CN1336967A - 用于燃料罐的涂有铬酸盐的表面处理钢板和其制造方法 - Google Patents
用于燃料罐的涂有铬酸盐的表面处理钢板和其制造方法 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 69
- 239000010959 steel Substances 0.000 title claims abstract description 69
- 239000002828 fuel tank Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 55
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 55
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 54
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000077 silane Inorganic materials 0.000 claims abstract description 34
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 13
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 13
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000008119 colloidal silica Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 68
- 229910052804 chromium Inorganic materials 0.000 claims description 48
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- 238000007747 plating Methods 0.000 claims description 47
- 239000003351 stiffener Substances 0.000 claims description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 68
- 230000007797 corrosion Effects 0.000 abstract description 68
- 239000000446 fuel Substances 0.000 abstract description 29
- 239000010960 cold rolled steel Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004848 polyfunctional curative Substances 0.000 abstract description 4
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 229960002050 hydrofluoric acid Drugs 0.000 abstract 1
- SHHGHQXPESZCQA-UHFFFAOYSA-N oxiran-2-ylmethylsilicon Chemical compound [Si]CC1CO1 SHHGHQXPESZCQA-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 42
- 238000000576 coating method Methods 0.000 description 34
- 239000011248 coating agent Substances 0.000 description 33
- 150000003839 salts Chemical class 0.000 description 24
