CN1070436A - 增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品 - Google Patents
增强弹性材料制品的带镀层的金属丝和用这种金属丝增强的弹性材料制品 Download PDFInfo
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- CN1070436A CN1070436A CN92110351A CN92110351A CN1070436A CN 1070436 A CN1070436 A CN 1070436A CN 92110351 A CN92110351 A CN 92110351A CN 92110351 A CN92110351 A CN 92110351A CN 1070436 A CN1070436 A CN 1070436A
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- zinc
- alloy
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- cobalt
- wire
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- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000012858 resilient material Substances 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000005728 strengthening Methods 0.000 claims abstract description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 20
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical group [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 11
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- 239000013536 elastomeric material Substances 0.000 claims description 2
- 235000012489 doughnuts Nutrition 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000007747 plating Methods 0.000 description 12
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000005491 wire drawing Methods 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- -1 nickel sulfate hexahydrate compound Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 101150004219 MCR1 gene Proteins 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B1/00—Constructional features of ropes or cables
- D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
- D07B1/0606—Reinforcing cords for rubber or plastic articles
- D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0607—Wires
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
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- D07B2201/20—Rope or cable components
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- D07B2201/201—Wires or filaments characterised by a coating
- D07B2201/2011—Wires or filaments characterised by a coating comprising metals
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2201/00—Ropes or cables
- D07B2201/20—Rope or cable components
- D07B2201/2001—Wires or filaments
