing a cost-effective and fire-retardant slotwall. In one aspect, the invention relates to a composition suitable for extruding a fire-retardant product. The composition comprises CPVC (chlorinated polyvinyl chloride),PVC, and a fire retardant, with the quantities CPVC, PVC, and fire retardant being selected such that a product made from the composition will meet at least one of the ASTM E84-01 and UL 723 fire retardant standards. The composition can include other ingredients, such as; 2.7-3.3 pph Zeolite, 0.36-0.44 pph Blowing Agent, 9-11 pph Process Aid, 2.475-2.525 pph Tin Stabilizer, 0.9-1.1 pph Ester Wax, 0.9-1.1 pph OPE (oxidated polyethylene) Wax, 2.7-3.3 pph Impact Modifier, and 2.7-3.3 TiO2.
In a preferred form, the composition comprises 50-100 pph of CPVC, 0-50 pph of PVC, and the fire retardant is of an amount sufficient such that the product made from the composition meets the fire-retardant standards.
Al Trihydrate can be used as the fire retardant and can comprise 0-50 pph of the composition.
In the currently most preferred form, the composition comprises 80 pph of CPVC, 20 pph of PVC, and 30 pph of Al Trihydrate.
In another aspect, the invention relates to a composition suitable for extruding a fire-retardant product, comprising 50-100 pph CPVC, 0-50 pph PVC, and a fire retardant in sufficient amount such that the product made from the composition is fire retardant.
The invention also relates to a slat for use in a slotwall, comprising a body having a front and a rear face; at least one channel formed in the body and opening onto the front face; and the body being made from a composition such that the body meets at least one of the ASTM E84-01 and UL 723 fire retardant standards.
The composition forming the body preferably comprises 50-100 pph of CPVC, 0-50 pph of PVC, and 0-50 pph of Al Trihydrate. In a currently most preferred form, the composition comprises 80 pph of CPVC, 20 pph of PVC, and 30 pph of Al Trihydrate.
The composition can include other ingredients, such as: 2.7-3.3 pph Zeolite, 0.36-0.44 pph Blowing Agent, 9-11 pph Process Aid, 2.475-2.525 pph Tin Stabilizer, 0.9-1.1 pph Ester Wax, 0.9-1.1 pph OPE Wax, 2.7-3.3 pph Impact Modifier, and 2.7-3.3 TiO2.
The invention also relates to a method for making a fire-retardant element of a predetermined configuration for use in a slotwall. The method comprises the steps of: forming a composition by mixing 50-100 pph of CPVC, 0-50 pph of PVC, and a fire retardant in a sufficient amount such that the element made from the composition meets at least one of the ASTM E84-01 and UL 723 fire retardant standards; extruding the composition to form a blank; and finishing the blank to form the element with the predetermined configuration.
The mixing can also include adding 0-50 pph Al Trihydrate as the fire retardant. The mixing can yet include the addition and mixing of 2.7-3.3 pph Zeolite, 0.36-0.44 pph Blowing Agent, 9-11 pph Process Aid, 2.475-2.525 pph Tin Stabilizer, 0.9-1.1 pph Ester Wax, 0.9-1.1 pph OPE Wax, 2.7-3.3 pph Impact Modifier, and 2.7-3.3 TiO2 along with the CPVC, PVC, and the Al Trihydrate.
In a preferred mixing process, the CPVC, Tin Stabilizer, and Zeolite are first mixed together until either the mixture temperature reaches a first predetermined temperature or for approximately 3 minutes. The Blowing Agent, Process Aid, Ester Wax, OPE Wax, Impact Modifier, TiO2 and the Al Trihydrate are then mixed with the CPVC, Tin Stabilizer, and Zeolite until either the mixture temperature reaches a second predetermined temperature, which is higher than the first predetermined temperature, or for approximately 3 minutes. The mixture is then cooled to a third predetermined temperature, which is lower than the second predetermined temperature, and the PVC is then added to and mixed with the mixture as it is cooled.
The finishing step can further comprise forming the blank into a shape having substantially the same cross section as the predetermined configuration. The forming step can included forming a channel in the blank suitable for use in a slotwall. After the initial forming, the blank is sized in accordance with the predetermined configuration. The sized blank is then pulled to reduce its thickness.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial perspective view of a slotwall panel for use in forming a slotwall in accordance with the invention.
FIG. 2 is a schematic view illustrating an extrusion process suitable for forming the slotwall panels of FIG. 1 .
FIG. 3 is a flowchart illustrating the major steps for the extrusion process of FIG. 2 .
DESCRIPTION OF THE INVENTION
FIG. 1 illustrates an extruded slotwall panel 10 suitable for forming a slotwall in accordance with the invention. The slotwall panel 10 can have a front face 12 and a rear face 14 , and upper and lower edges 16 , 18 , respectively. A series of inverted T-shaped slots 20 can be formed in the slotwall panel 10 such that they open onto the front face 12 and define T-shaped slats 21 and two half slats 23 each having edges 22 , which overlie the corresponding slot 20 . The slotwall panel 10 can be used in a slotwall panel storage system as disclosed in pending U.S. patent application Ser. No. 10/331,826, filed on Dec. 30, 2002 and hereby incorporated herein by reference.
The front face 12 comprising slats 21 and half slats 23 is generally planar except where interrupted by the slots 20 . The rear face 14 has an undulating surface that can follow the contour of the slots 20 . The rear face 14 could have a planar surface with the recesses being filled by solid material. However, to reduce the weight of the overall slotwall and the cost of manufacturing, it is preferred to optimize the amount of material when making the slotwall panel 10 .
The upper end 16 includes a longitudinal rib 24 , which corresponds to a longitudinal recess 26 formed in the lower end 18 . Slotwall panels 10 can be attached to a framed wall or similar building structure element, with horizontally orientated slotwall panels 10 stacked vertically such that the longitudinal rib 24 of one slotwall panel is received in the longitudinal recess 26 of the adjacent slotwall panel.
It is worth noting that while for simplicity sake the invention is described in the context of the extruded slotwall panel 10 , the invention is not limited to any particular slotwall element, e.g. a panel, sheet, slotwall panel, etc. Nor is the invention limited to any particular configuration for a particular slotwall element.
The slotwall panel 10 can be extruded using a well-known extrusion apparatus 40 , which is schematically illustrated in FIG. 2 . The extrusion apparatus 40 can form a manufacturing line in which the raw ingredients forming the slotwall panel 10 are mixed, then extruded into the desired shape, and finally cut into the desired length. The extrusion apparatus 40 begins with a mixer 42 , which mixes the various ingredients of the composition used to form the slotwall panel 10 . The mixer 42 can be supplied the ingredients from multiple hoppers 44 , each of which contains one of the elements of the composition forming the slotwall panel 10 . The mixer 42 comprises a mixing chamber 46 that is connected to the hoppers 44 . An agitator (not shown), that can be in the form of a rotating screw, can be provided in the mixing chamber 46 for stirring the ingredients. A heating element (not shown) or similar device can be provided with the mixing chamber 46 for heating the ingredients as they are stirred to form the extrusion composition.
The mixed ingredients can be fed to a cooler 48 to cool the mixture. The mixture is usually water-cooled and can include an agitator to continue the stirring of the mixture as it is cooled.
The cooled mixture can be fed through a screen 50 to remove any lumps or contaminants.
In order to form slotwall panels 10 , the screened mixture can be fed to a hopper 54 of an extruder 56 , which has a die 58 shaped to correspond to the cross-section of the slotwall panel 10 , such that the material leaving the die 48 is roughly shaped to the slotwall panel 10 . The mixed extrusion composition can be fed from the mixer 42 directly to the hopper 54 . Alternatively, the mixed extrusion composition can be fed into a temporary container, whose contents are then fed into the hopper 54 of the extruder 56 .
The extruder 56 can be a screw-type extruder, which can have one or multiple screws. The extruder 56 can also include a heating element (not shown) for heating the mixed extrusion composition as it passes through the extruder 56 . The extruder 56 can have additional hoppers or similar devices for introducing elements into the mixture as it passes through the extruder 56 . For example, a hopper 62 can be provided for adding a colorant.
The output or extrudate of the die 58 can be fed into a vacuum calibrator 66 , which performs an initial shaping operation on the material. The vacuum calibrator 66 can be an exact negative of an oversized cross-section of the slotwall panel 10 . Holes are formed in the vacuum calibrator and are connected to a low pressure source such that a vacuum is applied to the material as it passes through the vacuum calibrator. The vacuum draws the material against the surface of the vacuum calibrator to shape the extrudate as it slides through the vacuum calibrator. The vacuum calibrator 66 can be cooled by circulating cold water therethrough.
The material leaving the vacuum calibrator 66 can be fed to a sizer 68 , which performs a final sizing operation on the material. The sizer 68 can be dimensioned to correspond almost identically to the dimensions of the final product, in this case the slotwall panel 10 . The sizer 68 can be located within a water bath 70 , which cools the extruded material.
After final sizing, the water remaining on the extruded material can be removed by passing the extruded material through a forced air station 72 . The forced air station 72 blows pressurized air onto the surfaces of the extruded material to blow away any water remaining thereon.
After removing the excess water, the material can be stretched by a puller 74 , which comprises a pair of tracks 76 between which the material passes. The tracks are rotated at a rate greater than the extrusion speed of the material, resulting in the stretching of the material as it passes through the puller 74 .
The stretched material can be carried into a cutting station 78 , which cuts the material into slotwall panels 10 of a desired length. The cutting station 78 can be a saw, but other types of cutters can be used. The slotwall panels 10 can then prepared for packaging and shipping.
One advantage of the slotwall panel 10 is that it is made from a composition that renders the slotwall panel 10 fire retardant or fire resistant. The term fire-retardant is used in this application, but those skilled in the art will understand that fire resistant could be used instead of fire-retardant to describe the properties of the slotwall panel material. The fire-retardant characteristic of a product, such as the slotwall panel 10 , can be measured against known standards, which are currently ASTM E84-01 by ASTM, 100 Barr Harbor Drive, West Conshohocken, Pa. 19428-2959, and UL 723, by Underwriters Laboratories, Inc., 333 Pfingsten Road, Northbrook, Ill. 60062-2096.
Both of these standards are applicable to building construction materials and have a two-prong criteria for determining whether a product is fire retardant. The two prongs are the flame spread rate and the smoke generation. For a product to be flame retardant, it must meet or exceed the threshold values for both the flame spread and smoke generation. The composition used to make the slotwall panel 10 in accordance with the invention results in a product that satisfies both the flame spread and smoke generation requirements for the identified standards.
The threshold values for the flame spread and smoke generation vary depending on the class of building materials. The described standards include three Wall and Ceiling Finishes Classifications: A, B, C. Class C is applicable to residential garage construction and is the lowest of the three standards. The flame spread threshold values are 25 Class A, 75 for Class B and 200 for Class C. The smoke generation threshold value for all three classes is 450. As long as the flame spread and smoke generation values are less than or equal to these threshold values, the product is considered fire retardant for that class. For the slotwall panel 10 to be used in a slotwall panel storage system in a garage as disclosed in co-pending patent application US20020232, the term fire retardant means the slotwall panel 10 , meets the threshold value for at least Class C.
The composition of one embodiment of the extruded slotwall panel 10 material according to the invention is set forth in Table 1, which lists the ingredients forming the composition, and for each ingredient, lists an exemplary sample, the Parts per Hundred of Resin by weight (PHR), and the percent weight of the entire composition.
TABLE 1
Composition
Ingredient
Exemplary Material
PHR (by Weight)
% Weight
CPVC
Kaneka H727
80
52
PVC
Georgia Gulf 5385
20
13
Al Trihydrate
Aluchem AC400
30
19.5
Zeolite
PQ Corp 401P
3.0
1.95
Blowing Agent
Bergen XO-118
0.4
0.25
Process Aid
Rohm & Haas K400
10
6.5
Tin Stabilizer
Rohm & Haas TM181
2.5
1.6
Ester Wax
Cognis G70
1
0.65
OPE Wax
Honeywell AC629A
1
0.65
Impact Modifier
Atofina DS
3
1.95
TiO 2
DuPont R102
3
1.95
Totals
153.9
100
The first two ingredients CPVC (chlorinated polyvinyl chlorine) and PVC (polyvinyl chlorine) form the resin mixture, which forms the core of the composition. The quantity of the remaining ingredients is referred to in terms of the resin mixture. For example, the resin mixture of the preferred composition comprises 80 parts by weight of CPVC and 20 parts by weight of PVC. The CPVC and PVC form 100% or 100 parts by weight of the resin mixture. The quantity (parts) of the remaining ingredients is described in terms of their relation to the resin mixture. For example, the Al Trihydrate is 30 parts by weight of the resin mixture. In other words, for every 100 lbs of resin mixture, 30 lbs of Al Trihydrate is added to the composition. The PHR values can be analogized to the measurements for a recipe to the composition.
The % Weight column shows the percentage of weight that the particular ingredient comprises of the entire composition. For example, the entire composition has 153.9 parts. The CPVC comprises 80 parts of the entire composition and 52% of the weight (80/153.9*100) of the composition.
The first three ingredients in the composition of the slotwall panel material (CPVC, PVC, and Al Trihydrate) impact the fire retardant characteristic of the resulting extruded slotwall panel 10 . The remaining ingredients in the composition are known in the extrusion of PVC and their function is well known. Therefore, the discussion of the ingredients for the composition of the slotwall panel material will focus on the first three ingredients, which impact the fire retardant characteristic of the resulting product extruded from the composition.
CPVC and PVC, from a mechanical standpoint, have similar characteristics for those characteristics relevant to the extrusion of the slotwall panel 10 . However, the CPVC and PVC differ in some of their flame retardant properties. While both CPVC and PVC have relatively low oxygen content, which retards the tendency for a flame to spread, CPVC does retard flame spread better than PVC. Of greater distinction are the smoke generation characteristics of the compounds. When exposed to fire, PVC generates a substantial amount of smoke, especially in comparison to CPVC. The smoke generation must be controlled to satisfy the fire retardant standards. The Al Trihydrate is added to the composition to help control the smoke generation.
The composition of the material of the embodiment of Table 1 balances multiple criteria for a marketable and fire retardant composition suitable for use in extruding a slotwall panel 10 for a slotwall storage system that can be used in residential construction. One consideration is to ensure that the resulting product made from the composition satisfies the fire retardant standards. Another consideration is the cost of the composition, which is impacted by the CPVC being substantially more costly than the PVC. Thus, the quantities of the preferred composition are inherently in conflict when the goal is to produce a low-cost, fire retardant slotwall panel. For example, it is desirable for cost reduction purposes to minimize the amount of CPVC used in the composition, which will result in an increase in the amount of PVC. However the increased PVC will negatively impact the fire retardant characteristic of the composition, especially the smoke generation characteristic, and require an increase in Al Trihydrate to reduce the smoke generation attributable to the increased PVC content. Of course, the addition of more Al Trihydrate in the composition necessarily results in an increased cost of the composition.
Slotwall panels 10 made from the composition of the embodiment of Table 1 easily meeting the fire retardant standards.
The composition illustrated in the embodiment of Table 1 strikes a balance between the competing criteria. However, variations in the quantities of the CPVC, PVC and Al Trihydrate from the quantities of the composition illustrated in the embodiment of Table 1 can be used and still achieve a cost-effective and fire-retardant slotwall panel 10 for a slotwall storage system. It has been found that the CPVC can vary between 60 to 100 parts of the resin mixture, the PVC can correspondingly vary between 40 to 0 parts of the resin mixture, and the Al Trihydrate can very between 20 to 50 parts of the composition and still yield a desirable fire retardant product. While Al Trihydrate is the fire retardant in the composition of the embodiment of Table 1, other fire retardants can be used in its place.
Table 2 illustrates the impact on the flame spread and smoke generation characteristics in response to variations in the amount of CPVC, PVC, and Al Trihydrate. The samples in Table 2 are identical except for the variation of CPVC, PVC, and Al Trihydrate.
TABLE 2
Effect on Flame Spread and Smoke Generation as
a function of the variation in CPVC, PVC, and Al Trihydrate
CPVC
PVC
AL Trihydrate
Sample
(PHR)
(PHR)
(PHR)
Flame
Smoke
1
100
0
15
9.20
389.00
2
100
0
30
9.80
183.00
3
100
0
45
7.30
160.00
4
80
20
30
9.00
313.60
5
75
25
15
10.20
615.00
6
75
25
30
9.72
359.10
7
75
25
45
12.50
339.00
8
50
50
15
10.30
878.00
9
50
50
30
8.12
515.10
10
50
50
45
6
299
The data shows that the smoke score improves as more Al Trihydrate is added, Also, the flame spread and and smoke generation scores worsen as the relative amount of PVC is increased. However, flame retardant samples can still be achieved with high percentages of PVC when used in combination with a large amount of Al Trihydrate, see sample 10 .
Table 3 illustrates the currently known range of quantities for the ingredients of the composition that will result in a satisfactory flame-retardant product when extruded.
TABLE 3
Ranges in Ingredients for the Composition
Ingredient
Exemplary Material
PHR (by Weight)
CPVC
Kaneka H727
50-100
PVC
Georgia Gulf 5385
50-0
Al Trihydrate
Aluchem AC400
15-50
Zeolite
PQ Corp 401P
2.7-3.3
Blowing Agent
Bergen XO-118
0.36-0.44
Process Aid
Rohm & Haas K400
9-11
Tin Stabilizer
Rohm & Haas TM181
2.475-2.525
Ester Wax
Cognis G70
0.9-1.1
OPE Wax
Honeywell AC629A
0.9-1.1
Impact Modifier
Atofina DS
2.7-3.3
TiO 2
DuPont R102
2.7-3.3
The invention lies in the proportion of the CPVC, PVC and Al Trihydrate forming the composition. The processing of the composition from raw materials to finish product done in accordance with the invention ensures that the end product will have desired structural and fire retardant characteristics.
FIG. 3 illustrates the main steps in the process 100 for taking the raw materials of the composition of the embodiment of Table 1 and converting them into a finished product. The process 100 begins by mixing the raw ingredients of Table 1 at step 102 . The mixing step 102 is complicated because of the different characteristics of the materials mixed. Most notably, PVC is susceptible to degradation or damage at a much lower temperature than CPVC. Care must be taken during the processing to make sure the PVC is not damaged.
The mixing step 102 begins by adding the CPVC, tin stabilizer, and Zeolite into the mixer 42 as quickly as possible. The three ingredients can be mixed at high speed until the temperature of the mixture reaches approximately 175 F, which takes approximately three minutes. The remaining ingredients, except for the PVC, can then be added in the order as listed in table 1, except that the Al Trihydrate can be added after the process aid. The resulting mixture can then be mixed in the mixer 42 on high speed until the temperature reaches 220 F, which takes approximately three minutes.
The mixture can then be cooled to approximately 130 F, such as by placing the mixture into a standard, water-jacketed, ribbon blender-type cooler. The PVC can then be added to the mixture in the cooler and blended with the other materials while the mixture is cooled to approximately 130 F, which takes approximately six minutes.
Once the mixing of all the ingredients is completed and the composition is cooled to the desired temperature, the composition can be passed through screen 50 to screen out any lumps or contamination. A 20 mesh screen can be used. After the material is screened, it can be transferred directly to the hopper 54 of the extruder 56 at step 104 . Alternatively, the composition can be pre-mixed prior to the time for extrusion and stored in suitable containers, such as polyethylene lined boxes, with the liner being closed after filling.
The composition in the hopper 54 of the extruder 56 can be extruded through the die 58 at step 106 to form an extrudate. The extrudate leaving the die 58 can be thought of as a continuous blank, which is formed and sized in subsequent finishing steps.
The extrudate exiting the die 58 can then be passed through the vacuum calibrator 66 to form the blank at step 108 . The vacuum of the vacuum calibrator 66 pulls the blank against the vacuum calibrator 66 to form the blank into the general shape of the slotwall panel 10 . The blank can be cooled while being calibrated since the vacuum calibrator 66 is cooled.
The calibrated blank can then be sized at step 110 by pulling the calibrated blank through the sizer 68 , which has an opening with cross section similar in shape to the cross section of the slotwall panel 10 , except slightly larger. The sizer 68 functions in a manner similar to a die. Since the sizer is positioned within a water bath, the blank can be cooled as it passes through the sizer 68 .
The sized blank can then be pulled at step 112 to stretch the blank and slightly reduce its thickness. The pulling of the sized blank can be accomplished by passing the sized blank between the tracks 76 .
After the pulling step 112 , the pulled blank can be cut at step 114 into the desired length to form the slotwall panel 10 . Preferably the cutting can be accomplished by using a saw. However, any cutting device (shears, laser, etc.) can be used. The slotwall panels 10 can then be packed for delivery.
The same main steps in the process 100 can be used for taking raw materials from the range of composition percentages set forth in Table 3 in the same manner as for the composition of the embodiment of Table 1 to form slotwall panels 10 .
While the invention has been specifically described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not of limitation, and the scope of the appended claims should be construed as broadly as the prior art will permit. | A fire retardant slotwall panel material having multiple slots forming multiple slats on which brackets and other devices can be mounted. The composition of the material for extruding the slotwall panels comprises CPVC, PVC and a fire retardant so that the resulting product will meet at least one of the ASTM E84-01 and UL 723 fire retardant standards. The composition can comprise 60-100 PHR of CPVC, 40-0 PHR of PVC and 20-50 PHR of fire retardant that can be AL Trihydrate. The composition of the material can include other ingredients such as: 2.7-3.3 PHR Zeolite, 0.36-0.44 PHR Blowing Agent, 9-11 PHR Process Aid, 2.475-2.525 PHR Tin Stabilizer, 0.9-1.1 PHR Exter Wax, 0.9-1.1 PHR OPE Wax, 2.7-3.3 PHR Impact Modifier, and 2.7-3.3 PHR TiO 2 . | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. Ser. No. 10/736,342 filed Dec. 15, 2003, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to a method for controlled increase of tilt angle of liquid crystal molecules by onium salts and to an aligned layer of liquid crystal molecules on a substrate having an orientation layer and a liquid crystal layer containing onium salt effective to increase the tilt angle of liquid crystal molecules.
BACKGROUND OF THE INVENTION
[0003] The vast majority of liquid crystal displays (LCD) require uniform liquid crystal (LC) molecular orientation, usually with a small angle between the LC director n and substrate; this angle is called the “pretilt” angle. A number of methods have been used to achieve tilted alignment of LCs. These are described in detail in Fundamentals and Applications of Liquid Crystals , published by Industrial Survey Association (1991). The most common technique to achieve oblique alignment involves deposition of a thin polymer layer on the substrate, which is subsequently rubbed. Rubbing of the polymer determines the azimuthal orientation of the LC molecular alignment, and induces a non-zero pretilt angle. Polyimide (PI) films are commonly used for rubbing alignment of LC's because of their outstanding thermal stability, low dielectric constant, excellent chemical resistance and high productivity. Furthermore, LC alignment on rubbed Pi film generally provides a stable pretilt angle preventing reverse tilt disclination of LC molecules with applied voltage. However, the pretilt angle depends on the properties of the orientation film itself. Thus to satisfy specific pretilt angle requirements for various LCD modes, specific polyimides have been made for controlling the pretilt angle. For example, polyimides with long alkyl and fluorinated alkyl side groups have been used to generate high LC pretilt angles. It has been suggested that steric interaction between LC molecules and branched long alkyl side chains is a possible cause for high pretilt angles.
[0004] The rubbing method suffers from several drawbacks, however, especially accumulation of static charges at the thin film transistor sites and generation of dust particles. Recently, new non-rubbing alignment techniques, based on photo-induced anisotropy of the polymerizable orienting layers, have been introduced. Typically the photosensitive polymer films are illuminated by polarized ultraviolet light, and the azimuthal orientation of the resulting planar alignment depends on the specifics of the photo-induced reaction. In contrast to the rubbing technique, neither excess charge nor dust is created on the substrates, yet control is maintained over both the tilt angle and the anchoring strength. The traditional rubbing technique establishes a unique direction of the tilted easy axis; this direction is determined by the direction of rubbing. On the other hand, for photoalignment there is a twofold degeneracy of the light-induced easy axis. This twofold degeneracy causes poor reproducibility of the pretilt angle and, more importantly, the appearance of defects at the resulting boundaries between orientation domains. This degeneracy may be partially removed during the filling of the LC cell because of the effect of flow alignment, but the resulting alignment is not temporally stable. To date, the most promising method to break this degeneracy involves oblique irradiation of the photoalignment layer. Oblique polarized irradiation makes an angle with the surface and the photoreaction for on-axis transition moments is much easier than that of off-axis ones. Consequently the tilt degeneracy is broken and the liquid crystals tilt in a preferred direction. Such an irradiation scheme requires specialized equipment and have proven difficult to implement in a large scale process.
[0005] Other non-contact for aligning LC molecules include a stretched polymer, a Langnuir Blodgett film, a grating structure produced by microlithography, oblique angle deposition of silicon oxide, and ion beam irradiation of a polyimide surface as in U.S. Pat. No. 5,770,826. The method places the LC's on a polyimide surface which has been bombarded with low energy (about 100 eV) Ar + ions.
[0006] This method has been extended to include diamond-like carbon (DLC), amorphous hydrogenated silicon, SiC, SiO 2 , glass, Si 3 N 4 , Al 2 O 3 , CeO 2 , SnO 2 , and ZnTiO 2 films as described in U.S. Pat. No. 6,020,946.
[0007] JP 2002038158 discloses a method for the formation of a liquid crystal layer containing liquid crystal molecules on a substrate and the orientation of the liquid crystal molecules. A pyridinium quaternary salt is added to the liquid crystal layer or a layer adjacent to it, and the inclination angle of the liquid crystal molecules is controlled by the action of the pyridinium quaternary salt. Although this invention provides an advantage in controlling the tilt angle of liquid crystal over other existing methods, it only provides a limited class of molecules that are capable of increasing the tilt; thus, further new materials for inducing LC pretilt are needed.
[0008] In all the methods of LC alignment described above, control of LC pretilt angle requires the use of a specific combination of the LC molecules and the alignment polymer or specific materials. Developing and optimizing such combination (of alignment polymers and LC's) is a difficult and time-consuming process. There is a need for alternative ways to control the pretilt angle of liquid crystal to the desired angle and in an easy manner.
SUMMARY OF THE INVENTION
[0009] The invention provides a process for forming a fixed liquid crystal layer having a predetermined tilt on an orientation layer that comprises:
a) adding a predetermined amount of an onium salt to a liquid crystal pre-polymer coating solution containing a liquid crystal pre-polymer and a UV initiator selected from the group consisting of benzophenone and acetophenone and their derivatives; benzoin, benzoin ethers, benzil, benzil ketals, fluorenone, xanthanone, alpha and beta naphthyl carbonyl compounds and ketones; b) coating the solution over the orientation layer; c) drying the coating to form a layer; and then d) UV irradiating the layer to fix the liquid crystal molecules.
BRIEF DESCRIPTION OF THE DRAWING
[0014] FIG. 1 is a cross-sectional schematic of a multilayer product of the invention process.
DETAILED DESCRIPTION OF THE INVENTION
[0015] All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc., 1995. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
[0016] The present invention provides a method for controlled tilt increase of oriented liquid crystal molecules by added onium salts as summarized above. The current invention is described by referring to FIG. 1 which shows a cross-sectional schematic view of an oriented liquid crystal multilayer film 5 . This structure comprises a substrate 10 of transparent material, such as glass or polymer. It should be understood that to be called as a substrate, a layer must be solid and mechanically strong so that it can stand alone and support other layers. A typical substrate is made of triacetate cellulose (TAC), polyester, polycarbonate, polysulfone, polyethersulfone, or other transparent polymers, and has a thickness of 25 to 500 micrometers. Substrate 10 typically has low in-plane retardation, preferably less than 10 nm, and more preferably less than 5 nm. In some other cases, the substrate 10 may have larger in-plane retardation (some short discussion of the relevance of retardation might be useful here or in the introduction) between 15 to 150 nm. Typically, when the substrate 10 is made of triacetyl cellulose, it has out-of-plane retardation around −40 nm to −120 nm. This is a desired property when the compensator is designed to compensate a liquid crystal state with an ON voltage applied. The in-plane retardation discussed above is defined as the absolute value of (n x −n y )d and the out-of-plane retardation discussed above is defined as [(n x +n y /2)−n z ]d, respectively. The refractive indices n x and n y are along the slow and fast axes in plane of the substrate 10 , respectively, n z is the refractive index along the substrate thickness direction (Z-axis), and d is the substrate 10 thickness. The substrate is preferably in the form of a continuous (rolled) film or web. Glass plates, ITO substrates, color filter substrates, quartz plates, silicon wafers, can also be used as substrates.
[0017] The substrate 10 can be used alone or as a pair. In the case of usage as a pair, if necessary, a spacer, a sealing agent or the like can also be used. In this invention, it is preferable that the layer adjacent to the liquid crystal layer is the layer nearest the liquid crystal layer 30 among the layers located between the substrate and the liquid crystal layer 30 . It is also acceptable that the layer adjacent to the liquid crystal layer 30 functions as an orientation film or a transparent electrode.
[0018] On the substrate 10 , an orientation layer 20 is applied, and a liquid crystal layer 30 is disposed on top of layer 20 . The orientation layer 20 can be oriented by various techniques. In one example, the orientation layer contains a rubbing-orientable material such as a polyimide or polyvinyl alcohol and can be oriented by a rubbing technique. In another example, the orientation layer 20 contains a shear-orientable material and can be oriented by a shear-alignment technique. In another example, the orientation layer 20 contains an electrically- or magnetically-orientable material and can be oriented by an electrical- or magnetic-alignment technique. In another example, the orientation layer can also be a layer of SiOx fabricated by oblique deposition. In another example, the orientation layer 20 contains a photo-orientable material and can be oriented by a photo-alignment technique. Photo-orientable materials include, for example, photo isomerization polymers, photo-dimerization polymers, and photo-decomposition polymers. In a preferred embodiment, the photo-orientable materials are cinnamic acid derivatives as disclosed in U.S. Pat. No. 6,160,597. Such materials may be oriented and simultaneously cross-linked by selective irradiation with linear polarized UV light.
[0019] Mainly liquid crystal molecules constitute the liquid crystal layer 30 . As the liquid crystal molecules, discotic liquid crystal molecules, rod-shaped (nematic) liquid crystal molecules, and cholesteric liquid crystal molecules can be used. Nematic liquid crystal molecules are especially preferred. Two or more types of liquid crystal molecules can also be used in combination. Components (such as a colorant, a dopant for tilt angle increase, dichroic colorant, polymer, polymerizing agent, sensitizing agent, phase transition temperature depressant, and stabilizer) can also be added to the liquid crystal layer in addition to the liquid crystal molecules. A variety of well established methods can be used to apply the liquid crystal layer 30 to the substrate. Accordingly, liquid crystal layer 30 can be coated on the orientation layer 20 using, the curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, printing coating method, and the like.
[0020] In one embodiment of the invention, the liquid crystal layer 30 is typically a nematic liquid crystalline pre-polymer when it is first disposed on the orientation layer 20 , and is cross-linked by a further UV irradiation, or by other means such as heat. In a preferred embodiment, the anisotropic layer contains a material such as a diacrylate or diepoxide with positive birefringence as disclosed in U.S. Pat. No. 6,160,597 (Schadt et al.) and U.S. Pat. No. 5,602,661 (Schadt et al). The optic axis in the anisotropic layer 30 is usually tilted relative to the layer plane, and varies across the thickness direction. The anisotropic layer 30 in accordance with the present invention is applied from a liquid medium containing a onium salt or a mixture of onium salts.
[0021] The onium salt increases the tilt angle of the liquid crystal molecules in layer 30 without detrimentally affecting its adhesion to orientation layer 20 .
[0022] In the present invention, onium salt is used for controlled increase of liquid crystal molecules tilt angle. In the scope of the invention, the onium salts are periodic group Va, VIa, and VIIa cations represented by general formula I below.
(R) b M + X − I
Wherein, R is a straight, branched or cyclic alkyl of 1 to 12 carbon atoms, an aryl of 6 to 12 carbon atoms, or an arylalkyl of 7 to 12 carbon atoms; cation M + is a cation chosen from periodic group Va, VIa, and VIIa; X − is a non-nucleophilic counter-ion; and the letter b is 2, 3, or 4.
[0023] R is a represent aromatic groups and generally have from 4 to 20 carbon atoms, may be selected from aromatic hydrocarbon rings, e.g. phenyl or naphthyl and hetero-aromatic groups including thienyl, furanyl and pyrazolyl, and may be substituted with alkyl groups, e.g. methyl, alkoxy groups, e.g. methoxy, chlorine, bromine, iodine, fluorine, carboxy, cyano or nitro groups, or any combinations thereof. Condensed aromatic-heteroaromatic groups, e.g. 3-indolinyl, may also be present.
[0024] When reference in this application is made to a particular group, unless otherwise specifically stated, the group may itself be unsubstituted or substituted with one or more substituents (up to the maximum possible number). For example, “alkyl” group refers to a substituted or unsubstituted alkyl group, such as arylalkyl group or sulfoalkyl group while “aryl” group refers to a substituted or unsubstituted aryl group (with up to six substituents) such as alkaryl or sulfoaryl group. The substituent may be itself substituted or unsubstituted. Examples of substituents on any of the mentioned groups can include known substituents, such as: chloro, fluoro, bromo, iodo; hydroxy; alkoxy, particularly those “lower afkyl” (that is, with 1 to 12 carbon atoms, for example, methoxy, ethoxy; substituted or unsubstituted alkyl, particularly lower alkyl (for example, methyl, trifluoromethyl); thioalkyl (for example, methylthio or ethylthio), particularly either of those with 1 to 12 carbon atoms; substituted or unsubstituted alkenyl, preferably of 2 to 12 carbon atoms (for example, ethenyl, propenyl, or butenyl); substituted and unsubstituted aryl, particularly those having from 6 to 20 carbon atoms (for example, phenyl); and substituted or unsubstituted heteroaryl, particularly those having a 5 or 6-membered ring containing 1 to 3 heteroatoms selected from N, O, or S (for example, pyridyl, thienyl, furyl, pyrrolyl); acid or acid salt groups; such groups as hydroxyl, amino, alkylamino, cyano, nitro, carboxy, carboxylate, acyl, alkoxycarbonyl, aminocarbonyl, sulfonamido, sulfamoyl, sulfo, sulfonate, or alkylammonium; and other groups known in the art. Alkyl substituents may specifically include “lower alkyl” (that is, having 1-12 carbon atoms), for example, methyl, ethyl, and the like. Further, with regard to any alkyl group or alkylene group, it will be understood that these can be branched or unbranched and include ring structures.
[0025] In a useful embodiment, the onium salts in the present invention are represented by formula (II):
(R) 2 M + X − II
wherein, R and X are as difined for formula (I) and M + is a halonium cation chosen from periodic group VIIa. Illustrative examples of the periodic group VIIa onium salts are shown below, but the invention is not limited to thereto.
[0026] In a further useful embodiment, the onium salts in the present invention are represented by formula (III):
(R) 3 M + X − III
wherein, R and X are as described for formula (I) and M + is a cation chosen from periodic group VIa. Illustrative examples of the periodic group Via onium salts are shown below, but the invention is not limited to thereto.
[0027] In a useful embodiment, the onium salts in the present invention are represented by formula (IV):
(R) 4 M + X − IV
wherein, R and X are as defined for formula (I) and M + is a cation chosen from periodic group Va.
[0028] Other suitable onium salts include those contained as part of a polymeric structure linked by the R groups of the salt.
[0029] In general onium salts are soluble in the coating solvent and addition of these salts to liquid crystal layer 30 does not change the refractive index of the liquid crystal layer 30 by more than about ±10 percent. More preferably such onium salts will not change the refractive index of the liquid crystal layer 30 by more than ±5 percent. Most preferably such refractive index will not change the refractive index of the liquid crystal layer 30 by more than ±2 percent. In addition, such onium salts are desirably capable of increasing the average tilt of the liquid crystal layer 30 by more than 30%. More preferably such onium salts will increase the average tilt of the liquid crystal layer 30 by more than 50%. Most preferably such onium salts are capable of increasing the average tilt of the liquid crystal layer 30 by more than about 95%.
[0030] The onium salt can be added into a coating solution of liquid crystal layer 30 . The onium salt is added in an amount appropriate to attain the desired tilt angle increase of the liquid crystal molecules without disturbing the orientation of the liquid crystal layer 30 . Typically, the onium salt is added up to 10 wt % of the anisotropic layer 30 . Usually, up to 5 wt % of the anisotropic layer and normally less than 2 wt % of the anisotropic layer is sufficient. The amount of the onium salt added is dependent on both the composition of the liquid crystal layer 30 and the tilt increase desired since both of these can impact the target.
[0031] The anisotropic layer may also contain addenda such as surfactants, light stabilizers and UV initiators. UV initiatiors include materials such as benzophenone and acetophenone and their derivatives; benzoin, benzoin ethers, benzil, benzil ketals, fluorenone, xanthanone, alpha and beta naphthyl carbonyl compounds and ketones. Preferred initiators are alpha-hydroxyketones.
[0032] The present invention is illustrated in more detail by the following non-limiting examples.
[0033] In examples described below in-plane retardation was measured to assess the quality of liquid crystal alignment. For samples with tilt angles near zero, the measured (effective) birefringence of the LC layer should be between 0.12-0.13. However, as tilt angle increases, the effective birefringence decreases. For a series of examples of approximately the same layer thickness, this should result in decreasing in plane retardation with increasing tilt angle. This is exactly what is seen for these examples, confirming good alignment for all examples.
EXAMPLE 1
Comparison
[0034] This example demonstrates the photo-alignment of liquid crystal molecules on a photo-aligned layer on a glass substrate.
[0035] On a clean glass plate, a coating solution containing a mixture of VANTICO Staralign™ 2110 and Staralign™ 2100 photo-aligning vinyl cinnamate polymers (in 30:70 wt % ratio; 1 wt % total solids in methyl ethyl ketone) was spun cast ((@ 700-1000 rpm). The sample was dried at 55° C. for 5 min. and then exposed to 308 nm polarized light (15-30 mJ/cm 2 ) at an inclination of 20 degrees away from normal angle of incidence to obtain a photo-aligned orientation layer. Typically this produced a 30-100 nm thick layer as measured by ellipsometry.
[0036] On the orientation layer a solution of liquid crystal prepolymer (LCP, CB483MEK from Vantico Co, 7 wt % in methyl ethyl ketone, supplied with photoinitiator) in methyl ethyl ketone was spun cast @ 700-1000 rpm. The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and the anisotropic layer was fixed by exposing to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen. In-plane retardation measurement indicated that liquid crystal molecules were aligned parallel to the direction of polarized irradiation. In-plane retardation, average tilt angle, and thickness of the anisotropic layer were measured by ellipsometry (J. A. Woollam Co., Model M2000V). The measured average tilt angle method had accuracy of +2.0 degrees.
EXAMPLE 2
Inventive
[0037] This example shows that addition of di(4-tert-butylphenyl)iodonium trifluoroacetate (1-3) salt to liquid crystal layer comprising of two liquid crystal molecules increases the average tilt angle.
[0038] A photo-aligned orientation layer was prepared as in Example 1. Di(4-tert-butylphenyl)iodonium trifluoroacetate (I-3) (0.25-1.5 wt % of dried liquid crystal layer) was added to LCP mixture CB483MEK (7 wt % solution with photoinitiator obtained from Vantico Co.) and spun cast on the orientation layer (@ 700-1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and liquid crystal layer cross-linked by exposing to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen.
TABLE I In Plane Wt % of Layer Retardation Average added Thickness, nm (measured @ Tilt Angle I-3 (nm) 550 nm) (± 2° ) Comparison 0 wt % 616 64 12 Example. 1 Inventive 0.25 wt % 592 48 15 Example. 2 0.50 wt % 552 48 27 2.0 wt % 594 47 33
The aforementioned examples in Table I clearly demonstrate that compared to comparison Example 1 addition of I-3 to liquid crystal layer in Inventive Example 2 increases the average tilt angle of liquid crystal molecules.
EXAMPLE 3
Inventive
[0039] This example shows that addition of diphenyliodonium hexafluorophosphate (II-1) salt to liquid crystal layer increases the average tilt angle.
[0040] A photo-aligned orientation layer was prepared as in Example 1. Diphenyliodonium hexafluorophosphate (II-1) (0.25-1.5 wt % of dried liquid crystal layer) was added to LCP mixture CB483MEK (7 wt % solution with photoinitiator obtained from Vantico Co.) and spun cast on the orientation layer (@ 700-1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and liquid crystal layer was cross-linked by exposure to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen.
TABLE II In Plane Wt % of Layer Retardation Average added Thickness, nm (measured @ Tilt Angle II-1 (nm) 550 nm) (± 2° ) Comparison 0 wt % 616 64 12 Example. 1 Inventive 0.50 wt % 549 46 25 Example. 3 1.00 wt % 594 43 33
The aforementioned examples in Table II demonstrate that compared to comparison Example 1 addition of diphenyliodonium hexafluorophosphate (II-1) in Inventive Example 3 increases the average tilt angle of liquid crystal molecules.
EXAMPLE 4
Comparison
[0041] This example demonstrates the photo-alignment of a single liquid crystal molecule on a glass substrate.
[0042] Liquid crystals were prepared following the general procedure described in WO2000048985(A1). A solution of a mixture of liquid crystals was made following the general procedure disclosed in WO2000048985(A1). Thus, a 7% by weight mixture of liquid crystals was made by mixing LC—I in methyl ethyl ketone. IRGACURE 369 (2-Benzyl 2-dimethylamino 1-(4-morpholinophenyl) butanone-1) from Ciba-Giegy (1% by weight of LCs), TINUVIN-123 (his (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate) (1% by weight of LCs), and 2,6-di-tert-butyl-p-cresol (2% by weight of LCs) were added to the LC solution.
[0043] A photo-aligned orientation layer was prepared as in Example 1. On the orientation layer a solution of LC-1 prepared above in methyl ethyl ketone was spun cast (700-1000 rpm. The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and the anisotropic layer was fixed by exposing to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen. In-plane retardation measurement indicated that liquid crystal molecules were aligned parallel to the direction of polarized irradiation. In-plane retardation, average tilt angle, and thickness of the anisotropic layer were measured by ellipsometry (J. A. Woollam Co., Model M2000V). The measured average tilt angle method had accuracy of ±2.0 degrees.
EXAMPLE 5
Inventive
[0044] This example shows addition of 1-3 salt to liquid crystal layer comprising of one liquid crystal molecule (LC-1) increases the average tilt angle.
[0045] A photo-aligned orientation layer was prepared as in Example 1. Di(4-tert-butylphenyl)iodonium hexafluorophosphate (11-33) (0.25-1.5 wt % of dried liquid crystal layer) was added to the methyl ethyl ketone solution of crosslinkable diacrylate nematic liquid crystal solution (prepared above) and spun cast on the orientation layer (@ 700-1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and liquid crystal layer was cross-linked by exposing to 365 nm light (300-1000 (mJ/cm 2 ) under an atmosphere of nitrogen.
TABLE III In Plane Wt % of Layer Retardation Average added Thickness, nm (measured @ Tilt Angle II-33 (nm) 550 nm) (± 2° ) Comparison 0 wt % 449 53 8 Example. 4 Inventive 0.50 wt % 473 51 17 Example. 5
[0046] The aforementioned examples in Table III demonstrate that compared to comparison Example 4 addition of di(4-tert-butylphenyl)iodonium hexafluorophosphate (II-33) in Inventive Example 5 increases the average tilt angle of liquid crystal molecules.
EXAMPLE 6
Comparison
[0047] This example demonstrates the alignment of a liquid crystal mixture comprising two liquid crystal molecules on a rubbed poly(vinylalcohol) (PVA) alignment layer.
[0048] An aqueous solution of poly(vinylalcohol) (PVA) (0.5% by weight) was spun cast (@ 700-1000 rpm) on a glass substrate. Sample was dried at 120° C. for 2 hours and then subjected to a rubbing treatment.
[0049] On the rubbed orientation layer a solution of liquid crystal prepolymer (LCP CB483MEK from Vantico Co, 7 wt % in methyl ethyl ketone, supplied with photoinitiator) in methyl ethyl ketone was spun cast @ 700-1000 rpm. The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and the anisotropic layer was fixed by exposing to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen. In-plane retardation measurement indicated that liquid crystal molecules were aligned parallel to the direction polarized irradiation.
EXAMPLE 7
Inventive
[0050] This example demonstrates addition of diphenyliodonium hexafluorophosphate salt (II-1) salt to liquid crystal layer increases its average tilt angle on a rubbed poly(vinylalcohol) (PVA) alignment layer.
[0051] A rubbed orientation was prepared as in Example 11. Diphenyliodonium hexafluorophosphate salt (II-1) salt (0.5 wt % of dried liquid crystal layer) was added to LCP mixture CB483MEK (7 wt % obtained from Vantico Co) and spun cast on the orientation layer (@ 700-1000 rpm). The sample was then heated at a temperature of 55° C. for 3 minutes to orient the nematic liquid crystalline layer and remove solvent. The sample was cooled to room temperature and liquid crystal layer cross-linked by exposing to 365 nm light (300-1000 mJ/cm 2 ) under an atmosphere of nitrogen.
TABLE IV In Plane Wt % of Layer Retardation Average added Thickness, nm (measured @ Tilt Angle II-1 (nm) 550 nm) (± 2° ) Comparison 0 wt % 561 67 0.2 Example. 4 Inventive 0.50 wt % 554 61 15 Example. 5
[0052] The aforementioned examples in Table IV clearly demonstrate that on a rubbed PVA orientation layer compared to Comparison Example 6 addition of diphenyliodonium hexafluorophosphate salt (II-1) to liquid crystal layer increases the average tilt angle of liquid-crystal molecules.
[0053] An overall observation of the “In-Plane Retardation”, taking into consideration the layer thicknesses and variation in average tilt angles in the inventive vs. comparative examples, is that the in-plane retardation is not significantly affected by the altered tilt angle.
[0054] The patents and other publications referred to herein are incorporated herein in their entirety. | A process for forming a fixed liquid crystal layer having a predetermined tilt on an orientation layer comprises: a) adding a predetermined amount of an onium salt to a liquid crystal pre-polymer coating solution containing a liquid crystal pre-polymer and a UV initiator selected from the group consisting of benzophenone and acetophenone and their derivatives; benzoin, benzoin ethers, benzil, benzil ketals, fluorenone, xanthanone, alpha and beta naphthyl carbonyl compounds and ketones; b) coating the solution over the orientation layer; c) drying the coating to form a layer; and then d) UV irradiating the layer to fix the liquid crystal molecules. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preparing copper phthalocyanine blue pigments characterized by good dispersing properties.
2. Prior Art
The introduction of phthalocyanine pigments in 1935 set new standards of excellence in the pigment consuming industries. They are characterized by their excellent light fastness, intensity, bleed and chemical resistance, extreme stability, and exceptionally high tinting strength. Phthalocyanine pigments are restricted to the blue and green regions of the spectrum. Because of their excellent color values, working properties and low cost in addition to durability, phthalocyanine blue and green pigments are used extensively.
It is desirable in the production of phthalocyanine blue to develop a product which will attain approximately 90 percent of its maximum strength by dispersing the dry powder in the vehicle using a high speed agitator. To accomplish this goal, it is necessary to find some means of protecting the particles when the aqueous cake is dried, thus reducing sintering and the formation of aggregates. This can be achieved by extending the product while in the aqueous phase with a suitable resin. Further, resinated pigments are generally softer in texture and disperse more readily in oil-ink applications, when compared to unresinated pigment. However, phthalocyanines must undergo some form of particle size reduction either by acid pasting or salt grinding. Resinating a phthalocyanine is complicated by the presence of strong acid and/or large amounts of salt, making it necessary to filter and wash out the excess salt or acid and reslurry the aqueous cake for resination which adds a great deal to the manufacturing cost of any product. Accordingly, it is a purpose of the instant invention to avoid the need for reslurrying.
STATEMENT OF RELEVANT PATENTS
To the best of applicant's knowledge, the following patents are the ones most relevant to a determination of patentability.
______________________________________Pat. No. Issued Inventor(s) Assignee______________________________________4,196,016 4/1/80 Simon --3,712,824 1/23/73 Kiyokawa et al Sakata Shokai Co.4,055,439 10/25/77 Babler et al Ciba-Geigy3,770,474 11/6/73 Langley et al Ciba-Geigy______________________________________
SUMMARY OF THE INVENTION
In accordance with the instant invention, an easily dispersible resinated copper phthalocyanine blue pigment is produced without reslurrying. These copper phthalocyanine blue pigments are produced by
(A) grinding,
1. copper phthalocyanine blue crystals with
2. an inorganic salt and digesting the ground copper phthalocyanine blue in
water containing
a strong mineral acid.
(B) separately preparing an emulsion by dissolving
1. a resin in
2. an organic solvent,
3. an emulsifying agent and
4. water
(C) mixing
1. the emulsified resin with
2. the digested ground copper phthalocyanine pigment and
(D) separating the pigment from the other materials.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Copper phthalocyanine blue is a well-known pigment product that has been produced at least since 1935 and there are many well-known processes for producing it. The two processes most generally employed are (1) heating phthalic anhydride, urea, a copper salt and a catalyst with or without a reaction medium such as chloronaphthalene or trichlorobenzene to 180° to 200° C. and (2) heating phthalonitrile and a copper salt with or without a reaction medium or solid diluent. The product that results is generally copper phthalocyanine blue pigment in the beta form and such products are generally purified by methods well known to those skilled in the art. In general, the purification processes involve boiling the crude copper phthalocyanine blue in a 10 percent aqueous acid solution preferably H 2 SO 4 , or 2.5 percent caustic solution, filtering, and washing with hot water at about 85° C. This results in a product that is about 95 percent pure which is a commercially pure product.
In accordance with the instant invention, the purified crude copper phthalocyanine blue is ground in a suitable apparatus such as a double arm mixer for about 5 to 15 hours with an inorganic salt and a monomeric alcohol containing up to 2 hydroxyl groups. Alternately the purified crude copper phthalocyanine blue may be milled in a ball mill for about 12 to 24 hours with an inorganic salt and a recrystallizing solvent. Milling may take place in a conventional ball mill such as one of steel which is approximately one-half full by volume with, for example, one inch by one inch steel rods. The mill should be rotated at about 70 percent of its critical speed (i.e., the speed at which the rods start rotating with the mill). It is necessary that a cascading action take place. Grinding times may exceed those set forth above by substantial amounts without any detrimental effects. However, obviously for economic reasons, it is undesirable to grind for any greater length of time than necessary. As used herein the terms "grind" or "grinding" include both "grinding" and "milling".
In the preparation of copper phthalocyanine blue pigment, it is generally preferred to grind or mill the material to from about 0.02 to 0.05 microns. The grinding or milling operation is conducted at ambient pressure and while there is some exothermic heating, no attempt is made to control the temperature.
In salt grinding in a double arm mixer the preferred inorganic salt is sodium chloride or sodium sulfate.
The monomeric alcohols which may be employed include glycols, particularly ethylene glycol, propylene glycol and diethylene glycol. Methanol or ethanol may also be used. The weight ratio of inorganic salt to pigment ranges from about 5:1 to 12:1 while the weight ratio of the alcohol to pigment ranges from about 0.5:1 to 2:1.
Where ball milling is employed, calcium chloride, sodium chloride, or hydrated aluminum sulfate are preferred in the presence of a crystallizing solvent which is a hydrocarbon or chlorinated hydrocarbon such as 1,1,1-trichloroethane.
Next the phthalocyanine material is digested by adding it to a vessel of water containing a strong mineral acid, preferably HCl or H 2 SO 4 . This aqueous solution preferably contains about 1 to 15 percent by weight of the mineral acid. The weight ratio of aqueous mineral acid solution to pigment is about 27:1 to 44:1. The pigment is added to the dilute acid with stirring at a temperature of about 75° to 100° C. and stirring continued for from about one-half to 6 hours. The digested pigment is then cooled to from about 40° to 60° C. Time is not critical in this matter but generally it should be cooled as fast as practical using the means available. Obviously, refrigeration would cool it the most rapidly but also there would be an expense involved in refrigeration. The costs of a slower cooling process versus the cost of refrigeration would obviously have to be optimized. However, the temperature must be reduced to not more than 60° C. If the temperature exceeds 60° C., foaming becomes a problem.
In a separate container, an emulsion is prepared by dissolving a resin in an organic solvent, adding an emulsifying agent and mixing with water. The resin employed may be either a natural resin such as rosin, copal, dammar and shellac or processed natural resins such as polymerized rosin, rosin esterified with aliphatic monohydric or polyhydric alcohols and/or monohydric or polyhydric phenols. Synthetic resins may be employed such as maleic acid resins, phenol resins, urea resins, melamine resins, aldehyde resins, ketone resins, polyester resins, acrylate resins, polyvinylacetate resins, polystyrene resins, polyisobutylene, cellulose esters, cellulose ethers, rubber derivatives, polyamides, epoxide resins and silicone resins.
Suitable organic solvents include any solvent capable of dissolving the resin such as benzol, toluol, carbon tetrachloride, ethyl acetate, diethyl ether, methylisobutyl ketone, and the like. A preferred solvent is 1,1,1-trichloroethane.
The resin is added to the solvent and stirred until dissolved. The amount of resin is about 5 to 10 percent by weight based on the pigment yield. The amount of solvent is not critical, a preferred amount being about 30 to 70 percent by weight based on the pigment yield. An emulsifying agent, preferably a sulfonated aliphatic polyester, is added to the resin-solvent mixture in order to facilitate emulsification of the resin with the solvent. Conventional surfactants may be employed for this purpose such as those listed below. The amount of emulsifying agent is by weight about 0.5 to 30 percent based on the pigment yield. The preparation of the resin-solvent emulsion is generally performed by mixing the above components with water at ambient temperature and pressure.
In a most preferred embodiment of the instant invention, the resin-solvent-emulsifying agent solution is added to a water solution of a surfactant containing about 0.5 to 5.0 percent by weight surfactant. The weight ratio of the resin-solvent-emulsifying agent solution to surfactant solution is about 0.1:1 to 1.1.
The surfactant can be any anionic, cationic or nonionic surfactant which modifies the properties of a liquid medium at a surface or interface usually by reducing surface tension or interfacial tension. Anionic surfactants include the alkyl aryl sulfonates and lauryl alcohol sulfates. Typical anionic surfactants include sodium oleate, sodium laurate, sodium palmitate, sodium stearate, sodium naphthanate, sulfonated castor oil, sulfonated petroleum, sulfonated tall oil and the like. A particularly preferred anionic is sodium lauryl sulfate.
The cationic surfactants which are suitable include primary, secondary or tertiary amines and the quaternization products derived therefrom. The preferred primary amines are fatty acid or mixed fatty acid amines containing 6 to 18 carbon atoms, and particularly cocoamine. Secondary and tertiary amines and quarternary ammonium compounds from fatty amines containing from 8 to 22 carbon atoms are particularly useful. Typical of the tertiary amines are the heterocyclic tertiary amines such as the alkylimidazolines and oxazolines which form water-soluble salts with various acids and polyethoxylated amines containing a fatty acid radical containing 12 to 22 carbon atoms. Specific examples of quaternary ammonium compounds include disoya dimethylammonium chloride, dicocodimethyl-ammonium chloride, oxtadecyl octadecenyl diethyl ammonium chloride and the like.
A wide variety of nonionic surfactants are known and suitable. Particularly useful are the polyether alcohols such as cogeneric mixtures of conjugated polyoxyalkylene compounds containing in particular oxypropylene and oxyethylene groups. Such products are sold as Pluronic® Polyols by BASF Wyandotte Corporation. Such surface active agents are more particularly described in U.S. Pat. No. 2,677,700 and U.S. Pat. No. 2,674,619. Also useful are alkylene oxide-alkylene diamine block polymers, the polyoxyethylene glycol or polyoxyethylene glycerol esters of such acids as coconut fatty acid, stearic acid, oleic acid, and rosin/fatty acid combinations, monoesters of polyhydric alcohols and particularly the fatty acid esters such as lauric ester, sorbitol and the like.
The digested ground copper phthalocyanine pigment is then mixed with the emulsified resin generally for about 10 minutes. The mixture is then heated and maintained at the elevated temperature preferably for more than about 1 hour. There is no known maximum time period but for economic reasons the time generally would not exceed 2 hours. The temperature preferably would not exceed 75° C. and generally would be at least about 70° C. Preferably, the solvent is removed by azeotropic distillation. The pigment is then removed by filtration after which it is washed, generally with water, until it is acid and salt free. It is then micromilled to a powder.
For a more complete understanding of the invention, reference is made to the following illustrative example thereof. All parts and percentages are by weight and all temperatures are in degrees Centigrade unless otherwise indicated.
EXAMPLE 1
156 grams of crude caustic purified copper phthalocyanine blue of at least 92 percent purity were charged to a dough mixer along with 1372 grams of sodium chloride and 247 grams of ethylene glycol and the mass mixed 8 hours at 75° to 85° C.
1200 grams of the ground phthalocyanine blue-salt mixture was then stirred into 2688 milliliters of water containing 216 milliliters of concentrated sulfuric acid (98 percent H 2 SO 4 ) and stirred for 2 hours at 90° C. The pigment slurry was then cooled to 60° C. by stirring in a container surrounded by air at ambient temperature.
In a separate container, an emulsion was prepared by dissolving 4.5 grams of rosin in 21.6 grams of 1,1,1-trichloroethane. To this was added 0.85 grams of a sulfonated aliphatic polyester sold under the trademark NEKAL WS-25 by GAF Corporation. This rosin-solvent-emulsifier mixture was slowly poured into 150 milliliters of water containing 3.2 grams of sodium lauryl sulfate with vigorous agitation.
The emulsion was then added to the digested pigment slurry over a 10 minute period at 60° C. Next, the mixture was heated with steam through a sparger to 75° C. and maintained at that temperature for 1 hour. The solvent was then removed by azeotropic distillation after which the pigment was isolated by filtration and washed acid free and free of salts. After drying at 75° C., the product was reduced to a powder by micromilling.
The product developed 90 percent of maximum strength by stirring into oil-ink vehicles compared to 70 percent of maximum strength for a similar product wherein the resin-solvent emulsion was omitted. When the inks are compared for grit elimination on a NPIRI grind gauge, the treated product is significantly better for both coarse and fine grit.
EXAMPLE 2
An easily despersible copper phthalocyanine blue pigment is prepared as described in Example 1 with the exception that the grinding step is performed in a ball mill with sodium chloride and 1,1,1-trichloroethane. | Copper phthalocyanine blue pigments are produced by
(A) grinding,
1. copper phthalocyanine blue crystals with
2. an inorganic salt and digesting the ground copper phthalocyanine blue in
water containing
a strong mineral acid.
(B) separately preparing an emulsion by dissolving
1. a resin in
2. an organic solvent,
3. an emulsifying agent and
4. water
(C) mixing
1. the emulsified resin with
2. the digested ground copper phthalocyanine pigment and
(D) separating the pigment from the other materials. | 2 |
This application is a division of application Ser. No. 08/771,147, filed Dec. 20, 1996 now U.S. Pat. No. 5,785,493.
BACKGROUND OF THE INVENTION
1. Field of the invention
The present invention relates to a turbocharger for an internal combustion engine, and more particularly, to an improvement of a compressor housing thereof.
2. Description of the Related Art
A turbocharger for an internal combustion engine receives exhaust gas from an engine exhaust pipe, rotationally drives a turbine wheel in a turbine housing, compresses air within a compressor housing under the action of rotation of compressor impellers arranged via a drive shaft integrally formed with the turbine wheel, and supplies the compressed air to the engine. The compressor housing and the compressor impeller in the turbocharger as described above are generally made of aluminum alloy castings.
An engine with a turbocharger is now demanded to have a supercharging effect from a low-revolution region of the engine. In the turbocharger, making an outside diameter of a curved profile portion of the compressor impeller and a gap formed between the profile portion and the inner wall surface of the compressor housing corresponding thereto as small as possible while improving a blade-shape of the compressor impeller is favorable for improving efficiency of the compressor. However, the small gap involves a risk that the curved profile portion of the compressor impeller rotating at an extra-high velocity may come into contact with the inner wall surface of the compressor housing due to slight shaft vibration, resulting in breakage of the impeller, or further in destruction of the drive shaft.
In a conventional turbocharger, therefore, it has been the usual practice to provide a gap of from about 0.3 mm to 0.5 mm between the inner wall surface of the compressor housing and the curved profile portion of the compressor impeller.
Making the gap between the impeller and the housing as small as possible by a thermal-spray coating provided in the housing is already known, for example, for a gas turbine (as disclosed in JP-B2-50-690, JP-A-52-72335, and JP-A-52-85031). More recently, JP-B2-04-40559 proposes a method of, in a turbocharger for automobile, forming by thermal spray a resin coating comprising a mixture of soft metal and resin or graphite onto the inner wall surface of a compressor housing as a means of making the above gap small and preventing occurrence of a damage to the compressor impeller even upon contact with the compressor impeller.
As a means of making the gap between the compressor impeller and the housing in a turbocharger of an internal combustion engine small, and preventing occurrence of a damage to the impeller even upon contact with the compressor impeller, JP-A-06-307250 proposes a turbocharger in which a wall member separately formed from a composite material comprising a resin such as PTFE (polytetrafluoroethylene) or a mixture of the resin and graphite or glass wool is attached onto a wall surface of at least the portion of the compressor housing wall surface corresponding to a curved profile portion of the compressor impeller.
In the conventional art, the presence of a necessary minimum gap T within a range of from 0.3 to 0.5 mm between the curved profile portion of the compressor impeller and the inner wall surface of the compressor housing puts restriction on improvement of compressor efficiency.
A thermal spray coating technique recently proposed, on the other hand, while being effective for improving compressor efficiency, needs making a consideration in productivity with respect to thermal spray equipment, capability to handle many different types of compressors and masking of products, and thus the problem is that a product cost is higher.
Even when the thermal spray coating technique is replaced by a technique for improving compressor efficiency, in which a separately formed resin member is attached to the wall surface and a gap between the compressor housing inner wall surface and the curved profile portion of the compressor impeller of a turbocharger is made small, it is important to rotate the compressor impeller at extra-high velocity without damaging the compressor impeller upon contact between the wall member and the compressor impeller. That is, it is important, upon contact of these members, to smoothly shave the compressor housing wall member without causing any damage such as deformation or breakage to the compressor impeller.
SUMMARY OF THE INVENTION
The present invention has an object to provide a turbocharger in which the wall surface member is made of a resin member excellent in machinability for allowing contact with the compressor impeller in extra-high velocity rotation so as to minimize the gap between the inner wall surface and the curved profile portion of the compressor impeller, thereby improving compressor efficiency, as well as causing no risk of damage to the compressor impeller even upon contact of these members, by a low-cost technique excellent in productivity. In the present invention, furthermore, the material of the wall member is taken into consideration so that, even when the wall member is shaven by a contact with the compressor impeller and the shaven chips reach the cylinder, there would be no bad effect on the engine cylinder.
In order to achieve the above object, the present invention is characterized in that a resin wall member which is located on an inner periphery of a metal member of a compressor housing and is correspondingly to a curved profile portion of a compressor impeller is made of PPS (polyphenylene sulfide). More specifically, the foregoing wall member is tightened and fixed by means of connecting bolts engaged with screw holes formed in the foregoing compressor housing. Further, a slight gap defined by the inner periphery of the wall member and the shape of the curved profile portion in the outer periphery of the compressor impeller is set so that the gap on the inlet side of the compressor impeller is larger than that on the outlet side of the compressor impeller.
In the present invention, furthermore, taking account of expansion of the wall member, the contact portion between the compressor housing and the wall member is limited to only the attachment surface, and gaps are provided between these members without the above contact portion.
In the present invention having the construction as described above, the wall member made of PPS resin or a composite material comprising a mixture of PPS resin and graphite or glass wool provided correspondingly to the curved profile portion of the compressor impeller is shaven away without damaging the compressor impeller upon contact of the curved profile portion of the compressor impeller with the wall member attached to the compressor housing, because the wall member is made of a material softer than that of the metal composing the compressor impeller.
The gap between the curved profile portion of the compressor impeller and the wall member provided correspondingly thereto can therefore be set to a value closer to zero than the value of the gap of from 0.3 mm to 0.5 mm required in the conventional art. Particularly during extra-high velocity rotation of the compressor impeller, i.e., during temperature rise caused by adiabatic compression on the compressor side, the fore-going gap can be set to perfectly zero in consideration of thermal expansion of the wall member. In the present invention, for example, even upon occurrence of contact between the compressor impeller and the wall member attached to the compressor housing as a result of shaft vibration, the wall member attached to the compressor housing is shaven in response to the extent of contact, thus maintaining the gap of zero.
This means that the gap of from 0.3 mm to 0.5 mm existent between the inner wall of the compressor housing and the compressor impeller in the conventional art can be adjusted substantially to zero, thus resulting in an improved compressor efficiency.
The wall member attached to the compressor housing can be resin-formed in a mold or the like, and then incorporated in the compressor housing (metal member), and the wall member thus made of a resin can be shaven with the compressor impeller during preliminary operation such as during confirmation of fluid performance. A similar result is available by incorporating a resin-formed wall member into the compressor housing (metal member), previously cutting the wall member so that the gap becomes null upon thermal expansion in the actual operating state (during extra-high velocity operation), incorporating the compressor impeller and rotationally driving the same. Further, the wall member may be forcedly shaven with the compressor impeller during actual operation without previously applying cutting or other working.
Various methods are conceivable, taking account of productivity, for integrally forming the wall member of the compressor housing and the compressor housing (metal portion). For integration of a resin member and the metal member, it is possible to attach the resin member to the metal member of the compressor housing with the use of a metal member insert mold or the like. A wall member made of a PPS resin excellent in heat resistance, oil resistance and chemical resistance can be screw-connected directly with the compressor housing (metal member). A further improved productivity is available by achieving such a construction. In this case, it is desirable to provide a gap for allowing expansion of the wall member for portions other than the contact surface of these members.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view illustrating an embodiment of a turbocharger for an internal combustion engine according to the present invention;
FIG. 2 is a partially enlarged view of the compressor A shown in FIG. 1;
FIG. 3 is a partially enlarged view of a portion P shown in FIG. 2; and
FIG. 4 is a reduced fragmentary view taken in 10 the direction of the arrow Q of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a sectional view illustrating a turbocharger for automobile, in which a portion A represents a compressor portion and B, a turbine portion.
Exhaust gas from an internal combustion engine for automobile is introduced from an inlet 101 of a turbine housing into a scroll 102, flows from a larger cross-section toward a narrower cross-section, and is discharged from an outlet 103 into an exhaust pipe. At this point, a turbine impeller 2 is rotated at a high velocity (at least 100,000 rpm) under the effect of energy of exhaust gas.
A drive shaft 3 of this turbine is bearing-connected to a bearing housing 110 through bearings 111 and 112.
The bearing housing 110 is further provided with a lubricant path 113 for supplying lubricant to the bearings and a cooling water path 114 for circulating cooling water for the engine to cool the turbocharger.
The turbine portion B is assembled by attaching a shroud 115 onto a side of the bearing housing 110, then inserting the drive shaft 3 through the bearings 111 and 112, securing a turbine wheel 2 to an end of this drive shaft 3, and screw-fixing the same to the bearing housing 110 with screws 116 so as to cover the outer side with a turbine housing 1.
Upon rotation of the drive shaft 3 by rotation of the turbine wheel 2, a compressor impeller 4 attached to the other end of the drive shaft 3 rotates in the compressor housing 5, compresses air sucked from an inlet 50 of the compressor housing 5 with the compressor impeller 4, and discharges compressed air to a scroll 51, which is then pumped to an intake manifold of the internal combustion engine.
The compressor portion A is assembled by pressure-inserting a sleeve 510 with a thrust metal 511 from the opposite turbine side of the drive shaft 3 into the drive shaft 3.
Then, a seal ring 513 is engaged with grooves provided on an end face of the bearing housing 110 on the opposite turbine side, and another seal ring 514 is attached to the outer periphery of the sleeve 510. A seal plate 8 is then attached so as to come into contact with these rings.
Then, a compressor impeller 4 is inserted into the drive shaft 3, and the drive shaft 3 and the compressor impeller 4 are secured with a screw 41 at the tip of the drive shaft 3.
Finally, the compressor impeller 4 is covered from outside with the compressor housing 5, engaged with a spigot 515 on the outer periphery of the seal plate 8. A portion of the seal plate 8 composing this spigot 515 and a flange 517 for attaching the compressor formed in the bearing housing 110 are inserted and secured between an annular portion of the compressor housing and a C-ring 516 attached in a groove formed on the compressor housing 5.
Although the main body of the compressor housing 5 is made of aluminum alloy castings, a wall member 5b made of a resin is integrated with the portion facing the curved profile portion 4a of the compressor impeller 4 after assembly. The wall member 5b is made by resin-forming of a PPS (polyphenylene sulfide) resin or a composite mixture of a PPS resin and graphite or glass fiber softer than the compressor impeller 4.
The wall member 5b is directly connected and secured to the main body of the housing 5 with screw members 7 engaging with holes 6 provided on a flat annular surface 52 facing the seal plate 8 of the main body of the compressor housing 5 on an annular surface 5d at right angles to the drive shaft 3 of the compressor impeller 4.
Further, the wall member 5b comprises a cylinder portion 5e extending in parallel with the drive shaft 3, and a curved portion 5c connecting the cylinder portion 5e and the annular surface 5d.
FIG. 2 is a sectional view illustrating only the compressor housing 5.
FIG. 3 is an enlarged view of the portion D delimited with a one-point chain line in FIG. 2.
FIG. 4 is another representation of FIG. 2 as viewed in the arrow Q direction in a reduced scale.
The relationship between the compressor housing 5 and the peripheral members will be described further in detail below with reference to these drawings.
A recess 5f is formed in the portion of the compressor housing 5, which faces the curved profile portion of the compressor impeller 4. This recess 5f comprises an annular portion facing the seal plate 8 for receiving the wall member 5b, a cylinder portion along the drive shaft and a portion having the curved surface portion connecting these portions.
The wall member 5b attached to this recess 5f serves as the wall surface of the compressor housing 5 facing the curved profile 4a of a plurality of compressor blades 4b forming the compressor impeller 4.
The compression efficiency of the compressor is higher according as a gap T between the housing wall surface and the profile of the impeller is smaller. In this embodiment, this gap T is designed to become substantially zero during usual operation by the use of thermal expansion of the wall member 5b on the basis of the principle of the present invention.
For the wall member 5b, the size R 1 from the center to the inside diameter of the cylinder portion, the size R 2 to the outside diameter thereof, and the size R 3 to the center of the screw hole 7a are determined from a forming mold, thus determining the size L 2 between the center of the screw hole and the inside diameter of the cylinder portion.
The screw hole 7a is provided through the center of an accommodation recess 5bg of the screw top 7b of the screws 7 provided on the same circle periphery.
The wall member 5b is in contact only on the housing-side surface 5b 10 of the annular surface on which the screw hole 7a is formed, and forms an attachment surface.
As shown in FIG. 4, gaps G 1 to G 4 are formed between the other wall surfaces of the wall member attachment recess of the compressor housing 5 and the corresponding wall member.
At the room temperature, the gap G 3 between the axial end face 5bl of the cylinder portion 5e of the wall member 5b and the wall surface 5b 2 of the corresponding recess is set to about 300 to 400 μm, the gap G 1 between the surface 5b 3 of the cylinder portion 5e of the wall member 5b and the corresponding wall surface 5b 4 , about 250 μm, the gap G 4 between the surface 5b 5 of the curved portion 5c thereof and the corresponding wall surface 5b 6 , 500 to 600 μm, and the gap G 2 between the outer periphery edge 5b 7 of the annular surface portion 5d of the wall member 5b and the corresponding wall surface 5b 8 , 300 to 400 μm as in the gap G 3 .
PPS has a thermal expansion coefficient of 2 to 7×10 -5 (1 to 6×10 -5 when glass is contained). These values of gaps are therefore based on an extent of expansion at about the thermal deformation temperature of 250° C. so that the wall member 5b, even when expanding toward the housing 5, does not come into contact with the recess wall surface of the housing. Or, when the wall member comes into pressure contact with the recess wall surface of the housing as a result of expansion, the reaction thereof may cause cracks or rupture in the wall member 5b.
Because impact stress resulting from contact with the compressor impeller 4b concentrates on the curved portion 5e of the wall member 5b, the thickness thereof is designed to become gradually larger from the cylinder portion 5e toward the annular surface 5d. That is, the thickness T 4 of the cylinder portion is larger than thickness T 2 of the annular surface portion.
The top 7b of the screw 7, designed to perfectly fit in the accommodation recess 5bg, never projects to the surface facing the seal plate 8 of the compressor housing 5, so as not to cause resistance to the flow of air therethrough.
The depth T 1 of the recess 5f and the thickness T 2 of the wall member 5b are designed to ensure sinking of the wall member 5b into the recess 5f by a depth within a range of from 100 to 200 μm at the room temperature so that the seal plate 8 side end face 5g of the metal portion of the compressor housing 5 and the seal plate 8 side end face of the annular surface portion 5d of the wall member 5b become substantially flush upon ordinary operation.
The screw 7 is designed to have a longitudinal length L 1 longer than the distance T 3 between the end face of the seal plate 8 and the bottom surface of the screw accommodation recess of the wall member 5b, so that the screw 7 does not come off the screw hole 7a even when it loosens.
Furthermore, even when the loosening screw 7 jumps out to the seal plate 8 side to tilt on the impeller 4 side, the strong flow of air during rotation of the impeller 4 pushes out the screw 7 which thus never comes into contact with the impeller 4.
The surface of the wall member 5 facing the impeller may previously be shaven and then assembled so that the gap T from the impeller becomes null as a result of thermal expansion at about the ordinary operating temperature. In this example, however, the impeller itself was provided with the shaving function.
More specifically, it was designed so that the gap T between the surface of the wall member 5b and the compressor impeller 4 became null upon assembly, and the molded wall member 5b without any working was incorporated into the compressor housing 5. A test similar to the rotation test carried out without fail before assembly into the automobile was conducted, and the surface of the wall member 5b was shaven by means of the compressor impeller 4 into a desired shape.
In the rotation test, revolutions of the compressor impeller 4 was increased up to about 160,000 rpm on the maximum. cutting traces of from 0.03 to 0.05 mm remained on the surface of the wall member 5b. The cutting traces were shallower on the inlet side than on the outlet side of the compressor. The results of some tests taking account of manufacturing errors of the individual parts suggested that a design to bring the initial gap T to zero caused cutting traces of from 0.05 to 0.15 mm.
Another fact found in these tests is that the wall member 5b made of a resin thermally expands under the effect of temperature increase of the compressor housing resulting from adiabatic compression of air during compressor operation. The foregoing cutting traces naturally include those coming from this thermal expansion.
The design values of the wall members 5b were therefore modified into values taking account of the foregoing two points (non-uniformity between outlet and inlet sides and thermal expansion coefficient).
That is, the thermal expansion coefficient was calculated in an anticipation of temperature increase from the room temperature to 80° C., and design was made with a radius R 1 larger by a value corresponding to this expansion.
Design was made also so that the radius was smaller on the outlet side than on the inlet side of the compressor.
In this example, a slight gap T is produced between the surface of the wall member 5b and the compressor impeller 4, and this gap T was slightly smaller on the outlet side than on the inlet side.
A similar rotation test carried out on the compressor of this example resulted in only a cutting trace of about 0.02 mm in a part on the outlet side of the compressor exit.
The same compressor after this initial cutting was subjected to several similar rotation tests, and no increase in cutting traces was observed.
The results of tests carried out on various materials of the wall member 5b are shown in Table 1.
TABLE 1__________________________________________________________________________ Material PPS PPS Polyphenylene- PBT Polyphenylene- sulfide PTFE Polybutylene sulfide Glass- Polytetrafluoro- terephthalateItem No mixing reinforced ethylent No mixing__________________________________________________________________________Inter-Machinability in ⊚ ∘ X Δferenceinterferencewith Damage to impeller No deformation, Worn Deformed Wornimpeller no wearHardness (D785) 90 ˜ 100 90 ˜ 100 58 80 ˜ 90Deforma- ∘ (medium) ⊚ (little) ∘ Δ (large)tion atThermal deforma- 250° C. 250° C. 50° C. 220° C.high tion temperature or over or over or over or overtempera-(Test method:ture D785)Continuous service 210° C. 210° C. 250° C. 140° C.temperature or over or over or over or over(Test method:UL746B)Linear expansion 2 ˜ 7 1 ˜ 6 10 ˜ 17 2 ˜ 5coefficient × 10.sup.-5(test method:UL746B)Over-all judgement ⊚ ∘ X Δ__________________________________________________________________________
The turbocharger shown in Table 1 had previously been subjected to a rotation test similar to that with a compressor having a wall member of the above-mentioned PPS and initially shaven, and was continuously operated at a continuous service temperature shown in Table 1. "Deformation at a high temperature" in Table 1 shows the result thereof.
The wall member made of PPS (no mixing) was shavable by the impeller because the material was relatively brittle, with no deformation nor wear in the impeller. The thermal deformation temperature was at least 250° C. or over, and the continuous operation at 210° C. did not give a large amount of deformation.
When using a glass-reinforced PPS mixing PPS with graphite or glass wool, the linear expansion coefficient is reduced by 70 to 50%. While the overall hardness was almost the same as in the PPS material, there was observed a slight trace of wear on the impeller, attributable to the contact between the mixture and the impeller. The amount of deformation upon temperature increase is led to a smaller value corresponding to the decrease in the linear expansion coefficient, which is superior to those of the others.
This means that the gap T between the wall member and the impeller does not fluctuate much at all temperatures ranging from the room temperature to high temperatures. Even when designing so as to achieve a gap T of null at high temperatures, the gap T does not widen so much at relatively low temperatures, so that the compressor can be operated at a high efficiency.
When using PTFE (polytetrafluoroethylene), a very high viscosity resulted in production of chamfer, leading to a deformation of the impeller.
Although polytetrafluoroethylene alone poses some difficulties in practice, deposition of a hard PPS on the surface of a substrate made of this polytetrafluoroethylene gives a wall member provided with advantages of the both materials. In this case, the impact alleviating effect of polytetrafluoroethylene can be expected.
When using a no-mixing material of PBT (polybutylene terephthalate), the deformation temperature is low, resulting in serious deformation at high temperatures, and the long period of time of contact between the impeller and the wall caused wear of the impeller.
However, if a mixed material suitable for this PBT is available, it would show the same tendency as the glass-reinforced PPS, and can be used in practice.
The judging symbols ∘, x and Δ do not represent in or outside the scope of the present invention, but shows easiness of practical application at the present level of art for practical application, and a low rating does not mean exclusion from the scope of the present invention.
It was confirmed that PPS had satisfactory affinity to engine lubricant and gasoline, and shaven chips, if coming into cylinders, did not exert any adverse effect on the engine.
Damage to the wall member caused by deviated contact or strong tightening of the screw 7 was prevented by placing a plain washer 10 between the screw member 7 and the bottom surface of the screw accommodation recess.
The gaps provided at portions other than the attachment portion of the wall member 5b served also to adjust expansion deformation of the wall member 5b toward the impeller into an appropriate amount. Without these gaps, all expansion toward the metal housing would appear on the impeller side. In addition, this may cause deformation of, or damage to, the wall member itself.
Furthermore, as shown in FIG. 4, the wall member is secured in the axial direction by three screws.
Since this limits axial thermal deformation to an amount corresponding to thickness T 1 of the wall member made of a resin, there is only a slight amount of deformation.
In the radial direction, on the other hand, a thermal deformation corresponding to the size L 2 of the resin wall member with the securing screw as reference, is led to a larger amount of deformation as compared with that in the axial direction.
To avoid this inconvenience, imbalance in the amount of deformation is absorbed by making the gap between the resin wall member and the compressor impeller larger for the radial direction G 11 than that for the axial direction G 10 .
Because performance of a compressor mainly depends upon the gap in the axial direction, possibility to reduce the clearance in the axial direction is favorable for achieving higher performance.
According to the present invention, as described above, the surface of the compressor housing facing the impeller is formed into a separate piece from a PPS resin, which is assembled into the housing, and the gap between the two members is brought substantially to zero by the use of thermal expansion of the resin in ordinary operation.
Because of these features of the invention, a turbocharger of an internal combustion engine provided with a compressor having a high efficiency is available by a relatively simple process.
More specifically, the features are as follows. Portions other than the attachment surface of the wall member can be arranged with a gap so as not to come into contact with the compressor housing itself. This permits elimination of excessive deformation, crack or breakage caused by thermal expansion.
Provision of a stopper for attachment screw permits prevention of damage to the engine caused by falling of a screw. | A turbocharger for an internal combustion engine having a housing wall member located on an inner periphery of a metal compressor housing and facing a curved profile portion of the compressor impeller. The housing wall member is separately formed of a resin such as polyphenylene sulfide and integrally held and secured to the compressor housing. | 5 |
FIELD OF THE INVENTION
The invention relates to an optical information recording medium that permits information to be recorded thereon and reproduced therefrom by laser beam irradiation, and more particularly to a phase-change type optical disk wherein information is recorded thereon by creating a phase change in a recording layer and is reproduced therefrom by utilizing a difference in optical properties between the amorphous state and the crystal state of the recording layer.
In recent years, magneto-optical disks and phase-change type optical disks have been proposed as optical information recording media utilizing optical technology. Among them, phase-change type optical disks record information by changing the recording layer from the crystal state to the amorphous state or vice versa and reproduce information by utilizing a difference in light reflectance or light transmittance between the crystal state and the amorphous state of the recording layer. In the conventional phase-change type optical disks, the light absorption in the amorphous state, Aa, is generally higher than the light absorption in the crystal state, Ac. For this reason, when the pitch of recording tracks of the phase-change type optical disk is decreased in order to increase the track density, recording of information by applying a laser beam to a certain recording track to cause a phase change in the recording layer causes light to be absorbed by an amorphous record mark having high light absorption present in adjacent record tracks, resulting in temperature rise/crystallization, that is, the so-called cross erasing.
Rendering the light absorption in the amorphous state, Aa, lower than the light absorption in the crystal state, Ac, is considered effective for preventing the cross erasing. Methods for rendering Aa lower than Ac are disclosed, for example, in Japanese Patent Laid-Open Nos. 149238/1989 and 93804/1995 and Proceedings of The 5th Symposium for Society for the Research of Phase-change Type Recording (Dai 5 Kai So-henka Kiroku Kenkyukai Shinpojumu Yokoshu), p. 92-94. In these methods, however, it is difficult to render Aa much lower than Ac while maintaining the large difference between Ra and Rc, particularly for a short-wavelength light source.
Further, the conventional phase-change type optical disks have an additional problem that, due to the nature of the construction, heat load is increased and, consequently, the possible number of times of rewriting of information is small and, particularly, in the case of low linear velocity, is significantly limited. For example, in the construction shown in FIG. 1 on page 94 of Proceedings of The 5th Symposium for Society for the Research of Phase-change Type Recording, a light absorptive reflective layer (a very thin gold layer) is provided just on the substrate. In this construction, at the time of information recording, the reflective layer absorbs the laser beam and consequently is heated, and this causes heat load to be applied to the substrate located just under the reflective layer, resulting in limited possible number of times of rewriting of information. In particular, at a low linear velocity of not more than 8 m/sec, the possible number of times of rewriting is significantly limited.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a phase-change type optical disk that can inhibit cross erasing and, at the same time, has excellent rewrite cycling properties.
According to the first feature of the invention, a phase-change type optical disk comprises: a substrate; and, provided on the substrate in the following order, a first dielectric layer, a second dielectric layer, a third dielectric layer, a recording layer, a fourth dielectric layer, and a reflective layer, the refractive index n2 of the second dielectric layer and the refractive index n3 of the third dielectric layer satisfying the relationship n2<n3, the light absorption of the recording layer in amorphous state being lower than that of the recording layer in crystal state. Preferably, the refractive index n1 of the first dielectric layer and the refractive index n2 of the second dielectric layer satisfy the relationship n1>n2.
In the phase-change type optical disk of the invention, when the wavelength of a light source used in information recording/reproduction is λ, the refractive index of the first dielectric layer at the wavelength λ is preferably more than 1.7. Preferably, the reflective layer is formed of a metal selected from the group consisting of gold, aluminum, titanium, copper, chromium, and alloys of the metals. The thickness of the reflective layer is preferably 40 to 300 nm.
According to the invention, when the refractive indexes n2, n3 of the second dielectric layer and the third dielectric layer provided between the substrate and the recording layer are set so as to satisfy the relationship n3>n2, Ra can be rendered higher than Rc in the recording layer to render Aa lower than Ac. Further, when the refractive indexes n1, n2 of the first and second dielectric layers among the first, second, and third dielectric layers provided between the substrate and the recording layer are set so as to satisfy the relationship n1>n2, the degree of freedom can be increased for the thickness of each of the layers. Further, according to the invention, since no light absorptive layer is present between the recording layer and the substrate, the temperature rise around the surface of the substrate can be inhibited to reduce the heat load applied to the substrate. This can increase the possible number of times of rewriting of information.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be explained in more detail in conjunction with the appended drawings, wherein:
FIG. 1 is a diagram showing the construction of a phase-change type optical disk according to a preferred embodiment of the invention;
FIG. 2 is a diagram showing one example of optical properties of an optical disk according to a preferred embodiment of the invention;
FIG. 3 is a diagram showing the relationship between the ratio of the refractive index of the first dielectric layer to the refractive index of the second dielectric layer and the thickness of the fourth dielectric layer for a phase-change type optical disk according to a preferred embodiment of the invention wherein Ac is larger than Aa;
FIG. 4 is a diagram illustrating temperature rise upon information recording; and
FIG. 5 is a diagram showing cross erasing properties.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the invention will be described in conjunction with the appended drawings. FIG. 1 is a cross-sectional view of a phase-change type optical disk according to a preferred embodiment of the invention. The phase-change type optical disk has a structure comprising: a transparent substrate 10; and, provided on the transparent substrate 10 in the following order, a first dielectric layer 11, a second dielectric layer 12, a third dielectric layer 13, a recording layer 15, a fourth dielectric layer 14, and a reflective layer 16.
FIG. 2 is a diagram showing the relationship between the change in n3/n2 ratio and the Aa and Ac values, determined by optical calculation according to the matrix method. As is apparent from FIG. 2, when the relationship n2<n3 is satisfied, Aa is lower than Ac. Preferably, the refractive index ni of the first dielectric layer and the refractive index n2 of the second dielectric layer satisfy the relationship n1>n2. Even though the relationship n1>n2 is not satisfied, it is not impossible to realize Aa <Ac. In this case, however, when n1=n2 or n1<n2, the thickness of the fourth dielectric layer, which can realize Aa<Ac, is limited, making it difficult to ensure satisfactory rewrite cycling properties. FIG. 3 is a diagram showing the lower limit of the thickness of the fourth dielectric layer, which can realize Aa<Ac, determined by optical calculation according to the matrix method. From FIG. 3, it is apparent that, when n1≦n2, the thickness of the fourth dielectric layer should be not less than 90 nm. In order to improve the rewrite cycling properties, the thickness of the fourth dielectric layer is preferably as small as possible and not more than 60 nm. For this reason, it is preferred to satisfy the relationship n1>n2.
Thus, in the recording layer, when the light absorption in the amorphous state, Aa, has been rendered lower than the light absorption in the crystal state, Ac, as shown in FIG. 4, application of a laser beam spot SP to one record track (groove) T1 in a phase-change optical disk to form a record mark M1 and consequently to record information creates temperature distribution as shown in FIG. 4 around the record track T1 in the recording layer 15 by heat energy of the laser beam. For this reason, when record marks M2, M3 in amorphous state with information recorded thereon are present in adjacent record tracks (lands) T2, T3, the record marks M2, M3 are influenced by the temperature of the laser beam spot SP. Since, however, the light absorption of the record marks M2, M3 in amorphous state, Aa, is lower than the light absorption of the recording track T1 in crystal state, Ac, the amount of laser beam absorbed in the record marks M2, M3 is reduced, inhibiting the temperature rise of the record marks M2, M3. This can prevent the record marks M2, M3 from being erased, that is, can prevent cross erasing.
In this case, when the refractive index n1 of the first dielectric layer 11 is identical to the refractive index n0 of the substrate 10, the substrate 10 is optically identical to the first dielectric layer 11, making it impossible to attain the effect of rendering Ra higher than Rc, that is, optical interference effect. Therefore, the refractive index n1 of the first dielectric layer 11 should be larger than the refractive index n0 of the substrate 10. Since plastic substrates and glass substrates generally have a refractive index of about 1.5, n1 should be larger than 1.7.
Further, in this construction, no light absorptive layer is provided between the substrate 10 and the recording layer 15. This can inhibit the temperature rise around the surface of the substrate 10, can reduce the application of heat load to the substrate, and can improve rewrite cycling properties. The reflective layer 16 is formed of a metallic material in order to enhance radiation properties and to improve rewrite cycling properties. The thickness of the reflective layer 16 is preferably 40 to 300 nm. When the thickness of the reflective layer 16 is less than 40 nm, satisfactory radiation properties cannot be provided, resulting in deteriorated rewrite cycling properties, while when the thickness exceeds 300 nm, the reflective layer 16 is likely to be separated.
Preferred embodiments of the invention will be described. A phase-change type optical disk as shown in FIG. 1 was prepared as follows. Polycarbonate was provided as the substrate 10. A 60 nm-thick ZnS--SiO 2 layer was sputtered on the substrate 10 to form the first dielectric layer 11. A 90 nm-thick SiO 2 layer was then sputtered on the first dielectric layer 11 to form the second dielectric layer 12. A 50 nm-thick ZnS--SiO 2 layer was then sputtered on the second dielectric layer 12 to form the third dielectric layer 13. A 12 nm-thick Ge 2 Sb 2 Te 5 layer was sputtered on the third dielectric layer 13 to form the recording layer 15. A 40 nm-thick ZnS--SiO 2 layer was then sputtered on the recording layer 15 to form the fourth dielectric layer 14. Finally, a 120 nm-thick aluminum layer was sputtered on the fourth dielectric layer 14 to form the reflective layer 16. Thus, a phase-change type optical disk as shown in FIG. 1 was obtained. In this case, the refractive index n of the third dielectric layer 13 (ZnS--SiO 2 ) was 2.1, and the refractive index n of the second dielectric layer 12 (SiO 2 ) 1.5. The pitch of guide grooves for record tracks (track pitch) as shown in FIG. 4 was 1.1 μm.
For this phase-change type optical disk, the light absorption of the recording layer 15 in crystal state, Ac, and the light absorption of the recording layer 15 in amorphous state, Aa, were measured and found to be 90% (Ac) and 60% (Aa), respectively. Further, for the phase-change type optical disk, a rewrite test was carried out under conditions of rotation at a linear velocity of 5 m/sec, a wavelength of 660 nm, and a numerical aperture of an object lens of 0.6 in an optical head. A signal of 1 MHz and duty=50% was first recorded on a land potion. Thereafter, a signal of 1.5 MHz and duty=50% was repeatedly recorded on both groove portions adjacent to the land portion to measure a change in carrier of the 1 MHz signal. As is apparent from FIG. 5, repetition of rewriting of information on the adjacent groove portions did not have an influence on the 1 MHz signal at all. In FIG. 5, the difference between a carrier Ci of 1 MHz signal, as measured in such a state that no information is recorded on the adjacent tracks, and a carrier C1 of 1 MHz signal, as measured after repetition of recording of 1.5 MHz signal on the adjacent tracks a predetermined number of times, that is, Ci-C1, is indicated. A signal of 1 MHz and duty=50% was repeatedly recorded on the phase-change type optical disk. As a result, there was no change in carrier and noise of 1 MHz signal until the recording was repeated 500,000 times.
A second preferred embodiment will be explained. Polycarbonate was provided as the substrate 10. A 100 nm-thick ZnS layer was sputtered on the substrate 10 to form the first dielectric layer 11. A 50 nm-thick SiN layer was then sputtered on the first dielectric layer 11 to form the second dielectric layer 12. An 80 nm-thick ZnS layer was then sputtered on the second dielectric layer 12 to form the third dielectric layer 13. A 15 nm-thick GeSb 2 Te 4 layer was sputtered on the third dielectric layer 13 to form the recording layer 15. A 20 nm-thick ZnS--SiO 2 layer was then sputtered on the recording layer 15 to form the fourth dielectric layer 14. Finally, a 100 nm-thick aluminum layer was sputtered on the fourth dielectric layer 14 to form the reflective layer 16. Thus, a phase-change type optical disk was obtained. In this case, the refractive index of the second dielectric layer 12 (SiN) was 1.9, and the refractive index of the first dielectric layer 11 and the third dielectric layer 13 (ZnS) was 2.3. The pitch of guide grooves for record tracks (track pitch) as shown in FIG. 4 was 1.1 μm.
For this phase-change type optical disk, Ac and Aa in the recording layer 15 were 85% and 65%, respectively. For the phase-change type optical disk, a rewrite test was carried out under conditions of rotation at a linear velocity of 5 m/sec, a wavelength of 660 nm, and a numerical aperture of an object lens of 0.6 in an optical head. In the same manner as in the above preferred example, a signal of 1 MHz and duty=50% was first recorded on a land potion, followed by repeated recording of a signal of 1.5 MHz and duty=50% on both groove portions adjacent to the land portion to measure a change in carrier of the 1 MHz signal. Also for this phase-change type optical disk, repetition of rewriting of information on the adjacent groove portions did not have an influence on the 1 MHz signal at all. A signal of 1 MHz and duty=50% was repeatedly recorded on the phase-change type optical disk. As a result, there was no change in carrier and noise of 1 MHz signal until the recording was repeated 500,000 times.
An additional preferred embodiment will be explained. Polycarbonate was provided as the substrate 10. A 100 nm-thick SiN layer was sputtered on the substrate 10 to form the first dielectric layer 11. A 20 nm-thick SiO 2 layer was then sputtered on the first dielectric layer 11 to form the second dielectric layer 12. A 100 nm-thick ZnS layer was then sputtered on the second dielectric layer 12 to form the third dielectric layer 13. A 13 nm-thick GeSb 2 Te 4 layer was sputtered on the third dielectric layer 13 to form the recording layer 15. A 50 nm-thick ZnS--SiO 2 layer was then sputtered on the recording layer 15 to form the fourth dielectric layer 14. Finally, a 100 nm-thick aluminum layer was sputtered on the fourth dielectric layer 14 to form the reflective layer 16. Thus, a phase-change type optical disk was obtained. In this case, the refractive index of ZnS was 2.3, the refractive index of SiN 1.9, and the refractive index of SiO 2 1.5. The track pitch was the same as that in each of the above preferred embodiments, that is, 1.1 μm.
For this phase-change type optical disk, Ac and Aa in the recording layer 15 were 80% and 60%, respectively. For the phase-change type optical disk, a rewrite test was carried out under conditions of rotation at a linear velocity of 5 m/sec, a wavelength of 860 nm, and a numerical aperture of an object lens of 0.6 in an optical head. In the same manner as in the above preferred example, a signal of 1 MHz and duty=50% was first recorded on a land potion, followed by repeated recording of a signal of 1.5 MHz and duty=50% on both groove portions adjacent to the land portion to measure a change in carrier of the 1 MHz signal. Also for this phase-change type optical disk, repetition of rewriting of information on the adjacent groove portions did not have an influence on the 1 MHz signal at all. A signal of 1 MHz and duty=50% was repeatedly recorded on the phase-change type optical disk. As a result, there was no change in carrier and noise of 1 MHz signal until the recording was repeated 500,000 times.
Materials for the dielectric layer, the recording layer, and the reflective layer constituting the phase-change type optical disk according to the present invention are not limited to those described in the preferred embodiments. In particular, the reflective layer may be formed of, besides the metals described in the preferred embodiments, a metal selected from gold, aluminum, titanium, copper, chromium, and alloys of the above metals.
As described above, the phase-change type optical disk can inhibit cross erasing on adjacent record tracks at the time of recording and can narrow the track pitch of record tracks to improve the record density. Further, the absence of a light absorptive layer between the recording layer and the substrate can inhibit the temperature rise around the surface of the substrate, can reduce the application of heat load to the substrate, and can improve rewrite cycling properties. Furthermore, since the light absorption of the recording layer in amorphous state is reduced, erasing of data can be prevented even in the case of high power caused by a fluctuation in a reproduction laser beam and, in addition, when the wavelength of the laser beam source is shortened in the future, erasing of data by the reproduction laser beam can be prevented.
The invention has been described in detail with particular reference to preferred embodiments, but it will be understood that variations and modifications can be effected within the scope of the invention as set forth in the appended claims. | A first dielectric layer, a second dielectric layer, a third dielectric layer, a recording layer, a fourth dielectric layer, and a reflective layer are provided in that order on a substrate to constitute a phase-change type optical disk. The first dielectric layer, the second dielectric layer, and the third dielectric layer are constructed to satisfy the relationships: n1>n2 and n3>n2 wherein n1 represents the refractive index of the first dielectric layer, n2 represents the refractive index of the third dielectric layer, n3 represents the refractive index of the second dielectric layer. According to the above construction, the light reflectance of the amorphous area can be increased to lower the light absorption of the amorphous area, realizing inhibition of cross erasing. Further, since no light absorptive layer is present between the substrate and the recording layer, the temperature rise around the surface of the substrate can be inhibited to reduce the thermal deformation of the substrate. This can improve rewrite cycling properties. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to portable electronic devices which utilize batteries. More particularly, the present invention relates to portable medical devices. Still more particularly, the present invention relates to methods and apparatus for the maintenance and management of the batteries of such portable medical devices.
2. Description of the Prior Art
Battery management is a concern in any portable electronic device, but is a primary concern in portable medical devices. The need for more comprehensive battery maintenance in portable and implantable medical devices has been noted, for example, in U.S. Pat. No. 4,080,558 to Sullivan, U.S. Pat. No. 5,411,537 to Munshi, et. al., U.S. Pat. No. 5,483,165 to Cameron, et. al., and U.S. Pat. No. 5,470,343 to Fincke, et. al.