- 229910000990 Ni alloy Inorganic materials 0.000 description 16
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- 238000002360 preparation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- 229910000851 Alloy steel Inorganic materials 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
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- 229910000648 terne Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910020220 Pb—Sn Inorganic materials 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- GBSWEJRAVNWKCB-UHFFFAOYSA-N C12=C(N=C(N=C2)N2CCNCC2)C(NC2=CC(=C(C=C2)OC2=CC=C3C(=C2)N=CN3C)C)=NC=N1 Chemical compound C12=C(N=C(N=C2)N2CCNCC2)C(NC2=CC(=C(C=C2)OC2=CC=C3C(=C2)N=CN3C)C)=NC=N1 GBSWEJRAVNWKCB-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- -1 zincio Chemical class 0.000 description 1
Classifications
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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/37—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds
- C23C22/38—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also hexavalent chromium compounds containing also phosphates
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
- B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
- B60K15/03—Fuel tanks
- B60K2015/03032—Manufacturing of fuel tanks
- B60K2015/03039—Manufacturing of fuel tanks made of a combination of non metallic and metallic materials
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
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- Metallurgy (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
本发明涉及具有优良的耐表面腐蚀性和耐燃料腐蚀性和接缝加工性的涂有铬酸盐的表面处理的钢板、和用于制备表面处理钢板的铬酸盐溶液。具体地,本发明的铬酸盐溶液包括(a)一种主溶液,由加入50-80重量%的磷酸、20-40%重量氢氟酸、300-2000重量%胶体氧化硅、5-15%重量的硫酸、25-40%重量的磷酸钠而制备,以具有0.4-0.8三价铬的比率和7-50g/l的溶解的铬的铬溶液中的铬计;和(b)一种硬化剂水溶液,包括2-10%重量一种环氧硅烷或缩水甘油硅烷,以总硬化剂溶液计,把pH控制在2-3之间,把10-60%重量的所述的硬化剂水溶液加入到主溶液中。把铬酸盐溶液涂布在镀有锌/锌基合金的钢板上,并在140-250℃下烘烤所述的涂有铬酸盐溶液的钢板,来制备用于汽车燃料罐的表面处理钢板。
Description
发明背景
(a)发明领域
本发明涉及用于汽车燃料罐的无铅表面处理的钢板、更具体地,涉及具有优良的耐表面腐蚀性和耐燃料腐蚀性和接缝加工性的涂有铬酸盐的表面处理的钢板,及其制造方法,
(b)相关技术的描述
通常,要求储存汽车燃料的燃料罐应在暴露于环境中的外表面上是耐腐蚀的(下面称为“耐表面腐蚀性”),以及在其与燃料接触的内表面上是耐腐蚀的(下面称为“耐燃料腐蚀性”)。
燃料罐的制备通常是把钢板压制成形杯状的上部或下部罐体,并通过耐焊接法如点焊或缝焊、或结合法如锡焊或钎焊,把上下体彼此焊接在一起。在这方面,由于两部分在燃料罐中彼此焊接,要求用于制成燃料罐的钢板具有良好的焊接性和良好的加工性。
镀有铅锡合金的冷轧钢板的镀铅锡合金钢板广泛用作燃料罐的钢板。然而,由于含有引起环境污染的铅,镀铅锡合金钢板的用途受到限制。
韩国专利申请97-703448和日本专利公开开9-59783公开了可代替镀铅锡合金钢板的无铅表面处理钢板。上述发明涉及在镀锌镍(Zn-Ni)合金钢板上的特别的涂布铬酸盐溶液。然而,上述技术要求在处理铬酸盐之前在锌镍合金镀层上的微小裂缝成形法,因此制造法复杂。另外,在这种结构中,甚至在与燃料中所含的最小量的水气接触中铬容易洗脱,这就导致燃料的耐腐蚀性降低。
为了解决这些问题,本发明提供了用于表面处理钢板的铬酸盐溶液,该处理钢板不需要在镀层下形成微小裂缝并可防止铬在国际申请WO00/32843中的铬的洗脱。
当制造燃料罐时,由于汽车公司把表面处理钢板用于燃料罐来各方面地开发汽车的外观,提高了焊合加工的可能性。当燃料罐用焊合加工来制造时,进行焊合处理的表面处理的钢板的涂层形成接缝,另外涂层剥离。
另外,最近汽车公司有用镀熔融锌板来代替电镀钢板的趋势,以降低成本并提高车身的耐表面腐蚀性。然而,镀熔融锌钢板不适宜于用作汽车的燃料罐,这是由于其具有如在焊合加工的涂层处的裂缝或剥落的问题,即使其具有良好的耐表面腐蚀性。
因此,需要开发铬酸盐溶液和处理其的方法,其同时满足耐表面腐蚀性和耐燃料腐蚀性和焊合加工性。
发明概述
因此,本发明解决了上述问题。本发明提供了一种无铅的涂有铬酸盐的表面处理钢板,其可防止焊合加工时的涂层的裂缝,从而提高了加工后的耐表面腐蚀性和耐燃料腐蚀性。
本发明的另一个目的是提供用于制造涂有铬酸盐的表面处理钢板的铬酸盐溶液,其可提高加工后的耐表面腐蚀性和耐燃料腐蚀性。
本发明的另一个目的是提供粘接到镀熔融锌钢板上的并可防止由于在焊合加工时压机平面之间由于磨损而出现的裂缝或剥落的铬酸盐溶液。
本发明的另一个目的是提供一种无铅的涂有铬酸盐层的表面处理钢板的方法,其加工后具有优良的耐表面腐蚀性和耐燃料腐蚀性。
为了达到上述目的,本发明提供一种树脂溶液,包括:(a)一种主溶液,由加入50-80重量%的磷酸、20-40%重量氢氟酸、300-2000重量%胶体氧化硅、5-15%重量的硫酸、25-40%重量的磷酸钠而制备,以具有0.4-0.8三价铬的比率和7-50g/l的溶解的铬的铬溶液中的铬计;和(b)一种硬化剂水溶液,包括2-10%重量一种环氧硅烷或缩水甘油硅烷,以总硬化剂溶液计,把pH控制在2-3之间,把10-60%重量的所述的硬化剂水溶液加入到主溶液中。其中,由磷酸控制所述硬化剂水溶液的pH。
为了达到上述目的,本发明提供一种制造用于燃料罐的表面处理钢板的方法,包括以下步骤;把锌/锌基合金电镀在低碳含量钢上;把 1的铬酸盐溶液涂布在镀有锌/锌基合金的钢板上,使得干燥后具有30-150mg/m2的铬含量的涂布层;并在140-250℃下烘烤所述的涂有铬酸盐溶液的钢板。其中,所述电镀步骤包括在电镀或熔融状态把锌/锌基合金吸入钢板上。
为了达到上述目的,本发明提供了一种无铅的涂有铬酸盐溶液的表面处理钢板。