- D07B2201/201—Wires or filaments characterised by a coating
- D07B2201/2013—Wires or filaments characterised by a coating comprising multiple layers
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/30—Inorganic materials
- D07B2205/3021—Metals
- D07B2205/3071—Zinc (Zn)
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2205/00—Rope or cable materials
- D07B2205/30—Inorganic materials
- D07B2205/3021—Metals
- D07B2205/3085—Alloys, i.e. non ferrous
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- D—TEXTILES; PAPER
- D07—ROPES; CABLES OTHER THAN ELECTRIC
- D07B—ROPES OR CABLES IN GENERAL
- D07B2501/00—Application field
- D07B2501/20—Application field related to ropes or cables
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S57/902—Reinforcing or tire cords
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Ropes Or Cables (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Tires In General (AREA)
- Insulated Conductors (AREA)
- Tyre Moulding (AREA)
Abstract
本发明涉及用来增强弹性材料制品尤其是增强
车用轮胎的金属丝。所述的金属丝具有由锌—镍或
锌—钴合金的两个同心层构成的镀层,其中径向内镀
层的锌含量大于90%,径向外镀层的镍或钴含量大
于50%。
Description
本发明涉及带有双镀层的金属丝,具体地说,涉及用来增强弹性材料制品的钢丝,以及用这种金属丝增强的弹性材料制品,尤其是车用轮胎。
已知的保护掺入弹性材料中的金属丝免遭腐蚀并且使金属丝和弹性材料粘合良好,是用金属合金将金属丝包覆起来。
一种已长期用来镀敷增强弹性材料制品用的金属丝的合金是铜和锌和合金,更具体地说,是一种含有约60%-70%铜和约40%-30%锌的合金。
正如已经知道的,镀有上面提到的一层合金的金属丝,在一段时间后对弹性材料的粘结变差,而且不能满意地防止腐蚀。为克服这两种缺点,曾提出使用其它类型的合金来镀敷金属丝。
特别是,曾经提出用黄铜(Cu-Zn)与加入的镍或钴或其它金属作为合金第三元素的三元合金来构成金属丝的镀层。用这类合金,在减少对弹性材料的粘结随时间变差和防止金属丝腐蚀方面有所改进,但是这些改进不足以使按此方式增强的弹性体制品(尤其是轮胎)的质量水平有重大改进。
在本申请人持有的欧洲专利283,738中叙述了在这两方面都令人满意的一种不同的解决方法。该方法包括用两个同心的叠合镀层镀覆金属丝,二层由选自锌-镍合金和锌-钴合金的合金制成,其中径向更靠内的一层含锌是在60%和90%之间(包括首尾数值),径向更靠外的一层的含镍或钴量在60%和80%之间(包括首尾数值)。
根据上述欧洲专利的金属丝虽然解决了防止腐蚀和对弹性材料的粘结随时间变差合乎要求这两个问题,但是对大规模工业生产来说仍然存在一些问题。
工业生产中不能令人满意之处发生在镀层形成后金属丝的拉伸阶段,包括金属丝在拉丝期间过分频繁地断裂,而且在拉板上磨损过多。
根据本发明,已经发现有可能制得用来增强弹性材料制品的金属丝和用这种金属丝增强的弹性材料制品,它们保持着根据欧洲专利283,738已经令人满意地达到的那些良好性能,即,在一段时间内对弹性材料的粘结和金属丝的耐腐蚀性合乎要求,而且这些金属丝还没有该专利存在的拉丝方面的缺点,令人惊奇的是,这是通过调节径向内层中的镍量或钴量做到的。
本发明的第一方面涉及用来增强弹性材料制品的金属丝,该金属丝带有两个同心镀层,径向上彼此叠合,两层均由选自锌-钴合金和锌-镍合金的合金构成,其特点在于,构成径向内层的合金的锌含量大于90%,而构成径向外层的合金的镍或钴含量大于50%。
本发明的另一方面涉及复以网状物的弹性材料混合物制品,特别是车用轮胎,在弹性材料中掺有增强用的金属丝,金属丝上带有在径向上彼此叠合的两个同心层构成的镀层,两层均由选自锌-钴合金和锌-镍合金的合金构成,该制品的特点在于,构成径向内镀层的合金含锌量大于90%,构成径向外镀层的合金的含镍或含钴量大于50%。
根据以下以实施例形式给出的对本发明某些实施方式的说明,将会更好地理解本发明。
本发明中使用的金属裸丝是通常的金属丝,尤其是在橡胶工艺、特别是轮胎工艺中众所周知的钢丝。在这种裸丝的表面上,用选自特殊的镀锌的钴合金和特殊锌-镍合金形成第一镀层。