A defibrillator is a device capable of delivering a preset amount of electrical energy to a patient's heart for the purpose of terminating an arrhythmia. For portable defibrillators, batteries are used to provide the electrical energy delivered. Historically, portable defibrillator maintenance has been problematic due to insufficient means to ensure comprehensive management of the batteries. As portable medical devices are intended for relatively long-term monitoring and, in the case of portable defibrillators, intended for therapeutic shock delivery for patients at risk from sudden cardiac death due to tachyarrhythmias, a comprehensive battery management program is essential.
Historically portable defibrillator design has been concerned with ensuring that the devices function properly when needed. Problems may arise if the batteries of the defibrillators are at less than full capacity or are worn out or are accidentally taken off their chargers so that the batteries are nonfunctional.
Therefore, there is a need in the portable electronic device industry, and, in particular, in the portable medical electronic device industry to implement a comprehensive way of informing the patient, as precisely as possible, of the status of that patient's device, and particularly the status of the device battery. This status should include not only the current conditions of the device battery but also other information, such as an indication of how much time remained in which the device would be operable.
SUMMARY OF THE INVENTION
The present invention is preferably utilized in connection with a patient-worn energy delivery system for imparting electrical therapy to the body of a patient responsive to an occurrence of a treatable condition. The present invention is designed to constantly monitor and comprehensively inform the patient of the condition of the device, and particularly the condition of the device battery.
The system includes a monitor-defibrillator worn by the patient. The monitor-defibrillator monitors the patient's ECG to detect life threatening arrhythmias and delivers a cardioverting or defibrillating shock if needed. The monitor-defibrillator records system operational information and ECG signal data. Periodically the patient is required to off-load this information to a patient base station. This is accomplished when the monitor-defibrillator is connected to a patient base station at the time battery charging is initiated. Thus, the patient base station is coupled with the monitor-defibrillator for periodic battery charging, device maintenance and the offloading of data. When a monitor-defibrillator is inserted into the monitor interface connector, the patient base station retrieves battery status from the monitor. The patient base station analyzes this information and may schedule maintenance operations or patient notifications if certain conditions are met.
The primary functions performed by the patient base station are providing data communication interfaces to the various components of the system, battery pack charging and maintenance, monitor-defibrillator maintenance, monitor-defibrillator data retrieval and storage, facilitating monitor-defibrillator initialization via the physician programming console and providing visual and audible feedback for patient interactions.
The patient base station provides means to simulate the operation of various monitor-defibrillator and electrode harness hardware functions. These enable the patient base station to verify that the monitor-defibrillator and the electrode harness hardware is functioning properly.
A physician programming console is also utilized, which is an IBM PC-AT compatible computer. The physician programming console facilitates programming of the patient base station and the monitor-defibrillator. Also included is an electrode harness, worn by the patient on the chest, which contains electrodes for sensing ECG signals from the heart and large surface area electrodes for delivering therapy pulses to the heart in the event of the occurrence of a treatable arrhythmia.
The monitor-defibrillator indicates the future time or activity level remaining at which the device could operate. The apparatus considers the rates of discharge and the rates of use and the amount of energy taken out of the battery. The device also monitors the number of charge cycles on the battery, the date when the battery was installed and other pertinent information such as battery pack expiration parameters.
The monitor-defibrillator itself includes circuitry to monitor the capacity of the battery. Thus, if the monitor-defibrillator undergoes some kind of abnormality, for example, some component begins drawing more current than the normal average current of the device, the circuit will detect the abnormality and the current will trip a comparator. The comparator alerts the computer and the remaining run time of the battery pack will be adjusted accordingly and can be displayed to the patient.
The patient base station also periodically performs a capacity check on the monitor-defibrillator when the monitor-defibrillator is coupled to the patient base station during charging and maintenance operations. This is a more comprehensive check than the one performed internal to the monitor-defibrillator. The patient base station can discharge the battery fully, charge it up fully and then discharge the battery. The current that's being discharged is precise, thus, over a period of time the processor could calculate whether the actual capacity of the battery is meeting the specifications. Factors such as the amount of charge and the rate of discharge are considered.
Having the capability to perform the monitoring functions on the monitor-defibrillator rather than solely at some remote base station is beneficial because the battery is necessarily contained in the monitor-defibrillator or attached to it via an electrical connector. Thus, if the patient has traveled away from the base station, that patient would have to return to the base station to be certain that sufficient capacity remained in the battery.
The objects and advantages of the invention will become apparent from the following description of certain present preferred embodiments taken in conjunction with the attached drawings and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a patient base station block diagram showing the patient base station, physician's programming console and the monitor-defibrillator connected to either the patient base station or the electrode harness.
FIG. 2 is a block diagram showing the patient base station computer, real-time clock, counter timer, analog/digital converter and backup battery, and monitor-defibrillator battery connection.
FIG. 3 is a block diagram for the battery load test function.
FIG. 4 is a diagrammatic perspective view of the monitor-defibrillator and patient base station.
FIG. 5 is a block diagram for the patient base station patient interface module.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
An apparatus is provided for monitoring and supporting the monitor-defibrillator electronics and the rechargeable battery pack provided therein. The system 10 of the present invention is shown schematically in FIG. 1. As can be seen from FIG. 1, the present system 10 involves a number of interrelated components. A monitor-defibrillator 12 is included which is operatively connectable via an interface module 26, to either a patient base station 30 or an electrode harness 66 having two groups of electrodes 14, 16. A group of delivering electrodes 14 is provided for delivering a cardioverting or defibrillating shock when necessary to a patient. Another group of electrodes 16 performs sensing operations in which the physiological condition of a patient may be monitored. The delivering electrodes 14 are operatively connected to a converter-defibrillator 19 located within the monitor-defibrillator 12. The electrode harness 66 also includes a patient display 24 with the capability of displaying visual messages, enunciating audio messages and activating audio alarms. The patient display 24 also includes various buttons for providing the patient with a means of input to the device. The operation of the electrode harness/monitor-defibrillator are more particularly described in co-pending application Ser. No. 08/651,274, assigned to the present assignee and hereby incorporated by reference herein.
The battery pack 18 is responsible for providing the necessary power to operate the converter-defibrillator circuitry for delivering the cardioverting or defibrillating shock. Therefore, it is important that the energy capacity of battery 18 be ensured. The monitor-defibrillator 12 preferably utilizes a high-energy-density nickel-cadmium battery. Preferably, the battery is comprised of five 1.2 volt cells connected in series to yield six volts.
The monitor-defibrillator 12 also includes battery control circuitry 20 which can activate the battery 18 to deliver its charge to the converter-defibrillator 19 and subsequently to the delivery electrodes 14 when necessary. The battery control circuitry 20 is responsive to certain data conditions of the patient. For this reason, the battery control 20 is operatively connected to data storage/processor 22, also located within the monitor-defibrillator 12. The data storage/processor 22 receives data from the sensing electrodes 16. The data storage/processor 22 in the monitor-defibrillator preferably utilizes non-volatile memory. The data storage/processor 22 stores programmable system operational parameters, system operating status information, digitized ECG episodes and the results of hardware diagnostic tests. This data, through subsequent analysis, provides the means to allow reconstruction of ECG events and analysis of device performance.
The monitor-defibrillator 12 is able to perform various system and battery checks. Energy usage of the monitor-defibrillator 12 is monitored in real time to determine the useful energy remaining of the battery 18 per charge. The patient display 24 located on the electrode harness 66 indicates the operating time remaining for the battery 18. The patient may access this function at any time by pressing a button on the patient display 24. The run-time parameter is available to an external host via the communications interface located in the interface module 26. A low battery condition as determined by the monitor-defibrillator 12 is recorded in non-volatile memory of the data storage/processor 22. The patient is also alerted to a low battery condition by the patient display 24.
The monitor-defibrillator 12 monitors the battery current consumption and, if required, makes an appropriate adjustment to the battery run-time parameter based on sampling the real-time monitor-defibrillator current consumption. The current is monitored by an analog circuit in the monitor-defibrillator 12 and is input into a comparator at a trip level of current. The voltage is monitored but is not sent to the comparator. The trip level is a level of current that is based on a precalculated worst case (i.e., maximum) average current developed for the device. For the particular hardware used with the present invention, the amount of typical maximum run current (i.e., the trip level current) is 74 milliamperes. If the measured current exceeds the trip level, the comparator trips and the analog to digital converter in the data storage/processor 22 is commanded to read the analog representation of the current that is being drawn by the monitor-defibrillator 12. The monitor-defibrillator 12 measures the time period of excessive current draw and the amount of current above the trip level. Based on the measured readings, time is deducted from the battery runtime parameter by the monitor-defibrillator. The updated runtime remaining may be accessed by the patient at any time, as discussed above.
As long as the actual, measured current of the monitor-defibrillator 12 is less than the trip level current, the data storage/processor 22 presumes that the actual current is the same as the trip current when deducting time from the battery runtime parameter. Thus, although the typical maximum run current is provided as 74 mils, the battery 18 is nearly always providing a current below 74 milliamps.
The patient has the capability to access buttons on the patient display 24 that when activated will cause the remaining run time to be indicated. If a patient is very active so as to cause one of the sensing electrodes 16 to have fallen off or otherwise become disconnected from the patient, an alarm is sounded. The activation of this alarm also utilizes energy which will be subtracted from the run time.
The current measuring capability of the monitor-defibrillator 12 does not include current drawn by the converter-defibrillator 19. The monitor-defibrillator 12 tracks the periods when the converter-defibrillator 19 is actively drawing current from the battery 18 and makes adjustments to the battery run time to compensate for the energy loss.
The monitor-defibrillator 12 also makes adjustments for depletion of battery 18 capacity during periods when the device is not being used. When not in use (such as when stored on a shelf or taken by the patient on a day's outing as a spare device) the monitor-defibrillator 12 will automatically power itself up at specified intervals and make adjustments to the battery run time to compensate for energy losses due to self-discharge of the battery and current draw of monitor-defibrillator 12 components when powered down.
The monitor-defibrillator 12 will utilize measures intended to reduce depletion of battery 18 capacity in order to maximize available energy if a treatment pulse is required. The monitor-defibrillator 12 will be optimized to execute its monitoring functions as rapidly as possible and then enter a low power operating mode until the monitoring functions must again be executed. The monitor-defibrillator can be kept in a low power operating mode when not performing necessary system operating functions. Additionally, when possible, high current devices will be powered down after completing their required tasks. An example would be the analog to digital converter. By scheduling analog to digital conversion readings at the beginning of monitoring functions, the analog to digital converter can be powered down sooner than if analog to digital readings are interspersed throughout the monitoring functions.
If the run time parameter indicates that the depletion of battery 18 capacity has reached the level at which the battery 18 should be recharged utilizing the patient base station 30, then the patient display 24 will provide notification. The notification will consist of visual and/or audio indicators. The notification will require acknowledgment by the patient before it will be discontinued. The notification will be repeated at predetermined intervals, for example, every 15 minutes, until the battery 18 is recharged by the patient base station 30. The monitor-defibrillator 12 can also determine the available device operating time (prior to recharging the battery), taking into account at least: (1) adjustments for abnormally high current draw of the device including adjustments for converter operation or operation of other high current draw devices as well as adjustments for excessive current draw from a defective component; (2) adjustments for normal current draw during an elapsed time period; (3) adjustments for device fault conditions such as failure of a battery load test or a problem with operation of the converter; and (4) adjustments for depletion of battery capacity during periods of non-use. The patient display 24 or alarms can be used to notify the patient of the available device operating time.
The monitor-defibrillator 12 will also utilize an analog to digital converter located in the data storage/processor 22 to supervise the battery 18 voltage during operation of the converter-defibrillator 19. The converter-defibrillator 19 may be operated in either a fast charge mode or a slow charge mode. The fast charge mode minimizes the time to charge the converter-defibrillator 19 but at a maximized current draw from the battery 18. The slow charge mode minimizes the capacitor charging current but with an increased time to charge the converter-defibrillator 19. The converter-defibrillator 19 is normally operated in fast charge mode.
If the battery 18 voltage falls below a level at which the monitor-defibrillator 12 can reliably operate the converter-defibrillator 19, then the monitor-defibrillator 12 will switch the converter-defibrillator 19 to a slow charge mode. This will permit the battery 18 voltage level to recover to a level at which the monitor-defibrillator 12 can again reliably operate the converter-defibrillator 19. Use of the slow charge mode permits the converter to be operated and a therapy pulse delivered to the patient when the battery 18 capacity is low.
If during operation of the converter-defibrillator 19 in the slow charge mode the battery 18 voltage falls below a level at which the monitor-defibrillator 12 can reliably operate the converter-defibrillator 19, then the monitor-defibrillator 12 will deactivate the converter and evaluate the energy capability stored in the converter. If the energy stored in the converter is sufficient to deliver at least a minimal energy pulse, such as, for example, 30 joules, then the treatment cycle will continue with delivery of the available energy. If there is not enough energy stored in the converter to deliver a minimal energy pulse, then the converter will be discharged. In addition, notification will be given using the patient display 24 that the device is disabled and medical assistance should be provided to the patient.
If the monitor-defibrillator 12 determines that the battery 18 capacity has fallen below a level at which the system performance data is in danger of being corrupted then the monitor-defibrillator 12 will remove operating power. The removal of operating power will reserve the remaining battery 18 capacity for maintenance of the data storage/processor 22. The integrity of the data storage is essential to evaluating the proper operation of the device. Since this low level of battery 18 capacity is inadequate for reliable operation of the monitor-defibrillator, the best possible use of the remaining battery 18 capacity is to preserve the operational history of the device stored in the data storage/processor 22. When this state has been reached, the monitor-defibrillator will refuse to power up until connected to the patient base station 30. If required, the patient base station 30 will provide additional energy to the monitor-defibrillator 12 to insure proper functioning during this power up sequence. The patient base station will then retrieve the operational history from the monitor-defibrillator 12 and recharge the battery 18.
The analog to digital converter located in the data storage/processor 22 is powered up each interim cycle to sample the analog inputs. This interim cycle is preferably every 5 milliseconds, which generally corresponds to the ECG sampling rate. After sampling the analog inputs, the analog to digital converter is powered down to conserve battery power. There are entire portions of the monitor-defibrillator 12 that periodically go into a low current sleep mode.
On a routine basis the patient is required to couple the monitor-defibrillator 12 with the patient base station 30 (see FIG. 4). When the monitor-defibrillator 12 is removed from the electrode harness 66 and inserted in the receptacle 31 of the patient base station, connection is made between the monitor-defibrillator interface 26 and a monitor-defibrillator interface 32 located within the patient base station 30. The patient base station monitor-defibrillator interface 32 is thus operatively connected to the data storage/processor 22 of the monitor-defibrillator 12. In this way, the monitor-defibrillator interface 32 can download information from the memory of the data storage/processor circuitry 22; i.e., information, that was received from both the sensing electrodes 16 regarding the patient's physiological data, and also from the battery control circuitry 20 regarding the operating history of the monitor-defibrillator 12.
The monitor-defibrillator interface 32 of the patient base station 30 is also operatively connected to the battery 18. In this way, the patient base station 30 can perform comprehensive tests as to the operating parameters of the battery 18. Further, charging of the battery 18 can also be performed through the monitor-defibrillator interface 32. The battery 18 of each monitor-defibrillator 12 requires periodic charging. Thus, monitor-defibrillators 12 that are not in use are to be stored on a patient base station charging port (i.e., coupled to the monitor-defibrillator interface 32), where they undergo charging and maintenance operations. The patient base station 30 provides battery status information to the patient by way of a visual display including indicator lights as well as by audio alarms provided by the patient interface 46.
The power required to charge the battery 18 of the monitor-defibrillator 12 is supplied by either an internal or an external power supply. As shown in FIG. 1, an internal power supply 38 may be used which is operatively connected to the charger interface module 34. A switch mode type power supply 38 is preferred. However, a linear type power supply 38 could also be utilized. If a linear type power supply 38 is used, a heat sink and a fan would be needed in the patient base station 30. Use of a switch mode type power supply 38 would eliminate the fan, reduce the size of the heat sinks and would reduce the size of the system package and is thus preferred.
The power supply 38 utilizes a power entry module 36. The power entry module 36 provides a standard IEC 320 type power entry connector. The power entry module 36 functions over a full range of standard household international voltages and frequencies. The power entry module 36 shall preferably use a standard international "1/0" icon for power status indication.
The monitor-defibrillator interface 32 is operatively connected to the charger interface module 34 within the patient base station 30. The charger interface module 34 provides a standard PC-AT compatible ISA type interface and provides all the necessary bus signals for computer control of the various charger interface module functions. In this way, data received by the monitor-defibrillator interface 32 from the data storage/processor 22 of the monitor-defibrillator 12 is provided to a computer 40. In this way, communication is then established for transfer of operational data to the patient base station mass data storage area 42. This data is a record of device performance and any ECG data that may have been stored within the monitor-defibrillator 12 during patient monitoring.
Thus, the patient base station initiates data retrieval operations from the monitor-defibrillator 12 if operational or ECG data is stored within the internal memory included in the data storage/processor 22 of the monitor-defibrillator 12. As part of normal maintenance of the monitor-defibrillator 12, this data is transferred to the patient base station 30 for long-term data storage 42. The patient base station 30 may store retrieved data on a removable floppy disk, removable or fixed hard disk or other removable media. In the preferred embodiment, the data is stored on a fixed hard disk. At the successful completion of data transfer, the computer 40 of the patient base station 30 issues a clear memory command via the monitor-defibrillator interface 32 to the monitor-defibrillator 12. This command erases the temporary memory in the data storage/processor 22 in the monitor-defibrillator 12. In the embodiment utilizing rotating media, the patient base station notifies the patient when the removable media requires replacement due to inadequate storage area remaining.
The computer 40 utilized by the patient base station 30 incorporates an imbedded, PC-AT-compatible computer architecture. The computer 40 preferably utilizes an Intel™80×86 type central processing unit, with a performance no less than that of a 25 MHz 80386SX Intel™ processor. The computer 40 preferably includes two standard PC-AT type serial ports. A modem interface port 44 should also be available for connecting the computer 40 to a telephone modem (not shown). The modem interface 44 is designed to interface to a telephone modem with no less than 14.4 kpbs data rate capability. The modem preferably interfaces to the single board computer 40 via one of its serial ports.
A physician's programming console ("PPC") interface 48 provides a communication link from the patient base station ("PBS") 30 to a physician's programming console 70. The physician's programming console interface 48 contains an ethernet communications module 52 for providing a standard 10 Mbps data link to the physician's programming console 70. This module 52 preferably interfaces to the single board computer 40 via an expansion bus 54. Data transfers between the patient base station 30 and the physician's programming console 70 are handled via the ethernet port 52. This allows the significant amount of data generated by the monitor-defibrillator 12 to be offloaded in a reasonable time at the physician's office during thc patient's periodic visits. The external panel connection for the high speed physician's programming console 70 data link can use a standard BNC type female connector. A serial communications port 50 is also part of the physician programming console interface 48 and is provided for connection of the computer 40 to the physician's programming console 70. Data transfer from the patient base station 30 to the physician's programming console 70 can also occur via high speed modem interface 44 from the patient's home.
The computer 40 is operatively connected to an ISA type expansion bus 54. The expansion bus 54 is designed to be capable of supporting up to four 16 bit expansion modules or cards. The computer 40 utilizes the expansion bus 54 to facilitate communications, control and status transfers to and from the charger interface module 34 and ethernet communication module 52 of the physicians programming console interface 48. The expansion bus 54 also provides power to the computer 40 and the ethernet communication module 52 from the charger interface module 34.
The operating system and applications software for the patient base station 30 may be stored on rotating media in the mass data storage area 42. However, the preferred embodiment embeds this software in non-volatile read only memory, such as EEPROM or FLASH memory. These embodiments allow the device to operate without need of rotating media. Additional non-volatile memory is provided to store certain manufacturing information and device-specific data. These memory locations are written to only during the initial manufacturing processes and are then write inhibited by hardware means. As shown in FIG. 2, a real time clock may be implemented in conjunction with the computer 40 to maintain date and time of day information. The clock has backup power 62 provided to maintain operation if power is removed from the patient base station. A counter-timer 72 is provided to coordinate time critical operations. An analog to digital converter 64 is also provided.
The patient base station computer 40 controls battery charging, both rapid charging and float charging once the full charge point is reached. The computer 40 also controls discharging of the battery 18, as required. A battery capacity test is periodically performed to verify the stored energy capacity of the monitor-defibrillator battery pack 18. The system processor 40 controls all battery capacity measurement operations by discharging the battery 18 to a defined starting level, rapid-charging the battery 18 to full potential, implementing a timed discharge cycle to deplete the battery 18 and calculating the actual energy capacity. This process can determine if a bad cell is present in the battery pack, or the measured battery capacity is less than a defined acceptable limit.
The patient interface module 46, as shown in FIG. 5, can have a visual display 47, battery status LED indicators 51, acknowledge push button 57 and ambient light sensor 49. The patient interface module 46 can be operatively associated with the charger interface module 34 and the analog to digital converter 64. The analog to digital converter 64 with an analog multiplexer is preferably provided within the patient base station 30. This analog to digital converter 64 allows the single board computer 40 (FIG. 1) to monitor the charging current of the charger/discharger 34, discharging current of the charger/discharger 34, the battery voltage present at the monitor-defibrillator interface 32, the ambient light sensor 49 of the patient interface module 46 and the ambient temperature within the patient base station 30 enclosure via a temperature sensor 55 (shown in FIG. 2).
Referring again to FIG. 1, the patient interface 46 in the patient base station 30 indicates the status of the monitor-defibrillator battery 18 during the battery capacity test cycle. The patient interface 46 preferably incorporates a front panel mounted vacuum fluorescent (VF) type display 47 (shown in FIG. 4). This display 47 may be a character type with standard 5 mm, 5×7 dot characters. The PBS display 47 is preferably arranged in one of the following configurations: a 2 line by 40 character or a 4 line by 20 character. The PBS display 47 is controlled by the single board computer 40 via the charger interface module 34 through a parallel data interface. As an alternative, a graphics type LCD may be used for the PBS display 47. If an LCD display is used, the patient base station may include an ambient light sensor 49 to control the LCD backlight for improved readability.
In addition, the patient base station 30 tracks battery 18 usage and notifies the patient when replacement of the battery 18 is required. If the battery 18 expiration parameters have been exceeded (the expiration date or the number of charge cycles), the battery 18 can still be used by the monitor-defibrillator 12, but the patient will be notified to replace the monitor-defibrillator 12 as soon as possible. The number of charging cycles performed on the battery 18 is recorded in the monitor-defibrillator memory of the data storage/processor 22. Also, the date the battery 18 was installed in the monitor-defibrillator 12, the type of cell used in the battery 18, and the expiration date of the battery 18 as well as any other pertinent information is stored in monitor-defibrillator data storage/processor 22.
The communications interface created when the patient base station 30 and attached monitor-defibrillator 12 is connected to the physician's programming console 70 is utilized during the initial configuration programming of the monitor-defibrillator 12. Preferably, the following information is configured: name, address, telephone number, hospital, attending physician, medications; monitor-defibrillator detection and treatment parameters such as heart rate threshold or rate cutoff, defibrillation energy to be delivered in therapy pulses; and monitor-defibrillator manufacturing data such as device serial numbers, monitor-defibrillator battery pack and expiration date, electrode harness(s) and expiration date(s).
A data communications protocol facilitates the transfer of digital information between the patient base station 30 and the physician's programming console 70. This protocol consists of transferring data in blocks or frames. To ensure the integrity of transmitted and received data, the protocol implements error checking techniques.
The patient base station 30 to physician's programming console 70 communications protocol consists of transferring data in frames. Communication frames are transferred via the serial communication port 50. Serial communication port 50 hardware control lines are utilized to provide handshaking between the patient base station 30 and the physician's programming console 70 that will delimit the frame boundaries. Each communication cycle consists of a command frame sent from the physician's programming console 70 to the patient base station 30, followed by a response frame sent from the patient base station 30 to the physician's programming console 70. Each command frame will contain a command code followed by any relevant data, followed by an error checking code such as a CRC code.
If the command is successfully processed by the patient base station 30, the patient base station 30 will return a response frame that contains an ACK code, followed by the original received command code, followed by any relevant data, followed by an error checking code such as a CRC code.
If the command is not successfully processed by the patient base station 30, the patient base station 30 will return a response frame that contains a NAK code, followed by the original received command code, followed by any relevant data, followed by an error checking code such as a CRC code.
If a command frame is received by the patient base station 30 that contains an invalid error checking code, the patient base station 30 will ignore the communication frame. The physician's programming console 70 will be responsible for monitoring the patient base station 30 response. If the patient base station 30 does not respond to a command frame the physician's programming console 70 can elect to resend the frame.
If a response frame is received by the physician's programming console 70 that contains an invalid error checking code, the physician's programming console 70 can elect to resend the frame.
Another data communications protocol facilitates the transfer of digital information between the monitor-defibrillator 12 and the patient base station 30. The protocol consists of transferring data in blocks or frames.
The patient base station ("PBS") 30 to monitor-defibrillator ("M-D") 12 communications protocol consists of transferring data in frames. Communication frames are transferred via the PBS/M-D interface 32. PBS/M-D interface 32 hardware control lines are utilizcd to provide handshaking between the patient base station 30 and the monitor-defibrillator 12 that will delimit communication frame boundaries. Each communication cycle consists of a command frame sent from the patient base station 30 to the monitor-defibrillator 12, followed by a response frame sent from the monitor-defibrillator 12 to the patient base station 30. Each command frame will contain a command code followed by any relevant data, followed by an error checking code such as a CRC code.
If the command is successfully processed by the monitor-defibrillator 12, the monitor-defibrillator 12 will return a response frame that contains an ACK code, followed by the original received command code, followed by any relevant data, followed by an error checking code such as a CRC code.
If the command is not successfully processed by the monitor-defibrillator 12, the monitor-defibrillator 12 will return a response frame that contains a NAK code, followed by the original received command code, followed by any relevant data, followed by an error checking code such as a CRC code. The patient base station 30 will determine and execute a response appropriate for the failed monitor-defibrillator 12 command process.
If a command frame is received by the monitor-defibrillator 12 that contains an invalid error checking code, the monitor-defibrillator 12 will return a response frame that contains a code indicating that the command was not properly received and should be resent. The patient base station 30 can elect to resend the command frame.
If a response frame is received by the patient base station 30 that contains an invalid error checking code, the patient base station 30 can elect to resend the frame or initiate monitor-defibrillator 12 fault condition processing.
The patient base station 30 offers a collection of commands that the physician's programming console 70 can utilize during communications with the patient base station 30. The command set provides a means to initiate various patient base station 30 and monitor-defibrillator 12 diagnostic, configuration, and data retrieval procedures.
The physician's programming console 70 can gain access to various monitor-defibrillator 12 information and operational features by issuing commands to the patient base station 30 via the serial communications port 50. Upon receipt of these commands, the patient base station 30 will issue the appropriate commands to the monitor-defibrillator 12 via the PBS/M-D interface 32, that will carry out the desired operation. The patient base station 30 will return to the physician's programming console 70 the monitor-defibrillator 12 response to the operation.
A digital output from the monitor-defibrillator data storage/processor is provided to control the activation of the battery test load. Activation of the load places a high current demand on the monitor-defibrillator battery 18. This determines if the monitor-defibrillator battery pack contains any defective cells. The monitor-defibrillator 12 can determine the available device operation time (prior to recharging the battery) utilizing adjustments for abnormally high current draw, normal current draw, device fault conditions, and depletion of battery capacity during periods when the device is not in use.
Upon command from the patient base station or the monitor-defibrillator display, the monitor-defibrillator 12 performs a battery load test. The monitor-defibrillator 12 returns a pass-fail indication to the patient base station or the display. Load tests are most often performed with the display as the host. If the battery 18 fails the load test, the battery voltage measurement prior to the load test and at the point of failure are stored in the monitor-defibrillator non-volatile memory.
Referring to FIG. 3, the patient base station 30 provides circuitry in the charger interface module 34, that can charge or discharge the monitor-defibrillator 12 battery pack 18. The charger interface module 34 connects to the monitor-defibrillator 12 battery pack 18 via the PBS/M-D interface 32. Prior to battery pack 18 maintenance operations, the patient base station 30 will retrieve battery pack 18 identification information from the monitor-defibrillator 12 via the PBS/M-D interface 32.
Two charging modes are provided; rapid charging and float charging. During the rapid charge cycle the charger interface module 34 supplies charging current at the one hour charge rate of the battery pack 18. During float charge operations, the charger interface module 34 supplies charging current at the continuous maintenance rate of the battery pack 18.
The rapid and float charge current rates supplied by the charger interface module 34 arc adjustable by the patient base station computer 40. The patient base station computer 40 will configure the charger interface module 34 to supply a charge current rate that is appropriate for the connected battery pack 18.
During the discharge cycle, the charger interface module 34 provides a resistive load to the battery pack 18 that discharges the battery pack 18 at the one hour discharge rate of the battery pack 18. The discharge resistive load applied by the charger interface module 34 is adjustable by the patient base station computer 40. The patient base station computer 40 will configure the charger interface module 34 to apply a resistive load that causes a one hour current drain rate that is appropriate for the connected battery pack 18.
The battery charger interface module 34 can be controlled by the patient base station computer 40 or by the monitor-defibrillator 12 via the PBS/M-D interface 32. Monitor-defibrillator 12 control of the charger interface module 34 is accomplished by activating I/O control lines located in the PBS/M-D interface 32. These I/O lines will configure the charger interface module 34 for the desired charge/discharge operation. Alternately, the patient base station computer 40 can control the I/O lines and configure the charger interface module 34 for the desired charge/discharge operation. Under normal operation the monitor-defibrillator 12 controls the configuration of the charger interface module 34. The patient base station 30 configuration of the charger interface module 34 is a redundant feature that can be utilized if certain monitor-defibrillator 12 fault conditions exist such as a totally discharged monitor-defibrillator 12 battery pack 18.
Battery pack 18 charge and discharge cycles are initiated by the patient base station computer 40. When a monitor-defibrillator 12 is connected to the patient base station 30, the patient base station 30 retrieves monitor-defibrillator 12 battery operational status data from the data storage/processor 22 via PBS/M-D interface 32. The retrieved battery operational status data includes information such as the remaining battery capacity, fault condition flags, expiration parameters, battery maintenance parameters, and battery identification information. The patient base station 30 analyzes the retrieved battery data to determine the appropriate battery pack 18 maintenance procedure.
If the patient base station 30 determines that a rapid charge cycle is required, a command to initiate a rapid charge cycle will be sent to the monitor-defibrillator 12 via the PBS/M-D interface 32. Upon receipt of this command, the monitor-defibrillator 12 will configure the charger interface module 34 for rapid charge operation by activating I/O control lines located in the PBS/M-D interface 32. The monitor-defibrillator 12 will monitor the rapid charge sequence for completion and fault conditions. Successful rapid charge completion is determined by the monitor-defibrillator 12 monitoring the voltage level at the battery pack 18 positive terminal via the A/D converter located in the data storage/processor module 22. Successful rapid charge completion can also be declared if the monitor-defibrillator 12 detects a defined change in battery pack 18 temperature. The monitor-defibrillator 12 monitors the battery temperature via a temperature sensor located in the battery pack 18 and the A/D converter located in the data storage/processor module 22. When the monitor-defibrillator 12 detects a successful rapid charge completion, the monitor-defibrillator 12 will configure the charger interface module 34 for float charge operation by activating I/O control lines located in the PBS/M-D interface 32, reset the monitor-defibrillator 12 runtime parameter to the maximum value, and issue a rapid charge complete communications frame to the patient base station 30 via the PBS/M-D interface 32.
The rapid charge cycle will be aborted if the monitor-defibrillator 12 detects one of the following conditions: a battery pack 18 over voltage condition; a battery pack 18 over temperature condition; or a defined time interval elapsed without a rapid charge completion detected. The limit values are manufacturing parameters that are stored in the monitor-defibrillator 12 data storage/processor module 22.
If the monitor-defibrillator 18 aborts the rapid charge cycle the following operations will be performed: the monitor-defibrillator 12 will configure the charger interface module 34 for float charge operation by activating I/O control lines located in the PBS/M-D interface 32; the monitor-defibrillator 12 will set it's runtime parameter to zero, which will cause patient warning messages on the display 24; and the monitor-defibrillator 12 will issue a rapid charge fault communications frame to the patient base station 30 via the PBS/M-D interface 32. If the patient base station 30 receives a rapid charge fault communications frame from the monitor-defibrillator 12, the following operations will be performed: the event will be logged in the patient base station 30 operations log file located in the data storage module 42; and the patient base station 30 will activate a patient warning message that indicates the monitor-defibrillator 12 should be serviced.
During the rapid charge cycle, the patient base station 30 will insure proper charge operation by monitoring various system parameters. The system parameter limit values are stored in the data storage module 42 during the patient base station 30 manufacturing process.
The charging current supplied to the battery pack 18 is monitored for proper levels via an A/D converter 64 (FIG. 5) channel connected to the charger interface module 34. If the measured current is outside the defined limits, the patient base station 30 will abort the rapid charge cycle.
The charging voltage on the battery pack 18 is monitored for proper levels via an A/D converter 64 channel connected to the charger interface module 34. If the measured voltage is outside the defined limits, the patient base station 30 will abort the rapid charge cycle.
The patient base station 30 will abort the rapid charge cycle if the counter timer 72 (FIG. 2) indicates the charge cycle exceeded the maximum charge completion interval.
If the patient base station 30 determines that a rapid charge cycle abort is required, the following operations will be performed: an abort rapid charge cycle command will be issued to the monitor-defibrillator 12 via the PBS/M-D interface 32; the patient base station 30 will configure the charger interface module 34 for float charge operation; the patient base station 30 will issue a command to the monitor-defibrillator 12 to set the runtime parameter to zero, which will cause patient warning messages on the display 24; the event will be logged in the patient base station 30 operations log file located in the data storage module 42; and the patient base station 30 will activate a patient warning message that indicates the monitor-defibrillator 12 should be serviced.
The patient base station 30 may initiate a discharge cycle of the monitor-defibrillator 12 battery pack 18. The discharge cycle is utilized both during the battery capacity test as well as during the process of reconditioning the battery energy storage capabilities.
If the patient base station 30 determines that a discharge cycle is required, a command to initiate a discharge cycle will be sent to the monitor-defibrillator 12 via the PBS/M-D interface 32. Upon receipt of this command the monitor-defibrillator 12 will set the monitor-defibrillator 12 runtime parameter to zero and configure the charger interface module 34 for discharge operation by activating I/O control lines located in the PBS/M-D interface 32. The monitor-defibrillator 12 will monitor the discharge sequence for completion and fault conditions. Successful discharge completion is determined by the monitor-defibrillator 12 detecting the defined final discharge voltage threshold on the battery pack 18 positive terminal via the A/D converter located in the data storage/processor module 22. When the monitor-defibrillator 12 detects a successful discharge completion, the monitor-defibrillator 12 will configure the charger interface module 34 for float charge operation, by activating I/O control lines located in the PBS/M-D interface 32, and issue a discharge complete communications frame to the patient base station 30 via the PBS/M-D interface 32.
The discharge cycle will be aborted if the monitor-defibrillator 12 detects one of the following conditions: a battery pack 18 over temperature condition; or a defined time interval has elapsed without the detection of the discharge complete condition. The limit values are manufacturing parameters that are stored in the monitor-defibrillator 12 data storage/processor module 22.
If the monitor-defibrillator 12 aborts the discharge cycle the following operations will be performed: the monitor-defibrillator 12 will configure the charger interface module 34 for float charge operation by activating I/O control lines located in the PBS/M-D interface 32; and the monitor-defibrillator 12 will issue a discharge fault communications frame to the patient base station 30 via the PBS/M-D interface 32. If the patient base station 30 receives a discharge fault communications frame from the monitor-defibrillator 12, the event will be logged in the patient base station 30 operations log file located in the data storage module 42 and a patient warning message will be activated on the PBS display 47 that indicates the monitor-defibrillator 12 should be serviced.
During the discharge cycle, the patient base station 30 will insure proper discharge operation by monitoring various system parameters. The system parameter values are stored in the data storage module 42 during the patient base station 30 manufacturing process.
The discharge current drawn from the battery pack 18 is monitored for proper levels via an A/D converter 64 channel connected to the charger interface module 34. If the measured current is outside the defined limits, the patient base station 30 will abort the discharge cycle.
The discharge voltage on the battery pack 18 is monitored for proper levels via an A/D converter 64 channel connected to the charger interface module 34. If the measured voltage is outside the defined limits, the patient base station 30 will abort the discharge cycle.
The patient base station 30 will abort the discharge cycle if the counter timer 72 indicates the discharge cycle exceeded the maximum discharge completion interval.
If the patient base station 30 determines that a discharge cycle must be terminated, the following operations will be performed: an abort discharge cycle command will be issued to the monitor-defibrillator 12 via the PBS/M-D interface 32; the patient base station 30 will configure the charger interface module 34 for float charge operation; the patient base station 30 will issue a command to the monitor-defibrillator 12 to set the runtime parameter to zero, which will cause patient warning messages on the display 24; the event will be logged in the patient base station 30 operations log file located in the data storage module 42; and the patient base station 30 will activate a patient warning message that indicates the monitor-defibrillator 12 should be serviced.
The rapid charge cycle or discharge cycle will not be initiated if the monitor-defibrillator 12 determines that the battery pack 18 temperature is outside a set of defined limits. The limit values are manufacturing parameters that are stored in the monitor-defibrillator 12 data storage/processor module 22.
If the monitor-defibrillator 12 is removed from the patient base station 30 prior to completion of all battery pack maintenance operations, a message and alarm will be activated on the patient interface module 46. The message will indicate the monitor-defibrillator maintenance is not complete and to return the monitor-defibrillator to the patient base station. The interrupted maintenance procedure will be continued if the removed monitor-defibrillator 12 is reconnected to the patient base station 30.
The energy delivery capabilities of the battery pack 18 are periodically verified by testing the battery 18 energy capacity and high current delivery capabilities. The patient base station 30 will perform an energy capacity test on the battery pack 18 if the elapsed time from the last capacity test, as indicated by data retrieved from monitor-defibrillator data storage/processor module 22 via the PBS/M-D interface 32, exceeds the maximum time interval parameter stored in the data storage module 42, or status data retrieved from monitor-defibrillator data storage/processor module 22 via the PBS/M-D interface 32, indicates that the battery 18 operational performance was deficient during the previous patient monitoring cycle.
The battery 18 energy capacity test procedure consists of the following operations: the patient base station 30 will activate a message on the patient interface 46 visual display 47 that indicates the monitor-defibrillator 12 is being tested and to wait for the test to complete; the patient base station 30 initiates a battery discharge cycle to condition the battery for a full charge cycle; initiate a rapid charge cycle when the discharge cycle is complete to charge the battery 18 to full capacity; the patient base station 30 initiates a second discharge cycle when the rapid charge cycle is complete; and the patient base station 30 initiates a final rapid charge cycle at the completion of the second discharge cycle to ready the battery 18 for service. The duration of the second discharge cycle is timed by a counter timer located in the monitor-defibrillator 12 data storage/processor module 22. At the completion of the second discharge cycle the monitor-defibrillator 12 will compare the measured battery 18 discharge time with an acceptance parameter stored in storage/processor module 22. If the capacity discharge time is within the acceptable limit, monitor-defibrillator 12 will issue a capacity discharge pass communications frame to the patient base station 30 via the PBS/M-D interface 32.
If the capacity discharge time is not within the acceptable limit, the monitor-defibrillator 12 will set a battery capacity fault status flag located in the data storage/processor module 22, and issue a capacity discharge fault communications frame to the patient base station 30 via the PBS/M-D interface 32. The patient base station 30 will log the event in a log file located in the data storage module 42. Whenever the patient base station 30 receives a capacity discharge fault indication from the monitor-defibrillator 12, a patient warning message will be activated which indicates that the monitor-defibrillator 12 should be serviced as soon as possible. Each time a monitor-defibrillator 12 is connected to the patient base station 30, the patient base station 30 will retrieve the monitor-defibrillator 12 battery capacity fault status flag located in the data storage/processor module 22. If the battery capacity fault status flag is active, the patient base station 30 will initiate normal battery maintenance operations, with the exception of the battery capacity test which will no longer be performed. The patient base station 30 will also issue a command to the monitor-defibrillator 12 to set the runtime parameter to zero. This will cause repeated patient warning messages on the patient display 24.
If the battery status information indicates that the expiration date of the battery 18 has been exceeded (status information is entered during the initial configuration programming) or if the maximum number of charge cycles has been exceeded, the patient will be notified by the patient base station 30 that the monitor-defibrillator 12 should be serviced. The notification sequence will be activated until the patient acknowledges receipt by pressing a button 57 (FIG. 4) on the patient interface 46, or the monitor-defibrillator 12 is removed from the patient base station 30. Normal battery maintenance will continue so that the patient may use the monitor-defibrillator 12.
When a rapid charge cycle or battery discharge cycle is initiated, the patient base station 30 will deactivate the particular one of the battery status LED indicators 51 which is the "READY" LED indicator on the patient interface module 46 and activate the particular one of the battery status LED indicators 51 which is the "CHARGING" LED indicator. During the rapid charge cycle, the patient base station 30 displays a message on the patient interface visual display 47 that the monitor-defibrillator battery 18 is being charged and the monitor-defibrillator 12 is not ready for use.
If monitor-defibrillator maintenance operations are complete at the conclusion of a successful rapid charge cycle, the patient base station performs the following:
A message is displayed on the PBS display 47 indicating that the monitor-defibrillator 12 is ready for use; the PBS 30 "READY" LED 51 is activated; the "CHARGING" LED 51 is deactivated; and the monitor-defibrillator 12 is powered down.
The patient base station 30 logs the following battery maintenance information into a maintenance log: the start and completion times of battery operations; the length of the charge/discharge cycles; any abnormal conditions; and the charge cycle count, and if enabled, the battery voltage measurements taken during charge and discharge cycles. The maintenance log is stored in the data storage module 42.
The patient base station 30 issues various diagnostic test commands to the monitor-defibrillator 12. These tests are performed on a regular basis. Some tests are performed each time the monitor-defibrillator 12 is connected to the patient base station 30. Others are performed only as required. The monitor-defibrillator 12 executes the received commands and reports the test results to the patient base station 30. The patient base station 30 maintains a log of the test results on the mass storage media 42. If a fault is detected during any diagnostic procedure, the patient is notified of the condition along with the appropriate corrective action.
Variations of the preferred embodiment are possible. For example, the preferred patient base station system utilizes a charger interface module board. Stacked on top of that board are purchased assemblies of PC104 boards which form the CPU module 40 and Ethernet module 52. These boards are ISA compatible because the expansion bus 54 is an ISA type bus. The stacks of PC104 boards require a great deal of cabling which is very costly. Thus, all of the major system functions could be implemented on a single PC board. This would eliminate much of the cabling.
In accordance with the patent statutes we have described principles of operation and preferred embodiments of our invention. It should be understood, however, that within the scope of the appended claims, the invention may be practiced in a manner other than as illustrated and described. | A battery management system preferably has a base station utilized in connection with a portable electronic device for providing electrical therapy to the body of a patient in response to the occurrence of a treatable condition. The portable device can have a rechargeable battery, memory, data processor for determining available operating time for the portable device prior to recharging, and a display panel, or alarm, to inform the patient of such available operating time. The portable device data processor contains an analog to digital converter which is used to obtain and record data regarding the patient, the battery, and the portable device operational status. The base station can have a receptacle to receive the portable device, including a port for transferring data between the memory of the portable device and the base station, a power supply associated with the port for supplying charging current to the battery, a computer for exchanging information with the portable device memory, and a battery maintenance portion. The maintenance portion can perform tests on the battery to evaluate the condition thereof. The base station can further include a display and alarms to inform the patient regarding the condition of both the battery and the portable device. The portable device can also include a converter-defibrillator and a second battery maintenance portion which can operate independently of the base station. Tests can be performed, during operation of the portable device, to evaluate the condition of the battery while the portable device is separated from the base station. | 6 |
CONTINUITY DATA
[0001] This is a non-provisional of provisional patent application No. 61/174,044 filed on Apr. 30, 2009, and priority to that application is hereby claimed.
FIELD OF THE INVENTION
[0002] The present invention relates to a device that is formed to fit against a toilet in such a manner that the device is weighted down and provides traction while also elevating the user so the user can use a standard-sized toilet.
BACKGROUND OF THE PRESENT INVENTION
[0003] Children and other little people often have a difficult time reaching the toilet. This is due to their small stature, which causes practical issues that may be frustrating and embarrassing to this person. In addition, potty training is difficult enough for parent and child. When height limitations are included into the process, it merely makes the objective that much more complicated to achieve. Because of this, there is a need for a toilet helper so that children and little people can use a standard-sized toilet.
[0004] Specialized toilets are typically 14-inches in height. Meanwhile, standard toilets are typically 16-inches in height. This difference in inches is vastly important when relating to a little person trying to comfortably use a standard toilet. In addition, it can be relatively costly and inefficient for a specialized, shorter toilet to be installed in a restroom. As such, there is a need for an item that can effectively boost the little person up to use a standard toilet. Moreover, the helping boost must remain balanced, stationary and adapt to various restroom conditions such as density and clutter. The present invention solves this need by incorporating a main body with a first extension and a second extension to essentially fit around the front of the toilet base to ensure a consolidated and stationary platform.
[0005] Another problem is that little people and children often must stand on a platform or elevated item. This actually causes some people to feel uneasy, as it is not a natural feeling. Particularly when water from a sink or shower stall makes the surface slippery, significant danger can result. The present invention provides a means for traction and support to prevent slippage of the person and also the sliding of the actual apparatus.
[0006] U.S. patent application Ser. No. 11/516,309 filed by McDowell on Sep. 6, 2006 is a toilet training stool. Unlike the present invention, McDowell requires an elevated platform to be installed with sidewalls. McDowell ultimately requires a substantial amount of installation as the sidewalls encompass the toilet in an elevated manner. In contrast, the present invention solves the toilet training and use need by providing a unitary base that is placed in front of the toilet base to ensure a consolidated and stationary platform.
[0007] U.S. Pat. No. 5,259,612 issued to Matherne et al on Nov. 9, 2003 is a portable support for a basketball goal system. Matherne supports a basketball pole that is mounted to a base that fills with water. Unlike the present invention, Matherne is not configured with a middle, first extension and second extension. In addition, Matherne does not account for a person stepping on its base and traction elements to avoid slippage.
[0008] Other items relating to toilet training and toilet aide relate to pans and seat assistance. In that regard, the present invention is novel in that it is formed to fit against a toilet in such a manner that the device is weighted down and provides traction while also elevating the user so the user can use a standard-sized toilet. In addition, liquid is used inside the present invention middle for weight and its first extension and second extension to ultimately provide a platform that does not require extensive installation or impediment.
SUMMARY OF THE PRESENT INVENTION
[0009] The present invention is a device that assists children and other little people with their use of the toilet. The present invention is formed so that its interior elements are placed on the floor and flush against the base of a toilet. The top covering in one embodiment is formed with a rough tread to prevent the user from slipping. The bottom covering also is rough to prevent skidding.
[0010] The present invention is placed under the toilet and slid toward the toilet base so that it rests tightly against the toilet base. The present invention in the preferred embodiment is unitary. The first extension and the second extension hug the sides of the toilet base. The middle is flush against the front of the toilet base. In the preferred embodiment, the top covering with the rough tread is placed on the top of the middle. The bottom covering is placed on the first extension and the second extension in the preferred embodiment as well.
[0011] The interior of the present invention is formed to be hollow. A fill and dump opening provides an opening at the top of the present invention. The fill and dump opening is formed so that liquid can be poured into the hole of the fill and dump opening. The liquid serves to provide weight and additional stability to keep the present invention in one sustained position. In an additional embodiment, the liquid is pleasant smelling so that the pleasant smell is emitted. This embodiment offers the dual function of providing a pleasant fragrance to the restroom while also serving as a weight. Moreover, the embodiment with the liquid features is configured such that the liquid will not sour over time. Essentially, one embodiment utilizes the fill and dump valve. In an additional embodiment, the liquid is filled into the hollow interior of the present invention and then sealed in such a manner as to prevent evaporation. This embodiment is molded to effectively secure a liquid lock.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a top view of the present invention.
[0013] FIG. 2 is a front view of the present invention.
[0014] FIG. 3 is a bottom view of the present invention.
[0015] FIG. 4 is a rear view of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] The present invention is a device that assists children and other little people with the use of standard-sized toilets. As we see in FIG. 1 , the present invention is comprised of a horseshoe, or U-shaped apparatus to fit around the front of the toilet stool or base. In the preferred embodiment, the present invention is formed into a unitary piece comprising of the middle ( 10 ), first extension ( 20 ) and the second extension ( 30 ). However, in an additional embodiment, the present invention can be comprised of three pieces of the middle ( 10 ), first extension ( 20 ) and the second extension ( 30 ). In that embodiment, the pieces are secured and formed by making two holes with a plug or threaded plug.
[0017] The height of the present invention is envisioned to be around 4 inches. The first extension ( 20 ) and second extension ( 30 ) that slide around the toilet stool or base are each between 12 inches and 14 inches long. The middle (10) is between 4 inches and 6 inches long. The width of the first extension ( 20 ) and the width of the second extension ( 30 ) are between 5 inches and 8 inches.
[0018] As we see from the top view of FIG. 1 , a top ( 40 ) is formed with a rough tread to reduce slipping. In an additional embodiment, the top ( 40 ) is a covering that is secured via conventional means to the top ( 40 ) of the present invention. In an additional embodiment, the rough tread of the top ( 40 ) or covering encompasses the entire top portion of the present invention. The rough tread of the top ( 40 ) is rough or grooved in order to help prevent the user from slipping. An additional embodiment forms grooves into the top ( 40 ) so that any water that finds its way onto the top ( 40 ) is diverted into the grooves and consequently below the primary surface so as not to puddle in a position where the user can slip. In addition to the top of the present invention, FIG. 3 shows the bottom where the preferred embodiment also has a rough tread formed from a bottom ( 60 ) or bottom covering. The bottom ( 60 ) is formed with the rough tread so that the present invention does not slip. An additional embodiment also relates placing the unitary or three-piece present invention onto a U-shaped pad to keep the present invention from moving from incidental contact. The U-shaped pad in the preferred embodiment is formed via material that is rough enough to refrain from skidding. The U-shaped pad is formed to fit around the toilet stool or base. It should be noted that in the preferred embodiment, the portions of the present invention that touch the toilet stool or base are curved.
[0019] The interior of the present invention is formed to be hollow. This means that in one embodiment of the present invention, the interior of the middle ( 10 ), first extension ( 20 ) and second extension ( 30 ) are hollow. A fill and dump opening ( 50 ) provides an opening at the top of the present invention. In the preferred embodiment, the fill and dump opening ( 50 ) is placed at the rear of the apparatus so as not to interfere. In addition, a fill and dump opening ( 50 ) in the preferred embodiment is located on first extension ( 20 ) and second extension ( 30 ) to accommodate right-handed and left-handed users. The fill and dump valve ( 50 ) is formed so that liquid can be poured into the hole of the fill and dump valve ( 50 ), which leads into the hollow interior of the present invention. The liquid serves to provide weight and additional stability to keep the present invention in one sustained position. In an alternative embodiment, a pleasant-smelling conventional liquid being housed in the hollowed interior of the present invention can permeate throughout the room. In still an additional embodiment, the main body, first extension, and second extension are slightly pliable so that when a little person or child puts pressure on the upper surface through the natural force of standing, the surface will slightly press inward. This force will push the surface into the hollow interior, which will in turn force air out of one-way valves that prevent the liquid from escaping. When air pushes out of the one-way valves, the pleasant fragrance of the liquid will permeate through the restroom.
[0020] The present invention is placed under the toilet and slid toward the toilet base so that the interior sides of the first extension ( 20 ) and second extension ( 30 ) rest tightly against the toilet stool or base. The first extension ( 20 ) and the second extension ( 30 ) hug the sides of the toilet base. The middle ( 10 ) is flush against the front of the toilet stool or base. The dimensions mentioned above are based on standard toilets, meaning that the dimensions of the present invention are formed so that the present invention can adequately serve its purpose of assisting children and other little people.
[0021] It also is important to note that the fill and dump opening ( 50 ) of the present invention in the preferred embodiment may be at the back of the first extension ( 20 ) or the second extension ( 30 ) so that it is not a tripping hazard. In addition, this aspect permits either a left-handed user or a right-handed user to more comfortably use the fill and dump opening ( 50 ) depending on which extension it is located. In addition, the present invention in the preferred embodiment is flat along the bottom for increased strength and durability. The rough tread ( 60 ) also may be located along the entire portion of the top and bottom surface for stability and traction. Moreover, the front of the present invention can be either squared off or rounded.
[0022] In all embodiments, in order to construct the present invention to be formed in the manner described above, a hollow heavy casting is made. Pellets are included into the form and then heated and turned in all directions so that the pellets melt. The preferred embodiment is to have the pellets made out of plastic. After the heating process, the present invention molding is cooled and opened in order to remove the formed plastic of the present invention. In the preferred embodiment, fill holes also are molded in. It also should be noted that the present invention is formed to be sealed tightly. It should be noted that the present invention is molded such that the unitary apparatus is sealed tight in such a manner as described so that there is a liquid lock to prevent the liquid from escaping. The liquid, meanwhile, fills the entire hollow chamber that serves as the interior of the present invention.
[0023] Having illustrated the present invention, it should be understood that various adjustments and versions might be implemented without venturing away from the essence of the present invention. The present invention is not limited to the embodiments described above, and should be interpreted as any and all embodiments within the scope of the following claims. | A device for small children and other little people to assist in the safe and comfortable use of standard-sized toilets. The device is either a unitary apparatus or three-piece apparatus formed with a middle, a first extension, and a second extension and formed to fit firmly against a toilet base in a manner that prevents sliding and movement. The device is hollow in such a manner that an odorless or pleasant-smelling liquid can be used to weight the device down while also emitting a pleasant smell for the restroom. A top and a bottom also are attached to the main body, first extension and second extension in order to provide additional safety. | 0 |
FIELD OF THE INVENTION
This invention relates to scaffolding consisting of a number of platforms which may be suspended in a vertical array by vertically extending chains.
BACKGROUND OF THE INVENTION
Collapsible scaffolding of the type to which the invention relates is disclosed in British patent specification No. 2 151 290A. The corners of a number of platforms are connected at intervals to chains. The platforms may be arranged in a stack with the lowest platform supported on the ground. A winch may be used to raise the remaining platforms into a vertically spaced array. Alternatively, the uppermost platform may be fixed at a position above ground and the remaining platforms lowered to form the array. Guides for the winch cables fixed on each platform interfit as the scaffolding collapses after use and ensure that the platforms form a stack in a controlled fashion. Guard rails extend between the chains. The known scaffolding suffers from a number of disadvantages. Each of the guides consists of a vertical tube with a bell-mouth at its lower end for receiving the upper end of the next lower guide. The guides are subjected to considerable stresses as they begin to interlock. Modern fabrication techniques make it desirable for the framework of each platform to be manufactured from glass reinforced plastics (GRP) and guides of this type are not suited for use with a GRP framework. The guard rails fixed to the chains induce the chains to fall neatly into the interiors of the platform as the scaffolding collapses.
OBJECTS OF THE INVENTION
It is a principal object of the invention to provide an improved guide arrangemnt which suffers minimal stressing as the scaffolding collapses to form a stack.
It is another object of the invention to provide a guide arrangement suitable for use with platforms having metal or GRP frameworks.
It is a further object of the invention to provide collapsible scaffolding with a guide rail arrangement which induces the chains to fall within the platform interiors as the scaffolding collapses.
SUMMARY OF THE INVENTION
In accordance with the invention, at least one of the platforms of collapsible scaffolding has a support framework including an outer frame member consisting of a beam formed with a channel in its underside and provided with an upstanding rib on its upper side, so that the rib interfits with the channel of of the frame of the immediately superposed platform when the scaffolding collapses. It will be understood that the outer frame member of the lowest platform need not be provided with a channel. The rib may form a toe-plate which bounds the platform.
At least one guard rail associated with each side of each platform may be in the form of a tube through which passes a chin or cable, in which is incorporated a tension spring to cause the support chains to be drawn together as the scaffolding collapses and the support chains slacken, with the result that the chains fall into the space defined within the toe-plate.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of partly collapsed scaffolding in accordance with the invention.
FIGS. 2A to 2D are plan view fragments of the FIG. 1 embodiment.
FIG. 3 is a section on line III--III in FIG. 2B through an outer frame member fabricated from glass reinforced plastic (GRP).
FIG. 4 is a section on line IV--IV in FIG. 2B through the outer frame member,
FIG. 5 is an end view of a platform of the FIG. 1 embodiment showing the kick plate 12,
FIG. 6 is a section through an outer ram member fabricated from steel, for a bottom platform,
FIG. 7 is a section through an outer frame member fabricated from steel, for a platform other than a bottom platform. FIGS. 6 and 7 are of a second embodiment.
FIG. 8 shows a corner fitment, of the FIG. 1 embodiment.
FIG. 9 shows a guard rail.
DESCRIPTION OF PREFERRED EMBODIMENT
The present invention is applicable to scaffolding of the type disclosed in British patent specification No. 2 151 290A, the disclosure of which is incorporated herein by reference. The construction and operation of the scaffolding will not, therefore, be described in detail, except to the extent necessary to explain the invention.
Referring to FIGS. 1 to 5, and in particular to FIG. 1, scaffolding includes a number of superposed platforms 1A to 1D. Each platform includes a framework having an outer frame member 3 provided at each corner with a suspension plate 4 to enable the platform to be linked to that immediately above and/or below it by chains 5. Opposite sides of the outer frame members are interconnected by cross pieces 16 which together with the outer frame member 3, support a deck plate 6 including a trap door 6a.
The platforms 1A, 1B and 1C are illustrated resting one upon another in a collapsed stack, and the platform 1D as having been raised by means of a winch into an extended operational position. Continued operation of the winch will raise all of the remaining platforms, other than the lowest.
As each raiseable platform is raised, a ladder 8 pivoted to its underside rotates into an almost upright position.
The outer frame member 3 of each of the platforms, 1A, 1B, 1C and 1D includes four hollow sections 11 extruded or otherwise formed from glass reinforced plastic. The ends of the sections 11 are cut at 45° as shown at 3e in FIG. 2A, and receive the steel corner fitments 9 as shown in FIGS. 3 and 8. Each fitment includes two arms 9 at right angles to each other which are inserted into the meeting ends of the hollow sections 11 and secured by bolts 10. The fitment of the lowest platform 1A is provided with a foot 2 and suspension plate 4. The fitment intermediate platforms 1B and 1C has two suspension plates 4, one of which extends up and the other down. The fitment of the uppermost platform 1D has a suspension plate 4 on its underside and a bracket on its upper side for attachment to rigid superstructure of the top platform.
The steel fitment 9, 4 ensures a structurally sound joint at each of the corners which corners are vulnerable to damage when the scaffolding is in use. The outer frame member 3, as shown in FIGS. 3 and 4, has a hollow box beam portion 11 and an upwardly projecting kick plate 12. The beam 11 and plate 12 are molded as an integral unit. The upper end of the kick plate 12 is a longitudinal thickened rib 13.
The lower wall of the beam portion 22 is shaped to have a longitudinal channel 14, the sides of which are complementary to the rib 13. The channel 14 tapers towards the top at a total included angle of 60° to facilitate mating of the rib 13 and the channel 14 of adjacent platforms. The channel 14 and rib 13 are flattened at 15 for safety and to reduce stresses applied during mating of rib 13 and channel 14.
The plate 12 serves as a toe-or-kick-plate of the assembled platform.
The cross pieces 16 of the support frame serve with the outer frame member 3 to support the deck and are joined to the outer frame member by glass reinforced plastic tubes 17 inserted into their ends and passing through apertures in the outer frame member. The outer ends of the tubes 17 being closed by PVC caps 18. The tubes are made fast with the cross pieces by pins 19.
In an alternative embodiment outer frame member 3 may be fabricated from separate interwelded steel components as shown in FIG. 6 for the lowest platform and FIG. 7 for the intermediate platforms.
The ends 12a of each of the kick-plates 12 terminate at short of the ends of the hollow sections 11 so as to provide space for chains to be connected to the suspension plates and also to permit the chains to fall into the platform space between the plates 12.
Stowing of the chains in this way is facilitated by a tension spring 26 connecting two horizontal lengths of chain 21 extending between each pair of vertical chains 5 and within a tubular guard rail 22. The spring 26 arrangement is positioned along the vertical chains by the requisite distance needed to enable the spring 26 to kink the vertical chains 5 as they slacken and in consequence fall within the space defined within the kick-plates 12 for neat and unobstructive stowage.
The spring containing guard rail 22 may be the topmost or the middle one of three guard rails associated with each platform. | The outer support frame of a platform of collapsible scaffolding consists of a box beam surmounted by a kick plate, the upper edge of which locates in a channel in the base of the support frame of the next higher platform. | 4 |
FIELD OF APPLICATION
Present invention is related to the mining area, particularly to the pyrometallurgic area, specifically to the smelting and conversion process that occurs in furnaces and converters for production of refined metals when applying a field of mechanical waves in their interior.
PREVIOUS STATE OF THE ART
Within the mining processes, for example copper, a Converter, the Teniente Converter, used as the sole primary fusion system, has a system allowing injection of dry concentrate through injecting tuyeres, thereby turning it into an autonomous system. The Teniente Converter is the smelter's most important furnace since it defines its operational cycles. Once the equipment's operational conditions have been defined regarding concentrate composition, the fusion capacity and kinetics of the process depend on flow and oxygen enrichment of air blown through tuyeres.
The Teniente Converter (basically a horizontal cylinder with an outer mantle or shell lined ( 22 ) in its interior with refractory material ( 20 ) of determinate thickness within which 1250° C. chemical reactions occur, with dry concentrate injecting tuyeres ( 14 ), openings ( 16 ) and ( 18 ), air blowing tuyeres ( 17 ) and a drainage system ( 15 ) placed at a certain height over ends of the Converter) is fed with a copper concentrate of approximately 28% copper content, injecting additionally through blowing tuyeres oxygen enriched air that produces a series of reactions that increase copper concentrate until it reaches 75% copper contents. (See FIGS. 1 and 2 ).
The Teniente Converter operation is based on heat generated by pyritical decomposition and sulphur oxidisation reactions and consists mainly of melting the solid raw materials that are fed into it, oxidise part of the load and obtain as a product two liquid phases, one rich in copper (white metal, of higher density) and another formed basically by oxides present in the bath (slag, of lesser density which remains over the metallic bath or white metal). Additionally, gases rich in sulphur dioxide are generated during the operation, which are sent to the acid plant for treatment. The Teniente Converter delivers as a final product white metal, slag and gases.
The white metal in the Teniente Converter is a liquid solution comprised basically by a mixture of copper and iron sulphides (Cu 2 S and FeS) and contains additionally a part of the impurities present in the concentrates. Ellimination of these impurities occurs during the subsequent conversion processes.
White metal's higher density in relation to slag causes the white metal drops to descend through the bath to form a melted metal phase at the bottom of the furnace.
The melt's slag is formed by oxides fed to the converter; iron oxides produced by FeS oxidisation. Within the types considered the following are found: Fayalite (2FeOSiO 2 ), Magnetite (Fe 3 O 4 ) Silica (SiO 2 ), Allumina (Al 2 O 3 ), calcium oxides (CaO), copper oxides (Cu 2 O) and White Metal (Cu 2 S) trapped mechanically.
The desirable characteristics for slag are:
Should be miscible with the metal bath (white metal).
Low copper solubility.
Be fluid in order to minimise metal bath, concentrate and particle entrapment, and to allow adequate evacuation through the slag taphole.
The gas is formed basically by sulphur dioxide (SO 2 ), oxygen (O 2 ), Nitrogen N 2 ) and water steam (H 2 O).
Today, the process of obtaining white metal by Teniente Converter (CT) operation is subject to several problems whose solution has been attempted by different means. Amongst these difficulties we can mention the lack of online measurement of levels of the different phases. Currently, this measurement is carried out with a rod that is inserted into to the liquid metal thereby locating an operator over the converter, with the inherent risks involved by this technique. Furthermore, another main problem in CT operation is the formation of accretions at ends of air blowing tuyeres that inject oxygen enriched over the bath, since obstruction of airflow consequently decreases the chemical reactions within the converter, thereby decreasing its fusion capacity. Additionally, the accretions adhere firmly to the refractory material and part of this last is removed together with them, producing serious wear due to use of the tuyeres cleaning machine to eliminate the accretions, ultimately producing internal ruptures evidenced at short term by the leakage of material to the exterior.
Furthermore, the slag entraps mechanically as well as chemically, in approximately the same proportions, a significant copper content (around 8%). This copper must be recovered subsequently in a slag treatment furnace with the greater cost involved for the complete process.
In the white metal phase chemical reactions occur due to oxygen injection. These chemical reactions have their own kinetics given by the contact surface between the bubbles and fluid metal that corresponds to the interphase where the chemical reactions occur.
An increase in the chemical reactions means an increase in the production of desired metal in a fixed time period. This has its basis in kinetics, v=ke −E/k*T , where E is the activation energy. In this way, the emission of mechanical, for example sonic, waves speeds up a specific reaction, as it is able to supply a certain amount of energy (activation energy) and control it, meaning also that it is selective.
Specialized literature is aware of the fact that mechanical waves travel through solids as well as liquids and gases. Effectively, application of ultrasound in gases and metals in liquid state at high temperatures behaves like mechanical waves in general (See “Ultrasound Fundamentals” Jack Blitz, Alhambra Editorial, 1 st Spanish edition of 1969, pages 31-33).
Because of this, present invention employs mechanic wave transmission of certain characteristics to maximise the physical-chemical coupling of different media. Additionally, using the transmission and reflective properties of these mechanical waves that travel through different media (of different densities), it supplies an online and non-invasive measurement of parameters very important for an optimal operation of the process.
BRIEF DESCRIPTION OF THE INVENTION
Present invention consists of a system for generating mechanical waves, sonic as well as ultrasonic, of specific characteristics, transmitted to the interior of a CT so as to maximise the physical-chemical coupling of different media. Additionally, using the transmission and reflective properties of these mechanical waves that travel through different media (of varying densities), it supplies an online and non invasive measurement of parameters that are very important for an optimal operation of a process.
So, a system has been implemented that increases the kinetics of chemical reactions and in consequence, an increase in the production of metal.
This higher production of metal results from the higher efficiency of oxygen reactions within the metal bath. The reaction capacity of oxygen per unit of volume of the metal bath per time unit in a converter or furnace is measured through the SBSR (Specific Bath Smelting Rate), and is theoretically defined by:
SBSR=e·f·Qo/V
Bath
Where: e=efficiency of oxygen consumption; f=oxygen enrichment; Qo=air flow; and V Bath =bath volume.
The CT, under influence of the mechanical wave field (for example sonic, ultrasonic or infrasonic) that operates on the metal bath, slag and injected air improves its fusion cycle in terms of an increase in production of metal bath (V Bath ), in presence of the mechanical wave field.
Additionally there is a quicker homogenisation of the mixture, which stabilises the temperature as well as the density of the mixture, allowing it to approach thermal equilibrium. On the other hand the system eliminates the accretions that form at the ends of the air blowing tuyeres, permitting a relatively constant flow of air to the CT reacting with the higher density fluid, thus extending the operational time of the CT by avoiding the interruption of the process to eliminate said accretions through use of the tuyere cleaning machine that uses sharp tools to do the job.
As a result there is an increase in the useful life of the refractory as well as the CT.
Certainly, another result is the ellimination, to some extent, of the metal entrapped in the slag. The selective attack of the mechanical waves on the different components of the slag inhibits the entrapment of metal by it, thus reducing the quantity of copper trapped mechanically, because said waves deliver enough energy to make the metal drops decant, reducing it greatly.
Another aim of present invention is to provide continuous and discrete on line measurements of temperature and phase levels.
In all industrial processes, the stabilisation of variables is essential for achieving a good process control. In pyrometallurgical converters, a good control of the level of the white metal allows to decrease the copper loss due to drag by the slag and also avoids foaming.
Moreover, a good control of the level of slag avoids unnecessary heat loss. Meaning that if we subject converters that contain in their interior fluids of different densities to mechanical waves, these will have different propagation behaviours, and as it is known that their reflection coefficient depends on the media they are transmitted through, the phase levels and the refractory wear can be determined in real time or on line by relating these different reflection coefficients.
On line measurement of temperature of metal bath and slag and eventually of the temperature of the gaseous phase of the CT, allows a constant monitoring of the system, so as to take the corresponding action for a better use of the energy to increase fusion. Additionally it allows to avoid high fluctuations in temperature that produce thermal shock in the refractory. For this reason, the proposed measuring system submits the information directly to the Central Control System of the process in order to execute the programmed operations for each situation.
In the same way, the system detects the white metal and slag levels within certain discrete ranges.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the general schematic structure of a Pirometallurgical Converter, (Convertidor Teniente (Previous State of the Art)).
FIG. 2 shows a cross section of FIG. 1 (Previous State of the Art).
FIG. 3 corresponds to a first application of the invention to a transducer, set up to apply mechanical waves to travel longitudinally with the airflow.
FIG. 4 corresponds to a second application of the invention to a transducer set up to apply mechanical waves to travel transversally with the airflow.
FIG. 5 corresponds to a third application of the invention to a transducer set up to apply mechanical waves that propagate in a resonant chamber, so as to apply a large number of components of different amplitudes of said waves with the airflow.
FIG. 6 is a graph of the SBSR (Specific Bath Smelting Rate) index, where the curves show this index with and without the application of aforementioned waves. The different curves are parametrised depending on the number of tuyeres that inject air into the metal bath.
FIG. 7 shows the invention system applied to the CT, in a schematic form and cross section.
FIG. 8 presents a block diagram of the invention, showing the transducers with their respective sensors attached to the shell or mantle of the CT.
FIG. 9 shows a schematic figure of the circuit for the measurement of the time lapsed between the emission ot the signal and reception of the different echos of the signal, while doing the discrete and continuous measurement of phase levels.
FIG. 10 is an example of a descrete measurement of the phase levels.
FIG. 11 is an example of a continuous measurement of the phase levels.
DETAILED DESCRIPTION OF THE INVENTION
Present invention consists in a non-invasive system and method to apply mechanical waves directly to a metal fluid at temperatures of around 1250° C. Essentially it consists in a series of transducers that generate mechanical waves that travel to the fluid metal through the oxygen-injecting tuyeres of a converter or pirometallurgical furnace.
This system consists in a means to generate electrical signals ( 1 ), transducers, for conversion from electric to mechanic signals ( 5 ) and a mechanical connection ( 21 ) to ensure a perfect coupling with the mantle or shell ( 22 ) of the CT, through one of the blowing tuyeres ( 19 ) into which air is injected. (FIG. 7)
Additionally it has an analogical/digital interface ( 27 ), sonic sensors ( 6 ) and a unit ( 26 ) for processing signals and acquiring data for the monitoring of important variables of the process.
In FIG. 7 a schematic diagram shows the invention system (A) which has in its interior a layout of sonic transducers ( 5 ), set up to agree with the propagation direction and amplitudes of the mechanical waves ( 33 ) to be applied to the metal bath ( 12 ) and slag ( 11 ). The breaking or removal of accretions ( 30 ) can also be seen, as well as the detachment of copper from the slag ( 35 ), whereas in the sector to which the mechanical waves have not been applied, the copper trapped ( 38 ) in the slag has not been able to come loose.
In FIG. 3 a transducer is set up to apply mechanical waves in a longitudinal direction to the airflow is described. For this purpose the air blowing tuyere has been placed in a side duct to form an angle equal to or less than 90° (α) with the airflow entrance and the transducer, remaining this last linearly and directly at the height of the oxygen enriched air inciding in the metal bath. Thus the mechanical waves travel in a longitudianl directin with the airflow that reaches said metal bath.
FIG. 4 describes a second application of the transducer, set up to apply mechanical waves that travel transversally with the airflow. This last can be done with a straight tuyere in the direction of the entrance of the airflow, and this time at least one transducer is placed transversally to the air blowing tuyere ( 19 ). This ensures that the mechanical waves travel in a transversal direction with the airflow that reaches the metal bath.
FIG. 5 shows a third application of the invention, with a transducer within the resonant chamber which is part of the air blowing tuyere ( 19 ), forming a truncated cone attached to the shell of the CT in the truncated or narrowest end. In this way the transducer emits the mechanical waves which will resound first in the chamber, producing waves with a variety of components of different amplitudes that travel with the airflow to the interior of the CT.
The invention system (A) is coupled or joined to a pirometallurgical converter by one the blowing tuyeres ( 19 ) through a coupling piece ( 21 ) that ensures the mounting and a perfect seal between them. The coupling piece ( 21 ) adheres to the shell ( 22 ) of the CT by mechanical means. The shell is covered by refractory ( 29 ). The blowing tuyere ( 19 ) that injects air ( 32 ) enters the invention system and follows on into the interior of the tuyere ( 19 ) till it reaches the metal fluid ( 12 ). The waves ( 33 ) that come from the transducer ( 5 ) are transmitted through the air ( 32 ) that circulates through the tuyere ( 19 ) till it reaches the metal fluid ( 12 ) where it gets incorporated producing physical-chemical phenomena that allow to optimise the CT operation.
Another action developed by the invention, consists on preventing the formation of accretions in the blowing tuyeres and elliminating the wear of the refractory ( 29 ) resulting from the cleaning of said accretions. It is a well known fact that the highest refractory wear in the tuyeres area ( 19 ) of the CT is due to the chemical reactivity that occurs in head of the tuyere and to the effect of the sharp tools of the tuyeres cleaning machine that uses a mechanical attack to clean the accretions. Avoiding the formation of accretions means a sharp decrease in the wear of the refractory ( 29 ). The ellimination of the refactory ( 20 ) wear and decrease or ellimination of the mechanical attack of the tuyere cleaning machine avoids interrupting the process due to filtrations in the tuyeres.
Another result of the use of the invention is to lower the copper ( 38 ) entrapped by the slag ( 11 ). The selective attack of the mechanical waves ( 33 ) over the different components of slag ( 11 ) makes the copper detach ( 35 ) from the slag ( 11 ) at least in its mechanical aspect, as the application of these waves delivers enough energy to decant the white metal drops trapped in the slag and reduce the Cu2O avoiding losses, and minimizing subsequent treatment to the slag ( 11 ) to extract its copper content.
Discrete Measurement of Phase Levels for a Pyrometallurgical Converter
The measurement is based on the determination of the level of a reflected ultrasonic, sonic or infrasonic signal (echo pulses), in the limiting zone between the different existing phases present in the interior of the CT (from here on called interphases) needed to be maintained between certain levels during the operation. To do this measurement, an ultrasonic, sonic or infrasonic transducer ( 5 ) is used with the capacity to generate a signal of intermediate power and detect the reflected signal by at least one sensor ( 6 ), placed directly beside or integrated to, the transducer, or by one or more sensors placed around the shell of the CT. Considering the density difference between the phases ( 11 , 12 and gases), the ultrasonic or sonic signal reflected by the different interphases will have a different level characteristic of each phase. The measurement of the amplitude of the reflected signal indicates the phase present in front of the transducer at that moment, delivering thereby a discrete measurement of the position of the interphase.
The resolution of this measurement is determined by the number of transducers and the distances between them, but for the purpose of having an alarm system that warns when the phase is at a certain level, only one transducer is needed.
An electronic circuit has been implemented capable of measuring the time lapsed between the echo pulses, which must be done in real time, integrated with the electronics that detect and preamplify the echoes.
The signal received is digitalised and processed by a DSP (Digital Signal Processor). The processor determines the amplitude of the signal and thereby determines the phase facing each transducer.
The position of the transducers is known so the information thus obtained allows to determine, in a discrete range, the position of the different interphases, o the alarm states defined (on the basis of the position of the transducers). These discrete levels and alarm state values are stored finally in a outgoing memory that can be read through a serial RS-232, RS-485 or Ethernet TCP/IP communication port, which are the most common communication standards of digital data in the industrial equipment field.
Another objective, in consequence, is to make available the measurement in the RS-232, RS-485 and TCP/IP communication standards and allow the incorporation of these values to the instrumentation network of the pyrometallurgical converter, so they can be available in a Centralized Control System. This Centralized System must analyse the values obtained against the control references attired and execute the previously programmed actions (operating registries, levels of different alarms, etc).
Continuous Measurement of Phase Levels for Pyrometallurgical Converter
The measurement is based on determination of the time of propagation of a sonic, ultrasonic or infrasonic signal between the interphases that separate the different phases whose level must be known. To do this measurement a sonic, ultrasonic or infrasonic transducer ( 5 ) with capacity to generate an intermediate power signal and detect the reflected signal(echo pulses). Considering the density difference between the phases, the ultrasonic signal is reflected by the different interphases, returning a fraction of the power to the transducer that generated it. The measurement of the propagation time of the signal, between the moment in which it is emitted by the transducer and the moment in which the different echoes are received, considering a constant propagation speed, allows us to determine the position of the different interphases relative to the transducer.
An electronic circuit has been implemented capable of measuring the time lapsed between the echo pulses, which must be done in real time, intehrated with the electronics that detect an preamplify the echoes. This circuit has a crystal local oscillator that allows precise measurement of timelapsed between the emission of the signal and the recption of the different echoes of it.
The signal received is digitalised and processed by a DSP (Digital Sygnal Processor). The time measurements obtained thus are stored in an outgoing memory that can be read through a serial RS-232, RS-485 or Ethernet TCP/IP communication port, in the same manner as the discrete range measurement.
Likewise, if the on line temperature is known, corrective measures may be taken that contribute to a better operation of the CT. The avoidance of high fluctuations of temperature that provoke thermal shocks in the refractory allow to increase the CT operating time. As the mechanical waves are reflected with different amplitudes while crossing different media, these differences allow to directly relate the temperatures of the different media. Therefore, the unit that acquires and treats the signals ( 26 ), commands a power source ( 1 ) through an analogous/digital interface ( 27 ). The power source ( 1 ) controls a set of sonic transducers ( 5 ) attached to the shell ( 22 ) of a pirometallurgical converter (CT), by coupling pieces ( 21 ). The ultrasonic or sonic transducers ( 5 ), excited by the power source, emit mechanical waves ( 33 ) in the form of pulses that travel through the shell ( 22 ) and the refractory material ( 20 ). The mechanical waves ( 33 ) encounter the slag ( 11 ) or the metal bath ( 12 ), some are reflected and are received by sonic sensors ( 6 ), which in turn send analogous signals back to the power source. These signals are amplified and sent by means of an analogous/digital interface ( 27 ) from the power source to the unit that acquires and processes the signals ( 26 ), where they are processed and transformed in digital data sent to a computer ( 24 ) through a digital interface ( 25 ) between the computer( 24 ) and the unit for acquisition and processing of signals ( 26 ). The data received by the computer can be observed through a procedure for displaying and monitoring said information.
The transducer of FIG. 3 can be mentioned as an example, operating at a frequency of 20 Khz. and a nominal power of 4 Kw, that applied to a situation like the one described in FIG. 7 allows to increase the reaction kinetics ( 34 ), detaching the copper entrapped ( 35 ) in the slag ( 11 ) and maintaining the air entrance ( 32 ) to the white metal ( 12 ) free of accretions ( 39 ). On the other hand, the greater quantity of chemical reactions that occur in the zone of direct application of ultrasonic waves will generate a higher concentration in the outgoing gases (sulphur dioxide) allowing in turn a better performance of the acid plant that receives those outgoing gases. | A system for generating mechanical waves for use in smelting and conversion processes that occur in furnaces and converters for a higher production of refined metals, consisting in a electrical signal generator, transducers that convert said electrical signals in mechanical waves placed on the outer end of air blowing tuyeres, a coupling means between said system and the shell of the converter, at least one resonant chamber that envelopes the air blowing tuyere and at least one transducer placed inside said resonant chamber, for applying mechanical waves that contain a great number of components of different amplitudes that travel with the airflow into the converter or pyrometallurgical furnace. The field of mechanical waves allows a higher efficiency in the oxygen reactions within the metal bath and slag, increasing the kinetics of chemical reactions, allowing a quicker homogenisation of the metal bath and reducing notoriously the copper trapped mechanically by the slag, all this leading to a higher production of metal. | 5 |
FIELD OF THE INVENTION
The present invention relates to rigid polymeric foams. Specifically, the invention relates to urea-modified isocyanurate rigid foams and a method for making such foams.
BACKGROUND OF THE INVENTION
Rigid polyurethane foams are recognized as excellent thermal insulation materials. Yet, they are not truly flame retardant. Isocyanurate foams are considerably more flame-retarding, but the unmodified foams made therefrom are highly cross-linked and are extremely brittle. Previous attempts have been made to reduce the brittleness of the isocyanurate foams by employing modifiers to reduce the amount of cross-linking. For example, flame-retardant urethane-modified polyisocyanurate rigid foams have been known since 1966 (Ashida, Polyisocyanurate Foams, Chap. 6, The Handbook of Polymeric Foams and Foam Technology, edited by D. Klempner and K. C. Frisch, Hauser Publishers, 1991, p 96); also amide-, carbodiimide- and imide-oxazolidone-modified polyisocyanurate foams. Ashida, ibid, p 97-8. Heat resistant and flame-retardant polyisocyanurate-polyurea foams prepared by reaction of diisocyanates with aqueous solutions of trimerization catalysts were disclosed in East German Patent 126,460. Urea-modified isocyanurate foams were disclosed in U.S. Pat. No. 4,425,446. The disclosed foams were useful in retrofitting wall cavities with insulating material, in that the material was substantially completely risen before setting or gelling. The urea-linkages were formed by an initial reaction between water and a multifunctional isocyanate which causes early rising of the foam. Additionally, the patentee discloses further modification of the formulation by the addition of a primary or secondary terminated polyamine, to form additional urea linkages. The polyisocyanurates of the present invention have rise times which exceed their gel times and set times.
Secondary amines have previously been proposed as curing agents for TDI-based flexible polyurethane foams, Gattuso et al Secondary Amine Extended Flexible Polyurethane-Urea Foams, Polyurethanes 88, Proceedings of the S.P.I. 31st Annual Technical/Marketing Conference, Oct. 19-21, 1988.
U.S. Pat. No. 3,846,351 describes the use of secondary phenylene diamines in combination with polyols as catalysts and chain extenders in the production of flexible polyurethane foams. More recently, it has been shown in U.S. Pat. No. 4,578,446 to House et al that N-alkylated methylenedianilines are suitable curing agents for urethane prepolymers, i.e., in elastomer production via non-RIM processes. In U.S. Pat. No. 4,801,674 to Scott et al, N-alkylated methylene dianilines are disclosed as suitable curing agents for RIM applications. However, neither patent discloses the unexpected beneficial results achieved with the rigid polyisocyanurate foams present invention.
SUMMARY OF THE INVENTION
The invention relates to a rigid urea-modified polyisocyanurate composition with improved dimensional stability and flame retardency and a method for making the same. The method for making a dimensionally stable rigid urea-modified polyisocyanurate having a density of from 1-12 p.c.f., dimensional stability at 100% relative humidity (R.H.) and 70° C. of less than 2% change in linear dimension in any direction and a limiting oxygen index (L.O.I) greater than 22 comprising reacting an organic polyisocyanate, a blowing agent and an N,N'-disubstituted aromatic diamine having the structure ##STR1## where R is selected from the group consisting of a monovalent alkyl- or alkenyl moiety containing from 3 to about 20 carbon atoms or a monovalent aromatic moiety containing from 6 to about 10 carbon atoms, R 2 is H or C 1 , C 2 or C 3 alkyl group and R 3 is H or a C 1 , C 2 or C 3 alkyl group in an amount such that the NCO/NH ratio is from 1 to 9 in the presence of a catalytically effective amount of a first catalyst which catalyzes the blowing reaction between an isocyanate and water, if water is used as a blowing agent, and a second trimerization catalyst which catalyzes the formation of isocyanurate bonds, said diamine and an amine produced by water, if used as a blowing agent, constituting the sole sources of active hydrogen.
The foams of the invention are commercially desirable because of their reduced flammability, lower friability, excellent insulating properties and dimensional stability compared to available polyisocyanurate foams. Also important is the greater isotropicity imparted to the rigid foams through the use of specific N,N'-di-sec-alkyl-substituted aromatic diamines, i.e., the greater uniformity of load-bearing properties between the directions, parallel to rise and perpendicular to rise.
In a preferred embodiment, also, the invention relates to a dimensionally stable, rigid urea-modified polyisocyanurate having substantially no urethane linkages and a density of 1.5-6.
DETAILED DESCRIPTION OF THE INVENTION
Although rigid foam polyisocyanurates modified only by urea linkages have been proposed for the application in retrofitting wall cavities with insulating material, a reaction in which the gel time was longer than the initial rise time is required. Moreover, there was no requirement for dimensional stability since the walls provided the necessary boundaries and warping or shrinking after installation is of relatively minor importance.
On the other hand, it is essential to the production of uniform insulating panels for original building construction that the panels be dimensionally stable after their formation and not be subject to shrinkage or warping or aging. This latter objective is achieved by reacting a polyfunctional isocyanate composition primarily with a polyfunctional amine in the presence of a blowing catalyst and a trimerization catalyst to produce a rigid isocyanurate foam. A major amount of the urea linkages in the final rigid foam is derived from the polyfunctional amine, although water may be used as a blowing agent, alone or with other known blowing agents, and will react with the polyfunctional isocyanate to produce additional urea linkages. In any case, it is important that the amines and, optionally water, as a blowing agent, are the sole source of active hydrogen, i.e., the sole isocyanate-reactive materials in the reaction mixture to avoid the formation of other types of linkages in the final rigid foams, such as urethane linkages (from polyols). A first catalyst, such as those known in the art as blowing catalysts, is incorporated in the reaction mixture if water is used as a blowing agent. A second catalyst known for promoting the trimerization reaction to produce an isocyanurate is also incorporated in the reaction mixture. In accordance with the invention, the initial reaction taking place, catalyzed by the blowing catalyst, is between the water, if present as a blowing agent, and a polyfunctional isocyanate to form a primary amine. Next, the primary amine, if water is present, and the polyfunctional amine react with additional polyfunctional isocyanate molecules to produce an isocyanate-capped substituted urea intermediate compound in the following manner: ##STR2## R 4 is a divalent alkaryl or aryl group and R,R 2 and R 3 are as defined hereinbefore. Thus, if ##STR3## the final reaction, catalyzed by the trimerization catalyst, is as follows: ##STR4##
The incorporation of water in the reaction mixture as the blowing agent causes the formation of additional urea linkage in the final foam product as well as produces carbon dioxide to form the cells of the foam. Alternatively, part or all of the water may be replaced by a conventional blowing agent such as chlorofluorocarbons hydrochlorofluorocarbons (HCFC), hydrofluoroalkanes (HFA), acetone, methylenechloride, methychloroform, etc. "Handbook for Reducing and Eliminating CFC's in Flexible Polyurethane Foams", EPA Publication 21A-4002, April 1991, page 21 et seq.
The product is a rigid urea-modified isocyanurate foam having substantially no urethane linkages, excellent insulating properties, is non-friable and exhibits flame retardance, dimensional stability on aging and a density of 1 to 12 p.c.f., preferably 2 to 8 p.c.f. and most preferably 1.5 to 6 p.c.f.
Flame retardancy, as measured by the Butler Chimney Test, is excellent and is in the range 71% to 98%.
Multi-functional isocyanates which can be used in the invention are well known in the production of polyurethanes and polyureas and include monomers and polymers containing at least two isocyanate groups. Thus, diisocyanates and higher functionality polyisocyanates are intended and include both aliphatic and aromatic multifunctional isocyanates such as 2,4- and 2,6-toluene diisocyanate and mixtures thereof (inclusively referred to sometimes as TDI); diphenylmethane diisocyanate (MDI), polymeric MDI (PAPI-27) and modified MDI.
Blowing catalysts are well known. However, catalysts used in the present invention must provide a reaction profile such that the blowing reaction of water and the multifunctional isocyanate is more rapid than the trimerization reaction and is substantially complete prior to the formation of the isocyanurate. Suitable blowing catalysts include: bis-dimethyl aminoethyl ether (NIAX A-1 sold by Union Carbide) dimethylamino-ethoxylethanol, N,N-dimethyl-3-[2-dimethyl amino ethoxy]propylamine (Thancat DD sold by Texaco), triethylene diamine (Dabco 33LV).
Trimerization catalysts are also well known. In the present invention, the formation of isocyanurates takes place after the urea reaction has substantially been completed. Any of the conventional trimerization catalysts can be used in the invention including the following representative examples: TMR-2 from Air Products, substituted triazines, such as Polycat 41 from Air Products, alkali metal salts of organic acids such as potassium octoate or hexoate, phospholines, etc.
The sole isocyanate-reactive component (i.e., sole source of active hydrogen), except when water is used as the blowing agent, is an N,N'-disubstituted aromatic secondary diamine of the following structure, ##STR5## where R is selected from the group consisting of a monovalent alkyl or -alkenyl moiety containing from 3 to about 20 carbon atoms or a monovalent aromatic moiety containing from 6 to about 10 carbon atoms, R 2 is H or C 1 , C 2 or C 3 alkyl and R 3 is H or C 1 , C 2 or C 3 alkyl in an amount such that the NCO/NH ratio is from 1 to 9.
Preferred R groups are secondary alkyl and, of these, the secondary butyl group is especially preferred. Examples of secondary and tertiary alkyl groups which may be used in the practice of this invention include iso-propyl,-sec-butyl, sec-pentyl, sec-hexyl, sec-heptyl, sec-octyl, sec-nonyl-sec-decyl, sec-undecyl, sec-dodecyl, sec-tridecyl, sec-tetradecyl, sec-pentaldecyl, sec-hexadecyl, sec-heptadecyl, sec-octadecyl, sec-nonadecyl, and sec-eicosyl moieties. Examples of secondary alkenyl groups are the unsaturated counterparts of the aforementioned alkyl groups. Tertiary alkyl or alkenyl groups, i.e., those which are fully substituted at the carbon atom bound to the nitrogen may be useful in the practice of this invention, but there is the risk that the size and/or shape of the molecule may prevent the reaction or slow it down due to hindrance.
The amount of diamine added to the multi-functional isocyanate is determined by the isocyanate/amine ratio, NCO/NH, which can be from amount 1 to about 9, and is preferably 3-7.
Additionally, the diamines can be blends of the above diamines or can be blended with another secondary diamine having a single aromatic ring with the following structural formula ##STR6## where R is selected from the group consisting of a monovalent alkyl- or alkenyl moiety containing from 3 to about 20 carbon atoms or a monovalent aromatic moiety containing from 6 to about 10 carbon atoms. Exemplary compounds useful in blends, in addition to the previously mentioned dianiline compounds are N,N'-di-sec-butyl-p-phenylene diamine and N,N'-di-sec-octyl-p-phenylene diamine.
The urea-modified polyisocyanurates are obtained by the following procedure. The reactants, including auxiliaries, are mixed in a conventional manner by bringing the "A-side", comprising the multi-functional isocyanate, into contact with the "B-side", comprising the remaining reactants, catalysts, curing agents, blowing agents, combustibility modifiers, surfactants, etc., into contact in a nozzle and directed onto a conveyor or into a mold. The foam cures in from about 12 to 18 hours and, preferably overnight at ambient temperatures.
The mixture of isocyanate-reactive components also may contain other materials, such as surfactants, combustibility modifiers, curing agents, etc. Examples of surfactants include the sodium salts of sulfonates or of fatty acids, amine salts of fatty acids, alkali metal or ammonium salts of sulfonic acids, polyether siloxanes, and the like. The component mixture also may contain pigments, dyes, flame retardants, stabilizers, plasticizers, fungicides and bactericides, and fillers.
EXAMPLES
General Preparation of the Polyurethane Foams. The procedure illustrates formulations based on the one-shot method; however, with minor modifications, it can be used in a two-stage process. The MDI-based isocyanate, PAPI 27, a widely used isocyanate for foams, which is a polymeric MDI (PMDI), is used to illustrate the invention, but other MDI-based isocyanates are available and may be used in the invention. The functionality of PAPI 27 is about 2.7.
Laboratory Scale. The diamine(s) of the examples, catalysts, foam stabilizers, water, and/or other blowing agents, and any other additives or auxiliaries were mixed by hand. The polyisocyanate, weighed out separately, was then added to the cup containing the mixture of isocyanate-reactive components and was thoroughly blended. This mixture was poured into a cardboard box and allowed to rise freely. The cream time, gel time and rise time were recorded. These samples were allowed to post-cure for one week at ambient temperature before testing.
Large Scale. The formulations below may also be used on a large scale by using low and high pressure foam machines, mixing machines which may or may not be attached to sprayers, and reaction injection molding machines.
Mechanical Properties. The mechanical properties of the foams produced in the following examples are determined by the following ASTM method Nos. (D-1622-36) density; compressive strength (D-1621-36) dimensional stability (D-2126-36); closed cell content; K factor (D-257-35) and percent closed cells (D-2856-36). Flammability is defined by the Butler Chimney Test (ASTM No. D-3014-36) or Limiting Oxygen Index (LOI) (ASTM #D-2863-35). Friability is measured by ASTM #C-421-18.
EXAMPLE I
Each of the formulations in Table 1 were used to make a rigid foam according to the invention. The blowing agent in samples 1 and 4 was CFC (F11A); HCFC 123 and HCFC 141b were used in Samples 2 and 3, respectively. The NCO/NH ratio was increased to 7 in Sample #4, using CFC-11 as the blowing agent to further decrease density. The sole source of active hydrogen in these samples is N,N'-di-sec-butyl4,4'-methylene dianiline (Unilink® 4200 available from UOP). The NCO/NH ratio was high (5) so that the foams contained only urea and isocyanurate linkages. The results shown in Table I indicate that the product foams were highly fire resistant (LOI as high as 27.5% and Butler Chimney Values up to 96.5%, and more isotropic than conventional rigid foams containing other linkages, such as urethane, etc., linkages.
TABLE 1______________________________________Formulation and Properties of Urea-Isocyanurate Foams(Physical Blowing Agent) Sample No.Formulation 1 2 3 4______________________________________PAPI 27 PMDI 134 134.0 134.0 134.0Unilink-4200 31.0 31.0 31.0 22.1L-5421-Silicone Surfactant 2.0 31.0 31.0 22.1TMR-2 (Dalco) 2.0 2.0 2.0 2.0Trimerization CatalystCFC-11 20 0 0 35.HCFC-123 20 0 0HCFC-141b 0 20 0NCO/NH.sub.2 Ratio 5 5 5 7Reaction ProfileCream Time (sec) 13 13 13 16Rise Time (sec) 31 40 63 47Physical PropertiesDensity, Kg/m = 3 (p.c.f.) 41.9 54.4 36.6 29.6 (2.6) (3.4) (2.3) (1.9)Compressive Strength,KPa (psi)Parallel to rise 269.8 311.8 156.6 110.4 (39.1) (45.2) (22.7) (16.0)Perpendicular to rise 151.8 178.1 90.3 69.0 (22.0) (25.9) (13.1) (10.0)Coefficient to isotropicity 1.8 1.8 1.7 1.6Index (C.I.I.)K-Factor, W/mK (BTU in/ft.sup.2hr °F.)Initial 0.022 0.021 0.027 0.029 (0.159) (0.151) (0.189) (0.199)FlammabilityButler Chimney 89 95.0 96.5 79(% wt. remained)Oxygen Index 26.0 27.0 27.5 24.0Friability 12.0 8.1 7.3 33.0(% wt. loss)Dimensional Stability (PercentDimensional Change)50% R.H. at 70° C.after 24 hr.a 0.25b 0.0c 0.35vol 0.6after 1 weeka 0.63b 1.01c 1.75vol 3.5______________________________________ 1. polymeric diphenylmethane diisocyanate 2. N,Ndi-sec-butyl 4,4'methylene dianiline
EXAMPLE II
The additional samples were prepared, in the same way as Example I, using water as the blowing agent, at NCO/NH ratio of 3,5 and 7, respectively, in Sample Nos. 1, 2, and 3. The results are shown in the following Table 2, indicating good dimensional stability and flame resistance, very low K-factors. Sample No. 4 was prepared using 50% water/50% CFC-11 blowing agents at NCO/NH 2 ratio of 7. Compressive strengths and isotropicity index were good to excellent.
TABLE 2______________________________________ Sample No.Formulation 1 2 3 4______________________________________ 100% 100% 100% 50%PAPI 27 PMDI 201 200 202 168Unilink-4200 51.6 31.0 22.1 22.1DC-5098 3.0 3.0 3.0 3.0TMR-2 (Dalco) 1.5 1.5 1.5 1.5Polycat 41 0.5 0.5 0.5 0.5Dabco T-12 0.1 0.1 0.1 0.1Water 4.5 4.4 4.6 2.3CFC-11 0 0 0 17.5NCO/NH ratio 3 5 7 7Appearance ok ok ok okReaction ProfileCream Time (sec) 9 9 8 9Gel Time (sec) 48 51 51 57Rise Time 76 66 69 71Physical PropertiesDensity, Kg/m.sup.3 2.1 1.94 1.97 1.98 (33.6) (31.0) (31.5) (31.7)K-Factor, (BTU in/ft.sup.2 hr °F.)Initial 0.194 0.182 0.186 0.184After 48 hrs. 0.213 0.208 0.211 0.190After 1 week 0.213 0.233 0.246 0.210Compressive Strength, (psi)Parallel to rise 22.3 22.4 17.7 29.6Perpendicular to rise 19.0 19.4 14.9 15.9Coefficient of isotropicity 1.2 1.2 1.2 1.9Index (C.I.I.)Flame RetardancyButler Chimney 80 78 81 80(% wt. remained)Oxygen Index 22 22.5 23.5 24.0Friability (% wt. loss) 20 36 34 41% Closed Cell 81 67 86 78Dimensional Stability (PercentDimensional Change)(100% R.H. at 70° C.)After 24 hoursa -0.6 -0.2 -0.4 0b -0.4 -0.6 -0.4 -0.8c -0.4 -0.4 -0.2 -1.0vol -1.3 -1.1 -1.0 -1.7After 1 weeka -0.6 0.8 -0.4 0b -0.6 0.6 -0.4 -0.8c -0.4 0.4 -0.6 -0.8vol -1.5 -1.7 -1.3 -1.5______________________________________
EXAMPLE III
Three additional samples were prepared using a different diamine, N,N'-di-sec-octyl-methylene dianiline (UL-8100) in Sample #1, and blends of N,N'-di-sec-butyl-methylene dianiline (UL-4200 from UOP) with N,N'-di-sec-butyl-4,4'-phenylene diamine (UL-4100) (Sample #2) and di-sec-octyl-methylene dianiline (Sample #3). The formulations and results are shown in the following Table 3.
