CN107208277B - 燃料罐用钢板 - Google Patents
燃料罐用钢板 Download PDFInfo
- Publication number
- CN107208277B CN107208277B CN201680007528.9A CN201680007528A CN107208277B CN 107208277 B CN107208277 B CN 107208277B CN 201680007528 A CN201680007528 A CN 201680007528A CN 107208277 B CN107208277 B CN 107208277B
- Authority
- CN
- China
- Prior art keywords
- overlay film
- steel plate
- crackle
- fuel
- chemical conversion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 66
- 239000010959 steel Substances 0.000 title claims abstract description 66
- 239000000446 fuel Substances 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 108
- 239000011248 coating agent Substances 0.000 claims abstract description 106
- 208000037656 Respiratory Sounds Diseases 0.000 claims abstract description 71
- 239000000126 substance Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 66
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 229910007567 Zn-Ni Inorganic materials 0.000 claims abstract description 63
- 229910007614 Zn—Ni Inorganic materials 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000002828 fuel tank Substances 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 230000002940 repellent Effects 0.000 claims description 17
- 239000005871 repellent Substances 0.000 claims description 17
- 230000000007 visual effect Effects 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 description 71
- 238000005260 corrosion Methods 0.000 description 71
- 238000000034 method Methods 0.000 description 35
- 239000003502 gasoline Substances 0.000 description 27
- 230000006866 deterioration Effects 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 238000012545 processing Methods 0.000 description 16
- 239000011701 zinc Substances 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 230000002542 deteriorative effect Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 206010011376 Crepitations Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
-
- 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
- B32B1/00—Layered products having a non-planar shape
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/84—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for corrosive chemicals