根椐本发明,可提供涂有铬酸盐溶液的无铅表面处理钢板,该铬酸盐溶液紧密地粘附在镀熔融锌层或锌/锌基合金电镀层上,从而其可促进钢板和涂层之间在焊合接加工时的粘附,并提高耐表面腐蚀性和耐燃料腐蚀性,甚至在加工后也如此。
附图简述
优选实施方案的描述
参照附图介绍本发明优选的实施方案。
本发明的无铅表面处理钢板如下制备:电镀锌或锌-镍合金、或把熔融的锌镀在冷轧钢板上,并用电镀或镀熔融的锌来把铬酸盐溶液涂布在上这钢板上。
在本发明中把具有低于或等于0.03%碳含量的低碳钢板用作冷轧钢板。
下面,详细介绍用于铬酸盐层的铬酸盐溶液。
用于本发明的铬酸盐溶液的特性为:
首先,为了保持涂布的铬酸盐层和锌或锌合金层之间的安全粘接,最佳化加入到铬酸盐溶液中的硬化剂含量。因此,当加工涂有铬酸盐层的表面处理钢板时,可明显防止铬酸盐涂层的破坏。因此,没必要如现有技术那样在镀层表面上形成微小的裂缝,从而工艺变得简单,并降低了成本。
第二,通过明显降低6价铬的洗脱同时提高了铬酸盐涂层的疏水性,获得了优良的耐燃料腐蚀性。
第三,由于向铬酸盐溶液中加入了添加剂而改善了铬酸盐层的结构,本发明的表面处理钢板可在加工后保持优良的耐表面腐蚀性和耐燃料腐蚀性。
本发明的铬酸盐溶液包括主溶液和硬化剂溶液。
除了铬的水溶液外,主溶液还包括磷酸、氢氟酸、胶体氧化硅、硫酸和磷酸钠作为添加剂,其中加入磷酸钠来改善涂层的结构。另外,硬化剂溶液包括环氧硅烷或缩水甘油硅烷水溶液。
如下制备主溶液中的铬水溶液作为主要组分。
首先,把70-200g/l的无水铬酸加入到蒸馏水中并溶解。然后,把乙二醇加入到溶解的铬酸盐中,并把6价的铬还原到三价的铬,从而三价的铬与总铬之比(还原比)为0.4-0.8。当还原比小于0.4时,不能通过三价铬来得到耐表面腐蚀性的效果,并且当溶解的6价铬增加时洗脱的铬的量增加。另外,当还原比大于0.8时,溶液变成凝胶,从而降低了溶液的稳定性。
因此,通过向铬的水溶液中加入蒸馏水来把铬的浓度设定为7-50g/l。限制铬的浓度的原因为加入到钢板上的铬的含量。在本发明中当把铬酸盐涂布在镀钢板的表面上时,用辊涂法。当用辊涂法时,粘附到钢板上的铬的含量取决于辊的旋转速率和加在辊之间的压力。因此,考虑这些性能,需要制备形成最佳涂层的溶液。当铬水溶液中的铬含量低于7g/l时,粘附到钢板上的铬的量不足的,当大于50g/l时,表面外观不好,且溶液的稳定性降低。
为了改善如上制备的铬酸盐溶液的材料性能,加入磷酸、氢氟酸、胶体氧化硅和硫酸。
磷酸的含量优选为50-80%重量,以铬组分计。若磷酸低于50%重量,溶液性能和表面性能的改善效果不足。若磷酸大于80%重量,还原比提高,从而溶液的稳定性降低,并且过量的磷酸降低耐表面腐蚀性。
加入氢氟酸来改善耐表面腐蚀性并涂层的均匀性。若加入的氢氟酸以铬组分计小于20%重量,耐表面腐蚀性不足,但超过40%重量,在溶液中出现沉淀物,从而溶液的稳定性降低。因此,氢氟酸的含量优选为20-40%重量。
优选加入以铬组分计300-2000%重量的在胶体状态pH2-4的氧化硅作为氧化硅。氧化硅在烘烤时形成交联键,从而防止在基体金属上形成氧化锌。另外,因为氧化硅是疏水的,其可提高表面耐水性并改善涂层的粘附性。然而,若氧化硅小于300%重量,上述效果不充分,而若氧化硅大于2000%重量,则溶液的稳定性和涂层的粘附性降低。
硫酸通过调节溶液的颜色可提高钢板的表面性能。另外,它可通过改善溶液的流动来提高溶液的稳定性。若以铬组分计硫酸低于5%重量,则表面材料性能的效果降低,而大于15%重量时,溶液的稳定性和耐表面腐蚀性降低。
本发明主溶液的制备为:向铬溶液中加入上述组分,另外加入如下所述的磷酸钠,并混合它们。
加入磷酸钠的原因是改善铬涂层的材料性能。即,磷酸钠可防止涂层在焊合加工时出现裂缝,从而在加工后可保持耐表面腐蚀性和耐燃料腐蚀性。若磷酸钠小于25%重量,改善涂层结构的效果降低。相反,若磷酸钠高于40%重量,在溶液中出现沉淀,从而溶液的稳定性降低。因此,磷酸钠的量优选25-40%重量。
把硬化剂溶液加入到如上制备的主溶液中来制备本发明的铬酸直溶液。
加入到主溶液中的硬化剂促进铬酸盐的交联,从而形成了铬涂层并同时保持铬酸盐涂层和基体金属的粘附性。因此,考虑镀在钢板上的锌或锌合金的种类和上述效果,选择硬化剂种类是重要的。考虑上面所述的,本发明的硬化剂包括环氧硅烷和缩水甘油基硅烷。