TABLE 3______________________________________Urea-modified Isocyanurate Foams Using Unilink 8100 Sample No. 1 2 3Formulation (8100) (4200-4100) (8100-4200)______________________________________PAPI 27 134 200UL-8100 33.2 0 17.2UL-4200 0 20.7 34.4UL-4100 0 7.3 0TMR-22.0 2.0 1.5Polycat 41 0 0 2.5Dabco T-12 0 -- 0.1CFC-11 20.0 25.0 0L-5421 2.0 2.0 0DC-5098 0 0 3.0Water 0 0 4.4NCO/NH ratio 5 5 3Reaction ProfileCream Time (sec) 12 9 7Gel Time (sec) -- 74 69Rise Time (sec) 46 87 .sup.˜90*Physical PropertiesDensity, p.c.f. Kg/m.sup.3 2.61 2.1 1.98 (41.8)K-Factor, BTU in/ft.sup.2 hr °F.Initial 0.155 0.161 0.182After 24 hrs. -- 0.168 0.188After 1 week 0.024 0.181 0.198Compressive Strength KPa(psi)Parallel to rise 32.0 31.1 23.2Perpendicular to rise 27.3 18.3 19.0C.I.I. 1.2 1.7 1.2FlammabilityButler Chimney 87 81 74(% wt. remained)Oxygen Index 23.5 24.5 22.0Friability 10 21 20(% wt. loss)% Closed Cell 81 81 59______________________________________ | Rigid urea-modified polyisocyanurate foams with improved dimensional stability and flame retardancy have densities of 1-12 p.c.f., a limiting oxygen index greater than 22 and dimensional changes at 100% R.H. and 70° C. of less than 2% in any linear dimension and a method of making same. The method comprises reacting an organic polyisocyanate, a blowing agent and an N,N'-dialkyl aromatic diamine in the presence of a trimerization catalyst and, if water is used as the blowing agent, a blowing catalyst, wherein the N,N'-dialkyl aromatic diamine and an amine produced by water, if used, constitute the sole sources of active hydrogen. | 8 |
FIELD OF THE INVENTION
[0001] This invention relates to the sawmill industry. More particularly in relates to a machine for removing the outer portion of wood present on the logs near the base or “butt” end of a log. Such machine is suited for use in sawmills and plywood mills where logs are being processed into lumber or plywood blocks. More particularly, it is suited for use in conjunction with a debarking machine.
BACKGROUND TO THE INVENTION
[0002] In the sawmill industry logs are processed, after debarking, by running them through sawing stands that remove wood from the logs to produce squared cants and boards. As logs are rarely of a uniform diameter along their entire length, initial portions of the log must be removed from where the log is widest. Most trees have an enlarged diameter at their base, giving rise to logs with swelled butt ends. Partial slabs remove from such swelled butt ends are a nuisance to manage in a sawmill. They are not large enough to be converted into lumber, and they are difficult to convey to chippers for disposal. Consequently, one method of dealing with the logs having swelled butt ends is to buck the logs, cutting transversely across the log to remove the swelled butt end. Unfortunately, this is a costly the procedure as it removes a portion of the log, wasting good wood that could be turned into lumber.
[0003] A design for an existing machine for removing root swellings from timber logs is disclosed in U.S. Pat. No. 4,363,342 issued in 1982 to Bruks Mekaniska of Sweden. According to the design of this machine a log is rotated while a fixed-position cylindrical milling cutter is used to remove the excess wood present in the swelled butt. This procedure has the disadvantage that the log must be rotated. Rotation of the log is inconvenient because of the large mass of the log, and additionally, logs are rarely perfectly straight and cylindrically even. Therefore the positioning of the rotating log with respect to the milling head is less precise than would be preferred.
[0004] Existing reducers like the Swedish “Bruks” machine have the disadvantage that they operate “off-line”. Logs need to be taken out of the processing line, reduced and re-introduced in the line. They also involve a slow process that requires the log to be rotated against an axially fixed rotating milling head. These procedures also involves the cost of an additional operator.
[0005] A few years ago Valon Kone (a Finnish manufacturer) experimented with modifying a ring debarker to incorporate cutting plates that would remove wood in conjunction with the operation of normal debarker scraper plates that remove bark. However, due to limitations on the structure of the debarker ring, it was not possible to rotate the ring fast enough to produce a satisfactory result.
[0006] One other manufacturer on the Canadian west coast has experimented with a fixed diameter chuck head carrying cutting knives mounted to effect an encircling action around a log. While this configuration was able to remove wood from the butt end of logs, its operation was not fully satisfactory due to the fixed diameter system used to process logs.
[0007] This unit was suited for only a very narrow range of log diameters. In addition, it's compact design did not allow for the removed debris to fly-off, causing the head to “pack-up” within a short time, requiring frequent stoppages for cleaning.
[0008] An improved mechanism for removing wood from the swelled butt-end of a log would be highly desirable. This invention addresses such an objective.
[0009] The invention in its general form will first be described, and then its implementation in terms of specific embodiments will be detailed with reference to the drawings following hereafter. These embodiments are intended to demonstrate the principle of the invention, and the manner of its implementation. The invention in its broadest and more specific forms will then be further described, and defined, in each of the individual claims which conclude this Specification.
SUMMARY OF THE INVENTION
[0010] It is a feature of the invention that the butt end of a flared log may be shaped to remove flared portions by exposing the butt end to a cutting action arising from cutting heads that rotate about the log. This shaping can be effected in a preferred embodiment through use of rotating cutting heads that may be moved inwardly and outwardly with respect to the log while such cutting heads are being rotated about the log.
[0011] According to the invention in one aspect, a log with a swelled butt end to be milled is passed axially through the central region of a rotatable frame. The log may be advanced through sequential positions whereat the log remains stationary while milling heads pass over the outer surface of the log portion that is being milled. Alternately and preferably, the log may be advanced axially through the rotatable frame while the rotatable frame is oscillating or rotating, causing the milling heads carried within the rotating frame to be passed over the outer surface of the log along circular or spiral paths. In this latter case, it is necessary for the rotatable frame to have a sufficient degree of angular freedom and speed of angular rotation to ensure that, taking into account the rate of advancement of the log, all portions of the outer surface of the log constituting the swelled butt end will be subject to milling by the milling heads.
[0012] The machine according to the invention operates on the basis of powered rotating cutting-edges carried by at least one, and preferably multiple milling heads that are, in turn, mounted within the rotating frame through displaceable cutting head supports. Each milling head is preferably mounted at and embraced by the ends of a pair of pivoting arms. The pivoting arms, as a preferred cutting head support, are supported for rotation about pivoting arm axes that are carried by the rotating frame.
[0013] The pivoting arms for the respective heads are preferably linked to allow them to move in a ganged array, advancing the milling heads generally radially towards and away from the central region of the rotating frame. The milling heads do not necessarily move precisely along radii extending outwardly from the central axis of the rotating frame. Rather they swing in arcs into the central region of the rotating frame.
[0014] Each pivoting arm has a bell-cranked protruding arm portion and an associated linking strut that extends to a further protruding portion of the next adjacent pivoting arm. Such further protruding portion is on the side of each pivoting arm axis opposite from the end of the pivoting arm that carries a milling head. Collectively, the struts extending between the pivoting arms form a closed circle. One of the struts is expandable longitudinally and lockable in its position, allowing any slackness and backlash present in the circular linkage to be eliminated.
[0015] In order to position the milling heads within the rotatable frame, one or more linear actuators in the form of an air or hydraulic cylinder, or similar mechanism, extends from a fixed position on the rotatable frame to a special extended portion associated with one of the pairs of pivoting arms. Expansion or contraction of this linear actuator means causes all of the pivoting arms to rotate about their respective pivoting axis, advancing the milling heads into the interior region of the rotatable frame, or allowing such milling heads to be withdrawn from such interior region. In this manner, logs and swelled butts of differing diameters may be accommodated.
[0016] The rotating frame is carried within an exterior stationary frame that provides bearings upon which the rotating frame may rotate. Rotation in the preferred design is not continuous but only partial. Full cutting operation is achieved by oscillating the rotatable frame.
[0017] Based on the presence of 4 milling heads, the rotating frame must be free to rotate through at least 90 degrees of angular rotation within the stationary frame in order to provide full circumferential coverage of the outside surface of a log. This is sufficient angular rotation for the rotating frame to permit at least one milling head to bear against every portion of the outside surface of a log that is held in a fixed position during the milling operation.
[0018] In cases where the log is being passed through the central region of the rotating frame in a state of continuous motion, the rotating frame preferably is free to rotate through more than the minimum angular degree needed to process the outside surface of the stationary log. It is preferable, based on four milling heads, to provide freedom for the rotating frame to rotate through 135 degrees of rotation. This allows for 22½ degrees of motion for the milling heads within which they may accelerate, decelerate, and reverse their direction of rotation. Based on the presence of three milling heads, the rotating frame must be free to rotate through at least 120 degrees, more preferably 185 degrees, of angular rotation. With two milling heads, at least 180 degrees of angular rotation must be available in order to process a stationary log.
[0019] The milling heads must be powered to enable them to effect their cutting action. Preferably, this is achieved by means of individual electrical motors mounted at the respective axis for each of the pivoting arms. A suitable linkage between each motor and its respective milling head may be effected through use of a belt drive, or equivalent.
[0020] A primary positioning means is required to rotate and reciprocate the rotating frame. Preferably this is achieved by mounting a servo motor to the outer stationary frame. This servo motor is connected to the rotating frame through belts, gears, chain or the like.
[0021] Power for the electric motors and fluid for the actuating cylinder present in the rotating frame are provided by cables and a hose that are laid down within a groove formed around the outer circumferential edge of the rotating frame. As the degree of angular rotation for this rotating frame is limited, the cable and hose is fed from a folding cable tray that pays-out and receives the linking cable and hose.
[0022] The machine according to the invention has a particular advantage in that it allows the process of removing wood from the swelled butt end of a log to be carried out “on-line”, with the log in continuous axial motion as it progresses towards or, preferably, away from a de-barking machine. The butt reducer machine of the invention includes the feature that it will adjust to the diameter of the log to be reduced. And in removing wood from the outer circumferential surface of the log, longitudinally over the span of the flared butt end, it will provide a smooth surface finish on the log, allowing wany boards of improved finish to be removed from the log.
[0023] Preferably, this butt reducer is to be located immediately after a ring debarker. Advantageously, the log support and advancement mechanism of the debarker machine may be relied upon to hold the log while the butt portion of the log is being advanced through the butt-removal station. In some cases, it may be necessary to slowdown the debarker from it's normal speed of 300-400 fpm to 100-120 fpm while the butt removal process is being carried out. This may extend the processing time for the log in the debarker machinery by 2 to 3 seconds. However, this is still a considerable improvement over the prior art alternative of removing the swelled butt portion of the log off-line.
[0024] In this manner, a useful machine may be provided which is particularly suited to shaping the flared butt-end portions of logs, rendering the logs more nearly cylindrical before the logs are passed through subsequent stations were they are reduced to cants and/or boards.
[0025] The foregoing summarizes the principal features of the invention and some of its optional aspects. The invention may be further understood by the description of the preferred embodiments, in conjunction with the drawings, which now follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] [0026]FIG. 1 is a pictorial view of a butt removal station incorporating the machine of the invention as a log approaches longitudinally to be passed therethrough.
[0027] [0027]FIG. 2 is a side view of the station of FIG. 1 showing log infeed and outfeed means.
[0028] [0028]FIG. 2A is a face view of the stationary and rotating frames of the butt remover, with four pivoting arms carrying milling heads installed therein poised to commence cutting.
[0029] [0029]FIGS. 2B and 2C are the view of FIG. 2A showing respectively advancement of the cutting heads to engage a log and the positioning of the milling heads upon completion of the milling action.
[0030] [0030]FIG. 3 is a pictorial view of the pivoting arms and milling heads of the preferred 4-head variant of the invention as in FIG. 1 with their associated linkages, shown separately from the frames in which they are mounted.
[0031] [0031]FIG. 4 is a pictorial view of the stationary and rotating frames that carry the pivoting arms and milling heads, without such arms and milling heads being present.
[0032] [0032]FIG. 5 is a modified version of the reducer of FIGS. 1 and 3, showing three pivoting arms carrying three milling heads, actuated by separate hydraulic or air cylinders.
[0033] [0033]FIG. 6 is a modified version of the reducer of FIGS. 1 and 3, showing linkages between two pivoting arms carrying two milling heads.
[0034] [0034]FIG. 7 is an exit-side cut-away pictorial view through the apparatus of FIGS. 1 and 3 showing details of the mounting of the pivot arms, and motors in the rotating frame for driving the milling heads.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0035] In FIG. 1 a log 1 approaches a butt-reducer station 2 according to the invention having an outer fixed frame 3 and an inner rotating frame 4 . The rotating frame 4 consists of two disc-shaped plates 5 supported on roller bearings 6 . The plates 5 are joined by bars 7 that cause them to rotate in unison on the bearings 6 .
[0036] One of the plates 5 is grooved around its circumferential edge 8 . One of the bearings 6 has a circular flange 9 that interfits into the grooved edge 8 to stabilize the pair of plates laterally. The other bearing 6 has a smooth face on its circumferential surface.
[0037] Logs 1 are fed into the butt-reducer station 2 as shown in FIG. 2 by an infeed system 10 . The log infeed system 10 may comprise paired rollers 11 that are slideably mounted and actuated in response to a feedback control system using sensors 12 to maintain the central alignment of the log 1 . A further sensor 12 A on a roller detects the speed of advancement of the log 1 . Alternately, two path-interrupting sensors 36 , 36 A may be used to determine log speed. In some cases log debarker machines rely upon such a roller-based log support system. The two roller pairs 11 A closest to the reducer station 2 could be the exit rollers from a debarker.
[0038] On the other side of a debarker, further roller pairs 11 B also provide support for the log 1 . By whatever means the logs 1 are supported, the infeed system 10 feeds the logs 1 axially into the butt reducer station 10 .
[0039] The roller pair 11 having sensors 12 will adjust to the diameter of the butt-end 1 A of a log 1 as it passes-by spreading apart to accommodate its passage. This displacement may be sensed and used as a measure of the width of the butt-end of the log as this width may be required to control the butt-cutting process to follow. This same roller pair sensing arrangement may also detect the diameter of the main portion of the log 1 , which dimension is used by the controller 30 to control the cutting process in the reducer station 2 .
[0040] As shown in FIG. 2A, the rotating frame 4 supports a linked assembly of rotatable cutting heads 13 . These milling head 13 , which may be about 30 inches long in their axial length, are powered by motors 14 through belts 15 or equivalent linkages.
[0041] Each milling head 13 is mounted on and embraced by a pair of pivoting arms 16 . These arms 16 , together with milling head actuators 34 constitute actuatable displaceable milling head supports. The pivoting arms 16 are carried about pivoting axes 46 that are supported by the rotating frame 4 through support plates 17 welded to the disc-shaped plates 5 at spaced intervals.
[0042] The pivoting arms 16 for the respective heads 13 are preferably linked by linkage bars 31 to allow them to move in a ganged array, advancing the milling heads 13 generally radially towards and away from the central region 32 of the rotating frame 4 .
[0043] Each pivoting arm 16 has a bell-cranked protruding arm portion 32 and an associated linking strut 31 that extends to a further protruding portion 33 of the next adjacent pivoting arm 16 . Such further protruding portion 33 is on the side of each pivoting arm axis opposite from the end of the pivoting arm 16 that carries a milling head 13 . Collectively, the struts 31 extending between the pivoting arms 16 form a closed circle. One of the struts 31 A is expandable longitudinally and lockable in its position, allowing any slackness and backlash present in the circular linkage to be eliminated.
[0044] In order to position the milling heads 13 within the rotatable frame 4 , one or more mill head linear actuators 34 in the form of an air or hydraulic cylinder, or similar mechanism, extends from a fixed position on the rotatable frame 4 to a special extended portion 35 associated with one of the pairs of pivoting arms 16 . Expansion or contraction of this linear mill head actuator means 35 causes all of the pivoting arms to rotate about their respective pivoting axes 46 , advancing the milling heads 13 into the interior region 32 of the rotatable frame 4 , or allowing such milling heads 13 to be withdrawn from such interior region 32 . In this manner, logs 1 and swelled butts 1 A of differing diameters may be accommodated.
[0045] The control system for the butt-reducer station 2 in the preferred mode of operation detects the arrival of a log 1 through path-interrupting sensors 36 , 36 A, and waits until about 6 inches of the butt-end 1 A of the log 1 has entered between the milling heads 13 . At this point, the mill head actuator 34 is caused by the controller 30 to rotate the pivot arms 16 , advancing the milling heads 13 towards the butt-end 1 A.
[0046] Simultaneously, a frame positioning system 18 causes the rotating frame 4 to rotate. The frame positioning system 18 may operate on the basis of a positioning or stepping servo-motor 19 mounted on the fixed frame 3 to drive a chain 20 that engages a cogged track 21 on one of the circular plates 5 of the rotating frame 4 —see FIGS. 4 and 7. By this means, rotation of the positioning motor 19 will correspondingly rotate and position the rotatable frame 4 .
[0047] To maintain tension in the chain 20 a linear actuator 22 preferably in the form of an air or hydraulic cylinder 22 mounted to the fixed frame 3 causes, through linkages 23 , a sprogged wheel 24 to take up any slack in the chain 20 .
[0048] The frame positioning system 18 in the preferred embodiment with four milling heads 13 causes the rotating frame 4 to oscillate through a range of about 135 degrees while the milling heads 13 engage the butt-end 1 A of the log 1 . During this reciprocating displacement of the rotating frame 4 , the milling head positioning actuator(s) 34 cause the milling heads 13 to advance into the butt-end 1 A of the log 1 , removing unwanted wood. This combined reciprocating action of the rotatable frame 3 and inward displacement of the milling heads 13 is shown sequentially in FIGS. 2A, 2B and 2 C.
[0049] While the cutting action on the butt-end 1 A is occurring, the log 1 in the preferred variant is advancing. As the log 1 is being presented with its butt-end 1 A in advance of the log 1 , and as the cutting action only commences once the butt-end 1 A is between the milling heads 13 , the advancement of the log does not interfere with the cutting action. Cutting and rotation of the frame 4 under guidance from a controller 30 occurs at such a rate as to ensure that the diameter of the butt-end 1 A is reduced to the main diameter of the log 1 before the butt-end 1 A has passed beyond the milling heads 13 .
[0050] While a range of rotation of 90 degrees would be sufficient to reduce the butt-end 1 A of a stationary log 1 using four milling heads 13 , a preferred range of 135 degrees allows time for the rotating frame 4 to accelerate and reverse while still ensuring that the entire circumferential span of the butt-end 1 A of a normal log 1 is reduced. Oscillation may also be effected within the ranges of 120-150 degrees. In special cases where the butt-end 1 A is of a particularly extended length, it may be necessary for an operator or the control system to reduce the speed of the log 1 as it passes through the reducing station 2 .
[0051] As log 1 passes through the reducing station 2 , it is received as it exits the machine by a log outfeed system 38 . As shown in FIG. 1B this may optionally be based on a traditional chain carrier having a chain 39 that supports the log 1 . One or more hold-down rollers 40 may be positioned above the log 1 to stabilize the log 1 on the chain 39 . Sensor 41 detects both the arrival of a log 1 at the outfeed conveyor, and its final passage past the sensor 41 .
[0052] While the preferred embodiment of the system relies upon the use of four milling heads 13 , the system of the invention may operate with three, two and even only one milling head 13 . Systems with three and two milling heads are shown in FIGS. 5 and 6 respectively. These systems have the advantage of a symmetrical layout that results in balanced loads, etc.
[0053] In FIG. 5 the linkages 31 between the pivoting arms 16 of FIG. 3 have been replaced by three pivot arm linear actuators 42 which separately control the positioning of each pivoting arm 16 . Each pivot-arm linear actuator 42 is anchored at one end to a plate 5 of the rotating frame 4 and connected at its other end to a pivot arm 16 . Actuators 42 act in synchronization with the positioning of the rotating frame 4 , which is also subject to control by the controller 30 through the controller's actuation of the positioning motor 19 . This same synchronized action is effected in case of the FIG. 3 and FIG. 6 configurations wherein the controller 30 provides commands 51 , 52 , 53 to the milling head actuators 34 through servo-valve 43 , and other system elements.
[0054] [0054]FIGS. 5 and 6 depict preferred symmetrically balanced milling head configurations. A single milling head system would not enjoy the benefits of being symmetrically balanced. However, a butt-reducer station 2 with a single head could still operate on the basis of the invention, albeit with reduced efficiency.
[0055] Conclusion
[0056] The foregoing has constituted a description of specific embodiments showing how the invention may be applied and put into use. These embodiments are only exemplary. The invention in its broadest, and more specific aspects, is further described and defined in the claims which now follow.
[0057] These claims, and the language used therein, are to be understood in terms of the variants of the invention which have been described. They are not to be restricted to such variants, but are to be read as covering the full scope of the invention as is implicit within the invention and the disclosure that has been provided herein. | A butt reducer machine is provided to remove excess wood from the swelled butt ends of logs. Cutting heads supported on pivoting arms, carried in turn within a rotating frame, are caused to oscillate circumferentially about the portion of the log to be removed. This butt-removal process may be carried out while a log is in motion longitudinally, either before or after the log enters a de-barking machine. The process may also be effected on a stationary log. | 1 |
BACKGROUND OF THE INVENTION
Growth hormone, which is secreted from the pituitary, stimulates growth of all tissues of the body that are capable of growing. In addition, growth hormone is known to have the following basic effects on the metabolic process of the body:
1. Increased rate of protein synthesis in all cells of the body;
2. Decreased rate of carbohydrate utilization in cells of the body;
3. Increased mobilization of free fatty acids and use of fatty acids for energy.
A deficiency in growth hormone secretion can result in various medical disorders, such as dwarfism.
Various ways are known to release growth hormone. For example, chemicals such as arginine, L-3,4-dihydroxyphenylalanine (L-DOPA), glucagon, vasopressin, and insulin induced hypoglycemia, as well as activities such as sleep and exercise, indirectly cause growth hormone to be released from the pituitary by acting in some fashion on the hypothalamus perhaps either to decrease somatostatin secretion or to increase the secretion of the known secretagogue growth hormone releasing factor (GRF) or an unknown endogenous growth hormone-releasing hormone or all of these.
In cases where increased levels of growth hormone were desired, the problem was generally solved by providing exogenous growth hormone or by administering an agent which stimulated growth hormone production and/or release. In either case the peptidyl nature of the compound necessitated that it be administered by injection. Initially the source of growth hormone was the extraction of the pituitary glands of cadavers. This resulted in a very expensive product and carried with it the risk that a disease associated with the source of the pituitary gland could be transmitted to the recipient of the growth hormone. Recently, recombinant growth hormone has become available which, while no longer carrying any risk of disease transmission, is still a very expensive product which must be given by injection or by a nasal spray.
Other compounds have been developed which stimulate the release of endogenous growth hormone such as analogous peptidyl compounds related to GRF or the peptides of U.S. Pat. No. 4,411,890. These peptides, while considerably smaller than growth hormones are still susceptible to various proteases. As with most peptides, their potential for oral bioavailability is low. The instant compounds are non-peptidyl agents for promoting the release of growth hormone which may be administered parenterally, nasally or by the oral route.
SUMMARY OF THE INVENTION
The instant invention covers certain heterocyclic-fused lactam compounds which have the ability to stimulate the release of natural or endogenous growth hormone. The compounds thus have the ability to be used to treat conditions which require the stimulation of growth hormone production or secretion such as in humans with a deficiency of natural growth hormone or in animals used for food production where the stimulation of growth hormone will result in a larger, more productive animal. Thus, it is an object of the instant invention to describe the heterocyclic-fused lactam compounds. It is a further object of this invention to describe procedures for the preparation of such compounds. A still further object is to describe the use of such compounds to increase the secretion of growth hormone in humans and animals. A still further object of this invention is to describe compositions containing the heterocyclic-fused lactam compounds for the use of treating humans and animals so as to increase the level of growth hormone secretions. Further objects will become apparent from a reading of the following description.
DESCRIPTION OF THE INVENTION
The novel heterocyclic-fused lactams of the instant invention are best described in the following structural formula I: ##STR1## L is ##STR2## n is 0 or 1; p is 0 to 3;
q is 0 to 4;
w is 0 or 1;
X is C═O, O, S(O) m , ##STR3## --CH═CH--; m is 0 to 2; ##STR4## is an R 1 , R 2 independently disubstituted five- or six-membered heterocycle containing from one to three heteroatoms selected from nitrogen, oxygen or sulfur; where R 1 , R 2 are as defined below;
R 1 , R 2 , R 1a , R 2a , R 1b and R 2b are independently hydrogen, halogen, C 1 -C 7 alkyl, C 1 -C 3 perfluoroalkyl, C 1 -C 3 perfluoroalkoxy, --S(O) m R 7a , cyano, nitro, R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --, R 5b R 12b N(CH 2 ) v --, R 5b R 12b NCO(CH 2 ) v --, phenyl or substituted phenyl where the substituents are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or hydroxy; v is 0 to 3 and m is 0 to 2;
R 7a and R 7b are independently hydrogen, C 1 -C 3 perfluoroalkyl, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl where the substitutents are phenyl or substituted phenyl; phenyl or substituted phenyl where the phenyl substitutents are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or hydroxy;
R 3a and R 3b are independently hydrogen, R 9 , C 1 -C 6 alkyl substituted with R 9 , phenyl substituted with R 9 or phenoxy substituted with R 9 ;
R 9 is ##STR5## R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --,
R 7b CO(CH 2 ) v --, R 7b O(CH 2 ) v CO--, R 5b R 12b N(CH 2 ) v --,
R 5b R 12b NCO(CH 2 ) v --, R 5b R 12b NCS(CH 2 ) v --,
R 5b R 12c NN(R 12b )CO(CH 2 ) v --,
R 5b R 12c NN(R 12b )CS(CH 2 ) v --,
R 5b R 12b NCON(R 12a )(CH 2 ) v --,
R 5b R 12b NCSN(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CSN(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )COO(CH 2 ) v --, R 5b R 12b NCOO(CH 2 ) v --
or R 13 OCON(R 12a )(CH 2 ) v --, where v is 0 to 3;
R 12a , R 12b and R 12c are independently R 5a , OR 5a or COR 5a , R 12a and R 12b , or R 12b and R 12c , or R 12a and R 12c , or R 12b and R 5b , or R 12c and R 5b , or R 13 and R 12a can be taken together to form --(CH 2 ) r --B--(CH 2 ) s -- where B is CHR 1 , O, S(O) m or NR 10 , m is 0, 1 or 2, r and s are independently 0 to 3 and R 1 and R 10 are as defined;
R 13 is C 1 -C 3 perfluoroalkyl, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, where the substitutents are hydroxy, --NR 10 R 11 , carboxy, phenyl or substituted phenyl; phenyl or substituted phenyl where the substituents on the phenyl are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or hydroxy;
R 10 and R 11 are independently hydrogen, C 1 -C 6 alkyl, phenyl, phenyl C 1 -C 6 alkyl, C 1 -C 5 alkoxycarbonyl or C 1 -C 5 alkanoyl-C 1 -C 6 alkyl;
R 4 , R 4a , R 5 , R 5a and R 5b are independently hydrogen, phenyl, substituted phenyl, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl, C 3 -C 10 alkenyl, substituted C 3 -C 10 alkenyl, C 3 -C 10 alkynyl or substituted C 3 -C 10 alkynyl where the substituents on the phenyl, alkyl, alkenyl or alkynyl are from 1 to 5 of hydroxy, C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, fluoro, R 1 , R 2 independently disubstituted phenyl, R 1 , R 2 independently disubstituted phenyl C 1 -C 3 alkoxy, C 1 -C 20 -alkanoyloxy, C 1 -C 5 alkoxycarbonyl, carboxy, formyl or --NR 10 R 11 where R 1 , R 2 , R 10 and R 11 are as defined above; or R 4 and R 5 can be taken together to form --(CH 2 ) r --B--(CH 2 ) s -- where B is CHR 1 , O, S(O) m or N--R 10 , r and s are independently 1 to 3, m is 0, 1 or 2 and R 1 and R 10 are as defined above;
R 6 is hydrogen, C 1 -C 10 alkyl, phenyl or phenyl C 1 -C 10 alkyl;
A is ##STR6## where x and y are independently 0-3;
R 8a and R 8b are independently hydrogen, C 1 -C 10 alkyl, trifluoromethyl, R 1 , R 2 independently disubstituted phenyl, substituted C 1 -C 10 alkyl where the substitutents are from 1 to 3 of imidazolyl, indolyl, hydroxy, fluoro, --S(O) m R 7a , C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, R 1 , R 2 independently disubstituted phenyl, R 1 , R 2 independently disubstituted phenyl C 1 -C 3 alkoxy, C 1 -C 5 alkanoyloxy, C 1 -C 5 alkoxycarbonyl, s carboxy, formyl or --NR 10 R 11 where R 1 , R 2 , R 7a , R 10 , R 11 and m are as defined above; or R 8a and R 8b can be taken together to form --(CH 2 ) t -- where t is 2 to 6; and R 8a and R 8b can independently be joined to one or both of R 4 and R 5 to form alkylene bridges between the terminal nitrogen and the alkyl portion of the A group wherein the bridge contains from one to five carbon atoms; and pharmaceutically acceptable salts thereof.
In the above structural formula and throughout the instant specification, the following terms have the indicated meanings:
Heterocycles described by formula I include, but are not limited to: pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, triazole, pyridine, pyridazine, pyrazine and pyrimidine.
It is intended that the lactam portion of Formula I be fused to the heterocycle at any two adjacent atoms of the heterocycle such that the heteroatoms are at any position of the Het group and that one or two of the nitrogen heteroatoms can be at the bridgehead positions (the positions shared by both Het and the lactam ring). In addition, one or more unsaturations may be present in the Het group. It should be noted that all positional isomers with the heteroatoms taking various in the Het group are included within the scope of this invention.
The alkyl groups specified above are intended to include those alkyl groups of the designated length in either a straight or branched configuration. Exemplary of such alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary butyl, pentyl, isopentyl, hexyl, isohexyl, and the like.
The alkoxy groups specified above are intended to include those alkoxy groups of the designated length in either a straight or branched configuration. Exemplary of such alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy, pentoxy, isopentoxy, hexoxy, isohexoxy and the like.
The term "halogen" is intended to include the halogen atoms fluorine, chlorine, bromine and iodine.
Certain of the above defined terms may occur more than once in the above formula and upon such occurrence each term shall be defined independently of the other.
Preferred compounds of the instant invention are realized when in the above structural formula:
n is 0 or 1;
p is 0 to 3;
q is 0 to 2;
w is 0 or 1;
X is O, S(O) m , ##STR7## --CH═CH--; m is 0 to 2;
R 1 , R 2 , R 1a , R 2a , R 1b and R 2b are independently hydrogen, halogen, C 1 -C 7 alkyl, C 1 -C 3 perfluoroalkyl, --S(O) m R 7a , R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --, phenyl or substituted phenyl where the substituents are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or hydroxy;
R 7a and R 7b are independently hydrogen, C 1 -C 3 perfluoroalkyl, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl where the substitutents are phenyl; phenyl and v is 0 to 3;
R 3a and R 3b are independently hydrogen, R 9 , C 1 -C 6 alkyl substituted with R 9 , phenyl substituted with R 9 or phenoxy substituted with R 9 ;
R 9 is ##STR8## R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --,
R 7b CO(CH 2 ) v --, R 5b R 12b N(CH 2 ) v --,
R 5b R 12b NCO(CH 2 ) v --, R 5b R 12b NCS(CH 2 ) v --,
R 5b R 12c NN(R 12b )CO(CH 2 ) v --,
R 5b R 12b NCON(R 12a )(CH 2 ) v --,
R 5b R 12b NCSN(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CSN(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )COO(CH 2 ) v --, R 5b R 12b NCOO(CH 2 ) v --
or R 13 OCON(R 12a )(CH 2 ) v --, and v is 0 to 3;
R 12a , R 12b and R 12c are independently R 5a , OR 5a or COR 5a , R 12a and R 12b , or R 12b and R 12c , or R 12a and R 12c , or R 12b and R 5b , or R 12c and R 5b , or R 13 and R 12a can be taken together to form --(CH 2 ) r --B--(CH 2 ) s -- where B is CHR 1 , O, S(O) m or NR 10 , m is 0, 1 or 2, r and s are independently 0 to 3 and R 1 and R 10 are as defined;
R 13 is C 1 -C 3 perfluoroalkyl, C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, where the substitutents are hydroxy, --NR 10 R 11 , carboxy, phenyl or substituted phenyl; phenyl or substituted phenyl where the substituents on the phenyl are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or hydroxy;
R 10 and R 11 are independently hydrogen, C 1 -C 6 alkyl, phenyl C 1 -C 6 alkyl, or C 1 -C 5 alkanoyl-C 1 -C 6 alkyl;
R 4 , R 4a , R 5 , R 5a and R 5b are independently hydrogen, phenyl, substituted phenyl, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl where the substituents on the alkyl or phenyl are from 1 to 5 of hydroxy, C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, fluoro, R 1 , R 2 independently disubstituted phenyl, R 1 , R 2 independently disubstituted phenyl C 1 -C 3 alkoxy, C 1 -C 20 -alkanoyloxy, C 1 -C 5 alkoxycarbonyl, carboxy or formyl; R 4 and R 5 can be taken together to form --(CH 2 ) r --B--(CH 2 ) s -- where B is CHR 1 , O, S(O) m or N--R 10 , r and s are independently 1 to 3, m is 0, 1 or 2 and R 1 and R 10 are as defined above;
R 6 is hydrogen, C 1 -C 10 alkyl or phenyl C 1 -C 10 alkyl;
A is ##STR9## where x and y are independently 0-2;
R 8a and R 8b are independently hydrogen, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl where the substitutents are from 1 to 3 of imidazolyl, indolyl, hydroxy, fluoro, --S(O) m R 7a , C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, R 1 , R 2 independently disubstituted phenyl, R 1 , R 2 independently disubstituted phenyl C 1 -C 3 alkoxy, C 1 -C 5 alkanoyloxy, C 1 -C 5 alkoxycarbonyl, carboxy, formyl or --NR 10 R 11 where R 1 , R 2 , R 7a , R 10 , R 11 and m are as defined above; or R 8a and R 8b can be taken together to form --(CH 2 ) t -- where t is 2 to 4; and R 8a and R 8b can independently be joined to R 5 to form alkylene bridges between the terminal nitrogen and the alkyl portion of the A group wherein the bridge contains from one to five carbon atoms;
and pharmaceutically acceptable salts thereof.
Additional preferred compounds are realized in the above structural formula when:
n is 0 or 1;
p is 0 to 2;
q is 0 to 2;
w is 0 or 1;
X is S(O) m or --CH═CH--;
m is 0 or 1;
R 1 , R 2 , R 1a , R 2a , R 1b and R 2b are independently hydrogen, halogen, C 1 -C 7 alkyl, C 1 -C 3 perfluoroalkyl, --S(O) m R 7a , R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --, phenyl or substituted phenyl where the substituents are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or hydroxy;
R 7a and R 7b are independently hydrogen, C 1 -C 6 alkyl or substituted C 1 -C 6 alkyl where the substitutents are phenyl and v is 0 to 2;
R 3a and R 3b are independently hydrogen, R 9 , C 1 -C 6 alkyl substituted with R 9 or phenoxy substituted with R 9 ;
R 9 is ##STR10## R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --,
R 7b CO(CH 2 ) v --, R 5b R 12b N(CH 2 ) v --,
R 5b R 12b NCO(CH 2 ) v --,R 5b R 12c NN(R 12b )CO(CH 2 ) v --,
R 5b R 12b NCON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CSN(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )COO(CH 2 ) v --, R 5b R 12b NCOO(CH 2 ) v --,
or R 13 OCON(R 12a )(CH 2 ) v --, where v is 0 to 2;
R 12a , R 12b and R 12c are independently R 5a or OR 5a , R 12a and R 12b , or R 12b and R 12c , or R 12a and R 12c , or R 12b and R 5b , or R 12c and R 5b , or R 13 and R 12a can be taken together to form --(CH 2 ) r --B-- (CH 2 ) s -- where B is CHR 1 , O, S(O) m or NR 10 , m is 0, 1 or 2, r and s are independently 0 to 2 and R 1 and R 10 are as defined;
R 13 is C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, where the substitutents are phenyl or substituted phenyl; phenyl or substituted phenyl where the substituents on the phenyl are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or hydroxy;
R 10 and R 11 are independently hydrogen, C 1 -C 6 alkyl, phenyl C 1 -C 6 alkyl, or C 1 -C 5 alkanoyl-C 1 -C 6 alkyl;
R 4 , R 4a , R 5 , R 5a and R 5b are independently hydrogen, C 1 -C 10 alkyl or substituted C 1 -C 10 alkyl where the substituents are from 1 to 5 of hydroxy, C 1 -C 6 alkoxy, fluoro, R 1 , R 2 independently disubstituted phenyl, C 1 -C 20 -alkanoyloxy, C 1 -C 5 alkoxycarbonyl or carboxy; where R 1 and R 2 are as defined above;
R 6 is hydrogen or C 1 -C 10 alkyl;
A is ##STR11## where x and y are independently 0-1;
R 8a and R 8b are independently hydrogen, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl where the substitutents are from 1 to 3 of imidazolyl, indolyl, hydroxy, fluoro, --S(O) m R 7a , C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, R 1 , R 2 independently disubstituted phenyl, R 1 , R 2 independently disubstituted phenyl C 1 -C 3 alkoxy, C 1 -C 5 alkanoyloxy, C 1 -C 5 alkoxycarbonyl, carboxy, formyl or --NR 10 R 11 where R 1 , R 2 , R 7a , R 10 , R 11 and m are as defined above; or R 8a and R 8b can be taken together to form --(CH 2 ) t -- where t is 2; and R 8a and R 8b can independently be joined to R 5 to form alkylene bridges between the terminal nitrogen and the alkyl portion of the A group wherein the bridge contains from one to five carbon atoms;
and pharmaceutically acceptable salts thereof.
Still further preferred compounds of the instant invention are realized in the above structural formula when;
n is 0 or 1;
p is 0 to 2;
q is 1;
w is 1;
X is S(O) m or --CH═CH--;
m is 0 or 1;
R 1 , R 2 , R 1a , R 2a , R 1b and R 2b are independently hydrogen, halogen, C 1 -C 7 alkyl, C 1 -C 3 perfluoroalkyl, --S(O) m R 7a , R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, phenyl or substituted phenyl where the substituents are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, or hydroxy;
R 7a and R 7b are independently hydrogen, C 1 -C 6 alkyl or substituted C 1 -C 6 alkyl where the substitutents are phenyl and v is 0 or 1;
R 3a and R 3b are independently hydrogen, R 9 or C 1 -C 6 alkyl substituted with R 9 ;
R 9 is ##STR12## R 7b O(CH 2 ) v --, R 7b COO(CH 2 ) v --, R 7b OCO(CH 2 ) v --,
R 7b CO(CH 2 ) v --, R 5b R 12b N(CH 2 ) v --,
R 5b R 12b NCO(CH 2 ) v --,R 5b R 12c NN(R 12b )CO(CH 2 ) v --,
R 5b R 12b NCON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )CON(R 12a )(CH 2 ) v --,
R 5b R 12c NN(R 12b )COO(CH 2 ) v --, R 5b R 12b NCOO(CH 2 ) v --
or R 13 OCON(R 12a )(CH 2 ) v --, where v is 0 to 2;
R 12a , R 12b and R 12c are independently R 5a , R 12a and R 12b , or R 12b and R 12c , or R 12a and R 12c , or R 12b and R 5b , or R 12c and R 5b , or R 13 and R 12a can be taken together to form --(CH 2 ) r --B--(CH 2 ) s -- where B is CHR 1 , O, S(O) m or NR 10 , m is 0, 1 or 2, r and s are independently 0 to 2 and R 1 and R 10 are as defined;
R 13 is C 1 -C 6 alkyl, substituted C 1 -C 6 alkyl, where the substitutents are phenyl or substituted phenyl; phenyl or substituted phenyl where the substituents on the phenyl are from 1 to 3 of halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy or hydroxy;
R 10 and R 11 are independently hydrogen, C 1 -C 6 alkyl or C 1 -C 5 alkanoyl-C 1 -C 6 alkyl;
R 4 , R 4a , R 5 , R 5a and R 5b are independently hydrogen, C 1 -C 10 alkyl or substituted C 1 -C 10 alkyl where the substituents are from 1 to 3 of hydroxy, C 1 -C 3 alkoxy, fluoro, R 1 , R 2 independently disubstituted phenyl, C 1 -C 20 -alkanoyloxy, C 1 -C 5 alkoxycarbonyl or carboxy; where R 1 and R 2 are as defined above;
R 6 is hydrogen;
A is ##STR13##
where x and y are independently 0 or 1;
R 8a and R 8b are independently hydrogen, C 1 -C 10 alkyl, substituted C 1 -C 10 alkyl where the substitutents are from 1 to 3 of imidazolyl, indolyl, hydroxy, fluoro, --S(O) m R 7a , C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl, R 1 , R 2 independently disubstituted phenyl, C 1 -C 5 alkanoyloxy, C 1 -C 5 alkoxycarbonyl or carboxy, where R 1 , R 2 , R 7a , and m are as defined; or R 8a and R 8b can be taken together to form --(CH 2 ) t -- where t is 2; and R 8a and R 8b can independently be joined to R 5 to form alkylene bridges between the terminal nitrogen and the alkyl portion of the A group wherein the bridge contains from one to five carbon atoms; and pharmaceutically acceptable salts thereof.
Representative preferred growth hormone releasing compounds of the present invention include the following:
1. 3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]butanamide;
2. N-Ethyl-4'-[[7(R)-[[3-amino-3-methyl-1-oxobutyl]amino]-6,7,8,9-tetrahydro-8-oxo-5H-pyrido[2,3-b]azepin-9-yl]-methyl][1,1'-biphenyl]-2-carboxamide;
3. 3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]-methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
4. 3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
5. 3-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R )-yl]-3-methylbutanamide
6. N-Ethyl-4'-[[6(R)-[[3-amino-3-methyl-1-oxobutyl]amino]-5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-4-yl]-methyl][1,1'-biphenyl]-2-carboxamide;
7. 3-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-3-methylbutanamide;
8. 3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
9. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl]-3-amino-3-methylbutanamide;
10. N-Ethyl-4'-[[6(R)-[[3-amino-3-methyl-1-oxobutyl]amino]-1,4,5,6,7,8-hexahydro-5-oxo-pyrrolo[3,2-b]azepin-4-yl]-methyl][1,1'-biphenyl]-2-carboxamide;
11. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[(methylamino)-carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]-azepin-6(R)-yl]-3-amino-3-methylbutanamide;
12. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[[(methylamino)-carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-pyrrolo[3,2-b]azepin-6(R)-yl]-3-amino-3-methylbutanamide;
13. 3-[2(R)-Hydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]-methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
14. N-Ethyl-4'-[[7(R)-[[3-[2(R)-hydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-6,7,8,9-tetrahydro-8-oxo-5H-pyrido[2,3-b]azepin-9-yl]methyl][1,1'-biphenyl]-2-carboxamide;
15. 3 -[2(R)-Hydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]-butanamide;
16. 3-[2(R)-Hydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]-methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]butanamide;
17. 3-[2(R)-Hydroxypropyl]amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-3-methylbutanamide
18. N-Ethyl-4'-[[6(R)-[[3-[2(R)-hydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-4-yl]methyl][1,1'-biphenyl]-2-carboxamide;
19. 3-[2(R)-Hydroxypropyl]amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R )-yl]-3-methylbutanamide;
20. 3-[2(R)-Hydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]-methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]butanamide;
21. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl]-3-[2(R)-hydroxypropyl]amino-3-methylbutanamide;
22. N-Ethyl-4'-[[6(R)-[[3-[2(R)-hydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-1,4,5,6,7,8-hexahydro-5-oxo-pyrrolo[3,2-b]azepin-4-yl]methyl][1,1'-biphenyl]-2-carboxamide;
23. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[(methylamino)-carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]-azepin-6(R )-yl]-3-[2(R)-hydroxypropyl]amino-3-methylbutanamide;
24. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[[(methylamino)-carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-pyrrolo[3,2-b]azepin-6(R)-yl]-3-[2(R)-hydroxypropyl]-amino-3-methylbutanamide;
25. 3-[2(S),3-Dihydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
26. N-Ethyl-4'-[[7(R)-[[3-[2(S),3-dihydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-6,7,8,9-tetrahydro-8-oxo-5H-pyrido[2,3-b]azepin-9-yl]methyl][1,1'-biphenyl]-2-carboxamide;
27. 3-[2(S),3-Dihydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[(methylamino)carbonyl]amino]-[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide;
28. 3-[2(S),3-Dihydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]-methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]butanamide;
29. 3-[2(S),3-Dihydroxypropyl]amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-3-methylbutanamide
30. N-Ethyl-4'-[[6(R)-[[3-[2(S),3-dihydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-4-yl]methyl][1,1'-biphenyl]-2-carboxamide;
31. 3-[2(S),3-Dihydroxypropyl]amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-3-methylbutanamide;
32. 3-[2(S),3-Dihydroxypropyl]amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]-methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]butanamide;
33. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl]-3-[2(S),3-dihydroxypropyl]amino-3-methylbutanamide;
34. N-Ethyl-4'-[[6(R)-[[3-[2(S),3-dihydroxypropyl]amino-3-methyl-1-oxobutyl]amino]-1,4,5,6,7,8-hexahydro-5-oxo-pyrrolo[3,2-b]azepin-4-yl]methyl][1,1'-biphenyl]-2-carboxamide;
35. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[(methylamino)-carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]-azepin-6(R)-yl]-3-[2(S),3-dihydroxypropyl]amino-3-methylbutanamide;
36. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[[(methylamino)-carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-pyrrolo[3,2-b]azepin-6(R)-yl]-3-[2(S),3-dihydroxypropyl]-amino-3-methylbutanamide;
37. 2-Amino-2-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]-azepin-7(R)-yl]propanamide;
38. N-Ethyl-4'-[[7(R)-[[2-amino-2-methyl-1-oxopropyl]amino]-6,7,8,9-tetrahydro-8-oxo-5H-pyrido[2,3-b]azepin-9-yl]-methyl][1,1'-biphenyl]-2-carboxamide;
39. 2-Amino-2-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]-methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]propanamide;
40. 2-Amino-2-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]propanamide;
41. 2-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-2-methylpropanamide
42. N-Ethyl-4'-[[6(R)-[[2-amino-2-methyl-1-oxopropyl]amino]-5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-4-yl-]methyl][1,1'-biphenyl]-2-carboxamide;
43. 2-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-[[(methylamino)carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-2-methylpropanamide;
44. 2-Amino-2-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-[[[(methylamino)carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]propanamide;
45. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl]-2-amino-2-methylpropanamide;
46. N-Ethyl-4'-[[6(R)-[[2-amino-2-methyl-1-oxopropyl]amino]-1,4,5,6,7,8-hexahydro-5-oxo-pyrrolo[3,2-b]azepin-4-yl]-methyl][1,1'-biphenyl]-2-carboxamide;
47. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[(methylamino)-carbonyl]amino][1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]-azepin-6(R)-yl]-2-amino-2-methylpropanamide and
48. N-[1,4,5,6,7,8-Hexahydro-5-oxo-4-[[2'-[[[(methylamino)-carbonyl]amino]methyl][1,1'-biphenyl]-4-yl]methyl]-pyrrolo[3,2-b]azepin-6(R)-yl]-2-amino-2-methylpropanamide.
Representative examples of the nomenclature employed are given below: ##STR14##
The compounds of the instant invention all have at least one asymmetric center as noted by the asterisk in the structural Formula I above. Additional asymmetric centers may be present on the molecule depending upon the nature of the various substituents on the molecule. Each such asymmetric center will produce two optical isomers and it is intended that all such optical isomers, as separated, pure or partially purified optical isomers or racemic mixtures thereof, be included within the ambit of the instant invention. In the case of the asymmetric center represented by the asterisk in Formula I, it has been found that the compound in which the amino substituent adjacent to the lactam carbonyl is above the plane of the structure, as seen in Formula Ia, is more active and thus more preferred over the compound in which said substituent is below the plane of the structure. In the substituent (X) n , when n=0, the asymmetric center is designated as the R-isomer. When n=1, this center will be designated according to the R/S rules as either R or S depending upon the value of X. ##STR15##
The instant compounds are generally isolated in the form of their pharmaceutically acceptable acid addition salts, such as the salts derived from using inorganic and organic acids. Examples of such acids are hydrochloric, nitric, sulfuric, phosphoric, formic, acetic, trifluoroacetic, propionic, maleic, succinic, malonic and the like. In addition, certain compounds containing an acidic function such as a tetrazole or carboxy can be isolated in the form of their inorganic salt in which the counterion can be selected from sodium, potassium, lithium, calcium, magnesium and the like, as well as from organic bases.
The compounds (I) of the present invention are prepared from aminolactam intermediates such as those of formula II. The preparation of these intermediates is described in the following reaction Schemes. ##STR16##
Starting with either commercially available or synthetic heterofused-cycloalkanones 1, and following the procedures described by Fisher, et al, in U.S. Pat. No. 5,206,235 and references cited therein, for the preparation of benzo-fused lactams, the corresponding oximes 2 were prepared and rearranged to the hetero-fused lactams 4 via the intermediate O-tosyl oxime 3 as shown in Scheme 1. ##STR17##
Conversion of substituted hetero-fused lactam 4 to the requisite α-amino derivative II can be achieved by a number of methods familiar to those skilled in the art, including those described for the corresponding benzo-fused lactams by Watthey, et al, J. Med. Chem., 28, 1511-1516 (1985) and references cited therein. One common route proceeds via the intermediacy of an α-halo (chloro, bromo or iodo) intermediate which is subsequently displaced by a nitrogen nucleophile, typically azide. A useful method of forming the α-iodolactam intermediate 5 involves treating the hetero-fused lactam 4 with two equivalents each of iodotrimethylsilane and iodine at low temperature, as illustrated in Scheme 2. ##STR18##
Elaboration of the iodolactam 5 to the desired α-amino lactam intermediate II is achieved by the two-step procedure illustrated in Scheme 2. Typically, iodolactam 5 is treated with sodium azide in N,N-dimethylformamide at 50°-100° C. to give the α-azido derivative 6. Alternatively, tetramethylguanidinium azide in a solvent such as methylene chloride can be employed to achieve similar results. Hydrogenation with a metal catalyst, such as platinum on carbon, or alternatively, treatment with triphenylphosphine in wet toluene, results in formation of the amine derivative II. Formation of the α-amino derivatives of six-, seven-, eight-and nine-membered hetero-fused lactams is achieved by the routes shown in Scheme 2.
Chiral hetero-fused aminolactams are obtained by resolution of the racemates by classical methods familiar to those skilled in the art. For example, resolution can be achieved by formation of diastereomeric salts of the racemic amines with optically active acids such as D- and L-tartaric acid. Determination of absolute stereochemistry can be achieved in a number of ways including X-ray analysis of a suitable crystalline derivative.
Intermediates of formula II can be further elaborated to new intermediates (formula III) which are substituted on the amino group (Scheme 3). Reductive alkylation of II with an aldehyde is carried out under conditions known in the art; for example, by catalytic hydrogenation with hydrogen in the presence of platinum, palladium or nickel catalysts or with chemical reducing agents such as sodium cyanoborohydride in an inert solvent such as methanol or ethanol. ##STR19##
Attachment of the amino acid sidechain to intermediates of formula III is accomplished by the route shown in Scheme 4. Coupling is conveniently carried out by the use of an appropriately protected amino acid derivative, such as that illustrated by formula IV, and a coupling reagent such as benzotriazol-1-yloxytris(dimethylamino)-phosphonium hexafluorophosphate ("BOP") or benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate ("PyBOP") in an inert solvent such as methylene chloride. Separation of unwanted side products, and purification of intermediates is achieved by chromatography on silica gel, employing flash chromatography (W. C. Still, M. Kahn and A. Mitra, J. Org. Chem., 43, 2923 (1978)) or by medium pressure liquid chromatography. ##STR20##
The protected amino acid derivatives IV are, in many cases, commercially available in t-butoxycarbonyl (BOC) or benzyloxycarbonyl (CBz) forms. A useful method to prepare the preferred sidechain 11 is shown in Scheme 5. ##STR21##
Reaction of isobutylene with N-chlorosulfonylisocyanate 7 in diethyl ether gives the azetidinone derivative 8. Removal of the chlorosulfonyl group with aqueous sodium sulfite followed by reaction with di-t-butyldicarbonate gives the BOC-protected intermediate 10. Alkaline hydrolysis gives the protected amino acid derivative 11 in good overall yield.
Intermediates of formula VII can be prepared as shown in Scheme 6 by treatment of the desired lactam intermediate V with an alkylating agent VI, wherein Y is a good leaving group such as Cl, Br, I, O-methanesulfonyl or O-(p-toluenesulfonyl). Alkylation of intermediates of formula V is conveniently carried out in anhydrous dimethyl formamide (DMF) in the presence of bases such as sodium hydride or potassium t-butoxide for a period of 0.5 to 24 hours at temperatures of 20°-100° C. Substituents on the alkylating agent VI may need to be protected during alkylation. A description of such protecting groups may be found in: Protective Groups in Organic Synthesis, T. W. Greene, John Wiley and Sons, New York, 1981. ##STR22##
Alkylating agents VI are, in some cases commercially available compounds or may be prepared as described in EPO publications 253,310; 291,969; 324,377 and the references cited therein.
Compounds of formula I wherein R 3a or R 3b is a tetrazole are prepared as described in Scheme 7 by alkylation of V with a suitably substituted alkylating agent VI containing a nitrile as tetrazole precursor. Elaboration of nitrile 12 to the desired tetrazole product 13.. is carried out by treatment with trimethyltin azide in refluxing toluene. ##STR23##
A useful method to prepare a preferred alkylating agent 18 is shown in reaction Scheme 8, and in U.S. Pat. No. 5,039,814. ##STR24##
As outlined in Scheme 8, benzonitrile is treated with sodium azide and zinc chloride to give 5-phenyltetrazole 14 which is converted to the N-trityl derivative 15 by treatment with triphenylmethyl chloride and triethylamine. The zinc reagent 16 was prepared by treatment with n-butyllithium followed by zinc chloride. Coupling with 4-iodotoluene using the catalyst bis(triphenylphosphine)nickel(II) dichloride gives the biphenyl product 17 in high yield. Treatment with N-bromosuccinimide in refluxing carbon tetrachloride, in the presence of a radical initiator such as benzoyl peroxide or 2,2'-azobisisobutyronitrile (AIBN), gives bromide 18.
Intermediates of formula II where R 3a or R 3b is a carbamate, semicarbazide or urea derivative, wherein this functionality is attached to the phenyl ring by a nitrogen atom are prepared from intermediate 19, obtained by alkylation of V with a derivative of formula VI wherein R 3a or R 3b is a nitro group as shown in Scheme 9. ##STR25##
A useful method of synthesizing a preferred alkylating agent 23 is shown in reaction Scheme 10. ##STR26##
Reaction of 4-tolylboronic acid 20 with 2-bromonitrobenzene 21 in the presence of a transition metal catalyst such as tetrakis(triphenylphosphine)palladium(O) in a mixed solvent system containing aqueous sodium hydroxide, water, 2-propanol and benzene at elevated temperatures for several hours gives the coupled product 22 in good overall yield. Chromatographic purification and separation of unwanted by-products is conveniently performed on silica, eluting with common organic solvents such as hexane, ethyl acetate and methylene chloride. Conversion of 22 to the bromide derivative 23 is accomplished by the aforementioned treatment with N-bromosuccinimide.
As shown in Scheme 11, reduction of the nitro group of 19 is achieved by hydrogenation in the presence of a metal catalyst, such as palladium on carbon, in a protic solvent such as methanol or ethanol. It may be appreciated by one skilled in the art that for certain compounds where catalytic hydrogenation is incompatible with existing functionality, alternative methods of reduction are indicated, such as chemical reduction with stannous chloride under acidic conditions. It should also be noted that the protecting group G in intermediate 19 must be compatible with the experimental conditions anticipated for reduction. For example, intermediate 19 wherein G is t-butoxycarbonyl (BOC) is stable to the conditions of catalytic reduction employed in the conversion to 24. Intermediate 24. may also be further elaborated to a new intermediate 25 by reductive alkylation carried out under the conditions described above. ##STR27##
Elaboration of 25 to carbamate compound 26 is achieved by reaction with the appropriate chloroformate reagent in pyridine or in methylene chloride with triethylamine as shown in Scheme 12. ##STR28##
Transformation of amine intermediate 25 to urea derivatives is accomplished in several ways. Terminally disubstituted compounds 28 can be obtained directly by reaction of 25 with a disubstituted carbamoyl chloride 27 in an inert solvent such as methylene chloride in the presence of triethylamine or 4-dimethylaminopyridine. In addition, mono-substituted compound 30 wherein either R 5b or R 12b is hydrogen is obtained from 25 by reaction with an isocyanate 29 as shown in Scheme 13. Terminally unsubstituted urea 30, wherein R 12b is hydrogen, is also prepared from amine 25 by reaction with trimethylsilyl isocyanate (29; R 12b is (CH 3 ) 3 Si). ##STR29##
Alternatively, amine 24 is converted to an isocyanate 31 by treatment with phosgene or an equivalent reagent such as bis(trichloromethyl)carbonate (triphosgene) as indicated in Scheme 14. Subsequent reaction of 31 with primary or secondary amines in an inert solvent such as methylene chloride gives the corresponding urea derivative 28 in good yield. Isocyanate 31 is also converted to substituted semicarbazides 32 or hydroxy- or alkoxyureas 33 by reaction with substituted hydrazines or hydroxy- or alkoxylamines, respectively. ##STR30##
Intermediates of formula II where R 3a or R 3b is a carbazate or carbamate derivative where attachment to the phenyl ring is through the oxygen atom of the carbazate or carbamate linkage are prepared from acetophenone intermediate 34 as indicated in Scheme 15. ##STR31##
Oxidative rearrangement of 34 through the use of a peroxy-carboxylic acid (Baeyer-Villager reaction) such as m-chloro-perbenzoic acid gives the ester 35 which is hydrolyzed in the presence of a strong base such as sodium or lithium hydroxide to give phenol 36. Reaction of 36 with isocyanate 29 leads directly to carbamate 37. Additionally, treatment of 36 with N,N'-carbonyldiimidazole in dimethylformamide can form an activated intermediate which will react with substituted hydrazine reagents to give a carbazate product 38.
Intermediates of formula II wherein R 3a or R 3b is R 5b R 12b NCON(R 12a )CH 2 --, R 5b R 12b NCSN(R 12a )CH 2 --, R 5b R 12c NN(R 12b )CSN(R 12a )CH 2 --, R 5b R 12c NN(R 12b )-- CON(R 12a )CH 2 -- or R 13 OCON(R 12a )CH 2 -- can be prepared from the t-butyl ester intermediate 39 as described in Scheme 16. Removal of the t-butyl ester through the use of trifluoroacetic acid will give the carboxylic acid 40. It may be appreciated by one skilled in the art that the protecting group G in 39 must therefore be compatible with the strongly acidic conditions employed for ester cleavage; hence G is taken as benzyloxycarbonyl. Conversion of the carboxylic acid to the benzylamine derivative 41 can be achieved by a five-step sequence consisting of: 1) formation of a mixed anhydride with isobutyl chloroformate; 2) reduction with sodium borohydride to the benzyl alcohol; 3) formation of the mesylate with methanesulfonyl chloride; 4) formation of the azide by reaction with sodium azide, and finally, 5) reduction of the azide with tin(II) chloride. The benzylamine intermediate 41 can be further elaborated to 42 by the aforementioned reductive amination procedure. ##STR32##
Reactions of amine 42 with the appropriate reagents to form urea-linked compounds 43 and 44 and carbamate-linked compound 45 are illustrated in Scheme 17. Terminally unsubstituted urea 43, wherein R 12b is hydrogen, is also prepared from amine 42 by reaction with trimethylsilyl isocyanate (29; R 12b is (CH 3 ) 3 Si). ##STR33##
As shown in Scheme 18, hydrazide compound 46 can be prepared from intermediate 42 by a two-step procedure consisting of activation of the amine via treatment with N,N'-carbonyldiimidazole followed by treatment with the appropriately substituted hydrazine derivative R 5b R 12c NN(R 12b )H. ##STR34##
A useful preparation of the protected benzylamine intermediate 51 is shown in Scheme 19. Metallation of 4-bromobenzyl t-butyldiphenylsilylether 47 with n-butyllithium followed by treatment with triisopropyl borate gives the aryl boronic acid 48. Reaction of 48 with 2-bromo-N-(t-butoxycarbonyl)benzylamine 49 in the presence of tetrakis(triphenylphosphine)palladium(O) and sodium hydroxide in a mixed solvent system at elevated temperature gives the coupled product 50 in good yield. Desilylation and conversion to the O-methane-sulfonate 51 is achieved by treatment with tetrabutylammonium fluoride followed by methanesulfonyl chloride. Reaction of 51 with intermediates of formula V is carried out using the conditions described in Scheme 6. ##STR35##
Compounds of formula I wherein R 3a or R 3b is taken as R 5b R 12b NCO are prepared by several methods. For example, as shown in Scheme 20, compound 52 wherein R 5b and R 12b are both hydrogen is conveniently prepared by hydrolysis of the nitrile precursor 12. ##STR36##
Thus, treatment of nitrile 12 with hydrogen peroxide and a strong base, such as potassium carbonate, in a polar solvent, such as dimethylsulfoxide at temperatures of 25° C. to 150° C. results in formation of the amide derivative 52. The precursor 12 is prepared from an appropriate alkylating agent VI, where R 3a is cyano, as described in Scheme 6.
A useful method of preparing the alkylating agent 55 is outlined in Scheme 21 ##STR37##
Thus, treatment of 4-(methylphenyl)trimethyl stannane 53 with 2-bromobenzonitrile in dimethylformamide at 100° C. in the presence of bis(triphenylphosphine)palladium(II) chloride results in coupling to form the biphenyl nitrile 54 in high yield. Conversion to bromide 55 is achieved by the aforementioned treatment with N-bromosuccinimide.
Compounds of formula I wherein R 3a or R 3b is taken as R 5b R 12b NCO-- and R 5b and/or R 12b is other than hydrogen (56) are prepared from the corresponding carboxylic acid derivative 40 as shown in Scheme 22. ##STR38##
Coupling of the carboxylic acid derivative 40 with R 5b R 12b NH is conveniently carried out by the use of the previously described coupling reagents benzotriazol-1-yloxytris(dimethylamino)-phosphonium hexafluorophosphate ("BOP") or benzotriazol-1-yloxytripyrrolidinophosphonium hexafluorophosphate ("PyBOP") in methylene chloride. The requisite carboxylic acid precursors are prepared as illustrated in Scheme 23 for the biphenyl compound 40. ##STR39##
Alkylation of V with t-butyl 4'-bromomethyl-biphenyl-2-carboxylate 57 (prepared as described in EPO Publication 324,377) in the presence of sodium hydride as previously described in Scheme 6 gives the adduct 58 in high yield. Hydrolysis of the t-butyl ester to give the acid 40 is achieved by treatment with a strong acid, such as trifluoroacetic acid, in an inert solvent such as methylene chloride. It is noted that the protecting group G in this instance must be inert to strongly acidic conditions, for example G is benzyloxycarbonyl (CBz).
Conversion to intermediates of formula II is carried out by simultaneous or sequential removal of all protecting groups from intermediate VII as illustrated in Scheme 24. ##STR40##
Removal of benzyloxycarbonyl (CBz) groups can be achieved by a number of methods known in the art; for example, catalytic hydrogenation with hydrogen in the presence of a platinum or palladium catalyst in a protic solvent such as methanol. In cases where catalytic hydrogenation is contraindicated by the presence of other potentially reactive functionality, removal of benzyloxycarbonyl groups can also be achieved by treatment with a solution of hydrogen bromide in acetic acid. Removal of t-butoxycarbonyl (BOC) protecting groups is carried out by treatment of a solution in a solvent such as methylene chloride or methanol, with a strong acid, such as hydrochloric acid or trifluoroacetic acid. Conditions required to remove other protecting groups which may be present can be found in Protective Groups in Organic Synthesis T. W. Greene, John Wiley and Sons, N.Y. 1981.
As shown in Scheme 25, intermediates of formula II are elaborated to compounds of formula I by reductive alkylation with an aldehyde by the aforementioned procedures. The products, obtained as hydrochloride or trifluoroacetate salts, are conveniently purified by reverse phase high performance liquid chromatography (HPLC) or by recrystallization. ##STR41##
A route to the sub-class of compounds of formula I that can be described by formula IX is shown in Scheme 26. ##STR42##
Thus, intermediates of formula VIII are reacted with R 4 --NH 2 neat or in a polar solvent such as dimethylsulfoxide at temperatures of 50° C. to 200° C., to give compounds of formula IX. Intermediates of formula VIII may themselves be prepared by the transformations described in the preceding reaction schemes.
It should be appreciated by one skilled in the art that the order of the alkylation step (Scheme 6) and the reductive alkylation step (Scheme 25) may be reversed to facilitate the reaction or to avoid unwanted reaction products. Thus, as demonstrated in Scheme 27, intermediate V is deprotected using the aforementioned conditions, and the resulting amine intermediate X is reacted with an appropriate aldehyde under the reductive alkylation conditions described previously. The new intermediate thus obtained (XI), may then be treated with alkylating agent VI following the procedures described in Scheme 6 to give, after removal of any protecting groups, compounds of formula I. ##STR43##
It is again noted that the order of carrying out the foregoing reaction schemes is not significant and it is within the skill of one skilled in the art to vary the order of reactions to facilitate the reaction or to avoid unwanted reaction products.
The growth hormone releasing compounds of Formula I are useful in vitro as unique tools for understanding how growth hormone secretion is regulated at the pituitary level. This includes use in the evaluation of many factors thought or known to influence growth hormone secretion such as age, sex, nutritional factors, glucose, amino acids, fatty acids, as well as fasting and non-fasting states. In addition, the compounds of this invention can be used in the evaluation of how other hormones modify growth hormone releasing activity. For example, it has already been established that somatostatin inhibits growth hormone release. Other hormones that are important and in need of study as to their effect on growth hormone release include the gonadal hormones, e.g., testosterone, estradiol, and progesterone; the adrenal hormones, e.g., cortisol and other corticoids, epinephrine and norepinephrine; the pancreatic and gastrointestinal hormones, e.g., s insulin, glucagon, gastrin, secretin; the vasoactive intestinal peptides, e.g., bombesin; and the thyroid hormones, e.g., thyroxine and triiodothyronine. The compounds of Formula I can also be employed to investigate the possible negative or positive feedback effects of some of the pituitary hormones, e.g., growth hormone and endorphin peptides, on the pituitary to modify growth hormone release. Of particular scientific importance is the use of these compounds to elucidate the subcellular mechanisms mediating the release of growth hormone.
The compounds of Formula I can be administered to animals, including man, to release growth hormone in vivo. For s example, the compounds can be administered to commercially important animals such as swine, cattle, sheep and the like to accelerate and increase their rate and extent of growth, and to increase milk production in such animals. In addition, these compounds can be administered to humans in vivo as a diagnostic tool to directly determine whether the pituitary is capable of releasing growth hormone. For example, the compounds of Formula I can be administered in vivo to children. Serum samples taken before and after such administration can be assayed for growth hormone. Comparison of the amounts of growth hormone in each of these samples would be a means for directly determining the ability of the patient's pituitary to release growth hormone.
Accordingly, the present invention includes within its scope pharmaceutical compositions comprising, as an active ingredient, at least s one of the compounds of Formula I in association with a pharmaceutical carrier or diluent. Optionally, the active ingredient of the pharmaceutical compositions can comprise a growth promoting agent in addition to at least one of the compounds of Formula I or another composition which exhibits a different activity, e.g., an antibiotic or other pharmaceutically active material.
Growth promoting agents include, but are not limited to, TRH, diethylstilbesterol, theophylline, enkephalins, E series prostaglandins, compounds disclosed in U.S. Pat. No. 3,239,345, e.g., zeranol, and compounds disclosed in U.S. Pat. No. 4,036,979, e.g., sulbenox or peptides disclosed in U.S. Pat. No. 4,411,890.
A further use of the disclosed novel heterocyclic-fused lactam growth hormone secretagogues is in combination with other growth hormone secretagogues such as GHRP-6, GHRP-1 or GHRP-2 as described in U.S. Patent No. 4,411,890; and publications WO 89/07110 and WO 89/07111 and B-HT 920 or in combination with growth hormone releasing factor and its analogs or growth hormone and its analogs. A still further use of the disclosed novel heterocyclic-fused lactam growth hormone secretagogues is in combination with α 2 adrenergic agonists or β 3 adrenergic agonists in the treatment of obesity or in combination with parathyroid hormone or bisphosphonates, such as MK-217 (alendronate), in the treatment of osteoporosis. A still further use of the disclosed novel heterocyclic-fused lactam growth hormone secretagogues is in combination with IGF-1 to reverse the catabolic effects of nitrogen wasting as described by Kupfer, et al, J. Clin. Invest., 91, 391 (1993).
As is well known to those skilled in the art, the known and potential uses of growth hormone are varied and multitudinous. Thus, the administration of the compounds of this invention for purposes of stimulating the release of endogenous growth hormone can have the same effects or uses as growth hormone itself. These varied uses of growth hormone may be summarized as follows: stimulating growth hormone release in elderly humans; prevention of catabolic side effects of glucocorticoids; treatment of osteoporosis; stimulation of the immune s system; treatment of retardation; acceleration of wound healing; accelerating bone fracture repair; treatment of growth retardation, treating renal failure or insufficiency resulting in growth retardation; treatment of physiological short stature, including growth hormone deficient children; treating short stature associated with chronic illness; treatment of obesity and growth retardation associated with obesity; treating growth retardation associated with Prader-Willi syndrome and Turner's syndrome; accelerating the recovery and reducing hospitalization of burn patients; treatment of intrauterine growth retardation, skeletal dysplasia, hypercortisolism and Cushings syndrome; induction of pulsatile growth hormone release; replacement of growth hormone in stressed patients; treatment of osteochondro-dysplasias, Noonans syndrome, schizophrenia, depression, Alzheimer's disease, delayed wound healing, and psychosocial deprivation; treatment of pulmonary dysfunction and ventilator dependency; attenuation of protein catabolic response after a major operation; reducing cachexia and protein loss due to chronic illness such as cancer or AIDS. Treatment of hyperinsulinemia including nesidioblastosis; adjuvant treatment for ovulation induction; to stimulate thymic development and prevent the age-related decline of thymic function; treatment of immunosuppressed patients; improvement in muscle strength, mobility, maintenance of skin thickness, metabolic homeostasis, renal hemeostasis in the frail elderly; stimulation of osteoblasts, bone remodelling, and cartilage growth; stimulation of the immune system in companion animals and treatment of disorders of aging in companion animals; growth promotant in livestock and stimulation of wool growth in sheep.
The compounds of this invention can be administered by oral, parenteral (e.g., intramuscular, intraperitoneal, intravenous or subcutaneous injection or implant), nasal, vaginal, rectal, sublingual, or topical routes of administration and can be formulated in dosage forms appropriate for each route of administration.
Solid dosage forms for oral administration include capsules, tablets, pills, powders and granules. In such solid dosage forms, the active compound is admixed with at least one inert pharmaceutically acceptable carrier such as sucrose, lactose, or starch. Such dosage forms can also comprise, as is normal practice, additional substances other than inert diluents, e.g., lubricating agents such as magnesium stearate. In the case of capsules, tablets and pills, the dosage forms may also comprise buffering agents. Tablets and pills can additionally be prepared with enteric coatings.
Liquid dosage forms for oral administration include pharmaceutically acceptable emulsions, solutions, suspensions, syrups, the elixirs containing inert diluents commonly used in the art, such as water. Besides such inert diluents, compositions can also include adjuvants, such as wetting agents, emulsifying and suspending agents, and sweetening, flavoring and perfuming agents.
Preparations according to this invention for parenteral administration include sterile aqueous or non-aqueous solutions, suspensions, or emulsions. Examples of non-aqueous solvents or vehicles are propylene glycol, polyethylene glycol, vegetable oils, such as olive oil and corn oil, gelatin, and injectable organic esters such as ethyl oleate. Such dosage forms may also contain adjuvants such as preserving, wetting, emulsifying, and dispersing agents. They may be s sterilized by, for example, filtration through a bacteria-retaining filter, by incorporating sterilizing agents into the compositions, by irradiating the compositions, or by heating the compositions. They can also be manufactured in the form of sterile solid compositions which can be dissolved in sterile water, or some other sterile injectable medium immediately before use.
Compositions for rectal or vaginal administration are preferably suppositories which may contain, in addition to the active substance, excipients such as cocoa butter or a suppository wax.
Compositions for nasal or sublingual administration are also prepared with standard excipients well known in the art.
The dosage of active ingredient in the compositions of this invention may be varied; however, it is necessary that the amount of the active ingredient be such that a suitable dosage form is obtained. The selected dosage depends upon the desired therapeutic effect, on the route of administration, and on the duration of the treatment. Generally, dosage levels of between 0.0001 to 100 mg/Kg of body weight daily are administered to patients and animals, e.g., mammals, to obtain effective release of growth hormone.
The following examples are provided for the purpose of further illustration only and are not intended to be limitations on the disclosed invention.
EXAMPLE 1
3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]-butanamide
Step A: 8-Acetoxy-5,6,7,8-tetrahydroquinoline
To 9.7 g of 5,6,7,8-tetrahydro quinoline in 36 mL of acetic acid was added 7.2 mL of 30% hydrogen peroxide and the mixture was warmed to 70° C. for 5 h. Another 7.2 mL of hydrogen peroxide was added and the mixture was stirred an additional 12.5 h at 70° C. The solution was then concentrated in vacuo. Solid potassium carbonate (20 g) was then added followed by 20 mL of chloroform and the thick paste was stirred at 20° C. for 4 h. The paste was then extracted 4× with 50 mL portions of boiling chloroform by filtration. The combined filtrate was concentrated in vacuo to yield 18 g of yellow oil. Acetic anhydride (50 mL) was then added to this oil and the mixture was heated at 90° C. under argon for 5 h. The excess acetic anhydride was then distilled off in vacuo and the residual liquid was distilled via Kugelrohr at 0.5 torr and 150° C. to afford 12.3 g of product characterized by its NMR.
Step B: 8-Hydroxy-5,6,7,8-tetrahydroquinoline
To 10 g of 8-acetoxy-5,6,7,8-tetrahydroquinoline in 30 mL of methanol was added 30 mL of 30% sodium hydroxide in water. The mixture was heated to reflux for 2 min and the methanol was removed in vacuo. The residual organic product was extracted with chloroform. The chloroform extracts were dried over sodium sulfate and evaporation of the solvent gave 8 g of product as an oil, characterized by its NMR.
Step C: 8-Oxo-5,6,7,8-tetrahydroquinoline
To a solution of 7 g of 8-hydroxy-5,6,7,8-tetrahydroquinoline in 150 mL of isopropyl acetate was added 14 mL of dimethyl sulfoxide and 33 mL of triethylamine. This mixture was stirred at -10° C. and 14 mL of phenyldichlorophosphate was added dropwise over 9 min. After an additional 15 min at 0° C. and 15 min at 20° C., the mixture was quenched with 50 mL of a saturated aqueous sodium bicarbonate solution. The product was extracted with ethyl acetate and flash chromatographic purification on silica gel afforded 2.22 g of ketone characterized by its NMR.
Step D: 8-Oximino-5,6,7,8-tetrahydroquinoline
A solution of 2.22 g of 8-oxo-5,6,7,8-tetrahydroquinoline, 2.1 g of hydroxylamine hydrochloride, and 4.1 g of sodium acetate in 15 mL of 3:1 ethanol-water was heated at 70° C. for 1 h. The reaction mixture was then diluted with water and extracted with dichloromethane. Evaporation of the extracts gave 1.95 g of product which was pure enough by NMR to be used in the next step.
Step E: 5,6,7,8-Tetrahydroquinoline-8-tosyloxime
To 1.95 g of 8-oximino-5,6,7,8-tetrahydroquinoline in 15 mL of pyridine was added 2.9 g of tosyl chloride. After 2 h the pyridine was removed in vacuo and the residual solid was taken up in 50 mL of chloroform and flash chromatographed on silica gel using ethyl acetate as eluent. 3.3 g of purified product was obtained characterized by its NMR and mass spectra.
Step F: 5,6,7,9-Tetrahydro-8H-pyrido[2,3-b]azepin-8-one
To 3.3 g of tosyl oxime (Step E) and 20 g of potassium acetate was added 70 mL of ethanol and 80 mL of water. The mixture was heated at 100° C. for 12 h, cooled to room temperature and diluted with water. The pH was adjusted to 10 with 10% sodium hydroxide and the mixture was extracted with dichloromethane. The combined extracts were evaporated to yield 2.5 g of product and flash chromatographic purification gave 1.35 g of the product characterized by its NMR and mass spectra.
Step G: 5,6,7,9-Tetrahydro-7-iodo-8H-pyrido[2,3-b]azepin-8-one
To a solution of 300 mg of 5,6,7,9-tetrahydro-8H-pyrido[2,3-b]azepin-8-one in 3 mL of dichloromethane at 0° C. was added 0.84 mL of N,N,N',N'-tetramethylethylenediamine (TMEDA) and 0.78 mL of trimethylsilyl iodide. After 30 min, 720 mg of solid iodine was added in one portion. The reaction mixture was stirred at 0° C an additional 40 min before dichloromethane and excess aqueous sodium sulfite was added to reduce the excess iodine. The mixture was extracted with dichloromethane and the extracts were evaporated to yield 550 mg of the crude product. Flash chromatographic separation on silica gel with ethyl acetate gave 333 mg of purified product s characterized by its NMR and mass spectra.
Step H: 7-Azido-5,6,7,9-tetrahydro-8H-pyrido[2,3-b]azepin-8-one
To 333 mg of the intermediate obtained in Step G in 6 mL of dimethylformamide (DMF) was added 600 mg of sodium azide. The mixture was stirred at 20° C. 20 h before addition of water and extraction with dichloromethane. The extracts were combined and dried over sodium sulfate. Evaporation of the solvent gave 223 mg of the product characterized by its NMR and mass spectra.
Step I: 7-Amino-5,6,7,9-tetrahydro-8H-pyrido[2,3-b]azepin-8-one
To 230 mg of the intermediate obtained in Step H in 10 mL of tetrahydrofuran was added 280 mg of triphenylphosphine. The mixture was stirred at 20° C. 18 h before 7 drops of water was added. The solution was then heated at 65° C. for 1 h. The solvent was removed in vacuo and the residue was flash chromatographed on silica gel using 100:20:5:3 (v:v) chloroform:methanol:acetic acid:water to afford 209 mg of pure amine characterized by its NMR and mass spectra.
Step J: 4,4-Dimethylazetidin-2-one
A 3-neck 3 L round bottom flask equipped with a magnetic stirrer, thermometer, cold finger condenser and nitrogen bubbler was charged with 1 L of ether. The flask was cooled to -65° C. and into it was condensed 500-600 mL of isobutylene. The cold finger condenser was replaced with a dropping funnel and 200 mL (325 g, 2.30 mol) of chlorosulfonyl isocyanate was added dropwise over 1.5 hours. The mixture was maintained at -65° C. for 1.5 hours then the dry ice/acetone cooling bath replaced with methanol/ice and the internal temperature slowly increased to -5° C. at which time the reaction initiated and the internal temperature rose to 15° C. with evolution of gas. The internal temperature remained at 15° C. for several minutes then dropped back down to -5° C. and the mixture stirred at -5° C. for 1 hour. The methanol/ice bath was removed and the reaction mixture warmed to room temperature and stirred overnight.
The reaction mixture was transferred to a 3-neck 12 L round bottom flask fitted with a mechanical stirrer and diluted with 2 L of ether. The well stirred reaction mixture was treated with 2 L of saturated aqueous sodium sulfite. After 1 hour, an additional 1 L of saturated aqueous sodium sulfite was added followed by sufficient sodium bicarbonate to adjust the pH to approximately 7. The mixture was stirred another 30 minutes then the layers allowed to separate. The ether layer was removed and the aqueous layer reextracted with 2×1 L of ether. The combined ether extracts were washed once with 500 mL of saturated aqueous sodium bicarbonate and once with 500 mL of saturated aqueous sodium chloride. The ether layer was removed, dried over magnesium sulfate, filtered and concentrated under vacuum to give 33 g of a pale yellow oil. The aqueous layer was made basic by the addition of solid sodium bicarbonate and extracted with 3×1 L of ether. The combined ether extracts were washed and dried as described above, then combined with the original 33 g of pale yellow oil and concentrated under vacuum to give 67.7 g of product. Further extraction of the aqueous layer with 4×1 L of methylene chloride and washing and drying as before gave an additional 74.1 g of product. Still further extraction of the aqueous layer with 4×1 L of methylene chloride gave an additional 21.9 g of product. The combined product (163.7 g, 1.65 mol, 72%) was used in Step H without purification. 1 H NMR (200 MHz, CDCl 3 ): δ 1.45 (s, 6H), 2.75 (d, 3 Hz, 2H), 5.9 (br s, 1H).
Step K: N-(t-Butoxycarbonyl)-4,4-dimethylazetidin-2-one
A 5 L, 3-neck round bottom flask equipped with a magnetic stirrer, thermometer, nitrogen bubbler and addition funnel was charged with 88.2 g (0.89 mol) of 4,4-dimethylazetidin-2-one (Step J), 800 mL of methylene chloride, 150 mL of triethylamine (1.08 mol) and 10.9 g (0.089 mol) of 4-dimethylaminopyridine. To the stirred solution, at room temperature was added dropwise over 15 minutes a solution of 235 g (1.077 mol) of di-t-butyl-dicarbonate in 300 mL of methylene chloride. The reaction mixture was stirred at room temperature overnight, then diluted with 1 L of methylene chloride and washed with 500 mL of saturated aqueous ammonium chloride, 500 mL of water, and 500 mL of saturated aqueous sodium chloride. The organic layer was separated, dried over magnesium sulfate, filtered and concentrated under vacuum to afford 180.3 g of crude product as an orange solid. The material was used directly in Step I without purification. 1 H NMR (200 MHz, CDCl 3 ): δ 1.50 (s, 9H), 1.54 (s, 6H), 2.77 (s, 2H).
Step L: 3-t-Butoxycarbonylamino-3-methylbutanoic acid
A 3 L, 3-neck round bottom flask equipped with a magnetic stirrer, thermometer, nitrogen bubbler and addition funnel was charged with 180.3 g (0.89 mol) of N-(t-butoxycarbonyl)-4,4-dimethylazetidin-2-one dissolved in 1 L of tetrahydrofuran. The solution was cooled to 0°-5° C. and treated dropwise with 890 mL of 1.0M aqueous lithium hydroxide over 30 minutes. The reaction mixture was stirred at 0°-5° C. for 2 hours, then diluted with 1 L of ether and 1 L of water. The layers were allowed to separate and the aqueous layer was reextracted with an additional 1 L of ether. The aqueous layer was acidified by the addition of 1 L of saturated aqueous sodium bisulfate, then extracted with 1×1 L and 2×500 mL of ether. The combined organic layer and ether extracts were washed with 500 mL of saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated under vacuum to give 173 g of a yellow oil that solidified upon standing. The material was slurried with warm hexane, then filtered and dried under high vacuum to afford 168.5 g (0.775 mol, 87%) of product as a white solid. 1 H NMR (200 MHz, CDCl 3 ): δ 1.39 (s, 6H), 1.44 (s, 9H), 2.72 (s, 2H). FAB-MS: calculated for C 10 H 19 NO 4 217; found 218 (M+H,54%).
Step M: [1,1-Dimethyl-3-oxo-3-[[6,7,8,9-tetrahydro-8-oxo-5H-pyrido[2,3-b]azepin-7-yl]amino]propyl]carbamic acid, 1,1-dimethylethyl ester
To 68 mg of 3-t-butoxycarbonylamino-3-methylbutanoic acid in 1 mL of DMF was added 60 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC). The mixture was stirred at 20° C. for 2 h before 50 mg of 7-amino-5,6,7,9-tetrahydro-8H-pyrido[2,3-b]azepin-8-one was added and the reaction was stirred an additional 18 h. The DMF was removed in vacuo and the residue was purified by preparative silica gel layer chromatography to yield 52 mg of the product characterized by its NMR and mass spectra.
Step N: 3-Amino-3-methyl-N-[6,7,8,9-tetrahydro-8-oxo-9-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-5H-pyrido[2,3-b]azepin-7(R)-yl]butanamide
To 31 mg of the intermediate obtained in Step M in 2 mL of DMF was added 20 mg of 60% sodium hydride/oil dispersion. After 2 min, 60 mg of N-triphenylmethyl-5-[2-(4'-bromomethylbiphen-4-yl)] tetrazole was added. After an additional 5 min, ice and saturated aqueous ammonium chloride solution was added to stop the reaction. The products were extracted with ethyl acetate and purified by PTLC on silica gel to afford 41 mg of the alkylated product. This was treated with 1 mL of neat trifluoroacetic acid for 2 min, then 3 mL of methanol and 3 drops of concentrated hydrochloric acid for 30 min. The solvent was removed in vacuo and PLC of the residual material gave 28 mg of the title compound characterized by its NMR and mass spectra.
EXAMPLE 2
3-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R)-yl]-3-methylbutanamide
Step A: 4-Oximino-4,5,6,7-tetrahydrothianaphthene
A solution of 10.9 g of sodium acetate, 9.33 g of hydroxylamine hydrochloride and 10.1 g of 4-keto-4,5,6,7-tetrahydrothianaphthene in 22 mL of water and 66 mL of ethanol was heated to 50° C. for 2 hr, poured into water, extracted with ethyl acetate, and the solvent removed in vacuo to give 11.63 g of a crude mixture of E and Z oximes. Flash chromatography yielded 11.13 g of E-oxime and 188 mg of Z-oxime which were characterized by NMR and Mass spectroscopy.
Step B: 4,6,7,8-Tetrahydro-4H-thieno[3,2-b]azepin-5-one
A solution of 2.28 g of the E-oxime (Step A) and 2.6 g of tosyl chloride in 40 mL of pyridine was left to stir for 14 hr. The excess pyridine was removed in vacuo leaving a brown residue which gave 3.86 g of a mixture of tosyl oxime and unreacted oxime after flash chromatography. A suspension of 3.36 g of the mixture and 22.5 g of potassium acetate in 70 mL of ethanol and 130 mL of water was heated to reflux for 14 hr, poured over ice, extracted with ethyl acetate and the solvents removed in vacuo. Flash chromatography gave 750 mg of clean lactam which was characterized by NMR and Mass spectroscopy.
Step C: 4,6,7,8-Tetrahydro-6-iodo-4H-thieno[3,2-b]azepin-5-one
A solution of 1.0 g of the lactam (Step B), 1.85 mL of TMEDA and 1.75 mL of TMSI in 10 mL of methylene chloride was stirred for 30 min at 0° C. After the addition of 2.3 g of iodine, the reaction mixture was left to stir for 2 hr at 0° C., warmed to room temperature, quenched with sodium sulfite solution and extracted with ethyl acetate. The insoluble material was filtered and dried in vacuo to give 476 mg of clean alpha-iodo lactam which was characterized by NMR and Mass spectroscopy. The solvents were removed from the extracts in vacuo to give 630 mg of alpha-iodo lactam which was contaminated with some starting lactam and characterized by NMR and Mass spectroscopy.
Step D: 6-Azido-4,6,7,8-tetrahydro-4H-thieno[3,2-b]azepin-5-one
A solution of 476 mg of the alpha-iodo lactam (Step C) and 530 mg of sodium azide in 5 mL of dimethyl formamide was heated at 70° C. for 2 hr, quenched with water, extracted with ethyl acetate and the solvents removed in vacuo to give 355 mg of clean alpha-azido lactam which was characterized by NMR and Mass spectroscopy.
Step E: 6-Amino-4,6,7,8-tetrahydro-4H-thieno[3,2-b]azepin-5-one
A solution of 370 mg of the alpha-azido lactam (Step D) and 470 mg of triphenylphosphine in 8 mL of distilled tetrahydrofuran was stirred for 40 hr at which point a precipitate formed. After adding 1 mL of water, the reaction mixture was heated to 70° C. for 2 hr, quenched with 10% sodium hydroxide solution, extracted with ethyl acetate and the solvents removed in vacuo. Flash chromatography, using dilute acetic acid in the eluent, gave 556 mg of the acetic acid salt of the alpha-amino lactam which was characterized by NMR and Mass Spectroscopy.
Step F: [1,1-Dimethyl-3-oxo-3-[(5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-6-yl)amino]propyl]carbamic acid 1,1-dimethylethyl ester
A solution of 190 mg of the acetic acid salt of the alpha-amine lactam from Step E, 300 mg of 3-t-butoxycarbonylamino-3-methylbutanoic acid and 500 mg of bis(2-oxo-3-oxazolidinyl)phosphinic chloride in 5 mL of methylene chloride and 300 μl distilled trimethyl-amine was stirred for 18 hr, quenched with water, extracted with ethyl acetate and the solvents removed in vacuo. Flash chromatography gave 142 mg of [1,1-dimethyl-3-oxo-3-[(5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-6-yl)amino]propyl]carbamic acid 1,1-dimethylethyl ester which was characterized by NMR and Mass spectroscopy.
Step G: 3-Amino-N-[5,6,7,8-tetrahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]-4H-thieno[3,2-b]azepin-6(R )-yl]-3-methylbutanamide
To a solution of 22 mg (0.058 mmol) of [1,1-dimethyl-3-oxo-3-[(5,6,7,8-tetrahydro-5-oxo-4H-thieno[3,2-b]azepin-6-yl)amino]-propyl]carbamic acid 1,1-dimethylethyl ester (Step F) in 1 mL of DMF was added 20 mg of sodium hydride (60% oil dispersion). After 5 min at 20° C., 34 mg of N-triphenylmethyl-5-[2-(4'-bromomethylbiphen-4-yl)] tetrazole was added. After another 15 min, the reaction was quenched with water and extracted with ethyl acetate. The extracts were s combined, dried (sodium sulfate), filtered, and evaporated to yield 67 mg of crude products. Preparative layer chromatographic (PLC) purification on silica gel gave 25 mg of protected product. This was dissolved in 0.25 mL of neat trifluoroacetic acid for 2 min then 1 mL of methanol and 2 drops of conc. HCl was added. The mixture was stirred 2 h at 20° C. The solvent and acids were removed in vacuo, and PLC of the crude gave 10 mg of the title compound characterized by its mass and NMR spectra.
EXAMPLE 3
N-[1,4,5,6,7,8-hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl ]-3-amino-3-methylbutanamide
Step A: 4-Oximino-4,5,6,7-tetrahydroindole
A solution of 6.08 g of sodium acetate, 5.15 g of hydroxylamine hydrochloride, and 5.25 g of 4-keto-4,5,6,7-tetrahydro indole in 12 mL of water and 36 mL of ethanol was heated at 50° C. for 3 hr, quenched in water, extracted with ethyl acetate and dried over magnesium sulfate. The solvents were removed in vacuo to give a mixture of oxime isomers which was characterized by NMR and Mass spectroscopy.
Step B: E-4-(O-4-methylphenylsulfonyl)oximino-4,5,6,7-tetrahydroindole
A solution of 600 mg of the oxime mixture from Step A and 770 mg of tosyl chloride in 13 mL of pyridine was stirred at room temperature for 20 hr and then the solvents removed in vacuo. Flash chromatography yielded 267 mg of the E-tosyloxime which was characterized by NMR and Mass spectroscopy.
Step C: 4,6,7,8-Tetrahydro-pyrrolo[3,2-b]azepin-5(1H)-one
A solution of 2.3 g of the E-tosyloxime (Step B) and 22 g of potassium acetate in 80 mL of ethanol and 160 mL of water was heated to reflux for 3 hr, poured into ice water, extracted with ethyl acetate and chloroform, dried over sodium sulfate, and the solvents removed in vacuo. Flash chromatography yielded 1.06 g of lactam which was characterized by NMR and Mass spectroscopy.
Step D: 4,6,7,8-Tetrahydro-6-iodo-pyrrolo[3,2-b]azepin-5(1H)-one
To a solution of 1.06 g of the lactam obtained in Step C in 10 mL of methylene chloride and 3.2 mL of TMEDA cooled to 0° C. was added 4.0 mL of trimethylsilyl iodide and stirred for 15 min. After the addition of 2.7 g of iodide, the reaction mixture was stirred for 20 hr while warming to room temperature, quenched with sodium sulfite solution, extracted with ethyl acetate and chloroform, dried over sodium sulfate, and the solvents removed in vacuo to give 1.93 g of material.
Step E: 6-Azido-4,6,7,8-tetrahydro-pyrrolo[3,2-b]azepin-5(1H)-one
A solution of 1.93 g of the alpha-iodo lactam crude material (Step D) and 2.3 g of sodium azide in 20 mL of dimethyl formamide was heated to 60° C. for 3 hr, quenched with water, extracted with ethyl acetate and chloroform, dried over sodium sulfate, and the solvents removed in vacuo. Flash chromatography gave 426 mg of alpha-azido lactam which was characterized by NMR and Mass spectroscopy.
Step F: 6-Amino-4,6,7,8-tetrahydro-pyrrolo[3,2-b]azepin-5(1H)-one
A solution of 426 mg of alpha-azido lactam (Step E) and 586 mg of triphenylphosphine in 15 mL of THF was stirred at room temperature for 40 hr at which point a precipitate formed. After the addition of 1 mL of water, the reaction mixture was heated at 60° C. for 3 hr, cooled down, and the solvents removed in vacuo. Flash chromatrography using dilute acetic acid in the eluent gave 444 mg of the acetic acid salt of the alpha-amino lactam which was characterized by NMR and Mass spectroscopy.
Step G: [1,1-Dimethyl-3-oxo-3-[(5,6,7,8-tetrahydro-5-oxo-4H-pyrrolo[3,2-b]azepin-6-yl)amino]propyl]carbamic acid 1,1-dimethylethyl ester
A solution of 100 mg of 3-t-butoxycarbonylamino-3-methylbutanoic acid in 5 mL of DME and 65 μl of N-methylmorpholine was cooled to -15° C. After the addition of 60 μl of isobutylchloroformate, the reaction mixture was left to stir for 3 hr at which point a precipitate formed. The precipitate was filtered off, washed with DME, and the mother liquors concentrated to give liquid product. A solution of the liquid product and 33 mg of the acetic acid salt of the alpha-amino lactam (Step F) in 2 mL of methylene chloride and 200 μl of triethylamine was stirred for 48 hr and the solvents removed in vacuo. Flash chromatography gave 30 mg of the alpha-amide lactam which was characterized by NMR and Mass spectroscopy.
Step H: N-[1,4,5,6,7,8-hexahydro-5-oxo-4-[[2'-(1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl]pyrrolo[3,2-b]azepin-6(R)-yl]-3-amino-3-methylbutanamide
To a solution of 30 mg of amide-lactam (Step G) in 1.5 mL of DMF was added 10 mg of sodium hydride (60% oil dispersion). After 5 min at 20° C, 47 mg of N-triphenylmethyl-5-[2-(4'-bromomethylbiphen-4-yl)]-tetrazole was added. The mixture was stirred 15 min and water was added to quench the reaction. The mixture was extracted with ethyl acetate and purified by PLC and the protecting groups were removed as described in Example 2, Step G to afford 8 mg of product characterized by its NMR and mass spectra. | There are disclosed certain novel compounds identified as heterocyclic-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible meat products more efficient, and in humans, to increase the stature of those afflicted with a lack of a normal secretion of natural growth hormone. Growth promoting compositions containing such heterocyclic-fused lactams as the active ingredient thereof are also disclosed. | 2 |
FIELD OF THE INVENTION
The present invention relates to memories, and, more particularly, to a method for testing a dynamic memory.
BACKGROUND OF THE INVENTION
The principle of dynamic storage relies on the holding, for a very short period of about one millisecond, of the charge of a capacitance associated with a MOS transistor. Thus, a dynamic memory is characterized especially by its period of retention of a piece of information. This sets the minimum data refreshing frequency needed to preserve the information in the memory. The refreshing of the data is obtained by setting up a read type access and then a write type access on each of the cells of the memory.
The retention time of a dynamic memory depends on the technology used, variations inherent in the manufacturing process, the structure of the memory cell, the supply and bias voltages used, and the memory. The retention time is tested on each of the cells of the dynamic memories at the end of manufacture. The testing of this retention time actually comprises two steps.
A first step known as a characterizing step includes making very precise measurements of this retention time on one or more cells of a batch of dynamic memory circuits. A value is obtained characterizing the memory and its method of manufacture for a batch or series of batches. The measurement of the retention time is done in practice by successive approximations, in specifying the real retention time by increasingly approaching values. In one practical example, a "1" is written in a cell of the dynamic memory, then reread at the end of one millisecond for example. If a "0" is read, it means that the information has been lost. Since the data has been lost, the "1" has to be rewritten and then a read access has to be done again, but at the end of a shorter period of time, such as, 500 microseconds for example. If a "1" is read, it means that the retention time in the example ranges from 500 microseconds to 1 millisecond.