-
- 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
-
- 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
- C23C22/07—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 phosphates
-
- 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
- C23C22/36—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 phosphates
- C23C22/361—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 phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
-
- 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
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Abstract
本发明的燃料罐用钢板具备:位于铁基体的单面或两面的Zn‑Ni合金镀层;和,位于前述Zn‑Ni合金镀层的上层的无机系无铬化学转化覆膜,前述Zn‑Ni合金镀层具有从该Zn‑Ni合金镀层与前述无机系无铬化学转化覆膜的界面至前述Zn‑Ni合金镀层与前述钢板的界面为止的裂纹,前述无机系无铬化学转化覆膜表面的水接触角为50度以上。
Description
技术领域
本发明涉及燃料罐用钢板。
背景技术
出于最近对环境限制的举动,对不使用有害金属的材料的市场需求提高。因此,汽车领域中,对于作为燃料罐的主流材料的铅-锡合金镀层钢板,向无铅的原材料的转换推进。针对封入有燃料中的内表面耐腐蚀性(以下,也称为“燃料耐腐蚀性”)之类的特异的要求性能,提出了大量汽车内外板中使用有实效的锌系镀层钢板的提案(例如参照以下的专利文献1~专利文献3等)。
利用上述那样的锌系镀层钢板的技术是以铬酸盐处理为前提的,因此,与不使用有害金属的近年来的市场需求不相容。因此,如以下的专利文献4~专利文献9中所记载那样,提出了不使用铬的无铬酸盐的燃料罐用镀锌系钢板。
现有术文献
专利文献
专利文献1:日本特开平5-106058号公报
专利文献2:日本特开平9-324279号公报
专利文献3:日本特开平9-324281号公报
专利文献4:日本特开2004-169122号公报
专利文献5:日本特开2007-186745号公报
专利文献6:日本特开2013-133527号公报
专利文献7:日本特开2013-227646号公报
专利文献8:日本特开2011-38139号公报
专利文献9:WO2007/011008
发明内容
发明要解决的问题
然而,将上述专利文献4~专利文献9中公开的无铬酸盐的燃料罐用镀锌系钢板的燃料耐腐蚀性与以往的利用铬酸盐处理的锌系镀层钢板的燃料耐腐蚀性相比时,更严格的条件下的燃料耐腐蚀性(例如,更长期的耐腐蚀性、由于加工而产生覆膜损伤的情况下的耐腐蚀性等)是不充分的,需要进一步的改良。
例如,上述专利文献4和专利文献5中公开了有机树脂主体的无铬酸盐覆膜。然而,上述有机树脂主体的无铬酸盐覆膜长时间暴露于燃料环境中时,有机树脂由于燃料而溶胀,镀层界面的密合性降低。这样的有机树脂的溶胀推定为耐腐蚀性不足的因素。
上述专利文献6和专利文献7中公开了磷酸系的无机无铬酸盐覆膜。然而,磷酸系无机无铬酸盐覆膜的耐水性未必充分,燃料中存在凝结水的情况下,特别是耐腐蚀性不足。
上述专利文献8中记载了,在具有裂纹的锌-镍合金镀层上形成有无铬酸盐的化学转化处理层。然而,该化学转化处理层是以氨基甲酸酯系水性树脂为主体的,因此,耐腐蚀性得到提高,但不会赋予对劣化汽油的耐腐蚀性。而且其理由如后述那样是由于,该化学转化处理膜中的磷酸、钒、钛、锆赋予对劣化汽油的耐腐蚀性是不充分的。
上述专利文献9中记载了,用包含有机硅化合物的水系金属表面处理剂对锌系镀层钢板进行覆膜而成的钢板。然而,该钢板虽然耐腐蚀性得到提高,但是不会赋予对劣化汽油的耐腐蚀性。
因此,本发明是鉴于上述问题而作出的,本发明的目的在于,提供:在劣化汽油那样的含有有机酸、进而还含有凝结水那样的各种燃料环境下、不使用铅、铬等之类的环境负荷物质就可以实现优异的耐腐蚀性的燃料罐用钢板。
用于解决问题的方案
本发明人等对无铬酸盐锌系镀层钢板的燃料耐腐蚀性的改善进行了研究,结果发现:使锌系镀层为Zn-Ni合金镀层,并且在上述镀层形成规定的裂纹,进而,以无铬化学转化覆膜为无机物主体,在此基础上,对覆膜表面赋予拒水性,从而可以得到显著的改善效果。
基于上述那样的见解而完成的本发明的主旨在于如下所示。