首先,制备包括环氧硅烷的硬化剂溶液的方法如下:
包括环氧硅烷的硬化剂的制备为:把2-10%重量的环氧硅烷加入到蒸馏水中并加入少量磷酸来防止与主溶液混合时胶凝。因此,把硬化剂溶液的pH设定到类似于主溶液的pH,2~3。有多种方法设定pH。其中,优选加入磷酸。若加入的环氧硅烷低于2%重量,铬交联反应很小发生。若加入的环氧硅烷多于10%重量,溶液的稳定性降低。
若加入的含有环氧硅烷的硬化剂溶液以主溶液计小于10%,交联反应进行得不充分。若加入的含环氧硅烷的硬化剂溶液大于50%重,则溶液的稳定性降低。因此,以主溶液计加入的含有环氧硅烷的硬化剂溶液的量优选为10-50%重量。
然后,制备包括缩水甘油硅烷的硬化剂溶液的方法如下:首先,制备包括环氧硅烷的硬化剂溶液的方法如下:
包括缩水甘油硅烷的硬化剂的制备为:把2-10%重量的缩水甘油硅烷加入到蒸馏水中并加入少量磷酸来防止与主溶液混合时胶凝。因此,把硬化剂溶液的pH设定到类似于主溶液的pH,2-3。若加入的缩水甘油硅烷低于2%重量,形成铬酸盐交联键所需的硬化剂的量增加并且铬的总量降低,从而在铬涂布时加入到钢板上的铬的量降低。若加入的缩水甘油硅烷多于10%重量,溶液的稳定性降低,从而在溶液中出现沉淀。
若加入的含有缩水甘油硅烷的硬化剂溶液以主溶液计小于20%,在适宜的温度和时间下不出现交联反应。因此,铬酸盐变成大分子并不形成涂层。然后,当加热和冷却时,大多数铬盐洗脱,结果耐表面腐蚀性明显降低。若加入的含缩水甘油硅烷的硬化剂溶液大于60%重量,则铬酸盐溶液中的硬化剂组分进行铬还原,结果溶液的稳定性降低。因此,以主溶液计加入的含有缩水甘油硅烷的硬化剂溶液的量优选为20-60%重量。
特别地,加入到硬化剂中的缩水甘油硅烷在用铬酸盐处理镀熔融锌钢板时增强了镀层和铬涂层之间的粘附性。这是因为缩水甘油硅烷提高与熔化的镀锌板的反应性,其防止涂层剥落或通过溶剂渗透的表面洗脱。
通过把铬酸盐涂布在锌基合金电镀钢板或镀熔融锌钢板上,如上制备的铬酸盐溶液可用作燃料罐的钢板。另外,可把树脂涂布在燃料罐的铬酸盐涂层的上侧。
因为本发明的镀锌钢板包括镀锌基合金钢板,如Zn或Zn-Ni,本发明不限于说明书中例举的锌基合金。
形成铬酸盐涂层的方法包括反应型、电解液型、和涂布型。然而,反应型和电解液由于其使六价铬溶易洗脱而出现了水污染。因此,考虑耐表面腐蚀性和最少的污染,优选涂布型。
三步辊涂器可用于把铬酸盐溶液涂布在镀锌/锌基合金钢板上。通过每个辊的驱动方向、辊动速率、和每个辊的粘附压力来调节粘附到钢板上的铬酸盐的量。
以在镀钢板上的干燥后的涂层量计,铬酸盐的量优选为30-150mg/m2。若其量小于30mg/m2,耐表面腐蚀性不足,而若其量大于150mg/m2,不经济且铬洗脱,降低了涂层的性能。
涂有铬酸盐的钢板的烘烤温度优选为140-250℃。若烘烤温度低于140℃,涂层的硬化反应不充分。相反,若烘烤温度高于250℃,在其表面上出现裂缝,从而降低了耐表面腐蚀性。
现在提出优选的实施方案以有助于理解本发明。仅为了更清楚理解本发明提供下面的实施方案,但本发明决不限于此。
实施方案
实施例1
根椐本发明的方法以表1的组成制备铬酸盐溶液的实施例。
表1
实施例 | 铬浓度(还原比0.5)(g/l) | 磷酸(重量%) | 硫酸(重量%) | 氢氟酸(重量%) | 磷酸钠(重量%) | 胶体氧化硅(重量%) | 环氧硬化剂(重量%) |
比较例1 | 24 | 60 | - | 25 | - | 800 | 30 |
比较例2 | 60 | 6 | 25 | - | 800 | 30 | |
比较例3 | 6 | 25 | - | 800 | 30 | ||
比较例4 | 60 | 6 | 25 | - | - | 30 | |
比较例5 | 60 | 6 | - | - | 800 | 30 | |
比较例6 | 60 | 6 | 25 | - | 800 | - | |
实施例1 | 60 | 6 | 25 | 35 | 800 | 30 | |