适合用来形成本发明金属丝第一镀层的特殊的锌-钴和锌-镍金属合金,其特点是锌含量大于90%。
如果在用来形成第一镀层的金属合金中存在钴,则钴对锌的相对百分含量的降低会提高金属丝的“拉伸性”。
根据以上所述,钴含量以少于5%为宜,最好是不超过2%。
金属丝的第一镀层可以用任何已知方法形成,尤其是欧洲专利申请283,738中所说的两种方法之一。
例如,采用用电镀槽同时沉积锌和镍两种金属的方法,其中用来在根据本发明的金属丝上形成第一镀层的两种金属的数量如前所
述,电镀槽的成分和沉积的操作方法如下:
槽温在10和30℃之间(包括首尾数值)
电镀槽的pH在4和8之间(包括首尾值)
电流强度(安/平方分米)在5和30之间(包括首尾值)
硫酸镍六水合物,170克/升
硫酸锌10克/升
硼砂10克/升
氯化铵14克/升
十二烷基硫酸钠1克/升
作为实例,如果本发明金属丝的第一镀层是上述特定百分含量的锌-钴合金,则电镀槽和操作方法如下:
槽温55℃
槽液pH2±0.1
电流强度(安/平方分米)在60和80之间(包括首尾值)
硫酸钴七水合物120克/升
硫酸锌七水合物620克/升
硫酸钠75克/升
在形成镀层本身期间和带镀层的金属丝受拉伸之前,第一镀层的优选厚度调节在0.25至2微米之间(首尾值包括在内)。
这一厚度的检验是用常用一类的定量分析方法进行的。
本文中提到的各个厚度值应用这种方法检验。
在第一层之上,本发明的金属丝具有由选自镍-锌和钴-锌合金的一种合金构成的第二镀层,其特点在于,它的镍含量或钴含量大于50%;镍含量最好是在70%和100%之间(首尾值包括在内),或者是,钴含量应在70%和90%之间。
第二镀层也按照欧洲专利283,738所述的方法,利用在电镀槽中同时沉积各金属组分的方法形成。
例如,对于用来形成本发明金属丝第二镀层的电镀槽,当第二层是具有上述优选百分含量的锌和镍的合金时,电镀槽的操作条件如下:
槽温60℃
pH2.5±0.1
电流强度(安/平方分米)在25和35之间
硫酸镍六水合物550克/升
硫酸锌20克/升
硼酸35克/升
硫酸钠35克/升
再次作为实例,如果第二镀层由上述优选百分含量的锌和钴的合金构成,所用的电镀槽的操作条件应如下所示:
浴温55℃
pH2±0.1
电流强度(安/平方分米)在60和80之间(首尾值包括在内)
硫酸锌620克/升
硫酸钴125克/升
硫酸钠75克/升
在形成镀层期间和将带镀层的金属丝拉伸之前,第二层的优选厚度在0.25与2微米之间(首尾值包括在内)。
因此,在离开镀槽时金属丝的整个镀层厚度是在0.5和4微米之间(首尾值包括在内)。
将完成了具有上述特征的两个同心叠合镀层的本发明金属丝通过常用的拉板进行通常的拉丝操作,以便将其总外径减小到通用的数值,使之适合于弹性材料制品的增强用。
特别是在用于车辆轮胎的场合,拉丝操作以接连通过的方式进行,直到金属丝的初始直径(可以在0.70和3.70毫米之间变化)减小到0.12毫米和0.30毫米之间(首尾值在内),使得第一镀层的值在0.15和0.40微米之间(首尾值在内),第二镀层在0.05和0.20微米之间(首尾值在内),镀层的总厚度最终在0.20和0.60微米之间(首尾值在内)。
测定拉伸金属丝上两镀层的存在可以用X-射线衍射技术和/或俄歇电子能谱(AES)方法。
正如下面报导的实验结果所证实的,根据本发明的金属丝解决了先前所述的问题。
对于这些试验,使用三种根据本发明的特定的金属丝,文中标作
金属丝A、B和C,还使用一种根据欧洲专利283,738的已知的特定金属丝,文中标作金属丝N1。
上述这些特定的金属丝全由C70钢(一种普通钢,用来制造轮胎中指定使用的金属丝,其碳含量最高达0.70%)制成,具有相同的尺寸和结构;更准确地说,在拉伸之前,这些金属丝的总外径均为1.40毫米,带有由两个同心叠合层构成的镀层,各层的厚度不大于2微米。
上述金属丝的特征列在表1:
表1
金属丝名称 A B C N1
第一层 95%Zn 98%Zn 98%Zn 70%Zn
5%Co 2%Co 2%Co 30%Co
第二层 80%Ni 80%Ni 90%Ni 80%Ni
20%Zn 20%Zn 10%Zn 20%Zn
所有上述的特定的金属丝都进行拉丝处理,将它们的最终直径减小到0.25毫米,镀层平均厚度内层为0.35微米,外层0.15微米。
为此,使用19个基本上已知的V32型碳化钨制成的拉板,在普通的润滑剂浴中(Zeller Gmelin公司的VSV 351/IL油)拉丝,所得结果列在表2中。
表2具体列出了由于拉丝造成的镀层重量损失的平均百分数,在必须更换拉板时已拉伸的金属丝重量的平均百分数,以及对于每次断丝而言,已拉丝重量的平均百分数,N1金属丝的值假定为100。
表2
金属丝名称 A,B,C N1
镀层重量损失 20-30% 最少40%
每个拉板制造的金属丝量 300 100
每次断丝制造的金属丝量 400 100
列在表2的实验结果清楚地表明,使用本发明的金属丝,减少在金属丝完成镀覆后进行的拉丝期间在拉板上的磨损和降低在拉丝期间金属丝的破裂频率这两个问题都得到了解决。
对于用根据欧洲专利283,738的已知金属丝和用本发明的金属丝制成的小帘布作了进一步的试验,以确定对弹性材料的粘结值和小帘布与弹性材料之间的粘结随时间的恶化情况。
对于这些进一步的试验,使用根据表3配方配制的混合物。
表3
混合物的组分 重量用量
天然橡胶 100
氧化锌 8
6PPD抗臭氧剂 2
TMQ抗氧化剂 1