Since a "1" has been read, the read access has refreshed the data element. It is possible to carry out a new read access after a slightly longer period of time, such as, 750 microseconds, for example. This procedure is continued until the value of the retention time has been specified with sufficient precision.
Once one or more manufactured batches of DRAMs have been characterized, all the memories of these lots are tested. This operation is designed to ascertain that all the cells of all these memories have a retention time included in the interval that has been measured for characterization. This is the testing step.
This testing step is very lengthy. Indeed, the retention time has to be guaranteed for each of the cells of each of the memories. Furthermore, it is not possible to limit the operations to only one reading per cell. Ideally it is necessary, in each memory, to measure these values for all the positions of a single `1` among the zeros and a single zero among the `1`'s. In practice, only 5 or 6 readings are done per cell with tests known as zero-field tests, one-field tests, and checkerboard pattern tests.
Even if it is possible to carry out word access operation, the retention times with current technologies being about 1 millisecond, it is already necessary to take up nearly 25 seconds for testing just one 1-megabit memory. The testing of the dynamic memories is therefore very lengthy which means that it is very costly.
SUMMARY OF THE INVENTION
In view of the foregoing background, it is therefore an object of the invention to provide a method for the testing of dynamic memories that enables a major reduction in testing times without accepting any loss in the reliability of the measurements made.
The invention uses the principle of retention of dynamic memories, namely capacitive holding. More specifically, the approach of the invention is based on the leakages that cause the loss of information in a dynamic memory cell. Indeed, the measurement of the retention time is nothing other than the measurement of the influence of the losses of current in the cell. These current losses are due partly to the bit line voltages, the bias voltages of the transistors used, and especially the bias voltage of the bulks when the transistors of the cells are MOS transistors made in wells (P type transistors using N well technology, N type transistors using triple well technology).
The principle of the invention is as follows: by acting in a controlled way on at least one of the factors that are known to increase the current leakages, a controlled and known reduction will be obtained in the retention time of the dynamic memory cell. A reduced retention time is obtained as opposed to the true retention time which is the retention time measured under the normal operational conditions of the memory.
In the testing method according to the invention, a reduced retention time is measured and it is ascertained that this time corresponds to the true retention time expected. Through this procedure, the testing time is very substantially reduced without any loss of quality (namely reliability).
In practice, to enable a comparison of the retention time of the measurement with the true retention time expected for the cell, it is enough, in the phase of characterizing the dynamic memory, to make a first characterization which will give the true retention time measured under normal conditions of operation, and a second characterization to measure the corresponding reduced value under conditions of modified operation which make it possible to increase the leakages in a known and controlled way. There is thus obtained the value (or interval of values) characteristic of the true retention time of the dynamic memory.
The method according to the invention gives rise to an additional step of characterization but, in return, a great deal of time is gained in testing memory cells. In the practical example of a true retention time of 1 millisecond, it is possible to obtain a reduced retention time of about a hundred microseconds.
Thus, the invention relates to a method for testing a dynamic memory comprising a step for the verification of the retention time of each of the cells of the memory. The verification step includes, for each cell, an operation for writing an information element in the cell and an operation for reading the cell at the end of a specified time. This verification step comprises a phase for the modification of operation between the write operation and the read operation to increase the leakage currents in the cell. The specified time corresponds to a reduced retention time in the cell.
Preferably, the phase for modifying the operation includes the modification of at least one bias voltage of one or more transistors of the memory cell. It may be the bit line voltage of the cell or the bias voltage for the bulk of one of more transistors of the cell. It may also be the gate control voltage of one or more access transistors of the cell. The choice of either modification or of a combination of these modifications depends on the structure of the cell and the reduced retention time to be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the invention shall be described in detail in the following description given by way of an indication that in no way restricts the scope of the invention and is made with reference to FIGS. 1 and 2, each representing an exemplary dynamic memory cell of the prior art.
FIG. 3 is a flow chart illustrating the method for testing a dynamic memory in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows an exemplary cell of a dynamic memory of the prior art. It is a memory known as the type with a MOS transistor with access by information bit. This structure has been chosen solely to illustrate the invention which can be applied to any type of dynamic memory cell structure.
The cell 1 thus comprises an access transistor N1 and an information storage capacitor which, in the example, is the capacitance of a capacitor CMEM. This capacitor is connected between the source of the access transistor and a bias line of a potential Vplot of about Vdd/2.
The access transistor N1 is controlled at its gate by a row selection line of the memory Rowi. The transistor N1 has its drain connected to a bit line referenced BL. This bit line is connected to an input/output amplifier circuit by associated bit line selection transistors (not shown).
The principle of storage and reading is well known. It is based on the voltage stored by the capacitor CMEM. Briefly, in write mode, if it is sought to write a 0, the 0 level (GND) is applied to the bit line BL. The row of the cell to be written is selected by applying an appropriate potential to the row selection line Rowi to turn the access transistor N1 on. The capacitor CMEM then stores a zero level.
If this cell is read before the information is lost (when the retention time is not exceeded), the bit line BL is precharged to Vdd/2. If the corresponding row selection line Rowi is activated to make the access transistor N1 conductive, the potential of the bit line will be modified according to the charge stored by the capacitor CMEM. The resulting potential is compared with the reference level Vdd/2.
The information is stored in the cell so long as the capacitor is not discharged. This capacitor gets discharged through the access transistor owing to the current leakages inherent in the structure. It is these leaks that determine the retention time of the dynamic memory cell.
In the invention, the biasing conditions of the access transistor of the cell are acted upon to increase the current leakages. Then, a reduced retention time is obtained. In testing, it is ascertained that the cell has a reduced retention time corresponding to the true retention time of the dynamic memory.
To increase the current leakages, it is possible to act on at least one of the potentials applied to the transistor of the cell. In the example shown, the access transistor N1 is an N type transistor made in a P type well. The bulk of an N type transistor is usually biased at a potential Vbulk connected to the ground GnD. According to the principle of the invention, between the write operation and the read operation of the verification step, it is possible to temporarily modify this bias potential Vbulk of the bulk and lower this potential by a transistor threshold voltage. In the example, there will then be Vbulk=Gnd-Vtn. In doing so, the leakage of current in the access transistor N1 and the capacitor CMEM is increased.
It is also possible to act on the bit line voltage. Indeed, in normal operation, it is common practice after a write operation to carry the bit line to a potential of some hundreds of millivolts (200 millivolts for example) to reduce the leakages due to the access transistor N1. In the invention, for the testing of the retention time, the bit line is taken to zero volts so as to increase the leakages with respect to a normal mode of operation. By temporarily biasing the bit line to zero volts in the verification step, between the write operation and the read operation, instead of 200 millivolts applied in normal operation mode, it is possible to obtain a reduced retention time of 100 microseconds instead of one millisecond obtained in normal operating mode. It is also possible to act on the gate voltage of the access transistor.
The invention has been explained with reference to FIG. 1. It can be applied more generally to all the DRAM cell structures. In particular, it can also be applied to cells that use the MOS transistor gate parasitic capacitance as a storage capacitor and have several access transistors.
FIG. 2 thus shows an exemplary structure of a DRAM cell with four MOS transistors per bit: two access transistors N1 and N2 and two storage transistors N3 and N4. These four transistors are all herein of an N type, made in P type wells. Ideally, there is one well for the access transistors and one well for the storage transistors but, in general, to gain space, there is only one well in which the four transistors are made. In the example, they are made in the same well and their bulk is at a same potential Vbulk equal to the ground potential.
The two access transistors N1 and N2 are controlled at their gate by the same row selection line of the memory Rowi. The transistor N1 has its drain connected to a bit line BLA while the transistor N2 has its drain connected to the complementary bit line BLB.
The storage transistors N3 and N4 have their source connected to the ground Gnd. Their drain is connected to the source of the associated access transistor: N1 for the transistor N3 and N2 for the transistor N4. Finally, the gate of one storage transistor is connected to the drain of the other storage transistor (and therefore to the source of the access transistor associated with this other storage transistor). This dynamic memory cell structure is also known as the quasi-static RAM memory cell QSRAM for it is derived from the structure of a static RAM.
In this case, the principle of the invention includes modifying at least one of the bias potentials of the cell, preferably the bit line potential BLA or BLB and/or the bulk potential Vbulk of the storage transistors and/or the access transistors. It is possible to modify the bulk potential of only one of the groups of transistors, preferably the storage transistors, if these two groups are made in two different wells.
In any case, what has to be done is to temporarily modify at least one of the bias voltages applied to the cell, between the write operation and the read operation, to increase the current leaks, but without damaging the cell (without causing stress to it). The choice of one or more bias voltages to be modified depends on the structure of the dynamic memory cell in question, of which FIGS. 1 and 2 represent only some examples of the prior art. The method of the invention can be applied as well to P type transistor cells, and to transistor cells without wells. It is not limited to the structures described in the present application.
According to the structure of the cell and the reduced retention time to be achieved, action will be taken on only one of the bias voltages of the transistors of the cell or on several voltages at a time. The method of the present invention can be used to obtain a reduced retention time that is far smaller than the true retention time corresponding to the normal conditions of operation (or use). For example, if this reduced retention time is equal to 100 microseconds for a true retention time of 1 millisecond, and when it is known that the test has to be performed on all the cells of all the memories at the end of manufacture, it is possible to realize the considerable gain in time obtained by the testing method according to the invention.
Furthermore, the verification tests thus include verifying the behavior under temperature. Now the temperature tests are costly in terms of equipment (for heating) and time. By using the reduced retention time to perform these temperature tests, precious time is gained. This entails the assumption that the steps for characterizing the true retention time and the reduced retention time comprise a phase of characterization in temperature.
In practice, the step of verifying a dynamic memory cell according to the invention will comprise an operation for writing an information element in the cell (under normal biasing conditions), an operation for temporarily modifying a potential of at least one of the transistors of the cell to increase the current leaks in this cell, and then a read operation (under normal biasing conditions) at the end of a specified time corresponding to the expected reduced retention time.
This expected reduced retention time is determined in an additional characterizing step prior to the verification step in which this duration is measured under specified modified access conditions. A flow chart illustrating the method for testing a dynamic memory in accordance with the present invention will now be described with reference to FIG. 3. From the start at Block 20, the method for testing a dynamic memory comprises the step of verifying a retention time of each of the memory cells of the dynamic memory, wherein each memory cell comprises one or more transistors. The verifying step includes the steps of writing an information element to the memory cell at Block 22, and temporarily increasing leakage currents in at least one of the transistors to cause a specified time of the memory cell to correspond to a reduced retention time at Block 24. The method further includes the step of reading the information from the memory cell at the end of the reduced retention time at Block 26. The method of the present invention obtains a reduced retention time that is smaller than the true retention time corresponding to the normal conditions of operation. A significant amount of time is thus gained in testing a dynamic memory by temporarily reducing the retention time of each memory cell. It is thus possible to establish the correspondence between the tested reduced retention time and the true retention time that is characteristic of the memory and guaranteed for users of these memories, in a range of temperature. | A method for the testing of the retention time of a piece of information in a dynamic memory cell includes increasing the leakages of current in this cell to accelerate the loss of information. Under these testing conditions, a reduced retention time is controlled to approach the true retention time obtained under conditions of normal reading. This method makes it possible to reduce the time taken to test the retention time of the dynamic memories while at the same time being very reliable. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to the blocking of lens blanks, and more particularly to the precision attachment of blocks to lens blanks for their conversion into finished lenses.
In the finishing of lens blanks for eye glasses, it is necessary to translate a prescription provided by an oculist or optometrist into lenses which are suitable and appropriate for mounting into a frame that meets the physical requirements of the user.
The prescription specifies the various powers of the users lenses, and their optical axes, along with the users pupilary distance (P.D.) and the measurements of the frame that has been selected. A pupilary distance is the measure of the separation between the pupils of the user. It is apparent that the pupilary distance varies from one user to another, and that it must be coordinated with the measurements of the selected frame.
In translating a lens prescription into a finished product, an optical technician begins by selecting a lens blank in accordance with the user's optical correction. In the general case where the lens has a toric, i.e. toroidal, outer surface and a spherical inner surface, the lens has an optical center and prescribed optical axis in accordance with the required cylindrication of the lens. In the special case where the lens has only spherical surfaces, it has only an optical center.
The optical center and axis of a lens blank are located using an instrument known as a lensometer. The blank is positioned in the viewer of the lensometer and a reticle is focused on it. A typical lensometer reticle has a triplet of parallel lines and an orthogonal bisecting line. When the bisecting line is focused on the lens blank, its spherical power is indicated by the focusing control. The lens blank is then centered horizontally.
In the next step, the triplet is focused on the lens and the focusing control provides an indication of the cylindrical power (which is given by the difference between the indicated value and the spherical reading). The lens blank is then centered vertically.
In the final step, the reticle is rotated until the bisector appears as a solid, unfragmented line. The amount of rotation indicates the inclination of the optical axis and the intersection of the bisector and the central line of the triplet gives the optical center.
The optical center and two points on the optical axis are then marked using an inking lever mechanism appended to the lensometer.
Once marked the lens blank is removed from the lensometer and a "cutting" line drawn on it through the three points to indicate the optical axis. In the next step a special scale is placed along the optical axis to locate the "finishing center". The latter is at the position by which the optical center is de-centered to accommodate the lens to the frame of the user. Thus if the P.D. is 68 millimeters and the frames have a bridge size, nose span, of 14 millimeters and a lens size of 48 millimeters making a total frame span of 62 millimeters, the optical center of each lens blank must be de-positioned by three millimeters (one-half of the difference between the frame span and the P.D.)
A temporary mounting known as a "block" is then temporarily affixed to the lens at the finishing center. The block is in the form of an alloy with a pattern that allows the lens blank to be rotated with respect to a finishing wheel.
It is apparent that if the optical axis is not properly located, or if the finishing center is not properly located, the finished lens will be in error.
In addition, the manual techniques in present use require operators with considerable skill, and are time consuming.
Even if the operator is highly skilled, he is confronted wit play and inexactness in the instruments that he uses.
The result is that an estimated 30 percent of the lenses are incorrectly blocked, of which about fifteen percent are so inaccurate that they must be discarded. While the remaining fifteen percent are not rejected, they are nonetheless less accurate than they should be.
Accordingly, it is an object of the invention to increase the precision with which lens blanks can be blocked. A related object is to eliminate the need for the marking of lens blanks. Another related object is to eliminate the need for special scales in the de-centering of lens blanks.
Another object is to reduce the number of rejects encountered in the blocking of lenses. A related object is to raise the level of accuracy of lens blanks that are accepted.
A further object is achieve the precision blocking lenses with only semi-skilled operators.
SUMMARY OF THE INVENTION
In accomplishing the foregoing and related objects, the invention provides a holder by which a lens blank can be adjusted with precision relative to a lensometer and then to a blocker.
The holder has two degrees of translational motion and one degree of rotation. This permits accurate location of the optical center and axis of the blank. The holder can then be zeroed and the lens de-positioned in either or both of the translational directions to locate a finishing center for pupilary distance and bifocal adjustment.
The accuracy of the finishing center located using the holder is maintained by transferring the holder, with the blank, to a blocker. This eliminates any need for marking of the blanks, and the need for using auxiliary scales to de-center the blank.
As a result the required skill of the operator is significantly reduced and the quality of the final, finished product is considerably increased.
In accordance with one aspect of the invention, the holder is formed by frames which are nested within one another and slidable relative to one another.
In accordance with another aspect of the invention the holder has graduated scales for each degree of translation for controlled depositioning of the lens blank.
DESCRIPTION OF THE DRAWINGS
Other aspects of the invention will become apparent after considering several illustrative embodiments taken in conjunction with the drawings in which:
FIGS. 1A and 1B are diagrams of a lens blank being processed in accordance with the prior art;
FIG. 2 is a perspective view of a holder in accordance with the invention;
FIG. 3 is a perspective view of a lensometer with the holder of FIG. 2 in position; and
FIG. 4 is a perspective view of a blocker with the holder of FIG. 2 in position.
DETAILED DESCRIPTION
Turning to the drawings, FIG. 1A shows an illustrative lens blank 10 as it appears during the second stage of blocking in accordance with the prior art.
During the first stage, the blank 10 was positioned on a lensometer (not shown) and marked (temporarily) with three dots, 11-1, 11-2 and 11-3. The central dot 11-2 is at the optical center of the blank 10, while the adjoining dots 11-1 and 11-3 are points on the cutting line.
After the dots 11-1, 11-2, and 11-3 are formed on the blank, it is removed from the lensometer and the optical axis 12 is drawn on the blank through the dots, using, for example, a felt tip pen. When this is done, the blank 10 is ready for decentering in accordance with the prior art. This is accomplished by positioning a graduated scale 13 on the blank 10 along the axial line 12, with the origin 13-0 of the scale 13 at the optical center indicated by the dot 11-2. The blank is then de-centered according to the difference between the F.D. (frame distance) and the P.D. (pupilary distance). For the particular example of FIG. 1A the blank is decentered by about 3 millimeters and the F.C. (frame center) indicated by the mark 14.
The scale is then removed and the blank 10 placed on a blocker (not shown), with the F.D. mark 14 overlying the corresponding indicator 15-2 on the blocker and the axis 12 overlying axial indicators 15-1 and 15-3 on the blocker. The blocker is then operated to form an alloy hub 16 that is centered on the F.D. mark 14.
Once the hub 16 is formed, it is used to secure the blank 10 in the grinding machine (not shown) by which the blank is ground into the desired finished product for proper mounting in the frame (not shown) of the user.
The hub or block 16 is formed in standard fashion of alloy that tends to adhere to the glass surface or ordinary lens blanks. The adhesive is enhanced by lightly spraying the blank with a standard adhesive substance. Once the grinding operation is completed, the block 16 is removed, for example by lightly tapping the lens.
It is apparent that the prior art blocking as typified by FIG. 1A and 1B is slow, cumbersome and inaccurate.
The invention overcomes the difficulties of the prior art by using a holder 20 of the kind pictured in FIG. 2.
The holder 20 is formed by an outer frame 21, an intermediate frame 22 and an inner frame 23.
The inner frame 23 is movable vertically within the intermediate frame 22 by an adjusting knob 23k which is treaded through the intermediate frame 22 and extends through a slot 21s in the outer frame 21.
In addition the inner frame 23 has a central member 23c which is rotatable within the frame 23 and holds the lens blank 10. A retainer 23r, which can be a rubber ring, secures the blank 10 and provides an appropriate gripping surface for rotating the member 23c. After a suitable rotation has taken place, as explained below, the blank 10 is securely held in place by tightening set screws 23s-1 through 23s-4 associated with clamps 23k-1 through 23k-4.
The rotor member 23c is removable from the inner frame 23 and replacable with other rotor members to hold different sizes of lens blanks. In current practice the largest lens blanks have a maximum dimension of 75 millimeters and the smallest blanks have a maximum dimension of 58 millimeters.
The intermediate frame 22 is movable horizontally within the outer frame 21 by an adjusting knob 22k which is treaded through the outer frame 21.
The outer frame 21 includes an adjustable scale 21c which can be accurately positioned with respect to a scale 22p on the intermediate frame 22 by an adjusting knob 21a.
A similar adjustable scale 22c can be positioned with respect to a scale 23p on the inner frame 23, by an adjusting knob 22a which extends through the slot 21s in the outer frame 21.
To maintain the relative displacements of the frames 21 through 23 relative to one another, a dovetail groove and tonque can be used as shown. A dovetail tongue 21t is also provided at the vertical edges of the outer frame 22 for positioning the holder in a mount as explained below.
In use, the holder 20 of FIG. 2 is inserted into a modified lensometer 30 of the kind illustrated in FIG. 3. The lensometer 30 has a standard reticle 31, a source of illumination 32 for the riticle and axial adjustment control 33, as well as a power adjustment control 34 and a view 35.
The lensometer 30 is modified by having a special mount 36 for the holder 20, with a dovetail slot 36d for the dovetail tongue 21t. In addition the mount is pivotable about an axis 37 to permit the lens blank 10 within the holder 20 to be seated against a reticle lens (not visible in FIG. 3), despite the fact that some of the lens blanks used in the holder 20 have appreciable curvature.
Once the lens blank 10 in the holder 20 is seated against the reticle lens of the lensometer 30, the control 34 is set with the spherical power of the lens blank. The adjusting knob 22k (FIG. 2) is manipulated until the verticle line of the reticle is in focus, so that it passes through the optical center of the lens blank.
The control 34 is next set with the cylindrical power of the lens blank and the adjusting knob 23k manipulated until the triplet of the reticle is in focus. The optical center of the lens blank is then at the intersection of the verticle line and the middle line of the triplet.
In the next step the control 33 is set with the optical axis and the central member 23c rotated until the vertical line from the reticle is unfragmented.
The set screws 23s-1 through 23s-4 are secured (to prevent any further, inadvertent rotation) and the scales 21c and 22c are zeroed. Zeroing takes place by operating adjusting knob 21a until the center line of scale 21c is opposite the center line of scale 22p. Similarly, adjusting know 22a is operated until the center line of scale 22c is opposite the center line of scale 23p. Zeroing may take place with the holder in or out of the mount 36.
As a result of the foregoing operations the optical center of the lens blank 10 is precisely determined with respect to the holder 20. This is by contrast with the manual manipulation of the lens blank required in the prior art. It will be understood that the particular sequence of operations is merely illustrative, and other sequences may be employed as well.
In the first step of achieving precision blocking in accordance with the invention, the lens blank 10 in the holder 20 is de-positioned to the proper finishing center and the proper bifocal center.
If the lens blank 10 is not to be bifocal, it is only necessary to de-center the established optical center by moving the inner frame 23 from side to side using the knob 22k. Since the movable scale 21c is zeroed at this point with respect to the fixed scale 22p, the de-centering is accomplished by operating the knob 22k until the desired difference appears between the two scales 21c and 22p.
A similar de-positioning occurs between the zeroed scales 22c and 23p where a bifocal correction is to be made.
After the blank 10 is suitably de-positioned relative to the holder 20, it is inserted into a mount 41 of the modified blocker 40 shown in FIG. 4.
The mount 41 is similar to the mount 36 of the modified lensometer. Since the mount 41 assures that the lens blank 10 will be properly positioned, it is only necessary to operate the blocker in standard fashion, permitting molten alloy to flow along a feed tube 42 to a die position 43, where the desired block or hub is formed, similar to the block 16 of FIG. 1, except that it is formed with precision and without resort to the inaccurate manual techniques of the prior art.
While various aspects of the invention have been set forth by the drawings and the specification, it is to be understood that the foregoing detailed description is for illustration only and that various changes in parts, as well as the substitution of equivalent constituents for those shown and described may be made without departing from the spirit and scope of the invention as set forth in the appended claims. | Method and apparatus for the precision blocking of lens blanks using a holder to de-center the blank and fix its optical axis. The holder is then used to position the blank with respect to a blocker by which an alloy hub or "block" is removably affixed to the blank so that it can be properly gripped for conversion into a finished lens product. | 8 |
FIELD OF THE INVENTION
This invention relates to multi-variable processes.
BACKGROUND OF THE INVENTION
The invention is particularly concerned with methods and systems for displaying variables of multi-variable processes.
SUMMARY OF THE INVENTION
According to one aspect of the present invention a method for displaying variables of a multi-variable process, comprises deriving a multi-dimensional display representation in parallel coordinates of a feasible region of the process-variables, the representation being derived from sets of values for the process-variables accumulated respectively from multiple operations of the process, deriving a further set of values for said variables within said region and displaying them within said representation, and defining within the display representation available ranges for the variables according to the values of other variables within said further set.
According to another aspect of the present invention a system for displaying variables of a multi-variable process, comprises means for providing a multi-dimensional display representation in parallel coordinates of a feasible region of the process-variables, the representation being derived from sets of values for the process-variables accumulated respectively from multiple operations of the process, means for deriving a further set of values for said variables within said region and displaying them within said representation, and means for defining within the display representation available ranges for the variables according to the values of other variables within said further set.
The definition of available ranges of the process-variables in the method and system of the invention may be carried out by reference to convex hulls calculated for each pair of variables from the accumulated sets of values. A convex hull in orthogonal coordinates is a closed polygon that encloses all relevant data points of the two-dimensional space, whereas in parallel coordinates it is a pair of spaced linear curves that as between corresponding parallel axes, bound the region occupied by the lines that represent (in the parallel-coordinate space) those data points. A feature of convex hulls used in the present invention is that when the value of one variable is fixed a range of values from maximum to minimum of the other can be derived.
The invention may be applied to monitoring and optimisation of multi-variable processes. More especially, the invention is applicable to ensuring safe and efficient on-line operation of multi-variable processes, in particular by providing a display representation including warning alarm limits on some or all of the variables where these limits are continuously re-calculated in accordance with current operating conditions. Furthermore, the invention is applicable to assist selection of values for the variables of the process and to systems for providing display representations for use in such selection.
According to a feature of the present invention a method for selection of values for variables of a multi-variable process, comprises a first step of deriving a multidimensional display representation in parallel coordinates of a feasible region of the variables, the representation being derived from sets of values for the process-variables accumulated respectively from multiple operations of the process, a second step of selecting, so as to fix, a value within said region for one of said variables and defining available ranges for the other variables in accordance with the selection made, and a third step of selecting, so as to fix, a value within the available range defined for one of the remaining unfixed-value variables and re-defining the available ranges for the other unfixed-value variables in accordance with the selections so far made, this third step being repeated until values for all unfixed-value variables have been fixed by the selections made.
According to another feature of the invention a system for providing a display representation for use in selection of values for variables of a multi-variable process, comprises means storing sets of values for the process-variables accumulated respectively from multiple operations of the process, display means providing a multi-dimensional display representation in parallel coordinates, the representation including in accordance with the stored sets of values, display of a feasible region of the variables, and selection means that is operable successively to select, so as to fix, values within said region for all said variables in turn, said display means being operative upon each operation of the selection means to define available ranges for such of the other variables that remain of un-fixed value.
BRIEF DESCRIPTION OF THE DRAWINGS
A method and system according to the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic representation of a system according to the invention in the context of collection and utilisation of data derived from operation of a multi-variable processing plant;
FIG. 2 is illustrative of a plot in multidimensional space defined by parallel coordinate axes, of operation of the multi-variable processing plant of FIG. 1 ;
FIG. 3 shows in part a multiplicity of plots corresponding to that of FIG. 2 resulting from variation of operation of the multi-variable process;
FIGS. 4 to 6 are illustrative of displays provided during successive stages of the method according to the invention, for assisting with selection of values for the variables of operation of the processing plant of FIG. 1 ;
FIGS. 7 to 10 are illustrative of further displays provided according to the invention to assist further in selection of values for variables of operation of the processing plant of FIG. 1 ; and
FIGS. 11 to 13 are illustrative of displays derived in varying circumstances during on-line monitoring of operation of the processing plant of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
The example of method and system to be described is related to the operation of a multi-variable process carried out by a simple, notional processing plant. Details of the plant and its purpose are not of consequence, and indeed the method and system of the invention are related more specifically to operation of the plant as an example of a multi-variable process rather than to the purpose of the process performed, being applicable in the generality to any situation involving a multi-variable process. In the context of description of the present specific example, however, there are fourteen variables involved in plant-operation, and of these, eleven are control variables to the extent that their values determine the outcome of the process. The remaining three variables are quality variables in the sense that their values define, or more especially are defined by, that outcome.
Referring to FIG. 1 , the plant 1 has an input 2 and an output 3 between which there are a multiplicity of processing stages 4 . The processing within each stage 4 is carried out in accordance with one or more variables that, in this example, are regulated by eleven controllers 5 . The values of these variables for each operation or ‘run’ of the process are communicated to a data collection unit 6 to be accumulated in a store 7 . The term ‘run’ in this context may refer to a discrete operation of the process, but it may also refer to what applies at a discrete point in time within continuous operation.
The outcome at the output 3 of each run of the process, is submitted to a unit 8 for analysis in respect of its quality as determined according to three variables. The values of these three quality variables are accumulated in a store 9 , so that each run of the process and its outcome is defined by an accumulated set of fourteen values, eleven in the store 7 and three in the store 9 , for the fourteen variables respectively.
As the process is run again and again, a multiplicity of different sets of fourteen values are accumulated to provide a historical record in the stores 7 and 9 of the successive runs. This record is used in the method of the present invention to assist selection of the values of the various variables appropriate to achieving a particular outcome. More especially, the fourteen values of each individual set, eleven in the store 7 and three in the store 9 , are brought together in a merge unit 10 and each scaled to the range 0 to 1. The scaled values are then processed in a unit 11 according to a convex-hull model to plot them in an electronic display unit 12 . The scaled values of each set are plotted in fourteen-dimensional space using a system of parallel coordinates as illustrated in FIG. 2 .
Referring to FIG. 2 , the fourteen values are plotted on fourteen equally-spaced, parallel axes X 01 -X 14 representing the fourteen variables respectively. The first three, axes, X 01 -X 03 , are used for the quality variables, and the plots are joined up to form a polygonal line L that is representative of the single fourteen-value operating point of the process. The other sets of process-values are each correspondingly plotted against the same axes X 01 -X 14 resulting in a multiplicity of polygonal lines corresponding to the line L; this is illustrated in part in FIG. 3 . Each polygonal line is representative of an individual operating point or run of the process from the historical record.
Referring further to FIG. 3 , convex hulls H for all pairs of adjacent variables of the parallel-axis system, are calculated in the unit 11 and displayed. Between each pair of adjacent axes X 01 -X 14 there will be an upper and lower hull H defining upper and lower limiting boundaries between those two axes, of the operating-point lines. The upper and lower hulls H of the successive pairs of adjacent axes join together to define top and bottom boundaries or chains TC and BC respectively. Calculation of the convex hulls applicable to all the other pairings of variables is also made, but are not displayed in display unit 12 .
Once the calculation of all the convex hulls has been completed, a display as shown in FIG. 4 is provided in which the upper and lower hulls H are restricted for simplicity to those parts lying within the range 0 and 1. In this way, the upper and lower hulls H are seen more clearly as joining up together as top and bottom chains TC and BC respectively, defining (for example, in colour red) the upper and lower boundaries of a region within which feasible operation of the process can take place. Clearly, the larger the number of historical sets of operational data used, with as wide as possible range of values for the individual variables, the more accurately will this region, be defined.
It is optional whether representation in the form of FIG. 3 is provided by the display unit 12 , but representation in the form of FIG. 4 is displayed and utilised for the selection of the process-variables to be used in optimum, or otherwise, operation of the process. The steps of selection begin with fixing the first variable, that is to say, the variable of axis X 01 . This is a quality variable and the selection made establishes the value, Q 1 , this variable is to have in the outcome of the prospective process-run. The selection may be made by moving a cursor up the axis X 01 in the display using a mouse (not shown), and clicking at the appropriate position.
The selection of the value Q 1 of the first variable, brings about display of a polygonal line L 1 (for example in colour blue) representing the operating point that would result in the event that the other thirteen variables were each fixed at the midpoints of their available ranges. In this regard, a calculation is made for each of these unfixed variables of the restricted range of values which is open for selection in respect of that variable as a consequence of the selection of value Q 1 for the first variable. The range is derived in each case by reference to the convex hull between the fixed first variable and the unfixed variable. These ranges are denoted in the display for each unfixed variable by the intersection with its respective axis X 02 -X 14 of two lines R 1 (for example in colour green) that diverge from the immediately preceding axis X 01 -X 13 ; the lines R 1 are tangential to the convex hull between the fixed first variable and the unfixed variable. The lines R 1 that intersect the axis X 02 of the second variable diverge from the selected value Q 1 on the axis X 01 , whereas in each other case (for the variables of axes X 03 -X 14 ) they diverge from the mid-point of the available range of the variable of the immediately preceding axis X 02 -X 13 . It is this mid-point that is assumed selected for each of the unfixed variables, in the plotting of the line L 1 .
The next step is the selection of the value Q 2 of the variable of the second axis X 02 . Selection is made by moving the cursor up the axis X 02 and clicking the mouse at the appropriate position, and has the effect of changing the display to that shown in FIG. 5. A new line L 2 is displayed joining the fixed points Q 1 and Q 2 between axes X 01 and X 02 and extending from point Q 2 through the mid-points of the available ranges of the other twelve, unfixed variables. These available ranges, which are denoted by divergent lines R 2 (for example in colour green), are each derived by reference to the overlap with the range previously calculated for the fixed value Q 1 and denoted by lines R 1 . The available range defined for each unfixed variable by the lines R 2 is restricted by virtue of the overlap to the range of values of that variable which is available for selection having regard to both selected values Q 1 and Q 2 . The lines R 1 and L 1 may, as indicated in FIG. 5 , be retained in the display (but for example now in colour grey) for reference purposes to indicate the range available for each unfixed variable before selection of value Q 2 , and the previous course of the line L 1 from the axis X 02 .
The selection method now proceeds to the step of selecting in a similar way the value Q 3 of the third variable (axis X 03 ), and then on from there through successive steps until the values Q 4 -Q 14 of all the remaining variables have been selected to complete definition of the value-set for the desired operating point. The display changes as the selections are made, and for example appears as in FIG. 6 when the values Q 1 -Q 5 of the first five variables have been selected. In this case, lines R 5 identify the available ranges for the remaining variables of axes X 06 -X 14 , and lines R 4 show the ranges available immediately before the value Q 5 was selected. The polygonal line L 5 interconnects the already-selected values Q 1 -Q 5 and the mid-point values of the available ranges of the remaining unfixed variables, whereas line L 4 shows its previous course from axis X 05 .
As each individual selection is made to fix the value Qn of the next unfixed variable (in the order of the axes X 01 -X 14 ); so the restricted range due to each already-fixed variable is calculated using the relevant convex hull between those fixed and unfixed variables. The available range is displayed for each unfixed variable using, lines Rn. The lines Rn define the available range of each unfixed variable as the portion of the relevant axis X which is common to (overlapped by) the restricted ranges derived for that variable and each of the fixed variables. The polygonal line Ln is established passing through all the values Q selected for the currently-fixed variables and also through the mid-points of the available ranges of the unfixed variables.
The polygonal line Ln connects the fixed values of the fixed variables and the working (or suggested) values of the unfixed variables. To ensure that the line Ln always represents a feasible operating point of the process, the working values of the unfixed variables apart from that to the immediate right of the last fixed variable, are calculated using a more restricted range than that displayed. In this regard, the range due to the fixed variables is overlapped with the ranges due to the working values of all the unfixed variables to the left of the one whose working value is being calculated to give the working range, and the mid-point of this range is taken as the working value. These working ranges may be optionally displayed in a different colour from the ranges due to the fixed variables.
Throughout the method of the invention as the display progresses step-by-step from that of FIG. 4 to that of FIGS. 5 and 6 , and so on until all selections have been made, the operator is presented with information that enables selection of feasible values of the variables consistent with desired objectives of economy, efficiency and outcome of the process. The information is derived without the need to fit a functional model to the historical data and the disadvantages associated with this, and is applicable to adjustment or re-setting of the controllers 5 of the plant 1 for optimisation of plant-operation.
The values of the variables that have been fixed in the display of unit 12 can be changed. This enables the operator to search for sets of values that give the ‘best’ ranges for the unfixed variables, and in this regard the ‘best’ range in any particular case may simply be a narrow range about a desired value. The limits within which each fixed variable can be moved while holding the other fixed variables constant, are calculated using the convex hulls between the fixed variables, and are included in the display. This display changes continuously as the fixed variable is changed.
These characteristics of the display may be used with particular advantage if the controllable variables are fixed and arranged to the left of all the quality variables. The controllable variables can then be moved until satisfactory values of the quality variables are obtained.
The latter functionality of the display is illustrated in the example of FIGS. 7 to 10 . In this example, variables p 11 , p 12 , p 13 and p 14 are considered to be ‘process’ variables which can be manipulated, and variables q 7 and q 8 are considered to be ‘quality’ variables which depend on the process variables.
In FIG. 7 , point Fp 11 is the value to which the variable p 11 has been set, and points Wp 12 to Wpl 4 and Wq 7 and Wq 8 are the working values of variables p 12 to p 14 and q 7 and q 8 respectively. These points are joined by a polygonal line L 1 , and line-pairs RF 1 to RF 5 display the ranges of the respective variables p 12 to p 14 and q 7 and q 8 , that are due to variable p 11 having the value Fp 11. The range in each case is shown by the intercept the line-pair makes with the axis of the relevant variable.
A line-pair RW 2 (the upper line of which is co-linear with the upper line of the line-pair RF 2 ) show by their intercepts on the axis p 13 the range of variable p 13 that is due to variable p 11 having the value Fp 11 and the variable p 12 having the value Wpl 2 . The value Wp 13 is the mid-point of this range. Similarly, a line-pair RW 3 displays the range of variable p 14 that is due to variables p 11 , p 12 and p 13 having the values Fp 11 , Wp 12 and Wp 13 respectively, and value Wp 14 is the mid-point of this range. Line-pairs RW 4 and RW 5 correspondingly display ranges, with mid-points Wq 7 and Wq 8 , of the variables q 7 and q 8 that are due respectively to the values set for the four variables p 11 to p 14 , and the five variables p 11 to p 14 and q 7 .
FIG. 8 , illustrates the display that results from now setting the variables p 11 to p 14 to the values Fp 11 to Fp 14 respectively. Carets at Up 11 and Lp 11 indicate the calculated limits (as referred to above) between which the value of variable p 11 may be moved while holding variables p 12 , p 13 and p 14 at values Wp 12 , Wp 13 and Wp 14 respectively. Similarly, carets at Up 12 and Lp 12 indicate the limits between which the variable p 12 may be moved while holding variable p 11 at value Fp 11 , variable p 13 at value Fp 13 , and variable p 14 at value Fp 14 . Carets Up 13 and Lp 14 and Up 14 and Lp 14 are correspondingly provided for the variables p 13 and p 14 , and the upper carets Up 11 to Up 14 are joined by polygonal line UC and the lower carets Lp 11 to Lp 14 by polygonal line LC.
FIG. 9 illustrates the effect of moving the point Fp 13 to the current lower limit represented by caret Lpl 3 . The limits represented by the other carets have in general changed, and so too have the ranges of variables q 7 and qB represented by the line-pairs RF 4 and RF 5 . In particular, the upper limit of variable p 14 represented by caret Upl 4 , has moved down to the current value Fp 14 , indicating that the convex hull between axes p 13 and p 14 is setting the most restrictive lower limit on variable p 13 .
FIG. 10 illustrates the situation when the user, by experimenting with the values of variables p 11 to p 14 , has discovered settings for these variables which keep the value of variable q 8 within a narrow range near the value 0.5, as evidenced by the intercepts of both lines RF 5 with the axis of variable q 8 , close to this value.
The display techniques described above may be used to determine appropriate warning alarm levels on plant variables during process operation, and to display those alarm levels and the current values of the corresponding variables to the processing operator. This is achieved as illustrated in FIG. 1 , using a further electronic display unit 13 . The display unit 13 is driven from an alarm-algorithm unit 14 in accordance with data from the unit 11 and the values of the process variables in real time, supplied from the unit 6 . All the variables are treated as of fixed value.
Whenever a new set of values for the process variables is received from the unit 6 , the unit 14 identifies which variables have values lying in the ‘best-operating’ zone or region defined between the relevant top and bottom chains of convex hulls. Upper and lower limits for all variables are calculated from these values within the best-operating zone using the relevant convex hull as for the display of unit 12 . Furthermore, the unit 14 identifies which, if any, of the variables have values that lie outside these limits, and gives warning by indication in the display of unit 13 or otherwise, of the condition. As each new set of values is received, the display changes, and the limits on all the variables are recalculated and shown in the display of unit 13 , exactly as if the point had been moved by the program-user in offline operation. The quality variables are treated no differently from the control variables in determining the on-line alarm limits.
In this way the display unit 13 provides representation of warning alarm limits for all variables simultaneously. These limits are always calculated using the current values of all the other variables; no model-fitting or statistical assumptions are required.
Displays provided by the unit 13 in three different circumstances are illustrated in FIGS. 11 to 13 , for ten variables plotted against axes Xa-Xj.
Referring to FIG. 11 , the plotted values Qa to Qj are all within the current best-operating zone defined between top and bottom chains Tc and Bc respectively. Upper and lower current limits calculated for the individual variables and plotted on the respective axes Xa-Xj are joined up to provide polygonal lines UL and LL. The lines UL and LL define the zone within which the values of the variables are to be retained. In this example, all values Qa to Qj are within the zone, but this is not so in the circumstances of the displays illustrated in FIGS. 12 and 13 .
In the circumstances of the display of FIG. 12 , the value Qc for the variable plotted on the axis Xc is on the upper limit UL, and the values Qb, Qg, Qi and Qj for the variables plotted on axes Xb, Xg, Xi and Xj respectively, are on the lower limit LL. On the other hand, in the circumstances of the display of FIG. 13 , the values Qc and Qd of the variables plotted on axes Xc and Xd, are the only ones within the best-operating zone between the limit lines UL and LL. In both cases, as illustrated in FIGS. 12 and 13 , a caret (for example of colour red) is included in the display where a variable-value is on the boundary or outside the best-operating zone. More particularly, a downwardly-directed caret DC is displayed on the relevant axis of any variable where the value is on or above the line UL and an upwardly-directed caret UC is correspondingly displayed where the value is on or below the line LL.
The process operator can interact with the display unit 13 to adjust one or more of the fixed values Qa-Qj up or down their respective axes experimentally, to see the effect this has on the limits of the other variables. When an alarm condition exists, and several variables are on or beyond their limits, adjusting the value Q of even one of them may be found to move the limit lines UL and LL outwardly from one another sufficiently to relieve the alarm condition on the others.
Accordingly, by using the on-line display of unit 13 , the operator can not only monitor the current settings and results of the process, but can also be made aware of alarm situations and receive guidance in focussed investigation of the remedial action necessary. | Control and output-quality variables of a process plant ( 1 ) are plotted against parallel axes in a display unit ( 7 ). Convex hulls between pairs of variables are calculated from sets of the variable-values accumulated historically in stores ( 7, 9 ) during successive runs of the process, and hulls (HH; TC, BC) between successive axis-pairs are displayed. New variable-values for process optimization are fixed for the variables taken in turn, each selection being made within displayed ranges (Rn—Rn) derived from the hulls effective between the respective variable and the variables already fixed. A display unit ( 13 ) provides on-line parallel-axis display of variable-values from the plant ( 1 ), showing alarm carets (DC, UC) where values violate limits (UL, LL) determined by the convex hulls, and allowing variation in the displayed-value for observing the resultant effect in avoiding alarm situation and towards optimization. | 6 |
PRIORITY
The present application claims priority to a U.S. provisional patent application filed on May 24, 2007 and assigned U.S. Provisional Patent Application Ser. No. 60/939,891, the entire contents of which and the references cited therein are incorporated herein by reference. The following published references relate to the present application. The entire contents of these references are incorporated herein by reference: Adam O'Donovan, Raniani Duraiswami, and Jan Neumann, Microphone Arrays as Generalized Cameras for Integrated Audio Visual Processing, Jun. 21, 2007, Proceedings IEEE CVPR; Adam O'Donovan, Ramani Duraiswami, Nail A. Gumerov, Real Time Capture of Audio Images and Their Use with Video, Oct. 22, 2007, Proceedings IEEE WASPAA; Adam O'Donovan, Ramani Duraiswami, Dmitry N. Zotkin, Imaging Concert Hall Acoustics Using Visual and Audio Cameras, April 2008, Proceedings IEEE ICASSP 2008; and Adam O'Donovan, Dmitry N. Zotkin, Ramani Duraiswami, Spherical Microphone Array Based Immersive Audio Scene Rendering, Jun. 24-27, 2008, Proceedings of the 14 th International Conference on Auditory Display.
BACKGROUND
Over the past few years there have been several publications that deal with the use of spherical microphone arrays. Such arrays are seen by some researchers as a means to capture a representation of the sound field in the vicinity of the array, and by others as a means to digitally beamform sound from different directions using the array with a relatively high order beampattern, or for nearby sources. Variations to the usual solid spherical arrays have been suggested, including hemispherical arrays, open arrays, concentric arrays and others.
A particularly exciting use of these arrays is to steer it to various directions and create an intensity map of the acoustic power in various frequency bands via beamforming. The resulting image, since it is linked with direction can be used to identify source location (direction), be related with physical objects in the world and identify sources of sound, and be used in several applications. This brings up the exciting possibility of creating a “sound camera.”
To be useful, two difficulties must be overcome. The first, is that the beamforming requires the weighted sum of the Fourier coefficients of all the microphone signals, and multichannel sound capture, and it has been difficult to achieve frame-rate performance, as would be desirable in applications such as videoconferencing, noise detection, etc. Second, while qualitative identification of sound sources with real-world objects (speaking humans, noisy machines, gunshots) can be done via a human observer who has knowledge of the environment geometry, for precision and automation the sound images must be captured in conjunction with video, and the two must be automatically analyzed to determine correspondence and identification of the sound sources. For this a formulation for the geometrically correct warping of the two images, taken from an array and cameras at different locations is necessary.
SUMMARY
Due to the recognition that spherical array derived sound images satisfy central projection, a property crucial to geometric analysis of multi-camera systems, it is possible to calibrate a spherical-camera array system, and perform vision-guided beamforming. Therefore, in accordance with the present disclosure, the spherical-camera array system, which can be calibrated as it has been shown, is extented to achieve frame-rate sound image creation, beamforming, and the processing of the sound image stream along with a simultaneously acquired video-camera image stream, to achieve “image-transfer,” i.e., the ability to warp one image on to the other to determine correspondence. One of the ways this is achieved is by using graphics processors (GPUs) to do the processing at frame rate.
In particular, in accordance with the present disclosure there is provided an audio camera having a plurality of microphones for generating audio data. The audio camera further has a processing unit configured for computing acoustical intensities corresponding to different spatial directions of the audio data, and for generating audio images corresponding to the acoustical intensities at a given frame rate. The processing unit includes at least one graphics processor; at least one multi-channel preamplifier for receiving, amplifying and filtering the audio data to generate at least one audio stream; and at least one data acquisition card for sampling each of the at least one audio stream and outputting data to the at least one graphics processor. The processing unit is configured for performing joint processing of the audio images and video images acquired by a video camera by relating points in the audio camera's coordinate system directly to pixels in the video camera's coordinate system. Additionally, the processing unit is further configured for accounting for spatial differences in the location of the audio camera and the video camera. The joint processing is performed at frame rate.
In accordance with the present disclosure there is also provided a method for jointly acquiring and processing audio and video data. The method includes acquiring audio data using an audio camera having a plurality of microphones; acquiring video data using a video camera, the video data including at least one video image; computing acoustical intensities corresponding to different spatial directions of the audio data; generating at least one audio image corresponding to the acoustical intensities at a given frame rate; and transferring at least a portion of the at least one audio image to the at least one video image. The method further includes relating points in the audio camera's coordinate system directly to pixels in the video camera's coordinate system; and accounting for spatial differences in the location of the audio camera and the video camera. The transferring step occurs at frame rate.
In accordance with the present disclosure, there is also provided a computing device for jointly acquiring and processing audio and video data. The computing device includes a processing unit. The processing unit includes means for receiving audio data acquired by a microphone array having a plurality of microphones; means for receiving video data acquired by a video camera, the video data including at least one video image; means for computing acoustical intensities corresponding to different spatial directions of the audio data; means for generating at least one audio image corresponding to the acoustical intensities at a given frame rate; and means for transferring at least a portion of the at least one audio image to the at least one video image at frame rate.
The computing device further includes a display for displaying an image which includes the portion of the at least one audio image and at least a portion of the video image. The computing device further includes means for identifying the location of an audio source corresponding to the audio data, and means for indicating the location of the audio source. The computing device is selected from the group consisting of a handheld device and a personal computer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts epipolar geometry between a video camera (left), and a spherical array sound camera. The world point P and its image point p on the left are connected via a line passing through PO. Thus, in the right image, the corresponding image point p lies on a curve which is the image of this line (and vice versa, for image points in the right video camera).
FIG. 2 shows a calibration wand consisting of a microspeaker and an LED, collocated at the end of a pencil, which was used to obtain the fundamental matrix.
FIG. 3 shows a block diagram of a camera and spherical array system consisting of a camera and microphone spherical array in accordance with the present disclosure.
FIGS. 4 a and 4 b : A loud speaker source was played that overwhelmed the sound of the speaking person ( FIG. 4 a ), whose face was detected with a face detector and the epipolar line corresponding to the mouth location in the vision image was drawn in the audio image ( FIG. 4 b ). A search for a local audio intensity peak along this line in the audio image allowed precise steering of the beam, and made the speaker audible.
FIGS. 5 a and 5 b show an image transfer example of a person speaking. The spherical array image ( FIG. 5 a ) shows a bright spot at the location corresponding to the mouth. This spot is automatically transferred to the video image ( FIG. 5 b ) (where the spot is much bigger, since the pixel resolution of video is higher), identifying the noise location as the mouth.
FIG. 6 shows a camera image of a calibration procedure.
FIG. 7 graphically illustrates a ray from a camera to a possible sound generating object, and its intersection with the hyperboloid of revolution induced by a time delay of arrival between a pair of microphones. The source lies at either of the two intersections of the hyperboloid and the ray.
DETAILED DESCRIPTION
I. Real Time Capture of Audio Images and Their Use With Video
A. Beamforming
Beamforming with Spherical Microphone Arrays: Let sound be captured at N microphones at locations Θ s =(θ s ,φ s ) on the surface of a solid spherical array. Two approaches to the beamforming weights are possible. The modal approach relies on orthogonality of the spherical harmonics and quadrature on the sphere, and decomposes the frequency dependence. It however requires knowledge of quadrature weights, and theoretically for a quadrature order P (whose square is related to the number of microphones S) can only achieve beampatterns of order P/2. The other requires the solution of interpolation problems of size S (potentially at each frequency), and building of a table of weights. In each case, to beamform the signal in direction Θ=(θ,φ) at frequency f (corresponding to wavenumber k=2πf/c, where c is the sound speed), we sum up the Fourier transform of the pressure at the different microphones, d s k as
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In the modal case (J. Meyer & G. Elko, 2002, A Highly Scalable Spherical Microphone Array Based on an Orthonormail Decomposition of the Soundfield, IEEE ICASSP 2002, vol. 2, pp. 1781-1784, the entire contents of which are herein incorporated by reference), the weights w N are related to the quadrature weights C n m for the locations {Θ s }, and the b n coefficients obtained from the scattering solution of a plane wave off a solid sphere
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For the placement of microphones at special quadrature points, a set of unity quadrature weights C n m are achieved. In practice, it was observed that for {Θ s } at the so-called Fliege points, higher order beampatterns were achieved with some noise (approaching that achievable by interpolation (N+1)=√{square root over (S)}). In our beamformer, we use one order lower than this limit, and the Fliege microphone locations, though we also consider the case where weights are generated separately and stored in a table.
Joint Audio-Video Processing and Calibration: In A. O'Donovan, R. Duraiswami, and J. Neumann, Microphone Arrays as Generalized Cameras for Integrated Audio Visual Processing, Proc. IEEE CVPR, 2007, there is provided a detailed outline of how to use cameras and spherical arrays together and determine the geometric locations of a source. The key observation was that the intensity image at different frequencies created via beamforming using a spherical array could be treated as a central projection (CP) camera, since the intensity at each “pixel” is associated with a ray (or its spherical harmonic reconstruction to a certain order). When two CP cameras observe a scene, they share an “epipolar geometry” ( FIG. 1 ). Given two cameras and several correspondences (via a calibration object such as the calibration wand 100 shown in FIG. 2 ), a fundamental matrix that encodes the calibration parameters of the camera and the parameters of the relative transformation (rotation and translation) between the two camera frames can be computed. Given a fundamental matrix of a stereo rig, points can be taken in one camera's coordinate system and related directly to pixels in the second camera's coordinate system. Given more video cameras, a complete solution of the 3D scene structure common to the two cameras can be made, and “image transfer” that allows the transfer of the audio intensity information to actual scene objects made precisely. Given a single camera and a microphone array, the transfer can be accomplished if we assume that the world is planar (or that it is on the surface of a sphere) at a certain range.
General Purpose GPU Processing: Recently graphics processors (GPUs) have become an incredibly powerful computing workhorse for processing computationally intensive highly parallel tasks. Recently NVidia released the Compute Unified Device Architecture (CUDA) along with the G8800 GPU with a theoretical peak speed of 330 Gflops, which is over two orders of magnitude larger than that of a state of the art Intel processor. This release provides a C-like API for coding the individual processors on the GPU that makes general purpose GPU programming much more accessible. CUDA programming, however still requires much trial and error, and understanding of the nonuniform memory architecture to map a problem on to it. In the present disclosure we (referring to the Applicants) map the beamforming, image creation, image transfer, and beamformed signal computation problems to the GPU to achieve a frame-rate audio-video camera.
B. Exemplary System Setup
With reference to FIG. 3 , audio information was acquired using a previously developed solid spherical microphone array 302 of radius 10 cm whose surface was embedded with 60 microphones. The signals from the microphones are amplified and filtered using two custom 32-channel preamplifiers 304 and fed to two National Instruments PCIe-6259 multi-function data acquisition cards 306 . Each audio stream is sampled at a rate of 31250 samples per second. The acquired audio is then transmitted to an NVidia G8800 GTX GPU 308 installed in a computer running Windows® with an Intel Core2 processor and a clock speed of 2.4 GHz with 2 GB of RAM. The NVidia G8800 GTX GPU 308 utilizes a 16 SIMD multiprocessors with On-Chip Shared memory. Each of these multiprocessors is composed of eight separate processors that operate at 1.35 GHz for a total of 128 parallel processors. The G8800 GTX GPU 308 is also equipped with 768 MB of onboard memory. In addition to audio acquisition, video frames are also acquired from an orange micro IBot USB2.0 web camera 310 at a resolution of 640×480 pixels and a frame rate of 10 frames per second. The images are acquired using OpenCV and are immediately shipped to the onboard memory of the GPU 308 . A block diagram of the system is shown by FIG. 3 a.
The preamplifiers 304 , data acquisition cards 306 and graphics processor 308 collectively form a processing unit 312 . The processing unit 312 can include hardware, software, firmware and combinations thereof for performing the functions in accordance with the present disclosure.
C. Real-Time Processing
Since both pre-computed weights and analytically prescribed weights capable of being generated “on-the-fly” are used, we present the generation of images for both cases.
Pre-computed weights: This algorithm proceeds in a two stage fashion: a precomputation phase (run on the CPU) and a run-time GPU component. In stage 1 pixel locations are defined prior to run-time and the weights are computed using any optimization method as described in the literature. These weights are stored on disk and loaded at Runtime. In general the number of weights that must be computed for a given audio image is equal to P M F where P is the number of audio pixels, M is the number of microphones, and F is the number of frequencies to analyze. Each of these weights is a complex number of size 8 bytes.
After pre-computation and storage of the beamformer weights in the run-time component the weights are read from disk and shipped to the onboard memory of the GPU. A circular buffer of size 2048×64 is allocated in the CPU memory to temporarily store the incoming audio in a double buffering configuration. Every time 1024 samples are written to this buffer they are immediately shipped to a pre-allocated buffer on the GPU. While the GPU processes this frame the second half of the buffer is populated. This means that in order to process all of the data in real-time all of the processing must be completed in less then 33 ms, to not miss any data.
Once audio data is on the GPU we begin by performing an in place FFT using the cuFFT library in the NVidia CUDA SDK. A matrix vector product is then performed with each frequency's weight matrix and the corresponding row in the FFT data, using the NVidia CuBlas linear algebra library. The output image is segmented into 16 sub-images for each multi-processor to handle. Each multiprocessor is responsible for compiling the beamformed response power in three frequency bands into the RGB channels of the final pixel buffer object. Once this is completed control is restored to the CPU and the final image is displayed to the screen as a texture mapped quad in OpenGL.
On the fly weight computation: In this implementation there is a much smaller memory footprint. Where as we needed space to be allocated for weights on the GPU in the previous algorithm this one only needs to store the location of the microphones. At start up these locations are read from disk and shipped to the GPU memory. Efficient processing is achieved by making use of the addition theorem which states that
P n ( cos γ ) = 4 π 2 n + 1 ∑ m = - n n Y n - m ( Θ ) Y n m ( Θ s ) ( 3 )
where Θ is the spherical coordinate of the audio pixel and Θ s is the location of the s th microphone, γ is the angle between these two locations and P n is the Legendre polynomial of order n. This observation reduces the order n 2 sum in Eq. (2) to an order n sum. The P n are defined by a simple recursive formula that is quickly computed on the GPU for each audio pixel.
The computation of the audio proceeds as follows. First we load the audio signal onto the GPU and perform an inplace FFT. We then segment the audio image into 16 tiles and assign each tile to a multiprocessor of the GPU. Each thread in the execution is responsible for computing the response power of a single pixel in the audio image. The only data that the kernel needs to access is the location of the microphone in order to compute γ and the Fourier coefficients of the 60 microphone signals for all frequencies to be displayed. The weights can then be computed using simple recursive formula for each of the Hankel, Bessel, and Legendre polynomials in Eq. (2).
While performance of the beamformer may be a bit worse, there are several benefits to the on-the-fly approach: 1) frequencies of interest can be changed at runtime with no additional overhead; 2) pixel locations can be changed at runtime with little additional overhead; 3) memory requirements are drastically lower then storing pre-computed weights.
Beamforming: Once a source location of interest is identified, we can use the results of the beamforming to obtain the beamformed sound from that direction, by taking the beamforming results at frequencies of the microphone array effectiveness, and appending to that the frequencies from outside the band from the Fourier transform of the signal from the microphone closest to the direction.
D. Results
Vision guided beamforming: Several authors have in the past proposed vision guided beamforming. The idea is that vision based constraints can help us to not steer the beamformer in directions that are not promising. Often these constraints require the source to lie in some constrained region. One crucial difference here is that the quality of the geometric constraints provided by the epipolar geometry is much stronger. We illustrate in FIG. 4 a this example with a case where a speaker's voice is beamformed in the presence of severe noise using location information from vision. Using a calibrated array-camera combination having a spherical microphone array 400 and a camera 410 and computing hardware (see FIG. 3 ), we applied a standard face detection algorithm to the vision image 420 and then used the epipolar line 430 induced by the mouth region 440 of the vision image 420 to search for the source in the audio image 450 ( FIG. 4 b ).
Image transfer: Noise source identification via acoustic holography seeks to determine the noise location from remote measurements of the acoustic field. Here we add the capacity to visually identify the source via automatic warping of the sound image. This implementation also has application to areas such as gunshot detection, meeting recording (identifying who's talking), etc. We used the method of precomputed weights. An audio image was generated at a rate of 30 frames per second and video was acquired at a rate of 10 frames per second. In order to reduce the effects of incoherent reverberation and spurious peaks we incorporated a temporal filter of the audio image prior to transfer. Once the audio image is generated a second GPU kernel is assigned to generate the image transfer overlay which is then alpha blended with the video frame.
The audio video stereo rig was calibrated according to A. O'Donovan, R. Duraiswami, and J. Neumann, Microphone Arrays as Generalized Cameras for Integrated Audio Visual Processing, Proc. IEEE CVPR, 2007, the entire contents of which are incorporated herein by reference. The audio image transfer is also performed in parallel on the GPU and the corresponding values are then mapped to a texture and displayed over the video frame. To decrease pixilation artifacts the kernel also performs bilinear interpolation. Though the video frames are only acquired at 10 frames per second the over-laid audio image achieves the same frame rate as the audio camera (30 frames per second).
Image transfer example: A person speaks. The spherical array image 500 ( FIG. 5 a ) shows a bright spot 510 at the location corresponding to the mouth. This spot 510 is automatically transferred to the video image 520 ( FIG. 5 b ) (where the spot 530 is much bigger, since the pixel resolution of video is higher), identifying the noise location as the mouth.
II. Microphone Arrays as Generalized Cameras for Integrated Audio Visual Processing
A. MOTIVATION AND PRESENT CONTRIBUTION
In most previous work, the fusion of the audio-visual information occurs at a relatively late stage. In contrast, the present disclosure takes the viewpoint that both cameras and microphone arrays are geometry sensors, and treats the microphone arrays as generalized cameras. Computer-vision inspired algorithms are employed to treat the combined system of arrays and cameras. In particular, the present disclosure considers the geometry introduced by a general microphone array and spherical microphone arrays. The latter show a geometry that is very close to central projection cameras, and the present disclosure shows how standard vision based calibration algorithms can be profitably applied to them. Several experiments are presented herein that demonstrate the usefulness of the considered approach.
Arrays of microphones can be geometrically arranged and the sound captured can be used to extract information about the geometrical location of a source. Interest in this subject was raised by the idea of using a relatively new sensor and an associated beamforming algorithm for audiovisual meeting recordings (see FIGS. 4 a and 4 b ). This array has since been the subject of some research in the audio community. While considering the use of the array to detect and to beamform (isolate) an auditory source in the meeting system, it was observed that this microphone array is a central projection device for far-field sound sources, and can be easily treated as a “camera” when used with more conventional video cameras. Moreover, certain calibration problems associated with the device can be solved using standard approaches in computer vision.
The present disclosure relates to spherical microphone arrays. However, we (referring to the applicants) were naturally led to how other microphone arrays could be included in the framework as generalized cameras, similar to the recent work in vision on generalized cameras, that are imaging devices that do not restrict themselves to the geometric or photometric constraints imposed by the pinhole camera model, including the calibration of such generalized bundles of rays. In the most general case, any camera is simply a directional sensor of varying accuracy.
Microphone arrays that are able to constrain the location of a source can be interpreted as directional sensors. Due to this conceptual similarity between cameras and microphone arrays, it is possible to utilize the vast body of knowledge about how to calibrate cameras (i.e. directional sensors) based on image correspondences (i.e. directional correspondences). Specifically, the fact that spherical arrays of microphones can be approximated as directional sensors which follow a central projection geometry is utilized. Nevertheless, the constraints imposed by the central projection geometry allow the application of proven algorithms developed in the computer vision community as described in the literature to calibrate arbitrary combinations of conventional cameras and spherical microphone arrays.
Below there is a brief review of some relevant work. Next, in section C, there is provided some background material on audio processing, to make the present disclosure self contained, and to establish notation. Section D describes the algorithms developed for working with the spherical array and cameras, and results are described. Section E has conclusions and discusses applications of the teachings according to the present disclosure to other types of microphone arrays.
B. PRIOR WORK
Microphone arrays have long been used in many fields (e.g., to detect underwater noise sources), to record music, and more recently for recording speech and other sound. The latter is of concern here, and there is a vast literature on the area. An introduction to the field may be obtained via a pair of books that are collections of invited papers that cover different aspects of the field (M. S. Brandstein and D. B. Ward (editors), Microphone Arrays Signal Processing Techniques and Applications, Springer-Verlag, Berlin, Germany, 2001; Y. A. Huang and J. Benesty, ed. Audio Signal Processing For Next Generation Multimedia Communication Systems, Kluwer Academic Publishers 2004). Solid spherical microphone arrays were first developed (both theoretically and experimentally) by Meyer and Elko (J. Meyer and G. Elko. “A highly scalable spherical microphone array based on anorthonormal decomposition of the soundfield,” Proceedings IEEE ICASSP, 2:1781-1784, 2002; J. Meyer and G. Elko, “Spherical Microphone Arrays for 3D sound Recording,” Audio Signal Processing For Next Generation Multimedia Communication Systems Ed. Y. A. Huang and J. Benesty, 67-89, Kluwer Academic Publishers 2004) and extended by Li et al. (Z. Li, R. Duraiswami, E. Grassi, and L. S. Davis, “Flexible layout and optimal cancellation of the orthonormality error for spherical microphone arrays,” Proceedings IEEE ICASSP, 4:41-44, 2004; Z. Li and Ramani Duraiswami; “Hemispherical microphone arrays for sound capture and beamforming,” Proceedings IEEE WASPAA, 106-109, 2005).
There are several papers that consider combined audio visual processing. Pointing a pan-tilt-zoom camera at a sound source has been achieved by several authors, while a few employ the knowledge of the location of the sound source obtained from vision to improve the audio processing. Several authors have performed joint audio-visual tracking using various approaches (particle filtering, learning a probabilistic graphical model using low level audio and visual features, finding the pixels that create sound via an efficient formulation of canonical correlation analysis, and built a large efficient industrial system). Modern image processing and computer vision techniques were used to define new features for sound recognition.
One paper describes the development of the joint geometry of an underwater sonar camera system (Shahriar Negahdaripour, “Epipolar Geometry of Opti-Acoustic Stereo Imaging,” IEEE Transactions on Pattern Analysis and Machine Intelligence, 2007). There is a difference however in the methods used in that paper, which relies on active probing of the scene using acoustic pulses, and then images it rather like LADAR, using a time of flight map for the reflected signals. Due to the large error in the 3rd coordinate of their estimates the authors chose to treat the sensor as a 2D sensor, with the two retained image dimensions as range and one angular coordinate. In contrast, the present disclosure discusses microphone arrays whose “image” geometry is similar to that in regular central projection cameras, and do not actively probe the scene but rely on sounds created in the environment. The sensor described herein would be useful in indoor people and industrial noise monitoring situations, while the sensor described by Shahriar Negahdaripour would be useful in underwater imaging.
C. BACKGROUND
C.1. Source Localization and Beamforming
Assume that the acoustic source that produces an acoustic signal y(t) is located at point p and K microphones are located at points q 1 , . . . , q k . The signal s m (t) received at the m th microphone contains delayed versions of the source signal, its convolution with the channel impulse response, and noise (or other sources) and is given by
s m ( t )= r m −1 y ( t−τ m )+ y ( t )å h* m ( q m ,p,t )+ z m ( t ). (4)
where the first term on the right is the direct arriving signal, r m =∥p−q m ∥ is the distance from the source to the m th microphone, c is the sound speed, τ m =r m /c is the delay in the signal reaching the microphone, h* m (q m ,p,t) is the filter that models the reverberant reflections (called the room impulse response, RIR) for the given locations of the source and the m th microphone, star denotes convolution, and z m (t) is the combination of the channel noise, environmental noise, or other sources; it is assumed to be independent at all microphones and uncorrelated with y(t).
In general τ m will not be measurable as the source position is unknown. Knowing the locations of two microphones, m and n respectively, We denote the time difference of arrival (TDOA) of a signal between receivers m and n as τ mn =τ n −τ m . TDOAs are usually obtained using a generalized cross-correlation (GCC) between signal frames (short pieces of the signal of length N) s m and s n acquired at the m th and n th sensors respectively [10]. Let us denote by r mn (τ) the GCC of s n (t) and s m (t) and its Fourier transform by R mn (ω)). Then,
R mn (ω)= W mn (ω) S m (ω) S* n (ω), (5)
where W mn (ω) is a weighting function. Ideally, r mn (τ) (computed as the inverse Fourier transform of R mn (ω)) will have a peak at the true TDOA between sensors m and n (τ mn ). In practice, many factors such as noise, finite sampling rate, interfering sources and reverberation might affect the position and the magnitude of the peaks of the cross correlation, and the choice of the weighting function can improve the robustness of the estimator. The phase transform (PHAT) weighting function was introduced in C. H. Knapp and G. C. Carter, “The generalized correlation method for estimation of time delay”, IEEE Transactions on Acoustics, Speech and Signal Processing, 24:320-327, 1976:
W mn (ω)=| S m (ω) S* n (ω)| −1 . (6)
The PHAT weighting places equal importance on each frequency by dividing the spectrum by its magnitude. It was later shown that it is more robust and reliable in realistic reverberant acoustic conditions than other weighting functions designed to be statistically optimal under specific non-reverberant noise conditions.
Source localization using time delays: The availability of a single time delay between a pair of receivers, places the source on a hyperboloid of revolution of two sheets, with its foci at the two microphones (see FIG. 7 ). In human hearing, time delays between the two ears places the source on this hyperboloid (also mislabeled the “cone of confusion”), and humans have to use other cues to resolve ambiguities. In general purpose arrays, additional microphones can be added, and intersect the hyperboloids formed by delay measurements with each pair. Measurements at three collinear microphones restrict the source to lie on a circle whose center lies on the axis formed by the microphones, while knowing the time delays between 4 non-collinear microphones in principle can provide the exact source location. However, TDOAs are very noisy, and the non-linear intersection algorithms may give poor results with the noisy input data, and various methods to improve the algorithms are still being developed by researchers.
Beamforming: The goal of beamforming is to “steer” a “beam” towards the source of interest and to pick its contents up in preference to any other competing sources or noise. The simplest “delay and sum” beamformer takes a set of TDOAs (which determine where the beamformer is steered) and computes the output SB(t) as
s B ( t ) = 1 K ∑ m = 1 K s m ( t + τ m l ) , ( 7 )
where l is a reference microphone which can be chosen to be the closest microphone to the sound source so that all τ ml are negative and the beamformer is causal. To steer the beamformer, one selects TDOAs corresponding to a known source location. Noise from other directions will add incoherently, and decrease by a factor of K −1 relative to the source signal which adds up coherently, and the beamformed signal is clear. More general beamformers use all the information in the K microphone signal at a frame of length N, may work with a Fourier representation, and may explicitly null out signals from particular locations (usually directions) while enhancing signals from other locations (directions). The weights are then usually computed in a constrained optimization framework.
Beampattern: The pattern formed when the, usually frequency-dependent, weights of a beamformer are plotted as an intensity map versus location are called the beampattern of the beamformer. Since usually beamformers are built for different directions (as opposed to location), for source that are in the “far-field,” the beampattern is a function of two angular variables. Allowing the beampattern to vary with frequency gives greater flexibility, at an increased optimization cost and an increased complexity of implementation.
Localization via Steered Beamforming: One way to perform source localization is to avoid nonlinear inversion, and scan space using a beamformer. For example, if using the delay and sum beamformer the set of time delays {circumflex over (τ)} mn corresponds to different points in the world being checked for the position of a desired acoustic source, and a map of the beamformer power versus position may be plotted. Peaks of this function will indicate the location of the sound source. There are various algorithms to speed up the search.
C.2. Spherical Microphone Arrays
The present disclosure is concerned with solid spherical microphone arrays (as in FIGS. 3 and 4 ) on whose surface several microphones are embedded. In J. Meyer and G. Elko, “A highly scalable spherical microphone array based on anorthonormal decomposition of the soundfield,” Proceedings IEEE ICASSP, 2:1781-1784, 2002, an elegant prescription that provided beamformer weights that would achieve as a beampattern any spherical harmonic function Y n m (θ k ,φ k ) of a particular order n and degree m in a direction (θ k , φ k ) was presented. Here
Y n m ( θ , φ ) = ( - 1 ) m 2 n + 1 4 π ( n - m ) ! ( n + m ) ! P n m ( cos θ ) ⅇ ⅈ m φ , ( 8 )
where n=0, 1, 2, . . . and m=−n, . . . , n, and P n |m| is the associate Legendre function. The maximum order that was achievable by a given array was governed by the number of microphones, S, on the surface of the array, and the availability of spherical quadrature formulae for the points corresponding to the microphone coordinates (θ i ,φ i ), i=1, . . . , S. In Li, R. Duraiswami, E. Grassi, and L. S. Davis, “Flexible layout and optimal cancellation of the orthonormaility error for spherical microphone arrays,” Proceedings IEEE ICASSP, 4:41-44, 2004, the analysis is extended to arbitrarily placed microphones on the sphere.
Since the spherical harmonics form a basis on the surface of the sphere, building the spherical harmonic expansion of a desired beampattern, allowed easy computation of the weights necessary to achieve it. In particular if one desires a beampattern that is a delta function, truncated to the maximum achievable spherical harmonic order p, in a particular direction (θ 0 ,φ 0 ), then the following algorithm can be used
δ ( p ) ( θ - θ 0 , φ - φ 0 ) = 2 π ∑ n = 0 p - 1 ∑ m = - n n Y n m * ( θ 0 , φ 0 ) Y n m ( θ , φ ) , ( 9 )
to compute the weights for any desired look direction. This beampattern is often called the “ideal beampattern,” since it enables picking out a particular source. The beampattern achieved at order 6 is shown in FIG. 3 . A spherical array can be used to localize sound sources by steering it in several directions and looking at peaks in the resulting intensity image formed by the array response in different directions.
The ability of an array to isolate a sound source from a given look direction is often quantified by the directivity index and is given in dB:
DI ( θ 0 , θ s , ka ) = 10 log 10 ( 4 π H ( θ 0 , θ 0 ) 2 ∫ Ω s H ( θ , θ 0 ) 2 ⅆ Ω s ) , ( 10 )
where H(θ,θ 0 ) is the actual beampattern looking at θ 0 =(θ 0 ,φ 0 ) and H(θ 0 ,φ 0 ) is the value in that direction. The DI is the ratio of the gain for the look direction θ 0 to the average gain over all directions. If a spherical microphone array can precisely achieve the regular beampattern of order N as described in Z. Li and Ramani Duraiswami, “Flexible and Optimal Design of Spherical Microphone Arrays for Beamforming,” IEEE Transactions on Audio, Speech and Language Processing, 15:702-714, 2007, its theoretical DI is 20 log 10 (N+1). In practice, the DI index will be slightly lower than the theoretical optimal due to errors in microphone location and signal noise.
Spherical microphone arrays can be considered as central projection cameras. Using the ideal beam pattern of a particular order, and beamforming towards a fixed grid of directions, one can build an intensity map of a sound field in particular directions. Peaks will be observed in those directions where sound sources are present (or the sound field has a peak due to reflection and constructive interference). Since the weights can be pre-computed and a relatively short fixed filters, the process of sound field imaging can proceed quite quickly. When sounds are created by objects that are also visualized using a central projection camera, or are recorded via a second spherical microphone array, an epipolar geometry holds between the camera and the array, or the two arrays. Below experiments which were conducted by us (referring to the applicants) are described which confirm this hypothesis.
D. EXPERIMENTS WITH SPHERICAL ARRAYS AND CAMERAS
A 60-microphone spherical microphone array of radius 10 cm was constructed. A 64 channel signal acquisition interface was built using PCI-bus data acquisition cards that are mounted in the analysis computer and connected to the array, and the associated signal processing apparatus. This array can capture sound to disk and to memory via a Matlab data acquisition interface that can acquire each channel at 40 kHz, so that a Nyquist frequency of 20 kHz is achieved. The same Matlab was equipped with an image-processing toolbox, and camera images were acquired via a USB 2.0 interface on the computer. A 320×240 pixel, 30 frames per second web camera was used. While, the algorithms should be capable of real-time operation, if they were to be programmed in a compiled language and linked via the Matlab mex interface, in the present work this was not done, and previously captured audio and video data were processed subsequently.
Camera and Array Calibration: The camera was calibrated using standard camera calibration algorithms in OpenCV, while the array microphone intensities were calibrated as described in the spherical array literature. We then proceeded with the task of relative calibration of the array 302 ( FIG. 3 ) and the camera 310 . To calibrate this system 300 , we built a wand 100 that has an LED 102 and a small speaker 104 (both about 3 mm×3 mm) collocated at the tip or end 110 of a pencil 112 (see FIG. 2 ). When a button is pressed, the LED 102 lights up and a sound chirp is simultaneously emitted from the speaker 104 . Light and sound are then simultaneously recorded by the camera and microphone array respectively. We can determine the direction of the sound by forming a beam pattern as described above which turns the microphone array into a directional sensor.
In FIG. 6 there is shown an example sample acquisition. Notice the epipolar line 600 passing through the microphone array 302 having a plurality of microphones as the user holds the calibration wand 100 in the camera image 610 .
As one can see the calibration recovered the epipolar geometry between the camera 310 and the array 302 very accurately. The same procedure can also be used to calibrate several (hemi-)spherical microphone arrays since both are equivalent to internally calibrated cameras, and thus also have to conform to the epipolar geometry. FIG. 1 shows how the image ray projects into the spherical array and intersects the peak of the beam pattern.
D.1. One Camera and One Spherical Array
In this case, the camera image and “sound image” are related by the epipolar geometry induced by the orientation and location of the camera and the microphone array respectively. We will assume that the camera is located at the origin of the fiducial coordinate system. For each sound we thus have the direction r mic , which we need to correspond to the projection of the 3D location of the sound source into the camera image p cam .
If we have precalibrated the camera, then we can transform p cam into normalized image coordinates r cam =K −1 p cam where K is the internal calibration matrix of the camera (we disregard the radial distortion parameters). If the camera coordinate system and the microphone coordinate system are related by a rotation matrix R and a translation vector T, then each correspondence is related by the essential matrix E:
0=r mic t Er cam =r mic r [T] x , Rr cam (10)
To compute the essential matrix E and extract T and R, we follow Y. Ma, J. Kosecka, and S. S. Sastry, “Motion recovery from image sequences: Discrete viewpoint vs. differential viewpoint,” Proceedings ECCV, 2:337-353, 1998. We decide among the resulting four solutions by choosing the solution that maximizes the number of positive depths for the microphone array and the camera.
If the camera is not calibrated, then the direction in the microphone and the pixel in the image would be related by the fundamental matrix F:
0==r mic t Fp cam =r mic t [T] x RK −1 p cam (11)
We can solve for F using a multitude of algorithms as described in R. Hartley and A. Zisserman, Multiple View Geometry in Computer Vision. Cambridge University Press, Cambridge, UK, 2000, we chose to use a linear algorithm for which we need at least 8 correspondences, followed by non-linear minimization that takes into account the different noise characteristics of the image and microphone array “image” formation process.
The epipolar geometry induces by the essential or fundamental matrices, allows us interchangeably to transfer a point from an image to a 1-D space in the microphone array directional space defined by r mic (Fp cam )=0, or a directional measurement from the microphone array to an epipolar line defined by the equation p cam (F t r mic )=0.
D.2. N Cameras and One Spherical Array
Multicamera systems with overlapping fields of view, attached to microphone arrays are now becoming popular to record meetings. The location of speakers in an integrated mosaic image is a problem of interest in such systems. For multiple cameras, we only need to know the calibration information from two cameras, to use a method similar to the one described in J. P. Barreto and K. Daniilidis, “Wide area multiple camera calibration and estimation of radial distortion,” OMNIVIS 2004—Workshop on Omnidirectional Vision and Camera Networks, Prague, Czech Republic, 2004 to calibrate the remaining cameras. Since the microphone is already intrinsically calibrated, we only need to determine the internal calibration parameters for a single camera, compute the calibration between the spherical array and the calibrated camera, reconstruct the correspondences in space, and then use the 3D points to calibrate the system of cameras as described by Barreto et al. The results could then be further improved using bundle-adjustment as described in B. Triggs, P. F. McLauchlan, R. I. Hartley, and A. W. Fitzgibbon, “Bundle adjustment—a modern synthesis,” B. Triggs, A. Zisserman, and R. Szeliski, editors, Vision Algorithms: Theory and Practice, LNCS:1883. Springer-Verlag, 298-373, 1999.
Similarly, one could also use two (hemi-)-spherical microphone arrays, and an arbitrary number of uncalibrated cameras. First, we can calibrate the two microphone arrays using the epipolar constraint as described earlier. Then we can reconstruct the calibration points in space using the computed calibration. Due to the omnidirectional nature of the microphone array, we can be sure that all the calibration points are “visible” to both microphone arrays and thus can be reconstructed. We can now use the reconstructed structure to compute the projection matrices for each of the cameras. We can now use all the cameras and the microphone arrays together with the reconstructed points to initialize a bundle-adjustment procedure.
D.3. Example Application: Speaker Tracking and Noise Suppression
Using the epipolar geometry between a spherical microphone array and a camera in a meeting room scenario. The microphone array was used to detect the direction of sound sources in the scene, in this case the speaker in the room, and then the epipolar geometry, to project the epipolar line into the camera image. We can now employ a simple face detector along the vicinity of the epipolar line to located the exact position of the speaker in the image. In our system we use a face detector based on Haar wavelets as implemented in OpenCV (see R. Lienhart, L. Liang, and A. Kuranov, “A detector tree of boosted classifiers for real-time object detection and tracking,” Proceedings IEEE ICME, 2:277-280, 2003). This allows us then to accurately zoom into the image and display a detailed view of the speaker. Since the search space is greatly reduced, the localization can be done extremely fast, and also switching from one speaker to the next can be done instantly.
In FIG. 4 b there is shown the sound image where the peak indicates the mouth region, this peak is located and using the epipolar geometry projected into the image resulting in a epipolar line. We now search along this line for the most likely face position, triangulate the position in space and then set our zoom level accordingly.
The knowledge of the face location can help improve the recorded audio as well. We will now present an example in which an extremely loud music interference was played from a location to the left of the subject, and below him, after the face was initially detected as above. Once the face rectangle was extracted, a template match was used to detect the mouth region. The epipolar line from the image passing through this region was then constructed on the soundfield image. The lower panel of FIG. 4 shows the sound field image generated, where the distracter can be seen to be extremely bright compared to the source. The location corresponding to the mouth was passed to the beamforming algorithms, and the sound from this location was extracted. A further refinement of the algorithm could be to throw an explicit null at the location of the other source.
E. CONCLUSIONS AND OTHER CONSIDERATIONS
In accordance with the present disclosure, there is presented a novel approach that considers the geometrical restrictions introduced by microphone array measurements, and those introduced by cameras in a joint framework, which allows localization and calibration problems to be more efficiently solved. The theoretical sections above consider the general situation, and then the case of the spherical array is described in detail. The ideas were validated experimentally.
We believe that the approach considered here, of imaging the sound field using a spherical array(s) and the actual scene using camera(s) will have many applications, and several vision algorithms can be brought to bear. For example, when multiple cameras will be used with multiple spherical arrays, we can build a joint mosaic of the image and the soundfield image. Such an analysis can easily indicate locations where sounds are being created, their intensity and frequencies. This may have applications in industrial monitoring and surveillance.
The audio camera in accordance with the present disclosure and its accompanying software and processing circuitry can be incorporated or provided to computing devices having regular microphone arrays. The computing devices include handheld devices (mobile phones and personal digital assistants (PDAs)), and personal computers. The microphone arrays provided to these computing devices often include cameras in them or cameras connected to them as well. In such computing devices, these microphones are used to perform echo and noise cancellation. Other locations where such arrays may be found include at the corners of screens, and in the base of video-conferencing systems. Using time delays, one can restrict the audio source to lie on a hyperboloid of revolution, or when several microphones are present, at their intersection. If the processing of the camera image is performed in a joint framework, then the location of the audio source can be quickly performed in accordance with the present disclosure, as is indicated in FIG. 7 .
It would also be useful to consider some specialized systems where the camera and microphones are placed in a particular geometry. For example, the human head can be considered to contain two cameras with two microphones on a rigid sphere. A joint analysis of the ability of this system to localize sound creating objects located at different points in space using both audio and visual processing means could be of broad interest.
The contents of all references cited above are incorporated herein by reference in their entirety.
The described embodiments of the present disclosure are intended to be illustrative rather than restrictive, and are not intended to represent every embodiment of the present disclosure. Various modifications and variations can be made without departing from the spirit or scope of the disclosure as set forth in the following claims both literally and in equivalents recognized in law. | Spherical microphone arrays provide an ability to compute the acoustical intensity corresponding to different spatial directions in a given frame of audio data. These intensities may be exhibited as an image and these images are generated at a high frame rate to achieve a video image if the data capture and intensity computations can be performed sufficiently quickly, thereby creating a frame-rate audio camera. A description is provided herein regarding how such a camera is built and the processing done sufficiently quickly using graphics processors. The joint processing of and captured frame-rate audio and video images enables applications such as visual identification of noise sources, beamforming and noise-suppression in video conferencing and others, by accounting for the spatial differences in the location of the audio and the video cameras. Based on the recognition that the spherical array can be viewed as a central projection camera, such joint analysis can be performed. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is broadly concerned with improved clamps used for clamping workpieces to fixtures, and especially so-called swing clamps which simultaneously move in axial and rotational directions to allow easy placement and removal of workpieces. More particularly, the invention is concerned with such clamps including a shiftable piston equipped with a workpiece-engaging outer head, where piston movement is guided and controlled via an internal cam assembly made up of a specially configured cam track and cam follower ball arrangement. Such cam assemblies are provided with spring units serving to bias and self-center the follower balls into the associated tracks, providing many operational advantages including increased clamp speeds and reduction in clamp wear and damage.
2. Description of the Prior Art
Hydraulic clamps are commonly used in manufacturing operations to hold and clamp workpieces to stationary fixtures, so that the workpieces may be machined or otherwise worked upon. Typical hydraulic clamps include a cylinder body adapted for attachment to a fixture and a piston telescopically received within the cylinder body for movement between an retracted, clamping position and an extended, release position. A clamping head is attached to the distal end of the piston for holding and clamping workpieces to the fixture when the piston is in its retracted, clamping position. Commonly, several such clamps are mounted to a single fixture so that a workpiece may be securely held at several locations while it is being worked upon.
Swing clamps are hydraulic clamps that include swinging mechanisms serving to swing the clamping heads away from the workpiece when the pistons are extended to their release positions. Swing clamps make it easier to load and unload workpieces from fixtures, especially in confined spaces.
One type of swinging mechanism used in swing clamps is a cam assembly having a curved cam track or groove formed in either the piston or the cylinder body and a corresponding cam follower ball attached to the other of the piston and cylinder body. The follower ball moves along the curved cam track when the piston is shifted which serves to rotate the piston and clamping head as described.
Conventional cam assemblies in swing clamps are subject to premature wear over time that interferes with the swinging operation of the clamps. Specifically, when the cam follower ball moves in the track, it is subject to circumferential forces tending to push the ball to the sides of the groove. Over time, the cam ball wears down the edges of the track and creates dimples along the length thereof. The dimples and worn regions of the cam track often catch the ball during piston movement, creating a “choppy” clamp operation. When a clamp is used in severe conditions, its cam ball may completely wear down the edges of the track, causing the ball to completely roll out of the groove.
Excessive wear on the cam grooves of a clamp can be a serious problem. In many clamping operations, it is important for the clamping head to swing to a precise location away from the workpiece, and then return to the same exact starting position when the clamp is shifted to its clamping position. When the cam groove on a clamp become worn, the swing clamp can no longer achieve this precise and repeatable swinging movement. Thus, the entire swing clamp must be replaced, even though the remaining parts of the clamp are in good condition.
U.S. Pat. No. 5,820,118 describes a decided improvement in the swing clamp art. In this patent, uses may of a special cam track design which inhibits the cam follower ball from prematurely wearing the cam track edges. Specifically, the cam track described in the '118 patent includes a central arcuate region and a pair of substantially planar side faces extending tangentially from the central arcuate region. This construction forces the cam follower ball to be more centrally seated within the cam track without pushing up against the edges of the cam track.
SUMMARY OF THE INVENTION
The present invention is directed to further improvements in shiftable clamps, and particularly the swing clamps described above. Broadly speaking, the clamps of the invention include a hollow body for attachment to a fixture, with the body presenting an interior wall. A piston is telescopically received within the body for movement between clamping and released positions. A cam assembly is used for guiding and controlling relative movement between the piston and body, with the cam assembly having a cam track formed in one of the interior wall of the body and the outer wall of the piston, and a cam follower received within the cam track and attached to the other of the interior wall of the body and the outer wall of the piston. The specific improvement of the invention involves the use of a spring for biasing the ball toward the cam track. It has been discovered that use of such a spring affords a number of operational advantages, including improved clamping speeds and reduced wear.
In preferred forms, the biasing spring forms part of a spring unit having a follower-engaging component with a spring remote from the follower, thereby biasing the follower through the component. The spring may be of any desired construction, for example a bellville spring or a small coil spring. In the usual case, the cam follower is a ball and the spring unit is mounted within a recess on the clamp body; the component has an arcuate face in direct engagement with the ball, whereas the spring is within the recess.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a fixture equipped with a plurality of clamps in accordance with the invention, shown with the clamps engaging and clamping a workpiece to the fixture;
FIG. 2 is a vertical sectional view of a preferred clamp of the invention;
FIG. 3 is a fragmentary sectional view taken along line 3 — 3 of FIG. 2 and illustrating the construction of a bellville spring assembly used for biasing the cam follower ball into the cam groove of the piston;
FIG. 4 is a sectional view similar to that of FIG. 3 , but depicting the use of a coil spring assembly; and
FIG. 5 is a sectional view similar to that of FIG. 3 , but illustrating the use of a removable sleeve forming a part of the overall clamp body.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawings, FIG. 1 illustrates a fixture 10 equipped with a plurality of clamps 12 adapted to releasably hold a workpiece 14 in position on the fixture 10 . As illustrated, the exemplary fixture 10 includes a base 16 supporting an upright mounting box 18 , the latter having a workpiece-supporting wall 20 . The clamps 12 are threadably secured within threaded bores provided in wall 20 as will be described. Briefly, in operation the clamps 20 are selectively movable between the clamping position depicted in FIG. 1 to thus hold workpiece 14 in place, and a retracted, swung-away position allowing removal of the workpiece 14 after it is worked upon, and positioning of another workpiece 14 in its place.
In more detail, the body 22 has an elongated segment 30 presenting an inner wall 32 as well as a threaded exterior wall 34 . Each clamp 12 includes an elongated, tubular body 22 together with a piston 24 telescopically received within the body 22 , and a cam assembly broadly referred to by the numeral 26 for guiding and controlling relative movement between piston 24 and body 22 . As shown, each piston 24 supports an outer clamping head 28 adapted to engage workpiece 14 which mates with the clamp bores in wall 20 . A recess 33 is formed in segment 30 and extends outwardly from wall 32 as shown. The base of segment 30 is internally threaded at 36 and receives a correspondingly threaded cup-shaped plug 38 . The body 22 also has a somewhat enlarged outer portion 40 remote from plug 38 which has an inner wall 42 concentric with wall 32 , thus defining an annular stop shoulder 44 . The portion 40 has an inner sealing ring 46 and retainer 48 . Finally, the portion 40 includes a hydraulic fluid port 50 which communicates with passageway 52 .
Piston 24 includes a base 54 equipped with a sealing ring 56 engaging surface 32 , a guide section 58 presenting an outer surface 59 and extending upwardly from base 54 , and a rod 60 extending beyond portion 40 . A relatively large translation spring 62 is seated within plug 38 and engages the underside of base 54 as shown. As illustrated in FIG. 2 , the section 58 has a slightly reduced diameter as compared with base 54 but has a greater diameter than rod 60 .
The assembly 26 includes a plurality (here three, two of which are shown) of circumferentially spaced apart cam tracks 64 a , 64 b . . . formed in the outer surface 59 of piston section 58 . The preferred tracks 64 are configured for guiding the piston along different paths during piston movement. For example, the track 64 a is configured so as to cause piston 24 (and thereby head 28 ) to swing during retraction and extension of the piston, whereas track 64 b is essentially rectilinear so that the piston 22 merely reciprocates without any swinging movement. In addition, the assembly 26 includes a cam follower ball 66 which is secured to body segment 30 adjacent inner surface 32 ; the ball 66 is seated within one of the tracks 64 as will be readily apparent from a consideration of FIGS. 2 and 3 .
One possible geometry of the cam tracks 64 and the follower ball 66 is described in detail in the referenced U.S. Pat. No. 5,820,118, incorporated herein by reference. Briefly however, the cam follower has an outer peripheral surface presenting a radius of curvature R, whereas the cam track includes a central arcuate region 68 having a radius of curvature R′ substantially equal to the radius R. Moreover, the track 64 has a pair of opposed, substantially planar side face 70 , 72 extending from arcuate region 68 , with the side faces 70 , 72 each having a proximal end converging into the region 68 and an opposed distal end that diverges from the region 68 , with the distal ends also diverging from one another. In other embodiments, the cam track has a geometry which matches that of the cam follower. Specifically, the cam track has essentially the same radius of curvature as the corresponding cam follower.
The preferred assembly 26 also has a spring unit 74 seated within the recess 33 which biases the ball 68 toward and into the adjacent track 64 . Referring to FIG. 3 , the unit 74 includes a force-transmitting annular component 76 having an arcuate face 78 engaging ball 66 , and an opposite, substantially planar face 80 . In the depicted embodiment, a bellville spring 82 is disposed between the inner surface of recess 33 and face 80 , and thereby biases ball 68 .
FIG. 4 illustrates a somewhat modified embodiment wherein a resilient elastomeric plug 84 is used to house a spring unit 86 . In this case a through-bore 88 is provided in the segment 30 and is configured to receive plug 84 . The latter includes an annular wall 90 defining a recess 92 . The unit 86 is similar to unit 74 in that it includes a component 94 identical with component 76 . However, in this case a coil spring 96 is seated within recess 92 and engages the planar face of component 94 .
FIG. 5 illustrates a still further embodiment of the invention wherein the body 22 a is formed using an outer tubular wall 98 together with an inner, replaceable sleeve 100 the latter being equipped with a recess 33 a . The recess 33 a houses the identical spring unit 74 described with reference to FIG. 3 . Use of a replaceable sleeve 100 permits ready repair of a clamp 12 in the field.
Each clamp 28 is in the form of an elongated element 101 presenting a workpiece-engaging underside 102 . A screw 104 is employed to attach each element 101 to the outer end of each rod 60 .
After the clamps 12 are installed on wall 20 of fixture 10 by threading the segments 30 thereof into the pre-drilled holes in wall 20 , the clamps may be used for holding workpieces 14 in place. Turning to FIG. 2 , it will be seen that the spring 62 of each clamp 12 serves to bias the corresponding piston 22 to its extended position where, in the illustrated embodiment, the head 28 is swung laterally to a clearing position allowing removal and replacement of a workpiece 14 onto the fixture. When this is done, the individual clamps are actuated by application of hydraulic fluid through the ports 50 , whereupon the pressurized fluid passes downwardly between the walls 32 , 59 and engages base 54 , thereby moving the piston downwardly against the bias of spring 62 . During such movement of the pistons, the heads 28 are swung laterally owing to the configuration of cam tracks 64 a and follower balls 66 until the heads come into proper holding relationship with the workpiece 14 . After operations on workpiece 14 are completed, the pressurized hydraulic fluid is relieved, thereby permitting the springs 62 to return the individual pistons 22 and clamps 28 to their extended and swung-away positions.
The provision of spring units in accordance with the invention provides a number of significant operational advantages. First, the spring units insure that the biased cam follower balls 66 self-center in the associated tracks 64 a . Thus, the balls 66 are constrained in both vertical and horizontal planes, providing a stationary point for the cam tracks 64 a for proper guidance through both axial and rotary motion. In essence, the components 76 act as bearing races allowing the balls 66 to rotate as the pistons move through their strokes, while at the same time biasing the balls 66 so that they remain fully engaged in the tracks 64 a.
This construction reduces the static and dynamic frictional forces generated between the balls 66 and the track 64 a , especially during starting movement of the pistons, allowing smoother tracking and essentially eliminating the tendency of the balls to drag within the tracks, rather than to rotate. The spring units give an even load distribution and, owing to the self-centering action of the spring units, the balls 66 are inhibited from riding up on the edge of the tracks. At the same time, the design allows a degree of ball float within the tracks to compensate for manufacturing and operational variations. It has been found that cam damage during inadvertent arm contact, a frequent problem in the art, is reduced with the present invention. Consequently, higher clamp speeds are possible as compared with current designs, while at the same time eliminating the wear and operational problems commonly encountered with conventional clamps.
Although not shown in detail, it will be appreciated that the clamps of the invention may assume a variety of different configurations. For example, while in the illustrated embodiment the hydraulic clamp is single acting, making use of the translation spring 62 , the invention is not so limited. Thus, it is well within the skill of the art to employ a double acting hydraulic design wherein pressurized hydraulic fluid is used to move the piston 22 in both directions. Additionally, while a rotatable cam follower ball is preferred, other follower designs could be employed. | An improved shiftable clamp ( 12 ) adapted for connection to a fixture ( 10 ) is provided, wherein the clamp ( 12 ) is selectively operable to engage and hold a workpiece ( 14 ) to the fixture ( 10 ). The clamp ( 12 ) includes a tubular body ( 22 ) and a piston ( 24 ) telescopically received within the body ( 22 ). Movement of the piston ( 24 ) is guided and controlled by way of a cam assembly ( 26 ) including a cam track ( 64 ) formed in the piston ( 24 ) and an associated cam track follower ball ( 66 ) mounted on the body ( 22 ). A spring unit ( 74 ) is also provided on the body ( 22 ) and includes a spring ( 82, 96 ) serving to self-center and bias the ball ( 66 ) into the track ( 64 ). This insures that the ball ( 66 ) smoothly rotates during movement of piston ( 22 ) and reduces wear and premature clamp failure. | 1 |
TECHNICAL FIELD
The invention relates to a compound with novel branching alkyl chains and a method for preparing the same, in particularly, relates to a class of organic electronic material with branching alkyl chains and a method for preparing the same. The invention belongs to the field of organic functional material and the field of organic electronics.
BACKGROUND
The structure of an organic conjugated molecule comprises a conjugated system consisting of delocalized π electrons, thereby presenting special optical, electric and magnetic properties, etc. which catches a wide attention of scientists and has become the focus of studies of the last 20 years. Synthesis based on organic conjugated molecules and functionalization and instrumentalization studies involve many kinds of disciplines such as chemistry, physics, electronics, material sciences, etc. They are multidisciplinary frontiers, filled with vigor and opportunities, and are among one of the important directions of future development of chemistry.
Due to their characteristics of lightness, thinness and flexibility, readiness for modification, etc., organic conjugated molecules have broad prospects of application in the field of photoelectric material. A series of remarkable results have already been obtained, especially in the fields of organic solar cell (OPV), organic light emitting diode (OLED) and organic field effect transistor (OFET), etc. Furthermore, since the organic field effect transistors have the characteristics of readiness for processing, low cost, capacity of large scale flexible preparation, readiness for integration, etc., present obvious advantages in studies in the fields of electronic paper, electronic label, active matrix addressing, sensor and storage, etc., and are considered as having great market potentials.