(1)一种燃料罐用钢板,其具备:位于铁基体的单面或两面的至少形成于单面的Zn-Ni合金镀层;和,位于前述Zn-Ni合金镀层的上层的无机系无铬化学转化覆膜,前述Zn-Ni合金镀层具有从该Zn-Ni合金镀层与前述无机系无铬化学转化覆膜的界面至前述Zn-Ni合金镀层与前述钢板的界面为止的裂纹,前述无机系无铬化学转化覆膜表面的水接触角为50度以上。
(2)根据(1)所述的燃料罐用钢板,其中,前述铁基体的单面具有前述Zn-Ni合金镀层和前述无机系无铬化学转化覆膜,与前述单面相反的面不具有前述Zn-Ni合金镀层和前述无机系无铬化学转化覆膜。
(3)根据(2)所述的燃料罐用钢板,其中,不具有前述Zn-Ni合金镀层和前述无机系无铬化学转化覆膜的面的水接触角低于10度。
(4)根据(2)或(3)所述的燃料罐用钢板,其中,不具有前述Zn-Ni合金镀层和前述无机系无铬化学转化覆膜的面的Zn和/或Ni的附着量为0.01~0.5g/m2。
(5)根据(1)~(4)中任一项所述的燃料罐用钢板,其中,前述无机系无铬化学转化覆膜含有:选自硅烷偶联剂、硅烷偶联剂的缩聚物、二氧化硅、硅酸盐、磷酸、磷酸盐中的一种以上;和,选自Ti、Zr、V、Mo、W中的一种以上金属的化合物。
(6)根据(1)~(5)中任一项所述的燃料罐用钢板,其中,前述无机系无铬化学转化覆膜含有拒水剂。
(7)根据(6)所述的燃料罐用钢板,其中,前述拒水剂为选自聚烯烃蜡、硅系树脂、氟系树脂中的1种以上。
(8)根据(1)~(7)中任一项所述的燃料罐用钢板,其中,对前述Zn-Ni合金镀层进行截面观察的情况下,前述裂纹在每100μm的视野中存在有5个以上且50个以下。
(9)根据(8)所述的燃料罐用钢板,其中,对前述Zn-Ni合金镀层进行截面观察而得到的、每100μm的视野中的前述裂纹的个数X个与前述水接触角Y(度)满足以下的(I)式所示的关系。
Y≥-0.18X+56.5···(I)
(10)根据(9)所述的燃料罐用钢板,其中,对前述Zn-Ni合金镀层进行截面观察的情况下,前述裂纹在每100μm的视野中存在有5个以上且低于50个、且裂纹的最大宽度低于0.5μm。
发明的效果
如以上说明,根据本发明,可以提供:在劣化汽油那样的含有有机酸、进而还含有凝结水那样的各种燃料环境下、不使用铅、铬等之类的环境负荷物质就显示出优异的耐腐蚀性的燃料罐用钢板。
附图说明
图1为比较裂纹个数少的情况(裂纹少)与裂纹个数多的情况(裂纹多)示出的、(I)式的关系的说明图。
具体实施方式
以下,对本发明的优选实施方式进行详细说明。
以下详述的本发明涉及对各种燃料的耐腐蚀性优异、不使用铅、铬酸盐处理而对环境良好的、利用锌系镀层钢板的燃料罐用钢板。另外,本发明涉及以汽车、二轮车、生产设备、建筑设备为代表的、封入燃料的罐或上述罐的部件中使用的钢板。
本发明的实施方式的燃料罐用钢板具备:位于铁基体的单面或两面的Zn-Ni合金镀层;和,位于该Zn-Ni合金镀层(以下,也简单称为“镀层”)的上层的、无机系无铬化学转化覆膜(以下,也简单称为“化学转化覆膜”)。
将本发明的实施方式的燃料罐用钢板用于燃料罐用钢板的情况下,将具有Zn-Ni合金镀层和位于该Zn-Ni合金镀层的上层的无机系无铬化学转化覆膜的面(单面)作为燃料罐内表面(以下,称为内表面)。此时,与单面相反的面成为燃料罐外表面(以下,称为外表面)。
本发明的钢板可以在两面均具有Zn-Ni合金镀层。但是,为了使钢板的焊接性良好,优选成为燃料罐外表面的面不具有镀层。另外,例如,钢板用于二轮车用燃料罐那样重视燃料罐外表面的涂装的美观的用途的情况下,为了使涂装外观良好,优选燃料罐外表面不具有镀层。另一方面,钢板用于燃料罐外表面也要求高度的耐腐蚀性的用途的情况下,优选燃料罐外表面具有镀层。本发明的钢板可以根据用途而控制外表面与内表面的镀层的有无。
为了形成在外表面不具有镀层的状态,进行电镀时,可以采用对作为非镀覆面的外侧不进行通电的方法。或可以采用如下方法:进行镀覆后,对作为非镀覆面的外侧利用电化学(例如阳极电解处理)或者机械(例如刷子磨削)的方法来去除镀层。而且,也可以将前述方法组合。
利用前述记载的方法形成的非镀覆面(成为外表面的面)的接触角以水接触角计设为低于10度,更优选设为低于5度。由此涂装性得以改善。为了使前述接触角成为确实的接触角,有效的是,抑制钢板的表面氧化,在这一点上,期望在非镀覆面侧也存在极微量的Zn和/或Ni。其附着量理想的是,优选为0.01~0.3g/m2、更优选为0.01~0.1g/m2。
此处,本实施方式的燃料罐用钢板的母材没有特别限定,只要为作为锌系镀层钢板的母材而一般使用的钢板即可,可以适当利用公知的母材。
在上述钢板的至少单面形成的Zn-Ni合金镀层是至少含有由锌和镍形成的合金的合金镀层。这样的Zn-Ni合金镀层例如可以通过电镀法等公知的镀覆法形成。
上述Zn-Ni合金镀层的特征在于,具有从镀层的表层(换言之,Zn-Ni合金镀层与无铬化学转化覆膜的界面)至铁基体(换言之,作为母材的钢板与Zn-Ni合金镀层的界面)为止的裂纹。另外,形成于Zn-Ni合金镀层的上层的无机系无铬化学转化覆膜的特征还在于,覆膜的表面的水接触角为50度以上。