实施例2 | 10 | 80 | 11 | 30 | 40 | 1300 | 20 |
实施例3 | 24 | 60 | 8 | 40 | 30 | 1000 | 50 |
实施例4 | 50 | 13 | 35 | 33 | 1500 | 40 | |
实施例5 | 70 | 10 | 30 | 27 | 1800 | 30 |
表1中的比较例2与本发明人提交的国际专利公开WO00/32843的组成相同。作为硬化剂的环氧硅烷是由日本Shinetsu Kagaku公司制备的产品。
把如上制备的铬酸盐溶液用三步辊涂器涂布锌或锌-镍合金电镀钢板上。镀在钢板上的锌或锌-镍合金板上的镀含量示于表2。涂布在电镀钢板锌的铬酸盐的铬的量以50-150mg/m2,以干燥后的干燥的涂层计。
在140-250℃下烘烤涂有铬酸盐溶液的镀钢板。
如下测定用上述方法制备的表面处理的钢板的耐表面腐蚀性和耐燃料腐蚀性。
根椐日本工业标准测试(JIS Z2371)用盐喷测试来测定耐表面腐蚀性。盐喷测试中所用的测试件用1kg/m2的压力和1ml/小时在35℃洒5%NaCl溶液到样品的表面上。在钢板的平面上和加工部分处重复测定耐表面腐蚀性。把切成尺寸为75×150mm的样品作为平面放在盐喷测试器中并加以测量。然后,把试样冲成95mmφ并形成直径为50mm、长度为25mm的杯作为加工件。在外部件中测定耐表面腐蚀性。经过测定时间后,从测试器中取出试样、用蒸馏水洗涤并干燥。根椐出现的锈的量,分类耐表面腐蚀性的级别。
测试耐表面腐蚀性的另一方法是循环腐蚀测试。循环腐蚀测试包括喷4小时NaCl溶液、在60℃下干燥4小时并在95%湿度和50℃下加湿18小时。上述循环是一个循环/1天。如下测定耐表面腐蚀性并示于表2中。
把面对燃料的平面切成95mmφ并形成直径为50mm、高度为25mm的杯。把包括常规汽油30ml和5%氯化钠(NaCl)水溶液的燃料加入杯中,测定耐燃料腐蚀性。
为了模拟汽车的驱动状况,使用摇动设备,从而在杯中所含的溶液处于摇动状态。把杯了静止3个月。然后取出杯子、用蒸馏水洗涤并干燥。根椐出现的锈的量,同耐表面腐蚀性一样分类耐燃料腐蚀性的级别,并列于表2中。
表2
实施例号 | 铬酸盐处理的量 | 耐表面腐蚀性 | 耐燃料腐蚀性 | |||
SST(720小时) | CCT(30个循环) | 3个月 | ||||
平面 | 处理a | 平面e | 处理a | |||
比较实施例A | 镀熔融Pb-Sn合金钢板(105g/m2) | | | × | × | ○ |
比较实施例B | Nn-Ni合金电镀(20g/m2)+比较例2(80mg/m2) | | | | ○ | |
实施例A-1 | Nn-Ni合金电镀(20g/m2)+实施例1(80mg/m2) | | | | | |
实施例A-2 | 纯锌电镀(40g/m2)+实施例1(50mg/m2) | ○ | | ○ | | |
实施例B | Nn-Ni合金电镀(20g/m2)+实施例2(50mg/m2) | | | | | |
实施例C | Nn-Ni合金电镀(20g/m2)+实施例3(130mg/m2) | | | | | |
实施例D | Nn-Ni合金电镀(20g/m2)+实施例4(80mg/m2) | | | | | |
实施例E | Nn-Ni合金电镀(20g/m2)+实施例5(100mg/m2) | | | | | |
实施例A-3 | Nn-Ni合金电镀(20g/m2)+实施例1(130mg/m2) | | | | | |
实施例A-4 | Nn-Ni合金电镀(20g/m2)+实施例1(100mg/m2) | | | | | × |
比较实施例C | 纯锌(40g/m2)+特别的铬酸盐(30-50mg/m2) | × | × | × | × | |
比较实施例D | Nn-Ni合金电镀(20g/m2)+特别的 | ○ | | | ○ | × |
比较实施例E | Nn-Ni合金电镀(20g/m2) | × | × | × | × | × |
比较实施例F | 镀锌钢板(20g/m2)+比较例2(10mg/m2) | × | × | × | × | × |
比较实施例G | 镀熔融锌钢板(90g/m2)+比较例2(80mg/m2) | | × | | × | × |