络合钴盐(Manobond 680C) 0.5
HAF灯黑 50
加速剂-Santocure MCR 1
硫 6
对于后面这些试验,试样按ASTM D2229-80准备,它规定将弹性材料的棱形小块在151℃硫化30分钟,弹性材料中掺杂着小帘布(由5根直径0.25毫米的金属丝组合而成),彼此间隔约12毫米,包埋在弹性材料内12.5毫米深处。
测定橡胶与金属的粘结的试验包括测定从含有帘布的棱形小块中拉出各个帘布所需的力,以及测定从小块中用力拉出的帘布被弹性材料覆盖的程度。
为了测定粘结随时间恶化的情况,试验仍如先前所述,但是在试样经老化处理之后进行对帘布的抽拉试验,老化处理是将试样在温度为65℃、相对温度90%的环境内放置预定的4天。
使用上述的混合物和小帘布制备试样,其数目与用带有上述不同类型镀层的金属丝构成的小帘布的数目相同。
试验结果列在表4。
表4
由含小帘布的混合物
制成的试样 A,B,C N1
从未经老化的试样
中拉出小帘布所需 537牛顿 414牛顿
之力的平均值
从老化后的试样中拉
出小帘布所需之力的 450牛顿 350牛顿
平均值
从未经老化的试样中
拉出的小帘布的覆盖 4 4
指数
从老化后的试样中拉
出的小帘布的覆盖指数 3 2
本文中覆盖指数的数值有以下含义:
覆盖指数4表示小帘布完全被弹性材料覆盖;
覆盖指数3表示小帘布的2/3被弹性材料覆盖;
覆盖指数2表示小帘布的1/3被弹性材料覆盖;
覆盖指数1表示小帘布完全没有弹性材料覆盖。
还用由本发明金属丝制成的小帘布和由镀黄铜(67.5%铜和32.5%锌)N2金属丝制成的小帘布掺加到硫化的弹性材料中作了进一步的试验,以便确定这些帘布与弹性材料的粘结特点的差别以及对构成帘布的金属丝的腐蚀情况。
上述小帘布仍是5×0.25形式的小帘布(即,由5根直径0.25毫米的金属丝构成),彼此的不同只是制成它们的金属丝不同;因此这些帘布在本文中用标记制成它们的金属丝的同样标记表示。
使用上述混合物形成缓冲层,以及根据本发明的小帘布A、B、C和上面提到的镀黄铜的帘布N2,制成尺寸165R13型具有P4胎面的轮胎。
从轮胎上割下20厘米宽的断片,在盐水雾室中进行老化处理。
试样经受的处理条件如下:
暴露时间 20到40天
盐水浓度 5%氯化钠水溶液
雾密度 在80平方厘米面积上
1.5毫升/时
室内温度 45℃
按此方式老化后,除去断片中形成胎面的弹性材料以便回收含有小帘布(研究对象)的缓冲结构层,注意小帘布与它们掺入的弹性材料的粘结特点和构成小帘布的金属丝中腐蚀的存在。
对于未在盐水雾室中老化的断片记录类似的数据,即,由硫化轮胎本身记录数据。
测定粘结值时,从缓冲层织物小条中撕下3个小帘布,每个帘布由一个小帘布与相邻的小条隔开,保持撕裂角恒定为90度。
记录的数据列在表5。
表5
粘结力 覆盖度 腐蚀迹象
带有帘布A,B,C的缓冲
层的轮胎,未在盐水雾 11牛顿 4 无
水中处理
带有帘布A,B,C的缓冲
层的轮胎,在盐水雾室 9牛顿 4 无
中处理20天
带有帘布A,B,C缓冲层
的轮胎,在盐水雾室中 6牛顿 3 无
处理40天
带有N2帘布缓冲层的轮
胎,未经盐水雾室处理 8牛顿 4 无
带有N2帘布缓冲层的轮
胎,在盐水雾室中处理 6牛顿 3 无
20天
带有N2帘布缓冲层的轮
胎,在盐水雾室中处理 3牛顿 1 痕量
40天
前面列出的从小块中抽拉试验(ASTM D2229-80)得到的粘结力值和刚刚列出的对护胎层织物小条撕裂试验的数值之间的差别是由于所进行的试验类型不同。
总之,根据所有这些试验结果,由根据本发明的金属丝制成的小帘布在掺入弹性材料中之后,显示出比用镀黄铜金属丝制成的小帘布更好的粘结性和耐腐蚀性。
Claims (14)
1、一种用来增强弹性材料制品的金属丝,带有由两个径向上叠合排列的同心层构成的镀层,两层均由选自锌-钴合金和锌-镍合金的合金制成,其特点在于,构成径向内镀层的合金的锌含量高于90%,构成径向外镀层的合金含镍或含钴量大于50%。
2、根据权利要求1的金属丝,其特点在于,径向内镀层由锌和钴的合金构成。
3、根据权利要求2的金属丝,其特点在于,径向内镀层由锌含量高于90%的锌-钴合金构成,径向外镀层由镍含量在70%和100%之间(首尾值包括在内)的锌-镍合金构成。
4、根据权利要求1的金属丝,其特点在于,径向内镀层由锌含量高于90%的锌-钴合金构成,径向外镀层由钴含量在70%和90%之间(首尾值包括在内)的锌-钴合金构成。
5、根据权利要求3和4的金属丝,其特点在于,径向内镀层中的钴含量最好低于5%。
6、根据权利要求3和4的金属丝,其特点在于,径向更靠内镀层的钴含量最好不超过2%。
7、网状弹性材料混合物形式的制品,其中掺加着带有镀层的增强用金属丝,镀层由彼此径向叠合的两个同心层构成,两层均由选自锌-钴合金和锌-镍合金的合金制成,该制品的特点在于,构成径向内镀层的合金的锌含量高于90%,构成径向外镀层的合金含镍或含钴量超过50%。
8、根据权利要求7的制品,其特点在于,增强金属丝的径向内镀层由锌-钴合金构成。
9、根据权利要求7的制品,其特点在于,增强金属丝的径向内镀层由锌含量高于90%的锌-钴合金构成,金属丝的径向外镀层由镍含量在70%和100%(首尾值包括在内)之间的锌-镍合金构成。
10、根据权利要求7的制品,其特点在于,增强金属丝的径向内镀层由锌含量高于90%的锌-钴合金构成,金属丝的径向外镀层由钴含量在70%和90%之间(首尾值包括的内)的锌-钴合金构成。