The organic field effect transistor is an active device regulating the electric circuit in an organic semiconductor by electric field. Its major device structure comprises the 4 following classes: (1) bottom gate bottom contact (BG/BC); (2) top gate bottom contact (TG/BC); (3) bottom gate top contact (BG/TC); and (4) top gate top contact (TG/TC) (Di, C. A.; Liu, Y. Q.; Yu, G.; Zhu, D. B. Acc. Chem. Res., 2009, 42, 1573). The organic field effect transistor consists essentially of electrodes, a dielectric layer, and an organic semiconductor layer, etc. It is essentially a capacitor carrying mobile charges. By applying a voltage between the gate electrode and the source electrode/drain electrode, charges will be induced at the interface between the semiconductor layer and the dielectric layer. When a small voltage is applied between the two electrodes, i.e., the source electrode and the drain electrode, an electric current is formed in the channel. Therefore, the magnitude of the induced charge at the interface can be controlled by adjusting the magnitude of the gate electrode voltage to achieve the on/off of the device, and the amplification of the signal is achieved by controlling the magnitude of the electric current by the voltage between the source electrode and the drain electrode.
The core of the organic field effect transistor is the organic semiconductor layer. The organic semiconductor layer can be classified into p type materials (transporting holes) and n type materials (transporting electrons) based on the difference of the carrier transported in the material; and it can also be classified into organic small molecular materials and organic conjugated polymer materials based on the difference of the type of the organic conjugated molecules. The organic conjugated polymer has been highly regarded because it enables the preparation of the device at a large scale with low cost by solution processing.
The studies on the p type polymer semiconductor materials were initially concentrated on polythiophene systems. The mobility of a sterically regular poly(3-hexylthiophene) (P3HT) can reach 0.05-0.2 cm 2 V −1 s −1 (Sirringhaus, H.; Brown, P. J.; Friend, R. H.; Nielsen, M. M.; Bechgaard, K.; Langeveld-Voss, B. M. W.; Spiering, A. J. H.; Janssen, R. A. J.; Meijer, E. W.; Herwig. P.; de Leeuw, D. M. Nature, 1999, 401, 685). Thereafter, more molecular construction units entered the radar screen of the researchers. These new structures conferred new vigor into this research area. For example, a mobility of 0.94 cm 2 V −1 s −1 was obtained for an organic conjugated polymer based on diketo-pyrrolo-pyrrole (DPP) in 2010 (Li, Y.; Singh, S. P.; Sonar, P. Adv. Mater., 2010, 22, 4862). In 2011, Bronstein reported that a mobility up to 1.94 cm 2 V −1 s −1 was obtained for a DPP-based polymer by different way of connection of the same construction blocks (Bronstein, H.; Chen, Z.; Ashraf, R. S.; Zhang, W.; Du, J.; Durrant, J. R.; Tuladhar, P. S.; Song, K.; Watkins, S. E.; Geerts, Y.; Wienk, M. M.; Janssen, R. A. J.; Anthopoulos, T.; Sirringhaus, H.; Heeney, M.; McCulloch, I. J. Am. Chem. Soc. 2011, 133, 3272). A compound obtained by the copolymerization of DPP and thiophene presented a mobility of 0.97 cm 2 V −1 s −1 . By a structural modification that used biselenophene to replace bithiophene, a mobility of up to 1.5 cm 2 V −1 s −1 was obtained (Ha, J. S., Kim, K. H., Choi, D. H. J. Am. Chem. Soc. 2011, 133, 10364). Isoindigo type molecules are a family of molecules of significance in addition to DPP. In 2011, we reported that a mobility of 0.79 cm 2 V −1 s −1 and a device stability under high humidity up to 3 months were obtained for a polymer based on isoindigo structures (Lei, T.; Cao, Y.; Fan, Y.; Liu, C. J.; Yuan, S. C.; Pei, J. J. Am. Chem. Soc. 2011, 133, 6099).
In contrast, the development of n type polymer semiconductors is relatively slow. Among them, Facchetti and Marks reported that an electron mobility of 0.01 cm 2 V −1 s −1 was obtained for a polymer based on thiophene and fluorobenzene (Letizia, J. A.; Facchetti, A.; Stern, C. L.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 13476). Zhan et al. reported that a copolymer based on perylene diimide and dithienothiophene exhibited a good field effect performance and its electron mobility can reach 0.013 cm 2 V −1 s −1 (Zhan, X.; Tan, Z.; Domercq, B.; An, Z.; Zhang, X.; Barlow, S.; Li. Y.; Zhu, D.; Kippelen, B.; Marder, S. R. J. Am. Chem. Soc. 2007, 129, 7246). Moreover, a naphthalenedicarboximide based polymer reported by Facchetti in 2009 exhibited an electron mobility up to 0.85 cm 2 V −1 s −1 (Chen, Z.; Zheng, Y.; Yan, H.; Facchetti, A. J. Am. Chem. Soc. 2009, 131, 8).
Compared to the traditional silicon solar cells, the organic solar cells have the advantages of low cost, light weight, simple processing, readiness for large scale preparation and readiness for preparing flexible devices, etc. The structure of a device of an organic heterojunction solar cell is primarily classified into two types: one is the forward cell and the other is the reverse cell. The forward cell consists of an anode (generally ITO glass), a hole transport layer (generally PEDOT:PSS), active layer (composed of organic molecular such as organic conjugated polymers and fullerene derivatives, etc.), an electron transport layer, and a cathode (such as aluminum electrode). The reverse cell consists of a cathode (generally ITO glass), an electron transport layer (generally oxide semiconductors such as zinc oxide, etc.), an active layer (composed of organic molecular such as organic conjugated polymers and fullerene derivatives, etc.), an electron transport layer (generally semiconductors such as molybdenum trioxide, etc.), and an anode (such as silver electrode). The active layer is obtained by blending the two materials, i.e., the donor and the acceptor, and solution processing or evaporation them, in which the organic conjugated polymer can serve as both the donor and the acceptor. In an ideal bulk heterojunction structure, the donor and the acceptor form an alternating co-continuous phase, which results in a microphase separation at a scale of tens of nanometers which not only can separate the excitons generated by optical excitation with high efficiency, but also can effectively transport the carriers after the exciton separation to the electrodes to generate the electric current (J. Peet, A. J. Heeger, G. C. Bazan, Acc. Chem. Res. 2009, 42, 1700).
In recent years, studies on the organic bulk heterojunction solar cells based on the solution processing of polymers have achieved remarkable results. In 2007, Prof Heeger et al. increased the power conversion efficiency of PCDTBT from 2.8% to 5.5% by controlling the morphology of the active layer with additives (J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, G. C. Bazan, Nat. Mater. 2007, 6, 497), and in the same year, a laminated device was prepared which obtained an power conversion efficiency of 6.5% (J. Y. Kim, K. Lee, N. E. Coates, D. Moses, T-Q Nguyen, M. Dante, A. L. Heeger, Science 2007, 317, 222). Yu group of University of Chicago and Yang group of University of California at Los Angeles reported a series of polymers based on thienothiophene and benzodithiophene structures and results of more than 5% power conversion efficiency were obtained (Y. Liang, L. Yu, Acc. Chem. Res. 2010, 43, 1227). Moreover, for the first time a polymer bulk heterojuction solar cell with a power conversion efficiency of more than 7% was reported, in which PTB7 achieved a power conversion efficiency up to 7.4% (Y. Liang, Z. Xu, J. Xia, S-T. Tsai, Y. Wu, G. Li, C. Ray, L, Yu, Adv. Mater. 2010, 22, E135). Cao group increased the power conversion efficiency of PECz-DTQx from 4% to 6.07% using PFN modified electrodes, and recently increased the efficiency of a bulk heterojunction solar cell with an inverted structure to 8.37% which passed the certification by National Center of Supervision and Inspection on Solar Photovoltatic Products Quality (Z. He, C. Zhang, X. Huang, W-Y. Wong, H. Wu, L. Chen, S. Su, Y. Cao, Adv. Mater. 2011, 23, 4636), and achieved the best results reported by current publications. Studies show that the efficiency of solar cells has close correlation to the mobility rate of polymers. Generally, the higher the mobility of the polymer, the higher of the efficiency of the solar cell (Chen, J.; Cao, Y. Acc. Chem. Res., 2009, 42, 1709). Therefore, increasing the mobility of the polymer has great significance on the studies on solar cells.
Organic conjugated polymers are a class of polymers obtained by polymerization of covalent bonds through conjugation from aromatic compounds. In order to ensure their good solubility and solution manufacturability, at least one solubilizing group needs to be introduced into at least one aromatic structure to increase their solubility. For example, the organic conjugated polymer as shown in the following formula:
wherein Ar 1 and Ar 2 are fragments of aromatic compounds, respectively; R 1 and R 2 are solubilizing groups introduced into the aromatic core Ar 1 , generally a group such as alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl, alkynyl, etc.; and n is the number of the repeating unit of the polymer, i.e., polymerization degree.
In primary studies (Lei, T.; Cao, Y; Zhou, X.; Peng, Y; Bian, J.; Pei, J. Chem. Mater 2012, 24, 1762.), we found that if a solubilizing group (such as an alkyl chain) is distributed in every one of the polymer units (as shown in FIG. 1( a )), it will affect the π-π stacking of the polymerization, thereby greatly affecting the mobility of the carriers in the polymer. This is because the van der Waals' radius between alkyl chains is 3.6-3.8 Å, while the distance of the π-π interaction is 3.4 Å (see the circle in FIG. 1( a ) which indicates the repulsive effect of the alkyl chain against the aromatic group). As to this, we moved this alkyl chain from the smaller aromatic core Ar 2 to the larger aromatic core Ar 1 , thereby increasing the mobility. On the other hand, traditionally a 2-branching alkyl chain (obtainable from Guerbet alcohol) is used as the solubilizing group (such as FIG. 1( b )) to avoid affecting the π-π stacking so as to achieve high mobility (Li, Y. Acc. Chem. Res., 2012, 45, 723; Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem. Rev., 2012, 112, 2208; Beaujuge, P. M.; Fréchet J. M. J. J. Am. Chem. Soc. 2011, 133, 20009; Wen, Y. Liu, Y. Adv. Mater 2010, 22, 1331; Chen, J.; Cao, Y. Acc. Chem. Res., 2009, 42, 1709). The purpose of the design is to ensure the π-π stacking while ensuring the solubility of the polymer.
SUMMARY
In view of the research efforts of the current polymer field effect transistor material and the low mobility of the polymers in the solar cell material researches, the object of the application is to provide compounds containing a type of novel branching alkyl chains, and apply them to the preparation of organic conjugated molecules, especially organic conjugated polymers. This novel branching alkyl chain ensures the solubility of the polymer while greatly increasing the mobility of the polymer material. This result has great significance on the polymer field effect transistor. Meanwhile, this result can also be used for small molecular field effect transistor materials and not limited to polymer field effect transistors. Because of the important status of the mobility of carriers in organic electronics, compounds and polymers containing these novel branching alkyl chains can also be applied to organic solar cell materials, organic light emitting diode materials, and organic field effect transistor materials, etc.
In the first aspect of the invention, a compound containing a branching alkyl chain having the general formula as shown in the following Formula (I) is provided:
The aforementioned structure is different from a Guerbet alcohol (m=1). In the structure of Formula (I), m is an integer more than 1; R can be various substituents, such as halogen atoms (F, Cl, Br, I), hydroxyl, amino, trifluoromethanesulfonate group (MsO), p-toluenesulfonate group (TsO), azide group (N 3 ), cyano, alkenyl, alkynyl, alkoxy, etc.; R 3 and R 4 are the same or different, independently selected from alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl and alkynyl; R 5 is hydrogen, hydroxyl, alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl or alkynyl.
In Formula (I), m can, for example, be an integer of 2˜18, an integer of 2˜10, an integer of 3˜18, an integer of 3˜10, an integer of 3˜5, or an integer of 3˜4.
As a substituent of R, the alkenyl can, for example, be C2-C6 alkenyl. C2-C4 alkenyl, or ethenyl.
As a substituent of R, the alkynyl can, for example, be C2-C6 alkynyl, C2-C4 alkynyl, or ethynyl.
As a substituent of R, the alkoxy can, for example, be C1-C36 linear or branching alkoxy, or C1-C18 linear or branching alkoxy.
As a substituent of R 3 , R 4 and R 5 , the alkyl can, for example, be C1-C36 linear or branching alkyl, or C1-C18 linear or branching alkyl.
As a substituent of R 3 , R 4 and R 5 , the halogen substituted alkyl can, for example, be C1-C36 linear or branching halogen substituted alkyl, or C1-C18 linear or branching halogen substituted alkyl.
As a substituent of R 3 , R 4 and R 5 , the alkoxy can for example, be C1-C36 linear or branching alkoxy, or C1-C18 linear or branching alkoxy.
As a substituent of R 3 , R 4 and R 5 , the halogen substituted alkoxy can, for example, be C1-C36 linear or branching halogen substituted alkoxy, or C1-C18 linear or branching halogen substituted alkoxy.
As a substituent of R 3 , R 4 and R 5 , the alkenyl can, for example, be C2-C18 alkenyl, C2-C10 alkenyl, or C2-C6 alkenyl.
As a substituent of R 3 , R 4 and R 5 , the alkynyl can, for example, be C2-C18 alkynyl, C2-C10 alkynyl, or C2-C6 alkynyl.
Several specific examples of the aforementioned branching alkyl chains are given below.
When R is hydroxyl, m=2, R 3 and R 4 are 10 carbon-atom alkyls, R 5 is a hydrogen atom, the specific structure is as follows:
When R is halogen atom (such as I), m=2, R 3 and R 4 are 10 carbon-atom alkyls, R 5 is a hydrogen atom, the specific structure is as follows:
When R is hydroxyl, m=3, R 3 and R 4 are 14 carbon-atom alkyls, R 5 is a hydrogen atom, the specific structure is as follows:
When R is hydroxyl, m=3, R 3 and R 4 are 18 carbon-atom alkyls, R 5 is a hydrogen atom, the specific structure is as follows:
When R is amino, m=2, R 3 and R 4 are 10 carbon-atom alkyls, R 5 is a hydrogen atom, the specific structure is as follows:
The procedure for preparing the compounds containing branching alkyl chains as shown in Formula (I) is as follows:
(1) Starting from the diol as shown in Formula (a), protection by a protecting group (sometimes is abbreviated as PG) is conducted:
In this step, the protecting group can be selected from benzyl (Bn), various silicon protecting groups (such as trimethylsilyl (TMS), triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldimethylsilyl (TBDMS), t-butyldiphenylsilyl (TBDPS), etc.), methoxymethyl protecting group (MOM), tetrahydropyran protecting group (THP), p-methoxyphenyl protecting group (PMB), etc., and the reaction is as follows:
(2) The diol with one terminus protected (Formula (b) compound) is oxidized to obtain the carboxylic acid as shown in Formula (c). This oxidation can be selected from various reactions that oxidize alcohols to carboxylic acids, such as Jones oxidation (CrO 3 —H 2 SO 4 ) reaction, or performing oxidation step by step (first oxidized into an aldehyde and then oxidized into a carboxylic acid), etc.
(3) The carboxylic acid as shown in Formula (c) is subject to functional group transformation and nucleophilic substitution to introduce the R 3 and R 4 groups. Either of the following two methods can be selected:
(3a) The carboxylic acid is reacted with an alcohol (R′OH) and converted into an ester. This esterification can use various conditions, including esterification under various acidic or alkaline conditions. Subsequently, a nucleophilic substitution is conducted to introduce the R 3 and R 4 groups.
The R′ is alkyl, for example, C1-C36 linear or branching alkyl, for example, C1-C18 linear or branching alkyl, for example, C1-C8 linear or branching alkyl.
The most commonly used nucleophilic substituting reagent is the Grignard reagent. The Formula (d) compound can be subject to one-step nucleophilic substitution with the participation of corresponding Grignard reagents, and in the resulting Formula (e) compound, R 3 ═R 4 . Also, by way of stepwise addition of different Grignard reagents, different R 3 and R 4 groups can be introduced.
(3b) The carboxylic acid is converted to an acyl halide including groups such as acyl chloride, acyl bromide etc., then the nucleophilic substitution can be conducted to introduce the R 3 and R 4 groups.
The X is halogen, for example, Cl and Br.
In Schemes (3a) and (3b), the nucleophilic substituting reagent, in addition to the Grignard reagent, can be selected from other nucleophilic substituting reagents, such as alkyl lithium reagent (R 3 Li), alkyl copper lithium reagent (R 3 CuLi), etc.
(4) R 5 is introduced using different methods according to different types of the R 5 group:
(4a) When R 5 is alkoxy, a strong alkaline can react with an alcohol hydroxyl to generate an oxygen anion, which is subsequently subject to a nucleophilic substitution by R 5 ′X.
The X is a halogen atom (F, Cl, Br, I), trifluoromethanesulfonate group or p-toluenesulfonate group.
The R 5 ′ is selected from alkyl.
(4b) When R 5 is alkyl, halogen substituted alkoxy, alkenyl or alkynyl, the Formula (c) compound can be first reacted with trifluoromethanesulfonyl chloride to generate a good leaving group trifluoromethanesulfonate group, and then the substitution is conducted by nucleophilic substitution.
(4c) When R 5 is a hydrogen atom, the oxygen atom can be removed under the conditions of triethylsilane (Et 3 SiH) and trifluoroacetic acid.
(5) The protecting group is eliminated to generate the corresponding alcohol:
When the protecting group is a benzyl protecting group, silicon protecting group, methoxymethyl protecting group (MOM), tetrahydropyran protecting group (THP), p-methoxyphenyl (PMB) protecting group, etc, the corresponding method for removing it in the prior art can be selected to remove the protecting group to generate the corresponding alcohol, for example:
(6) The hydroxyl at position R can be subject to many types of substitution to convert to corresponding functional group, such as halogen, amino, cyano, azide group, trifluoromethanesulfonate group (MsO), p-toluenesulfonate group (TsO), alkenyl, alkynyl, and alkoxy, etc.
(6a) When R is halogen, the following reactions can be conducted, but they are not limited to these reactions.
(6b) When R is trifluoromethanesulfonate group (MsO) or p-toluenesulfonate group (TsO), an alkaline can react with an alcohol hydroxyl to generate an oxygen anion, which is subsequently subject to a nucleophilic substitution by MsCl or TsCl.
(6c) When R is an azide group (N 3 ), it can be obtained by a nucleophilic substitution between sodium azide (NaN 3 ) and halogen, trifluoromethanesulfonate group (MsO) or p-toluenesulfonate group (TsO):
In the aforementioned equation, X represents a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group.
(6d) When R is cyano, it can be obtained by a nucleophilic substitution between a cyanide (such as sodium cyanide, potassium cyanide) and halogen, trifluoromethanesulfonate group (MsO) or p-toluenesulfonate group (TsO):
In the aforementioned equation, X represents a halogen atom, trifluoromethanesulfonate group or p-toluenesulfonate group.
(6e) When R is amino group, the azide group or cyano group can be reduced to amino group, or it can be obtained by Gabriel amine synthesis.
(6f) When R is an alkenyl or alkynyl, it can be obtained by a nucleophilic substitution with a nucleophilic agent containing the alkenyl or alkynyl such as RLi, for example:
The branching alkyl chain in the aforementioned compounds as shown in Formula (I) can serve as a solubilizing group for the preparation of the organic conjugated molecules (especially the organic conjugated polymers) and increase the mobility of carriers in the organic conjugated molecule materials. Further, these organic conjugated molecules, serving as organic semiconductor materials, can be applied to photoelectric devices such as organic solar cells, organic light emitting diodes, and organic field effect transistors, etc.
In the second aspect of the invention, polymers with the aforementioned branching alkyl chains as shown in the following Formula (II) are provided:
In Formula (II), Ar 1 and Ar 2 represent different aromatic compound fragments; n is an integer which represents the polymerization degree of the polymer.
Wherein Ar 1 contains one or more branching alkyl chains in the compounds as shown in the General Formula (I).
n can, for example, be an integer of 1˜1,000,000, an integer of 1˜10,000, or an integer of 1˜1,000.
The polymer is obtained by polymerization of the Ar 1 and Ar 2 monomers. The polymerization can be conducted by coupling, for example, Suzuki coupling, Stille coupling, Negishi coupling, Sonogashira coupling, Heck coupling, Kumada coupling, Hiyama coupling, Buchwald-Hartwig coupling and carbon-hydrogen bond activation coupling (Berrouard, P.; Najari, A.; Pron, A.; Gendron, D.; Morin, P.-O.; Pouliot, J.-R.; Veilleux, J.; Leclerc, M. Angew. Chem., Int. Ed. 2011, 51, 2068), etc., for example. Suzuki coupling, Stifle coupling, Sonogashira coupling, Heck coupling, Kumada coupling and carbon-hydrogen bond activation coupling.
In an embodiment of the invention, the number of methylenes between the alkyl side chain and the backbone in the polymer, i.e., m>1, for example, m can be an integer of 2˜18, an integer of 2˜10, an integer of 3˜18, an integer of 3˜10, an integer of 3˜5, or an integer of 3˜4. This can effectively reduce the effect of the alkyl chains on the π-π stacking of the polymer backbone, thereby greatly increasing the mobility of the polymer.
The polymer as shown in Formula (II) is polymerized from the aromatic compound monomer having the branching alkyl chains as shown in the following Formula (III) and the Ar 2 aromatic compound monomers. The wavy line in Formula (III) indicates the functional group required by the monomers to polymerize, for example, in order to perform Suzuki coupling, the functional group can be a halogen, boric acid or borate; in order to perform Stille coupling, the functional group can be a halogen or alkyl tin; in order to perform Sonogashira coupling, the functional group can be a halogen or ethynyl; in order to perform Fleck coupling, the functional group can be a halogen or ethenyl; in order to perform Kumada coupling, the functional group is a halogen; in order to perform carbon-hydrogen bond activation coupling, the functional group can be a halogen or hydrogen; and in order to perform Hiyama coupling, the functional group can be a halogen or silane.
The aromatic compound as shown in Formula (III) is, for example, the compounds as shown in the following Formulae III-1 to III-16:
R 6 , R 7 , R 8 , and R 9 represent substituents on the aromatic ring, for example, hydrogen atom, halogen atom (such as F, Cl, etc.), nitro, amino, cyano, alkyl, alkenyl, alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy, etc.
R 10 and R 11 represent one or more substituents on the aromatic ring, for example, hydrogen atom, halogen atom (such as F, Cl, etc.), nitro, amino, cyano, alkyl, alkenyl, alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy, etc.
a and a′ can be independently selected from the following structures: —S—, —O—, —Se—, —NR 12 —, etc.
b, b′, c and c′ can be independently selected from the following structures: —N═, ═N—, —CR 12 ═, ═CR 12 —, etc.
The aforementioned R 12 represents hydrogen atom, alkyl, alkenyl, alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy, aryl or heteroaryl, etc.
The aforementioned alkyl can, for example, be C1-C36 linear or branching alkyl, for example, C1-C18 linear or branching alkyl.
The aforementioned halogen substituted alkyl, can for example, be C1-C36 linear or branching halogen substituted alkyl, for example, C1-C18 linear or branching halogen substituted alkyl.
The aforementioned alkoxy can, for example, be C1-C36 linear or branching alkoxy, for example. C1-C18 linear or branching alkoxy.
The aforementioned halogen substituted alkoxy can, for example, be C1-C36 linear or branching halogen substituted alkoxy, for example, C1-C18 linear or branching halogen substituted alkoxy.
The aforementioned alkenyl can, for example, be C2-C18 alkenyl, C2-C10 alkenyl, or C2-C6 alkenyl.
The aforementioned alkynyl can, for example, be C2-C18 alkynyl, C2-C10 alkynyl, or C2-C6 alkynyl.
The aforementioned aryl can, for example, be phenyl or substituted phenyl, for example, phenyl.
The aforementioned heteroaryl can, for example, be thienyl, thiazolyl, pyridyl, furyl, for example, thienyl or thiazolyl.
The Ar 2 aromatic compound monomer can be selected from the follow structures:
wherein the wavy line indicates the functional group required for the polymerization with the Ar 1 monomers;
a and a′ can be independently selected from the following structures: —S—, —Se—, —O— and —NR 12 —;
b and b′ can be independently selected from the following structures: —N═, ═N—, —SiR 12 ═, ═SiR 12 —, —SiR 12 R 12 —, —CR 12 R 12 —CR 12 R 12 — and —CR 12 ═CR 12 —;
c can be selected from the following structures: —S—, —S(O)—, —S(O) 2 —, —O—, —N═, ═N—, —SiR 12 ═, ═SiR 12 —, —SiR 12 R 12 —, —CR 12 R 12 —CR 12 R 12 —, —CR 12 ═CR 12 —;
d can be selected from the following structures: —S—, —S(O)—, —S(O) 2 —, —O—, —N═, ═N—, —SiR 12 ═, ═SiR 12 —, —SiR 12 R 12 —, —CR 12 R 12 —CR 12 R 12 —, —CR 12 ═CR 12 —, —C(O)— and —C(C(CN) 2 )—;
g, h, g′ and h′ can be independently selected from the following structures: —CR 12 ═, ═CR 12 —, —C—, —C(O)— and —C(C(CN) 2 )—, —N═ and ═N—;
The aforementioned R 12 can be hydrogen atom, alkyl, alkenyl, alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy, aryl or heteroaryl etc.;
u is 1, 2, 3 or 4.
The Ar 2 aromatic compound monomer can, for example, be one of the following structures:
R 12 can be hydrogen atom, alkyl, alkenyl, alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy, aryl or heteroaryl, etc.; u is 1, 2, 3 or 4.
The aforementioned Ar 2 aromatic compound can have one or more substituents in its structure.
The synthesis of the Ar 1 aromatic compound having the branching alkyl chains can be started from aromatic compounds known in the literature, and obtained by reacting these compounds with the halide and amino compounds, etc. having the branching alkyl chain structure in the present disclosure. Specifically, there are the five following schemes:
(1) When the R in Formula (I) is halogen (X), a nucleophilic substitution can occur between X and the following nitrogen-containing aromatic compounds to prepare the aromatic compound in the General Formula (III), for example:
(2) When the R in the General Formula (I) is trifluoromethanesulfonate group (MsO) or p-toluenesulfonate group (TsO), because these good leaving groups have similar properties to halogen, they can also be used in the nucleophilic substitution reaction as shown in (1).
(3) When the R in the General Formula (I) is halogen (X), X is Br or I for preparing the corresponding Grignard reagent, thereby directly obtaining the alkyl substituted aromatic compound via Kumada coupling, for example:
(3) When the R in the General Formula (I) is amino, it can be reacted with an anhydride to generate a corresponding imide compound, for example:
The III-6 type compounds can be prepared from III-5 via multi-step reactions based on the prior art.
(4) When the R in the General Formula (I) is alkenyl, a Heck reaction can occur between it and an aromatic halide (X═Cl, Br or I) to obtain the corresponding arylalkenyl derivatives, for example:
(5) When the R in the General Formula (I) is alkynyl, Sonogashira reaction can occur between it and an aromatic halide (X═Cl, Br or I) to obtain the corresponding arylalkynyl derivatives, for example:
In the third aspect of the invention, the aforementioned polymer having the branching alkyl chain as shown in Formula (II), serving as an organic semiconductor material, can be applied to photoelectric devices such as organic field effect transistors, organic solar cells, and organic light emitting diodes, etc., proving that it can greatly increase the mobility of carriers in the organic semiconductor materials.
In the invention, compounds containing a type of novel branching alkyl chains have been designed, and effective synthetic schemes of the compounds containing this type of novel branching alkyl chains have been raised which enables easy transformation of functional groups. In the invention, it is further proved that compounds having this type of branching alkyl chains can be applied to organic conjugated polymers, and can effectively adjust the π-π stacking between molecules, also change the spectral properties and electrochemical properties of the polymers, and significantly increase the mobility of the organic electronic materials. Therefore, these results can be widely used in the field of organic electronics, including the field of organic photovoltaic cells (OPV), organic light emitting diodes (OLED), and organic field effect transistors, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows the effect of the position of the solubilizing group (such as the alkyl chain) on the π-π stacking of the organic conjugated polymers.
FIG. 2 shows the structural diagram of the organic conjugated polymer having the branching alkyl chains according to an embodiment of the invention.
DETAILED DESCRIPTION
The invention is further described in details by way of examples in relation to figures. However, they are by no means limiting the scope of the invention.
Example 1 to Example 3 are Method for Synthesizing Alcohols Protected by Benzyloxy
Example 1
Scheme for Synthesizing Compound 1: 1,3-propanediol (60 g, 0.79 mol) was added into a 500 ml round bottom flask, then solid KOH (17.7 g, 0.32 mol) was added to remove the trace moisture in the 1,3-propanediol. Under agitation at 90° C., benzyl chloride (39.8 g, 0.32 mol) was added into the 1,3-propanediol using a dropping funnel. Then temperature was increased to 130° C. for a 2h reaction. The reaction was stopped and cooled to the room temperature. After extraction of the organic phase using water/diethyl ether separation, the solvent was removed by reduced pressure rotatory evaporation, followed by reduced pressure distillation. 39.8 g colorless oily product Compound 1 was obtained with a yield of 77%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.36-7.28 (m, 5H), 4.51 (s, 2H), 3.79-3.75 (m, 2H), 3.66-3.64 (t, J=5.5 Hz, 2H), 2.44 (br. s, 1H), 1.88-1.83 (m, 2H).
Example 2
Scheme for Synthesizing Compound 2: At 0° C., 1,4-butanediol (40 g, 0.44 mol) was added into 200 ml dry THF. Sodium hydride (5.3 g, 0.22 mol) was added in batches within 30 min. The temperature returned to the room temperature for a 2h reaction. Benzyl bromide (38 g, 0.22 mol) was dissolved in 20 ml THF, which was dropped into the aforementioned system at 0° C. followed by reflux for 4 h. After the complete of the reaction, the reaction was quenched with cold water. The organic phase was extracted with diethyl ether. After drying the organic phase with anhydrous sodium sulfate, it was filtered, then subject to reduced pressure rotatory evaporation to remove the solvent, followed by reduced pressure distillation to obtain 28.1 g of colorless oily liquid 2 with a yield of 71%.
1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.36-7.26 (m, 5H), 4.52 (s, 2H), 3.65-3.61 (m, 2H), 3.53-3.50 (t, J=5.3 Hz, 2H), 2.36 (br. s, 1H), 1.73-1.65 (m, 4H).
Example 3
Scheme for Synthesizing Compound 3: At 0° C., 1,5-pentanediol (40 g, 0.39 mol) was added into 200 ml dry THF. Sodium hydride (4.6 g, 0.19 mol) was added in batches within 30 min. The temperature returned to the room temperature for a 2 h reaction. Benzyl bromide (33 g, 0.19 mol) was dissolved in 20 ml THF, which was dropped into the aforementioned system at 0° C. followed by reflux for 4 h. After the complete of the reaction, the reaction was quenched with cold water. The organic phase was extracted with diethyl ether. After drying the organic phase with anhydrous sodium sulfate, it was filtered, then subject to rotatory evaporation to remove the solvent, followed by reduced pressure distillation to obtain 23.1 g of colorless oily liquid 3 with a yield of 62%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.36-7.26 (m, 5H), 4.50 (s, 2H), 3.64-3.61 (t, J=6.5 Hz, 2H), 3.50-3.64 (t, J=6.5 Hz, 2H), 1.68-1.54 (m, 4H), 1.49-1.43 (m, 2H).
Example 4 to Example 6 are the Jones Oxidation and Protection by Esterification of the Alcohols Protected by Benzyloxy
Example 4
Scheme for Synthesizing Compound 4: Compound 1 (10 g, 60.2 mmol) was dissolved into 200 ml acetone. At 0° C. Jones reagent (26.72 g chromium trioxide: 23 ml concentrated sulfuric acid, diluted with water to 100 ml) was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H 2 SO 4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain 9.7 g colorless oily liquid 4 with a yield of 77%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.36-7.28 (m, 5H), 4.54 (s, 2H), 4.17-4.13 (q, J=7.0 Hz, 2H), 3.77-3.74 (t, J=6.2 Hz, 2H), 2.63-2.60 (t, J=6.2 Hz, 2H), 1.28-1.24 (t, J=7.1 Hz, 3H).
Example 5
Scheme for Synthesizing Compound 5: Compound 2 (26.6 g) was dissolved into 200 ml acetone. At 0° C., Jones reagent was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H 2 SO 4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain 24.2 g colorless oily liquid 5 with a yield of 70%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.36-7.27 (m, 5H), 4.49 (s, 2H), 4.14-4.08 (q, J=7.1 Hz, 2H), 3.52-3.49 (t, J=6.1 Hz, 2H), 2.44-2.40 (t, J=7.3 Hz, 2H), 1.97-1.91 (m, 2H), 1.26-1.22 (t, J=7.1 Hz, 3H).
Example 6
Scheme for Synthesizing Compound 6: Compound 3 (23.1 g) was dissolved into 200 ml acetone. At 0° C., Jones reagent was added dropwise until the orange red color was sustained without turning green. The temperature returned to the room temperature followed by agitation for 2h. The resultant mixture was vacuum suck filtrated and loaded onto a column which was eluted with acetone. After acetone was removed by vacuum rotatory evaporation, the organic phases were extracted with ethyl acetate for three times. The organic phases were combined and washed once with saturated saline. After dried with anhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentrated H 2 SO 4 were added for 12 h reflux reaction. After most solvent was removed by rotatory evaporation, water/ethyl acetate phase separation was conducted. The organic phase was washed with sodium bicarbonate solution, water, and saturated saline respectively, and then dried with anhydrous sodium sulfate. After the solvent was removed by rotatory evaporation, reduced pressure distillation was conducted to obtain a colorless oily liquid 6 with a yield of 62%. 1 H NMR (CDCl 3 , 400 MHz, ppm): δ 7.36-7.28 (m, 5H), 4.50 (s, 2H), 4.15-4.09 (q, J=6.8 Hz, 2H), 3.50-3.47 (t, J=5.8 Hz, 2H), 2.34-2.30 (t, J=7.0 Hz, 2H), 1.73-1.65 (m, 4H), 1.27-1.23 (t, J=6.9 Hz, 3H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 173.50, 138.48, 128.28, 127.52, 127.44, 72.82, 69.78, 60.14, 34.00, 29.11, 21.72, 14.19. ESI-HRMS: Calcd. for [M+H] + : 237.14852. Found: 237.14859. Calcd. for [M+Na] + : 259.13047. Found: 259.13068.
Example 7 to Example 9 are Reactions Between Esters and Grignard Reagents
Example 7
Scheme for Synthesizing Compound 7: Dry magnesium powders (2.88 g, 120 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromodecane (26.5 g, 120 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 4 was added dropwise into the system. After 5 h reflux, it was quenched with H 2 SO 4 (2 M) under ice bath, and then extracted with diethyl ether (3×50 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na 2 SO 4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 7 (12.4 g) was obtained with a yield of 60%. 1 H NMR (CDCl 3 , 400 MHz, ppm): δ 7.35-7.26 (m, 5H), 4.51 (s, 2H), 3.69-3.66 (t, J=6.0 Hz, 2H), 2.98 (s, 1H), 1.79-1.76 (t, J=6.0 Hz, 2H), 1.49-1.37 (m, 4H), 1.33-1.15 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 137.80, 128.36, 127.67, 74.06, 73.34, 67.25, 39.14, 37.73, 31.89, 30.27, 29.62, 29.60, 29.32, 23.65, 22.65, 14.07. ESI-HRMS: Calcd. for [M-OH] + : 429.40909. Found: 429.40925; Calcd. for [M+Na] + : 469.40160. Found: 469.40182. Elemental Anal.: Calcd. for C 30 H 54 O 2 : C, 80.65; H, 12.18. Found: C, 80.61; H, 12.16.
Example 8
Scheme for Synthesizing Compound 8: Dry magnesium powders and an iodine grain were added into a three-necked bottle. Under nitrogen protection. 1-bromodecane in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 5 was added dropwise into the system. After 5 h reflux, it was quenched with H 2 SO 4 (2 M) under ice bath, and then extracted with diethyl ether (3×50 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na 2 SO 4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 8 was obtained with a yield of 47%. 1 H NMR (CDCl 3 , 400 MHz, ppm): δ 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 1.68-1.62 (m, 2H), 1.52-1.48 (m, 2H), 1.43-1.38 (m, 4H), 1.32-1.26 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H) 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 138.36, 128.26, 127.51, 127.43, 73.84, 72.83, 70.93, 39.20, 36.05, 31.87, 30.25, 29.61, 29.59, 29.30, 23.87, 23.50, 22.63, 14.05. ESI-HRMS: Calcd. for [M-OH] + : 443.42474. Found: 443.42496; Calcd. for [M+Na] + : 483.41725. Found: 483.41761.
Example 9
Scheme for Synthesizing Compound 9: Dry magnesium powders and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromodecane in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 6 was added dropwise into the system. After 5 h reflux, it was quenched with H 2 SO 4 (2 M) under ice bath, and then extracted with diethyl ether (3×50 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na 2 SO 4 and rotatory evaporation, it was loaded onto the silica gel column for separation. Compound 9 was obtained with a yield of 58%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 7.35-7.25 (m, 5H), 4.50 (s, 2H), 3.50-3.47 (t, J=6.0 Hz, 2H), 1.63-1.57 (m, 2H), 1.40-1.20 (m, 40H), 1.12 (s, 1H), 0.90-0.86 (t, J=6.4 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 138.61, 128.30, 127.60, 127.45, 74.35, 72.88, 70.27, 39.23, 39.04, 31.90, 30.28, 30.26, 29.65, 29.63, 29.61, 29.33, 23.47, 22.67, 20.14, 14.09. ESI-HRMS: Calcd. for [M-OH] + : 457.44094. Found: 457.44063; Calcd. for [M+Na] + : 497.43290. Found: 457.43363.
Example 10 to Example 12 are Deoxygenation and Palladium Carbon Catalyzed Hydrogenation
Example 10
Scheme for Synthesizing Compound 10: Compound 7 (12.4 g, 27.8 mmol) was dissolved into 100 ml dry dichloromethane, to which Et 3 SiH (3.54 g, 30.5 mmol) and TFA (15.85 g, 139 mmol) were added. After 12 h reaction under the room temperature, Na 2 CO 3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichloromethane, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C (0.50 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 10 was obtained with a yield of 38%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.68-3.64 (t, J=7.0 Hz, 2H), 1.55-1.50 (q, J=6.8 Hz, 2H), 1.41 (br. s, 1H), 1.32-1.25 (m, 36H), 0.90-0.86 (t, J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 61.31, 37.01, 34.27, 33.75, 31.92, 30.07, 29.69, 29.65, 29.35. 26.57, 22.69, 14.10. ESI-HRMS: Calcd. for [M+Na] + : 363.35974. Found: 363.35895.
Example 11
Scheme for Synthesizing Compound 11: Compound 8 was dissolved into 100 ml dry dichloromethane, to which Et 3 SiH and TFA were added. After 12 h reaction under the room temperature, Na 2 CO 3 was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichloromethane, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 11 was obtained with a yield of 67%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.64-3.61 (t, J=6.6 Hz, 2H), 1.58-1.50 (m, 2H), 1.34-1.24 (m, 39H), 0.90-0.86 (t, J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 63.48, 37.25, 33.61, 31.92, 30.13, 29.97, 29.71, 29.66, 29.59, 29.35, 26.67, 22.68, 14.07. ESI-HRMS: Calcd. for [M+Na] + : 377.37539. Found: 377.37555.
Example 12
Scheme for Synthesizing Compound 12: Compound 9 was dissolved into 100 ml dry dichloromethane, to which Et 3 SiH and TFA were added. After 12 h reaction under the room temperature. Na 2 CO 3 was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichloromethane, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A colorless oily liquid 12 was obtained with a yield of 60%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.66-3.63 (t, J=6.6 Hz, 2H), 1.58-1.51 (m, 2H), 1.34-1.23 (m, 41H), 0.90-0.86 (t, J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 63.10, 37.42, 33.63, 33.53, 33.30, 31.93, 30.14, 29.72, 29.66, 29.36, 26.71, 22.90, 22.69, 14.10. ESI-HRMS: Calcd. for [M+Na] + : 391.39104. Found: 391.39139.
Example 13 to Example 15 are Reactions in which Hydroxyl is Converted to Iodide
Example 13
Scheme for Synthesizing Compound 13: Compound 10 (3.6 g, 10.6 mmol) was dissolved into dichloromethane, to which imidazole (0.93 g, 13.7 mmol) and triphenylphosphine (3.59 g 13.7 mmol) were added. Under ice bath, I 2 (3.48 g, 13.7 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na 2 SO 3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 13 with a yield of 95%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.21-3.17 (t, J=7.6 Hz, 2H), 1.83-1.77 (q, J=7.2 Hz, 2H), 1.40 (s, 1H), 1.33-1.24 (m, 37H), 0.90-0.86 (t, J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 38.64, 38.28, 32.88, 31.93, 30.03, 29.69, 29.65, 29.36, 26.41, 22.70, 14.12, 5.15. EI-MS: Calcd. for [M-I] + : 323. Found: m/z=323. Elemental Anal.: Calcd. for C 23 H 47 1: C, 61.32; H, 10.62. Found: C, 61.56; H, 10.60.
Example 14
Scheme for Synthesizing Compound 14: Compound 11 was dissolved into dichloromethane, to which imidazole and triphenylphosphine were added. Under ice bath, I 2 was added. After reacting under agitation at the room temperature for 4 h, Na 2 SO 3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 14 with a yield of 75%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.19-3.15 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 36.75, 34.60, 33.60, 31.93, 30.97, 30.08, 29.70, 29.66, 29.37, 26.66, 22.70, 14.11, 7.62. EI-MS: Calcd. for [M] + : 464. Found: m/z=464. Calcd. for [M-I] + : 337. Found: m/z=337. Elemental Anal.: Calcd. for C 24 H 49 I: C, 62.05; H, 10.63. Found: C, 62.35; H, 10.54.
Example 15
Scheme for Synthesizing Compound 15: Compound 12 was dissolved into dichloromethane, to which imidazole and triphenylphosphine were added. Under ice bath, I 2 was added. After reacting under agitation at the room temperature for 4 h, Na 2 SO 3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column to obtain a colorless oily liquid Compound 15 with a yield of 94%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.21-3.18 (t, J=7.0 Hz, 2H), 1.87-1.77 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 41H), 0.90-0.86 (t, J=6.8 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 37.25, 34.01, 33.59, 32.52, 31.94, 30.13, 29.71, 29.67, 29.37, 27.65, 26.67, 22.70, 14.12, 7.25. EI-MS: Calcd. for [M-I] + : 351. Found: m/z=351. Elemental Anal.: Calcd. for C 25 H 51 I: C, 62.74; H, 10.74. Found: C, 62.87; II, 10.70.
Example 16
Scheme for Synthesizing Compound 16: Dry magnesium powders (3.0 g, 124 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection. 1-bromotetradecane (34.3 g, 124 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the ether solution of Compound 5 (11 g, 49.5 mmol) was added dropwise into the system. After 5 h reflux, it was quenched with H 2 SO 4 (2 M) under ice bath, and then extracted with diethyl ether (3×50 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na 2 SO 4 and rotatory evaporation, it was loaded onto the silica gel column for separation. 22.3 g of Compound 16 was obtained with a yield of 79%. 1 H NMR (CDCl 3 , 400 MHz, ppm): δ 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 2.98 (s, 1H), 1.69-1.62 (m, 2H), 1.52-1.49 (m, 2H), 1.43-1.39 (m, 4H), 1.32-1.26 (m, 48H), 0.90-0.86 (t, J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 138.40, 128.33, 127.58, 127.51, 73.95, 72.90, 70.99, 39.24, 36.11, 31.92, 30.29, 29.70, 29.68, 29.65, 29.36, 23.92, 23.54, 22.68, 14.11. ESI-HRMS: Calcd. for [M-OH] + : 555.54994. Found: 555.55003.
Example 17
Scheme for Synthesizing Compound 17: Dry magnesium powders (2.72 g, 113 mmol) and an iodine grain were added into a three-necked bottle. Under nitrogen protection, 1-bromooctadecane (37.6 g, 113 mmol) in diethyl ether solution was added dropwise under room temperature. After the drop addition initiated the reaction, a one hour reflux was conducted. Then under an ice bath, the diethyl ether solution of Compound 5 (10 g, 45 mmol) was added dropwise into the system. After 5 h reflux, it was quenched with H 2 SO 4 (2 M) under ice bath, and then extracted with diethyl ether (3×50 mL). After the organic phases were combined, it was washed with water and saturated saline. After dried with anhydrous Na 2 SO 4 and rotatory evaporation, it was loaded onto the silica gel column for separation. 22.9 g of Compound 17 was obtained with a yield of 74%. 1 H NMR (CDCl 3 , 400 MHz, ppm): δ 7.34-7.26 (m, 5H), 4.51 (s, 2H), 3.50-3.47 (t, J=6.3 Hz, 2H), 1.66-1.63 (m, 2H), 1.52-1.48 (m, 2H), 1.43-1.39 (m, 4H), 1.32-1.21 (m, 64H), 0.90-0.86 (t. J=6.7 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 138.39, 128.32, 127.56, 127.49, 73.92, 72.89, 70.98, 39.24, 36.11, 31.92, 30.29, 29.70, 29.69, 29.66, 29.36, 23.92, 23.54, 22.68, 14.10. ESI-HRMS: Calcd. for [M-OH] + : 667.67514. Found: 667.67503.
Example 18
Scheme for Synthesizing Compound 18: Compound 16 (22 g, 38.4 mmol) was dissolved into 250 ml dry dichloromethane, to which Et 3 SiH (5.3 g, 46.1 mmol) and TFA (21.9 g, 192 mmol) were added. After 12 h reaction under the room temperature, Na 2 CO 3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichloromethane, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of AcOEt/MeOH (300 mL/200 mL), to which 5% Pd/C (1 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. A white solid 18 was obtained with a yield of 68%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.64-3.61 (t, J=6.8 Hz, 2H), 1.58-1.50 (m, 2H), 1.32-1.23 (m, 55H), 0.90-0.86 (t, J=6.6 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) 63.57, 37.24, 33.61, 31.93, 30.13, 29.99, 29.71, 29.67, 29.57, 29.37, 26.67, 22.69, 14.10.
Example 19
Scheme for Synthesizing Compound 19: Compound 17 (22.9 g, 33.4 mmol) was dissolved into 250 ml dry dichloromethane, to which Et 3 SiH (4.66 g, 40.08 mmol) and TFA (19 g, 167 mmol) were added. After 12 h reaction under the room temperature, Na 2 CO 3 (10 g) was added to quench the reaction until no bubble was generated. It was loaded onto a short silica gel column and eluted with dichloromethane, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation to obtain a colorless oily liquid. The resultant colorless oily liquid was dissolved into a mixed solvent of AcOEt/MeOH (300 mL/200 mL), to which 5% Pd/C (1 g) catalyst was carefully added. Then the reaction was conducted at the room temperature under one atmospheric pressure of hydrogen gas for 24h. It was loaded onto a flash column and eluted with ethyl acetate, then a rotatory evaporation was conducted and followed by it was loaded onto a silica gel column for separation. 12.9 g of white solid 19 was obtained with a yield of 67%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.63-3.60 (t, J=6.6 Hz, 2H), 1.57-1.51 (m, 2H), 1.32-1.24 (m, 71H), 0.90-0.86 (t, J=6.8 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 63.52, 37.26, 33.62, 31.95, 30.16, 29.99, 29.74, 29.69, 29.59, 29.39, 26.69, 22.70, 14.10.
Example 20
Scheme for Synthesizing Compound 20: Compound 18 (8.92 g, 19.1 mmol) was dissolved into dichloromethane, to which imidazole (1.56 g, 22.9 mmol) and triphenylphosphine (6.0 g, 22.9 mmol) were added. Under ice bath, I 2 (5.82 g, 22.9 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na 2 SO 3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column to obtain 10.8 g of colorless oily liquid Compound 20 with a yield of 98%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.19-3.15 (t, J=7.0 Hz, 2H), 1.83-1.76 (m, 2H), 1.32-1.22 (m, 55H), 0.90-0.86 (t, J=6.6 Hz. 6H). EI-MS: Calcd. for [M]+: 576. Found: m/z=576.
Example 21
Scheme for Synthesizing Compound 21: Compound 19 (11.27 g, 19.46 mmol) was dissolved into dichloromethane, to which imidazole (1.59 g, 23.4 mmol) and triphenylphosphine (6.14 g, 23.4 mmol) were added. Under ice bath, I 2 (5.93 g, 23.4 mmol) was added. After reacting under agitation at the room temperature for 4 h, Na 2 SO 3 (aq.) was added for quenching. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column to obtain 13.17 g of colorless oily liquid Compound 21 with a yield of 98%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.18-3.15 (t, J=7.0 Hz, 2H), 1.83-1.76 (p, J=7.1 Hz, 2H), 1.33-1.22 (m, 71H), 0.90-0.86 (t, J=6.6 Hz, 6H). 13 C NMR (CDCl 3 , 100 MHz, ppm) δ: 36.75, 34.60, 33.61, 31.96, 30.97, 30.10, 29.74, 29.72, 29.70, 29.40, 26.67, 22.72, 14.13, 7.55. EI-MS: Calcd. for [M]+: 688. Found: m/z=688.
Example 22
Scheme for Synthesizing Compound 22: Compound 14 (1.0 g, 2.15 mmol) was dissolved into 100 ml DMF. At the room temperature, sodium azide (0.7 g, 10.5 mmol) was added in batches. After reaction under agitation at 85° C. for 4h, DMF was removed by vacuum distillation. Extraction was conducted with petroleum ether. The organic phase was washed with saturated saline once and dried with anhydrous Na 2 SO 4 . The solvent was removed by vacuum to obtain the product 22 (0.81 g) with a yield of 100%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.26-3.22 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). EI-MS: Calcd. for [M]+: 379. Found: m/z=379.
Example 23
Scheme for Synthesizing Compound 23: Compound 22 (0.81 g, 2.15 mmol) was dissolved in 100 ml petroleum ether. Pd/C (0.1 g) was added. At the room temperature, hydrogenation was conducted for 12 h, followed by filtration with kieselguhr and column separation to obtain 0.6 g of colorless oily liquid Compound 23 with a yield of 80%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 3.26-3.22 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). EI-MS: Calcd. for [M]+: 354. Found: m/z=354.
Example 24 to Example 28 are Reactions for Preparing the Monomers for Polymerization
Example 24
Synthesis of Monomer M2: 6,6′-dibromoisoindigo (1.70 g, 4.04 mmol) and potassium carbonate (1.68 g, 12.1 mmol) were dissolved in DMF (100 mL). Compound 13 (4.19 g, 9.31 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 110° C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After solvation into CHCl 3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 3.79 g of dark red solid M2 with a yield of 88%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 9.09-9.07 (d, 8.6 Hz, 2H), 7.17-7.15 (dd. J=8.6 Hz, J 2 =1.6 Hz, 2H), 6.89-6.88 (d, J=1.6 Hz, 2H), 3.74-3.70 (t, J=7.4 Hz 4H), 1.71-1.56 (q, J=6.3 Hz, 4H), 1.42-1.26 (m, 74H), 0.90-0.86 (t, J=6.8 Hz, 4H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 167.49, 145.68, 132.55, 131.22, 126.66, 125.05, 120.44, 111.18, 55 38.39, 35.61, 33.44, 31.93, 30.96, 30.04, 29.70, 29.69, 29.66, 29.36, 26.62, 22.70, 14.12. Elemental Anal.: Calcd. for C 62 H 100 Br 2 N 2 O 2 : C, 69.90; H, 9.46; N, 2.63. Found: C, 69.78; H, 9.46; N, 2.62. ESI-HRMS: Calcd. for [M+H] + : 1063.62243. Found: 1063.62480.
Example 25
Synthesis of Monomer M3: 6,6′-dibromoisoindigo and potassium carbonate were dissolved in DMF (100 mL). Compound 14 was added under nitrogen protection. Reaction was conducted under agitation at temperature of 110° C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl 3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain a dark red solid M3 with a yield of 71%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.16 (dd, J 1 =8.6 Hz, J 2 =1.6 Hz, 2H), 6.93-6.92 (d, J=1.6 Hz, 2H), 3.73-3.69 (t, J=7.4 Hz, 4H), 1.68-1.64 (m, 4H), 1.34-1.22 (m, 78H), 0.89-0.86 (t, J=6.6 Hz, 12H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 167.68, 145.76, 132.60, 131.21, 126.72, 125.10, 120.41, 111.28, 40.61, 37.10, 33.52, 31.93, 30.81, 30.09, 29.69, 29.65, 29.36, 26.67, 24.47, 22.69, 14.12. Elemental Anal.: Calcd. for C 64 H 104 Br 2 N 2 O 2 : C, 70.31; H, 9.59; N, 2.56. Found: C, 70.50; H, 9.62; N, 2.53. ESI-HRMS: Calcd. for [M+H] + : 1091.65373. Found: 1093.65487.
Example 26
Synthesis of Monomer M4: 6,6′-dibromoisoindigo and potassium carbonate were dissolved in DMF (100 mL). Compound 15 was added under nitrogen protection. Reaction was conducted under agitation at temperature of 110° C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl 3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain a dark red solid M4 with a yield of 83%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 9.10-9.07 (d, J=8.6 Hz, 2H), 7.17-7.14 (dd, J 1 =8.6 Hz, J 2 =1.6 Hz, 2H), 6.92-6.91 (d, J=1.6 Hz, 2H), 3.74-3.70 (t, J=7.4 Hz, 4H), 1.67-1.62 (m, 4H), 1.36-1.22 (m, 82H), 0.89-0.86 (t, J=6.8 Hz, 12H). 13 C NMR (CDCl 3 , 100 MHz, ppm): δ 167.67, 145.76, 132.59, 131.23, 126.71, 125.10, 120.41, 111.26, 40.27, 37.39, 33.61, 33.36, 31.93, 30.13, 29.72, 29.66, 29.37, 27.78, 26.71, 24.22, 22.70, 14.12. Elemental Anal.: Calcd. for C 66 H 108 Br 2 N 2 O 2 : C, 70.69; H, 9.71; N, 2.50. Found: C, 70.79; H, 9.55; N, 2.49. ESI-HRMS: Calcd. for [M+Na] + : 1141.66698. Found: 1141.66836.
Example 27
Synthesis of Monomer M5: 6,6′-dibromoisoindigo (2 g, 4.76 mmol) and potassium carbonate (1.97 g, 14.28 mmol) were dissolved in DMF (100 mL). Compound 20 (6.0 g, 10.4 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100° C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl 3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 6.0 g of dark red solid M5 with a yield of 95%. 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.15 (dd, J 1 =8.6 Hz, J 2 =1.8 Hz, 2H), 6.93-6.92 (d, J=1.8 Hz, 2H), 3.73-3.69 (t, J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22 (m. 114H), 0.89-0.86 (t, J=6.6 Hz, 12H).
Example 28
Synthesis of Monomer M6: 6,6′-dibromoisoindigo (1.5 g, 3.57 mmol) and potassium carbonate (1.48 g, 10.71 mmol) were dissolved in DMF (100 mL). Compound 21 (5.41 g, 7.86 mmol) was added under nitrogen protection. Reaction was conducted under agitation at temperature of 100° C. for 15 h. After the complete of the reaction, the solvent was removed by rotatory evaporation. After dissolved into CHCl 3 (100 mL) and washed with water for three times, the organic phases were combined and washed with saturated saline once, and then dried with anhydrous Na 2 SO 4 . After rotatory evaporation, it was loaded onto a silica gel column for separation to obtain 4.95 g of dark red solid M6 with a yield of 90%. 1 H NMR (CDCl 3 , 400 MHz, ppm) 1 H NMR (CDCl 3 , 400 MHz, ppm) δ: 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.15 (dd, J 1 =8.6 Hz, J 2 =1.8 Hz, 2H), 6.93-6.92 (d, J=1.8 Hz, 2H), 3.73-3.69 (t, J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22 (m, 142H), 0.89-0.86 (t, J=6.6 Hz, 12H).
Example 29 to Example 31 are Polymerization for the Polymers
Example 29
Synthesis of Polymer P2: Under nitrogen protection. M2 (0.235 mmol), 5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.235 mmol), Pd 2 (dba) 3 (4.3 mg, 2 mol %), P(o-tol) 3 (5.7 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110° C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (236 mg, with a yield of 95%). Elemental Anal. Calcd: for (C 70 H 104 N 2 O 2 S 2 ) n : C, 78.52; H, 9.88; N, 2.62. Found: C, 77.78; H, 9.47; N, 2.55.
Example 30
Synthesis of Polymer P3: Under nitrogen protection, M3 (0.229 mmol), 5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.229 mmol), Pd 2 (dba) 3 (4.3 mg, 2 mol %), P(o-tol) 3 (5.6 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110° C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (238 mg, with a yield of 94%). Elemental Anal.: Calcd. for (C 72 H 108 N 2 O 2 S 2 ) n : C, 77.78; H, 9.92; N, 2.55. Found: C, 77.85; H, 9.75; N, 2.48.
Example 31
Synthesis of Polymer P4: Under nitrogen protection, M4 (0.229 mmol), 5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.229 mmol), Pd 2 (dba) 3 (4.2 mg, 2 mol %), P(o-tol) 3 (5.6 mg, 8 mol %), and 10 ml dry toluene solvent were added into a reaction flask. After reaction with agitation at temperature of 110° C. for 24 h, Soxhlet extraction was conducted with chloroform to obtain the product (220 mg, with a yield of 87%). Elemental Anal.: Calcd. for (C 74 H 112 N 2 O 2 S 2 ) n : C, 78.95; H, 10.03; N, 2.49. Found: C, 78.25; H, 9.91; N, 2.46.
Example 32
The optical physical properties and electrochemical properties of Polymers P2, P3, and P4 were characterized and the data are shown in the following table:
TABLE 1
The optical physical and electrochemical properties of Polymers P1-P4
Molecular
Decomposition
Weight M n
Temperature
λ max sol.
λ max film
E g opt
E HOMO
E LUMO
E g cv
E HOMO PES
Polymer
(kDa)/PDI
(° C.)
(nm) a
(nm) b
(eV) c
(eV) d
(eV) d
(eV) e
(eV) f
P1
20.4/2.0
390
706, 647
701, 637
1.60
−5.70
−3.70
2.00
−5.54
P2
18.4/2.0
384
711, 647
707, 641
1.60
−5.60
−3.70
1.90
−5.57
P3
39.2/3.2
392
718, 673
719, 653
1.58
−5.52
−3.74
1.78
−5.33
P4
37.3/2.3
374
719, 675
716, 647
1.58
−5.50
−3.74
1.76
−5.26
a Longest absorption wavelength of the solution (corresponding to 0-0 vibration absorption and 0-1 vibration absorption, respectively);
b longest absorption wavelength of the film (corresponding to 0-0 vibration absorption and 0-1 vibration absorption, respectively);
c band gap in the absorption spectrum;
d electrochemical measurement value;
e electrochemical band gap;
f photoelectron spectrum (PES) measurement value.
Among them, P1 is a 2-branching polymer (Lei, T.; Cao, Y.; Fan, Y.; Liu, C. J.; Yuan, S. C.; Pei, J. J. Am. Chem. Soc. 2011, 133, 6099), whose structure is as follows:
P2˜P4 are polymers synthesized in the invention. After the introduction of different branching alkyl chains, significant change occurred to the spectra and electrochemistry of P2˜P4. The absorption spectra apparently shifted to red, the HOMO energy levels apparently increased, and the band gaps apparently reduced. These changes were due to the changes of the mode of stacking between polymers.
Example 33
Device Processing and X-Ray Diffraction Characterization of the Organic Field Effect Transistor Comprising Polymers P1-P4
Processing of the organic field effect transistor (OTFT) was conducted with the device structure of bottom-gate/top-contact (BG/TC). For the substrate, doped silicon (n ++ -Si) was used as a gate electrode, and 300 nm silicon dioxide was used as an insulation layer. The substrate was washed with acetone, a detergent, water and isopropanol successively before dried with nitrogen blow. Then the substrate was cleaned with plasma beam for 15 minutes, and modified with octadecylsilane. Then the dichlorobenzene solution of the polymer was spin coated onto the substrate and annealed at different temperatures. Then at high vacuum, a layer of 30 mm gold electrode was coated by hot vapor deposition with a physical mask as the source electrode and the drain electrode. The measurement of the mobility of the polymer was conducted on a Keithley 4200 semiconductor characterization system.
The experiments proved that compared to P1, the mobility of P3 had great increase from the initial 0.79 cm 2 V −1 s −1 (P1) to 3.62 cm 2 V −1 s −1 . The threshold voltage also significantly decreased.
The X ray diffraction experiment was conducted on Beamline BL14B1 at Shanghai Synchrotron Radiation Facility with a wavelength of 1.2398 Å, and the measurement was conducted with an NaI counter. The experiments proved that the type of branching alkyl chains contained in the polymers effectively reduced the π-π stacking distance between polymers. This result also proved the huge effect of the novel alkyl chain of the disclosure in organic semiconductor devices.
TABLE 2
Performance of the organic field effect transistors
and results of the film glancing X-ray study
Annealing
Threshold
on/off
Temperature
Mobility
Voltage
ratio
d(Å) b
Polymer
(° C.)
(cm 2 V −1 s −1 ) a
(V)
I on /I off
L
π
P1
150
0.79 (0.45)
−18
>10 6
20.3
3.75
P2
200
0.40 (0.28)
−10
>10 5
23.7
3.61
P3
175
3.62 (2.98)
−2
>10 6
24.7
3.57
P4
175
1.76 (1.44)
−5
>10 6
26.1
3.57
a The measurement was conducted in air (RH = 50~60%). Maximal mobility values were shown outside the parentheses, while average values were shown in the parentheses.
b The layer phase distance (L) and π-π stacking distance (π) obtained in the X-ray study. | The invention discloses a compound having branching alkyl chains, the method for preparing the same and use thereof in photoelectric devices. By applying the branching alkyl chains as the solubilizing group to the preparation of organic conjugated molecules (for example, organic conjugated polymers), the number of methylenes between the resultant alky side chains and the backbone, i.e., m>1, which can effectively reduce the effect of the alkyl chains on the backbone π-π stacking, thereby ensuring the solubility of the organic conjugated molecule while greatly increasing the mobility of their carriers. It is suitable for an organic semiconductor material in photoelectric devices such as organic solar cells, organic light emitting diodes and organic field effect transistors, etc. | 7 |
REFERENCE TO EARLIER FILED APPLICATION
This application is a 371 national phase of PCT/US2014/022689, filed Mar. 10, 2014, and claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 61/777,890, filed Mar. 12, 2013, and titled 5 “METHODS FOR THE ELECTROLYTIC DECARBOXYLATION OF SUGARS,” which is incorporated, in its entirety, by this reference.
TECHNICAL FIELD
The present disclosure relates to methods of electrolytically decarboxylating sugar acids and electrolytically generating alkali metal, or ammonium hydroxide solutions.
BACKGROUND
The electrolytic decarboxylation of sugar acids has been employed in the production of xylitol and erythritol, as in U.S. Pat. Nos. 7,598,374, 7,955,489, and U.S. Patent Publication US 2011/0180418. For example, U.S. Pat. No. 7,955,489, describes the electrolytic decarboxylation of aqueous D - or L -arabinonic acid at specific ranges of neutralization—the ratio of alkali metal cations to arabinonic acid—to yield erythrose. Therein, the neutralization of arabinonic acid is maintained in solution by converting alkali metal araboninic acid salts to a protonated form using cation exchange resin and electrodialysis. Moreover, they describe adding un-neutralized arabinonic acid to the reaction solution over the course of the reaction to replace the arabinonic acid consumed at the anode.
Electrolytic cells can be constructed in many different configurations. However, all previously disclosed examples of carbohydrate acid electrolytic decarboxylations are carried out in single-compartment cells to maintain particular levels of neutralization. Too little neutralization results in a significant reduction in conductivity and reaction efficiencies, and too much neutralization can lead to reaction inefficiencies and product instabilities. Moreover, the presence of inorganic anions is detrimental to electrode life, reaction efficiencies, and downstream product purification efficiencies. Consequently the addition of non-reagent acids to control the degree of reactant neutralization is undesirable.
As sugar acids are often produced as alkali metal salts, there remains a need for cost-effective methods to maintain sugar acid neutralization without further conversion of alkali metal salts of carbohydrate acids with cation exchange resin, electrodialysis, or by addition of un-neutralized carbohydrate acids.
SUMMARY
The present disclosure includes cost-effective methods for electrolytically decarboxylating carbohydrate acids concomitantly with the electrolytic production of alkali metal hydroxide solutions, or ammonium hydroxide solutions. The disclosure provides a method of decarboxylating a sugar acid by providing a solution comprising a carbohydrate acid; electrolytically decarboxylating the carbohydrate acid in the anode compartment of a two-compartment electrochemical cell; and generating an alkali metal hydroxide solution, or ammonium hydroxide solution, in the cathode compartment. The compartments are separated by a cation exchange membrane. As the reaction proceeds, for every one molecule of carbohydrate acid which is decarboxylated or molecule of oxygen evolved, approximately two alkali metal ions migrate across the cation exchange membrane and are removed from the anolyte to the catholyte thus maintaining charge balance.
In a first embodiment the alkali metal hydroxide concentration of the catholyte is maintained sufficiently high and the cation membrane is selected to induce back-migration of hydroxide ions across the cation membrane from the catholyte to the anolyte. In this embodiment, the current efficiency for alkali metal hydroxide production is less than 100%, is preferably less than 90% and more preferably less than 75%. In a particular embodiment the carbohydrate acid is arabinonic acid.
In a second embodiment, an alkali metal hydroxide is added to the anolyte to maintain the suitable neutralization. Preferably the alkali metal hydroxide produced in the cathode chamber is added to the anolyte of a carbohydrate decarboxylation in order to maintain a preferred level of carbohydrate acid neutralization. In a particular embodiment the carbohydrate acid is arabinonic acid.
In a third embodiment, the decarboxylation of a carbohydrate acid occurs at an anode surface to yield an aldose, in which the ratio of sodium to carbohydrate acid is maintained by concurrently circulating the reactant solution through two sets of electrolytic cells, where one set of cells is a divided cell with a cationic membrane and the other is an undivided cell. In a particular embodiment the carbohydrate acid is arabinonic acid.
In a fourth embodiment, the carbohydrate acid reactant is obtained from a suitable carbohydrate starting material by alkali oxidation. Preferably, the alkali metal hydroxide produced in the cathode chamber is used in the alkali oxidation of subsequent carbohydrate acid reactant. For example, D -arabinonic acid may be prepared by oxidizing D -glucose with oxygen gas in an alkaline water solution; L -arabinonic acid may be prepared by oxidizing L -arabinose with oxygen gas and a platinum group metal catalyst in an alkaline water solution; methyl alpha- D -glucuronoside may be prepared by oxidizing methyl alpha- D -glucoside with oxygen gas and a platinum group metal catalyst in an alkaline water solution; D -gluconate may be prepared by oxidizing D -glucose with oxygen gas and a platinum group metal catalyst in an alkaline water solution.
DETAILED DESCRIPTION
Definitions
As used herein, the term “carbohydrate acid” refers to any aldonic acid, uronic acid or aldaric acid.
“Aldonic acid” refers to any polyhydroxy acid compound comprising the general formula HOCH 2 [CH(OH))] n C(═O)OH (where n is any integer, including 1-20, but preferably 1-12, more preferably 4-7), as well as derivatives, analogs and salts thereof Aldonic acids can be derived, for example, from an aldose by oxidation of the aldehyde function (e.g., D -gluconic acid).
“Uronic acid” refers to any polyhydroxy acid compound comprising the general formula O═CH[CH(OH)] n C(═O)OH (where n is any integer, including 1-20, but preferably 1-12, more preferably 4-7), as well as derivatives, analogs and salts thereof Uronic acids can be derived, for example, from an aldose by oxidation of the primary alcohol function (e.g., D -glucuronic acid).
“Aldaric acid” refers to any polyhydroxy acid compound comprising the general formula HO(O═)C[CH(OH)] n C(═O)OH (where n is any integer, including 1-20, but preferably 1-12, more preferably 4-7), as well as derivatives, analogs and salts thereof Aldaric acids can be derived, for example, from an aldose by oxidation of both the aldehyde function and the primary alcohol function (e.g., D -glucaric acid).
“Arabinonic acid” as used herein refers to an aldonic acid carbohydrate with chemical formula C 5 H 10 O 6 , including any stereoisomers, derivatives, analogs and salts thereof Unless otherwise indicated, recitation of “arabinonic acid” herein is intended to include, without limitation, the molecules: D-(−)-arabinonic acid, L(+)-arabinonic acid, D(−)-arabinonic acid, D-arabinonic acid, L-arabinonic acid, and D(−)-arabinonic acid and meso-arabinonic acid. Arabinonic acid is also referred to as arabonic acid and arabinoic acid.
“Gluconic acid” refers to an aldonic acid carbohydrate with chemical formula C 6 H 12 O 7 , including derivatives, analogs and salts thereof Unless otherwise indicated, recitation of “gluconic acid” herein is intended to refer to D-gluconic acid, D-(−)-gluconic acid, D(−)-gluconic acid.
“D-glucuronic acid” refers to an uronic acid carbohydrate with the chemical formula C 6 H 10 O 7 including derivatives, analogs, and salts thereof Unless otherwise indicated, recitation of “d-glucuronic acid” herein is intended to include, without limitation, the molecules d-(−)-glucuronic acid, d-glucuronic acid, (alpha)-d-glucuronic acid, (beta)-d-glucuronic acid, and (alpha,beta)-d-glucuronic acid.
“Methyl-d-glucuronoside” refers to an uronic acid carbohydrate with the chemical formula C 7 H 12 O 7 , including derivatives, analogs and salts thereof Unless otherwise indicated, recitation of “methyl-d-glucuronoside” herein is intended to include, without limitation, the molecules 1-O-methyl-(alpha)-d-glucopyranosiduronic acid, 1-O-methyl-(beta)-d-glucopyranosiduronic acid and 1-O-methyl-(alpha,beta)-d-glucopyranosiduronic acid.
“D-galacturonic acid” refers to an uronic acid carbohydrate with the chemical formula C 6 H 10 O 7 including derivatives, analogs, and salts thereof Unless otherwise indicated, recitation of “d-galacturonic acid” herein is intended to include, without limitation, the molecules d-(−)-d-galacturonic acid, d-galacturonic acid, (alpha)-d-galacturonic acid, (beta)-d-galacturonic acid, and (alpha,beta)-d-galacturonic acid.
“Erythrose” refers to an aldose (tetrose) carbohydrate with chemical formula C 4 H 8 O 4 , including any stereoisomers, derivatives, analogs and salts thereof Unless otherwise indicated, recitation of “erythrose” herein is intended to include, without limitation, the molecules: D-(−)-erythrose, L(+)-erythrose, D(−)-erythrose, D-erythrose, L-erythrose and D(−)-erythrose and meso-erythrose. A Fischer Projection of the D-erythrose structure (1) is provided below.
“Decarboxylation” as used herein refers to the removal of a carboxyl group (—COOH) by a chemical reaction or physical process. Typical products of a decarboxylation reaction may include carbon dioxide (CO 2 ) or formic acid.
The term “electrochemical” refers to chemical reactions that can take place at the interface of an electrical conductor (an electrode) and an ionic conductor (the electrolyte). Electrochemical reactions can create a potential between two conducting materials (or two portions of a single conducting material), or can be caused by application of external voltage. In general, electrochemistry deals with situations where an oxidation reaction and a reduction reaction are separated in space.
The term “electrolytic” as used herein refers to an electrochemical oxidation or reduction reaction that results in the breaking of one or more chemical bonds. Electrolytic reactions as used herein describe reactions occurring as a product of interaction with a cathode or anode.
As used herein, “derivative” refers to a chemically or biologically modified version of a chemical compound that is structurally similar to a parent compound and (actually or theoretically) derivable from that parent compound. A derivative mayor may not have different chemical or physical properties of the parent compound. For example, the derivative may be more hydrophilic or it may have altered reactivity as compared to the parent compound. Derivatization (i.e., modification) may involve substitution of one or more moieties within the molecule (e.g., a change in functional group) that do not substantially alter the function of the molecule for a desired purpose. The term “derivative” is also used to describe all solvates, for example hydrates or adducts (e.g., adducts with alcohols), active metabolites, and salts of the parent compound. The type of salt that may be prepared depends on the nature of the moieties within the compound. For example, acidic groups, for example carboxylic acid groups, can form, for example, alkali metal salts or alkaline earth metal salts (e.g., sodium salts, potassium salts, magnesium salts and calcium salts, and also salts quaternary ammonium ions and acid addition salts with ammonia and physiologically tolerable organic amines such as, for example, triethylamine, ethanolamine or tris-(2-hydroxyethyl)amine) Basic groups can form acid addition salts, for example with inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or with organic carboxylic acids and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid, methanesulfonic acid or p-toluenesulfonic acid. Compounds which simultaneously contain a basic group and an acidic group, for example a carboxyl group in addition to basic nitrogen atoms, can be present as zwitterions. Salts can be obtained by customary methods known to those skilled in the art, for example by combining a compound with an inorganic or organic acid or base in a solvent or diluent, or from other salts by cation exchange or anion exchange.
As used herein, “analogue” refers to a chemical compound that is structurally similar to another but differs slightly in composition (as in the replacement of one atom by an atom of a different element or in the presence of a particular functional group), but may or may not be derivable from the parent compound. A “derivative” differs from an “analogue” in that a parent compound may be the starting material to generate a “derivative,” whereas the parent compound may not necessarily be used as the starting material to generate an “analogue.”
Any concentration ranges, percentage range, or ratio range recited herein are to be understood to include concentrations, percentages or ratios of any integer within that range and fractions thereof, such as one tenth and one hundredth of an integer, unless otherwise indicated. Also, any number range recited herein relating to any physical feature, such as polymer subunits, size or thickness, are to be understood to include any integer within the recited range, unless otherwise indicated. It should be understood that the terms “a” and “an” as used above and elsewhere herein refer to “one or more” of the enumerated components. For example, “a” polymer refers to one polymer or a mixture comprising two or more polymers. As used herein, the term “about” refers to differences that are insubstantial for the relevant purpose or function.
Electrochemical Decarboxylation
The process of eletrolytically decarboxylating a carbohydrate acid in an electrochemical cell is describe below. The step of electrochemical oxidative decarboxylation of a reactant substrate can be performed on the reactant substrate. In some embodiments, the methods include the step of electrolytic decarboxylating the carbohydrate acid reactant to produce a carbohydrate.
The reactant can be provided as a solution placed in contact with an electrode. The solution includes the reactant and a solvent. The reactant can be dissolved in the solvent by any suitable method, including stirring and/or heating where appropriate. The solvent can be any solvent in which the reactant can dissolve to a desired extent. Preferably, the solvent is aqueous.
In one embodiment, any suitable carbohydrate acid capable of producing a carbohydrate as a product of an electrolytic decarboxylation step can be used as a reactant. In one embodiment, the reactant is arabinonic acid as well as suitable derivatives, analogs and salts of the reactants. Suitable reactants include derivatives and analogs of the carbohydrate acid reactant can include reactants with chemical structure variations that insubstantially vary the reactivity of the molecule from undergoing an electrolytic decarboxylation process to produce either erythrose or an intermediate that can be converted to erythrose.
The decarboxylation reaction is performed electrochemically. In one aspect, electrolytic decarboxylation of a reactant in a solution provides a desired product or intermediate that can be subsequently converted to the desired product. In some embodiments, the reactant is arabinonic acid, such as D- or L-arabinonic acid, and the product is an erythrose, such as D- or L-erythrose.
In some embodiments, at least about 10% of the acid is neutralized—that is it exists as a corresponding salt thereof. For example, the acid reactant solution can be provided with about 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100% of one or more reactant acids equivalents neutralized. In some embodiments, 10%-100% of at least one ribonic acid or arabinonic acid reactant is neutralized.
In one aspect, the pH or percent neutralization could be provided and/or maintained within a desirable range throughout the reaction, for example by using a divided electrolytic cell with a cation exchange membrane and adding an alkali metal hydroxide to the anolyte. In another aspect, the pH or percent neutralization could be provided and/or maintained within a desirable range throughout the reaction, for example by simultaneously passing the anolyte through two sets of electrolytic cells, one a divided electrolytic cell with a cation exchange membrane, and the other a single compartment cell. The reactant carbohydrate acid solution can have any suitable pH to provide a desired concentration of dissociated reactant. For a reactant solution comprising an arabinonic acid reactant, the pH can be between 3.0 and 6.0 during the decarboxylation reaction.
Optionally, the residual reactant can be recycled by separating the starting material from products, for example by use of a cation exchange chromatographic resin. A partially decarboxylated solution of carbohydrate acid can contain both the starting carbohydrate acid (e.g., arabinonic acid) and the product (e.g., erythrose). A partially reacted solution can be passed over a bed or column of ion exchange resin beads for a chromatographic separation of the reactant and the product.
Electrolytic Apparatus
The electrochemical decarboxylation of a carbohydrate acid reactant can be performed using a two compartment electrolytic cell divided by a cation exchange membrane. The electrochemical decarboxylation is performed by contacting a solution containing carbohydrate acid with an anode, where the reactant can be decarboxylated. Contact between the reactant material and the anode can elicit the decarboxylation, resulting in carbon dioxide and a product carbohydrate.
The cell includes an anode. The anode can be formed from any suitable material such as graphite, pyrolytic carbon, impregnated or filled graphite, glassy carbon, carbon cloth, or platinum. In some embodiments, the anode preferably comprises a carbon reactive surface where oxidation of the reactant acid can occur. In one embodiment, the anode surface comprises a highly crystalline graphitic material, such as a graphite foil flexible graphite. Other materials such as platinum or gold can also be used to form the anode's reactive surface. In one embodiment, the reactant carbohydrate acid is arabinonic acid and is oxidized at or near the anode's reactant surface forming erythrose.
The cell also includes a cathode where a reduction can occur within the electrochemical cell. The cathode can be formed from any suitable material having a desired level of electrical conductivity, such as stainless steel or nickel. In one embodiment, the decarboxylation reaction at the anode can be:
Arabinonic acid−2e − - - - - - - ->erythrose+CO 2 +2H +
The counter electrode reaction can be:
2H 2 O+2e − - - - - - >2OH − +H 2
Typically, some current can be lost to the production of O 2 gas at the anode.
The cell also includes a cation selective membrane dividing the anolyte and catholyte solutions and compartments. The membrane could include, for example, heterogeneous or homogenous membranes. The latter could be a polymeric membrane with sulfonate or carboxylate ion exchange groups. The polymer could be hydrocarbon based or fluorocarbon based. As an example, Nafion(R) 115 (DuPont™ Fuel Cell) membrane is a perfluorosulfonic acid membrane that selectively transports cations.
In one aspect, water is reduced at or near the surface of the cathode to hydroxide ion and hydrogen gas. As the reaction proceeds, alkali metal cations pass from the anolyte to the catholyte across a cation exchange membrane and act as the counter-ion to the hydroxide, generating a alkali metal hydroxide solution.
The electrochemical cell can be configured electrically in either a monopolar or bipolar configuration. In the monopolar configuration, an electrical contact is made to each electrode. In the bipolar configuration each electrode has a cathode and an anode side and electrical connection is made only to the electrodes positioned at the ends of the cell stack comprising multiple electrodes.
Alkali Oxidation of a Carbohydrate
In another aspect, the carbohydrate acid can be obtained from a suitable carbohydrate starting material by alkali oxidation. In one embodiment, the carbohydrate acid is arabinonic acid, which is prepared by oxidizing a starting material comprising glucose or fructose with oxygen gas in an alkaline water solution (for example, as described in U.S. Pat. Nos. 4,125,559 and 5,831,078, incorporated herein by reference). The starting material may include glucose, fructose, or a mixture thereof, and the starting material is reacted with an alkali metal hydroxide and oxygen gas in aqueous solution by first heating the alkali metal hydroxide in aqueous solution at a temperature between about 30° C. and 100° C. The starting material can be a D-hexose such as D-glucose, D-fructose or D-mannose, which can be present in various ring forms (pyranoses and furanoses) and as various diastereomers, such as (alpha)-D-glucopyranose and (beta)-D-glucopyranose. The starting material can be reacted with the alkali metal hydroxide in a stoichiometric amount, or in excess, using for example an amount of from 2 to 5 equivalents of the alkali metal per mole of the D-hexose. For example, alkali metal hydroxides may be sodium hydroxide or potassium hydroxide. The oxygen is preferably used in a stoichoimetric amount or in excess, but preferably with an amount of from 1 to 20 moles of O 2 per mole of the D-hexose starting material. The reaction can be carried out at above 30° C., and under a pressure of about 1 to 50 bars. The reaction may be performed continuously or batchwise, in a suitable solvent.
Alternatively, fructose (such as D-fructose) can be converted to D-arabinonic acid by reaction with oxygen gas in an alkaline water solution as described in J. Dubourg and P. Naffa, “Oxydation des hexoses reducteur par l'oxygene en milieu alcalin,” Memoires Presentes a la Societe Chimique , p. 1353, incorporated herein by reference. The carbohydrate acid can also be obtained from the noble metal catalyzed alkali oxidation of aldoses and aldosides. In a particular embodiment, the carbohydrate acid is arabinonic acid, which can be prepared by oxidizing a starting material such as D- or L-arabinose with oxygen gas and a noble metal catalyst in an alkaline water solution, see Bright T. Kusema, Betiana C. Campo, Päivi Mäki-Arvela, Tapio Salmi, Dmitry Yu. Murzin , “Selective catalytic oxidation of arabinose—A comparison of gold and palladium catalysts,” Applied Catalysis A: General 386 (2010): 101-108, incorporated herein by reference.
Gluconic acid can be prepared by oxidizing glucose with oxygen gas and a noble metal catalyst in an alkali water solution, for example, as described in Ivana Dencicl, Jan Meuldijkl, Mart Croonl, Volker Hessel “From a Review of Noble Metal versus Enzyme Catalysts for Glucose Oxidation Under Conventional Conditions Towards a Process Design Analysis for Continuous-flow Operation,” Journal of Flow Chemistry 1 (August 2011): 13-23, incorporated herein by reference. Methyl-d-glucuronopyranoside can be prepared by oxidizing glucose with oxygen gas and a noble metal catalyst in an alkali water solution, for example, as described in A. P. Markusse, B. F. M. Kuster, J. C. Schouten, “Platinum catalysed aqueous methyl-d-glucopyranoside oxidation in a multiphase redox-cycle reactor,” Catalysis Today 66 (2001) 191-197, incorporated herein by reference.
The alkali metal hydroxide used for the preparation of the carbohydrate acid reactant can be produced in the cathode compartment of an electrolytic cell described herein during a prior or simultaneous decarboxylation of a carbohydrate acid.
EXAMPLES
The following examples are to be considered illustrative of various aspects of the invention and should not be construed to limit the scope of the invention, which are defined by the appended claims.
Example 1
A plate and frame type electrochemical cell was prepared using a 0.12 m 2 anode, 0.12 m 2 cathode, a membrane dividing the chambers, and turbulence promoting plastic meshes between the electrodes and membrane on each side. The anode was graphite foil and the cathode was a sheet of Nickel 200. The membrane was cation exchange membrane FumaTech FKB. The anode and cathode were sealed into polyethylene flow frames which distribute solution flow across the electrode surfaces. Anolyte flow through the electrochemical cell was controlled at a linear flow rate of 7 cm per second across the anode and the catholyte flow rate was set to match. Power to the cell was provided by an external power supply at a current density of 150 mA/cm 2 . The initial anolyte consisted of a 2.5 Molar arabonic acid solution, which was 100% neutralized and in the sodium salt form. To maintain the desired neutralization of the arabonic acid (pH of 5.15 in the anolyte tank), sodium hydroxide was delivered to the anolyte tank. The catholyte was a 1.89M sodium hydroxide solution the concentration of which was maintained (+/−0.2 Molar) throughout the electrolysis by the addition of deionized water.
The electrolysis was run until 402 Amp-hours of charge had passed; the current efficiency for erythrose and sodium hydroxide formation was measured as 91% and 87% respectively.
Example 2
The following example used the same cell and electrolysis setup as Example 1; the parameter changed was the catholyte sodium hydroxide concentration. The catholyte concentration was maintained between 4.4 and 4.7M Sodium hydroxide by the addition of deionized water. The electrolysis was continued until 402 amp-hours of charge had passed. The current efficiency for erythrose formation was measured at 87%. The current efficiency for sodium hydroxide production in the catholyte was 64%. This back-migration of hydroxide again reduced the amount of caustic addition required to maintain the anolyte neutralization to 3.3 moles (compared to 6.7 moles when a 2M sodium hydroxide catholyte was used).
Example 3
The following example used the same cell and electrolysis setup as Example 1. In this experiment, the catholyte concentration was maintained at 5M sodium hydroxide by the addition of deionized water. The neutralization of the arabonic acid was maintained by the addition of 5.3M sodium hydroxide, which was produced as the catholyte during the decarboxylation of arabonic acid using the setup described in Example 1. The current efficiency for erythrose formation was 92%.
Example 4
The method of example 1 was repeated with anolytes consisting of 2.5 M D- gluconic acid, 2.5 Molar D -glucuronic acid, and 2.5 Molar D -galacturonic acid. The method decarboxylated D -gluconic acid to yield D -arabinose with a current efficiency of 100%. The method decarboxylated D -glucuronic acid to yield xylo-pent-1,5-diose with a current efficiency of 49%. The method decarboxylated D -galacturonic acid to yield L -arabino-1,5-diose with a current efficiency of 20%.
Example 5
The method of example 2 was used to produce 5.4 M sodium hydroxide. 100 grams of a 20% wt/wt solution of D -glucose was placed in a high pressure reaction vessel equipped with a gas shaft turbine. The vessel was purged with oxygen and then brought to 50 bar pressure of oxygen, with the temperature maintained at 45° C. 0.244 moles of sodium hydroxide from example 2 was added over 72 minutes, after which the reaction was allowed to proceed for another 25 minutes. The reaction yielded 17 grams of sodium arabonate. | Methods for decarboxylating carbohydrate acids in a divided electrochemical cell are disclosed using a cation membrane. The improved methods are more cost-efficient and environmentally friendly than conventional methods. | 2 |
This application claims the benefit of U.S. Provisional Patent Application No. 61/788,175 filed 15 Mar. 2013, titled “ADJUSTABLE STENCIL FOR PAINTING PARKING LOTS,” which is hereby incorporated by reference for all purposes as if fully set forth herein.
BACKGROUND
1. Field of the Invention
The present invention relates in general to the field of stencils for parking lot markings.
2. Description of Related Art
The making of a stencil has long been the preferred method of marking a surface by using the projected cut out idea, transferred onto a thin sheet of material, be it paper, plastic, metal etc. Users can then place the stencil on any number of surfaces and create the desired design by applying some sort of pigment. This method has undergone a variety of changes from simple transference of tribal signs to that of more elaborate family crest. The distinguishing of men on the battlefield was often done by stenciling the sign of the kingdom to shields and clothing, because of its ease of transference. But as the science of stenciling developed, so too did its forms and importance. Stencils have played some very important roles in the development of our shared history. The story is told of the young Johann Gutenberg, who entered the shop of his father and by accident, dropped a carved wooden letter into a bucket of pigmented liquid. He quickly retrieved it from the liquid and placed it on a surface to dry. Later when he moved the letter he noticed the impression left, and thus a stencil was marked in the mind of the man who would bring the world out of the age of the quill to the science of immoveable type. During the great wars in Europe, the training of airplane pilots to be accurate in bomb dropping was marked on the pretended field of battle by a large stenciled X, thus giving the pilot a viewable target from above. This type of stenciling is more in line with the application being presented, i.e., on the ground. Not simply the marking of personal items, but rather the stenciling of shared space. With the rise and expansion of cities, and thus the need for directional development, an ever increasing system of surface applications has become necessary. If one can mark a field, one then directs an ever expanding mass of transit by applying necessary information to the varied surfaces upon which they transverse. Thus parking lot striping allows the public to maintain order and share common spaces with safety. It has become necessary in the course of development to stencil certain spaces for those among us who suffer with some type of disability. Their preferred parking places have become the universal symbol for safety and preference. The need has also arisen for the shared space of transit to be marked with certain directional arrows, allowing for the ease of flow and the lessening of accidents and congestion. And with the rise of the modern fast food restaurant such pavement markings have taken on a life of their own. Entire packages of logos and local or regional fixed stencils exist to give the driver a since of local shared identity. Thus we see an every widening array of products filling the market to meet the needs of our ever changing transit experience.
There is a certain sense of excitement as a new business moves into a neighborhood. The new architecture, and clean curb appeal make for the ever increasing value of that neighborhood. However certain problems do exist for the owners of such business. One being that which this application addresses. Sadly the pavement marking industry, which has no problem in creating accurate zoned new construction fixed markings, stumbles in the later maintenance and care for such directional's. Here is the problem. Suppose an initial striper enters the parking lot striping industry. The initial striper then must make certain choices as to the font and sizes of lettering for such things as DRIVE THRU, ENTER, EXIT, ONLY, LOADING ZONE, ETC. The initial striper must also decide on a size of arrow for giving direction to the initial striper's customers. Such arrows vary from as little as 6″ to the ever sprawling 92″. Also the handicap marking for such business must be done in compliance with the ADA, usually requiring the initial striper to stencil a large blue box overlaid with a white wheelchair symbol. Finally, the initial striper completes the striping of the parking lot, and move on to the next job. The problem arises when the new striper follows the initial striper and tries to perform general maintenance in re-striping the parking lot. If the new striper has not chosen the same size of fixed stencils, arrows or, boxes, the new striper must make certain adjustments to the initial striper preexisting sizes. Thus over years of parking lot maintenance restriping various users have seen something that looked so easy, become an ever sprawling metamorphosis of dysfunction. Stripers have not always had the same font style or stencil size as the initial striper before them, and so users have only one option afforded to them in the course of performing their maintenance tasks. Paint a box over the existing stenciling and then apply a larger size stencil using another color. It's a common practice. This then becomes the pattern for those who follow the new striper, except they never are able to cover the new striper's square or arrow cleanly and accurately. It continues to get ever larger and larger. Or in the case of the arrows, they simply get a paint over, which leaves the old arrow, peering and poking out from under the new one. Most use a makeshift elaboration of boards, tape, paint paddles, etc. to try and maintain the size of the box or arrow, as the ability to mimic the same size is elusive. Thus the need to have an adjustable stencil for arrows, boxes, parking bumps, and lighting poles has led to the creation of just such a product.
While there are many stencils for painting parkings lot well known in the art, considerable room for improvement remains.
DESCRIPTION OF THE DRAWINGS
The novel features believed characteristic of the embodiments of the present application are set forth in the appended claims. However, the embodiments themselves, as well as a preferred mode of use, and further objectives and advantages thereof, will best be understood by reference to the following detailed description when read in conjunction with the accompanying drawings, wherein:
FIG. 1A is a plan view of a preferred embodiment of an adjustable stencil for painting parking lots according to the present application;
FIG. 1B is a partial cross-sectional view of the adjustable stencil for painting parking lots of FIG. 1A taken at IB-IB in FIG. 1A according to the present application;
FIG. 2 is a plan view of an alternative embodiment of an adjustable stencil for painting parking lots according to the present application;
FIG. 3A is a partial plan view of a preferred embodiment of an assembled adjustable stencil for painting parking lots according to the present application;
FIG. 3B is a partial cross-sectional view of the assembled adjustable stencil for painting parking lots of FIG. 3A taken at IIIB-IIIB in FIG. 3A according to the present application;
FIG. 4A is a perspective view of a preferred embodiment of a triangular assembled adjustable stencil for painting parking lots according to the present application;
FIG. 4B is a plan view of a preferred embodiment of a triangular assembled adjustable stencil for painting parking lots according to the present application;
FIG. 5A is a perspective view of a preferred embodiment of a square shaped assembled adjustable stencil for painting parking lots according to the present application;
FIG. 5B is a plan view of a preferred embodiment of a square shaped assembled adjustable stencil for painting parking lots according to the present application;
FIG. 6A is a perspective view of a preferred embodiment of a rectangular assembled adjustable stencil for painting parking lots according to the present application;
FIG. 6B is a plan view of a preferred embodiment of a rectangular assembled adjustable stencil for painting parking lots according to the present application;
FIG. 7A is a perspective view of a preferred embodiment of a circular assembled adjustable stencil for painting parking lots according to the present application; and
FIG. 7B is a plan view of a preferred embodiment of a circular assembled adjustable stencil for painting parking lots according to the present application.
While the assembly and method of the present application is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular embodiment disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present application as defined by the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Illustrative embodiments of the adjustable stencil assembly and method are provided below. It will of course be appreciated that in the development of any actual embodiment, numerous implementation-specific decisions will be made to achieve the developer's specific goals, such as compliance with assembly-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time-consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
The assembly is comprised of a series of stencils that allow the parking lot striper the ability to save time and resources by adjusting the arrow, box, bump, or pole application as needed, thus mimicking the size and stopping the sprawl. The fixed stencil industry is in need of a device that is both functional and efficient. With the creation of an adjustable stencil, a user can go as small or as large as needed, but keeping the original template intact.
The ability to adjust to the maintenance application needed is fast and easy with just the twist of a few T-knobs and the positioning of the adjustable paddles. The fixed stencil industry has not been relegated and as such has been found inefficient and wooden in its approach to directional stencil signage. With this device a user can remedy the frustration of the owner, community, and striper by keeping the original context as close to its original application as possible.
The adjustable Arrow, Square, and Bump stencils all consist of an elongated trunk which is mated with an elongated paddle. It is fixed with a handle in the middle separating the two routed or slotted vents. These are then screwed together. They affix together in a basic shape, such as an Arrow, Square or Rectangle, with Carriage bolts, washers and T-knobs. The Circle, follows the same trunk affixed to the paddle but is cut into two equal halves. It is also screwed together at the base, from the bottom into the top trunk.
Referring to FIG. 1A , a plan view of a preferred embodiment of an adjustable stencil for painting parking lots according to the present application is illustrated. The stencil is assembled from a series of trunks 101 or members. Trunk 101 is typically fabricated from a non-porous material such as high density plastic. Because the trunk 101 is exposed to various paints and chemicals it needs to be non-reactive. Trunk 101 is made from a single piece and includes a series of slotted vents 111 and 113 parallel to the length of the trunk 101 . Slotted vents 111 and 113 are designed to allow users to interconnect a plurality of trunks together to shape a stencil. While it is shown that there are two slotted vents in the trunk, it should be apparent that a single slotted vent or alternatively more slotted vents are possible. Along an edge of the trunk is a fastening means for securing a paddle (not shown). Typically the fastening means are a series of evenly spaced screws 121 . Screws 121 are designed to be recessed into the trunk 101 so that the top of the trunk 101 is flush or uniform without screw heads protruding from the upper surface of the trunk 101 .
Referring now also to FIG. 1B , a partial cross-sectional view of the adjustable stencil for painting parking lots of FIG. 1A taken at IB-IB in FIG. 1A according to the present application is illustrated. Trunk 101 includes an upper surface 101 a , a lower surface 101 b , an outboard surface 101 c , and inboard surfaces 101 d - 101 h . Inboard surfaces 101 d - 101 h are typically made from cutting a slot 115 and a corner 117 into the length of the trunk 101 . Slot 115 allows a paddle (not shown) to mechanically couple to the trunk 101 . It should be apparent that the slot 115 could be grooved to provide greater mechanical coupling strength to reduce the chance the paddle (not shown) can be inadvertently removed.
The slotted vent 111 located in trunk 101 includes three regions. First slot 111 a is located near the upper surface of the trunk 101 and only goes to a certain depth in the trunk 101 . Second slot 111 b is located near the lower surface of the trunk 101 and only goes to a certain height in the trunk 101 . The third slot 111 c connects the first slot 111 a and the second slot 111 b and provides an opening though the trunk 101 . Slots 111 a and 111 b allow the fasteners between different paddles to remain flush.
Referring now also to FIG. 2 , a plan view of an alternative embodiment of an adjustable stencil for painting parking lots according to the present application is illustrated. Trunk 201 is very similar to trunk 101 , however the screws 221 are shifted more inboard so that the screws 221 go through the paddle (not shown) into the trunk 201 . Moving the screws 221 provides a smoother upper or top surface of the trunk 201 .
Referring now also to FIG. 3A , a partial plan view of a preferred embodiment of an assembled adjustable stencil for painting parking lots according to the present application is illustrated. Coupled to trunk 301 is paddle 303 . Paddle 303 is made of plastic or rubber and is designed to provide flexibility to the stencil, thereby allowing the stencil to adjust to the surface irregularities of the parking lot. Users of the stencil can remove the paddle 303 from the trunk 301 and replace it as it becomes brittle with age or is too coated with paint to flex. Coupled to trunk 311 is paddle 313 . Trunk 301 is mechanically coupled to trunk 311 to form an acute angle. The mechanical coupling is accomplished by use of a carriage bolt, a series of washers, and a t-nut. An alternative embodiment uses a handle with a nut located inside the handle for tool less tightening and loosening of the nut. The t-nut allows a user to quickly adjust the friction between trunk 301 and trunk 311 . Therefore, the user can adjust the angle between the two trunks and prevent relative motion between the two trunks.
Referring now also to FIG. 3B , a partial cross-sectional view of the assembled adjustable stencil for painting parking lots of FIG. 3A taken at IIIB-IIIB in FIG. 3A according to the present application is illustrated. Carriage bolt 321 is located in the slotted vents of trunk 301 and trunk 311 . While a carriage bolt is shown, it should be apparent that other types of fasteners may be used to mechanically couple trunk 301 to trunk 311 . A t-nut 327 is used to secure the carriage bolt 321 to the trunks. It should be apparent that other types of fasteners are useable in place of the t-nut 327 or a t-knob. The use of a t-nut 327 provides the user with a tool less option to adjust the angle between the trunks without having to use a tool like a wrench. Another alternative to the t-nut 327 is a handle with an embedded nut. Washers 331 are used between the carriage bolt 321 and the trunk 311 along with between the t-nut 327 . Furthermore, it should be apparent that the washers 331 could have a locking function to increase friction and reduce the chance that the trunks loosen up.