:优良,○:良好,:中等,×;差 |
从表2中可知,实施例A-E中的耐表面腐蚀性和耐燃料腐蚀性优于比较例A、C-G。特别地,用本发明的溶液处理后的实施例A-E耐表面腐蚀性优于用比较例2涂布的情况。表2的特殊铬酸盐溶液使用包括铬浓度为30g/l和还原比为0.8、磷酸10%重量、钴5%和胶体氧化硅50%重量的铬水溶液的溶液。
另外,表1表明:涂有本发明实施例1的实施例A-1至A-4的耐表面腐蚀性和耐燃料腐蚀性优于比较例。另外,涂在纯锌电镀钢板上的实施例A-2的耐表面腐蚀性和耐燃料腐蚀性优于比较例。
实施例2
根椐本发明的方法以表3组成制备铬酸盐溶液的实施例。
表3
实施例号 | 铬浓度(还原比0.5)(g/l) | 磷酸(重量%) | 硫酸(重量%) | 氢氟酸(重量%) | 磷酸钠(重量%) | 胶体氧化硅(重量%) | 硬化剂(重量%) | |
环氧硅烷 | 缩水甘油硅烷 | |||||||
比较例7 | 24 | 60 | 6 | 25 | - | 800 | 30 | |
比较例8 | 60 | - | 25 | - | 800 | 30 | ||
比较例9 | - | 6 | 25 | - | 800 | 30 | ||
比较例10 | 60 | 6 | -5 | - | - | 30 | ||
比较例11 | 60 | 6 | - | - | 800 | 30 | ||
比较例12 | 60 | 6 | 25 | - | 800 | |||
实施例6 | 60 | 6 | 25 | 35 | 800 | 30 | ||
实施例7 | 10 | 80 | 11 | 30 | 40 | 1300 | 20 | |
实施例8 | 24 | 60 | 8 | 40 | 30 | 1000 | 50 | |
实施例9 | 50 | 13 | 35 | 33 | 1500 | 40 | ||
实施例10 | 70 | 10 | 30 | 27 | 1800 | 30 | ||
实施例11 | 30 | 70 | 8 | 35 | 35 | 1000 | 40 | |
实施例12 | 45 | 60 | 6 | 35 | 35 | 800 | 30 |
表3的比较例7与表1中的比较例2相同。作为硬化剂的缩水甘油硅烷是由日本Shinetsu Kagaku公司制备的产品(KBM403)。另外,在本发明中所用的制备底钢板的方法同于实施例1,除了把熔融的锌镀在钢板上。
测定耐表面腐蚀性和耐燃料腐蚀性与实施例1中的相同,表4示出其结果。
实施例号 | 铬酸盐处理的量 | 耐表面腐蚀性 | 耐燃料腐蚀性 | |||
SST(720小时) | CCT(30个循环) | 3个月 | ||||
平面 | 处理a | 平面e | 处理a | |||
比较例H | 镀熔融Pb-Sn合金钢板(105g/m2) | | | × | × | ○ |
比较例I-1 | 镀熔融锌(90g/m2)+比较例7(80mg/m2) | | × | | × | × |
比较例I-2 | 镀熔融锌(90g/m2)+比较例8(80mg/m2) | | × | | × | × |
比较例I-3 | 镀熔融锌(90g/m2)+比较例9(80mg/m2) | | × | | × | × |
比较例I-4 | 镀熔融锌(90g/m2)+比较例10(80mg/m2) | | × | | × | × |
比较例I-5 | 镀熔融锌(90g/m2)+比较例11(80mg/m2) | | × | | × | × |
比较例I-6 | 镀熔融锌(90g/m2)+比较例12(80mg/m2) | | × | | × | × |
实施例F-1 | 镀熔融锌(90g/m2)+实施例6(80mg/m2) | | | | | |
实施例G | 镀熔融锌(90g/m2)+实施例7(50mg/m2) | | | | | |
实施例H | 镀熔融锌(90g/m2)+实施例8(130mg/m2) | | | | | |
实施例I | 镀熔融锌(90g/m2)+实施例9(80mg/m2) | | | | | |