11、掺加带镀层的增强金属丝的汽车轮胎,该镀层由径向上彼此叠合排列的两个同心层构成,两层均由选自锌-钴合金和锌-镍合金的合金构成,所述轮胎的特点在于,构成径向更靠内镀层的合金的锌含量高于90%,构成径向更靠外镀层的合金的含镍或含钴量高于50%。
12、根据权利要求11的轮胎,其特点在于,增强金属丝的径向内镀层由锌-钴合金构成。
13、根据权利要求11的轮胎,其特点在于,增强金属丝的径向内镀层由锌含量高于90%的锌-钴合金构成,金属丝的径向外镀层由镍含量在70%和100%之间(首尾值包括在内)的锌-镍合金构成。
14、根据权利要求11的轮胎,其特点在于,增强金属丝的径向内镀层由锌含量高于90%的锌-钴合金构成,金属丝的径向外镀层由钴含量在70%和90%之间(首尾值包括在内)的锌-钴合金构成。
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BR (1) | BR9203578A (zh) |
CA (1) | CA2077784C (zh) |
DE (1) | DE69223214T2 (zh) |
ES (1) | ES2112283T3 (zh) |
IT (1) | IT1251401B (zh) |
RU (1) | RU2074269C1 (zh) |
TR (1) | TR26391A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106133195A (zh) * | 2014-03-29 | 2016-11-16 | 戴姆勒股份公司 | 用于汽车的构件、特别是结构构件,以及制造构件的方法 |
CN110722963A (zh) * | 2019-10-28 | 2020-01-24 | 厦门银丰科技有限公司 | 一种汽车天窗用遮阳帘卷簧及其制备方法 |
Families Citing this family (10)
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DE3635121B4 (de) * | 1985-10-15 | 2004-03-04 | Bridgestone Corp. | Verfahren zur Herstellung eines gummiartigen Verbundmaterials |
IT1273334B (it) * | 1994-02-24 | 1997-07-08 | Pirelli | Filo metallico trattato superficialmente per renderlo adatto all'impiego in elementi compositi in materiale elastomerico e procedimento per la sua realizzazione |
FR2725730A1 (fr) * | 1994-10-12 | 1996-04-19 | Michelin & Cie | Fil en acier inoxydable pour renforcer le sommet des enveloppes de pneumatiques |
IT1277689B1 (it) * | 1995-12-21 | 1997-11-11 | Pirelli | Cordicella metallica di rinforzo da impiegarsi particolarmente in manufatti compositi a matrice elastomerica procedimento ed apparato |
DE19615134C2 (de) * | 1996-04-17 | 2003-04-17 | Continental Ag | Haftvermittlersubstanz zwischen vulkanisierbarem Polymer und metallischem Festigkeitsträger, Verfahren zu deren Aufbringung sowie deren Verwendung |
DE69903588T2 (de) * | 1998-03-27 | 2004-03-18 | Pirelli Pneumatici S.P.A. | Oberflächenbehandeltes Metallkomponent für die Verstärkung von Strukturen für Produkte aus vulkanisiertem elastomerem Material und daraus hergestellter Gegenstand |
BR9904763B1 (pt) * | 1998-10-28 | 2010-02-23 | processo para produzir um fio metÁlico, e, fio metÁlico, utilizado como um elemento de reforÇo em pneus. | |
FR2864556B1 (fr) | 2003-12-24 | 2006-02-24 | Michelin Soc Tech | Cable a couches pour armature de carcasse de pneumatique |