Referring now also to FIG. 4A , a perspective view of a preferred embodiment of a triangular assembled adjustable stencil for painting parking lots according to the present application is illustrated. The any arrow or triangular shaped stencil 400 is formed by combining three trunks 401 , 411 , and 421 . Trunk 401 includes a paddle 403 and a handle 405 . Paddle 403 or mask in alternative embodiments is disposable so that the user can readily replace the paddle as it is covered in paint and becomes too inflexible or irregularly shaped to mask a straight line. Handle 405 is shown above the stencil; however other embodiments have a recessed handle to facilitate sliding one trunk over anther trunk to adjust the shape. Trunk 411 includes a paddle 413 and a handle 415 . Trunk 421 includes a paddle 423 and a handle 425 . It should be apparent that handle 425 is attached to trunk 421 by fasteners and allows the user to adjust and control the trunk 421 . While the mechanical couplings have not been shown for clarity purposes, the trunks are attached by using carriage bolts, t-nuts, and washers.
Referring now also to FIG. 4B , a plan view of a preferred embodiment of a triangular assembled adjustable stencil for painting parking lots according to the present application is illustrated. Trunks 401 , 411 , and 421 are arranged by the user to create a triangular region 451 . Paddle 423 overlaps paddle 403 and paddle 413 . The user then applies paint in the triangular region 451 to paint a triangle. While the mechanical couplings have not been shown for clarity purposes, the trunks are attached by using carriage bolts, t-nuts, and washers.
For assembling the “Any Arrow” the user should do the following. First lay the three elongated trunk pieces side by side. Next place them in the shape desired, a triangle for an arrow. Then make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Then place the top of one on the top of the other, connecting them at the top most parts. Next take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. This should have given the user the appearance of an inverted V. Next place the elongated trunk piece on the top, but at the bottom of the piece to the user's right. Make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. Next place the remaining unconnected pieces together. It is important to make sure the remaining trunk pieces just fastened are placed under the first trunk piece on the left. Make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. This should give the appearance of a triangle.
Referring now to FIG. 5A , a perspective view of a preferred embodiment of a square shaped assembled adjustable stencil for painting parking lots according to the present application is illustrated. The “any square” or square shaped stencil 500 is formed by combining four trunks 501 , 511 , 521 , and 531 . First trunk 501 includes a flexible rubber paddle 503 along with a handle 505 . Second trunk 511 includes a flexible rubber paddle 513 along with a handle 515 . Third trunk 521 includes a flexible rubber paddle 523 along with a handle 525 . Forth trunk 531 includes a flexible rubber paddle 533 along with a handle 535 . While the mechanical couplings have not been shown for clarity purposes, the trunks are attached by using carriage bolts, t-nuts, and washers. Trunk 501 includes a graduated scale 507 located on paddle 503 . Graduated scale 507 as illustrated is a series of evenly spaced indicators. The indicators could be grooves, lines, ridges, with and without numerical references. The graduated scale 507 allows users to keep the trunks parallel or square without having to resort to measure the distance or angle between the paddles. While it is shown that only one trunk 501 of “Any Square” stencil 500 has the graduated scale 507 it should be apparent that any of the trunks described here could feature embedded references to assist the painters.
Referring now to FIG. 5B , a plan view of a preferred embodiment of a square shaped assembled adjustable stencil for painting parking lots according to the present application is illustrated. Trunks 501 , 511 , 521 , and 531 are arranged by the user to create a square region 551 . The user then applies paint in the square region 551 to paint a square. While the mechanical couplings have not been shown for clarity purposes, the trunks are attached by using carriage bolts, t-nuts, and washers.
For assembling the “Any Square” the user should do the following. First lay the four elongated trunk pieces side by side. Then make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Then place the top of one on the top of the other, connecting them at the top most parts. Next take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. This should have given the user the appearance of an inverted V. Next place the elongated trunk piece on the top, but at the bottom of the piece to the user's right. Make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. Next place the remaining unconnected pieces together. It is important to make sure the remaining trunk pieces just fastened are placed under the first trunk piece on the left. Make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. Since the user is making the square repeat the process one more time, making sure the right trunk piece is on top of the last one fastened, but underneath the remaining unsecured trunk. Make sure the paddle sides are facing inward toward each other. Make sure the handle is facing upward. This should give the appearance of a square.
Typically, the user would find an existing painted square on a parking lot needing repainting. The user would take four trunks and position them so the paddles are facing inwards. The user would position or locate the paddles to just outside the existing painted square. The user would then start securing the first trunk to the second adjacent trunk through the use of fasteners and washers. The user would then continue securing further trunks to the assembly until all the trunks surrounding the existing painted square are secured. The user might have to reposition the paddles to insure proper placement as the stencil is assembled around the existing painted square. The user then can apply paint inside the paddles to repaint the existing painted square. Additionally, it should be apparent that the number of trunks to be used can be adjusted to match the number of sides of the shape to be painted. For example, if a six sided shape was desired, then six different trunks with paddles are used.
Referring now also to FIG. 6A , a perspective view of a preferred embodiment of a rectangular assembled adjustable stencil for painting parking lots according to the present application, as well as, to FIG. 6B a plan view of a preferred embodiment of a rectangular assembled adjustable stencil for painting parking lots according to the present application are illustrated. The rectangular stencil 600 or “Any Bump” is suitable for painting rectangles, quadrilaterals, and rectangular shaped objects such as speed bumps in parking lots. The stencil 600 includes an elongated first trunk 601 , an elongated second trunk 611 , a third trunk 621 , and a fourth trunk 631 . First trunk 601 includes a flexible rubber paddle 603 along with a handle 605 . Second trunk 611 includes a flexible rubber paddle 613 along with a handle 615 . While the assembly is shown without paddles and handles on the third and fourth trunks it should be apparent that they could be added to the stencil. While the mechanical couplings have not been shown for clarity purposes, the trunks are attached by using carriage bolts, t-nuts, and washers.
Assembling the “Any Bump” is as follows. First lay the two elongated trunk pieces along with the smaller trunk pieces in a row. Take the two longer trunk pieces and place them parallel horizontal to each other. Make sure the paddle side is facing inward. Make sure the handle side is up. Next place the smaller trunk piece under the right side of the top trunk piece toward the farthest right part. Make sure the paddle is facing inward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. This should give the appearance of a horizontal L. Next place the smaller trunk piece under the left side of the top longer top trunk piece. Make sure the paddle is facing inward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. Repeat this process on the remaining bottom left top trunk laying on the smaller trunk piece. This should give the appearance of an L. Make sure the paddle is facing inward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob. Next repeat the process on the bottom right bottom trunk laying on the smaller trunk piece. Make sure the paddle is facing inward. Take the carriage bolt and washer and place them in the aligned slotted vent. As the bolt protrudes through both trunks, place the second washer on the threaded extended portion and secure it with the supplied T-knob.
Referring now also to FIG. 7A , a perspective view of a preferred embodiment of a circular assembled adjustable stencil for painting parking lots according to the present application is illustrated. The “Any Pole” or circular stencil 700 is designed for masking out a circle, such as around a light pole base. Trunk 701 in combination with trunk 711 is designed to paint circular shaped areas of parking lots such as around a concrete base for a lamp. Paddle 703 is attached to trunk 701 through use of fasteners attached to the trunk 701 from the underside of the stencil. Additionally, trunk 701 includes a handle 705 to ease adjustment of the paddle relative to the other half of the stencil and to the parking lot. Paddle 713 is attached to trunk 711 through use of fasteners attached to the trunk 711 from the underside of the stencil. Additionally, trunk 711 includes a handle 715 to ease adjustment of the paddle relative to the other half of the stencil and to the parking lot.
Referring now also to FIG. 7B , a plan view of a preferred embodiment of a circular assembled adjustable stencil for painting parking lots according to the present application is illustrated. Because the diameter of the stencil is not readily adjustable, a user would have a variety of various “Any Pole” stencils to be able to paint around a variety of poles and circular concrete mounts.
The “Any Pole” comes assembled. The circular stencil is able to fit the pole base by simply aligning the two pieces together. Make sure the paddle portions are facing inward. If adjustment is needed on the pole this can be achieved by rotation of the stencil. Making sure that the inmost surface of the circle is touching the pole base.
It is apparent that an assembly and method with significant advantages has been described and illustrated. The particular embodiments disclosed above are illustrative only, as the embodiments may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. It is therefore evident that the particular embodiments disclosed above may be altered or modified, and all such variations are considered within the scope and spirit of the application. Accordingly, the protection sought herein is as set forth in the description. Although the present embodiments are shown above, they are not limited to just these embodiments, but are amenable to various changes and modifications without departing from the spirit thereof. | An adjustable stencil for painting parking lots. The adjustable stencil enables parking lot painters adjust the stencil for painting lines, stripes, boxes, and arrows on parking lots. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a method of exclusive control for a tuple-oriented file system, or more in particular to a method of exclusive control of areas in a page for a database management system for managing the data base storing data accessed by a plurality of transactions.
A database management system for managing the database storing data accessed by a plurality of transactions has recently been available in which records are configured as a tuple-oriented file system.
In the case where records of a data base are configured of a tuple-oriented file system, as described in Jim Gray, Andreas Reuter; TRANSACTION PROCESSING: CONCEPTS AND TECHNIQUES, Morgan Kaufmann Publishers, Inc., 1993, pp. 752-761 and pp. 794-819, each page contains a plurality of records, each of which in turn is represented as at least a tuple. An example page configuration is shown in FIG. 2. Page 201 includes a plurality of tuples 202 and a plurality of slots 203. Each slot stores the position in the page of the tuple indicated by the particular slot, and each tuple is uniquely identified by the page number and the slot number (hereinafter referred to as "the physical identification numbers"). A tuple can be added in the positive direction of address (incremental direction), and the slot in the negative direction of address (decremental direction).
The condition in each page is managed by a page header 207. Items managed by the page header include a leading offset 206 of an unoccupied area 205 in the page, the size of a vacant area which may occur when a tuple is eliminated or shortened, a maximum slot number assigned to the page and the number of slots in use.
In the case where a tuple is added to a page with an unoccupied area 205 larger than the size required for adding a new tuple, such a tuple is added from the leading offset 206 of the unoccupied area 205. In the case where the unoccupied area 205 is not sufficiently large as compared with the tuple to be added although the sum of the size of the unoccupied area 205 and the size of the entire vacant area 204 is larger than the size required for adding a new tuple, on the other hand, tuple addition is made possible by page compaction (as described later). When the sum of the size of unoccupied area and the size of the vacant area is not sufficiently large for adding a tuple, by contrast, either the tuple to be added can be inserted in another page or a part of the tuple to be added is inserted in the page and the remaining part of the tuple into another page.
A data base is normally accessed simultaneously by a plurality of transactions. In the above-mentioned tuple-oriented file system, assume that after a given transaction 1 deletes a tuple from a given page, another tuple is added by another transaction after compaction of the page, and the commitment has been carried out to update data before the termination of the first transaction. After that, when transaction 1 rolls back, the particular page may lack a vacant area sufficient to restore the deleted tuple, thereby making it impossible to restore the tuple.
A method for solving this problem is proposed by exclusively locking the page until the termination of a transaction that has accessed the page. According to another method, in the case where the unoccupied area or the vacant area in the page increases in size due to tuple deletion or otherwise by a transaction, an unoccupied area table used for managing the size of the unoccupied areas of the page is locked until the termination of the transaction, during which period a tuple reference is allowed while any process is prohibited which consumes the size of the unoccupied area or the vacant area of the page, thereby securing an area required for restoring a tuple.
In the former of the conventional methods described above, other tuples included in the same page cannot be accessed by other transactions until the termination of a transaction, and thus the parallelism of transactions is reduced. According to the latter of the conventional methods described above, on the other hand, although other tuples can be referenced or can otherwise be accessed for update, delete or the like which does not consume the unoccupied area or vacant area of the same page, a tuple cannot be added or updated as it consumes an unoccupied area. Thus the unoccupied or vacant area in a page cannot be used effectively.
With an object-oriented database, more than one tuple are normally combined to represent a complex data structure. In order to improve the access speed to these data, a storage schema is employed for arranging these tuples within the same page as far as possible. In the latter of the conventional methods described above, when a tuple is deleted or updated in a page, other tuples cannot be stored in the same page. The access speed to data having a complex structure is thus reduced.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a method of exclusive control of areas in a page for a tuple-oriented file system, in which a deleted tuple can be restored without changing the physical identification number thereof at the time of roll back processing of a given transaction on the one hand and without reducing the parallelism of transactions on the other hand.
A second object of the present invention is to provide a method of exclusive control of areas in a page for a tuple-oriented file system, in which a vacant area and an unoccupied area in a page can be effectively used.
According to one aspect of the invention for achieving the above-mentioned first object, there is provided a method of exclusive control of areas in a page by a system including tuple access means for performing the steps of requesting exclusive control of a tuple, requesting exclusive control of a page, requesting exclusive control of a vacant area in a page and deciding whether a vacant area in a page can be used, and means for executing an improved compaction (which means a compaction performed within areas other than the unoccupied area in a page) provided in addition to normal compaction means, means for deciding whether a transaction increasing the total size of the vacant area in a page is active, and means for preventing the vacant area of the same page from being used when the transaction is active.
According to a second aspect of the invention for achieving the second object, there is provided a method of exclusive control of areas in a page by a system comprising means for storing the position of the trailing end of a tuple in a page and means for executing an improved compaction, wherein the size of the vacant area and the position of the trailing end of a tuple in the same page is updated at the time of storing the tuple, and the management information of an unoccupied area is updated when the unoccupied area is used for storing a tuple.
The first object may alternatively be achieved in the following manner. In the case where a given transaction increases the size of a vacant area in a page by deleting a tuple from the page or otherwise, the use of the vacant area in the same page is prevented by requesting exclusive control of the vacant area.
In the case where a given transaction requires the use of a vacant area other than the unoccupied area of the page due to the addition, update or the like process of a tuple, the usability of the vacant area in the same page is decided by reference to the requesting means so that the vacant area is used only when it is usable.
Subsequently when the transaction that has increased the vacant area in the page rolls back, the exclusive control and the improved compaction according to the invention are performed in case a tuple to be restored in the unoccupied area cannot be so added (described later). This improved compaction manages by combining a plurality of vacant areas into a single continuous vacant area, and other transactions (excepting the transactions in the process of roll back) are prevented from using the particular continuous vacant area. As a result, an area is secured which is required for rollback of the transaction that has increased the vacant area in the page.
Consequently, a tuple can be restored by rollback of a transaction without changing the physical identification number of the tuple. The result is that exclusive control of the page is effected only during the period when the page is being accessed thereby to improve the parallelism of the transaction processing.
The second object of the invention is alternatively achieved in the following manner. Specifically, consider the case in which there is a single transaction for a page that has increased the total size of vacant areas in the page and that the unoccupied area in the page is not sufficiently large to store a tuple to be added, although the size required for storing a tuple is secured by adding the size of the vacant areas to the unoccupied area. If a tuple can be added to the areas following the position of the trailing end of the tuples in the page, a tuple is added at the position of the trailing end of the tuples in the page. Otherwise, a tuple is added by use of the page management method according to the invention from the position of the trailing end of the tuples in the page after execution of the improved compaction. The vacant areas in the page thus can be effectively utilized.
In the aforementioned case, the vacant area of the page which has been increased by an active transaction can be used only by the particular transaction. After the process for increasing the vacant area, the transaction may consume the vacant area by adding a tuple or otherwise. The restoration in the rollback operation, however, is performed in the reverse order of the transaction. When a tuple is restored in the vacant area, therefore, the consumed area is restored, with the result that the area required for tuple restoration is secured. Consequently, a tuple can be restored without changing the physical identification number of the tuple in the rollback operation.
Further, the first object of the invention may alternatively be achieved in the following manner. In the case where a given transaction deletes a tuple from a page, the binary positional information of the deleted tuple set in the page is reversed from a positive to negative value to indicate the deleted state. In the process, the image of the deleted tuple remains unchanged. The same transaction requests exclusive control of the same tuple until complete operation of the transaction, and other transactions are thereby prevented from using the space of the same tuple.
In the case where all the vacant areas other than the unoccupied area of a page can be used when a given transaction adds a tuple, on the other hand, reference is made to the binary positional information of all the tuples secured in the same page. When the positional information of a tuple is negative in value, the image of the tuple indicated by the positional information is referenced. On the assumption that the sum of the length of the tuple stored in the particular tuple image and the unoccupied area is longer than the length of the tuple to be added, exclusive control of the stored tuple is requested. Once the request for exclusive control is granted, a tuple can be added using the area of a deleted tuple.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing an example system configuration.
FIG. 2 is a diagram showing an example of tuple management in a page.
FIG. 3 is a diagram showing an example structure of the page header.
FIG. 4 shows a flowchart of an example algorithm for searching for a slot used for adding a tuple.
FIG. 5 is a flowchart showing an example algorithm for performing the compaction.
FIG. 6 is a flowchart showing an example algorithm for performing the improved compaction.
FIGS. 7A to 7C are flowcharts showing an example algorithm for adding a tuple.
FIG. 8 is a flowchart showing an example algorithm for deleting a tuple.
FIG. 9 is a flowchart showing an example algorithm of roll back for adding a tuple.
FIG. 10 is a flowchart showing an example algorithm of roll back for deleting a tuple.
FIGS. 11 to 15 are diagrams showing an example page used in the embodiments of the invention.
FIGS. 16A to 16C are flowcharts showing an algorithm for updating a tuple.
FIG. 17 is a flowchart showing an algorithm of roll back for updating a tuple.
FIGS. 18 to 23 show examples of updating a tuple. FIG. 24 is a block diagram showing a database management system.
FIG. 25 is a diagram showing the data structure of a page header.
FIG. 26 is a diagram showing an example structure of a tuple.
FIGS. 27A to 27B are flowcharts showing an algorithm for adding a tuple.
FIG. 28 is a flowchart showing an algorithm for deleting a tuple.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention will be described with reference to FIGS. 1 to 28.
A block diagram of a database management system embodying the invention is shown in FIG. 1. A database management system 1 for managing a database 2 includes a transaction management unit 3, an exclusive control management unit 4, a journal management unit 5 and a data access management unit 6.
A method for exclusive control of areas in a page according to the present invention, which is incorporated in the data access management unit 6, comprises a tuple access control unit 7, a page vacant area exclusive control notification unit 8, a tuple physical identifier exclusive control request processing unit 9, a page compaction unit 10, an improved page compaction unit 11, a page vacant area occupation decision/control processing unit 12 and a page exclusive control request processing unit 13.
According to this embodiment, the tuple exclusive control request processing unit 9, the vacant area occupation decision/control processing unit 12 and the page exclusive control request processing unit 13 are realized as a part of an algorithm used for the tuple access control unit 7. The page vacant area exclusive control request processing unit 8, on the other hand, is realized as a part of an algorithm for the vacant area occupation decision/control processing unit 12.
The page compaction unit 10 and the improved page compaction unit 11 are called as required by the tuple access control unit 7. The request for exclusive control issued by the tuple exclusive control request processing unit 9, the page exclusive control request processing unit 13 or the page vacant area exclusive control request processing unit 8 is managed by the exclusive control management unit 4. Also, the journal for which an acquisition request is issued from the data access management unit 6 at the time of tuple addition, deletion or update is acquired through the journal management unit 5.
First, a data structure used according to an embodiment of the invention will be described.
An example page structure is shown in FIG. 2. A page 201 includes a tuple 202 and slots 203. Each slot stores the position of a tuple indicated by the particular slot in the page, and each tuple is uniquely identified by the page number and the slot number (hereinafter referred to as "the physical identification numbers"). A tuple is added in the positive direction of address (incremental direction), and a slot in the negative direction of address (decremental direction). A page group is stored in the data base 2, and several pages are read into a memory 14 as required.
The page control information indicating the internal condition of each page is managed by the page header 207. The information thus managed include a leading offset 206 of an unoccupied area 205, the size of a vacant area 204 generated when a tuple is deleted or reduced in length, the maximum slot number assigned to the page and the number of slots in use. These data are initialized by the tuple access unit when a page is newly assigned, and updated at the time of tuple addition, deletion or updating. Also, in the case where a page is compacted during these processes, the data are updated by the page compaction unit 10 or the improved page compaction unit 11.
An example of page control information 207 is shown in FIG. 3. The page control information 207 includes an in-page assigned slot count management field 302, an active slot count management field 303, a vacant area total size management field 304, an unoccupied area leading offset management field 305 and a tuple trailing end offset management field 306. The tuple trailing end offset is a leading offset of a vacant area adjacent to an unoccupied area, and in the absence of a vacant area adjacent to an unoccupied area, has a value equal to that of the leading offset of the unoccupied area.
At the time of page initialization, the assigned slot count 302, the active slot count 303 and the vacant area total size 304 are set to zero, while the unoccupied area leading offset 305 and the tuple trailing end offset 306 are initialized to the length of the header 207.
The assigned slot count 302 is updated by the tuple access control unit 7 at the time of tuple addition or deletion, and by the page compaction unit 10 at the time of page compaction. The assigned slot count 302 is thus referenced by the page compaction unit 10, the improved page compaction unit 11 and the tuple access control unit 7. The active slot count 303 is referenced and updated by the tuple access control unit 7. The vacant area total size 304 and the unoccupied area leading offset 305 are updated by the tuple access control unit 7 and the page compaction unit 10, and referenced by the tuple access control unit 7. The tuple trailing end offset 207 is updated by the tuple access control unit 7 and the page compaction units 10, 11 and referenced by the tuple access control unit 7.
Now, an algorithm used in the invention is described. A page can be locked also by use of a semaphore. The request for fixing or releasing a page on the memory is assumed to be performed at the time of page lock request or unlock request respectively.
FIG. 4 shows an algorithm for determining a slot for adding a tuple at the time of tuple addition. This algorithm is executed at the tuple access control unit 7. Step 401 determines a leading slot, and step 402 loops by the number equivalent to the assigned slot count to determine a usable slot. Step 403 decides whether the particular slot is vacant (the value of the slot, if vacant, is -1). In the case where a slot is vacant, the possibility of exclusive locking (hereinafter referred to as "X lock") of the slot is tested to check to see whether the particular slot is vacant due to a specified state (for example, updating of a corresponding tuple) (step 404). In the case where locking is possible, the particular slot is in a specified state. The slot number for tuple addition is set to the related slot number (step 406), and the process is returned with a return value of 0 (step 407). In the case where the answer at steps 403 and 404 is NO, the next slot is determined (step 405) and another loop is carried out (step 402e). The processes including steps 402 through 402e are repeated until the condition indicated by step 402 is satisfied. Steps 402 and 402e constitute a pair, indicating that the steps between the pair are iterated by the assigned number of slots.
In the case where a slot for tuple addition cannot be determined after investigation of all assigned slots, the slot number for tuple addition is set to an assigned slot count +1 (step 408), with the process returned with a return value of 1 (step 409).
A normal compaction algorithm executed by the page compaction unit 10 is shown in FIG. 5. First, the work area is initialized (step 501). Then a leading slot is determined (step 502), and after the leading offset of the unoccupied area is located immediately after the header, looping is conducted the number of times equivalent to the assigned slot count (step 503). Step 504 decides whether a slot is in use or not, and if it is in use (when the slot value is not -1), the present slot number is held as a maximum occupied slot number (step 510). Decision is then made as to whether the slot value is zero or not (step 511), and if it is not zero, the tuple is copied from the leading offset of the unoccupied area of the work area (step 505) while updating the leading offset of the unoccupied area of the work area (step 506). After that, the next slot is determined (step 507). Upon completely copying all the tuples (step 503e), the occupied slot count, the assigned slot count and the tuple trailing end offset of the work area are updated (step 508) and the contents of the work area are copied to the page (step 509).
FIG. 6 shows an algorithm for the improved compaction executed by an improved page compaction unit 11 which constitutes one of the features of the invention. The difference with the algorithm shown in FIG. 5 is that the leading offset of the unoccupied area and the assigned slot count are not changed. The improved compaction is implemented in the following manner. First, the work area is initialized (step 601). Then, the leading slot is determined (step 602), and the tuple trailing end offset is set immediately after the header, after which the looping is effected the number of times equal to the assigned slot count (step 603). Step 604 decides whether a slot is in use or not, and if it is in use, the tuple is copied from the leading offset of the unoccupied area of the work area (step 605). The tuple trailing end offset of the work area is then updated (step 606), and the next slot is determined (step 607). Upon complete copying of all tuples (step 603e), the occupied slot count and the leading offset of the unoccupied area of the work area are updated (step 608), and the contents of the work area are copied to the page (step 609).
The tuple trailing end offset value can be determined by calculations without using the section 306. In the case where the tuple last offset section 306 shown in FIG. 3 is not used, the compaction and the improved compaction described above require no maintenance of the tuple trailing end offset section. Also, with the improved compaction, a variable representing the position of the tuple trailing end is held within the program and appropriately processed in place of the tuple trailing end offset.
FIGS. 7A to 7C show an algorithm for adding a tuple. This algorithm is executed by the tuple access control unit 7. In this algorithms, step 701 corresponds to the page exclusive control request processing unit 13, step 706 to the tuple exclusive control request processing unit 9, steps 707 and 708 to the vacant area occupation decision/control processing unit 12, and step 707 to the page vacant area exclusive control request processing unit 8.
First, a page to which a tuple is to be added is subjected to X lock at step 701. A slot is then determined by the slot search algorithm shown in FIG. 4 (step 702). The result of slot search is decided (step 703), and the data length required for insertion is determined (steps 704, 705).
The physical identifier of the tuple added at step 706 is X-locked, and step 707 decides whether the tuple can be added to the page. In the case where the tuple can be added, the tuple is added from the leading offset of the unoccupied area of the page (step 711). In the process, the unoccupied area leading offset and the tuple trailing end offset are both updated.
Consider the case in which a tuple can be added if compaction is carried out. First, an X-mode lock test is conducted on vacant areas of the page (step 708). If the lock is possible, step 716a decides as to whether a tuple can be added from the tuple trailing end offset. If a tuple cannot be so added, the compaction shown in FIG. 5 is carried out (step 709), and a tuple is added from the leading offset of the unoccupied area of the page (step 711). In the case where step 716a decides that a tuple can be added, a tuple is added from the tuple trailing end offset (step 712).
Assume, on the other hand, that only a self-transaction locks the vacant area of the same page. Step 716b decides whether a tuple can be added from the tuple trailing end offset, and if the tuple cannot be so added, the improved compaction shown in FIG. 6 is carried out (step 710). A tuple is thus added from the tuple trailing end offset (step 712). In the case where tuple addition is possible without the improved compaction, on the other hand, the step for carrying out the improved compaction is skipped, and a tuple is added from the tuple trailing end offset. When adding a tuple from the tuple trailing end offset, first, the trailing end offset is updated. Only in the case where the trailing end offset after adding a tuple exceeds the leading offset of the unoccupied area, the leading offset of the unoccupied area is made equal to the tuple trailing end offset.
After a tuple is added, the page is unlocked (step 714), and a signal "addition successful" is returned (step 718). In the case where step 707 decides that a tuple cannot be added to the page even after compaction or in the case where step 708 reveals that another transaction locks the vacant area of the page, on the other hand, the locking executed at step 706 and the locking of the page are released (steps 713, 715), and a signal "tuple addition impossible" is returned (step 717).
As described above, the tuple trailing end offset value can be determined by calculations without using the section 306. In the case where the tuple trailing end offset section 306 in FIG. 3 is not used, steps 717 and 718 are eliminated. Also, the same processing as that where the "tuple addition impossible" signal is returned is carried out in the case where the locking test of the page vacant area (step 708) shows that the locking is effected only by the same transaction (steps 710 and 712 become unrequited). Further, the updating of the tuple trailing end offset becomes unrequited.
FIGS. 16A to 16C show an algorithm for updating a tuple. This algorithm, like the algorithm for adding a tuple, is also executed by the tuple access control unit 7. Step 1601 corresponds to the tuple exclusive control request processing unit 9, step 1602 to the page exclusive control request processing unit 13, steps 1606 and 1614 to the page vacant area exclusive control request processing unit 8, and steps 1603, 1606, 1609, 1613 and 1614 to the vacant area decision/control processing unit 12, respectively.
First, a physical identifier of a tuple is subjected to X locking (step 1601). The tuple locking, however, is not required when the tuple to be deleted is X-locked at the time of search. Then the page having the tuple is X-locked (step 1602), and the tuple lengths before and after update are compared with each other (step 1603).
In the case where the tuple lengths before and after update are equal to each other, the tuple after update is overwritten on the position of the tuple before update (step 1604), and the page is unlocked (step 1605).
If the tuple length before update is shorter than that after update, in contrast, the vacant area of the page is secured by shared locking (hereinafter referred to as S-locking) (step 1606), and the tuple after update is overwritten on the position of the tuple before update (step 1607). Further, the difference between the tuple lengths before and after update is added to the length of the vacant area of the particular page. In the case where the trailing end position of the tuple before update is identical to the tuple trailing end position, the tuple trailing end offset is updated (step 1608).
When the tuple length after update is longer than that before update, the tuple length after update is compared with the unoccupied area (step 1609). In the case where the tuple length after update is equal to or shorter than the length of the unoccupied area, on the other hand, the tuple after update is added from the leading offset of the unoccupied area (step 1610), the length of the tuple before update is added to the length of the vacant area, the unoccupied area leading offset and the tuple trailing end offset are updated (step 1611), and the slot value indicating the tuple before update is changed to the head of the added tuple after update (step 1612).
In the case where the tuple length after update is longer than the unoccupied area length of the page, the sum of the vacant area length, the tuple length before update and the unoccupied area length is compared with the tuple length after update (step 1613). When the former is shorter than or equal to the latter, the page vacant area occupation lock test is conducted (step 1614). When the result shows that only the transaction identical to the transaction for which the tuple is to be updated is locked, decision is made as to whether a tuple can be added from the tuple trailing end offset (step 1615). If such a tuple cannot be added, the slot value indicating the tuple is set to -1 and the improved compaction is effected (step 1616). In an improved compaction, the leading offset value of the unoccupied area is kept unchanged while existing vacant areas are combined into a continuous vacant area, which may be added to the trailing end tuple of the last one of compacted tuples.
After that, a tuple is added from the tuple trailing end offset to update the vacant area length, the unoccupied area length and the tuple trailing end offset (step 1617).
In the case where the result of step 1614 shows that the locking is possible, decision is made as to whether a tuple can be added from the tuple trailing end offset (step 1618). If tuple addition is impossible, compaction is done with the slot value indicating a tuple set to zero (step 1619), and a tuple is added from the leading offset of the unoccupied area, so that the unoccupied area length, the vacant area length and the tuple trailing end offset are updated (step 1620). If the decision at step 1618 shows that addition is possible, step 1617 is executed.
Assume that the tuple length after update is found longer at step 1613 or locking is found impossible at step 1614, the particular page is released from the locking (step 1621). And the page to which a tuple after update can be added is searched for (step 1622), and taking advantage of the tuple add algorithm described above, an attempt is made to add the tuple after update to the page defined at step 1622 (step 1623). The result of tuple addition attempt is examined and if it shows a failure, the process returns to step 1622, while if the attempt is successful, the page having the updated tuple unlocked before is X-locked again (steps 1624 and 1625). The vacant area of the page is S-locked (step 1626), and the tuple before update is converted into a point format (step 1627). If required as with the update of the vacant area length or step 1608, the tuple trailing end offset is updated (step 1628).
As described above, in the case where the tuple trailing end offset section 306 shown in FIG. 3 is not used, the update of the tuple trailing end offset becomes unrequited. Also, in the case where only the same transaction is locked as a result of the page vacant area lock test (step 161) as in the case of addition, the same process is performed as when the test result is that the locking is impossible. Further, steps 1615, 1618, 1616 and 1617 become unrequired.
A tuple deletion algorithm is shown in FIG. 8. This algorithm is also executed at the tuple access control unit 7 like the update or add algorithm. Step 801 corresponds to the tuple exclusive control request unit 9, step 802 to the page exclusive control request unit 13, and step 804 to the vacant area occupation decision/control unit 12 and the page vacant area exclusive control request unit 8, respectively.
In FIG. 8, first, the tuple physical identifier is X-locked (step 801). The tuple need not be locked if a tuple to be deleted is X-locked at the time of search. Then the page having the tuple is X-locked (step 802). The tuple is deleted at step 803, the vacant areas of the page are subjected to a shared locking (hereinafter referred to as S-locking) (step 804). At the last step, the page lock is released (step 805). As described above, in the case where the tuple trailing end offset section 306 is not used, the update of the tuple trailing end offset is not required.
Now, algorithm for the rollback processing will be explained. According to this embodiment, it is assumed that the rollback processing is carried out in the reverse order to the processing for tuples. The rollback algorithm is executed entirely at the tuple access control unit 7.
FIG. 9 shows a rollback algorithm for adding a tuple. Step 901 corresponds to the page exclusive control request processing. A page having a tuple is locked (step 901), a tuple is deleted (step 902), and then the page locking is released (step 903). In tuple deletion, the leading offset of the unoccupied area is not updated.
FIG. 17 shows a rollback algorithm for updating a tuple. Step 1701 corresponds to the page exclusive control request processing unit 13, and step 1702 to the vacant area occupation decision/control processing unit 12.
First, the page to which a tuple is returned is X-locked (step 1701). Then, the length of the tuple before update (the tuple returned to the page as a result of roll back) is compared with the length of the tuple after update (the tuple deleted from the page as a result of rollback) (step 1702).
In the case where the lengths of the tuple before update is equal to that of the tuple after update, the tuple before update is overwritten from the position of the tuple after update (step 1703).
When the tuple before update is shorter than the tuple after update, the tuple before update is overwritten from the position where the tuple after update exists (1710), and the length difference is added to the vacant area length. When the trailing end position of the tuple after update is the tuple trailing end offset, the tuple trailing end offset is also maintained (step 1711).
In the case where the length of the tuple before update is longer than that after update, in contrast, the tuple length after update is added to the vacant area length (1705), and decision is made as to whether compaction is required (step 1705). If such compaction is required, the slot value representing the tuple after update is set to -1 and the improved compaction is carried out (step 1706). Further, the tuple before update is added from the tuple trailing end offset and the required information is updated (step 1707).
In the case where compaction is not required, on the other hand, the tuple before update is added from the head of the unoccupied area to update the required information (step 1708), followed by releasing the locking of the page (step 1709).
In the case where the tuple trailing end offset section 306 is not used, the update of the tuple trailing end offset is not required. Also, in view of the fact that the trailing end of the tuple is determined by execution of the improved compaction (step 1706), step 1707 adds a tuple before update using the particular improved compaction.
FIG. 10 shows an algorithm for the rollback processing for tuple deletion. Step 1001 corresponds to the page exclusive control request processing unit 13.
First, the page to which the tuple is returned is X-locked (step 1001). Then, decision is made to see whether compaction is required (step 1002). If compaction is required, the improved compaction shown in FIG. 6 is carried out (step 1003), and a tuple is added from the tuple trailing end offset (step 1004). In the case where compaction is not required, on the other hand, a tuple is added from the leading offset of the unoccupied area (step 1005) and finally the page is released from locking (step 1006).
In the case where the tuple trailing end offset section 306 is not used, the tuple trailing end offset need not be updated. Also, since the trailing end of a tuple is determined by execution of the improved compaction (step 1003), step 1004 adds a deleted tuple by taking advantage of the improved compaction.
Now, explanation will be specifically made about the aforementioned various algorithms with reference to embodiments.
1. Examples of Tuple Addition and Deletion (FIG. 11)
An example page used in the present embodiment is shown in FIG. 11. Numerals 1108 and 1109 designate a tuple stored in the page, numeral 1102 a vacant area, and numeral 1105 an unoccupied area. Numeral 1101 designates a page header for storing the information shown in FIG. 3. In this example, the assigned slot count is 4, the occupied slot count is 2, the leading offset of the unoccupied area is at the position designated by 1104, and the tuple trailing end offset is at the position indicated by 1103 in FIG. 11. The size of the vacant area of the page is the total sum of the size designated by 1102. Numerals 1106, 1107, 1110 and 1111 designates slots, in which numeral 1110 designates the leading offset of tuple 1 (1108), and numeral 1111 the leading offset of tuple 2 (1109). Numerals 1106, 1107 designate slots not in use, that is, unoccupied slots both having a value of -1.
(1) Example 1 of Tuple Addition
First, with the page under the condition shown in FIG. 11, an example of tuple addition is shown for the case in which there exists no transaction that has increased the vacant area in the page.
For tuple addition, the algorithm shown in FIGS. 7A to 7C is executed. In this example, step 702 (the algorithm of which is shown in FIG. 4) having the algorithm shown in FIG. 7A enables the slot 1107 to add a tuple.
In the case where the size required for tuple addition is smaller than the unoccupied area (1105), step 707 decides that a tuple can be added without compaction, and therefore a tuple is added from the position indicated by 1104.
On the other hand, consider the case in which the size required for tuple addition is larger than the unoccupied area but smaller than the size from the tuple trailing end offset (1103) to the slot trailing end. Since the answer at step 718 is YES, a tuple is added from the tuple trailing end offset.
Also, assume that the size required for tuple addition is larger than the size from the tuple trailing end offset (1103) to the slot trailing end but is smaller than the sum of the total size of the vacant area 1102 and the size of the unoccupied area. It is possible to add a tuple to the particular page by effecting the page compaction shown in FIG. 5.
(2) Example 2 of Tuple Addition
Now, explanation will be made about an example of tuple addition with regard to the case where a transaction with a tuple deleted from slot 1107 is active. The transaction with a tuple deleted is assumed to be not equal to the transaction with a tuple to be added.
The algorithm shown in FIGS. 7A to 7C is used also in this case. Step 702 searches for a slot for which addition is possible (with the algorithm shown in FIG. 4). According to this embodiment, the answer at step 403 is YES but NO at the next step 404 for slot 1107 (as the slot is X-locked). Therefore, the slot constitutes no candidate slot for tuple addition, but the next slot 1106 makes a candidate slot for tuple addition.
In the case where the size required for tuple addition is smaller than the unoccupied area (1105), a tuple is added in the same manner as in case (1) mentioned above.
Consider the case, on the other hand, in which the size required for tuple addition is larger than the unoccupied area but smaller than the size from the tuple trailing end offset (1103) to the slot trailing end and also in which the size required for tuple addition is larger than the size from the tuple trailing end offset (1103) to the slot trailing end but smaller than the sum of the total size of the internal vacant area 1102 of the page to the unoccupied area size. In the example under consideration, the vacant area of the page is locked, and therefore the answer at step 808 is negative thereby deciding that tuple addition to the page is impossible.
(3) Example 3 of Tuple Addition
Explanation will be made about the tuple addition for the case in which a transaction attempting to add a tuple has already deleted a tuple stored in slot 1107 from the page.
In this case also, the algorithm shown in FIGS. 7A to 7C is used. After locking the page, step 702 determines a slot that can be added (according to the algorithm shown in FIG. 4). In this embodiment, the answer for the slot 1107 is YES at step 403, as in the following step 404 (Although the slot is X-locked, the transaction under X-lock is identical to the transaction subjected to lock test), and therefore the slot 1107 constitutes a slot to be added.
In the case where the size required for tuple addition is smaller than the unoccupied area (1105), a tuple is added in the same manner as in the cases (1) and (2) described above.
In the event that the size required for tuple addition is larger than the unoccupied area but smaller than the size from the tuple trailing end offset (1103) to the slot trailing end, the answer at step 719 is YES and therefore a tuple is added from the tuple trailing end offset.
Also, consider the case in which the size required for tuple addition is larger than the size from the tuple trailing end offset (1103) to the slot trailing end but smaller than the sum of the total size of the vacant area 1102 and the size of the unoccupied area in the page. It is possible to add a tuple from the tuple trailing end offset of the page by carrying out the improved compaction shown in FIG. 6.
(4) Example of Tuple Deletion
A specific example of deletion of tuple 2 (1109) indicated by slot 1111 will be explained with reference to the case of FIG. 11. A tuple is deleted using the algorithm shown in FIG. 8.
First, the physical identifier of a tuple is X-locked, the page having a tuple is determined, the page is locked, and thus the value of the slot 1111 is set to -1. Then, the tuple trailing end offset 1103 is updated. In the process, a slot having a maximum slot value is determined from all the slots in use, and the particular slot value plus the size of a tuple indicated by the slot is used as a new tuple trailing end offset.
After that, the size of tuple 2 deleted is added to the size of the vacant area, and the vacant area of the page is S-locked thereby to release the locking of the page.
Now, a specific example of updating tuple 2 (1801) in FIG. 22 will be explained with reference to FIGS. 18 to 21.
(5) Example of Tuple Update (when tuple size is the same)
In this case, a tuple after update is overwritten on 1801 according to the algorithm shown in FIGS. 16A to 16C.
(6) Example of Tuple Update (when tuple size decreases)
In the case where the tuple size is reduced, a tuple after update is overwritten on tuple 2 (1801) after locking the vacant area, and the length reduced is added to the size of the vacant area.
(7) Example of Tuple Update (when tuple size increases)
Consider the case in which a tuple is increased in size and the tuple after update is included in the unoccupied area 1802 of the page. The tuple 2 (1901) is included in the unoccupied area as shown in FIG. 19, while the location thus far occupied by tuple 2 is vacated (1902). Also, in the case where a tuple facing the unoccupied area is updated as in the case of updating tuple 3 in FIG. 18, tuple 3 may be overwritten directly if the tuple length after update is smaller than the sum of the tuple length before update and the length of the unoccupied area.
Next, consider the case in which a tuple after update cannot be accommodated in the unoccupied area but compaction is possible to accommodate the tuple after update in the unoccupied area after compaction. First, the page is compacted, and tuple 2 (2001) after update is added.
Assume the case where a tuple cannot be accommodated in the page even after compaction, or where it can be accommodated in the page by compaction but such a compaction is impossible. As shown in FIG. 21, first, a page 2103 in which tuple 2 can be added (2104) is determined and a tuple is added. After that, the vacant area of page 2102 is locked, tuple 2 is converted into a point format (2101), and the physical identification number of tuple 2 (2104) is stored in the point format.
2. Example of Rollback
Now, a specific example of roll back processing will be explained. In the actual process, information required for rollback is acquired by tuple addition or deletion. Such operations are not explained in the embodiment under consideration.
(1) Specific Example of Rollback for Tuple Deletion
FIG. 12 shows the state immediately after tuple 2 is deleted from the page shown in FIG. 11 by a particular transaction and tuple 3 (1201) is added to the same page and committed by another transaction.
Now, explanation will be made about a specific example in which a particular transaction is rolled back. The algorithm shown in FIG. 10 is used for rollback to delete a tuple. First, the page involved is locked. The tuple deleted is indicated by slot 1202, which slot is X-locked at the time of tuple deletion. Therefore, other transactions are not used. As the next step, the position where the deleted tuple 2 is thus added is determined. In the process, the unoccupied area offset of the page and the tuple trailing end offset both represent the position indicated by 1203. Since the unoccupied area 1204 is not sufficiently large to add tuple 2, compaction is required. As shown by step 1003 in FIG. 10, therefore, the improved compaction is carried out (by the algorithm shown in FIG. 6).
As a result, as shown in FIG. 13, the tuple trailing end offset (1301) is changed. It then becomes possible to add tuple 2 from the position indicated by 1301. In the process, the physical identifier of the tuple is constituted of the page number of the corresponding page and the slot number (=4) of slot 1302. This is the same value as before tuple depletion. The tuple can thus be rolled back without changing the physical identifier of the tuple. In the case where the size of the unoccupied area is larger than the size required for adding tuple 2, the page is not compacted, and a tuple is added from the position indicated by the leading offset of the unoccupied area thereby to update the value of the leading offset of the unoccupied area and the tuple trailing end offset.
(2) Specific Example of Rollback for Tuple Addition and Deletion
Now, explanation will be made about a specific example of rollback for tuple addition and deletion with the same transaction. FIG. 14 shows an example in which tuple 2 is deleted from the page in the state shown in FIG. 11 and tuple 4 (1401) is subsequently added.
In rolling back a transaction, first, tuple 1401 is deleted. The algorithm shown in FIG. 9 is used for rollback to add a tuple. The page involved is locked, and the value of slot 1402 is set to -1. After that, the tuple trailing end offset and the size of the vacant area of the page are updated to unlock the particular page. The state of the page after deletion of tuple 4 is shown in FIG. 15. Numeral 1501 designates the position representing the tuple trailing end offset.
As the next step, tuple 2 that has been deleted is rolled back. The algorithm shown in FIG. 12 is used for adding tuple 2. First, the page in which tuple 2 has thus far existed is locked. Then, the position for tuple addition is determined in a manner which will not be described as it is similar to case (1).
(3) Specific Example of Rollback for Updating a Tuple
In the case where the tuple size remains unchanged, the tuple before update is overwritten directly. When a tuple is lengthened and accommodated in the same page as shown in FIGS. 19 and 20, the tuple before update is overwritten as it is. The example of FIG. 20 as rolled back is shown in FIG. 22. Consequently, tuple 2 is restored as indicated by 2201, and the remaining part constitutes a vacant area 2202. Also, the tuple trailing end position is required to be updated.
In the case where tuple 2' cannot be accommodated in the same page but pointed to another page as shown in FIG. 21, first, the point format 2101 is used as a vacant area 2301 as shown in FIG. 23, and tuple 2 (2302 in FIG. 23) before update is added from the leading offset of the unoccupied area. After that, tuple 2 (2104) of page 2103 is deleted.
In the case where the tuple is shortened, the process is carried out in a manner similar to restoration of the point format.
As described above, in the tuple updating process, the slot value of the tuple before update is set to 0. As a result, the slot corresponding to the tuple before update is not combined into the unoccupied area by the compaction process shown in FIG. 5. Consequently, at the time of rollback, the physical identification number of the tuple before update is prevented from being changed on the one hand and the total size of vacant areas is prevented from becoming inaccurate on the other hand.
Now, another embodiment of the invention will be explained. The feature of this embodiment is that the tuples constituting a vacant area are not considered collectively as a single vacant area but each vacant tuple is considered as an object for storing a tuple to be added.
A block diagram of a database management system according to this embodiment is shown in FIG. 24. This embodiment has substantially the same configuration as the embodiment shown in FIG. 1.
The tuple-oriented exclusive control method provided by the embodiment under consideration is incorporated into a data access management unit 6. The data access unit 6 includes a tuple access control unit 7 and a page compaction unit 10. Also, the tuple access control unit 7 includes a tuple physical identifier exclusive control request unit 9 and a page exclusive control request unit 13.
First, FIG. 25 shows the data structure of a page header for managing the state of the page used in the present embodiment. The page header 207' shown in FIG. 25 is adapted for managing the maximum slot number 302 assigned to the page in the page header 207 in FIG. 2, the number of slots in use 303, the total size 304' of vacant areas generated when a tuple is deleted or shortened (somewhat different from the one shown in FIG. 2 as described later), the leading offset 305 of the unoccupied area 205 and the information on the compaction size 307 stored as the size of a vacant area remaining after tuple addition in the tuple area from which a tuple has been deleted.
The compaction size 307 is initialized (cleared to 0) when a page is newly assigned or compacted. An example structure of a tuple stored in the page is shown in FIG. 26. The structure of this tuple may be identical to that shown in the embodiment of FIG. 1. Data for managing the tuple length 2601 representing the physical length of the tuple is stored in the head of the tuple, and data constituting the tuple in the succeeding areas. Decision as to whether a tuple to be added in an area of a tuple deleted can be stored or not is made by referring to the tuple length 2601.
FIGS. 27A and 27B show an algorithm for adding a tuple according to the embodiment under consideration. This algorithm is executed at the tuple access control unit 7 in FIG. 24.
When a tuple addition is requested, first; a page constituting a candidate for addition is searched for and the same page is X-locked. The page can alternatively be locked by use of a semaphore. Also, it is assumed that the request for fixing or releasing the page to or from memory is effected at the same time as the request of page lock or release.
Step 2702 compares the total size 304' of the vacant areas in the page header 207 for managing the internal state of the page with the length of a tuple to be added, and decides whether the tuple to be added can be added to the page. If decision is that there is no sufficient vacant area at this time point, no tuple can be added to the page and the "addition impossible" signal is returned (step 2703). Then a page constituting the next candidate is searched for. In the process, the total size 304' of vacant areas referred to is the total sum of all vacant areas in the page including the size of unoccupied areas.
When step 2702 decides that a tuple can be added, on the other hand, the next decision is as to whether the tuple to be added can be accommodated in the unoccupied area of the page (step 2704). The length of the unoccupied area can be determined using the leading offset 305 of the unoccupied area in the page header 207' for managing the internal state of the page.
In the case where the decision shows that the unoccupied area has no sufficient space to accommodate the tuple to be added, step 2705 defines the leading slot of the page, and step 2706 loops the number of times equal to the assigned slots thereby to determine a usable slot. Step 2707 decides whether the particular slot is vacant or not (If the tuple indicated by the slot is deleted, the slot is vacant, and the slot value represents an inverted value of an offset from the head of the page containing the tuple or the slot value assumes -1).
In the case where the slot is vacant, the particular slot is used to test whether the physical identifier of the tuple can be X-locked or not (step 2708). If the X-locking is possible, step 2709 decides whether the tuple length 2601 for the tuple area indicated by the deleted slot is longer than the length of the tuple to be added. In the case where the length of the area of the deleted tuple is longer than the tuple to be added, it is decided that the tuple to be added is to be stored in the tuple area involved.
In the case where the deleted tuple is shorter than the length of the tuple to be added, by contrast, the tuple area cannot be used for storage. In this case, however, in order to use the tuple length of the vacant tuple obtained at step 2709 subsequently as data for compaction, the tuple length of the vacant area is added to the compaction size 307 of the page header 207' for managing the internal state of the page (step 2710). At the same time, the value of the vacant slot is updated to -1.
In the case where the answer at steps 2707, 2708 and 2709 is NO, the next slot is determined (step 2711) and the looping is carried out again (step 2706e). Assume that an investigation of all the assigned slots shows that a slot for adding a tuple cannot be determined, step 2712 performs compaction using the compaction size 307 of the page header 207' for managing the internal state of the page.
In the case where the answer at step 2704 is YES or after performing the compaction, on the other hand, a slot number is newly assigned to the tuple to be added and the assigned slot count is set to +1 (step 2713). Then the physical identifier of the tuple is X-locked using the slot number determined at step 2713 (step 2714). A tuple to be added is inserted from the head of the unoccupied area to constitute a slot value as the head of the unoccupied area (step 2715). Upon complete insertion, the total size 304' of the vacant area of the page header 207' and the leading offset 305 of the unoccupied area are updated (steps 2716 and 2717).
In the case where the answer at step 2709 is YES, the applicable slot number is constituted as the determined slot number, i.e., the slot number capable of locking (step 2718). The physical identifier of the tuple thus is X-locked (step 2719). The tuple to be added is then inserted from the area indicated by the particular slot value, and the sign of the slot value expressed in binary code is reversed (step 2720). Upon complete insertion, the total size 304' of the vacant area of the page header 207' is updated (step 2721), and the compaction size 307 of the page header 207' is updated (step 2722). When tuple addition is complete, the page lock is released (step 2723) and the "addition successful" signal is returned (step 2724).
An algorithm for tuple deletion is shown in FIG. 28. First, the physical identifier of the tuple is X-locked (step 2801). The tuple locking, however, is not required when the tuple to be deleted is X-locked at the time of search. The page containing the tuple 1 is X-locked (step 2802). Then, step 2803 deletes the tuple. In the process, the sign of the slot value of the tuple expressed in binary notation is inverted into deletion mode (step 2804). The total size 304' of vacant areas is updated (step 2805). Upon complete tuple deletion, the page lock is released (step 2806).
In this way, when a tuple is deleted, the area of the tuple deleted is kept intact by setting the slot in deletion mode. At the time of roll back, therefore, the area of the deleted tuple can be restored simply by reversing the sign of the slot area. In other words, since exclusive control obtains for the deleted tuple, data for the tuple area is guaranteed.
Expression of the tuple deletion mode according to this embodiment is not limited to the method using the sign reversal of the slot value but can also be realized by identifying the tuple deletion with a flag set in the slot area or by setting a flag in the header of the tuple or the like indicating the deletion mode. | An area in a page for a tuple-oriented file system is exclusively controlled such that a tuple is added to, deleted from or updated in a page including a tuple area in use, a vacant area having a deleted tuple and an unoccupied area. In the case where a transaction is active for increasing the total size of the vacant area in a given page, the particular vacant area is locked to prevent another active parallel transaction from using the same vacant area. During the time when the transaction for increasing the total size of the vacant area remains active, other transactions can add a tuple to the unoccupied area or update a tuple in use in the same page to the extent that the particular page is not compacted. The transaction for increasing the total size of the vacant area can perform a special compaction for collecting a plurality of discrete vacant areas into a continuous vacant area without increasing the unoccupied area in the page. The roll back operation can thus be executed securely. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to personnel monitoring systems.
Electronic personnel monitoring systems have been utilized in the criminal justice field for maintaining control of persons subject to a term of house arrest. A person subject to house arrest is required to remain inside his home at all times or during specified hours. House arrest programs are considered useful alternatives to conventional incarceration for convicted criminals and for criminal defendants awaiting trial. Thus, a person sentenced to house arrest will not be subject to the influence of long term criminals in a prison environment. Moreover, the person sentenced to house arrest can maintain relationships with his family and community. The house arrest sentence may be arranged so that the subject person is permitted to leave the house during working hours, and hence may maintain his employment. Moreover, prison space is a scarce and expensive resource. House arrest sentencing conserves this resource.
To maintain effective control of persons subject to house arrest, the controlling authority must monitor their actual compliance with the house arrest program. Thus, the controlling authority must check to see if each monitored person is in his home. Although this theoretically could be done by having officers visit each home at frequent intervals, such an arrangement normally is impractical in that it would require a large number of officers to maintain effective, frequent surveillance of a large group of individual homes. Therefore, automatic systems have been developed for monitoring the presence of persons at their respective homes or other detention locations.
One system which has been widely adopted for this purpose is described in U. S. Pat. No. 4,747,120. As set forth in the '120 patent, telephone dialer means at a central location such as the office of the controlling authority automatically initiates telephone calls from the central location via the community telephone exchange to each home or other remote location where a person is to be monitored. Instruction signal means automatically provide an instruction signal perceptible to the monitored person at the remote location during each such telephone call. In response to this instruction signal, the monitored person performs a predetermined action resulting in transmission of return signals from the remote location to the central location via the telephone line. Test means are provided at the central location for automatically testing the return signals from each home or remote location to determine whether the predetermined action has been performed by the particular person who is supposed to be present at the remote location called. If the test means at the central location finds that the proper return signals have been returned when a particular person's home has been called, then the test means have automatically determined that the person is home. If not, an alarm is generated at the central location. Typically, the system includes an identifying object or tag such as a coded bracelet which is attached to each person to be monitored. The test means may include means for determining whether the identifying object associated with a person assigned to a particular remote location was employed to generate the return signals received from that location. If so, then the proper person is present.
Systems as described in the '120 patent provide effective monitoring of parolees and other persons subject to house arrest at reasonable cost and with excellent security. Other remote monitoring systems employ a small, low-powered radio transmitter secured to each monitored person and a combination radio receiver and telephone dialer at each remote monitoring location. The receiver normally detects radio frequency signals from the transmitter while the monitored individual is present. If the monitored individual leaves the vicinity of the transmitter, he takes the small transmitter out of range and hence the receiver no longer detects the transmitter signal. In response to such a loss of signal, the telephone dialer is activated to automatically place a call to the central office and transmit an alarm signal to the central office.
Both of these systems use the telephone network. One drawback which has limited application of these systems heretofore has been that some persons to be monitored do not have a telephone line available in their home. This problem in particularly severe in some rural areas, where many homes do not have telephone service. Even in highly developed, urban areas a significant portion of criminals are poor and do not have a home telephone. Accordingly, monitoring systems which require a telephone line to the home have not been useful in monitoring these individuals. Moreover, criminal justice authorities have been concerned that house arrest monitoring systems which require a telephone line will be viewed as discriminating against poor people. Thus, an impoverished person who does not have a telephone may be sent to a conventional jail because he cannot be placed on a house arrest monitoring program.
There have accordingly been needs for further improvement in personnel monitoring systems.
SUMMARY OF THE INVENTION
The present invention addresses these needs.
One aspect of the present invention provides apparatus for monitoring a plurality of persons at a plurality of preselected monitoring locations. The apparatus includes a plurality of local units. Each local unit is disposed at a monitoring location and thus associated with a person to be monitored at that particular monitoring location. Each local unit preferably includes detector means for determining the presence or absence of the associated person to be monitored and providing presence information accordingly. Each local unit preferably also includes report signal sending means for transmitting a report radio signal bearing the presence information through free space from the monitoring location. The apparatus further includes a mobile unit, which may be carried in a vehicle or on the person of a monitoring officer. The mobile unit includes report signal receiving means for detecting the report signal from the local unit at each monitoring location while the mobile unit is within range of the report signal from that local unit and recovering the presence information from the detected report signal. Thus, presence information regarding all of the persons to be monitored can be recovered by bringing the mobile unit within radio transmission range of all monitoring locations in a series.
Most preferably, the mobile unit includes presence status indication means for providing a perciptible indication at the mobile unit of the presence information recovered from each report signal during detection of the report signal. The mobile unit desirably further includes in-range indication means providing perceptible indication at the mobile unit whenever the mobile unit is detecting a report signal. Thus, a monitoring officer can determine whether the monitored persons are present at their respective monitoring locations merely by approaching the various monitoring locations and without physically inspecting each monitoring location. In a typical arrangement, each monitoring location may be the home of a parolee or other individual subject to supervision by a legal authority and the mobile unit may be carried in an officer's automobile. The officer can check that all of the parolees are present in their homes merely by driving his automobile along a route which takes him within range of the various homes. A single officer thus can check many parolees repetitively.
Preferably, each local unit includes a local unit radio receiver. The system may also include tag signal means carried by each person to be monitored for transmitting a tag radio signal associated with the monitored person. The radio receiver of each local unit is adapted to receive the tag radio signal associated with the person assigned to the location of that local unit. The detector means of the local unit preferably includes the radio receiver and means for providing a presence signal only while the radio receiver is receiving the associated tag signal and providing an absence signal when the radio receiver does not receive that tagged signal.
Most preferably, the mobile apparatus includes selectively operable callout signal sending means for sending a callout radio signal. The local unit radio receiver preferably is adapted to receive the callout signal as well as the tag signal. Callout signal indicating means may be provided at the local unit for providing a perceptible indication that a callout signal has been received upon reception of the callout signal by the local unit radio receiver. The perceptible callout indication may be an audible tone, illumination of a signal light or the like. In this arrangement, the local unit radio receiver is employed both as part of the detection means and also as a communication channel. The officer may send the callout signal whenever he wishes to see the monitored individual in person. In response to the perceptible callout indication, the monitored person knows that he should leave his home and present himself at a pre-selected location, typically in front of his home, where the officer can meet him. This callout capability greatly enhances the security of the system. Any attempt to defeat the system will be immediately apparent to the officer if the monitored person does not respond to a callout signal. Moreover, the officer can personally observe the monitored person at will without exposing himself to the possibility of attack or other dangers which may exist within the home. This greatly enhances officer's safety. In many cases, a single officer can safely monitor even relatively dangerous violence-prone individuals with reasonable safety.
Because the local unit need not be carried on the person of the parolee, the local unit can draw power from a normal electrical utility outlet in the parolee's home or else from a large, high capacity battery. Therefore, the report signal sending means may operate at a relatively high duty cycle, repetitively sending the report signal at reasonably short intervals such as every few seconds or less. This enhances the probability that the mobile unit will be able to detect the report signal. By contrast, the tag signal sending means may be arranged to send the tag signal at relatively long intervals, typically about thirty seconds or more, so as to conserve battery power. Moreover, the report signal transmitter may be positioned at a predetermined location in the home selected to enhance transmission to the outside environment, such as a location adjacent to a window. Therefore, the system can provide satisfactory detection of the report signal even if low powered transmitters are employed. The use of low powered transmitters is preferable inasmuch as it avoids the need for licenses from communications authorities.
Most preferably, the receiver of each local unit includes local code means defining a local identification code and means for rejecting radio signals which do not bear this local identification code. The local codes means in different local units typically defines different local identification codes. The tag signal means associated with each monitored person desirably includes means for incorporating the local identification code utilized by the associated local unit in the tag signal. The mobile unit typically includes means for selecting any one of the local identification codes and encoding the callout signal with the so-selected local identification code. Further, the local unit desirably includes means for encoding the report signal sent by that local unit with a report identification code. Different local units typically utilize different report identification codes, and the mobile unit preferably includes report identification code selection means for selecting any one of the report identification codes. The receiver of the mobile unit is arranged to respond only to radio signals bearing the so selected report identification code and to ignore other radio signals. Thus, the officer can set the callout signal sending means and the receiver of the mobile unit to cooperate with only one particular unit at a time. This avoids interference where plural local units are employed, and permits plural local units to operate on the same frequency. Desirably, the report identification code used by each local unit is different from the local identification code used by the same local unit. The tag signal sending transmitter, local unit receiver and report signal sending transmitter may all operate on the same radio frequency without appreciable interference.
Systems in accordance with preferred embodiments of the present invention can provide secure and effective personnel monitoring at minimal cost, and can be fabricated using readily available, standard components.
Further aspects of the present invention include monitoring methods and components, such as local and mobile units, useful in connection with the above-described apparatus.
These and other objects, features and advantages of the present invention will be more readily apparent from the detailed description of the preferred embodiment set forth below, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure a schematic block diagram of components utilized in apparatus according to one embodiment of the invention.
FIG. 2 is a further schematic diagram showing the same embodiment but on a smaller scale.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A monitoring system in accordance with one embodiment of the present invention includes a plurality of local monitoring units 10, of which two (10a,10b) are shown in FIG. 2. Each monitoring unit is disposed at a separate monitoring location. Thus, unit 10a is disposed in one home, whereas unit 10b is disposed in another. A tag 12 is carried by each person to be monitored, so that one such tag is associated with each monitored person. Each tag 12 is also associated with one local monitoring unit 10. For example, the monitored person carrying tag 12a is assigned to remain at the home monitored by local monitoring unit 1Oa. Thus, tag 12a is associated with local monitoring unit 10a. In the same fashion, tag 12b is associated with local monitoring unit 10b. The apparatus further includes a mobile unit 14, which may be carried in an automobile.
Each local unit 10 includes a housing 16 (FIG. 1). A conventional power supply unit 18 is mounted within housing 16. Power supply unit 18 is connected to a conventional plug 20 for drawing energy from a conventional utility outlet in the home. Local unit 10 further includes a backup battery power supply 22. Both of these components are arranged to supply low voltage DC power to the remaining components of the apparatus.
Each local unit 10 further incorporates a radio receiver 24 connected to a receiving antenna 26. Receiver 24 includes conventional components for amplifying and demodulating a radio frequency signal at a preselected operating frequency bearing encoded information in a trinary (+1, 0, --1) digital code so as to recover a series of code digits therefrom. Receiver 24 includes an identification code unit 28 arranged to define a local identification code in a form of a predetermined sequence of four trinary digits. In unit 10b depicted in FIG. 1, the sequence of this local identification code is "1, 0, -1, 1", whereas unit 10a (FIG. 2) uses a different local identification code, for example "0 0 -1 -1". Code unit 28 is arranged to test incoming signals for its particular local identification code and rejects all incoming signals which do not bear this code. Code unit 28 is arranged to pass signals which do bear this local identification code and to emit a valid reception signal whenever a signal bearing the code is received.
Receiver 24 further incorporates a timing latch unit 30 having first and second output states. Timing latch unit 30 is arranged to set itself to the first output state in response to receipt of a valid reception signal from code unit 28. Timing latch unit 30 is also arranged to start timing a predetermined tolerance period, desirably about 1.5 minutes, upon such receipt of a valid reception signal from code unit 28. Additionally, timing latch unit 30 is arranged to reset itself back to the second output state upon lapse of this predetermined tolerance period without receipt of a further valid reception signal from code unit 28. Receiver 24 also includes data recovery unit 32 arranged to provide digital outputs on lines 34 and 36 representing the information in an incoming radio frequency signal which has been passed by code unit 28. Further, receiver 24 includes an AC power failure detection circuit 40 arranged to provide a digital output depending upon whether the receiver is or is not obtaining power from power supply 18. The receiver, and the remaining components of local unit 10 receive power from battery backup unit 22 whenever the power from power supply unit 18 fails.
Local unit 10 further includes a tamper switch 44 mechanically connected to housing 16 and arranged to provide a signal whenever housing 16 is opened. Further, local unit 10 includes a contact request setting unit 46 having an actuator button 48 exposed on the outside of the housing 16. A callout reset unit 50, likewise having an actuator button 52 exposed on the outside of the housing is also included in the local unit. Callout reset unit 50 is connected to an audible alarm 54 disposed within housing 16.
Local unit 10 further includes an encoder 58. Encoder 58 incorporates a four-digit data latch 60 having four separate digital inputs. One such input is connected to the output 39 of power failure detection unit 40. Another input of latch 60 is connected to contact request setting unit 46. A third input of latch 60 is connected to an output 36 of data recovery unit 32, and further connected to reset unit 50. The fourth input 41 of latch 60 is connected to another output 34 of data recovery unit 32 and further connected to tamper switch 44. Latch 60 is arranged to hold each of its four digits in a given state indefinitely, and to change each particular digit to the opposite state only when a signal is received on the appropriate input of the latch. Thus, one digit value in latch 60 can be reset by a signal on receiver data recovery output 34 or by operation of tamper switch 44. Another digital value can be switched between states either by a signal on receiver data recovery output 36 or by a signal from reset unit 50. Yet another value can be switched by a signal from contact request unit 46. The fourth value is switchable by the output of power failure detector 40.
Encoder 58 further includes a code generating unit 62. Unit 62 is arranged to provide a preselected report identification code different from the local receiver code provided by unit 28, but having a predetermined relationship to the local receiver code. As illustrated, the report identification code generated by unit 62 is inverse to the local receiver code. That is, each trinary digit of the four digits in the report identification code is the opposite of the corresponding trinary digit in the local identification code. Encoder 58 is arranged to assemble the report identification code generated by unit 62, the current state output by latch and timing unit 30 and the current contents of latch 60 into a 9-digit digital message. Local unit 10 further includes a report signal transmitter 64 arranged to impress the 9-digit message from encoder 58 on a radio signal at the aforementioned preselected operating frequency, and to send this signal in a burstwise, repetitive mode on a predetermined duty cycle through an antenna 65. Preferably, report transmitter 64 is arranged to send repeated bursts at predetermined intervals spaced about two seconds apart or less, and desirably spaced about one-half second or less. Most preferably, the report transmitter 64 is arranged to send signal bursts at intervals of about 0.16 seconds. Each such signal burst desirably is about three milliseconds long, and includes several copies of the 9-bit message from encoder 58.
Tag 12 includes a tag signal transmitter 66 mounted in a small housing 68. Housing 68, and hence transmitter 66, are secured to the body of the person to be monitored by a strap 70. Strap 70 is permanently secured, as by rivets, around the wrist or ankle of the monitored person. Thus, strap 70 and hence tag transmitter 66 cannot be removed from the monitored person without severing strap 70. Tag transmitter 66 incorporates a severance detection circuit 72 for sensing severance of strap 70. Most preferably, strap 70 and severance detector 72 are arranged in accordance with copending, commonly assigned U.S. Pat. Application No. 200,088, filed May 27, 1988, the disclosure of which is hereby incorporated by reference herein. As more fully set forth in the '088 application, a plurality of electrical conductors (not shown) may be embedded in strap 70 so that the conductors extend side-by-side, lengthwise along the strap. The conductors are normally insulated from one another. Severance detection circuit 72 may be arranged to impose a potential between different ones of these conductors and to sense any momentary current flow between these conductors. Such a circuit can effectively detect attempts to sever the strap. Typically, the conductors are arranged in relatively close juxtaposition with one another to promote contacting of the conductors with one another during any attempt to sever the strap.
Transmitter 66 further includes a self-contained battery power supply 67, an RF sending unit 74 connected to an internal antenna 76 mounted within housing 68, and a code unit 78. Code unit 78 is arranged to define the same four digit trinary local identification code as defined by code unit 28 of the associated local monitoring unit 10. RF sending unit 74 is arranged to assemble the code provided by code unit 78 and the output of severance detection unit 72 into a digital message and to send a radio signal at the preselected operating frequency bearing this digital message. RF sending unit 74 is arranged to repeat this RF signal in a burstwise transmission scheme at a relatively low duty cycle, with relatively long repetition intervals between successive bursts. Desirably, the RF sending unit 74 of tag 12 is arranged to provide the tag signal at repetition intervals of about once every twenty seconds to about once every minute, about once every thirty-to-forty seconds being particularly preferred and about once every thirty-five seconds being most preferred.
Mobile unit 14 includes a manually operable code entry panel 80 incorporating four three-position switches 82, each having a 1 position, a 0 position and a -1 position for accepting a four-digit trinary code input. The mobile unit further includes a non-inverting code selector 84 adapted to select and supply a four-digit trinary code matching the settings of switches 82. Further, the mobile unit includes an inverting code selection device 86 adapted to select a code in which each digit is the inverse of the corresponding digit selected by one of switches 82. Mobile unit 14 includes an callout transmitter 88 and a manually operable callout switch 90. Transmitter 88 is arranged to operate only upon manual actuation of callout switch 90. The callout transmitter is connected to non-inverting code selector 84. Transmitter 88 is arranged to compose a message including the 4-digit code supplied by non-inverting code selector 84 and including a further digit having a predetermined, fixed value indicating that the message is a callout signal. Transmitter 88 is connected to a transmitting antenna 92 and arranged to operate on the aforementioned preselected operating frequency, and to send its message burstwise, on a duty cycle similar to that of report signal transmitter 64. Such burstwise transmission is continued only while callout switch 90 is actuated.
Mobile unit 14 also includes a receiving antenna 94 and receiver 96 connected thereto. Receiver 96 is arranged to accept the 4-digit trinary code provided by inverting code selector 86. Receiver 96 includes apparatus for demodulating radio signals at the preselected operating frequency, and further includes a code unit 97. Code unit 97 is arranged to block reception of any signal which does not bear the 4-digit trinary codes supplied by inverting code selector 86. Receiver 96 provides a valid reception signal output on an output line 98 whenever a signal bearing a 4-digit trinary code matching the code supplied by unit 86 is received and passed by code unit 97. Valid reception output line 98 is connected to an audio buzzer unit 100 arranged to emit a sound in response to each such signal. Receiver 96 is arranged to accept a 9-digit message encoded in the radio frequency signal, to treat the first four digits as an identifying code for comparison in code unit 97 and to treat the remaining five digits of a signal passed by unit 97 as each representing a particular item of status information. The receiver is arranged to pass the signals representing status information through a latching device or decoder 102 to a status reporting panel 104. Thus, each bit as supplied to latching decoder 102, controls the illumination or non-illumination of one lamp 106a-106e.
The mobile unit 14 further includes a power supply 108 connected to all other elements of the mobile units. Desirably, power supply 108 may include a device for connecting the apparatus to the electrical power supply of a vehicle when the mobile unit is carried on a vehicle.
In operation, tag 12b continually transmits a tag radio signal at thirty-five second intervals. This tag signal bears the local receiver code "1 0 -1 1" of the associated local monitoring unit 10b. Further, the tag signal carries a digit indicating that severance detection device 72 has not detected any attempts to sever or remove strap 70 from the monitored person. So long as the monitored person remains within his home, the tag 12b will remain within range of local unit 10b. Therefore, local unit receiver 24 will continually receive the tag signal at thirty-five second intervals. Each such signal causes code unit 28 to provide a valid reception signal. Accordingly, timing latch 30 is reset every thirty-five seconds and never reaches the end of its 1.5 minute predetermined timing period. Timing latch 30 remains in its first or normal output state and continually supplies a digit indicating its first or normal output state and hence indicating that the monitored person is present. Absent any unusual occurrence or any actuation by the monitored person, each of the four digits stored in latch 60 of encoder 58 also remains in a normal state. Thus, the 9-bit message assembled by encoder 58 and supplied to report signal transmitter 64 always includes a message digit indicating presence and four other digits each indicating normal status with regard to another condition, together with the four digits of the report signal identification code (-1 0 1 -1). Report signal transmitter 64 continually sends this same 9-bit message in bursts at 0.16 second intervals.
If the monitored person goes momentarily to a portion of the home where signal transmission is impaired, the signals from tag unit 12b may be momentarily interrupted. If such interruption lasts for about one minute or less, only one transmission from tag unit 12b will be missed, and hence timing and latch unit 30 will never reach the end of its full predetermined tolerance time cycle and will never reset itself to its second or absence status. However, if the monitored person goes out of transmitting range for more than about one minute, timing and latch unit 30 will reach the end of its predetermined tolerance timing period, and hence will reset itself to a second or absence output state. In this condition, the message assembled by encoder 58 will include a digit indicating that the timing and latch unit 30 is in its second or absence output state.
If the monitored person attempts to remove the tag 12b from his person by severing strap 70, severance detection circuit 72 will be actuated. A bit indicating this occurrence will be encoded in the next message sent by tag 12b. This will cause data recovery unit 32 to provide an appropriate output on output line 34, thus changing one digit stored in latch 60 and changing the corresponding digit in the report signal sent by report signal transmitter 64. Further, if any attempt is made to open the housing 16 of local monitoring unit 10b, tamper switch 44 will change the same digit in latch 60 and hence will cause the same change in the report signal. Upon loss of AC power to power supply unit 18, power failure detection circuit 40 will change the assigned power failure digit in latch 60, and hence in the report signal. Moreover, if the monitored person needs to meet with the monitoring officer, he may operate button 48 causing contact request switching unit 46 to change the contact request digit stored in latch 60 and hence also to change the contact request digit of the report signal sent by transmitter 64.
The monitoring officer has in his possession a list of monitoring locations and local receiver codes associated with each monitoring location. The monitoring officer follows a route which will take him past each monitoring location. As the monitoring officer brings the mobile unit 14 close to a particular monitoring location, he turns the switches 82 of code entry panel 80 to positions matching the local receiver code for that monitoring location. Thus, as the monitoring officer approaches the home where unit 10b is installed, he sets the switches 82 to the sequence 1 0 -1 1. This causes the local receiver code to be set in callout transmitter 88 and the inverse report signal code (-1 0 1 -1) to be set in receiver 96 of the mobile unit. Thus, the mobile unit is set to interact with local unit 10b. When the report signals from that particular local unit bearing the proper report signal code are received by receiver 96, audio buzzer unit 100 on the mobile unit is actuated. Each new burst of the report signal causes a new actuation of the audio buzzer unit so that the buzzer unit sounds repeatedly while receiver 96 is receiving report signals bearing the appropriate code. The five information digits of the report signal are latched in decoder 102. Each such digit controls one of the status reporting lamps 106 on report panel 104 of the mobile unit. Thus, when the audio buzzer unit 100 sounds, the officer need only look at status panel 104 to ascertain the condition of the particular local unit selected and the person monitored thereby. For example, lamp 106a is illuminated only if the presence digit in the report signal is in an abnormal condition, indicating that the local unit is not receiving tag signals from the associated tag unit and hence indicating that the monitored person is not present. Likewise, lamps 106b and 106d illuminate only where the corresponding digits in the report signal indicate loss of AC power or tampering respectively. Lamp 106c will be illuminated only if the monitored person has actuated contact request switching unit 46. If the monitoring officer is at a location which is known to be in range of local unit 10b, but audio buzzer unit 100 does not sound, then the monitoring officer knows that something has caused local unit 10b to become inoperative and hence can investigate further.
If the monitoring officer wishes to meet personally with the monitored person, he actuates callout switch 90 while in range of the particular local unit associated with that monitored person. Upon such actuation, transmitter 88 sends a signal bearing the proper local receiver identification code and bearing a digit recognizable by data recovery unit 32. Such a callout signal is received by receiver 24 in the same manner as a tag signal from tag unit 12b. However, in response to a digit indicating a callout signal, data recovery unit 32 of local unit receiver 24 changes the output on line 36 from its first or normal state to a second or callout state. In response to this change in status, callout reset unit 50 actuates audible alarm 54. This signals the monitored person that he should appear outside of his home at a preselected location (such as on the street in front of his home) for a meeting with the monitoring officer. Further, in response to the callout signal on output line 36, the callout digit in latch 60 is changed from a normal state to a callout state. The corresponding callout digit in the report signal sent by report signal transmitter 64 also changes from a normal state to a callout state, causing lamp 106e on the status panel of mobile unit 14 to illuminate. This confirms to the officer that the callout signal was received by local unit 10b. When the monitored person hears the alarm from audible alarm 54, he can acknowledge the callout signal by operating button 52, thereby causing reset unit 50 to switch the callout digit in latch 60 back to its normal state. The monitoring officer will see lamp 106e on status panel 104 go out, thus indicating to the officer that the monitored person has acknowledged the call. The officer can send a callout signal at any time while he is within range of the local unit. Typically, the officer will not require the monitored person to appear every time that the officer comes within range but rather will use this capability at random times so that the monitored person will never know when the officer may demand to see him in person. Further, the officer will use the callout capability when the monitored person has actuated the contact request switch 46. If the monitored person has actuated the contact request switch, the officer will see lamp 106c illuminated the next time that he monitors the signal from that particular local unit, and may send a callout signal in response so as to arrange for a meeting with the monitored person. After meeting with the officer, the monitored person can manually reset callout request switching unit 46.
The interaction between the mobile unit and every other local unit is the same as the interaction between the mobile unit and local unit 10b except that different codes are employed. Thus, the officer can check the status of many monitored persons by going into the vicinity of each local unit in sequence, thus bringing mobile unit 14 within the report signal transmission range of each local unit 10 in sequence by setting the appropriate codes on panel 80. Where there are several relatively closely spaced monitoring locations, and hence several closely spaced local units, the mobile unit may be within signal range of several local units simultaneously. However, receiver 96 of mobile unit 14 will accept only signals bearing the particular report identification code selected by operation of code entry panel 80 and associated components. Further, the callout signal sent by transmitter 88 will match the local identification code of only one local unit 10. Mobile unit 14 therefore will interact with only one local unit at a time.
Although all of the transmitters and receivers in the system operate on a common frequency, interference between signals does not present an appreciable problem. The repetitive tag signal and repetitive report signal transmitters operate burstwise. Each such transmitter is actually sending a signal only a very small percentage of the time. The intervals between bursts are considerably longer than the individual bursts. For example, a single report signal transmitter 64 sending three millisecond bursts at 0.16 second intervals will be active approximately 1.9% of the time, whereas a tag signal transmitter sending similar bursts at thirty-five second intervals will be active approximately 0.01% of the time. Therefore, the probability of interference between these repetitive signals is minimal, and the probability of interference between these repetitive signals and a callout signal sent by mobile unit 14 is also minimal.
Each local unit 10 and each mobile unit 14 incorporates a transmitter and a receiver operating on the same frequency and using relatively closely spaced antennae. Further, the operative components of the transmitter and receiver within each unit ordinarily are mounted in close proximity to one another, typically within the same housing. Thus, the signal from each transmitter is strongly coupled to the receiver in the same unit. The receiver in each such unit is normally operational at all times. Operation of the receiver is not stopped during operation of the transmitter in the same unit. Although it might first appear that such combined operation could cause overloading of the receiver RF sections, with consequent loss of sensitivity to incoming signals, this normally does not occur. Surprisingly, the sensitivity of the receivers used in this system typically is enhanced. Thus, during the intervals between bursts from a transmitter in a given unit, the receiver in that unit typically has greater sensitivity to incoming signals than a comparable receiver which is not mounted adjacent a transmitter. Although the present invention is not limited by any theory of operation, it is believed that outgoing signals from the transmitter in a particular unit excite the RF receiving section in the receiver of the same unit to the point of instability, and that such excitation renders the RF section in the receiver more sensitive rather than less sensitive to subsequent incoming signals. This effect occurs particularly in superheterodyne receivers. Superheterodyne receivers per se are well-known. A superheterodyne receiver includes a local oscillator adapted to generate a local signal at a frequency different than the frequency of the incoming signal. The receiver further includes a mixer for mixing the local signal with the incoming signal to thereby form a signal having a frequency equal to the beat frequency of the local and incoming signals, i.e., the difference in frequencies between incoming and local signals. Additionally, the receiver include devices for amplifying the beat frequency signal and demodulating it to recover the baseband or transmitted information. Desirably, each local receiver 24 of each local monitoring unit 10 and the receiver 96 of the mobile unit are all superheterodyne receivers.
The receivers and transmitters utilized in the system may all be common, commercially available components of the types utilized in addressable remote control systems. These units typically incorporate additional functional elements such as latches, timers and the like. These additional elements can be utilized as the corresponding functional elements of the structure discussed above. For example, many commercially available transmitters incorporate a latch 60 and code setting section 62 capable of functioning as the encoder 58 of the local unit 10. Moreover, more than one mobile unit may be used in conjunction with the several local units.
As will be appreciated, numerous variations and combinations of the features discussed above can be utilized without departing from the present invention as defined by the claims. Merely by way of example, a local unit 10 need not necessarily detect the presence or absence of the monitored person by detection of a radio frequency tag signal. Thus, the detector means of each local unit 10 may incorporate means for periodically emitting a perceptible action signal and determining whether a predetermined action has been performed by the monitored person.
The aforementioned U.S. Pat. 4,747,120 discloses a system using a passive encoded object carried on a tag worn by the monitored person. The same type of passive object can be used in a variant of this invention. The local monitoring unit in this variant would be arranged to determine whether the encoded object had been engaged with the local unit in response to the action signal. The local unit would adjust the report signal to indicate that the person is present if the encoded object was engaged in response to the last action signal and to indicate that the person is not present if the encoded object was not engaged in response to the last action signal.
As these and other variations and combinations of the features described above may be utilized without departing from the present invention as defined by the claims, the foregoing description of the preferred embodiments should be taken by way of illustration rather than by way of limitation of the present invention as defined in the claims. | A system for monitoring presence of persons at preselected monitoring locations. A plurality of local units, one at each monitoring location, determines whether the monitored person is present or absent at the monitoring location and sends report signals via free space radio transmission. A mobile unit, preferably mounted in a vehicle, passes within range of the various local units in order, and hence recovers status information. Desirably, the mobile unit provides a perceptible signal to an officer in the vehicle if the monitored person is absent. Each local unit may be arranged to receive radio signals from a tag carried by the monitored person and to provide an absence indication if the tag signals are no longer received. The same radio receiver as employed to receive the tag signals may also be employed to receive a callout signal sent by the mobile unit. The local unit may be arranged to provide an audible signal to the monitored person upon receipt of a callout signal, thus instructing the monitored person to present himself for inspection by the monitoring officer. The system permits an officer driving an automobile or walking a route carrying the mobile unit to monitor the status of any individuals in a house arrest program. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to a new compact unit in a forming section of a papermaking machine, more precisely to a self-supporting pre-assembled compact unit having an integrated save-all tray. The rolls supporting an outer and/or an inner forming wires are mounted onto the unit.
BACKGROUND OF THE INVENTION
[0002] A forming section in a conventional papermaking machine having, for example C-former and Crescent-former, usually comprises two loops of an industrial clothing running about a plurality of lead- and guide rolls, and a paper stock is delivered between these clothing by a headbox for forming a paper web therebetween. One loop of the clothing forms an outer wire loop while the second loop forms an inner wire loop. The paper stock is partly dewatered in the forming section, and water is drained through the wire and collected by a save-all tray situated under the wire. The save-all tray is usually made of a sheet metal and extends over a length of the wire wherein the drainage of the water through the wire occurs. Usually the save-all tray is mounted onto a machine frame part in the forming section. Then the water evacuates from the save-all tray and from the forming section. These two loops of clothing in the forming section could comprise different kind of clothing such as wires or a combination of different kind of wires and/or fabrics, felts and/or belts suitable for the partial dewatering of the paper web in the forming section of the machine.
[0003] Usually the lead rolls, stretch rolls, guide rolls and other elements supporting the outer- and the inner clothing are also mounted on the machine frame as illustrated in U.S. Pat. No. 5,409,575 (Savia et al), FIG. 1 . The frame is a rather heavy and complicated construction requiring a stable basement, as illustrated in U.S. Pat. No. 6,413,371 (Ahonen et al), comprising a lot of metal profiles and requiring many working man-hours to be erected. Only after the entire machine frame is erected on a prepared basement, it become possible to mount the big amount of different elements such as bearing houses, arms for supporting the rolls, the rolls of the forming section, different deflectors, the save-all tray for removing the drained water, carrying shafts, motors and other elements, and then to thread the machine clothing onto the rolls. Therefore, when the big amount of elements should be assembled to the frame, as illustrated also by U.S. Pat. No. 5,5582,688 (Bando et al) the assembling of the forming section takes a longer time, and the assembling work is rather costly. The conventional forming section requires rather big internal space in order to provide an access to all places of the frame to which all the elements as described above are to be mounted. Therefore, the conventional forming section has a rather big foot print.
[0004] As the rolls for both, the inner- and the outer clothing are mounted on the same frame as well as a forming roll, which is rather massive element, and all these rotating at the very high speed elements cause the vibrations, this vibrations could be transferred through the frame and interfere the machine performance.
[0005] The object of the invention is to minimize or eliminate these mentioned disadvantages, which is achieved by a new compact unit in accordance with claim 1 . Advantageous embodiments have the features stated in the dependent claims.
SUMMARY OF THE INVENTION
[0006] Contrary to the known paper machine layouts as described above, the forming section of the paper machine comprises a self-supporting pre-assembled compact unit according to the invention having an integrated save-all tray that defines the shape and dimensions of the unit. The rolls supporting of the outer forming wire and other required elements, for instance, such as the piping, walkways and the like, are mounted onto the self-supporting unit instead of being mounted to the entire machine frame as in the conventional paper machines. Thus, the self-supporting unit performs the function of a separate frame element for supporting the save-all tray and other elements when required. As the pre-assembled unit supporting the rotating rolls is separated from the entire machine frame, this design decreases the transfer of the vibrations created by the rotating rolls to the entire machine frame. When desired, in the alternative embodiments, the similar self-supporting unit with the integrated save-all tray might be provided for the mounting of the rolls supporting the inner forming clothing in the forming section of the paper machine or for both the inner- and the outer forming clothing.
[0007] The unit does not require a special basement for erecting and is dimensioned to fit into a standard transporting container. The unit is more maintenance friendly, provides easier wire change, decreases the erection time, decreases amount of walkways and other parts in the entire machine and thus decreases the material need, weight of the used material and costs as well as simplifies transportation of the machine to the site. The invention is applicable for any types of paper- or pulp making machines, such as paper-, newsprint-, board and tissue making machines. The unit in different modifications is adapted to different kinds of forming sections such as a C-former or a Crescent-former.
[0008] The unit according to the invention is to be used in the forming section, for instance, of a tissue-making paper machine, wherein the forming section comprises the inner- and the outer forming clothing. The clothing could be one of the forming fabric and a forming wire. The clothing is running about a number of rolls in endless loops and, when merging, form a forming zone between them situated about a forming roll. A headbox injects the paper stock between these two forming clothing in a forming gap. A paper web is being formed in the forming zone due to drainage of water through at least one of the clothing. The drained water is being evacuated by at least one tray from the forming section. The unit is a self-supporting unit and is arranged for supporting the tray and for the mounting the rolls supporting one of the forming clothing thereon.
[0009] The forming section in a paper machine comprises the inner clothing and the outer clothing, preferably forming wires, fabrics, felts or belts, each supported by a number of rolls and arranged in two endless loops forming, when merging, a forming zone therebetween. The headbox injects the paper stock between these two forming clothing, and a paper web is formed due to draining water through the at least one of the forming clothing or the forming wire in the forming zone about a forming roll. The forming roll is supported by a machine frame. The forming section for the paper machine according to the invention comprises at least one self-supporting unit with an integrated save-all tray; the unit supports the tray and acts as a separate frame element for supporting the integrated save-all tray and is made separate from the paper machine frame. The compact self-supporting unit is used for mounting of the rolls supporting the one of the forming wires thereon instead of mounting the rolls to the entire machine frame.
[0010] The unit may have a second tray for evacuation the drained water from the forming zone into the save-all tray that evacuates the water away from the forming section.
[0011] A method of assembling the forming section having a compact self-supporting forming unit according to the invention is comprises steps of mounting the unit on a floor, mounting the clothing supporting rolls and the arms onto the unit having pre-assembled piping beams and a cross walkway, threading the clothing onto the rolls, adjusting the rolls positions by the retraction device and rotating the arms so that to connect them to the rest of machine frame during the machine performance.
[0012] The unit and the forming section of the papermaking machine according to the invention will now be described more detailed with reference to the attached drawings:
[0013] FIG. 1 is a cross sectional view of a unit according to one embodiment of the invention for the Crescent-former type forming section
[0014] FIG. 2 is a three dimensional view of the unit of FIG. 1 showing the pre-piping beams, cross going walkways, mist- and outlet connections
[0015] FIG. 3 is a sectional view of the unit of FIG. 1 comparing to the container size
[0016] FIG. 4 is a cross sectional view of the compact unit
[0017] FIG. 4A is a view along the arrow C shows turning vanes guiding the drained water out of the forming area into the save-all tray
[0018] FIG. 5 is a cross sectional view showing the rolls adjustment
[0019] FIG. 6 is a schematic enlarged view in direction of arrow D in FIG. 5 of a roll retraction device with an electrical motor
[0020] FIG. 7 is a cross sectional view showing a splash shield with an integrated cross walkway
[0021] FIG. 8 is a view illustrating position of an adjustable mist- and water deflector
[0022] FIGS. 9A , 9 B are illustrating the securing of the unit by the arms to the machine frame during machine operation and a position for a wire change
[0023] FIG. 10 is an alternative embodiment of a unit with an integrated save-all tray and stationary vanes for directing water from the forming area into the save-all tray in a C-former type of the forming section.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] The compact unit 1 for the Crescent-former type twin wire forming section in a paper making machine, for instance in a tissue paper making machine, the unit 1 according to the invention and as shown in FIG. 2 is pre-assembled and self-supporting. The unit 1 , when delivered to the site, is ready to be mounted on a machine hall floor and does not require a special basement. As illustrated in FIG. 1 , the unit 1 comprises an integrated save-all tray 25 , which defines the unit 1 shape and dimensions. The unit 1 also has integrated pre-piping beams 10 , in which all cross going pipes 11 , necessary for the machine operation, are to be situated and also comprises integrated cross walkways 13 , 17 provided for the service personnel as illustrated in FIG. 1 and FIG. 7 . A number of rolls 2 are mounted to the compact unit 1 in the known way and provided with a roll retraction device 26 for a possible adjustment of the guiding rolls 2 position or stretching of the forming outer clothing 4 in the known manner.
[0025] As known in the art, in the twin wire forming section of the paper making machine a paper fibre stock is injected by a headbox 5 in a forming gap B between the two clothing, one forming outer wire 4 and one forming inner felt (not shown) in this particular embodiment, running together and merging in a forming zone A about a forming roll 3 . The forming roll 3 is mounted onto the machine frame 22 and supports the inner forming felt. A forming zone tray 6 collects the water drained through the outer wire 4 in the forming zone A and directs it into the save-all tray 25 by vanes 7 as shown in FIG. 4A . The forming zone tray 6 is swingable as it is attached between the arms 8 , which are rotatably about the axis 9 mounted onto the unit 1 . The tray 6 comprises a number of deflecting vanes 7 being mounted in the swingable zone tray 6 for directing the drained water. The usage of the deflecting vanes 7 provides a higher velocity of the evacuated water, and therefore this design allows the size of the save-all tray 25 integrated into the unit 1 to be decreased comparing to the conventional save-all tray dimension. Simultaneous rotation of the forming zone tray 6 together with the arms 8 permits easier opening of the forming gap B between the outer forming wire 4 and the inner (not shown) forming felt for providing the change of the wire or other services, if required.
[0026] The pre-piping beams 10 are also integrated into the unit 1 for situating the cross going necessary pipes 11 within it, which arrangement allows for a more compact design of the forming section, improves the pipe 11 protection and provides a cleaner design, which is easier to keep clean. The unit 1 is provided also with an adjustable mist- and water deflector 14 for treating the outer wire 4 and depleting the wire 4 from the water on the return run to the forming zone A. The unit 1 is completed with a swingable splash shield 12 which is provided with a cross walkway 13 (not shown here) situated on its inner side and used only when the shield 12 is not in a working up-right position, as illustrated in FIG. 1 , but is folded down about the axis 21 for service as shown in FIG. 7 . The shield 12 might be mounted separately to the floor, to the machine basement or to the unit 1 . During the machine operation, the shield 12 might be connected to some parts of the unit 1 in order to secure the working up-right position. When the paper machine is to be started, in order to ensure the relative position of the machine sections during the machine operation, the unit 1 should be connected to the other paper machine sections. The arms 8 mounted to the unit 1 are folded down and attached to the entire machine frame 22 (shown here in a dash line) by screws. The rotating rolls 2 causing the major vibrations are carried and supported by the separately situated unit 1 and not by the machine frame 22 itself, and therefore the entire frame 22 vibration is decreased while the arms 8 are able to transfer only minor vibrations from the unit 1 to the frame 22 .
[0027] As illustrated in FIG. 2 , in a three-dimensional view of unit 1 , a cross going walkway 17 is also integrated into the unit 1 . A mist connection 15 and an outlet connection 16 are arranged on a drive side of the unit 1 .
[0028] FIG. 3 illustrates a cross section of the unit 1 and how the unit 1 is fitted into a standard transport container 27 .
[0029] FIG. 4 illustrates the unit 1 according to the invention for the Crescent-former type forming section. For threading the clothing onto the rolls 2 or the change of the outer wire 4 , the forming gap B should be opened, and this is achieved by moving the roll 2 in a direction of arrow into a position of roll 2 ′ shown in the dash lines. The arms 8 are rotated about the axis 9 in the same direction, and the forming tray 6 moves in the position shown in a dash line. A special profile of the vanes 7 , directing the drained water from the tray 6 into the save-all tray 25 , serves a faster evacuation of the water drained into the forming zone A into the tray 25 and away from the forming unit 1 and thus allows decreasing of the tray 25 size, a possibility to integrate it within the self-supporting unit 1 eliminating in this way the massive machine frame part in the forming section and minimizing of the entire forming section foot print.
[0030] As mentioned earlier, the rolls 2 are mounted onto the unit 1 instead of being mounted onto the entire machine frame 22 and are provided with the roll retraction devices 26 as illustrated in FIG. 5 . These roll retraction devices 26 allow moving of the rolls 2 , when the forming gap B is to be opened for change of the wire 4 or for stretching the outer wire 4 in order to achieve the desired wire 4 tension.
[0031] The roll retraction device 26 is more detailed illustrated in FIG. 6 , the view seen in the direction of arrow D in FIG. 5 . The roll retraction device 26 comprises at least one electrical motor 18 and a composite shaft 19 .
[0032] The usage of the composite shafts 19 instead of conventional steel shafts minimizes vibrations due to its lighter weight. As the composite shafts 19 have lighter weight, they do not require the massive frame to be mounted thereon, they could be mounted onto the unit 1 without increased dimensions of the unit 1 . The use of the light-weight shafts 19 in the design allows fully use advantages provided by the higher speed electrical motors 18 as these shafts 19 have much lower inertia, and each start and stop of the motor 18 transfers faster to the corresponding roll 2 and thus to the wire 4 , which in its turn improves the control of the wire 4 run.
[0033] The design of the unit 1 according to the invention avoiding hydraulic control devices is more environmental friendly, less expensive and more maintenance friendly, decreasing an amount of man-working hours.
[0034] In FIG. 7 , the swingable splash shield 12 for use together with the unit 1 is shown in an upright working position and in a folded down non-working position. As known in the art, when the paper web is formed into the forming zone A and carried further to the next section by the inner fabric or the wire (not shown), the outer clothing or the wire 4 should be cleaned from the impurities prior to arriving to the forming zone A. In the self-supporting unit 1 between the wire 4 and the roll 2 there is a flooded nip 23 formed by a wire cleaning shower 20 or the similar known in the art device cleaning the wire 4 from the inside. In order to prevent spreading of the cleaning water into the machine room, the splash shield 12 is mounted adjacent to the flooded nip 23 position and catches the cleaning water penetrating the wire 4 during the machine operation. When the machine is stopped for some reason (for the service, clothing change or the like), the splash shield 12 is folded down for easier assess to all unit's 1 elements and an extra cross walkway 13 mounted on the bottom of the splash shield 12 is being available. The cleaning water is removed from the wire 4 by an adjustable mist- and water deflector 14 as shown in FIG. 8 , which is mounted onto the unit 1 . The position of the deflector 14 relative to the wire 4 can be adjusted even during the machine operation by a manually controlled screw 28 in order to achieve the best water depleting effect for the wire 4 . The deflector 14 is connected to a machine ventilation system for the evacuation of water and mist from the wire 4 .
[0035] When the machine is operated, the forming section including the self-supporting unit 1 should be connected to the rest of the papermaking machine. In the invention, the unit 1 is fixed to the machine frame 22 supporting the forming roll 3 and other elements by the arms 8 , and thus the forming gap B is closed as illustrated in FIG. 9A .
[0036] When the machine is to be served or the wire 4 is to be changed or removed, the arms 8 are disconnected from the frame 22 and rotated away, opening wider the forming gap B that allows removing/change the wire 4 or provide another required service in the position as shown in FIG. 9B .
[0037] FIG. 10 illustrates an alternative embodiment of the unit 1 adopted to a C-former in the twin wire forming section of the paper making machine, in which one clothing forms the outer wire, and the second clothing forms the inner fabric (not shown) and wherein the unit 1 is provided with an integrated save-all tray 25 and the stationary vanes 7 connected to a stationary forming tray 6 for directing water from the forming zone A into the integrated save-all tray 25 . This embodiment differs from the shown in FIG. 1 only by the stationary forming zone tray 6 , the stationary deflecting vanes 7 and the adjustment of the rolls 2 adjacent to the forming roll 3 by the roll retracting device 26 , when the forming gap B is to be open.