实施例J | 镀熔融锌(90g/m2)+实施例10(100mg/m2) | | | | | |
实施例K | 镀熔融锌(90g/m2)+实施例11(130mg/m2) | | | | | |
实施例L | 镀熔融锌(90g/m2)+实施例12(100mg/m2) | | | | | |
实施例F-2 | 镀熔融锌(90g/m2)+实施例7(130mg/m2) | | | | | |
实施例F-3 | 镀熔融锌(90g/m2)+实施例7(100mg/m2) | | | | | |
比较实施例J | 纯锌(40g/m2)+特别的铬酸盐(30-50mg/m2) | × | × | × | × | |
比较实施例K | Nn-Ni合金电镀(20g/m2)+特别的铬酸盐(80g/m2) | ○ | | | ○ | × |
比较实施例L | Nn-Ni合金电镀(20g/m2) | × | × | × | × | × |
比较实施例M | 镀锌钢板(20g/m2)+比较例7(10mg/m2) | × | × | × | × | × |
比较实施例N | 镀熔融锌钢板(90g/m2)+比较例7(80mg/m2) | | × | | × | × |
:优良,○:良好,:中等,×;差 |
从表4可知,实施例F-L的耐表面腐蚀性和耐燃料腐蚀性优于比较例H-N。特别地,在比较例L-1至L-6中,加入环氧硅烷作为硬化剂。结果,铬酸盐和材料之间的粘附性不足,从而出现剥离且耐表面腐蚀性降低。另外,因为溶剂渗入,耐燃料腐蚀性降低。然而,用本发明的硬化剂的铬酸盐溶液表示出更优良的性能。表4的特殊铬酸盐溶液使用包括铬浓度为30g/l和还原比为0.8、磷酸10%重量、钴5%和胶体氧化硅50%重量的铬水溶液的溶液。
若把本发明的实施例与比较例相比,测定本发明的实施例,表示出良好的耐表面腐蚀性,这是因为在盐喷测试和循环腐蚀测试中白锈出现的面积相对较小。这认为甚至在焊合加工后由于铬酸盐溶液,保持了镀熔融锌钢板的良好耐表面腐蚀性。
特别地,用本发明的铬酸盐溶液处理的镀熔融锌钢板,在加工后由于防止当燃料罐进行焊合加工时涂层的剥离从而具有改善的耐表面腐蚀性和耐燃料腐蚀性。
Claims (7)
1、一种用于制造汽车燃料罐的表面处理钢板的铬酸盐溶液,包括:(a)一种主溶液,由加入50-80重量%的磷酸、20-40%重量氢氟酸、300-2000重量%胶体氧化硅、5-15%重量的硫酸、25-40%重量的磷酸钠而制备,以具有0.4-0.8三价铬的比率和7-50g/l的溶解的铬的铬溶液中的铬计;和
(b)一种硬化剂水溶液,包括2-10%重量一种环氧硅烷或缩水甘油硅烷,以总硬化剂溶液计,把pH控制在2-3之间,
把10-60%重量的所述的硬化剂水溶液加入到主溶液中。
2、权利要求1的用于汽车燃料罐的铬酸盐溶液,其中,由磷酸控制所述硬化剂水溶液的pH。
3、权利要求1的用于汽车燃料罐的铬酸盐溶液,其中,当环氧硅烷加入硬化剂水溶液中时,硬化剂水溶液的含量为10-50%重量,以所述的主溶液计。
4、权利要求1的用于汽车燃料罐的铬酸盐溶液,其中,当缩水甘油硅烷加入硬化剂水溶液中时,硬化剂水溶液的含量为20-60%重量,以所述的主溶液计。
5、一种制造用于汽车燃料罐的表面处理钢板的方法,包括以下步骤:
把锌/锌基合金电镀在低碳含量钢上;
把权利要求1的铬酸盐溶液涂布在镀有锌/锌基合金的钢板上,使得干燥后具有30-150mg/m2的铬含量的涂布层;
在140-250℃下烘烤所述的涂有铬酸盐溶液的钢板。
6、权利要求5的制造用于汽车燃料罐的表面处理钢板的方法,其中,所述电镀步骤包括在电镀或熔融状态把锌/锌基合金吸入钢板上。
7、由权利要求5或6制备的表面处理钢板。
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JP2005290465A (ja) * | 2004-03-31 | 2005-10-20 | Nippon Steel Corp | 耐食性、耐指紋性、溶接性に優れた白色クロメート処理方法及び白色クロメート処理鋼板 |
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