US20060121302A1 (en) * | 2004-12-07 | 2006-06-08 | Erickson Gary C | Wire-arc spraying of a zinc-nickel coating |
EP2233611A1 (de) * | 2009-03-24 | 2010-09-29 | MTV Metallveredlung GmbH & Co. KG | Schichtsystem mti verbesserter Korrosionsbeständigkeit |
Family Cites Families (18)
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US2296838A (en) * | 1937-11-01 | 1942-09-29 | Nat Standard Co | Rubber adherent metal |
NL7702643A (nl) * | 1977-03-11 | 1978-09-13 | Akzo Nv | Voorwerp bekleed met een metaallegering, waaraan elastomeer materiaal is gehecht, alsmede werkwijze voor het vervaardigen van dat voorwerp. |
GB1598388A (en) * | 1978-05-26 | 1981-09-16 | Bekaert Sa Nv | Steel wire reinforcing elements |
US4226918A (en) * | 1978-08-03 | 1980-10-07 | National-Standard Company | Rubber adherent ternary Cu-Zn-Ni Alloy coated steel wires |
FR2445764A1 (fr) * | 1979-01-05 | 1980-08-01 | Bekaert Sa Nv | Nouveaux elements a base de fils d'acier pour le renforcement de compositions de caoutchouc |
JPS59162292A (ja) * | 1983-03-05 | 1984-09-13 | Sumitomo Metal Ind Ltd | 塗装後耐食性にすぐれた複層メツキ鋼板 |
JPS6050195A (ja) * | 1983-08-30 | 1985-03-19 | Nippon Steel Corp | めっき層濃度傾斜型Ζn合金めつき鋼板 |
US4446198A (en) * | 1983-09-08 | 1984-05-01 | The Goodyear Tire & Rubber Company | Copper-zinc-iron ternary alloy coated steel wire reinforcers in tires |
US4659631A (en) * | 1984-05-17 | 1987-04-21 | Sumitomo Metal Industries, Ltd. | Corrosion resistant duplex plated sheet steel |
CA1258999A (en) * | 1984-09-13 | 1989-09-05 | Thomas W. Starinshak | Quaternary brass alloy coated steel element and rubber reinforced therewith |
GB8426746D0 (en) * | 1984-10-23 | 1984-11-28 | Bekaert Sa Nv | Ferrous substrate |
GB8500323D0 (en) * | 1985-01-07 | 1985-02-13 | Bekaert Sa Nv | Steel reinforcing elements |
DE3635121B4 (de) * | 1985-10-15 | 2004-03-04 | Bridgestone Corp. | Verfahren zur Herstellung eines gummiartigen Verbundmaterials |
US4828000A (en) * | 1986-10-31 | 1989-05-09 | N. V. Bekaert S.A. | Steel substrate with brass covering layer for adhesion to rubber |
IT1225871B (it) * | 1987-03-02 | 1990-12-07 | Pirelli | Miglioramenti ai fili metallici per rinforzo di materiali elastomerici |
WO1989003901A1 (en) * | 1987-10-26 | 1989-05-05 | Sumitomo Electric Industries, Ltd. | Metal and composite thereof with rubber |