[0038] It is to be understood that the scope of the invention is not limited by the illustrated drawings and should be interpreted within the scope of the attached Claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. | The invention discloses a pre-assembled self-supporting unit ( 1 ) for a twine wire forming section. The unit comprises an integrated save-all tray ( 25 ) and other integrated elements such as cross walkway ( 17 ), piping beam ( 10 ), connecting arms ( 8 ). The rolls ( 2 ) for supporting at least one forming clothing loop ( 4 ) and the other elements are mounted onto this separate unit instead of being mounted onto the same machine frame. The unit provides a diminished foot print for the forming section, and it is dimensioned to fit in a standard transport container. | 3 |
FIELD OF THE INVENTION
[0001] This invention relates to a guide arrangement for minimizing the likelihood of an improper application of a pincer-like tightening tool for the plastic deformation of hose clamps provided with so-called “Oetiker” ears.
BACKGROUND OF THE INVENTION
[0002] Hose clamps with plastically deformable ears, so-called “Oetiker” ears, which have been sold by the hundreds of millions, have enjoyed an immense commercial success. They are widely used, for example, on the assembly line of the automotive industry to tighten hoses onto nipples by the plastic deformation of the ear. Though infrequently, an improper positioning of the pincer-like tightening tools which on the assembly line are usually pneumatically operated, may cause an incorrect deformation of the ear. This, in turn, requires that the piece with the incorrectly deformed ear has to be taken out of the assembly line, the incorrectly installed clamp then has to be removed, and a new clamp has to be installed and tightened before the work piece can be re-entered on the assembly line. Because of time requirements and extra work, this is an annoyance which is to be avoided as far as possible.
BACKGROUND OF THE INVENTION
[0003] The principal object of the present invention is to minimize the incorrect application of the tightening tool in hose clamps provided with plastically deformable ears. According to this invention, this is achieved by providing complementary guide profiles in the clamp and in the tightening tool so that the installer at the assembly line can interactively determine the correct application of the tightening tool when he or she senses mutual engagement of the guide profiles.
[0004] In one embodiment of the present invention involving so-called closed or endless clamps, guide surfaces are provided in the clamping ring by deep-drawn ridge-like embossments or projections forming male guide profiles extending outwardly within the areas of the connection of the clamping ring with the leg portions of the plastically deformable ear. The end surfaces of the jaws of the tightening tool are then provided with complementary notch-like cutouts forming female profiles so that the installer can feel the proper position of the tightening tool relative to the clamp when the notch-like cutouts are in engagement with the ridge-like embossments or projections.
[0005] In a preferred embodiment of this invention, which applies to so-called open clamps, usually made from galvanized steel or stainless steel band material, advantage is taken of the existence of overlapping band portions that exist from the point of the mechanical connection to the free end of the inner band portion when the mechanical connection, usually in the form of one or more hooks extending outwardly from the inner band portion into openings in the outer band portion, is engaged but before the plastically deformable ear in the outer band portion is plastically deformed to tighten the clamp. A typical clamp of this type is disclosed in U.S. Pat. No. 4,299,012 to Hans Oetiker. Once the mechanical connection is engaged, the inner band portion 11 b will extend with its full width underneath the gap of the non-deformed ear. In a clamp of this type, the guide profiles are provided according to this invention in parts of the two mutually overlapping band portions as will be described more fully hereinafter. Again, correct application of the tightening tool can be interactively sensed by the installer when the mutually complementary guide profiles formed by deep-drawn outwardly extending embossments or projections in the inner band portion which, extending through narrow slots in the outer band portion, engage with the notch-like cut-outs in the jaw members of the tightening tool.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] These and other objects, features and advantages of the present invention will become more apparent from the following description when taken in conjunction with the accompanying drawing which shows, for purposes of illustration only, several embodiments in accordance with the present invention, and wherein:
[0007] [0007]FIG. 1 is a somewhat schematic elevational view of a prior art hose clamp of the so-called closed or endless type, provided with two plastically deformable ears adapted to be plastically deformed by a pincer-like tightening tool to tighten, for example, a hose onto a nipple;
[0008] [0008]FIG. 2 is a side elevational view, similar to FIG. 1 and showing an endless two-ear clamp provided with deep-drawn male embossments or projections forming male guide profiles in accordance with this invention;
[0009] [0009]FIG. 3 is a somewhat schematic cross-sectional view, on an enlarged scale and showing the mutually complementary guide profiles in the clamp and in the tightening tool used in the embodiment of FIG. 2;
[0010] [0010]FIG. 4 is a somewhat schematic perspective view of a so-called open clamp with a guide arrangement in accordance with the present invention;
[0011] [0011]FIG. 5 is a partial plan view on the outer band portion of FIG. 4, with the parts thereof in the plane of the drawing for the sake of better understanding;
[0012] [0012]FIG. 6 is a cross-sectional view taken along line VI-VI of FIG. 5;
[0013] [0013]FIG. 7 is a partial plan view on the inner band portion of FIG. 4, again with the parts thereof in the plane of the drawing for the sake of better understanding;
[0014] [0014]FIG. 8 is a cross-sectional view taken along line VIII-VIII of FIG. 7;
[0015] [0015]FIG. 9 is a somewhat schematic elevational view of a tightening tool with modified jaw members for use in connection with the present invention;
[0016] [0016]FIG. 10 is a somewhat schematic cross-sectional view, similar to FIG. 6, of a modified embodiment of this invention with rectilinear openings 12 ′; and
[0017] [0017]FIG. 11 is a somewhat schematic cross-sectional view, similar to FIGS. 6 and 10 of a still further modified embodiment of this invention with male guide profiles in both the inner and outer clamping band portions.
DETAILED DESCRIPTION OF THE INVENTION
[0018] Referring now to the drawing, wherein like reference numerals are used throughout the various views to designate like parts, and more particularly to FIG. 1- 3 , the so-called closed or endless clamp generally designated by reference numeral 10 which is made from tubular stock realized by any known manufacturing method, includes two plastically deformed so-called “Oetiker” ears generally designated by reference numeral 13 which are disposed mutually opposite in the ring 11 . Each plastically deformable ear 13 includes two outwardly extending leg portions 14 and 15 interconnected by a bridging portion 16 , preferably provided with a reinforcement 17 of any known construction, for tightening the hose 3 onto a nipple 4 by plastic deformation of the ears with the assistance of a pincer-like tightening tool generally designated by reference numeral 20 and provided with jaw-like members adapted to engage in the area of the connection between the ring 11 and the outwardly extending leg portions 14 and 15 , as known in the art.
[0019] To minimize improper application of the tightening tool 20 , the clamp 10 according to the present invention (FIG. 2) is provided with ridge-like, deep-drawn projections or embossments 30 of more or less conical shape forming male guide profiles and schematically shown in FIGS. 2 and 3 which can be realized by deep-drawing. The jaw-like members 21 , in turn, are provided with complementary notch-like cutouts 22 forming female guide profiles whereby the depth h 1 (FIG. 3) of the cutouts 22 is greater than the projecting height h 2 of the projecting male guide profiles 30 in order to avoid a wedging action that might occur when compressive forces are applied to the tip of the projection or embossment 30 during application of the jaw members 21 in the course of tightening of the ear.
[0020] Though the arrangement of the guide profiles of FIGS. 2 and 3 are quite feasible, they may entail certain disadvantages as a result of the strengthening of the clamp material by the pressed-out male guide projections 30 in the areas of the connections between the clamping ring and the leg portions 14 and 15 , possibly also affecting the force requirements to plastically deform the ear and the elastic breathing capabilities of the clamp. These disadvantages are avoided in the preferred embodiment of this invention illustrated in FIGS. 4 through 8. FIG. 4 thereby illustrates a typical open clamp made from band material as illustrated in FIG. 19 of U.S. Pat. No. 4,299,012 to Hans Oetiker and as more fully described therein. The clamp of FIG. 4 again includes a clamping band 11 as well as a so-called “Oetiker” ear generally designated by reference numeral 13 that consists of outwardly extending leg portions 14 and 15 interconnected by a bridging portion 16 provided with a reinforcing groove or depression 17 . The mechanical connection may include in this type of clamp a so-called guide hook 31 and two cold-deformed deep-drawn support hooks 32 adapted to engage in openings 35 . To assure an inner clamping surface devoid of steps or gaps, the inner clamping band portion 11 b has a tongue-like extension 61 adapted to extend through an opening in the step-like portion 67 formed in the outer clamping band portion 11 a . When the mechanical connection 31 , 32 is engaged in apertures 35 and before the ear 13 is plastically deformed, the inner band portion 11 b extends with its full band width underneath the ear to bridge the gap. According to the present invention, the inner band portion 11 b is provided with a male guide profile 19 in the form of a deep-drawn ridge-like projection or embossment adapted to extend through slot-like openings 12 in outer band portion 11 a on both sides of the leg portions 14 and 15 . The inner ends of the leg portions 14 and 15 are also provided with small cutouts complementary to the male guide profile 19 , whereby the male guide profile 19 preferably extends in the inner band portion continuously from the left beginning thereof in FIG. 4 to the right end. As the inner band portion 11 b is fixed relative to the outer band portion 11 a by the mechanical connection 31 , 32 , 35 , the male guide profile 19 and the slot-like opening 12 only need to extend a short distance to the left of the leg portion 14 of the ear. On the other hand, the slot-like opening 12 to the right of leg portion 15 has to be of sufficient length to permit the male guide profile 19 to slide therethrough until the deformation of the ear reaches its maximum, i.e., the inner ends of the leg portions 14 and 15 come into contact with one another.
[0021] The jaw-like members of the tightening tool (not shown in FIGS. 4 - 8 ) are again provided with female guide profiles formed by notch-like cutouts of complementary shape as disclosed in connection with FIG. 3, bearing in mind what was said as regards the dimensions in the embodiment of FIGS. 2 and 3.
[0022] [0022]FIG. 9 illustrates the application of the present invention to a clamp which utilizes a tightening tool with modified jaw-like members 121 having a substantially flat bottom portion as schematically shown in FIG. 9. The substantially flat bottom portions of the jaw-like members 121 are then provided with notch-like cutouts 130 at the underside thereof which are shaped to engage with the male guide profiles as disclosed in connection with the other embodiments illustrated herein. With a tightening tool of FIG. 9, the male guide profiles may be somewhat extended in length, which in case of the embodiment of FIGS. 4 through 8 will also require a lengthening of the slot-like openings. The jaw-like members 12 of FIG. 9 may be modified to suit the requirements of any particular application whereby, for example, the length of the more or less flat bottom portion may be adapted to particular clamp sizes, for instance, by the use of interchangeable jaw members adapted to be selectively installed in pneumatic or hydraulic tightening tools.
[0023] While I have shown and described several embodiments in accordance with the present invention, it is understood that the same is not limited to the details shown and described herein but is susceptible of numerous changes and modifications a known to those skilled in the art. For example, the particular shape and dimensions of the male and female guide parts may be modified to adapt to particular conditions of the band material and/or tightening tools. The slot-like openings 12 may also be straight in cross section (FIG. 10) instead of converging in the upward direction (FIG. 6) in which case the male guide profiles may have a rectilinear portion terminating in a suitably tapering profile with the notch-like cutouts of complementary shape. Furthermore, the overlapping outer band portion 11 a alone may also be provided with male profiles 30 ′ (FIG. 11) in lieu of openings 12 and in lieu of the guide profile 19 in the inner clamping band portion. However, in that case, there will be no lateral guidance between the inner and outer band portions 11 b and 11 a which would preclude the inner band portion 11 b from sliding laterally relative to the outer band portion 11 a , especially in the area of overlap. To remedy this shortcoming, the inner band portion 11 b may then also be provided with a male profile 19 ′ of a shape complementary to the internal contours of the male profile 30 ′ so that mutual lateral guidance can then be achieved by engagement of the male guide profile 19 ′ of the inner clamping band portion 11 b from below into the pressed-out male guide profile of the outer clamping band portion 11 a.
[0024] An additional advantage of the male guide profiles in accordance with this invention resides in the automation possibility with the use of these guide profiles in the clamps to adjust a robot arm carrying the tightening tool by an optical imaging device of conventional construction optically determining coincidence with or deviation of the male guide profile from a predetermined position with a matrix whereby the male profile can also be made more visible by any conventional means such as appropriate lighting and/or painting. The adjustment of the position of the robot arm can be realized by electromechanical, electropneumatic or electrohydraulic means of any conventional type so as to eliminate any non-coincidence of the line formed by the male guide profile with a predetermined line in the matrix, as is conventional with such types of automatic positioning devices.
[0025] Thus, the present invention is capable of numerous modifications as known to those skilled in the art, and I therefore do not wish to be limited to the details shown and described herein but intend to cover all such changes and modifications as are encompassed by the scope of the appended claims. | A guide arrangement for minimizing incorrect emplacement of a tightening tool at a plastically deformable ear of a hose clamp which includes male guide profiles in the clamp adapted to cooperate with female guide profiles in the tightening tool to permit the installer to sense proper positioning of the tightening tool when the male guide profiles are in engagement with the female guide profiles in the tightening tool. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 09/567,643, filed May 9, 2000, pending, which is a divisional of application Ser. No. 09/434,147, filed Nov. 4, 1999, now U.S. Pat. No. 6,196,096 B1, issued Mar. 6, 2001, which is a continuation of application Ser. No. 09/270,539, filed Mar. 17, 1999, now U.S. Pat. No. 6,155,247, which is a divisional of application Ser. No. 09/069,561, filed Apr. 29, 1998, now U.S. Pat. No. 6,119,675, which is a divisional of application Ser. No. 08/747,299, filed Nov. 12, 1996, now U.S. Pat. No. 6,250,192 B1, issued Jun. 26, 2001.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates generally to a method and apparatus for sawing semiconductor substrates such as wafers and, more specifically, to a wafer saw and method of using the same employing multiple indexing techniques and multiple blades for more efficient sawing and for sawing multiple die sizes and shapes from a single semiconductor wafer.
2. State of the Art
An individual integrated circuit or chip is usually formed from a larger structure known as a semiconductor wafer, which is usually comprised primarily of silicon, although other materials such as gallium arsenide and indium phosphide are also sometimes used. Each semiconductor wafer has a plurality of integrated circuits arranged in rows and columns with the periphery of each integrated circuit being rectangular. Typically, the wafer is sawn or “diced” into rectangularly shaped discrete integrated circuits along two mutually perpendicular sets of parallel lines or streets lying between each of the rows and columns thereof. Hence, the separated or singulated integrated circuits are commonly referred to as dice.
One exemplary wafer saw includes a rotating dicing blade mounted to an aluminum hub and attached to a rotating spindle, the spindle being connected to a motor. Cutting action of the blade may be effected by diamond particles bonded thereto, or a traditional “toothed” type blade may be employed. Many rotating wafer saw blade structures are known in the art. The present invention is applicable to any saw blade construction, so further structures will not be described herein.
Because semiconductor wafers in the art usually contain a plurality of substantially identical integrated circuits arranged in rows and columns, two sets of mutually parallel streets extending perpendicular to each other over substantially the entire surface of the wafer are formed between each discrete integrated circuit and are sized to allow passage of a wafer saw blade between adjacent integrated circuits without affecting any of their internal circuitry. A typical wafer sawing operation includes attaching the semiconductor wafer to a wafer saw carrier, mechanically, adhesively or otherwise as known in the art, and mounting the wafer saw carrier on the table of the wafer saw. A blade of the wafer saw is passed through the surface of the semiconductor wafer, either by moving the blade relative to the wafer, the table of the saw and the wafer relative to a stationary blade, or a combination of both. To dice the wafer, the blade cuts precisely along each street, returning back over (but not in contact with) the wafer while the wafer is laterally indexed to the next cutting location. Once all cuts associated with mutually parallel streets having one orientation are complete, either the blade is rotated 90° relative to the wafer or the wafer is rotated 90°, and cuts are made through streets in a direction perpendicular to the initial direction of cut. Since each integrated circuit on a conventional wafer has the same size and rectangular configuration, each pass of the wafer saw blade is incrementally indexed one unit (a unit being equal to the distance from one street to the next) in a particular orientation of the wafer. As such, the wafer saw and the software controlling it are designed to provide uniform and precise indexing in fixed increments across the surface of a wafer.
It may, however, be desirable to design and fabricate a semiconductor wafer having various integrated circuits and other semiconductor devices thereon, each of which may be of a different size. For example, in radio-frequency ID (RFID) applications, a battery, chip and antenna could be incorporated into the same wafer such that all semiconductor devices of an RFID electronic device are fabricated from a single semiconductor wafer. Alternatively, memory dice of different capacities, for example, 4, 16 and 64 megabyte DRAMs, might be fabricated on a single wafer to maximize the use of silicon “real estate” and reduce thiefage or waste of material near the periphery of the almost-circular (but for the flat) wafer. Such semiconductor wafers, in order to be diced however, would require modifications to and/or replacement of existing wafer saw hardware and software.
SUMMARY OF THE INVENTION
Accordingly, an apparatus and method for sawing semiconductor wafers, including wafers having a plurality of semiconductor devices of different sizes and/or shapes therein, is provided. In particular, the present invention provides a wafer saw and method of using the same capable of “multiple indexing” of a wafer saw blade or blades to provide the desired cutting capabilities. As used herein, the term “multiple indexing” contemplates and encompasses both the lateral indexing of a saw blade at multiples of a fixed interval and at varying intervals which may not comprise exact multiples of one another. Thus, for conventional wafer configurations containing a number of equally sized integrated circuits, the wafer saw and method herein can substantially simultaneously saw the wafers with multiple blades and therefore cut more quickly than single blade wafer saws known in the art. Moreover, for wafers having a plurality of differently-sized or shaped integrated circuits, the apparatus and method herein provides a multiple indexing capability to cut non-uniform dice from the same wafer.
In a preferred embodiment, a single-blade, multi-indexing saw is provided for cutting a wafer containing variously configured integrated circuits. By providing multiple-indexing capabilities, the wafer saw can sever the wafer into differently sized dice corresponding to the configuration of the integrated circuits contained thereon.
In another preferred embodiment, a wafer saw is provided having at least two wafer saw blades spaced a lateral distance from one another and having their centers of rotation in substantial parallel mutual alignment. The blades are preferably spaced apart a distance equal to the distance between adjacent streets on the wafer in question. With such a saw configuration, multiple parallel cuts through the wafer can be made substantially simultaneously, thus essentially increasing the speed of cutting a wafer by the number of blades utilized in tandem. Because of the small size of the individual integrated circuits and the correspondingly small distances between adjacent streets on the wafer, it may be desirable to space the blades of the wafer saw more than one street apart. For example, if the blades of a two-blade saw are spaced two streets apart, a first pass of the blades would cut the first and third laterally separated streets. A second pass of the blades through the wafer would cut through the second and fourth streets. The blades would then be indexed to cut through the fifth and seventh streets, then sixth and eighth, and so on.
In another preferred embodiment, at least one blade of a multi-blade saw is independently raisable relative to the other blade or blades when only a single cut is desired on a particular pass of the carriage. Such a saw configuration has special utility where the blades are spaced close enough to cut in parallel on either side of larger integrated circuits, but use single blade capability for dicing any smaller integrated circuits. For example, a first pass of the blades of a two blade saw could cut a first set of adjacent streets defining a column of larger integrated circuits of the wafer. One blade could then be independently raised or elevated to effect a subsequent pass of the remaining blade cutting along a street that may be too laterally close to an adjacent street to allow both blades to cut simultaneously, or that merely defines a single column of narrower dice. This feature would also permit parallel scribing of the surface of the wafer to mutually isolate conductors from, for example, tie bars or other common links required during fabrication, with subsequent passage by a single blade indexed to track between the scribe lines to completely sever or singulate the adjacent portions of the wafer.
In yet another preferred embodiment, at least one blade of a multi-blade saw is independently laterally translatable relative to the other blade or blades. Thus, in a two-blade saw, for example, the blades could be laterally adjusted between consecutive saw passes of the sawing operation to accommodate different widths between streets. It should be noted that this preferred embodiment could be combined with other embodiments herein to provide a wafer saw that has blades that are both laterally translatable and independently raisable, or one translatable and one raisable, as desired.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a schematic side view of a first preferred embodiment of a wafer saw in accordance with the present invention;
FIG. 2 is a schematic front view of the wafer saw illustrated in FIG. 1;
FIG. 3 is a schematic front view of a second embodiment of a wafer saw in accordance with the present invention;
FIG. 4 is a schematic view of a first silicon semiconductor wafer having a conventional configuration to be diced with the wafer saw of the present invention;
FIG. 5 is a schematic view of a second silicon semiconductor wafer having variously sized semiconductor devices therein to be diced with the wafer saw of the present invention;
FIG. 6 is a schematic front view of a third embodiment of a wafer saw in accordance with the present invention;
FIG. 7 is a schematic view of a third silicon semiconductor wafer having variously sized semiconductor devices therein to be diced with the wafer saw of the present invention;
FIG. 8 is a top elevation of a portion of a semiconductor substrate bearing conductive traces connected by tie bars; and
FIG. 9 is a top elevation of a portion of a semiconductor substrate bearing three different types of components formed thereon.
DETAILED DESCRIPTION OF THE INVENTION
As illustrated in FIGS. 1 and 2, an exemplary wafer saw 10 according to the invention is comprised of a base 12 to which extension arms 14 and 15 suspended by support 16 are attached. A wafer saw blade 18 is attached to a spindle or hub 20 which is rotatably attached to the extension arm 15 . The blade 18 may be secured to the hub 20 and extension arm 15 by a threaded nut 21 or other means of attachment known in the art. The wafer saw 10 also includes a translatable wafer table 22 movably attached in both X and Y directions (as indicated by arrows in FIGS. 1 and 2) to the base 12 . Alternatively, blade 18 may be translatable relative to the table 22 to achieve the same relative X-Y movement of the blade 18 to the table 22 . A silicon wafer 24 to be scribed or sawed may be securely mounted to the table 22 . As used herein, the term “saw” includes scribing of a wafer, the resulting scribe line 26 not completely extending through the wafer substrate. Further, the term “wafer” includes traditional full semiconductor wafers of silicon, gallium arsenide, or indium phosphide and other semiconductor materials, partial wafers, and equivalent structures known in the art wherein a semiconductor material table or substrate is present. For example, so-called silicon-on-insulator or “SOI” structures, wherein silicon is carried on a glass, ceramic or sapphire (“SOS” ) base, or other such structures as known in the art, are encompassed by the term “wafer” as used herein. Likewise, “semiconductor substrate” may be used to identify wafers and other structures to be singulated into smaller elements.
The saw 10 is capable of lateral multi-indexing of the table 22 or blade 18 or, in other words, translatable from side-to-side in FIG. 2 and into and out of the plane of the page in FIG. 1 various non-uniform distances. As noted before, such non-uniform distances may be mere multiples of a unit distance, or may comprise unrelated varying distances, as desired. Accordingly, a wafer 24 having variously sized integrated circuits or other devices or components therein may be sectioned or diced into its non-uniformly sized components by the multi-indexing wafer saw 10 . In addition, as previously alluded, the saw 10 may be used to create scribe lines or cuts that do not extend through the wafer 24 . The wafer 24 can then subsequently be diced by other methods known in the art or sawed completely through after the blade 18 has been lowered to traverse the wafer to its full depth or thickness.
Before proceeding further, it will be understood and appreciated that design and fabrication of a wafer saw according to the invention having the previously-referenced, multi-indexing capabilities, independent lateral blade translation and independent blade raising or elevation are within the ability of one of ordinary skill in the art, and that likewise the control of such a device to effect the multiple-indexing (whether in units of fixed increments or otherwise), lateral blade translation and blade elevation may be effected by suitable programming of the software-controlled operating system, as known in the art. Accordingly, no further description of hardware components or of a control system to effectuate operation of the apparatus of the invention is necessary.
Referring now to FIG. 3, another illustrated embodiment of a wafer saw 30 is shown having two laterally-spaced blades 32 and 34 with their centers of rotation in substantial parallel alignment transverse to the planes of the blades. For a conventional, substantially circular silicon semiconductor wafer 40 (flat omitted), as illustrated in FIG. 4, having a plurality of similarly configured integrated circuits 42 arranged in evenly spaced rows and columns, the blades can be spaced a distance D substantially equal to the distance between adjacent streets 44 defining the space between each integrated circuit 42 . In addition, if the streets 44 of wafer 40 are too closely spaced for side-by-side blades 32 and 34 to cut along adjacent streets, the blades 32 and 34 can be spaced a distance D substantially equal to the distance between two or more streets. For example, a first pass of the blades 32 and 34 could cut along streets 44 a and 44 c and a second pass along streets 44 b and 44 d. The blades could then be indexed to cut the next series of streets and the process repeated for streets 44 e , 44 f , 44 g , and 44 h . If, however, the integrated circuits of a wafer 52 have various sizes, such as integrated circuits 50 and 51 as illustrated in FIG. 5, at least one blade 34 is laterally translatable relative to the other blade 32 to cut along the streets, such as street 56 , separating the variously sized integrated circuits 50 . The blade 34 may be variously translatable by a stepper motor 36 having a lead screw 38 or by other devices known in the art, such as high precision gearing in combination with an electric motor or hydraulics, or other suitable mechanical drive and control assemblies. For a wafer 52 , the integrated circuits, such as integrated circuits 50 and 51 , may be diced by setting the blades 32 and 34 to simultaneously cut along streets 56 and 57 , indexing the blades, setting them to a wider lateral spread and cutting along streets 58 and 59 , indexing the blades while monitoring the same lateral spread or separation and cutting along streets 60 and 61 , and then narrowing the blade spacing and indexing the blades and cutting along streets 62 and 63 . The wafer 52 could then be rotated 90°, as illustrated by the arrow in FIG. 5, and the blade separation and indexing process repeated for streets 64 and 65 , streets 66 and 67 , and streets 68 and 69 .
As illustrated in FIG. 6, a wafer saw 70 according to the present invention is shown having two blades 72 and 74 , one of which is independently raisable (as indicated by an arrow) relative to the other. As used herein, the term “raisable” includes vertical translation either up or down. Such a configuration may be beneficial for situations where the distance between adjacent streets is less than the minimum lateral achievable distance between blades 72 and 74 , or only a single column of narrow dice is to be cut, such as at the edge of a wafer. Thus, when cutting a wafer 80 , as better illustrated in FIG. 7, the two blades 72 and 74 can make a first pass along streets 82 and 83 . One blade 72 can then be raised, the wafer 80 indexed relative to the unraised blade 74 and a second pass performed along street 84 only. Blade 72 can then be lowered and the wafer 80 indexed for cutting along streets 85 and 86 . The process can be repeated for streets 87 (single-blade pass), 88 , and 89 (double-blade pass). The elevation mechanism 76 for blade 72 may comprise a stepper motor, a precision-geared hydraulic or electric mechanism, a pivotable arm which is electrically, hydraulically or pneumatically powered, or other means well known in the art.
Finally, it may be desirable to combine the lateral translation feature of the embodiment of the wafer saw 30 illustrated in FIG. 3 with the independent blade raising feature of the wafer saw 70 of FIG. 6 . Such a wafer saw could use a single blade to cut along streets that are too closely spaced for dual-blade cutting or in other suitable situations, and use both blades to cut along variously spaced streets where the lateral distance between adjacent streets is sufficient for both blades to be engaged.
It will be appreciated by those skilled in the art that the embodiments herein described while illustrating certain embodiments are not intended to so limit the invention or the scope of the appended claims. More specifically, this invention, while being described with reference to semiconductor wafers containing integrated circuits or other semiconductor devices, has equal utility to any type of substrate to be scribed or singulated. For example, fabrication of test inserts or chip carriers formed from a silicon (or other semiconductor) wafer and used to make temporary or permanent chip-to-wafer, chip-to-chip and chip-to-carrier interconnections and that are cut into individual or groups of inserts, as described in U.S. Pat. Nos. 5,326,428 and 4,937,653, may benefit from the multi-indexing method and apparatus described herein.
For example, illustrated in FIG. 8, a semiconductor substrate 100 may have traces 102 formed thereon by electrodeposition techniques requiring connection of a plurality of traces 102 through a tie bar 104 . A two-blade saw in accordance with the present invention may be employed to simultaneously scribe substrate 100 along parallel lines 106 and 108 flanking a street 110 in order to sever tie bars 104 of adjacent substrate segments 112 from their associated traces 102 . Following such severance, the two columns of adjacent substrate segments 112 (corresponding to what would be termed “dice” if integrated circuits were formed thereon) are completely severed along street 110 after the two-blade saw is indexed for alignment of one blade therewith, and the other blade raised out of contact with substrate 100 . Subsequently, when either the saw or the substrate carrier is rotated 90°, singulation of the segments 112 is completed along mutually parallel streets 114 . Thus, substrate segments 112 for test or packaging purposes may be fabricated more efficiently in the same manner as dice and in the same sizes and shapes.
Further, and as previously noted, RFID modules may be more easily fabricated when all components of a module are formed on a single wafer and retrieved therefrom for placement on a carrier substrate providing mechanical support and electrical interconnection between components.
As shown in FIG. 9, a portion of a substrate 200 is depicted with three adjacent columns of varying-width segments, the three widths of segments illustrating batteries 202 , chips 204 and antennas 206 of an RFID device. With all of the RFID components formed on a single substrate 200 , an RFID module may be assembled by a single pick-and-place apparatus at a single work station. Thus, complete modules may be assembled without transfer of partially-assembled modules from one station to the next to add components. Of course, this approach may be employed to any module assembly wherein all of the components are capable of being fabricated on a single semiconductor substrate. Fabrication of different components by semiconductor device fabrication techniques known in the art is within the ability of those of ordinary skill in the art, and therefore no detailed explanation of the fabrication process leading to the presence of different components on a common wafer or other substrate is necessary. Masking of semiconductor device elements not involved in a particular process step is widely practiced, and so similar isolation of entire components is also easily effected to protect the elements of a component until the next process step with which it is involved.
Further, the present invention has particular applicability to the fabrication of custom or non-standard IC's or other components, wherein a capability for rapid and easy die size and shape adjustment on a wafer-by-wafer basis is highly beneficial and cost-effective. Those skilled in the art will also understand that various combinations of the preferred embodiments could be made without departing from the spirit of the invention. For example, it may be desirable to have at least one blade of the independently laterally translatable blade configuration be independently raisable relative to the other blade or blades, or a single blade may be both translatable and raisable relative to one or more other blades and to the target wafer. In addition, while for purposes of simplicity some of the preferred embodiments of the wafer saw are illustrated as having two blades, those skilled in the art will appreciate that the scope of the invention and appended claims is intended to cover wafer saws having more or less than two blades. Thus, while certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the invention disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims. | A semiconductor wafer saw and method of using the same for dicing semiconductor wafers comprising a wafer saw including variable lateral indexing capabilities and multiple blades. The wafer saw, because of its variable indexing capabilities, can dice wafers having a plurality of differently sized semiconductor devices thereon into their respective discrete components. In addition, the wafer saw with its multiple blades, some of which may be independently laterally or vertically movable relative to other blades, can more efficiently dice silicon wafers into individual semiconductor devices. | 8 |
BACKGROUND
1. Field of the Invention
The present invention relates to the chemical vapor deposition of a tungsten film, and more particularly, to the nucleation of that deposition process on a semiconductor substrate with reduced gas phase particle formation and tungsten attack.
2. Description of the Related Art
The deposition of blanket tungsten (W) films using chemical vapor deposition (CVD) techniques is an integral part of many semiconductor fabrication processes. Typically the W film is deposited through the reduction of tungsten hexafluoride (WF 6 ) by hydrogen (H 2 ) or silane (SiH 4 ).
When H 2 is used as the reducing agent, the reaction has been found to (1) be rate-limited by the dissociation of H 2 into atomic H on the reaction surface; (2) produce a film with significant surface roughness; and (3) cause damage to device structures due to undesirable reactions at exposed Si and Ti surfaces. These undesired reactions lead to device performance problems such as high leakage current, high contact resistance and W film adhesion problems, and are often referred to as Device Attack.
SiH 4 reduction of WF 6 , unlike H 2 reduction, is not rate-limited by a dissociation step on a reactive surface. Therefore, SiH 4 reductions can result in higher W film deposition rates than H 2 reductions, when sufficient concentrations of SiH 4 are provided. At the same time, SiH 4 reduction reduces the tendency for Si and Ti attack by WF 6 or HF (HF is a formed in the H 2 reduction of WF 6 ). However, as the SiH 4 reduction of WF 6 to metallic W does not require a reactive surface, it can occur in the gas phase. This gas phase reduction or Gas Phase Nucleation (GPN) can lead to high particle counts in the deposition chamber and the subsequent incorporation of these particles into the deposited film. Thus, GPN like Device Attack can be a significant problem in blanket W depositions and typically conditions that reduce one problem promote the other. As a result, deposition processes must balance one against the other.
Another difficulty with blanket W depositions is the poor adhesion of the CVD W films to some insulating layers, for example silicon oxide, silicon nitride and the like. W adhesion can be enhanced through the deposition of an intermediate or adhesion film overlying the substrate surface and insulating layers. This adhesion film is most commonly a binary titanium/titanium nitride (Ti/TiN) layer or bilayer. Ti/TiN films have been found to be superior, with regard to contact-resistance values and resistance to typical W etch conditions, to other possible materials.
While it might seem that this Ti/TiN layer could prevent Si reduction of WF 6 during W depositions that use H 2 as the reducing agent, in practice this problem can actually be enhanced. The Ti/TiN surface is not very reactive toward H 2 dissociation; hence, the rate of dissociation is slowed and W film growth rate reduced. Thus while little or no Si may be exposed, the slowed W film growth rate allows time for any small area of exposed Si or weak spot in the Ti/TiN film to become a site for W rich nodule growth or Device Attack. In addition, WF 6 can react with Ti if the TiN barrier is breached to form TiF x . This reaction is commonly referred to as Ti attack and results in defects called volcanoes that reduce the integrity of the W film.
One prior art attempt to make such a trade-off, F. Cumpian et al. "Parametric Study of H 2 Doped SiH 4 /WF 6 Nucleation on Ti/TiN by Tungsten CVD Process", Proceedings of the Conference on Adv. Metallization and Interconnect Systems for ULSI Applications in 1995, pp. 529-534, (October, 1995), reported that both H 2 and SiH 4 were provided as reducing agents for a W deposition on a Ti/TiN coated substrate. While Cumpian et al. state that the addition of H 2 to SiH 4 eliminates defects caused by Ti attack, no mention of any effect on GPN or Si attack is made. In addition, Cumpian et al. reported a W growth rate plateau at approximately 80 nanometers/minute (nm/min).
Therefore, it would be advantageous to have a method of depositing a blanket W film that has little or no particulate formation due to GPN. It would also be advantageous to have a method of W deposition that has little or no undesirable chemical reactions taking place (Si or Ti attack). In particular, it would be advantageous to have a W film deposition process that provides for little or no GPN or Device Attack. Finally, it would be advantageous to have a W blanket film deposition process that provides both GPN and Device Attack reduction enhancements at deposition rates in excess of 100 nm/min, without adding additional costs resulting from reduced yields, additional process steps or costly process equipment or reagents.
SUMMARY
In accordance with the present invention, a tungsten film is deposited on a semiconductor substrate in two or more discrete stages at two or more discrete stations. The first stage of the deposition is an initiation/nucleation stage. This first stage first introduces initiation gases and then nucleation gases to a surface of the semiconductor substrate. The result is the nucleation of the tungsten film. These initiation/nucleation gases, their composition and flow rate, in combination with the temperature of the surface of the semiconductor substrate and the pressure of the reaction chamber, provide for the reduction or elimination of Gas Phase Nucleation (GPN), and Device Attack during the nucleation of the tungsten film.
In some embodiments of the present invention, the initiation/nucleation stage is performed at an initiation/nucleation or first station that is one of five deposition stations positioned within a single deposition chamber. Both initiation and nucleation gases are introduced to the surface of the semiconductor substrate, at the first station, using an individual gas supply system that creates a localized atmosphere at the substrate surface. After nucleation of the tungsten film is complete, the nucleation gases are turned off. The semiconductor substrate, having a first thickness of W deposited at a first rate, is then moved to a second deposition station and a new wafer is moved into place on the first station. The full thickness of the W film is achieved by additional W depositions at each of the other deposition stations. Thus a cycle of nucleation steps and other deposition steps is established until all substrates are coated to the desired thickness. Any number of deposition stations, each capable of having a localized atmosphere isolated from adjacent stations, are possible within the single chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be better understood, and its numerous objects, features, and advantages made apparent to those skilled in the art by referencing the accompanying drawings. For ease of understanding and simplicity, common numbering of elements within the illustrations is employed where the element is the same between illustrations.
FIG. 1 is a schematic diagram of a deposition system capable of performing a prior art tungsten deposition;
FIG. 2 is a block diagram illustrating the steps of a prior art deposition process that can be performed in the system of FIG. 1;
FIG. 3 is a schematic diagram of a deposition system capable deposition of a tungsten film in accordance with the method of the present invention; and
FIG. 4 is a block diagram illustrating the steps of a deposition process in the manner of the present invention.
DETAILED DESCRIPTION
Embodiments of the present invention will be described with reference to the aforementioned figures. These figures are simplified for ease of understanding and description of embodiments of the present invention only. Modifications, adaptations or variations of specific methods and or structures shown and discussed herein may become apparent to those skilled in the art. All such modifications, adaptations or variations that rely upon the teachings of the present invention, and through which these teachings have advanced the art, are considered to be within the spirit and scope of the present invention.
FIG. 1 is a schematic representation of a deposition system configured for a blanket tungsten (W) process in the manner of the prior art. Nucleation station 300 and four bulk deposition stations 310 are shown within vacuum chamber 400. Vacuum chamber 400 has a vacuum pumping port 470 coupled to a vacuum pump (not shown) through a pressure control device 460, for example a throttle valve, positioned appropriately therein. As known, the combination of port 470 and control device 460 coupled to chamber 400 can serve to maintain chamber 400 at a predetermined pressure as required by the specific process in use.
Each deposition station 310 has a process gas distribution line 450 coupled to a gas distribution manifold 350. Distribution manifold 350 supplies tungsten hexafluoride (WF 6 ), argon (Ar) and hydrogen (H 2 ) gases through distribution lines 450 to stations 310 for the deposition of a W film, as will be discussed hereinafter. WF 6 , Ar and H 2 gases are supplied to distribution manifold 350 through common gas line 436, which in turn is coupled to H 2 manifold 330 through valved H 2 line 434 and to WF 6 +Ar manifold 340 through valved WF 6 +Ar line 432. Manifolds 330 and 340 are furnished with reagent gases through valved input lines that are coupled to specific reagent gas sources (not shown). Thus, H 2 is supplied to manifold 330 through valved input line 415 and WF 6 and Ar to manifold 340 through valved input lines 420 and 425, respectively. In this manner, each deposition station 310 is uniformly supplied with reagent gases from a single distribution manifold 350.
Initiation/nucleation station 300 differs from stations 310 in that it is coupled to SiH 4 +Ar manifold 320 in addition to distribution manifold 350. Thus, a mixture of SiH 4 and Ar are supplied to station 300 from manifold 320 via gas distribution line 444 and valved line 442, while reagent gases from manifold 350 are delivered via distribution line 444 and 446 as shown. As described for manifolds 330 and 340, manifold 320 is supplied with reagent gases through input lines. Thus, input line 405 supplies SiH 4 to manifold 320 and input 410 supplies Ar. In this manner, nucleation station 300 has an independent supply of SiH 4 .
Each deposition station 310 and the initiation/nucleation station 300 have a heated substrate platen (not shown) for holding and heating a substrate (not shown) to a predetermined temperature and a gas distribution head (not shown) for dispersing the supplied gases over the substrate. In addition, each station 300 and 310 has a backside gas distribution system (not shown), to prevent deposition of the W film on the backside of the substrate, and a vacuum clamping manifold (not shown) for clamping the substrate to the platen. Finally, chamber 400 is equipped with a transport system (not shown) for transporting wafers or substrates into and out-of the chamber as well as between deposition stations.
Turning now to FIG. 2, the steps of the prior art deposition process are illustrated in block diagram format. In describing these steps, all reference to elements of a deposition system will be understood to be the system of FIG. 1.
In step 100, chamber 400 is pumped through vacuum port 470 to a predetermined base pressure. Typically, this base pressure is less than approximately 20 milliTorr (mT), although other appropriate pressures can be employed. Once the base pressure is achieved, step 110 provides for pressurizing chamber 400 with H 2 and Ar, provided through stations 300 and 310 from distribution manifold 350, to a pressure of between approximately 40 to 80 Torr (T). Typically, the flow rates of the H 2 and Ar are each between approximately 4 to 15 standard liters per minute (slm). As known, this sequence of pumping to a low base pressure and subsequent pressurization to a higher pressure serves to clean chamber 400 of atmospheric contaminants and provide a clean background atmosphere for the deposition process.
A first wafer or substrate is placed into chamber 400 and onto initiation/nucleation station 300 which has been heated to between approximately 350 to 475 degrees Centigrade (°C.), step 120. When the temperature has been reached, the flow of initiation gases is begun, step 130. The initiation gases of the prior art method are SiH 4 and Ar as supplied from manifold 320 at flow rates of approximately 15 to 75 and 1000 standard cubic centimeters per second (sccm), respectively. This flow is continued for a predetermined time, typically about 20 seconds or less, and the flow of SiH 4 stopped, step 140, just prior to beginning the flow of nucleation gases, step 150. Nucleation gas flow consists of WF 6 from manifold 350 as well as SiH 4 and Ar from manifold 320. Typically, the WF 6 flow rate from manifold 350 is between approximately 150 to 800 sccm and flow rates of SiH 4 and Ar from manifold 320 are as previously described. It will be understood, that while Ar is provided to station 310 during step 150, it's flow is continuous, and not switched on as are the WF 6 and SiH 4 from manifolds 350 and 320, respectively.
The presence of the nucleation gases provides for the growth of a W film at a rate of approximately 250 to 330 nm/min. Once a first thickness of W has been formed, step 160, all WF 6 and SiH 4 flow is stopped, step 170, and the wafer or substrate on first station 300 is transferred to a second or bulk deposition station 310, step 180A. Once station 300 is cleared, another wafer or substrate is loaded, step 180B, and steps 130 to 180A, step 220B, repeated until all wafers have the first thickness of W deposited thereon. At essentially the same time, steps 190, 200 and 210 are performed to form a second thickness of W at a rate of approximately 60 to 380 nm/min. Where as shown in FIG. 1, there is one first or initiation/nucleation station 300 and four second or bulk deposition stations 310, each wafer will have deposited thereon one first thickness of W and four second thickness of W. It is the sum of these individual depositions that forms the total amount of W deposited.
While the method described above, produces W films, it can be subject to GPN and/or Device Attack. As previously mentioned, process conditions that reduce GPN favor Device Attack and visa versa, thus the prior art method requires that a delicate balance between the two effects be maintained. Typically, maintaining this balance involves adjusting the SiH 4 flow is to slightly favor GPN. The amount of GPN that occurs is usually monitored using laser based, in-situ particle monitoring systems (not shown) to sample the chamber atmosphere, and not by measuring a particle count on an actual wafer. For a system, such as the one described in FIG. 1, having an in-situ monitor sensitive to particles greater than or equal to 0.2 micron (μm), and running a process slightly favoring GPN, a count of between approximately 250 to 400 particles per second (part/sec) is typical.
Turning now to FIG. 3, a system for forming W films in the manner of the subject invention is shown. The system of FIG. 3 is similar to the system of FIG. 1, hence only those structures that are changed from FIG. 1 are numbered differently. Thus, initiation/nucleation station 305 is supplied with SiH 4 and H 2 from manifold 325 and WF 6 and H 2 from manifold 345. Manifold 325 has an input 412 from a H 2 source, (not shown), and manifold 345 an input 416 from another H 2 source (not shown). In this manner, different flows of H 2 can be provided for each manifold. It will be noted that other than the absence of any coupling to the nucleation station, manifold 350 and its connections to supply manifolds 330 and 340, and to stations 310 are as previously described for FIG. 1. Also, chamber 400, pressure control device 460, vacuum pumping port 470, each bulk deposition station 310 and all heating and transport mechanisms (not shown) are as previously described.
Referring to FIG. 4, the steps of a deposition process in the manner of the present invention are illustrated in block diagram format. In describing these steps, all reference to elements of a deposition system will be understood to be the system of FIG. 3.
As previously described with respect to step 100 of FIG. 2, in step 105 of FIG. 4, chamber 400 is pumped to a predetermined base pressure, typically, less than approximately 20 mT, although other appropriate pressure can be employed. Once the base pressure is achieved, step 115 provides for pressurizing chamber 400, with H 2 through manifold 345 coupled to station 305, and with Ar and H 2 through manifold 350 coupled to each station 310, to a pressure of between approximately 40 to 80 T. Thus, unlike the prior art process, no Ar is supplied to initiation/nucleation station 305 (station 300 in FIG. 1). As discussed with respect to FIG. 2 this sequence of pumping to a low pressure pressurizing to a higher pressure serves to purge chamber 400 of gaseous contaminants. However, unlike the prior art method, only H 2 is provided to station 305, thus providing a local atmosphere essentially free of Ar.
A first wafer or substrate is placed into chamber 400 and onto initiation/nucleation station 305, step 120, and initiation gas flow is started, step 135. In accord with the present invention, the initiation gases used are SiH 4 and H 2 as supplied from manifold 325. The flow rate of SiH 4 is between approximately 15 to 75 sccm and that of H 2 , approximately 1000 sccm. In this manner a local atmosphere about the substrate is created. The SiH 4 flow is continued, as described previously, for a short predetermined time and stopped, step 140. Step 155, then begins the flow of the nucleation gases. In some embodiments of the present invention, nucleation gas flow consists of H 2 and WF 6 supplied to station 305 from manifold 345 and SiH 4 and H 2 supplied to station 305 from manifold 325. The approximate range of flow rates for each gas at station 305 are 1 to 15 slm of H 2 , 50 to 800 sccm of WF 6 and 15 to 75 sccm of SiH 4 . Thus, the nucleation gas flow of step 155, adds a separately controlled supply of WF 6 and H 2 to station 305. As was seen for steps 115 and 135, step 155 also provides gas flow to station 305 that is without Ar.
As described for the prior art process, the presence of nucleation gases at station 305 initiates the growth of a W film. However, in contrast to the prior art process, the W deposition rate is found to be approximately 540 nm/min, an increase of about 47%. In addition, this rate is also over 6 times the W deposition rate reported Cumpian et al., in the previously mentioned reference, as a deposition rate plateau.
Once a first thickness of W has been formed, step 160, the SiH 4 and WF 6 flows are stopped, step 170, and the wafer or substrate on station 305 is transferred to a first bulk deposition station 310, step 180A. Then, another wafer or substrate is loaded onto station 305, step 180B, and steps 135 to 180A, step 220B, repeated until all wafers have the first thickness of W deposited thereon. At essentially the same time, steps 190, 200 and 210 are performed to form a second thickness of W. In step 190, WF 6 flow is started at manifold 340 and coupled to station 310 through distribution manifold 350. Thus a second local atmosphere of gases, WF 6 , H 2 and Ar, is formed about the substrate at each station 310. The flow of WF 6 is continued until a second thickness of W is formed, step 200, and the WF 6 turned off, step 210. Where, as shown in FIG. 3, there is a single initiation/nucleation station 305 and four bulk deposition stations 310, each wafer will have deposited thereon one first thickness of W and four second thickness of W. It is the sum of these individual depositions that forms the total amount of W deposited.
It should be noted that the approximately 47% increase in deposition rate over the prior art process discussed with respect to FIG. 2 and the greater than 6-fold increase over the rate reported by Cumpian et al. as a plateau, is unexpected. As previously discussed herein and by Cumpian et al., H 2 reduction of WF 6 is rate limited by the dissociation of the H 2 on an active surface. Thus an increase in H 2 concentration above that amount which can absorb on the active surface should not increase the W deposition rate. Thus a plateau in the W deposition rate under such reaction conditions is expected (see Cumpian et al., FIG. 3, on p. 533).
It should also be noted, that as embodiments of the present invention reduce or eliminate GPN and/or Device Attack, that process conditions that slightly favor GPN are not required. Hence, embodiments of the present invention use process conditions that are optimized for the best possible film nucleation and growth. Thus, it has been found through in-situ process monitoring (not shown), that the number of particles greater than or equal to 0.2 μm is essentially zero, due to GPN, while also maintaining essentially no Device Attack.
Thus embodiments of the present invention have been described that provide a method for the initiation/nucleation of a W film with reduced Device Attack and GPN while maintaining a high W deposition rate. One of ordinary skill in the art will realize that while the description herein illustrate specific embodiments of the present invention, other embodiments are possible that are within the spirit and scope of the present invention. | A tungsten (W) film is formed on a surface of a semiconductor substrate by providing to that surface gas mixtures tailored for both reduced gas phase nucleation of particulates (GPN) and attack of exposed silicon (Si) or titanium (Ti) surfaces (Device Attack) while maintaining a high W deposition rate. An initiation step is performed where the surface is preconditioned with hydrogen (H 2 ) and silane (SiH 4 ). A subsequent nucleation step then uses a mixture of H 2 and SiH 4 to reduce tungsten hexafluoride (WF 6 ) and thus form a first thickness of the W film. In some embodiments, an alternate gas mixture can be employed to form a second thickness of W on the surface of the semiconductor substrate. | 2 |
FIELD OF THE INVENTION
The present invention relates to chair constructions, and more particularly relates to a chair construction employing a sling-type backrest which promotes chair stability, comfort and a variety of design alternatives.
BACKGROUND OF THE INVENTION
Various types of sling chairs have been known which provide a somewhat concave and/or giving backrest. Such chairs generally include a back portion and a seat portion, and may optionally include armrest portions. The back portion generally includes a back frame and a flexible yet supportive backrest made of fabric or other suitable material and mounted to the back frame. Different mechanisms have been employed for securing the backrest to the back frame, and these prior art mechanisms have suffered from several deficiencies. First, these prior art mechanisms often fail to provide a secure connection, which can result in the backrest being unsupportive of the seated individual. Further, the sling backrest for these chairs is frequently retained along the chair side rail supports, creating side-to-side sling tension, restricting the potential to add decorative chair features, and complicating assembly.
SUMMARY OF THE INVENTION
The present invention provides a connection assembly for a sling chair which allows for efficient chair assembly and results in a comfortable yet sturdy chair. The present invention includes a back frame member having side rails held in substantially parallel relation by a pair of cross bar members. In one embodiment, the cross bar members are generally curved so as to extend away from the back faces of the side rails, forming a concave back structure which can receive a sling member and, eventually, a seated occupant. The cross bar members are adapted to retain the sling member in secure fashion through upper and lower backrest assemblies. In this way, the sling member is not secured to the side rails, but rather to the cross bar members, resulting in better support, a more secure connection and more efficient assembly. The method of securing the sling member using a detachable support bar having a scaffold support element ensures that the sling member is efficiently and securely retained. The present invention also facilitates separate provisioning of decorative features to improve the chair's aesthetic qualities.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a right side view of an exemplary chair showing one embodiment of the present invention.
FIG. 2 is a rear elevational view of the back frame and backrest elements of the chair assembly of the present invention.
FIG. 3 is a bottom cross-sectional view of the upper backrest assembly of one embodiment of the present invention, taken along the line III-III of FIGS. 1 and 2 .
FIG. 4 is a bottom plan view of one embodiment of the bottom cross bar member of the present invention.
FIG. 5 is a right side cross-sectional view of the upper backrest assembly portion of one embodiment of the present invention, taken along the line V-V of FIGS. 2 and 3 .
FIG. 6 is a right side cross-sectional view of the lower backrest assembly portion of one embodiment of the present invention, taken along the line VI-VI of FIG. 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIGS. 1 through 6 , the present invention provides a single frame sling chair 10 , having a rigid frame 12 . FIG. 1 shows an overall, right side view of one embodiment of a chair according to the present invention, including monolithic welded frame 12 comprising frame rails 14 , seat 16 , armrests 18 and leg portions 20 . A backrest assembly 22 is also shown, including upper backrest assembly portion 24 and lower backrest assembly portion 26 . Upper backrest assembly portion 22 includes top cross bar 28 and detachable support bar 30 , described more completely hereafter. Top cross bar 28 may be integrally formed with top element 32 and connective fascia 34 , or may be secured to elements 32 and 34 as separate members. Top cross bar is secured to, and acts as a spreader between, frame side rails 14 , as shown in FIG. 2 .
As further shown in FIGS. 1 and 2 , lower backrest assembly portion 26 includes bottom cross bar 38 which is secured to frame rails 14 and acts as a spreader to hold frame rails 14 apart. Bottom cross bar 38 cooperates with top cross bar 28 to hold frame rails 14 in substantially parallel relation. A backrest 33 , such as a sling fabric member, is secured to the upper 24 and lower 26 backrest assembly portions to provide body support to individuals using the chair of the present invention.
In the embodiment as shown in FIG. 2 , top and bottom cross bar members are provided in substantially parallel relation. The crossbars 28 , 38 are provided of a curved or concave shape generally, and can be solid or hollow. As shown in FIGS. 1 and 2 , the crossbars 28 , 38 project at least partially outwardly away from respective back faces 15 of side rails 14 . The crossbars 28 , 38 can be any of a variety of section shapes, and can be adapted to accept a decorative casting 34 as part of or an attachment to crossbar, as shown in the exemplary embodiment of FIG. 2 . Decorative side castings 35 can also be provided as shown in FIG. 2 so as to flank sling member 33 . The sectional shape of side rails 14 as well as that of support bar 30 can be circular, oval, square, or other shape, for example. Further, support bar 30 and side rails 14 can be solid or hollow.
The remainder of the chair frame can have any arrangement for a seat bottom, it may have arms or no arms, and it may have any number of legs, or a pedestal instead of legs, and may be a rocker, swivel chair, swivel-rocker, swivel-glider, or a rigid monolithic frame.
The method of securing top 28 and bottom 38 cross bar members to back frame rails 14 can be by conventional means, such as by welding or by providing the frame rails with open interior slots for receiving respective ends of cross bar members 28 , 38 (not shown). The method of securing backrest 33 to top and bottom cross members involves upper 24 and lower 26 backrest assemblies. Upper backrest assembly 24 comprises at least top cross bar member 28 and detachable support bar 30 . As shown in FIGS. 2 , 3 and 5 , detachable support bar 30 is provided with a base portion 41 and a scaffold portion 42 , wherein scaffold portion can be “c”-shaped as shown for receiving a substantially rigid rod 50 . As shown in FIG. 5 , rod member 50 is placed through a loop 40 in sling member 33 , wherein the sling loop 40 and rod 50 rest in the channel created by scaffold portion 42 . Loop 40 can be formed, for example, by bending sling member edge back upon itself and securing the sling member to itself, such as via a hem or similar method. A portion of sling member 33 thus rests in the gap 43 created by the base portion 41 and cross bar member 28 . The support bar 30 can be secured to the bottom face 45 of top cross bar 28 using screws 46 mating with internal threads 47 in base portion 41 and cross bar 28 , for example. Alternative means of fastening support bar 30 to top cross bar 28 can be employed, such as sheet metal screws, hook and loop fasteners, clamps, or malleable plug members extending from support bar 30 into openings in cross bar 28 , for example.
As shown in FIGS. 2 , 4 and 6 , lower backrest assembly 26 comprises at least bottom cross bar 38 and rod member 60 . As shown in FIGS. 2 and 6 , bottom cross bar 38 can include an upper portion 52 and a lower portion 53 which join together at respective ends 38 a and 38 b , and which have respective inside walls 54 a and 54 b , outside walls 55 a and 55 b and interior facing walls 56 a and 56 b . Cross bar member 38 can be formed as a unitary, monolithic piece or can be formed by securing respective portions 52 and 53 together at ends 38 a and 38 b through welding or other attachment means. Regardless of how formed, the interior facing walls 56 a and 56 b cooperate to form a through-and-through slot 44 . As shown in FIG. 2 , slot 44 can extend for substantially the length of upper 52 and lower 53 portions. As shown in FIG. 6 , the end of fabric sling 33 opposite the end secured to upper bracket assembly is provided with a loop 58 for receiving rod member 60 . Loop 58 can be formed in a manner similar to that described for forming loop 40 . Rod member and sling loop portion 58 are then retained against outside walls 55 a and 55 b , which are respectively provided with inwardly extending portions 57 a and 57 b for such purpose. In one embodiment as shown in FIG. 6 , inwardly extending portions 57 a and 57 b are arcuate in cross-section. Portions 57 a and 57 b assist in providing the back assembly 22 with a low profile, minimizing the extent of rod and sling extension outside of the plane formed by outside walls 55 a and 55 b , which in turn minimizes sling member exposure to unnecessary wear and tear. As shown in FIGS. 4 and 6 , the securing of sling member 33 within lower bracket assembly 26 can be optionally enhanced through the employment of one or more machine screws 64 extending through openings 66 in lower cross bar member and mated with hollow receiving screw 65 or other similar securing element. In one embodiment of the invention, a screw receiving member such as a nut having an interior threaded surface is maintained within walls of cross bar 38 so as to receive screw 64 while not extending outwardly of the upper portion 52 of cross bar 38 . In this way, minimum visibility of attachment elements such as nuts and bolts can be maintained, which enhances the aesthetic qualities of the present invention.
It will be appreciated that the shape of top 28 and bottom 38 cross bar members can be adapted to suit particular chair requirements in accordance with the present invention. For example, the top cross bar member 28 can have a rounded rectangle cross-sectional shape, as shown in FIG. 5 , or can have a square, hexagonal, octagonal or other polygonal shape. Bottom cross bar member 38 can have a primarily rectangular shape with arcuate interior wall segments 57 a and 57 b as shown in FIG. 6 and described earlier. Alternatively, bottom cross bar member 38 can have a square, hexagonal, octagonal or other polygonal shape. In one embodiment, bottom cross bar member 38 has an octagonal shape and adjacent edges establish a receiving channel for retaining rod member 58 and looped hem 60 , again minimizing the outward extension of the sling fabric loop and rod member beyond the lower backrest assembly. In a further embodiment, a metal frame member (not shown) can be secured to upper 52 and lower 53 portions of bottom cross bar member 38 to conceal and protect sling member 33 and loop 60 .
By placing the sling entrapment at the top and bottom in the cross members, rather than in the side rails, the invention facilitates the creation of a comfortable concave shape to the back rest. Also, the invention thereby allows for shorter looped hems and dowels than would exist if the sling were attached to the side rails. The invention also permits sturdier and more rigid frame construction and leaves open more design possibilities for accessory items.
The method of assembling the backrest 22 to the frame 12 according to the present invention can occur in several ways. In one exemplary way, chair frame 12 is provided with top cross bar member 28 and bottom cross bar member 38 secured to side rails 14 as shown in FIG. 2 . Sling member 33 is provided with looped hems 40 and 58 at two ends thereof. Looped end 58 is manipulated through slot 44 in lower cross bar member so as to be positioned somewhat adjacent to wall portions 57 a and 57 b . Rod member 60 is then manipulated through looped end 58 such that any tension applied to the remainder of sling member, such as pulling on sling member from a location on the interior of lower cross bar member, will result in looped hem 58 contacting wall portions 57 a and 57 b . Machine screws and nuts or equivalent attachment means can assist in retaining sling member in place with respect to bottom cross bar member 38 .
Next, rod member 50 is placed through looped hem portion 40 of sling member 33 , and this arrangement is positioned over base portion 41 of support bar 30 and within scaffold portion 42 . Support bar 30 is then raised so as to align with the under face 45 of top cross bar member 28 . Threaded bolts 46 or similar attachment means can then be manipulated through base portion 41 , sling member 33 and top cross bar member 28 to securely maintain support bar and sling to top cross bar member 28 .
The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the claims of the application rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. | A sling chair includes a back frame member having side rails held in substantially parallel relation by a pair of cross bar members. In one embodiment, the cross bar members are generally curved so as to extend away from the back faces of the side rails, forming a concave back structure which can receive a sling member and, eventually, a seated occupant. The cross bar members are adapted to retain the sling member in secure fashion through upper and lower backrest assemblies, resulting in better support and more efficient assembly. This also facilitates separate provisioning of decorative features to improve the chair's aesthetic qualities. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to a method of producing a high-melting powder of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane from a solution of the compound in an organic solvent.
It is known that 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane (hereinafter sometimes referred to briefly as BDBP-TBA), when added to various resins, improves the fire resistance of the resins.
BDBP-TBA as such can be easily produced as a solution of high purity typically by a process in which tetrabromobisphenol A is converted to a diallyl ether which is then brominated in an inert solvent. Concentrating this solution yields a resinous solid having a melting point of 40°-50° C. However, it takes many hours to achieve solidification and it is also difficult to produce a granular, powdery or flaky solid by means of a chiller or a flaker. Furthermore, because of its low melting point, this resinous solid tends to undergo fusion and solidification in storage or stick to the equipment during use. In view of this disadvantage, development of a high-melting product has been demanded.
As a means for overcoming the above disadvantage, it is described in Japanese Patent Publication No. 57-289 that a BDBP-TBA product with a melting point of 80°-100° C. can be produced by the procedure of adding either a nonsolvent or a poor solvent to a solution of BDBP-TBA in a good solvent and stirring the mixture with a shear force.
However, the melting point of BDBP-TBA that can be obtained by the above procedure described in the prior art literature is 80°-100° C. and, moreover, the highest melting point actually mentioned in the production examples is 92° C. Moreover, since, in this prior art, a solution in a good solvent such as a halogenated hydrocarbon or an aromatic hydrocarbon is extracted with a poor solvent such as an alcohol, reclaiming the solvents for reuse requires a distillation or other fractionation procedure and, therefore, the technology is not reasonably acceptable. Moreover, this prior technology requires a special stirrer such as a twin-screw kneader or a homomixer but this requirement is onerous both equipment-wise and cost-wise.
SUMMARY OF THE INVENTION
This invention has for its object to provide a method of producing a high-melting grade of BDBP-TBA, which method permits reuse of the solvent as recovered and use of ordinary stirring equipment, not any special stirring equipment.
This invention, therefore, is concerned with a method of producing a high-melting powder of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane which comprises a step of adding water to a solution of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane in an organic solvent in the presence of a surfactant to give a water-in-oil emulsion and a subsequent step of removing the organic solvent in the presence of a crystal nucleus to give an aqueous dispersion of high-melting 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane crystals.
The mechanism of formation of a high-melting powder of BDBP-TBA in this invention seems to be as follows. Thus, as water is added to a solution of BDBP-TBA in an organic solvent in the presence of a surfactant, the water is emulsified into the organic solvent containing BDBP-TBA to give a water-in-oil emulsion. As the continuous oil phase containing BDBP-TBA is concentrated with progressive removal of the solvent under maintenance of the emulsion state, a concentrated BDBP-TBA solution extremely small in thickness is obtained, and crystallization takes place as the concentration of BDBP-TBA and the temperature become ripe for crystallization. If a crystal nucleus such as a BDBP-TBA powder or a water-insoluble metal hydroxide or oxide is concomitantly present in this system, this crystallization takes place at a high speed. With the progress of crystallization, the emulsion is disrupted and the water forms a continuous phase so that crystals of BDBP-TBA are obtained in the form of an aqueous dispersion.
In accordance with this invention, in which crystallization is caused to take place under the maintenance of an emulsion by a surfactant, no special stirrer of the shear type is required but the objective product can be obtained with an ordinary stirrer. Moreover, there occurs no intermingling of solvents but the organic solvent is distillatively recovered in good yield so that it can be reused after a procedure as simple as phasic separation from water. In addition, since BDBP-TBA is obtained as an aqueous dispersion, its handling in the post-crystallization procedures such as dehydrative filtration and drying is facilitated and made safer. Thus, the invention provides a simple, economic, safe and very reasonable method for producing a high-melting grade of BDBP-TBA.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The starting material BDBP-TBA to be dissolved in an organic solvent in the practice of this invention is preferably of a purity not less than 85% in terms of the liquid chromatographic peak area ratio calculated from UV detection data at 254 nm. If the purity of the starting material is less than 85%, the product BDBP-TBA tends to have a low melting point. As to the organic solvent solution of BDBP-TBA, it may be a solution of a low-melting resinous grade of BDBP-TBA in an organic solvent or a solution available from the bromination step of the precursor 2,2-bis(4'-allyloxy-3',5'-dibromophenyl)propane in the reaction-inert organic solvent.
The organic solvent for use in this invention is a solvent substantially insoluble in water, thus including but not limited to halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, ethylidene chloride, 1,2-dichloroethylene, 1,1,1-trichloroethane, trichloroethylene, etc. and aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, etc. In the method of this invention, however, since BDBP-TBA does not crystallize at any temperature over 80° C., the crystallizing temperature must not be higher than 80° C., although the temperature for solvent removal may be higher than 80° C. Thus, while even a high-boiling organic solvent can be recovered at a temperature below 80° C. by conducting distillation under reduced pressure, the use of an organic solvent having a boiling point higher than the boiling point of water or an organic solvent containing much water to form an azeotropic system is undesirable in view of the possible disruption of the water-in-oil emulsion or from economic points of view. Moreover, when this invention is carried into practice immediately following the bromination reaction, BDBP-TBA is available in the form of a solution in an organic solvent inert to bromine and, therefore, it is a reasonable choice to subject the solution as it is to the treatment of this invention without changing the organic solvent. Therefore, the preferred solvent for use in this invention is a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, ethylidene chloride and 1,2-dichloroethylene, among others.
The function of the surfactant for use in this invention is to insure formation of a water-in-oil emulsion and can be any of cationic, anionic and nonionic surfactants. However, a large majority of cationic surfactants contain nitrogen and, therefore, present coloration and odor problems if BDBP-TBA contains their residues. Thus, these surfactants are not recommended.
As to anionic surfactants, surfactants of the sulfate, sulfonate, sulfosuccinate, fatty acid and phosphoric ester types can be mentioned. However, since the metal salts or amine salts are strongly ionic, they tend to disrupt the water-in-oil emulsion in the course of solvent removal or an inversion of emulsion prior to crystallization so that the product BDBP-TBA may become increased in particle diameter to give a greater on-sieve percentage, thus detracting from the yield of the product. From these considerations, acidic phosphoric ester surfactants in particular are preferred. These surfactants can be used alone or in combination with other anionic surfactants of the sulfate, sulfonate, sulfosuccinate, fatty acid, phosphoric ester metal salt or amine salt type and/or nonionic surfactants of the ethoxylate type. The acidic phosphoric ester surfactants have the additional advantage that when the system is neutralized after formation of an aqueous dispersion of BDBP-TBA particles, its water-solubility is increased and its adsorption on the BDBP-TBA particles in the filtration step is decreased, thus facilitating the rinsing procedure.
The acidic phosphoric ester surfactant that can be used includes unneutralized phosphoric esters of the substituted phenol type which can be obtained by adding an average of 1-30 mols of ethylene oxide (EO) per mol of a substituted phenol, such as nonylphenol, dinonylphenol, octylphenol, dioctylphenol, styrenated phenol, distyrenated phenol, tristyrenated phenol, etc., with the aid of an alkali metal or tertiary amine catalyst to give a substituted phenol ethoxylate and reacting the ethoxylate with a phosphorylating agent such as phosphoric acid, polyphosphoric acid, phosphoric anhydride, phosphorus oxychloride, etc. These are mixtures composed predominantly of phosphoric monoesters and/or phosphoric diesters and containing small proportions of phosphoric triester, pyrophosphoric ester, inorganic phosphoric acid, etc. There can also be mentioned unneutralized phosphoric esters of the higher alcohol type which are obtainable by reacting higher alcohols or higher alcohol ethoxylates, which are obtainable by adding an average of 1-30 mols of ethylene oxide per mole of higher alcohols with the aid of an alkali metal or tertiary amine catalyst, with a phosphorylating agent such as phosphoric acid, polyphosphoric acid, phosphoric anhydride, phosphorus oxychloride, etc. The higher alcohols that can be used for this purpose are saturated or unsaturated natural or synthetic alcohols containing 8-18 carbon atoms. Natural alcohols are mixtures of alcohols derived from vegetable oils or animal fats or simple substances obtained by elaborate fractional distillation of them. Thus, plant-derived alcohols such as coconut alcohol, palm alcohol, palm kernel alcohol, etc., animal-derived alcohols such as tallow alcohol, hydrogenated tallow alcohol, etc., and such alcohols as n-octyl alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and linoleyl alcohol, all of which are obtainable by fractional distillation of the above-mentioned mixture alcohols, can be typically mentioned. Synthetic alcohols may for example be oxoalcohols or alcohols obtainable by condensation reaction of aldehydes, such as 2-ethylhexanol. Specifically, Dobanol 23, Dobanol 25 and Dobanol 45 manufactured by Shell Chemical Co., Diadol 11, Diadol 115L, Diadol 115H, Diadol 13 and Diadol 135 manufactured by Mitsubishi Kasei Corporation, Oxocol 1213, Oxocol 1215 and Oxocol 1415 manufactured by Kyowa Hakko Kogyo Co., and nonyl alcohol, undecyl alcohol, tridecyl alcohol and pentadecyl alcohol which can be obtained by fractional distillation of said alcohols can be mentioned. Moreover, secondary alcohols obtainable by oxidation of paraffin are commercially available in ethoxylated forms and, as examples, Softanol 30, Softanol 50, Softanol 70, Softanol 90 and Softanol 120 manufactured by Nippon Shokubai Co. can be mentioned. The phosphoric ester surfactants mentioned above can be used singly or in combination.
Nonionic surfactants of the ethoxylate type are substituted phenol ethoxylates and higher alcohol ethoxylates, containing an average of 40-90 weight % of ethylene oxide in each surfactant molecule. They may be mixtures of two or more species. Among typical substituted phenols are nonylphenol, dinonylphenol, octylphenol, dioctylphenol, dodecylphenol, didodecylphenol, styrenated phenol, distyrenated phenol, and tristyrenated phenol, and nonionic surfactants of the ethoxylated type can be obtained by adding an average of 40-90 weight % of ethylene oxide to these substituted phenols with the aid of, for example, an alkali metal or tertiary amine catalyst. The higher alcohols that can be used are saturated or unsaturated natural and synthetic alcohols containing 8-18 carbon atoms. Natural alcohols are mixture alcohols derived from vegetable oils or animal fats or simple substances obtainable by elaborate fractional distillation of them. As examples, alcohols of vegetable origin such as coconut alcohol, palm alcohol, palm kernel alcohol, etc., alcohols of animal origin such as tallow alcohol, hydrogenated tallow alcohol, etc., and n-octyl alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol and linoleyl alcohol which are obtainable by fractional distillation of such mixture alcohols can be mentioned. Examples of synthetic alcohols may include oxoalcohols, secondary alcohols which can be obtained by oxidation of paraffin, and alcohols obtainable by condensation of aldehydes, such as 2-ethylhexanol. Specifically, Dobanol 23, Dobanol 25 and Dobanol 45 manufactured by Shell Chemical Co., Diadol 11, Diadol 115L, Diadol 115H, Diadol 13 and Diadol 135 manufactured by Mitsubishi Kasei Corporation, Oxocol 1213, Oxocol 1215 and Oxocol 1415 manufactured by Kyowa Hakko Kogyo Co., nonyl alcohol, undecyl alcohol, tridecyl alcohol and pentadecyl alcohol which can be obtained by fractional distillation of the above alcohols can be mentioned. By adding an average of 40-90 weight % of ethylene oxide to these higher alcohols with the aid of, for example, an alkali metal or tertiary amine catalyst, nonionic surfactants of the ethoxylate type which can be used in this invention can be obtained. Softanol 50, Softanol 70, Softanol 90 and Softanol 120, all manufactured by Nippon Shokubai Co., which are ethoxylation products of secondary alcohols obtained by oxidation of paraffin can also be used in combination with said acidic phosphoric ester surfactants.
The preferred total level of addition of surfactants is 0.05-5 weight % based on BDBP-TBA. In the case of acidic phosphoric ester surfactants, a proportion of 0.05-3 weight % is particularly recommendable. If the proportion of acidic phosphoric ester surfactants is less than 0.05 weight %, a water-in-oil emulsion cannot be stably maintained so that it is difficult to obtain a powdery BDBP-TBA. If said limit of 3 weight % is exceeded, no commensurate increase in the effect can be realized. The use of an acidic phosphoric ester surfactant in combination with a different type of anionic surfactant and/or an ethoxylate type nonionic surfactant may produce the effect of depressing the viscosity of the water-in-oil emulsion immediately preceding crystallization of BDBP-TBA so that the burden on the stirrer can be alleviated. However, when the total amount of surfactants exceeds 5 weight %, no commensurate increase in the effect can be obtained and rather the COD of the waste water is increased to impose a burden on waste water treatment, thus detracting from the economics of operation.
The amount of water necessary for formation of a water-in-oil emulsion is 20-100 weight % relative to BDBP-TBA and the method and timing of addition of water are not critical only if a water-in-oil emulsion is formed before BDBP-TBA begins to crystallize. Therefore, the whole amount of water can be added before the beginning of recovery of the organic solvent or at an optional stage preceding the onset of crystallization after beginning of recovery of the organic solvent, either in bolus, in installments, or continuously. However, if BDBP-TBA is allowed to crystallize from a water-in-oil emulsion system which is deficient in water, desruption of the emulsion after crystallization may not be satisfactorily accomplished so that dispersion of crystals will be insufficient. If this is the case, a further amount of water can be added so as to achieve a complete dispersion of crystals. It is also possible to add water for the purpose of adjusting the viscosity of the aqueous dispersion but the excessive use of water is not economical, of course, because the burden of waste water disposal is increased. Therefore, the total amount of water in the aqueous dispersion is preferably controlled within the range of 50-200 weight % based on BDBP-TBA.
The crystallizing procedure of this invention includes an application of the phase-inversion emulsification technique which has been conventionally used for emulsifying oils in water and involves crystallization of BDBP-TBA from a water-in-oil emulsion prior to phase inversion. However, if the phase inversion takes place before crystallization, a stable oil-in-water emulsion is produced to considerably interfere with a further removal of the solvent. Moreover, the crystallization of BDBP-TBA is not completed in a short time regardless of temperature and the emulsion is disrupted on cooling with the result that BDBP-TBA particles conglomerate to form paste-like masses and, hence, the desired powder cannot be obtained. It is, therefore, necessary that crystallization be initiated as soon as BDBP-TBA has become ready to crystallize in the course of removal of the organic solvent and be completed in a relatively short time. This requirement can be met by adding a crystal nucleus. A suitable crystal nucleus is a high-melting powder of BDBP-TBA. It is necessary that 0.001-10 weight % of the crystal nucleus relative to BDBP-TBA be added before commencement of solvent recovery and/or in the course of solvent recovery before BDBP-TBA crystallizes. However, where the starting BDBP-TBA has not been thoroughly dissolved in the organic solvent but some crystals of BDBP-TBA remain in the organic solvent solution, the solution can be directly treated without addition of a crystal nucleus.
Meanwhile, when a resin is to be rendered flame-retardant with a halogen type flame retardant, it is common practice to use antimony oxide concomitantly in expectation of a synergistic effect. Since antimony oxide does not detract from the utility of the resin in fire retardation uses even if it finds its way into the substrate resin as a contaminant, antimony oxide can be utilized as said crystal nucleus for such applications. Similarly, metal hydroxides and oxides which are insoluble in water and organic solvents, such as aluminum hydroxide, magnesium hydroxide, silica, alumina, magnesium oxide, etc. can also be used as said crystal nucleus.
The BDBP-TBA crystals in an aqueous dispersion obtained by the above technique do not melt or fuse even at a temperature near 80° C. and, therefore, a further removal of the solvent can be carried out. Moreover, the dry powder of BDBP-TBA as a final product can be manufactured by performing, following the above process, a step of neutralizing the aqueous dispersion (where the acidic phosphoric ester surfactant is used), a step of filtrative collection of BDBP-TBA crystals, a rinsing step, a drying step, and, where necessary, a crushing/classifying step for size selection. The melting point of the resulting dry BDBP-TBA powder as determined with an automatic melting point measuring instrument (Mettler) at a temperature incremental rate of 2° C./min. is not lower than 100° C., thus meeting the object of this invention.
In accordance with this invention, crystallization is carried out in an emulsion state with the aid of a surfactant so that the objective product can be produced with an ordinary stirring means without requiring a special high-shear stirring machine. Moreover, since a high-melting BDBP-TBA is obtained as an aqueous dispersion, workability and safety in the subsequent production steps are improved. In addition, since the solvent used is not intermingled but is recovered as it is in high yield by distillation, it can be reused by a procedure as simple as phasic separation.
The following examples are intended to describe this invention in further detail without defining the scope of the invention. In the examples, all "parts" and "%" are by weight and all melting point values are those measured with an automatic melting point measuring instrument.
EXAMPLE 1
A 500 ml glass flask equipped with an anchor-shaped stirring blade was charged with 200 parts of BDBP-TBA of 87% purity having a melting point of 42° C. and 200 parts of methylene chloride and the BDBP-TBA was thoroughly dissolved. The flask was further charged with 200 parts of water, 1 part of nonylphenol ethoxylate (an average of 9 mols of EO added) phosphate, and, as a crystal nucleus, 10 parts of a BDBP-TBA powder having a melting point of 114° C. With the stirrer being driven at 300 rpm, the temperature was increased for distillative recovery of methylene chloride. When the concentration of BDBP-TBA in the methylene chloride phase as calculated from the recovery rate of methylene chloride reached 92% and the temperature became 60° C., crystallization took place, promptly giving rise to an aqueous dispersion. As the temperature was further increased to 70° C. for distillative recovery of methylene chloride, the recovery rate of methylene chloride reached 97%. This aqueous dispersion was cooled to ≦25° C., neutralized with sodium hydroxide and passed through a 1 mm mesh sieve, whereupon 2 parts of solid BDBP-TBA remained on the sieve. This aqueous dispersion was filtered, rinsed with approximately the same weight of water as the BDBP-TBA, and dried at 70° C. for 24 hours to provide 197 parts of a BDBP-TBA powder. This powder had a melting point of 104° C.
EXAMPLE 2
The same apparatus as used in Example 1 was charged with 200 parts of BDBP-TBA of 92% purity having a melting point of 45° C. and 200 parts of chloroform and the starting compound was thoroughly dissolved. The apparatus was further charged with 200 parts of water, 5 parts of nonylphenol ethoxylate (an average of 22 mols of EO added) phosphate and, as a crystal nucleus, 2 parts of a BDBP-TBA powder having a melting point of 114° C. With the stirrer driven at 300 rpm and the temperature maintained at 55° C., chloroform was recovered by distillation under reduced pressure. When the concentration of BDBP-TBA in the chloroform phase as calculated from the recovery rate of chloroform had reached 90%, crystallization took place giving rise to an aqueous dispersion, 100% of which passed a 1 mm mesh sieve. This dispersion was cooled, neutralized, filtered, rinsed and dried in the same manner as Example 1 to provide a powdery BDBP-TBA (199 parts) which had a melting point of 116° C.
EXAMPLE 3
The same apparatus as used in Example 1 was charged with 400 parts of a methylene chloride solution containing 50% of BDBP-TBA of 93% purity (containing 200 parts of BDBP-TBA) as obtained by brominating 2,2-bis(4'-allyl-3',5'-dibromophenyl)propane using methylene chloride as the reaction solvent. The apparatus was further charged with 100 parts of water, 1 part of distyrenated phenol ethoxylate (an average of 8 mols of EO added) phosphate, 3 parts of oleyl alcohol ethoxylate (containing an average of 57% of polyoxyethylene) and 0.1 part of a BDBP-TBA powder having a melting point of 114° C. With the stirrer driven at 300 rpm, the temperature was increased for distillative recovery of methylene chloride. When the temperature had reached 60° C., the concentration of BDBP-TBA in the methylene chloride phase as calculated from the recovery rate of methylene chloride was 88% and the contents had become a viscous paste. When 100 parts of water at 20° C. was added, crystallization took place and, at the same time, the viscosity of the contents decreased giving rise to an aqueous dispersion. As this aqueous dispersion was further heated at 75° C. to remove the methylene chloride, the recovery rate of methylene chloride reached 98%. The dispersion was then cooled to 25° C., neutralized with sodium hydroxide, and passed through a 1 mm mesh sieve. As a result, 100% of the dispersion passed through the sieve. This dispersion was further filtered, rinsed and dried to provide a dry powder of BDBP-TBA (200 parts), the melting point of which was 118° C.
EXAMPLES 4-13
The same apparatus as used in Example 1 was charged with 400 parts of a methylene chloride solution containing 50% of a BDBP-TBA composition of 90% purity, water, 5 parts of a BDBP-TBA powder having a melting point of 114° C., and a surfactant and the methylene chloride was recovered by distillation at atmospheric pressure. The temperature at which crystallization took place, the concentration of BDBP-TBA in methylene chloride phase as calculated from the recovery rate of methylene chloride, the amount of solid BDBP-TBA which remained on the 1 mm mesh sieve, and the melting point of the powdery BDBP-TBA obtained after the same after-treatment of the aqueous dispersion as described in Example 1 are shown in Tables 1 and 2.
TABLE 1__________________________________________________________________________ Example 4 Example 5 Example 6 Example 7 Example 8 Example 9__________________________________________________________________________Acidic phosphoric 2-Ethylhexanol Distyrenated Dinonyl- Lauryl Coconut Distyrenatedester surfactant phosphate phenol phenol alcohol alcohol phenol ethoxylate ethoxylate ethoxylate phosphate ethoxylate (EO 8 mols) (EO 7 mols) (EO 20 mols) (EO 8 mols) phosphate phosphate phosphate phosphateAmount (parts) 1.0 0.2 2.0 1.0 0.6 0.1Concomitant Nonylphenol -- Softanol 70 Octylphenol 2-Ethylhexanol --surfactant ethoxylate -- (EO 58%) ethoxylate ethoxylate -- (EO 60%) (EO 7 mols) (EO 20 mols) sulfate sulfomono- ammonium salt succinate 2NaAmount (parts) 2.0 -- 1.0 1.0 1.0 --Water initially 100 100 140 60 180 100added (parts)Water supplement- 100 60 60 240 -- 100ally added (parts)Timing of supple- At 90% con- At 91% con- After At 90% con- -- At 90% con-mental addition centration centration crystal- centration centration of BDBP-TBA of BDBP-TBA lization of BDBP-TBA of BDBP-TBAConcentration of 90 92 90 90 90 90BDBP-TBA (%) atcrystallizationTemperature (°C.) 56 57 57 55 60 59at crystalli-zationState of dis- Good Good Good Good Dispersed but Dispersed butpersion particle dia- particle dia- meter somewhat meter somewhat large largeOn 1 mm mesh sieve 3 0 0 2 7 20(parts)Melting point (°C.) 114 115 115 114 114 114of dried product__________________________________________________________________________ Note 1: "Parts" in this table represent parts by weight relative to 200 parts of BDBPTBA. Note 2: The "concentration of BDBPTBA at crystallization" was calculated from the initial amount of methylene chloride and the recovered amount of methylene chloride. Note 3: The "on 1 mm mesh sieve" was determined by sieving the aqueous dispersion with a 1 mm mesh sieve, rinsing the residue on the sieve, drying it and recording its weight. Note 4: As regards the "melting point of dried product", the aqueous dispersion was neutralized, filtered, rinsed with 200 parts of water, and dried at 70° C. for 24 hrs and its melting point was determined with an automatic melting point measuring instrument.
TABLE 2__________________________________________________________________________ Example 10 Example 11 Example 12 Example 13__________________________________________________________________________Surfactant Cetylpyridinium Sodium Sodium Distyrenated phenol chloride palmitate lauryl ethoxylate (EO 8 mols) benzene- phosphate, neutralized sulfonate with NaAmount (parts) 1.0 0.4 0.2 1.0Surfactant Dinonylphenol -- Dobanol 25 -- ethoxylate ethoxylate (EO 60%) (EO 70%)Amount (parts) 1.0 -- 8.0 --Water initially 100 160 140 120added (parts)Water supplement- 80 -- 60 --ally added (parts)Timing of supple- At 90% con- -- After --mental addition centration crystal- of BDBP-TBA lizationConcentration of 90 89 90 93BDBP-TBA (%) atcrystallizationTemperature (°C.) 56 60 57 60at crystalli-zationState of dis- Good Dispersed Dispersed Dispersed butpersion but particle but particle particle diameter diameter diameter somewhat large somewhat somewhat large largeOn 1 mm mesh sieve 8 15 20 24(parts)Melting point (°C.) 114 114 115 113of dried product__________________________________________________________________________ Note 1: "Parts" in this table represent parts by weight relative to 200 parts of BDBPTBA. Note 2: The "concentration of BDBPTBA at crystallization" was calculated from the initial amount of methylene chloride and the recovered amount of methylene chloride. Note 3: The "on 1 mm mesh sieve" was determined by sieving the aqueous dispersion with a 1 mm mesh sieve, rinsing the residue on the sieve, drying it and recording its weight. Note 4: As regards the "melting point of dried product", the aqueous dispersion was filtered, rinsed with 200 parts of water, and dried at 70° C. for 24 hrs and its melting point was determined with an automatic melting point measuring instrument.
EXAMPLE 14
The procedure of Example 3 was repeated except that 0.01 part of antimony trioxide with a mean particle diameter of 0.8-1.5 microns was used in lieu of 0.1 part of BDBP-TBA powder as the crystal nucleus. The procedure yielded an aqueous dispersion, 96% of which passed a 1 mm mesh sieve. The melting point of the filtered, rinsed and dried BDBP-TBA powder (192 parts) was 118° C.
EXAMPLE 15
The same apparatus as used in Example 1 was charged with 500 parts of a homogeneous 40% BDBP-TBA solution containing BDBP-TBA of 92% purity (containing 200 parts of BDBP-TBA composition) as obtained by bromination of 2,2-bis(4'-allyl-3',5'-dibromophenyl)-propane using carbon tetrachloride as the reaction solvent. The apparatus was further charged with 160 parts of water and 2 parts of octylphenol ethoxylate (an average of 7 mols of EO added) phosphate, and with the stirrer driven at 300 rpm, the temperature was increased for distillative recovery of carbon tetrachloride at atmospheric pressure. When the concentration of BDBP-TBA in carbon tetrachloride phase as calculated from the recovery rate of carbon tetrachloride had reached 85% at an internal temperature of 96° C., heating was discontinued. The contents at this stage were a viscous paste. After 1 part of a BDBP-TBA powder having a melting point of 114° C. was added, the temperature was lowered to 75° C., whereupon crystallization took place and the viscosity of the system decreased, giving rise to an aqueous dispersion. This aqueous dispersion was distilled under reduced pressure at 70°-75° C. for further recovery of the organic solvent. The final recovery rate of carbon tetrachloride was 98%. The dispersion was then cooled to 25° C. and neutralized with sodium hydroxide. The aqueous dispersion thus obtained passed a 1 mm mesh sieve 100% and the BDBP-TBA powder (198 parts) obtained after filtration, rinse and drying had a melting point of 116° C.
COMPARATIVE EXAMPLE 1
The same BDBP-TBA of 93% purity as used in Example 3 was dissolved in methylene chloride and the solution was concentrated under reduced pressure up to a temperature of 57° C. until the volatile content reached 1%. However, the solution remained a viscous liquid, failing to yield a solid. When it was cooled to 25° C., a resinous solid was obtained but its melting point was 45° C.
COMPARATIVE EXAMPLE 2
The procedure of Example 1 was repeated except that the surfactant (1 part of nonylphenol ethoxylate (an average of 9 mols of EO added) phosphate) was omitted from the charge. Though the methylene chloride was distilled off and recovered, with the BDBP-TBA-containing methylene chloride and water still forming distinct phases, deposits were formed on the flask wall and stirrer blade as the BDBP-TBA concentration and the system viscosity increased progressively so that no emulsification/dispersion could be achieved at all. Moreover, although concentration further continued until the concentration of BDBP-TBA in methylene chloride as calculated from the recovery rate of methylene chloride reached 94%, no crystallization could be obtained. When the system was cooled to 20° C., the deposits on the glass wall and stirrer blade solidified into resinous masses. The melting point of the masses was 44° C.
COMPARATIVE EXAMPLE 3
The procedure of Example 3 was repeated except that no crystal nucleus was added. When the concentration of BDBP-TBA in methylene chloride as calculated from the recovery rate of methylene chloride reached 87% and the temperature was 57° C., the viscous liquid underwent phase inversion to a low-viscosity oil-in-water emulsion. As this system was further heated, a further amount of methylene chloride was distillatively recovered but the rate of recovery was low and the recovery yield at an internal temperature of 80° C. was corresponding to a BDBP-TBA concentration of 90%. At this stage, BDBP-TBA in the emulsion had not formed crystals. Then, as this oil-in-water emulsion was cooled gradually at a rate of 10° C./hour, the BDBP-TBA particles conglomerated to form a paste-like mass at 50° C. | This invention relates to a method of producing a high-melting powder of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane characterized by comprising a step of adding water to a solution of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!-propane in an organic solvent in the presence of a surfactant to give a water-in-oil emulsion and a step of removing the organic solvent from the emulsion in the presence of a crystal nucleus to induce crystallization to give an aqueous dispersion of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane. In accordance with this invention, crystallization is carried out in the state of an emulsion under assistance of a surfactant so that an ordinary stirrer can be used in production without resort to any special high-shear stirring equipment. Moreover, since a high-melting grade of 2,2-bis 4'-(2",3"-dibromopropoxy)-3',5'-dibromophenyl!propane is obtained as an aqueous dispersion, workability and safety in the subsequent processing are improved. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the present invention are generally related to safety valves. More particularly, embodiments of the present invention pertain to subsurface safety valves configured to be actuated using wellbore pressure in the event of an unexpected pressure drop.
2. Description of the Related Art
Subsurface safety valves are commonly used to shut-in oil and gas wells and are typically fitted in a string of production tubing installed in a hydrocarbon producing well. The safety valves are configured to selectively seal fluid flow through the production tubing to control the flow of formation fluids upwardly should a failure or hazardous condition occur at the well surface.
Typically, subsurface safety valves are rigidly connected to the production tubing and may be installed and retrieved by conveyance means, such as tubing or wireline. During normal production, safety valves are maintained in an open position by the application of hydraulic fluid pressure transmitted to an actuating mechanism. The actuating mechanism in such embodiments may be charged by application of hydraulic pressure through hydraulic control systems. The hydraulic control systems may comprise a clean oil supplied from a surface fluid reservoir through a control line. A pump at the surface delivers regulated hydraulic fluid under pressure from the surface to the actuating mechanism through the control line. The control line resides within the annular region between the production tubing and the surrounding well casing.
In the event of a failure or hazardous condition at the well surface, fluid communication between the surface reservoir and the control line is interrupted. This, in turn, breaks the application of hydraulic pressure against the actuating mechanism. The actuating mechanism recedes within the valve, allowing a flapper to quickly and forcefully close against a corresponding annular seat—resulting in shutoff of the flow of production fluid. In many cases, the flapper can be reopened (and production flow resumed) by restoring the hydraulic fluid pressure to the actuating mechanism of the safety valve via the control lines.
For safety reasons, most surface controlled subsurface safety valves (such as the ones described above) are “normally closed” valves, i.e., the valves are in the closed position when the hydraulic pressure in the control lines is not present. The hydraulic pressure typically works against a powerful spring and/or gas charge acting through a piston. In many commercially available valve systems, the power spring is overcome by hydraulic pressure acting against the piston, producing axial movement of the piston. The piston, in turn, acts against an elongated “flow tube.” In this manner, the actuating mechanism is a hydraulically actuated and axially movable piston that acts against the flow tube to move it downward within the tubing and across the flapper.
Safety valves employing control lines, as described above, have been implemented successfully for standard depth wells with reservoir pressures that are less than 15,000 psi. However, wells are being drilled deeper, and the operating pressures are increasing correspondingly. For instance, formation pressures within wells developed in some new reservoirs are approaching 30,000 psi. In such downhole environments, conventional safety valves utilizing control lines are not operable because of the effects of hydrostatic pressure on the hydraulic fluid within the control line. In other words, high-pressure wells have exceeded the capability of many existing control systems, especially hydraulic control systems which rely on control lines, which are susceptible to reliability problems.
Therefore, a need exists for a subsurface safety valve that is suitable for use in high pressure environments. There is a further need for a subsurface safety valve that does not rely on a control system that requires the use of control lines conveying hydraulic fluid to an actuating mechanism. There is yet a further need for the ability to reopen the safety valve remotely from the surface of the well.
SUMMARY OF THE INVENTION
In one respect, the present invention provides a downhole valve for selectively sealing a bore. The downhole valve generally includes a closing member for seating in and closing the bore, and a pressure-actuated, retention member having first and second opposed piston surfaces for initially holding the valve in an open position but, in the event of a pressure differential between the piston surfaces, permits the closing member to operate and close the valve.
In another respect, the present invention provides a method of operating a downhole valve. The method generally includes providing the valve in a down hole tubular, the valve having a closing member and an axially movable retention member having a first piston surface and an opposing piston surface and an interfering member to interfere with the closing member and keep the valve in the open position. A sudden pressure drop in the wellbore, shifts the retention member due to a pressure differential between the first and second piston surfaces, and closing the valve due to the axial movement of the interfering member way from the closing member.
In yet another respect, the present invention provides a safety valve for use downhole. The safety valve generally includes a pivotly mounted flapper, biased towards a closed position for sealing a bore, an interfering member to hold the flapper in an open position, a first piston surface in fluid contact with the bore, a second opposing piston surface in fluid communication with a pressure chamber having restricted fluid communication with the bore, wherein the valve is constructed and arranged to close in the event of a pressure difference between the bore and the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features 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.
FIG. 1 is a cross-sectional view of a wellbore illustrating a string of production tubing having a subsurface safety valve in accordance with one embodiment of the present invention.
FIG. 2A is a cross-sectional view of the subsurface safety valve in an open position.
FIG. 2B is a cross-sectional view of the subsurface safety valve of FIG. 2A , shown in the closed position.
FIGS. 3A and 3B illustrate cross-sectional views of a subsurface safety valve in accordance with an alternative embodiment of the present invention.
FIGS. 4A–4C illustrate cross-sectional views of a subsurface safety valve in accordance with yet another embodiment of the present invention.
DETAILED DESCRIPTION
The apparatus and methods of the present invention allow for a subsurface safety valve for use in high pressure wells. Embodiments of the present invention provide safety valves that utilize normal wellbore pressure for actuation of the valve, which removes the need for hydraulic systems with control lines extending from the surface to the valve.
FIG. 1 is a cross-sectional view of an illustrative wellbore 10 . The wellbore is completed with a string of production tubing 11 . The production tubing 11 defines an elongated bore through which servicing fluid may be pumped downward and production fluid may be pumped upward. The production tubing 11 includes a safety valve 200 in accordance with one embodiment of the present invention. The safety valve 200 is used for controlling the upward flow of production fluid through the production tubing 11 in the event of a sudden and unexpected pressure loss (also referred to herein as a “pressure drop”) of production fluid may coincide with a corresponding increase in flow rate within the production tubing 11 . Such a condition could be due to the loss of flow control (i.e., a blowout) of the production fluid at the wellbore surface. In the event of such a condition, a subsurface safety valve, implemented according to embodiments of the current invention, automatically actuates and shuts off the upward flow of production fluid. Further, when flow control is regained at the surface, the safety valve can be remotely reopened to reestablish the flow of production fluid. Discussion of the components and operation of embodiments of the safety valve of the present invention are described below with reference to FIGS. 2A–2B , 3 A– 3 B, and 4 A– 4 C.
It should be understood, that as used herein, the term “production fluid” may represent both gases or liquids or a combination thereof. Those skilled in the art will recognize that production fluid is a generic term used in a number of contexts, but most commonly used to describe any fluid produced from a wellbore that is not a servicing (e.g., treatment) fluid. The characteristics and phase composition of a produced fluid vary and use of the term often implies an inexact or unknown composition.
FIG. 2A illustrates a cross-sectional view of a subsurface safety valve in a open position, in accordance with one embodiment of the present invention. The safety valve 200 comprises an upper housing 201 A threadedly connected to a lower housing 201 B, which, in turn, is threadedly connected to a bottom sub 202 . The upper housing 201 A makes up the top of the safety valve 200 and extends upward. Accordingly, the bottom sub 202 makes up the bottom of the safety valve 200 and extends downward. Both the upper housing 201 A and the bottom sub 202 are configured with threads to facilitate connection to production tubing 11 (or other suitable downhole tubulars) above and below the safety valve 200 , respectively.
The safety valve 200 comprises a flapper 203 and a flow tube 204 . The flapper 203 is rotationally attached by a pin 203 B to a flapper mount 203 C. The flapper 203 pivots between an open position and a closed position in response to axial movement of the flow tube 204 . As shown in FIG. 2A , the flapper 203 is in the open position creating a fluid pathway through the bore of the flow tube 204 , thereby allowing the flow of fluid through the valve 200 . Conversely, in the closed position, the flapper 203 blocks the fluid pathway through the bore of the flow tube 204 , thereby preventing the flow of fluid through the valve 200 .
As stated earlier, FIG. 2A illustrates the safety valve 200 in the open position. It can be seen that the flow tube 204 is positioned such that it physically interferes with and restricts the flapper 203 from closing. As will be described with reference to FIG. 2B , when the safety valve 200 is in the closed position, the flow tube 204 is translated sufficiently upward to enable the flapper 203 to close completely and shut off flow of production fluid.
While production fluid is being conveyed to the surface under stable and controlled conditions, the safety valve 200 remains in the open position. Under such conditions, the flow tube 204 remains bottomed out against an upward facing internal shoulder 230 of the bottom sub 202 , thereby restricting the flapper 203 from closing. The flow tube 204 is held in this position due to a net downward force resulting from the force exerted by a spring 211 biased towards the extended position. A gap 231 between the inner diameter of the upper mandrel 201 A and the outer diameter of the flow tube 204 allows piston surface 209 to be in fluid communication with the wellbore.
As shown in FIG. 2A , a pressure chamber 205 is located in the annular space between the outer diameter of the flow tube 204 and the inner diameter of the lower housing 201 B. The pressure chamber 205 is bound by a piston seal 206 on top and the tube seal 207 on bottom. A spring 211 is also located in the annular area between lower housing 201 B and the flow tube 204 . The spring is held in place by a spring retainer 212 and surface 213 of the flow tube 204 .
During normal operation, while the valve 200 is in the open position, the pressure chamber 205 is filled with production fluid that enters the pressure chamber 205 through an orifice 208 . In this embodiment, the orifice 208 is the only path for fluid to enter and exit the pressure chamber 205 . The orifice is designed to meter flow that passes through it, regardless of whether the fluid is entering or exiting the pressure chamber 205 . While the valve 200 is in the open position, the fluid flow through the orifice ensures that the pressure of the fluid inside the chamber is equalized with the pressure of the fluid flowing through the bore of the flow tube 204 .
As shown in FIG. 2A , a pressure chamber 205 is located in the annular space between the outer diameter of the flow tube 204 and the inner diameter of the lower housing 201 B. The pressure chamber 205 is bound by a piston seal 206 on top which is positioned between piston surface 209 and piston surface 210 and the tube seal 207 on bottom. A spring 211 is also located in the annular area between lower housing 201 B and the flow tube 204 . The spring is held in place by a spring retainer 212 and surface 213 of the flow tube 204 .
The pressure difference between the fluid within the pressure chamber 205 and the production fluid results in the pressure chamber 205 increasing in volume and the flow tube 204 being urged upward. It should be noted that as the flow tube 204 moves upward, it meets resistance as the spring 211 is compressed. Provided that the pressure difference is large enough and the pressure chamber 205 expands sufficiently, the flow tube 204 travels sufficiently upward so that it no longer restricts the flapper 203 from closing and shutting-in the well as seen in FIG. 2B .
After the flapper is closed, the pressure of the production fluid acting on the underside of the flapper 203 (pushing upward) is high enough to forceably keep the flapper 203 in the closed position. In terms of the pressure chamber 205 , it should be noted that starting from the instant of the rapid pressure loss (corresponding to the loss of flow control) the metered flow of fluid through the orifice allows for the pressure equalization process to resume. However, even after the pressure equalizes again, the pressure of the downhole fluid against the bottom-side of the flapper will keep it shut.
Embodiments of the present invention also provide functionality to remotely reopen the subsurface safety valve 200 . Obviously, this would be done after flow control apparatus at the surface of the wellbore are returned to working order. In order to reopen the safety valve 200 from the surface, fluid is pumped down to the safety valve 200 and the pressure is built up so that the pressure above the flapper 203 is the same as the pressure of the production fluid below the flapper 203 (i.e., pressure is equalized across the flapper 203 ).
It should be noted that by this time, the flow of fluid through the orifice 208 has allowed pressure of fluid within the pressure chamber 205 to again equalize with the pressure of fluid outside the pressure chamber 205 . The spring 211 stays compressed, and the pressure chamber 205 does not return to it's previous volume because the flow tube 204 is not allowed to move downwards due to the closed flapper.
However, once there is equal pressure on both sides of the flapper 203 , the spring 211 , biased towards the extended position, will urge the flow tube 204 downwards, which in turn will push the flapper to the open position. Thereafter, the flow tube will bottom out against a corresponding interior shoulder of the bottom sub 202 .
With reference to the discussion above, it can be understood that the amount of upward movement of the flow tube 204 is dependent on the difference in pressure (i.e., “pressure drop”) between the fluid in the pressure chamber 205 and the pressure of the fluid flowing through the bore of the flow tube 204 at the moment of loss of flow control. In other words, the higher the difference in pressure between the fluid in the pressure chamber and the fluid flowing through the bore of the flow tube 204 , the greater the amount of upward movement of the flow tube 204 . Maximizing upward movement of the flow tube 204 is important because it ensures that the flow tube does not restrict the flapper 203 from fully closing in the event of a loss of flow control.
Other embodiments of the present invention are envisioned for providing more upward movement of the flow tube for a given pressure drop. FIG. 3A , for instance, illustrates a cross-sectional view of a subsurface safety valve configured with bellows according to an alternative embodiment of the present invention. As will be described below, use of bellows for creating a pressure chamber is beneficial because bellows provide a large change in volume between the compressed and uncompressed position. Greater variance in the volume of the pressure chamber while the safety valve is in the open position versus closed position translates into more axial movement of the flow tube, which ensures complete closure of the flapper.
Referring now to FIG. 3A , a safety valve 300 is provided with a housing 301 that is threadedly connected to a bottom sub 302 . Both the housing 301 and the bottom sub 302 are configured with threaded connections to allow for installing the safety valve 300 in a string of production tubing 11 .
As with the embodiment described earlier, safety valve 300 comprises a flapper 303 and a flow tube 304 . The flapper 303 is rotationally attached by a pin 303 B to a flapper mount 303 C. The flapper 303 pivots between an open position and a closed position in response to axial movement of the flow tube 304 . As shown in FIG. 3A , the safety valve 300 is in the open position; the flow tube 304 restricts the flapper 303 from pivoting. However, with sufficient upward movement of the flow tube 304 , the flapper 303 can pivot to block the upward flow of production fluid.
An important component of this embodiment is the use of bellows 306 for creating an expandable pressure chamber 305 . The bellows 306 may be made of a variety of materials, including, but not limited to metals. For one embodiment, the bellows 306 are configured with pleated metal to facilitate a volumetric variance between its compressed and uncompressed positions.
The pressure chamber 305 is defined by the annular space between the bellows 306 and the flow tube 304 . The pressure chamber 305 is bound on the top by the connection between the bellows 305 and the bellows retainer 307 . The lower end of the pressure chamber 305 is bound by a cap 320 . There are two channels by which production fluid can enter the pressure chamber 305 : fluid can go past a packing 309 , or fluid can flow into the pressure chamber 305 via an orifice 308 . While the valve 300 is in the open position, the fluid flow through the orifice 308 and the packing 309 ensures that the pressure of the fluid inside the pressure chamber 305 is equalized with the pressure of the fluid flowing through the bore of the flow tube 304 . FIG. 3B provides a detailed view of the orifice 308 and the packing 309 .
In the context of the current application, the packing 309 can be thought of as a one-way valve. As seen in FIG. 3A , the packing 309 is configured to allow fluid to flow into the pressure chamber 305 , but not out of it. An orifice 308 is also provided to allow for fluid to flow into the pressure chamber 305 . It should be noted that the orifice 308 provides the only path by which fluid is allowed to flow out of the chamber. The orifice 308 is configured to meter the fluid that flows through at a relatively low flow rate.
A pressure equalization port 321 extending through the cap 320 is provided to ensure that the pressure on either side of the cap 320 is equalized. Further, the port 321 provides a secondary path for production fluid to reach the packing 309 in the event that the path formed around the bottom end of the flow tube 304 and through the area adjacent to the flapper 303 is plugged.
The safety valve 300 comprises a spring 311 that resists the upward movement of the bellows retainer 307 and the flow tube 304 . The bottom of the spring 311 rests against the bellows retainer 307 . The top portion of the spring 311 interfaces with a downward-facing internal shoulder of the housing 301 . In the open position of the safety valve 300 , with the flow tube 304 bottomed out, the spring 311 is fully extended. In the closed position of the safety valve 300 , with the flow tube 304 all the way up, the spring 311 is compressed and it exerts a downward force against the bellows retainer 307 .
In the event of a loss of flow control at the surface of the wellbore, there would be a pressure drop between the fluid flowing through the bore of the flow tube 304 and the fluid in the pressure chamber 305 . As with the previous embodiment, the pressure in the pressure chamber 305 is not reduced in concert with the pressure of the production flow because the metering effect of the orifice 308 does not allow the fluid to flow out of the pressure chamber 305 to allow for pressure equalization to occur immediately. As a result, the pressure chamber 305 expands by extending the bellows 306 axially, which, in turn, urges the bellows retainer 307 and flow tube 304 to move upward, compressing the spring 311 . Upon sufficient upward movement of the flow tube 304 , the flapper 303 will close to shut-in the wellbore.
As with the embodiment described earlier with reference to FIGS. 2A and 2B , the valve can be reopened by equalizing pressure on both sides of the flapper 303 and allowing the spring 311 to urge the flow tube 304 downwards. This, in turn, would return the flapper 303 to the open position.
FIG. 4A illustrates yet another embodiment of the present invention that is designed to provide additional axial movement of the flow tube for a given pressure drop. A cross-sectional view of a subsurface safety valve configured with extension rods sliding in their corresponding cylinders is provided. As will be described below, the axial movement of rods for expanding a pressure chamber is beneficial because the process of displacing rods in cylinders with fluid can yield a tremendous amount of axial movement of a flow tube for a given pressure drop. As stated earlier, complete upward movement of the flow tube ensures complete closure of the flapper.
Referring now to FIG. 4A , a safety valve 400 is provided with a housing 401 that is threadedly connected to a crossover sub 402 , which is threadedly connected to a lower housing 403 . The lower housing 403 is connected to a bottom sub 404 . Both the housing 401 and the bottom sub 404 are configured with threaded connections to allow for installing the safety valve 400 in a string of production tubing 11 . As with previously described embodiments, the safety valve 400 includes a flow tube 404 , spring 411 and flapper 406 , each of which provides generally the same functionality as with other embodiments described above.
The lower end 422 of the crossover sub 402 seals into the lower housing 403 at position 422 . It should be understood that because the lower end 422 of the crossover sub 402 is sealingly connected (e.g., press fit, static seal, etc.) to the lower housing 404 , production fluid is not able to flow past the seal between the lower end 422 of the crossover Sub 402 and the lower housing 404 . However, the lower end 422 of the crossover sub 402 does contain an orifice 408 that allows fluid to flow into and out of a pressure chamber 405 . Fluid arrives at the orifice 408 by flowing around the top or bottom of the flow tube 404 and within the annular space between the lower end 422 of the crossover sub 402 and flow tube 404 .
Referring now to FIG. 4A , a safety valve 400 is provided with a housing 401 that is threadedly connected to a crossover sub 402 , which is threadedly connected to a lower housing 403 . The lower housing 403 is connected to a bottom sub 423 . Both the housing 401 and the bottom sub 423 are configured with threaded connections to allow for installing the safety valve 400 in a string of production tubing 11 . As with previously described embodiments, the safety valve 400 includes a flow tube 404 , spring 411 and flapper 406 which is rotationally attached by a pin 406 B to a flapper mount 406 C, each of which provides generally the same functionality as with other embodiments described above.
The lower end 422 of the crossover sub 402 seals into the lower housing 403 at position 422 . It should be understood that because the lower end 422 of the crossover sub 402 is sealingly connected (e.g., press fit, static seal, etc.) to the lower housing 403 , production fluid is not able to flow past the seal between the lower end 422 of the crossover Sub 402 and the lower housing 403 . However, the lower end 422 of the crossover sub 402 does contain an orifice 408 that allows fluid to flow into and out of a pressure chamber 405 . Fluid arrives at the orifice 408 by flowing around the top or bottom of the flow tube 404 and within the annular space between the lower end 422 of the crossover sub 402 and flow tube 404 .
In the event of a sudden pressure drop, the fluid is not capable of immediately exiting the pressure chamber via the orifice 408 (for purposes of pressure equalization), so the pressure in pressure chamber 405 is higher than the pressure of the flowing production fluid. Consequently, the pressure chamber 405 expands and displaces the rods 421 upward from the cylinders. The rods 420 move the flow tube 404 upward against the spring 411 . After the flow tube 404 has moved sufficiently upward, the flapper 403 closes and shuts-in the well.
It can be seen from FIG. 4C that the collective cross-sectional area of rods 420 is considerably less than the annular area between the inner diameter of the lower housing 403 and the lower end of the crossover sub 402 . Accordingly, the use of rods 420 in this manner requires less expansion of pressure chamber 405 to achieve the required amount of axial movement of the flow tube 404 to allow the flapper 403 to close. This is because the volumetric change of the pressure chamber 405 need only be enough to displace the volume of the rods 420 , rather than the entire annular area between the lower mandrel and the sleeve 409 . While three rods 420 are shown for the current embodiment, it should be understood that the number of rods can vary based on the requirements of a particular implementation.
Those skilled in the art will recognize that safety valves according to embodiments of the present invention may be utilized in any wellbore implementation where a pressure differential (i.e. pressure drop) may arise. For instance, the safety valves described herein are fully functional if there is a pressure differential between fluid in the pressure chamber and fluid flowing through the bore of the safety valve, regardless of the absolute pressures of the respective fluids. Therefore, safety valves according to embodiments of the present invention may be utilized in low pressure wellbores as well as high pressure wellbores.
While the exemplary safety valves described herein are configured for use with production tubing, those skilled in the art will acknowledge that embodiments of the present invention may be configured for use in a variety of wellbore implementations. For example, some embodiments of the present invention may be implemented as safety valves configured for use with wireline. Yet other embodiments may be configured for use with drill pipe or coiled tubing.
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. | The present invention generally provides a downhole valve for selectively sealing a bore. The downhole valve generally includes a closing member for seating in and closing the bore, and a pressure-actuated, retention member having first and second opposed piston surfaces for initially holding the valve in an open position but, in the event of a pressure differential between the piston surfaces, permits the closing member to operate and close the valve. | 4 |
BACKGROUND OF THE INVENTION
The invention relates to multifocal spectacle lenses. Such lenses have a dioptric power varying according to the zone of vision on the lens, and are typically used for spectacle wearers suffering from presbyopia.
Multifocal lenses comprise lenses known as progressive lenses adapted to vision at all distances. These lenses usually comprise a torical or spherical surface, that may be adapted to the wearer of the spectacle lenses, and an aspherical surface chosen from a family of surfaces. Each point of an aspherical surface is usually characterised by a mean sphere S and by a cylinder C. Mean sphere S is defined from the formula S = n - 1 2 ( 1 R 1 + 1 R 2 )
in which:
R 1 and R 2 are the maximum and minimum radii of curvature expressed in meters, and
n is the refractive index of the lens material.
With the same definitions, cylinder C is given by the formula: C = ( n - 1 ) 1 R 1 - 1 R 2
Progressive multifocal ophthalmic lenses comprise a far vision region, a near vision region, an intermediate vision region, and a main meridian of progression passing through the three regions. For such lenses, the addition value A is defined as the variation in mean sphere between a reference point in the far vision region and a reference point in the near vision region.
Progressive multifocal ophthalmic lenses also comprise a main meridian of progression, also called principal line of sight; it is a line usually defined as the intersection of the line of sight with the aspherical surface of each lens when the wearer of the lenses fixes a point in the object space in front of him, at various distances.
French patent application FR-A-2 699 294 comprises in its preamble more detailed definitions of the various elements of a progressive multifocal ophthalmic lens (main meridian of progression, far vision region, near vision region, power addition value, etc..); it also describes the work carried out by the applicant to improve wearer comfort of such lenses.
One of the problems for multifocal lenses is the taking into account of binocularity. Indeed, human vision is the result of the combination of vision through two eyes, or fusion of the images provided by the two eyes. When the image of a point of the object space on the retina of the right and left eye is at two corresponding or homologous points, the images provided by both eyes are combined, so that the person wearing the spectacle lenses only sees one object point. There may be binocular vision with a single object point even if the two points are not perfectly homologous points, provided they are not too far from being homologous.
One of the constraints facing the manufacturer of multifocal lenses is to design lenses that will provide appropriate power correction for one eye—that is provide appropriate power for any direction of sight-, and also allow proper fusion of the images of the two eyes, that is allow binocular vision.
For lenses of the prior art that have symmetry with respect to the main meridian of progression, it is usual to partially rotate the lens by about 10° when fitting the lenses in the spectacle frame, so as to accommodate the accommodation convergence of the eyes. This solution is a very rough estimate, and is not fully satisfactory for ensuring binocular vision.
U.S. Pat. No. 4,606,622 discusses the problem of fusion of the images provided by the two eyes of the wearer of multifocal spectacle lenses. This document notably discusses the problems of binocular vision in multifocal progressive lenses, and suggests to fit the lens with a non-straight principal line of sight. This line is inclined towards the nose at least in the near vision zone. The right and left lenses are symmetrical. For ensuring binocularity, it is suggested to consider lines of sight originating from the two eyes, for a given point in the object space, and to consider the curvature of the lens at the points of intersection of these lines with the two spectacle lenses; each line of sight extends on one of the temporal and nasal sides of a lens, and due to symmetry of the lenses, the difference in the curvature is thus only considered on one single lens. This document therefore suggests that the curvature of the lens be substantially symmetrical on opposite sides of the intercept of the principal line of sight to ensure a good foveal vision.
U.S. Pat. No. 5,666,184 also discusses the problem of binocularity, and suggests to limit, in the near vision portion, the difference in astigmatism on a horizontal line, between points that are symmetric with respect to the prime line of sight.
The solution of these two documents—asymmetrical design with a symmetry of astigmatism with respect to the principal line of sight—may be appropriate for static vision: the difference between the images of a point in the object space is sufficiently limited for allowing binocular vision in the far and near vision zone of a multifocal lens, so that the lenses ensure a good foveal vision in these zones.
However, this solution does not bring a solution to the problem of dynamic vision, or vision of the wearer of the spectacle outside of the near and far vision zone. A number of wearers cannot adapt to multifocal lenses due to problems in dynamic vision, that may originate in bad or inappropriate binocular vision.
SUMMARY OF THE INVENTION
The invention provides a solution to this problem. It proposes an optical lens which ensures correct dynamic vision, and appropriate fusion of the images provided by the eyes outside of the static vision fields.
More specifically, the invention provides a pair of progressive ophthalmic spectacle lenses, each lens having an aspherical surface with a far vision zone, an intermediate vision zone and a near vision zone, and good monocular and binocular foveal vision along a principal meridian, each point M of the aspherical surface having a mean sphere defined by the formula: S = n - 1 2 ( 1 R 1 + 1 R 2 )
where R 1 and R 2 are maximum and minimum radii of curvature expressed in meters, and n is the refractive index of the lens material,
wherein, for a given direction of sight, the absolute value of the difference between a binocularity parameter for two points in the object space is as small as possible,
said binocularity parameter being defined, for a point (M) in the object space as the relative difference ΔS of the mean sphere for the points (M D , M G ) of the aspherical surface of the right and left lenses through which the wearer sees said point (M).
In one embodiment of the invention, the relative difference ΔS is defined by the formula Δ S = 100 × S D - S G ( S D + S G ) / 2
where S D and S G are the values of mean sphere at said points (M D , M G ) of the aspherical surface of the right and left lenses through which the wearer sees said point (M).
The said two points in the object space may be sampled on a vertical plane.
In this case, the vertical plane is preferably spaced about 80 cm from the lenses.
In another embodiment of the invention, the said points in the object space are sampled from a set of points in the object space are sampled from a set of points in the object space chosen so that points of the aspherical surface through which the wearer sees said points of said set are distributed on each of the right and left lenses.
Preferably, said given direction of sight corresponds to an object point in front of the wearer, at a distance of about 80 cm, and about 50 cm lower that the eyes of the wearer.
In one embodiment of the invention, the aspherical surface of each lens has an addition (A) defined as the difference in mean sphere between a reference point of the near vision zone and a reference point of the far vision zone, and the relative difference ΔS is less than a maximum value, said maximum value being a function of said addition.
In this case, said maximum value may be an increasing function of said addition.
The maximum value is preferably within 30% of a function f of the addition, with
f (A)=5.9×A−2.35
BRIEF DESCRIPTION OF THE DRAWINGS
Further features and advantages of the present invention will become more clear from the description which follows of one embodiment of the invention provided by way of non-limiting example with reference to the attached drawings, in which
FIG. 1 is a diagrammatic representation of an eye-lens system according to the invention;
FIG. 2 shows a top view of binocular vision of a point of the grid
FIGS. 3 to 6 show values of the mean sphere on the aspherical surface of several lenses;
FIGS. 7 to 9 show values of the binocularity parameter of the invention, for several pairs of spectacle lenses.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention proposes to improve the behaviour of the lenses in peripheral vision, for lenses which already have good foveal monocular or binocular vision on at least the principal line of sight or principal meridian.
The invention proposes taking into account, for defining ophthalmic spectacle lenses, a binocularity parameter which is defined for a given fixation point. This fixation point may be any point in the object space, since its only function is to allow the pupils to rest in a fixed position. For one point in the object space, the binocularity parameter is defined as the difference in mean sphere on the aspherical surfaces of the lenses between points of the surfaces corresponding to rays originating from both pupil centers and directed towards said point. Over the aspherical surface lens, that is for the whole vision field, the invention teaches that this difference should be as small as possible.
The invention also gives an upper limit or maximum value for this difference; when the difference lies below this limit for all points of the aspherical surface of the lens, or for the different peripheral directions, acceptable binocular vision is ensured for the whole field of vision of the lens, and the wearer of the spectacle lenses benefits from correct dynamic vision.
The maximum value depends on the addition (A). The maximum value is an increasing function of the addition (A). The maximum value of the binocularity parameter depends on the addition (A), to ensure an acceptable binocular vision over the aspherical surface of the lens, that is for the whole field of vision.
The rest of the present description discloses a preferred embodiment of the invention, where a grid is used for assessing the difference in mean sphere between the right and left lenses of a pair of spectacle lenses. FIG. 1 is a diagrammatic representation of an eye-lens system according to the invention, showing the grid.
On FIG. 1 is shown the right eye 1 , the spectacle lens 2 for the right eye and the grid used for the definition of the lenses according to the invention. FIG. 1 shows a set of Cartesian coordinates (O. x, y, z), the origin of which is point O, defined as follows. The origin O is the center of the rear surface of the right lens. It is located in the horizontal plane containing the center of rotation of the right eye, at a distance d of 27 mm from the center of rotation of the right eye. This distance d corresponds to the mean distance between the center of rotation of the eyes and their respective spectacle lenses, so that the center of each of the spectacle lens is in the (x, y) plane. The distance between the lenses is chosen identical to the mean distance between the pupils of the left and right eyes, that is at a value of 65 mm.
The x-axis is directed from the lens to the eyes; the y-axis is vertical, and the z-axis is horizontal and directed from the right to the left.
In the set of coordinates thus defined:
the center of the left eye is set at the coordinates (d, 0, 65 mm);
the center of the right eye is set at the coordinates (d, 0, 0 mm);
the center of the surface of the left spectacle lens facing the wearer is at the coordinates (0, 0, 65 mm); and
the center of the surface of the right spectacle lens facing the wearer is at the coordinates (0, 0, 0 mm), by definition of the origin.
In this set of coordinates, the invention proposes to use a vertical grid, the center of which is at a point G set at the coordinates (−800; 0; 32.5), in mm. In other words, the grid is at a distance of the surface of the spectacle facing the wearer of 80 cm, and is located in front of the wearer of the spectacle lenses, in the sagittal plane, in the horizontal direction of sight.
In the grid, a set (G, u, v) of coordinates is defined as follows. The u-axis is parallel to the z-axis defined above and the v-axis is parallel to the y-axis.
In the drawing of FIG. 1, the eye is directed so as to look at a given point F, the coordinates of which are (−800; −500; 32.5), or (0, −500) in the set of coordinates in the grid. The choice of this point F is representative of the position of the pupil. The exact choice of this point is not particularly essential for the invention, and the results of the invention are achieved for different choices of the point in the object space toward which the eye is directed.
FIG. 2 shows a top view of binocular vision to a point of the grid. FIG. 2 shows the grid 5 —that constitutes an object plane in this case, and a point M in this object plane. It also shows the right and left spectacle lenses 6 and 7 , as well as the pupils 8 and 9 of the right and left eyes. The sagittal plane is symbolised on FIG. 2 by the horizontal line passing through point F of the grid. The points CROD and CROG are the center of rotation of the right and left eyes. The point marked CRT is the center of rotation of the head.
FIG. 2 shows rays originating from point F, and rays originating from the point M, outside of the sagittal plane. The rays originating from point F pass near the center of the lenses, and through the center of the pupil of each eye. They are not exactly parallel, and form corresponding images on the retina, which are normally combined for ensuring binocular vision.
Due to the presence of spectacle lenses, rays originating from the point M are bent when passing through the spectacle lenses; they pass through the center of the pupil of the respective eye and reach the retina of the right and left eyes in positions which may not be combined to ensure binocular vision. The interrupted line going from the right lens to the point M 1 OD is representative of the position in the object plane where the right eye of the wearer sees the object point M. Similarly, the point M 1 OG is the point where the left eye sees the point M.
In order to ensure binocular vision, that is combination of the images in the right and left eye of a given point M into a single image, the invention suggests considering the difference in mean sphere between the points M D and M G of the aspherical surface of the lenses, where rays originating from the object point M impinges on the aspherical surface of the lenses.
The invention suggests setting an upper limit for this difference, for a set of points in the object space. This limit varies with the addition A to ensure good binocular vision, not only in static vision, but also in dynamic vision.
In other words, for a given point M in the object space, the invention suggests considering the rays originating from M and going to the center of the pupils of the right and left eyes, and determining the difference of mean sphere at the points of intersection of these rays with the aspherical surface of the lens. These two points of intersection are actually the points of the aspherical surface of the right and left lens through which the wearer sees said point M, in his perifoveal visual field.
Turning back to the example of the grid represented in FIG. 1, it is possible to consider a grid having a size of 3000×3000 mm; as for the set of points, it is sufficient to consider a set of 21×21 points, that is to consider 21 possible values of the each of the coordinates u and v. A different number of points, or a different distribution of the points does not change the results of the invention. This size of the grid, and the choice of the point toward which the eye is directed is sufficient in the examples to ensure that most peripheral directions for a lens of 50 mm radius are covered. In other words, the binocularity parameter may be calculated for a set of points distributed in the perifoveal visual field of the wearer of the lenses, or distributed over the surface of each lens.
The difference in mean sphere may then be calculated for each of these points in the object space. Results of these calculations are shown and discussed below. In the example discussed in relation to FIGS. 1 and 2, the invention suggests using a fixed direction of sight—that is a fixed position of the pupil, and further suggests selecting a set of points in the object space and calculating the difference in mean sphere for this fixed position of the eye. This ensures that the limitation to the mean sphere difference is indeed representative of the quality of dynamic vision.
FIGS. 3 to 6 show the values of the mean sphere on the aspherical surface of the lens, for each point of the grid; more specifically, FIGS. 3 to 6 show lines of points of the grid for which value of the mean sphere on the aspherical surface is the same. The horizontal axis shows in mm the position of each point along the z-axis, while the vertical axis shows in mm the position of each point along the y-axis. FIGS. 3 and 4 correspond respectively to the left and right eyes, for a lens of the prior art. FIGS. 5 and 6 correspond respectively to the left and right eyes, for a lens according to the invention. The lenses of FIGS. 3 to 6 have an addition of one diopter.
FIGS. 3 to 6 essentially show that the values for the left and right eyes are symmetrical; this is not surprising inasmuch as the lenses of the figures are symmetrical, a lens for the left eye being the image of a lens for the right eye with respect to the sagittal plane.
In other words, the limitation according to the invention of the difference between the mean sphere of the right and left lenses also causes an overall limitation of the absolute value of the mean sphere gradient of each lens.
FIGS. 7 to 9 show different values of the mean sphere difference for several lenses. The coordinates on the horizontal and vertical axis are the same as those of FIGS. 3 to 6 . These figures show the lines formed of points having the same relative value of the difference in mean sphere; more specifically, for a given point M of the grid, the rays to the right and left eyes through the right and left spectacle lenses are calculated. This provides values S D and S G of the mean sphere on the aspherical surface of the lens, at the point of intersection with the rays originating from point M.
The figures show a plot of the relative sphere difference ΔS, also called here binocularity parameter, defined by the formula: Δ S = 100 × S D - S G S _ = 100 × S D - S G ( S D + S G ) / 2
where {overscore (S)} is the half sum of the values S D and S G of the mean sphere for the right and left spectacle lenses. All figures are plotted for points of the grid corresponding to a spectacle lens having a diameter of 50 mm, centered on the looking point F.
FIG. 7 shows the relative values of the mean sphere difference for a lens of the prior art having an addition of one diopter. The peak to valley value of the binocularity parameter ΔS, that is the difference between the highest and the lowest value of ΔS over the lens is 6.49.
FIG. 8 shows the relative values, for a first embodiment of a lens according to the invention, that also has an addition of one diopter. In this case, the peak to valley value amounts to 3.01.
FIG. 9 shows a view of a second embodiment of a lens according to the invention. The peak to valley value reaches 3.28 on the lens.
FIGS. 7-9 are essentially symmetrical with respect to a vertical line. This is due to the definition of ΔS; ΔS is calculated for a looking point F of the grid in the sagittal plane, the right and left lenses being symmetrical with respect to the sagittal plane. Thus, ΔS is equal to zero for points of the object space in the sagittal plane. The diagrams of FIGS. 8 and 9 do not show high values of the difference ΔS, contrary to the one of FIG. 7 .
For an addition of two diopters, a peak to valley of 8 is appropriate.
The limitation of the invention on the mean sphere difference between pairs of points on the aspherical surface associated with the same point in the object space may be calculated for a pair of lenses, as explained above. This limitation depends on the addition A. As discussed above, it is is an increasing function of the addition (A).
Preferably, the maximum value for the mean sphere difference is within 30% of a function f of the addition, which may be written
f (A)=5.9×A−2.35
Where the right and left lenses are chosen to be symmetrical with respect to the sagittal plane, one point on the nasal side of a lens is the image of a point of the temporal side of the lens in the symmetry with respect to the sagittal plane.
The lenses of the invention may be defined using a theoretical wearer of the spectacles, having optometric parameters—distance between the eyes, position of the spectacle lenses, etc.—corresponding to the mean values of these parameters among possible wearers of the lens. Such parameters are known to the person skilled in the art.
The invention may be used for defining spectacle lenses, using optimisation processes known per se. As known per se, the surface of the lenses is continuous and continually derivable three times. The surface of progressive lenses may be obtained by digital optimization using a computer, setting limiting conditions for a certain number of lens parameters. The invention suggests to use as one of the limiting conditions the maximum value of the difference ΔS.
It should be understood that the grid system described above is but a solution for defining pairs of points on the aspherical surfaces of lenses, which correspond to a given point in the object space. One could use different points in the object space for defining pairs of points; the tests and experiments conducted by the applicant have shown that the choice of the set of points in the object space did not change the results of the invention; the set of points should only be representative of the area of the object field for which dynamic vision and binocularity is to be achieved. The looking point or fixation point F could also be different from the one selected in the preferred embodiment.
In the example of FIG. 2, the aspherical surface of the lens is directed away from the wearer, so that the mean sphere difference is measured for points of the outer surface of the lenses. The invention may as well be carried out for lenses where the aspherical surface is the surface facing the wearer.
The contents of European Patent Application entitled “Pair of Multifocal Progressive Spectacle Lenses,” having applicant Essilor International and inventors Bernard Bourdoncle and Sandrine Francois, and filed on Oct. 16, 1998 is incorporated herein by reference in its entirety. | The invention relates to a pair of progressive ophthalmic spectacle lenses; each lens has an aspherical surface with a far vision zone, an intermediate vision zone and a near vision zone, and good monocular and binocular foveal vision along the principal meridian. At each point of the aspherical surface there is a mean sphere which is proportional to the half sum of the maximum and minimum radii of curvature expressed in meters, and to the refractive index of the lens material. The invention suggests reducing, for a given direction of sight, the absolute value of the difference between a binocularity parameter for two points in the object space. The binocularity parameter is defined for a point in the object space as the relative difference ΔS of the mean sphere for the points of the aspherical surface of the right and left lenses through which the wearer sees said point. | 6 |
BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention relates generally to the field of methods for identifying toxicants and/or isolated component substances in a sample. The types of samples which may be analyzed include either a solid sample, a liquid sample or a gaseous sample. The present invention also relates to the field of biological toxicant identification agents, as a particularly described luminescent biological reagent, for example the luminescent bacteria, are employed in the claimed isolation, identification and quantitation methods and techniques disclosed herein. The present invention also relates to the field of toxicant detecting kits, as a kit for the identification of toxicants is described employing a luminescent biological reagent.
II. Description of the Related Art
When grown in appropriate liquid culture or on semi-solid culture media, suspensions of luminescent bacteria emit a constant level of light for extended periods. Luminescent bacteria are bacteria which emit light without excitation, (i.e., they glow in the dark). The origin of the emission is biochemical, and organisms which demonstrate this characteristic are described as exhibiting the phenomenon of bioluminescence. Most known examples of luminescent bacteria are marine. Two major subclasses of the luminescent organisms are 1) free living (Vibrio harveyi) and 2) symbiotic (Vibrio fischeri, Photobacterium phosphoreum, Photobacterium leiognathi). Other major bioluminescent organisms include fire flies (Photinus pyralis), crustaceans (Cyridina hilgendorfi), dinoflagellates (Gonyaulax polyhedra, Notiluca militaris), fungi (Omphalia flavida) and the sea pansy (Renilla reniformis).
The luminescence of bacteria has long been known to be sensitive to a wide variety of toxic substances (e.g., heavy metals, pesticides, etc.). The exquisite sensitivity of luminescent bacteria to a variety of substances has made them a popular choice in methods for the gross detection of the presence of toxic materials. For example, the use of luminescent bacteria has been discussed for the detection of toxins on solid surfaces, such as soil 5 , and in liquid substances, such as in the analysis of waste water 3 , as well an in the detection of toxins in gaseous samples 6 .
Luminescent bacteria have also been employed in the detection of toxicants in marine environments. 2 For example, Vasseur et al. describe a Microtox luminescent bacterial assay for the detection of toxicants in water (Photobacterium phosphoreum) 2 .
Another variety of luminescent bacteria used in the analysis of industrial waste water is described in the Baher patent. 3 Specifically, the Klebsiella planticola bacteria has been used to detect the presence of substances toxic to particular microorganisms (used to purify industrial chemical plant waste waters) indicated through monitoring the luminescence of the Klebsiella.
Luminescent bacteria have also been used for detecting the presence of specific substances in a sample, including antibiotics, heavy metals, enzyme inhibitors, pesticides, microbial toxins, volatile hydrocarbons, disinfectants, and preservatives. 6 For example, the Siemens patent describes the use of a luciferase-gene-transformed microorganism for detecting the presence of a toxicant in a sample through a demonstrated reduction in the luminescent signal emitted by the luminescent bacteria in the presence of a toxic substance 6 .
Others have reported the ability to detect the presence of particular classes of chemical toxicants using luminescent bacteria, particularly phenolic compounds. 7 For example, in Strom et al., the relative toxicity of a variety of particularly defined phenolic compounds, including hydroquinone, is described using a luminescent bacterium 7 .
Thus, some species and components of luminescent bacteria have been adapted for use to simply detect the general presence of a toxic substance in a sample. In the presence of toxicants, detection of the toxins is provided by an observed diminution in luminescent emission and intensity in a variety of luminescent bacteria. However, the value of the "detection" techniques currently available is limited by an inability to identify, in an isolatable form, the substance which constitutes the "detected" toxicant or foreign substance.
No methods have been described wherein a generically "detected" toxicant may be identified in an isolatable form using a luminescent bacteria. The ability to actually identify an isolated substance as a potential "toxicant" in a sample would provide a powerful industrial and research tool. Moreover, the ability to distinguish, by positive chemical analysis, the chemical structure of an isolated toxicant (using various chemical separation techniques known to those of skill in the art) would find great potential application in research, diagnostic medicine and industrial manufacturing processes.
Standard chemical visualization techniques for the localization of separated substances employ a variety of stains and staining procedures known to those skilled in the art (i.e., coomassie brilliant blue for gel electro-phoresis of proteins; 2-Naphthol or Resoranol for paper chromatography of sugars inhydrin for amino acid analysis with TLC). However, these techniques do not identify the potential toxicity of any visualized substance in the sample. No system has been proposed wherein a reagent may be used to provide a system wherein the potential toxicity of isolated substance in a sample may also be visualized and thereby identified.
Such a novel method for the simple, inexpensive and sensitive identification of a substance(s) in a sample or product which may be potentially lethal to an organism would also facilitate the further chemical elucidation of the chemical identity of the proposed toxicant through the subsequent use of various well known chemical analysis strategies available to those of skill in the art (such as mass spectrometry, nuclear resonance spectroscopy, infrared spectroscopy, x-ray crystallography, and chromatographic analysis). Thus, the complete chemical structure and identity of the potential toxicant could be determined if such a method, capable of identifying in an isolatable form the potential toxicant, were available. Such a system would be particularly valuable in the development of strategies to remove such identified toxicants from products intended for consumer use, and also in the development of procedures to render chemically identified toxicant(s) innocuous to animals and humans.
SUMMARY OF THE INVENTION
The present invention provides a rapid and accurate method for identifying a component substance (such as a toxin/toxicants) in a sample through the use of a luminescent biological agent employed together with chromatographic resolution techniques.
While any of a variety of luminescent bacteria may be used, those species found to be most particularly preferred for use in the practice of the present invention include Photobacterium phosphoreum, Vibrio fischeri, Vibrio harveyi and Photobacterium leiognathi. However, it is to be understood that the present inventive methods, reagents and kits may be practiced using any luminescent organism whose luminescence is specifically inhibited by an isolated component substance (for example, a potential toxicant) in a sample.
The present methods, reagents and kits may be used to isolate and identify a single toxicant, a number of individual toxicants, or a group of toxicants in or on a sample in the solid, liquid, or gaseous phase.
In part, the point of novelty of the present invention resides in the ability to identifiably isolate a component substance (for example, a toxicant) contained in a sample rapidly, and without the necessity of a separate biosensitivity assay of test sample. This is accomplished, for example, by applying a potentially toxicant-containing sample to a separation phase matrix, such as a chromatography paper sheet or a thin layer chromatography plate. The sample-exposed sheet is then exposed to a luminescent biological agent (i.e., the luminescent bacteria) according to the claimed method to accomplish, in one step, both the isolation of each distinct component substance of the sample and the potential toxicity of each of the distinct components in the test sample.
For example, according to the claimed invention, an unknown sample (for example a liquid unknown sample or a concentrated extract of a larger sample which potentially contains toxicants) may be spotted or streaked near one edge of a chromatography paper sheet at several points.
Most preferably, the sample "spots" or "streaks" are air dried to eliminate the carrier solvent in which the sample was dissolved. More applications of sample(s) can be overlaid onto the respective sample spots, if necessary, and dried. The end of the chromatography sheet closest to the spotted sample edge is then placed in contact with the solvent system of choice.
In the usual situation, the solvent of the solvent system will migrate through the "spotted" sample and through the length of the chromatography paper via capillary action and along the length of the chromatography sheet, thus separating the sample into its component parts onto particular locations or "segments" on the separation phase matrix (i.e., chromatography paper).
These locations or "segments" of the separation phase matrix (which provide the isolated components of the sample) are then exposed to a luminescent biological agent, and provide for the visualiation and identification of a distinct zone of luminescent inhibition" at locations or "segments" where luminescent inhibitory components of the sample are located.
Alternatively (to the above paper chromatography method), an unknown sample could be separated using TLC by spotting the sample on a thin layer chromatography plate. Thus, the sample would be spotted, and air dried analogously to that procedure followed for paper chromatography. However, the solvent in a TLC chamber is at the bottom of the chamber and therefore the solvent migration will be upward through the TLC plate separation phase matrix.
Depending on a variety of factors, including molecular polarity, the isolatable components in the sample will resolve, on the separation phase matrix, being more soluble in the solvent than having affinity for the silica gel or other separation phase matrix.
Resolution of the components in the mixture will depend on the polarity of the molecules in the sample verses the polarities of the stationary (e.g. paper, silica or alumina) and mobile (solvent) phases. The end result in the one dimensional TLC described is a linear array of components at different locations along the length of the chromatogram. The component substances of the sample thus migrate to isolatable locations or "segments" on the plate.
Vertical sections along one side or portion of the TLC plate may be sprayed with the luminescent biological agent to visualize toxicant location. Corresponding unsprayed zones of the plate may then be scraped off and eluted with an appropriate solvent or solvent mixture. In this manner, individual toxicants may be obtained for further separation, chemical identification, or quantitation using those laboratory techniques well known to those of skill in the art.
More toxicant may be obtained for specific chemical analysis of the thus "identified" locations or segments (areas of luminescent inhibition on the chromatogram) of the separation phase matrix by eluting identical segments from a second run selected separation phase matrix (TLC or chromatography paper) that has not been exposed to the luminescent biological agent. The chemical structural identity of the toxicant or isolated component substance of the sample may be elucidated according to standard laboratory techniques well known to those skilled in the art, such as mass spectroscopy (MS) 22 ; high performance liquid chromatography (HPLC) 10 ,11,12, 28 ; infrared spectroscopy (IR) 23 ; nuclear magnetic resonance (NMR) 22 ,24 ; thin layer chromatography (TLC) 9 ,26 ; x-ray crystallography 22 ,23 and the like.
As used in the present application, the term "luminescent" biological agent is defined as an organism or an extract of an organism, which emits heatless light under appropriate conditions. Most luminescent systems involve the use of molecular oxygen. Luciferin (a pigment) and a specialized form of a luciferase enzyme are included in many luminous organisms and enables these organisms to emit a heatless light in the presence of oxygen. Cypridina is an example of a marine organism which contains the luciferin pigment. For example, Cypridina contains a luciferin which, when reacted with the Cypridina luciferase enzyme in the presence of oxygen, emits a heatless bioluminesence. Vibrio fischeri 16 and Vibrio harveyi 17 contain an enzyme necessary to make light, a well as two reagent compounds (a long-chained aliphatic aldehydes and a vitamin derivative, which is a yellow pigment flavin mononucleotide. In reduced form (i.e., in the presence of oxygen) the pigment glows and allows the organism to emit a heatless light. For example, Cypridina contains a luciferin which, when reacted with the Cypridina luciferase enzyme in the presence of oxygen, emits a heatless bioluminescence. Similarly, fire flies possess a luciferin pigment which in the presence of the firefly luciferase and oxygen, provides a bioluminescence suitable for use in the practice of the present invention. Photobacterium leiognathia is a bacteria which is strongly bioluminescent. All organisms and plants which possess a luciferin/luciferase system would be included among those luminescent biological agents which could be used in the practice of the claimed invention.
The present invention also provides a kit for the identification of a toxicant in a sample, which includes a luminescent biological (for example, bacterial) agent. In a particularly preferred embodiment, the kit comprises a carrier means adapted to receive at least two container means and at least one separation phase matrix in close confinement therewith; at least one separation phase matrix; a first container means comprising a luminescent biological agent; and a second container means comprising a diluent for the luminescent biological agent.
Most preferably, the luminescent biological agent is a luminescent bacteria, such as Vibrio fischeri (ATCC No. 7744), Photobacterium phosphoreum, Photobacterium leiognathi, or Vibrio harveyi (ATCC No. 33843). In a most preferred embodiment of the kit, the luminescent biological agent is in a lyophilized form. Where the luminescent biological agent is in a lyophilized or dried form, the kit will include a diluent suitable for reconstituting the particular biological agent into its "glowing" form.
By way of example, where the luminescent biological agent is a luminescent bacterial agent, and the particular luminescent bacterial agent is a marine bacteria, a suitable diluent would comprise a salt solution of at least 1% by weight NaCl. A saline solution between 1% to 4% NaCl is even more particularly preferred. Most preferably, the diluent should constitute 3% by weight NaCl.
The diluent of the kit most preferably is a buffering agent which includes an NaCl concentration of the diluent should be a concentration which maximizes the luminescent characteristics of the particular marine bacterial species employed. The salt concentration of the diluent has been observed by the Inventors to affect the intensity of the bacteria's luminescence, and thus the bacteria's suitability as a "visualizing" agent for the described method. For example, where the luminescent bacteria is Vibrio fischeri, a marine luminescent bacteria, the diluent is most preferably about 0.5 M NaCl. Other diluents for marine luminescent bacteria may comprise a saline solution between 0.6-0.66 M NaCl (1%-4% by weight NaCl).
The separation phase matrix may comprise a chromatography paper sheet, a TLC plate, a Sepharose matrix, or virtually any matrix which is capable of separating a mixed sample into discernable, at least partially isolated, components. The separation phase matrix most preferred for use in the described kit is a TLC plate.
Most preferably, where the method to be used to isolate the components of the sample is paper chromatography, the chromatography paper sheet is most preferably Whatman chromatography paper 1M or 3M. Where the method for separation is TLC, the most preferred TLC plates are Whatman adsorption plates flexible backed aluminum or polyester #4410-222 plates.
The luminescent bacterial agent is to be suspended in a saline solution diluen. Where the bacteria is stored in lyophilized form, the lyophilized bacterial agent is reconstituted in the referenced saline diluent to regain its luminescent form prior to use.
Attempts by the Inventors of directly laying a TLC plate on the luminescent bacteria provided relatively low-sensitivity (i.e., a large amount of inhibitor substance or toxicant needed to be present to demarcate the presence of any isolated substance) for detection, as the discernable "zones" of luminescent inhibition were relatively faint. Therefore, most preferably, the reconstituted bacterial agent is placed into an aspirator spray bottle and sprayed onto sample-exposed separation phase matrix, (for example, the sample-exposed chromatography paper sheet or TLC plate).
The method of directly spraying a TLC plate with a suspension of the luminescent bacteria was demonstrated to provide the best results, with clearly defined "zones of luminescent inhibition" and wherein even minor (less distinct) zones of luminescent inhibition are discernable. At this time, spray application of the luminescent biological reagent thus constitutes the best mode for practicing this aspect of the invention.
However, other methods for achieving contact of the luminescent biological agent to a test sample may be employed to identify substances and/or toxicants in a sample. For example, a sheet of film with an agarose or acrylamide layer, or other solid surface or gel containing a rehydratable material therein capable of being stored in sheet form and rehydratable prior to use, are contemplated by the Inventors as constituting equally usable methods for practicing the claimed invention.
In such an embodiment, a dehydrated form of the luminescent biological agent would be incorporated into a porous or water permeable material which was amenable to being formed into a sheet form. The sheet, so impregnated with a dehydrated form of the luminescent biological agent, would be stored in dry form until needed for use. For use, the sheet with the bacterial agent in it should be rehydrated in a suitable rehydrating agent, such deionized water or a saline solution. Where the luminescent biological agent is a marine luminescent bacteria, such as Vibrio fischeri, the rehydrating agent would most preferably be a saline solution of at least 1% NaCl. Most preferably, the saline solution should be between 1-4% NaCl. A 3% NaCl solution is most preferred.
After the sheet has been rehydrated, the now "glowing" sheet would be laid over a sample of isolated component substances/toxicants to render the luminescent biological agent in contact with the test sample component substances. The existance of zones of luminescent inhibition could then be examined to identify potential toxicants of the sample.
The claimed invention also comprises a luminescent bacterial agent which is capable of identifying in isolatable form a component or mixture of components, substances or a toxicant in a sample. The presence of isolatable component substances or toxicants in a sample is visualized through the presence of discernable zones of inhibition surrounding the applied luminescent bacterial reagent (i.e., termed "zones of luminescent inhibition").
Any luminescent bacteria may be employed in the practice of the present invention. However, those luminescent bacterial agents preferred in the practice of the invention include Photobacterium phosphoreum, Photobacterium leiognathi, Vibrio fischeri, (ATCC Acc. 7744) and Vibrio harveyi (ATCC Acc. 33843). Among these exemplary bacteria, the Vibrio fischeri and Vibrio harveyi bacteria embody the even most preferred luminescent bacterial agents of the invention. The Vibrio fischeri (ATCC Acc. No. 7744) constitute the most particularly preferred embodiment of the claimed luminescent bacterial agent of the present invention.
As a method for identifying component substances in a sample, using a luminescent biological agent, the claimed method comprises: preparing a luminescent biological agent; obtaining a sufficient volume of the sample to provide a test sample; separating the component substances of the test sample by applying the test sample to a separation phase matrix to provide isolated component substances; and exposing the isolated component substances to a volume of the luminescent biological agent in a concentration sufficient to identify the isolated component substances of the sample. One or more zones of luminescent inhibition will become apparent on the luminescent biological agent-exposed separation phase matrix, and thus identify the isolated component substances in the sample. The concentration of luminescent biological agent sufficient to identify the isolated component substances of a sample is referred to as a "substance indicating amount". Where the test sample is being analyzed to identify potential toxicant(s), the amount of luminescent biological agent is defined as "toxin indicating amount". The necessary concentrations to provide this "indicating" effect is between 10 8 -10 9 bacterial cells/ml of diluent where the bacterial agent is contacted with the sample in the form of a liquid suspension.
Where paper chromatography is the technique used to separate component substances or toxicants in a test sample, chromatography paper (as the separation phase matrix) and an appropriate solvent system are used. Corresponding segments on a separate chromatogram (sample plus chromatography sheet) not exposed to luminescent bacteria may be used to obtain additional volumes of the component substances/toxicants of the sample, or where desired, to further chemically identify the isolated component substances of the sample. Additional sample or chemical analysis of the sample in purer form may be accomplished for example, by cutting out the chromatography paper segments (not exposed to luminescent bacteria) which correspond to the identified "zones of luminescent inhibition"; and eluting the isolated substances from the cut out chromatography paper segments with an appropriate solvent.
The isolated component substances or potential toxicants of the sample may then be analyzed using standard chemical and spectral means to chemically identify the isolated substances of the sample. If necessary, the eluate of the isolated components of the sample may be concentrated by techniques well known to those skilled in the art prior to chemical and spectral analysis to chemically identify the isolated substance or toxicant of the sample.
The luminescent biological agent of the claimed method may comprise a luminescent bacteria, a luminescent fungi, a luminescent fish extract, a luminescent dinoflagellate, a luminescent firefly extract, luminescent anthrogans, luminescent earthworm extract, luminecent coelenterate extract or a luminescent crustacean. (Cypridina organisms).
Most preferably, the luminescent biological agent is a luminescent bacteria, such as Vibrio fischeri (ATCC acc. 7744) Vibrio harveyi (ATCC Acc. 33843), Photobacterium phosphoreum, or Photobacterium leiognathi. The term "luminescent biological agent" as used in the present application may include an organism which has been modified to possess luminescence such as an organism genetically engineered to include the luciferase gene. According to the claimed methods, the test sample may comprise a liquid sample, a solid sample, or a gaseous sample. Most preferably, the sample is to be prepared as a liquid test sample for separation via a TLC plate separation phase matrix.
While the present methods may be used to isolate and identify virtually any substance(s) or toxicant(s) in a sample which is capable of inhibiting the luminescence of a luminescent biological agent (for example, a luminescent bacterial agent), preferred applications of the present method include the identification of isolated substances such as pesticides, herbicides, heavy metals and their salts, and plant extracts, from a sample. By way of example, pesticides which may be identified according to the present methods include DIAZANON®, LINDANE® and SEVIN®. By way of example, herbicides which may be identified according to the present methods include ROUNDUP® and WEED-B-GON®. Heavy metals which may potentially be identified according to the present methods include the identification of mercury, lead, cadmium and their respective salts.
According to the present method, the isolated substance or toxicant(s) in the sample may be chemically analyzed by any combination of laboratory techniques well known to those of skill in the art for the chemical characterization of an isolated or partially isolated substance. For example, MS, IR, NMR, HPLC, thin layer chromatography, etc are standard techniques which may be used to further chemically define an isolated substance in a sample. Any of these common laboratory techniques may be used alone or in combination to identify the chemical structure of substantially purified component substances or potential toxicants in a sample.
According to one preferred embodiment of the present method, wherein the separation technique is paper chromatography (separation phase matrix is chromatography paper), the developed chromatogram (having thereupon any isolatable component substances or toxicants of the sample) may be exposed to the luminescent bacterial agent by spraying a suspension of the luminescent bacterial agent, most preferably suspended in a saline solution, onto the developed chromatogram.
As the agent used to visualize the components/toxicants of a sample is of a biological nature, and therefore potentially sensitive (i.e., inhibited by chemicals) to components of a desired solvent to be used, failure to remove solvent could in itself cause nonspecific inhibition of luminescence. Thus, application of the luminescent bacterial suspension should be done after the complete evaporation of carrier solvent from the chromatogram. In addition, the developed chromatogram should also be allowed to dry a second time, after the separation solvent has passed through the sample "streaked" or "spotted" chromatogram, before the luminescent biological (for example, luminescent bacterial agent) is applied (for example sprayed) to the chromatogram.
Observation of a chromatogram exposed to the luminescent agent (the "sprayed" chromatogram) should be made while the chromatogram is still wet or at least moist with the suspension of luminescent biological reagent applied thereto. For example, luminescent bacteria are very sensitive to dehydration, and thus luminescence would be lost everywhere if the investigator does not examine the chromatogram within at least 1 hour of exposing the bacteria to the chromatogram. In practice, a bacteria-sprayed chromatogram remains moist and glowing from the luminescent biological agent for as long as 45 minutes to one hour, depending on the humidity of the environment.
The Inventors herein demonstrate that the inhibition of luminescence of particular species of luminescent bacteria employed according to the methods described herein, is discriminating as among potential toxicants and/or isolated component substances of a test sample. For example, the Inventors have found that the luminescence of one particular species of luminescent bacteria, Vibrio fischeri, is not inhibited by the pesticide, VOLCK oil spray. Neither does the luminescence of the Vibrio fischeri appear to be immediately inhibited by calcium ion. Moreover, all of the luminescent inhibition effects demonstrated through the use of luminescent bacteria, particularly Vibrio fischeri, are concentration dependent.
The methods of the present invention may be adapted for use in the identification of closely related components which may be present together in a test sample. For example, selective sensitivities as between different luminescent biological agents, particularly as between luminescent bacteria, may be used to tailor the disclosed method for use in a particular industry, or to test specific product lines. For example, the luminescence of the bacterial agent Vibrio fischeri is more sensitive to the pesticide DIAZANON® than to the pesticide LINDANE®. Similarly, the luminescence of this particular bacterial agent is more sensitive to the inhibitory action of SEVIN® as compared to LINDANE®. Selection of Vibrio fischeri bacteria would thus be indicated as particularly suitable for use in the described method where a sample is suspected to contain pesticides, such as in a pesticide production facility, or perhaps where foodstuffs are stored.
Thus, the particular species of luminescent bacteria may be selected on the basis of the specific use for which it is intended (i.e., for the identification of a particular class of related substances). For example, where an Investigator wishes to isolate and identify particular pesticides, he/she may select a luminescent bacteria which demonstrates a particular sensitivity to pesticides in general, over another, perhaps less sensitive, luminescent bacteria, for the analysis of a sample which may likely include pesticides. Therefore, a hierarchy of relative toxicant sensitivity, in regard to both the class of toxicant and particular luminescent bacteria, can be established.
The present invention provides a rapid (about 35 minutes) technique that can potentially identify a wide variety of environmentally and biologically harmful substances.
The Inventors have found that the methods described herein are capable of identifying herbicides and pesticides at their working strengths (i.e., DIAZANON®, LINDANE®, ROUNDUP® AND WEED-B-GON® diluted 1/150). Therefore, herbicides, pesticides and other environmental pollutants and contaminants may be identified according to the present method with the described kits as they occur in the environment in the air, in lakes, streams, ground water and in run-off from fields, for example, in relatively dilute form (for example diluted 1/1,000 from commercial stock concentration).
As used in the present disclosure, the term "toxicant" and "identified isolated component substance" of a sample is defined as a substance which is capable of inhibiting the luminescence of a luminescent biological agent, such as a luminescent bacteria, Vibrio fischeri.
Even more specifically, the term "toxicant" is broadly defined as a substance which is capable of inhibiting or potentially lethal to, a virus or a living organism, such as a plant, animal or microorganism. Even more specifically a toxicant potentially toxic to an animal such as a human may be identified using the described method. Toxicity to bacteria is recognized as an indication of toxicity of a substance to higher organisms, including humans. The Inventors hypothesize that forms of the biological agents which are represented by whole organisms, rather than extracts of whole organisms, will be both more sensitive and also be capable of identifying a broader range of substances and toxicants in a sample in smaller concentrations than with luminescent extracts from an organism.
As used in the present application, the term bioluminescence more specifically refers a living organism or from extracts of a living organism when combined under appropriate conditions. Lack of luminescence refers to the lack of light emission not necessarily related to the expiration of the organism.
The following abbreviations are used throughout the Specification:
ECD=Electron Capture Detection
TLC=Thin Layer Chromatography
NMR=Nuclear Magnetic Resonance Spectroscopy
M=Molar
HPLC=High Performance Liquid Chromatography
IR=Infra-Red Spectroscopy
MS=Mass Spectroscopy
D=Dimension
THF=Tetrahydrofuran
UV=Ultraviolet
BRIEF DESCRIPTION OF THE DRAWINGS
The file of this patent contains at least one drawing executed in color. Copies of this patent with color drawing(s) will be provided by the Patent and Trademark Office upon request and payment of the necessary fee.
FIG. 1 TLC plate with garlic extract sample in H 2 O. Not exposed to luminescent bacteria. TLC Plate identified those components which are ultraviolet light-absorbing. If compound absorbs the 254 nM light, then area where compound is located will not glow, and appears as a dark spot (V shape) in a garlic extract using fluorescent detection (254 nM excitation). Solvent used is 80:8:12 mixture of (H 3 CCN:H 2 O:NH 3 ). The V-shaped areas are not indicative of a bacteriotoxic agent. Results from these analysis indicate a compatible system for resolving ultraviolet absorbing and thereby identifiable components in a sample.
FIG. 2 TLC plate with garlic extract sample exposed to luminescent bacteria, Vibrio fisheri, same solvent as FIG. 1. Bioluminescence inhibition is evident as a dark circular region (about 10.5 cm from bottom of plate). This circular region is hypothesized to constitute allicin in the garlic extract.
FIG. 3 TLC plate with DIAZANON® and LINDANE® by fluorescence.
FIG. 4 TLC plate DIAZANON® and LINDANE® by bioluminescence.
FIG. 5 TLC for DIAZANON® dilution series. Plates demonstrate a dilution series of DIAZANON®. The presence of DIAZANON® is demonstrated at dim areas defining the "zone of luminescent inhibition" of the luminescent bacteria, Vibrio fischeri, in response to the pesticide. Dilutions employed of the pesticides were full strength, 1:128; 1:256; 1:512 and 1:1024.
FIG. 6 TLC for DIAZANON® dilution series with the luminescent bacteria, Vibrio fischeri (same dilutions as for FIG. 5).
FIG. 7 TLC of DIAZANON® with either UV 254 fluorescence or bioluminescence inhibition with luminous bacteria, Vibrio fischeri in a sample.
FIG. 8 TLC of DIAZANON®, ROUNDUP® and WEED-B-GON® identified at a dilution of 1/150 (working strength). Luminescent bacteria exposure time prior to examining the bacteria-sprayed plates was 35 minutes.
FIG. 9 TLC plates of two pesticides, DIAZANON® and LINDANE® and two herbicides, ROUNDUP® and WEED-B-GON®, taken in room lighting. Dilution of pesticides and herbicides=1/150.
FIG. 10 TLC plates of two pesticides, DIAZANON® and LINDANE® and two herbicides, ROUNDUP® and WEED-B-GONE® viewed by bioluminescence showing zones of luminescent inhibition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides methods, kits and luminescent biological (for example, bacterial) agents which are demonstrated to be surprisingly advantageous for the identification of specific toxicants or component substances in a sample. Moreover, techniques are proposed wherein the identified component substances of a sample may subsequently be chemically characterized or additional volumes of the isolated component ingredient (i.e., toxicant) be obtained employing a variety of chemical techniques in conjunction with the teachings of the present disclosure.
The novel use of a luminescent biological agent together with a separation phase matrix provides a unique method for the rapid and simple identification of potentially toxic (isolated) substances in a sample. The Inventors foresee the application of the present invention in the laboratory as well as in industry for the detection of environmental pollutants, particularly in water resources. Additionally, use of the described methods in the development and identification of therapeutically valuable components in plants and organisms, such as in garlic, is also considered an important application of the described invention.
Luminescent Bacteria as the Luminescent Biological Agent
Where the luminescent biological agent to be used is a luminescent bacterial agent, such as the luminescent bacteria Vibrio fischeri, the bacteria should constitute a suspension of bacteria at a final concentration of about 10 8 -10 9 bacteria cells/ml in the suspension to be used, for example, where the luminescent bacterial agent is sprayed onto a chromatogram.
A preferred method whereby the luminescent bacteria are prepared for use in the presently described invention is as follows. The bacteria must first be allowed to become fully "induced" in their luminescent system, i.e., the luminescent system of the bacteria should be allowed to reach complete development prior to harvesting of the bacteria from the culture. Determination of at what point a bacteria has reached full luminescent system development is well known to those of skill in the art 30 ,31.
Upon full development of the luminescent system of the bacteria, the bacteria should be harvested and then placed in a centrifuge tube. The bacteria are then to be centrifuged at a speed of 10,000×G for 30 minutes at room temperature. Thus centrifuged, the bacteria will form a pellet of cell "paste" at the bottom of the tube. About 1 gram of this cell paste (about 12 ml of cell "paste"=1 gram) of glowing bacteria is then to be diluted to a volume of 20 ml, by adding 20 ml of a diluent of choice. Where the luminescent bacteria is a marine bacteria, for example, the diluent is most preferably a buffered saline solution of between 1-4% NaCl. As diluted to 20 ml, the cell suspension constitutes a concentration of 10 10 -10 12 bacteria cells/20 ml (or 10 8 -10 9 cells/ml).
The following Examples are presented only to describe preferred embodiments and utilities of the present invention, and to satisfy best mode requirements. The examples are not meant to limit the scope of the present invention unless specifically indicated otherwise in the claims appended hereto. The following Examples are provided to demonstrate various aspects of the present invention.
EXAMPLE 1
Isolation of Identifiable Luminescent Inhibitory Toxicant in Garlic Extract Using Luminescent Bacteria
PROPHETIC EXAMPLE 2
Proposed Chemical Identification of Toxicants in a Garlic Extract
EXAMPLE 3
Identification of Pesticides in Sample with Luminescent Bacteria
EXAMPLE 4
Dilution Series of DIAZANON® or TLC with Vibrio fischeri
EXAMPLE 5
Solvent Polarity and Fluorescent and Bioluminescent Detection of DIAZANON®
EXAMPLE 6
Identification of Pesticides and Herbicides in a Sample with Luminescent Bacteria
EXAMPLE 7
Identification of Herbicides and Pesticides
PROPHETIC EXAMPLE 8
Proposed Identification of Heavy Metals in a Sample with Luminescent Bacteria
PROPHETIC EXAMPLE 9
Proposed Chemical Identification of a Toxicant in a Sample Isolated with Bioluminescence Methods
EXAMPLE 10
Identification of Toxicant in a Gaseous Phase Sample with Luminescent Bacteria
PROPHETIC EXAMPLE 11
Proposed Identification of a Toxicant on a Solid Surface Sample with Luminescent Bacteria
PROPHETIC EXAMPLE 12
Proposed Test Kits for Identifying Toxicants in a Sample
EXAMPLE 1
Isolation of Identifiable Luminescent Inhibitory Toxicant In Garlic Extract Using Luminescent Bacteria
The present example is presented to describe a method by which components of a substance which inhibit luminescent bacteria may be isolated. The sample analyzed in the present example is a garlic extract. For this experiment, the Inventors first prepared a garlic extract from garlic powder. The garlic powder was processed so as to form a liquid garlic extract. One (1) gram of garlic powder was blended with 5 ml. H 2 O. Other solvents such as ethanol, chloroform, or acetone may be used to blend the sample, but H 2 O was found to be the best solvent for the garlic.
A 5 ml. volume of the garlic extract was first applied ("spotted") to TLC plates at several points equidistant from one edge of the plate. The plate was inverted in a sealed TLC solvent container with a small amount of solvent in the bottom such that spotted samples were parallel to and above the solvent interface.
As the solvent (acetonitrile:water:aqueous ammonia, 8:1.5:0.5) migrated up the TLC plate, the individual components in the garlic extract were sufficiently separated to detect separate zones of luminescent inhibition upon exposing the developed chromatogram to a suspension of luminescent bacteria, Vibrio fischeri applied in a suspension of 0.5 M NaCl (See FIG. 1 and FIG. 2).
The Inventors applied the luminescent bacteria, Vibrio fischeri to the chromatogram specifically by spraying the described suspension of bacteria (contained in a buffered salt solution of 3% (0.5 M) NaCl at a pH of about 7) onto the developed chromatogram after the solvent in which the sample was contained had evaporated. Zones of luminescent inhibition were located prior to the dehydration of the bacteria on the chromatogram, i.e., at least within 1 hour after application of the bacteria.
The inhibition of bioluminescence of the bacteria caused by the presence of toxicants in isolated components of the garlic extract was then visualized. The bioluminescent inhibition effect of any toxicant in the garlic extract became apparent generally within a few minutes in the form of a clearly demarcated zone of bioluminescent inhibition (See FIG. 2). These zones of bioluminescent inhibition are areas on the chromatogram which were dimmer (i.e., less brightly emissive) than the more brightly emissive surrounding areas on the chromatogram (which did not include isolated components of the garlic extract which were capable of inhibiting the luminescence of the Vibrio fischeri). The areas wherein the chromatogram demonstrated greatest amounts and intensity of blue bioluminescence from the applied Vibrio fischeri bacteria identified areas of no component substances or instead isolated components of the garlic extract which were not toxic to the bioluminescence of the bacteria, and therefore according to the described method were considered not to constitute toxicants.
As stated, the inhibition of bacterial luminescence which occurs when a toxicant is detected, becomes apparent very soon, often within a few minutes, and grows more distinct with time and reaching a pronounced peak effect in the minutes before the chromatogram dries out, i.e., the zones of decreased luminescence show more contrast relative to the surrounding luminescence with time, prior to the chromatogram drying out. When the chromatogram is dried out, of course, all the luminescence of the bacteria on the chromatogram will be extinguished with the dehydration of the bacteria.
Curiously, with the described methods, those positions on the chromatogram to which the toxicants have migrated (i.e., the "zones of inhibition") appear to dry out faster than the remainder of the chromatogram which, for example, remains highly luminescent.
Alternatively, the identification of the different individual components of the garlic extract could have been accomplished using paper chromatography as the separation phase matrix for the sample or other such techniques well known to those of skill in the art.
FIG. 1--TLC Plate of Garlic Extract
This is a photograph of a TLC plate viewed by fluorescence. The actual plate was 20 cm by about 4.5 cm. In the photograph the plate is seen reduced to 13.0 cm by 2.95 cm. Dimensions below refer to dimensions of the photograph not of the original plate.
Sample
Aqueous Garlic Extract. Preparation: 1.0 g of powdered garlic suspended in 5.0 ml of H 2 O. Mixed with Vortex mixer for 1 minute. Centrifuged in table top centrifuge on high (about 1-2000 rpm, 60 seconds) to obtain straw yellow supernatant: the sample. Five μl applied at origin of plate: pencil lines seen near 1.7 cm from bottom of plate. The application zone is seen as a circle (faint) of about a 6 mm diameter centered on the line.
Development
The solvent system used was acetonitrile:water:25% ammonia (aqueous); 80:8:12. The sample was chromatographed in a closed chamber for approximately 20 minutes. The solvent front traveled about 4/5 of the distance of the plate. A faint demarkation line is seen at about 10.5 cm from the bottom of the plate showing the location of this solvent front.
Results
Major features of the chromatogram viewed by fluorescence excitation are a pronounced dark line at about 7.9 cm from the bottom of the plate several chevron or V-shaped dark areas in the 5.8-7.7 cm from the bottom region and a faint roughly circular shaped zone centered at about 8.8 cm from the bottom. The chevron shaped darkenings represent chemical components in the garlic resolved by the chromatographic process. The more or less circular zone at 8.8 cm (which can be more dramatically revealed by moving the photograph back and forth about 2 cm in the plane of the photograph) is the zone or near the zone of bioluminescence inhibition seen in photograph 2.
FIG. 2--TLC Plate of Garlic Extract
This is a photograph of a TLC plate (not the same one as in photograph 1, but a plate developed in an identical fashion except for a longer time) viewed by the emission of Vibrio fischeri luminous bacteria. The actual plate was 20 cm by about 4.2 cm. In the photograph the plate dimensions are 12.9 cm by 2.8 cm.
Sample
Aqueous garlic extract: the identical sample used in chromatogram of photo 1.
Development
Same as in photo 1 except chromatogram ran longer, front reaching near the end of plate, near 12.5 cm in photograph. The origin was centered on the pencil line visible at about 2.4 to 2.5 cm from bottom of plate.
Results
A very dark, nearly circular zone is seen centered at about 10.5 cm from bottom of plate. A faint second zone is seen at about 6.7 cm from the bottom. Several darkened regions can be seen at the edges of the plate. The dark areas which appear at the edges are artifacts, and represent places on the chromatogram sheet which were not adequately sprayed with the luminous bacterial suspension. The zone at 10.5 cm represents the lumotox effect i.e., the determination of the location of the component in garlic which inhibits the luminous bacteria.
Routinely, for preliminary analysis of the chromatograms, the plates were irradiated with a lamp emitting UV (254 nm) radiation. The TLC plate used had the F 254 backing and were therefore fluorescent everywhere that no UV absorbing samples or components existed. This preliminary detection system also revealed component substances as dark spots on a light background where heterocyclic or other UV absorbing compounds were present. However, fluorescent extinction and luminescence inhibition were often not in parallel. For example, some samples presented as very dark zones, as viewed by fluorescence (for example, garlic), had little or no bioluminescence inhibition, while other zones presented very faint or non-existent fluorescence extinction but had substantial ability to inhibit (extinguish) bioluminescence (e.g., garlic, LINDANE®, ROUNDUP®).
Particular sources of TLC plates and chromatography sheets include Sargent Welch (No. S18953-10-TLC plate with F 254 fluorescent material), Analtech (uniplate taperplate silica gel G-F, No. 81013), and Eastman-Kodak (Kodak chromatogram sheets silica gel absorbent with fluorescent indicator, catalog no. 122-4294) and Whatman (absorbent plates flexible-backed aluminum polyester, catalog no. 4410-22 (contains fluorescent indicator)).
The Albert et al. article 22 provides a description of analyzing mevinolin, a fungal metabolite employing standard laboratory techniques such as mass spectroscopy, nuclear magnetic resonance and x-ray analysis. These alternative standard laboratory techniques could be utilized to analyze eluted components from an unknown sample.
Upon isolation/separation of the various components in the garlic extract sample by a chromatography method, the inventors then applied the luminescent bacteria to the developed chromatogram. Most preferably, the luminescent bacteria is applied to the developed chromatogram in the form of a suspension contained in a buffered salt solution (about 0.3 M Na + /K + phosphate buffered saline (3% NaCl by weight) pH 7.0).
Prophetic Example 2--Proposed Chemical Identification of Toxicants in a Garlic Extract
The present prophetic example is provided to outline one proposed method by which the toxicant(s), as identified according to the method of the procedure outlined in Example 1 may be further characterized to identify the chemical structure of the isolated toxicant(s). This method may also be used where additional amounts of the isolated substance are desired or where the purity of the isolated substance is to be determined.
The particular "zones of luminescent inhibition" described above, which provide for the isolation of the component substances (i.e., toxicant) in the test sample, are used as reference points to isolate each component substance from an adjacent spotted sample which was run on the same or a separate TLC plate with the same sample. Unsprayed sections of the TLC plate, which correspond to zones of luminescent inhibition on the sprayed portion, may be scraped off and added to a sufficient volume of an appropriate solvent (i.e., distilled water, acetone, ethanol, ether, ethyl acetate-chloroform or other solvent mixtures) such that the isolated component substance of the sample may become dissolved in the solvent.
Subsequent removal of the solid TLC scrapings from the liquid eluate can be accomplished by various methods known in the art such as centrifugation or filtration. If necessary, the eluates containing dissolved toxicants may then be concentrated using standard techniques. These separated, (and in some cases, concentrated) isolated substances of the sample may be further resolved in other TLC solvent systems (or HPLC, paper chromatography, and the like) to verify purity or to obtain suitably pure isolated substances. These substantially pure isolated substances can then be identified using standard chemical and spectral methodologies. For example, such standard chemical and spectral methodologies include as HPLC, MS, IR, NMR, and the like.
Alternatively, two dimensional (2D) thin layer (TLC) can be run for higher resolution of the sample for more explicit identification of components therein. In the 2D method, a sample is spotted near one corner of the TLC sheet or plate, and run successively in two, usually perpendicular, directions, using different solvent systems or conditions. For example, the sample is chromatographed in the usual way (described above) on the TLC medium in the first direction using solvent system No. 1 (e.g., a basic non-polar system, ammonia:butanol:hexane in a 5:20:75 ratio). The chromatogram, containing components resolved in a linear fashion in this solvent system No. 1, is then to be removed from the chromatography chamber, dried fully to remove solvent molecules of this system No. 1 solvent, and then the thus dried chromatogram is rotated 90° to the orientation first used and chromatographed in the new orientation using a solvent system No. 2 (e.g., a polar, acetic system, such as acetic acid, acetone, ethanol in a 10:50:40 ratio). The components resolved into a linear array by system No. 1 move in the perpendicular direction with the solvent system 2 to provide even greater resolution of individual component substances in the sample.
This same basic approach can be utilized where luminescent bacteria are used to identify isolated component substances of a sample separated by paper chromatography systems, either 1D or 2D. As those in the art will appreciate, in using such systems, there are various ways to achieve separation such that toxicants can be obtained in relatively pure form. For example, another version of 2D paper chromatography may employ electrophoresis in one dimension and gravitational flow paper chromatography or isoelectric focussing in another dimension, or other two-dimension combination thereof (i.e., 1st D=paper chromatography, 2sn D=isoelectric focusing, etc.)
Example 3
Identification of Pesticides in Sample with Luminescent Bacteria
The present example is provided to demonstrate the use of the claimed methods and reagents for the identification of a pesticide in a sample of known substances. In this example, the pesticides identified were DIAZANON®, LINDANE® and SEVIN®. The luminescent bacteria used in the present example was Vibrio fischeri (ATCC 7744).
Identification of these individual pesticides and herbicides was achieved essentially according to the same methods described in Example 1. A suspension of Vibrio fischeri in a saline diluent was sprayed, using an aspirator bottle, on the developed chromatograms. Zones of luminescent inhibition appeared surrounding those areas on the plate where the DIAZANON® had migrated. Similar, less dim zones of inhibition, where LINDANE® had migrated (See FIG. 6 and FIG. 7). In a similarly run TLC with SEVIN®, the chromatogram also demonstrated zones of luminescent inhibition at those areas on the chromatogram where SEVIN® had migrated.
FIG. 3 and FIG. 4
These are photographs of the same TLC plate taken by two different conditions: Fluorescence and Bioluminescence, respectively.
Samples
5 μl samples of (1/32 by DIAZANON®) and (1/8 LINDANE®). The DIAZANON® sample was produced by serial dilution of the commercial diagram (25% w/v) 0,0, diethyl-0-[2-isopropyl-6-methyl-≮-pyrimidinyl]phosphorsthionate, Ortho Products. The DIAZANON® was diluted with ethanol by factors of 2 until a dilution of 1/32 commercial strength was reached. The LINDANE® (Ortho Products) was diluted in ethanol from the commercial 20% (w/v) gamma isomer of benzene hexachloride, until a final strength of 1/8 was reached.
Development
Acetonitrile: 25% Aqueous ammonia, 75:25
Results
FIG. 3 represents the results from this study using DIAZANON® and LINDANE® on a TLC plate viewed by 254 nm excitation. A prominent dark zone for DIAZANON® is located at 8.8 cm from bottom of FIG. 3. About 3 quite faint zones for LINDANE® at 8.2, 9.2, and 10.3 cm from bottom of FIG. 3 are demonstrated. DIAZANON® origin (application spot) at 2.5 cm from bottom of photo, LINDANE® origin at 3.0 cm.
FIG. 4 viewed by bioluminescence from Vibrio fischeri. Dark zone for DIAZANON® very close to zone for fluorescence extinction (at about 8.1 cm from photobottom). Several very dark zones for LINDANE® at about 8.0, 8.8, and 10.0 from photobottom. Also seen is slight inhibition zone at origin of LINDANE® sample. The several zones for LINDANE® indicate that several isomers or different inhibition compounds are present in the LINDANE® sample.
Example 4
Dilution Series of DIAZANON® on TLC with Vibrio fischeri
The present example is provided to demonstrate the sensitivity of the claimed invention to detect relatively low concentrations of a pesticide. An exemplary pesticide for demonstrating the sensitivity of the assay used here is DIAZANON®.
FIG. 5 and FIG. 6
Spot tests of DIAZANON® at several dilutions were performed at the following strengths: full strength (25% w/v DIAZANON®), 1:128; 1:256; 1:512; and 1:1024. No chromatography was done. 5 μl samples of the various DIAZANON® dilutions were applied to TLC plate material, sprayed with a suspension of Vibrio fischeri in a saline solution (3% NaCl WT/VOL.) and photographed. Marked inhibition occurred up to and including the D/256 dilution (D/252 appears by clerical mistake on sheet instead of D/256 which was used) of full strength (25% w/v) DIAZANON®. Faint inhibition is seen at dilution 1:512 and dilution 1:1024 (See FIG. 6, R).
The TLC plates with DIAZANON® demonstrate that the methods described herein are sufficiently sensitive to identify a pesticide in a sample at concentrations in which they are likely to occur in a land or water sample obtained in the environment.
Example 5
Solvent Polarity and Fluorescent and Bioluminescent Detection of DIAZANON®
The present example is presented to demonstrate the effect of varying the solvent polarity on the detection patterns, or "zones of inhibition" of Vibrio fischeri in the presence of DIAZANON®, a pesticide.
FIG. 7 and FIG. 8 provide photographs of TLC plates viewed by 254 nm irradiation (FIG. 7) and by bioluminescence (FIG. 8).
Samples
In each case, 5 μl of (DIAZANON®/8) was applied at origin on left and 5 μl of LINDANE®/8 was applied at right origin.
Development
Three solvent systems used. All composed of Hexane: THF mixtures. In FIG. 7 the left chromatogram was Hex:THF, 70:30 the middle chromatogram was Hex:THF, 80:20 the right chromatogram was Hex:THF, 90:10. (middle chromatogram contains clerical labeling error of 80 THF:20 HEX, which should be 80 HEX:20THF)
Results
FIG. 7 shows the decrease in polarity as the proportion of THFs lowered causes the DIAZANON® and faint LINDANE® spots or zones to be progressively diminished in mobility; to have smaller R f values; to migrate shorter distances from the origin.
FIG. 8 shows only the left-hand and right-hand TLC plates seen in FIG. 9. Dark bioluminescence zones of inhibition are seen in Photo 8 for DIAZANON® and LINDANE® samples.
Example 6
Identification of Pesticides and Herbicides in a Sample with Luminescent Bacteria
The present example is provided to demonstrate the use of the claimed methods and reagents for the identification of pesticides and herbicides in a known test sample using a luminescent biological agent.
In this example, the herbicides ROUNDUP® and WEED-B-GON® and the pesticides DIAZANON® and LINDANE® are identified in a test sample with the luminescent bacteria, Vibrio fischeri (ATCC 7744).
Example 7
Identification of Herbicides and Pesticides
Each sample was run on an individual TLC sheet. Photographs of the resulting 4 individual chromatograms are presented at FIG. 9 (room light) and FIG. 10 (Bioluminescence--chromatogram with luminescent bacteria).
Two solvent systems were used. The solvent systems used to identify the herbicides (ROUNDUP® and WEED-B-GONE®) was 100% ethanol. A 5 ml sample of an 8-fold dilution of these commercially available herbicides was used in the spotting of the TLC plates.
The solvent system used for the pesticides DIAZANON® and LINDANE® was Hexane:THF, 90:10. The pesticides were spotted at a concentration of 1.8. A 5 ml sample of an 8-fold dilution of these commercially available pesticides was used in the spotting of the TLC plates.
Two solvent systems were employed as no single system has yet been found to adequately resolve all compounds (i.e., the two pesticides and the two herbicides). Use of 100% ethanol causes DIAZANON® and LINDANE® to run at the front of the solvent system. Use of 90% Hexane, 10% THF causes ROUNDUP® and WEED-B-GONE® to stay at the origin. The TLC plates photographed are in the following order (left to right) (one sample per plate): DIAZANON®, LINDANE®, ROUNDUP®, and WEED-B-GONE®. In each case, the commercial strength was diluted by a factor of 8.
Results
a. Pesticides
The DIAZANON® sheet did present an entirely distinct "zone of inhibition", but the FIG. 10 only marginally indicates this characteristic, perhaps due to partial bacteria dehydration. The LINDANE® chromatogram presented as a distinct zone of inhibition culminating in a dark spot center about 2.9 cm from the bottom of the plate.
The ROUNDUP® chromatogram presented a clear zone of inhibition as seen at the origin, and at least one other inhibition zone centered at 4.5 cm from the bottom of the plate. The WEED-B-GONE® chromatogram presented as a large oval zone of luminescent inhibition (perhaps comprised of several components) starting at about 1.8 cm from the bottom of the TLC plate and stretching to beyond 6 cm from the bottom of the plate.
Example 7
Identification of Herbicides and Pesticides
The following example presents the results of three separately run experiments by the Inventors. These data demonstrate the reliability of the described methods for consistently identifying a component substance in a sample. The following list represents a description of the particular herbicides and pesticides, and the percent dilutions used thereof, in the described 3 separately run TLC plates.
WEED-B-GON®
10.8% w/v dimethylamino salt of 2,4 dichlorophenoxyacetic acid 11.6% w/v dimethylamino salt of 2-(2-methyl-4 chlorophenoxy)propionic acid
DIAZANON®
25% w/v O,O,diethyl-O-[2-isopropyl-6-methyl-4-pyrmidinyl]phosphorothio(n)ate
ROUNDUP®
41% w/v isopropylamino salt of glycophosphate N-(phosphoromethyl)glycine
LINDANE® (bark and leaf mineral spray)
20% w/v gamma isomer of benzene hexachloride liquid
LIQUID SEVIN® CARBAMYL
27% w/v 1-naphthyl-N-methyl carbamate
The following table presents the results obtained for identifying DIAZANON®, LINDANE®, ROUNDUP®, and WEED-B-GON® in three different tests conducted by the Inventors. These data demonstrate that the described method provides a system which possesses the ability to detect, with varying sensitivity, a variety of herbicides or pesticides in a sample on a consistent and reliable basis, as demonstrated by the closely corresponding "spots" for each run of the same component substance between the three separately run chromatograms.
TABLE 1______________________________________ Ratio of Herbicide/ Distance Spot Spot Spot Front Stan.Pesticide of Front 1 2 3 Fluor Biolu Dev.______________________________________Test 1 DIAZANON ® 2.38 0.63 -- -- 0.26 0.26 0.02 LINDANE ® 2.38 .88 1.38 1.66 0.37 0.37 0.02 0.58 0.57 0.00 0.70 -- ROUNDUP ® 2.36 0.00 0.13 1.38 0.00 0.00 0.00 0.06 -- -- 0.58 -- -- WEED-B- 2.36 0.66 1.64 1.88 0.28 0.28 0.02 GON ® 0.69 0.69 0.04 0.80 -- -- Test 2 DIAZANON ® 2.75 0.68 -- -- 0.26 0.25 0.01 LINDANE ® 2.19 0.83 1.23 1.55 0.38 0.35 0.03 0.56 0.57 0.00 0.70 -- -- ROUNDUP ® 2.00 0.00 0.12 1.22 0.00 0.00 0.00 0.06 -- -- 0.61 -- -- WEED-B- 2.25 0.65 1.35 1.79 0.28 0.28 0.020 GON ® 0.66 0.66 .01 0.80 -- -- Test 3 DIAZANON ® 2.79 0.68 -- -- 0.24 0.24 0.00 LINDANE ® 2.09 0.83 1.23 1.59 0.39 0.40 0.01 0.58 0.60 0.03 0.73 -- -- ROUNDUP ® 2.13 0.00 0.21 1.29 0.00 0.00 0.00 0.10 -- -- 0.60 -- -- WEED-B- 1.84 0.38 1.17 1.55 0.21 0.21 0.05 GON ® 0.64 0.63 0.02 0.84 -- --______________________________________ R.sub.f Values Represented in the Reported Values in the Table; R.sub.f = relative to the front; a fractin of the total distance which th solvent front migrated.
Prophetic Example 8
Proposed Identification of Heavy Metal Salts in a Sample with Luminescent Bacteria
The present prophetic example is provided to present a use of the claimed methods and reagents for the identification of a heavy metal in a sample. Specifically, the Inventors hypothesize that the described methods would be useful in the identification of the heavy metals such as mercury, lead and cadmium using the described luminescent biological reagents, such as the bacteria, Vibrio fischeri (ATTC Acc. No. 7744).
In the present example, the Inventors spotted the various metals on to a chromatography paper sheet, but did not run them through a chromatography separation process. Upon spotting of the various metals along one side of a chromatography paper sheet, the sample spots were allowed to dry. Upon drying, the spotted sheets were exposed to the luminescent bacteria Vibrio fischeri. Employing this method, the Inventors were able to visualize the presence of the heavy metal salts of mercury, lead, and cadmium.
To isolate the heavy metal spotted on the chromatography paper, the paper edge at which the sample was spotted should be exposed to a solvent system, most preferably an acidic solvent system.
Specific reference is made here to the RAININ® catalog 29 , wherein a standard technique (for the separation of heavy metals) is described using an ion chromatography metals column. Resolution of Pb ++ and Cd ++ is demonstrated in the reference RAININ® catalog.
Successive equal volumes of a heavy metal could be eluted using the HPLC procedure from the HPLC machine and spotted in an array or in a linear fashion on a sheet of (Whatman) chromatography paper. After the carrier solvent is evaporated or otherwise removed by drying, the sheet could be sprayed with a suspension of luminescent bacteria, such as Vibrio fischeri, as described. Zones of bioluminescent inhibition could be similarly visualized to identify the metal.
Prophetic Example 9--Proposed
Chemical Identification of a Toxicant in a Sample Isolated with Bioluminescence Methods
The present prophetic example is provided to outline a proposed method whereby the identified region provided on a chromatography sheet with the described luminescent agent, particularly a luminescent bacteria may be analyzed to ascertain the chemical identity of an isolated component substance of a sample.
A volume of sample containing sufficient concentration of toxicants would be applied to a chromatography paper, such as Whatman 1M or 3M and chromatographed using a solvent system which provides maximum separation of the sample components. Various solvent systems may be utilized and tested for separation efficiency as well understood by those skilled in the art. Small amounts of sample may be used to test for improved resolution in one dimensional (1D) chromatography solvent systems. Those solvents found most effective may then be utilized for larger scale separation on large sheets of chromatography paper for two-dimensional chromatography (2D).
Two dimensional chromatography may be necessary to resolve sample ingredients for subsequent identification of substantially pure compounds. By determining a combination of two solvent systems which effectively resolve the component toxicants, 2D chromatography can be run in duplicate.
Following the chromatography, the luminescent bacteria may be sprayed onto one of two identical sample sheets. Areas on the sheet which demonstrate a decreased luminescence would then be used to mark the corresponding areas of the unsprayed sheet. The corresponding areas on the unsprayed sheet are cut out and eluted with distilled water, appropriate solvents such as acetone or ethanol or a solvent mixture to provide individual, substantially pure toxicants for identification. This procedure can be repeated, and/or multiple 2D sheets may be run simultaneously, in order to accumulate sufficient quantities of various substantially pure toxicants.
In this manner, appropriate amounts of toxicants in a sample may be separated and then identified using standard chemical procedures. For example, small amounts of the purified component substances may be run on high pressure liquid chromatography (HPLC) and compared to known standards for identification 15 . As will be appreciated by those skilled in the art, additional standard techniques used for chemical identification may be employed such as spectral analysis: Mass spectra, infrared spectra (IR), nuclear magnetic resonance (NMR), and the like.
It will understood by those skilled in the art that multiple 2D chromatography sheets can be run simultaneously in which different sheets are sprayed with different luminescent bacteria. This would provide a more thorough analysis of toxicants which may be detectable by one luminescent bacterium, but not by another. Additionally, combinations of different luminescent bacteria in one spray solution may facilitate the thorough identification of most or all of the detectable isolated component substances in a sample. In this manner, a thorough analysis and identification of toxicants in a sample may be undertaken.
Essentially this same approach can be taken using thin layer chromatography (TLC), instead of paper chromatography as described above, for the initial separation and identification of toxic substances in a sample. Multiple TLC plates (e.g., Whatman 4856-840 with 1,000 μM silica layer) may be run simultaneously in the same solvent system utilizing 1D or 2D runs, as described above, for paper chromatography. In such a TLC approach to toxicant identification, toxicants would be identified by spaying the plates with luminescent bacteria, marking the zones of decreased luminescence, and scraping off the corresponding areas on the unsprayed portions of plates. The scrapings are then eluted with an appropriate solvent, such as distilled water, acetone or ethanol or a solvent mixture, concentrated (if required), and identified using HPLC, MS, IR, NMR, and the like.
By following either of the above procedures, the separation and identification of toxicants in a sample can be accomplished simply and rapidly. The standardization of this method to be used for the identification of toxicants in certain types of samples will be appreciated by those skilled in the art as providing simple, rapid, and inexpensive methodologies for toxicant identification. For example, certain types of samples (i.e., industrial effluent) could be tested to determine the initial separation system, the solvent systems, the luminescent bacteria (or combinations of luminescent bacteria), the elution protocol, and any subsequent techniques for quantitation and/or identification.
Through the use of standard curves of easily quantitated known compounds, the percent recovery in a given separation system can be determined. In this manner, amounts of identified toxicants can be quantitated and extrapolated back to the original sample volume applied. For example, the use of radiolabeled compounds, of known specific activity, which are separated by paper or TL chromatography, eluted, and counted for radioactivity, would provide an indication of the percentage recovery of a given compound. By comparing various radiolabeled chemical compounds in a given identification system (paper or TLC with different solvents and the like), one could correct for recovery losses of a given identification system.
When the separated toxicants are quantitated by certain chemical and spectral methods, the quantities may then be extrapolated to determine the quantities of individual toxicants present in the original sample. Thus, this method, in many cases, would allow for toxicant quantification.
These steps could be standardized into kits tailored for the analysis of specific types of samples (i.e., a kit for a certain industrial effluent or certain biological samples, such as foodstuffs, pharmaceuticals, and the like). These kits would comprise certain solvents and luminescent bacteria which would effectively resolve specific sample types thereby greatly simplifying and reducing the cost of toxicant detection, identification, and quantitation.
Alternatively, an unknown sample may be processed by the above procedure for identification and quantitation.
Prophetic Example 10
Identification of Toxicant in a Gaseous Phase Sample with Luminescent Bacteria
The present prophetic example is provided to outline a proposed method whereby an investigator may identify a toxicant present in a gaseous phase sample employing the methods with luminescent bacteria described herein.
As an initial step, the gaseous sample would be collected by techniques known to those skilled in the art. For example, a gas sample might be collected by filtration through a solid filter such that toxicants deposit onto the filter or by aspiration into a liquid such that toxicants dissolve in the liquid. In the case of a solid filter, the filter could then be eluted with distilled water or a suitable solvent, concentrated, chromatographed by paper or thin layer chromatography, and identified using certain luminescent bacteria as described in Example 6.
Prophetic Example 11
Identification of a Toxicant on a Solid Surface Sample with Luminescent Bacteria
The present prophetic example is provided to outline a proposed method whereby a toxicant on a solid surface sample may be identified with the described luminescent bacteria.
As in Example 7, methods for removing a toxicant from a solid surface so that it is collected in a concentrated liquid form will vary depending on the nature of the solid surface. Techniques for such removal will be apparent to those skilled in the art. Using the procedures outlined in Example 6, one skilled in the art would be capable of identifying and quantifying toxicants which were eluted from or removed from the solid surface. Alternatively, for direct detection of toxicants, the solid surface could be sprayed with a certain luminescent bacteria, or mixture of more than one luminescent bacteria, such as Vibrio fischeri and the surface observed for zones of decreased luminescence (i.e., zones of luminescent inhibition) substantially as has already been outlined in Example 1. Of course, these isolated component substances of the sample (potential toxicants) could then be chemically analyzed according to laboratory techniques well known to those of skill in the art to identify the chemical structure of the isolated component. By way of example, such laboratory techniques for determining the chemical structure of an isolated component substance include HPLC, MS, IR, NMR, and the like.
Prophetic Example 12
Proposed Test Kits for Identifying Toxicants in a Sample
The present prophetic example is provided to define those components which would comprise a proposed test kit useful for the identification of toxicants in a sample. Such a kit most preferably would comprise a carrier means adapted to receive at least two container means and at least one chromatography paper sheet in close confinement therewith. The kit should also include at least one chromatography paper sheet and a first container means comprising a luminescent bacterial agent. While any luminescent bacterial agent may be used in conjunction with the described kit, that bacterial agent most preferred is the Vibrio fischeri (ATTC Acc. No. 7744). Most preferably, the luminescent bacterial agent should be in lyophilized form in the container means. The lyophilized bacteria would then be suspended in a diluent solution. For example, where appropriate NaCl concentrations are within the lyophilized sample, deionized water may be employed as the diluent solution without any expected deleterious effects to the luminescence of the bacteria.
In a second container means, the kit should further comprise a diluent for a luminescent bacterial agent. Most preferably, the diluent should comprise a 0.5 M NaCl buffered saline solution at pH 7 where the bacteria is a marine bacteria and has not been lyophilized to include NaCl. The kit may optionally also include a separation solvent, such as acetonitrile, deionized water, or aqueous ammonia.
In other proposed forms of the presently proposed kit, the kit may further comprise an aspirator spray bottle to facilitate the easy application of suspended luminescent bacteria to a separation phase matrix such as a TLC plate or chromatography paper, chromatogram. In addition, the kit may comprise several vials of lyophilized luminescent bacteria. In other proposed forms of the presently proposed kits, the kit may further comprise instructions for the suspension and application of the luminescent bacteria to facilitate visualization of the isolated component substances of the test sample, and also in regard to the reaction time to be allowed and at what point the luminescent bacteria-exposed separation phase matrix should be read.
BIBLIOGRAPHY
The following references are specifically incorporated herein by reference in pertinent part.
1. Drucker et al. (1984) E.P. 153366.
2. Vasseur et al. (1983), presented at the International Symposium on Ecotoxicological Testing for Marine Environment, Belgium, pp. 12-14.
3. Baher (1988)--WPI 88-308491 (884).
4. Liebowitz (1984), Anal. Biochem., 137(1):161-163.
5. Gu, Z. (1987), Turangxue Jinzhan 15 (3):48-51).
6. Siemens (1990)--WO 88 DE 626--; WPI ACC No. 90-116654(9016)--Genlux Fursch. Biol. Verfahren.
7. Strom et al. (1986), ACTA Hydro Chim Hydrobiol., 14 (3):283-292.
8. Ugarova et al. (1987), Appl. Biochem. Biotechnical., 15(1):35-51.
9. Thin Layer Chromatography: A Laboratory Handbook 2nd ed, E. Stahl, Ed., Springer-Varlag, New York, N.Y., (1967).
10. HPLC of Small Molecules: A Practical Approach C. K. Lim; Ed., IRL Press, Oxford England (1986).
11. HPLC of Macromolecules: A Practical Approach R. W. A. Oliver, Ed., IRL Press, Oxford, England (1989).
12. Plant Drug Analysis: A Thin-Layer Chromatography Atlas, H. Wagner, S. Bladt, E. M. Zgainski, Springer-Verlag (eds.), New York, N.Y. (1984).
13. Alltech Bulletin, (1991) #183, Gas Chromatography Apparatus, p.11.
14. Thompson, B. C., Kugmack, J. M., Law, D. w., Winslow, J. J., eds. (1989), "Copolymeric Solid Phase Extraction for Quantitating drugs of Abuse in Urine by Wide-Bore Capillary Gas Chromatography" L C-G-C 7(10):846-850.
15. Merck Index, 11th ed. (1989), p. 878-879.
16. Johnson, F. H., (1972) J. Bact., 109:1101-1105.
17. Hastings, J. W., MAV (1973) Arch. Mikrobiol., 94:283-330.
18. Yetison, T., (1978) Appl. Environ. Microbio., 36:11-17
19. Williamson, K. L., (1989), Macroscale and Microscale Organic Experiments, D. C. Heath and Company, Lexington, Mass. ISBN 0-669-19429-8.
20. Shriner, R., Fuson, R., Curtin, D., The Systematic Identification of Organic Compounds, John Wiley and Sons, Inc., New York, Fifth Edition, (1964).
22. Alberts et al. (1980) Proc. Natl. Acad. Sci., U.S.A., 77(7):3957-3961.
23. Pannell et al. (1990) Organometallics, 9(9):2454-2462.
24. Hertel et al. (1991) J. Am. Chem. Soc., 113:657-665.
25. Fischer Scientific Catalog (1991-1992), p. 483.
26 Kamminga, D., (1985), J. Chromatog. 330:375-378.
27. Gunther, K., (1988) J. Chromatog., 448:11-30.
28. Armstrong, D. W., 91984) J. Liquid Chromatography, 7:353-376.
29. Rainin Scientific Catalog (1991-1992), p. 3-38.
30. Bioluminescence and Chemiluminescence: Basic Chemistry and Analytical Applications, Marlene A. DeLuca and William D. McElroy, eds., Academic Press (1981)
31. Bioluminescence and Chemiluminescence, In: Methods in Enzymology, Marlene A. DeLuca, eds., Academic Press, Vol. 57 (1978).
32. G. W. Mitchell and J. W. Hastings (1971) Analytical Biochemistry 39:243.
33. J. W. Hastings and G. Weber (1963), J. Opt. Soc. Am., 53:1410. | Methods for the isolation and identification of a toxicant in a sample are disclosed. Luminescent biological agents (i.e., bacteria) having sensitivity to a toxicant or an isolatable component in a sample are used to provide visually discernable zones of luminescent inhibition in the presence of a toxicant (or) in the presence of an isolatable sample component as separated by paper or thin layer chromatography. Kits for use in conjunction with the identification of a toxicant in a sample are also described, which include a luminescent biological reagent as the visualizing agent. Particular examples of luminescent agents include photobacterium leoganthi, photobacterium phosphoreum, Vibrio fischeri, Vibrio harveyi a luminescent fungi, a luminescent fish extract, a luminescent dinoflagellate and fluorescent microorganisms, such as Cypridina. Potential toxicants in a liquid sample, a solid sample, or in a gaseous sample may be identified and further chemically characterized using the described methods. The isolation of potential toxicants in a sample through the processing of a sample through a separation phase matrix such as chromatography paper or TLC plate, followed by exposure to luminescent biological agent, provides for a rapid and inexpensive method for identifying pesticides, herbicides and heavy metals in a known or unknown sample. | 8 |
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