US4746408A (en) * | 1987-11-05 | 1988-05-24 | Whyco Chromium Company, Inc. | Multi layer corrosion resistant coating |
DE69012132T2 (de) * | 1989-07-21 | 1995-01-19 | Bekaert Sa Nv | Stahlgegenstand für verstärkung von elastomeren. |
-
1991
- 1991-09-09 IT ITMI912376A patent/IT1251401B/it active IP Right Grant
-
1992
- 1992-08-28 KR KR1019920015575A patent/KR100264508B1/ko not_active IP Right Cessation
- 1992-09-02 AU AU22044/92A patent/AU661010B2/en not_active Ceased
- 1992-09-04 TR TR92/0871A patent/TR26391A/xx unknown
- 1992-09-07 JP JP23850492A patent/JP3163178B2/ja not_active Expired - Fee Related
- 1992-09-08 CN CN92110351A patent/CN1039138C/zh not_active Expired - Fee Related
- 1992-09-08 EP EP92115311A patent/EP0536545B1/en not_active Expired - Lifetime
- 1992-09-08 RU SU925052725A patent/RU2074269C1/ru not_active IP Right Cessation
- 1992-09-08 AT AT92115311T patent/ATE160312T1/de not_active IP Right Cessation
- 1992-09-08 DE DE69223214T patent/DE69223214T2/de not_active Expired - Fee Related
- 1992-09-08 ES ES92115311T patent/ES2112283T3/es not_active Expired - Lifetime
- 1992-09-09 US US07/942,263 patent/US5338620A/en not_active Expired - Lifetime
- 1992-09-09 BR BR929203578A patent/BR9203578A/pt not_active IP Right Cessation
- 1992-09-09 CA CA002077784A patent/CA2077784C/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106133195A (zh) * | 2014-03-29 | 2016-11-16 | 戴姆勒股份公司 | 用于汽车的构件、特别是结构构件,以及制造构件的方法 |
CN110722963A (zh) * | 2019-10-28 | 2020-01-24 | 厦门银丰科技有限公司 | 一种汽车天窗用遮阳帘卷簧及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
RU2074269C1 (ru) | 1997-02-27 |
ITMI912376A1 (it) | 1993-03-09 |
ES2112283T3 (es) | 1998-04-01 |
US5338620A (en) | 1994-08-16 |
EP0536545B1 (en) | 1997-11-19 |
IT1251401B (it) | 1995-05-09 |
DE69223214D1 (de) | 1998-01-02 |
TR26391A (tr) | 1995-03-15 |
KR930006250A (ko) | 1993-04-21 |
AU661010B2 (en) | 1995-07-13 |
JP3163178B2 (ja) | 2001-05-08 |
EP0536545A1 (en) | 1993-04-14 |
ATE160312T1 (de) | 1997-12-15 |
DE69223214T2 (de) | 1998-05-14 |
ITMI912376A0 (it) | 1991-09-09 |
CA2077784A1 (en) | 1993-03-10 |
AU2204492A (en) | 1993-03-11 |
CN1039138C (zh) | 1998-07-15 |
BR9203578A (pt) | 1993-04-13 |
KR100264508B1 (ko) | 2000-09-01 |
JPH05195459A (ja) | 1993-08-03 |
CA2077784C (en) | 2003-05-13 |
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