Zn-Ni合金镀层存在有裂纹时,以铬酸盐处理为前提的情况下,燃料耐腐蚀性提高是熟知的现象。这样的现象在基于进入至裂纹内的铬酸盐覆膜的锚固效果的覆膜密合性的提高、通过预先在镀层存在有裂纹从而加压加工时的新的裂纹产生被抑制的效果等中有说明。推测这样的效果在专利文献8中记载的钢板中也可见。
另一方面,近年来研究的无铬化学转化覆膜中,即使镀层中存在有裂纹,也无法期望显著的燃料耐腐蚀性的提高效果,相反地,燃料耐腐蚀性恶化。认为这是由于,铬酸盐覆膜中存在的Cr6+那样的强力的腐蚀抑制剂不存在。
为了发挥燃料耐腐蚀性、特别是在劣化汽油那样的含有有机酸、此外还含有凝结水的燃料环境下、进而加压加工等过程中覆膜的一部分受到损伤那样的条件下也发挥良好的耐腐蚀性,必须全部具备:在Zn-Ni合金镀层存在有裂纹、无铬化学转化覆膜为无机系、以及化学转化覆膜的表面的水接触角为50度以上。
本实施方式的Zn-Ni合金镀层的裂纹是指,从镀覆表层至铁基体为止的裂纹。裂纹的作用机制在前述那样的、锚固效果和加工时的新生裂纹的抑制的基础上,使显示出拒水性的无机系化学转化覆膜的表面积增加,推定是由于,通过上述表面积的增加,保护镀层、铁基体免受燃料中的腐蚀因子、特别是亲水性的腐蚀因子的效果。需要说明的是,上述裂纹的存在可以通过从截面用扫描型电子显微镜(Scanning Electron Microscope:SEM)等进行观察来确认。
本实施方式的无铬化学转化覆膜必须为无机系的覆膜。无机系的覆膜是指,不排除有机树脂的含有、但有机树脂的含量(相对于覆膜整体的固体成分质量的含量)低于50%、优选为30%以下、更优选为10%以下(包括零),而不是以有机树脂为主体的覆膜。无铬化学转化覆膜以有机树脂为主体的情况下(即,为有机系的覆膜的情况下),有机树脂受到基于燃料中的烃的溶胀作用,镀层与化学转化覆膜之间的密合性降低,并且以镀层的裂纹为起点腐蚀进行。如本实施方式的化学转化覆膜那样,通过设为无机系的覆膜,可以抑制这样的溶胀现象。
本实施方式的化学转化覆膜的表面的水接触角必须为50度以上。通过水接触角成为50度以上,通过与前述镀层的裂纹的效果的协同效果,保护镀层、铁基体免受燃料中的腐蚀因子、特别是亲水性的腐蚀因子,可以得到良好的耐腐蚀性。本实施方式的化学转化覆膜的表面的水接触角优选为55度以上、进一步优选为60度以上。需要说明的是,对于这样的水接触角,上限没有特别限定,优选具有接近作为理论极限的180度的值,但在本实施方式的镀层钢板上能够达到的水接触角的极限是120度左右。上述水接触角可以利用接触角计通过公知的方法来测定。
本实施方式的无机系无铬化学转化覆膜理想的是,含有:选自硅烷偶联剂、硅烷偶联剂的缩聚物、二氧化硅、硅酸盐、磷酸、磷酸盐中的一种以上;和,选自Ti、Zr、V、Mo、W中的一种以上金属的化合物。另外,本实施方式的无机系无铬化学转化覆膜理想的是,含有拒水剂。
此处,本实施方式的拒水剂是指,添加至无机系的化学转化覆膜中,具有增大水接触角的作用的物质。作为上述拒水剂的具体例,可以举出具有C-H键或者C-F键的有机树脂。作为拒水剂的更优选的具体例,可以举出聚烯烃蜡、硅系树脂、氟系树脂等。这些拒水剂以少量(例如相对于化学转化覆膜的固体成分质量的整体为10%以下)的添加可以得到规定的水接触角,因此,不存在本实施方式的化学转化覆膜不是无机系的覆膜的担心。
本实施方式的无机系无铬化学转化覆膜中,重要的是,以化学转化覆膜的表面的水接触角成为50度以上的方式,调整前述拒水剂。
具体而言,化学转化覆膜含有选自硅烷偶联剂、硅烷偶联剂的缩聚物中的一种以上作为主成分的情况下,这些成分具有C-H键,因此,即使不添加拒水剂也容易得到较高的水接触角,但更优选添加拒水剂。作为此时的拒水剂,使用选自聚烯烃蜡、硅系树脂、氟系树脂中的1种以上,相对于固体成分质量的整体可以添加0.1%以上。
另外,化学转化覆膜含有选自二氧化硅、硅酸盐、磷酸、磷酸盐中的一种以上作为主成分的情况下,一般不添加拒水剂时,难以得到规定的水接触角,因此,期望含有拒水剂。作为此时的拒水剂,使用选自聚烯烃蜡、硅系树脂、氟系树脂中的1种以上,相对于固体成分质量的整体可以添加1%以上。
本实施方式的无机系无铬化学转化覆膜的每单面的附着量优选为0.1~2g/m2、更优选为0.3~1g/m2。化学转化覆膜的每单面的附着量低于0.1g/m2时,对劣化汽油的耐腐蚀性有时降低,化学转化覆膜的每单面的附着量超过2g/m2时,为高成本,并且根据焊接条件而焊接性有时降低。上述化学转化覆膜的每单面的附着量的测定方法没有特别限定,可以通过公知的测定方法来测定,例如,可以通过重量法、荧光X射线法来测定。此处的重量法是指如下方法:测定面积一定的样品的重量后,形成化学转化覆膜,根据与之后的重量的差值而求出附着量。另外,荧光X射线法是指如下方法:预先利用重量法等手段,用附着量已知的样品制成标准曲线,根据目标试样的荧光X射线强度算出附着量。
此处,本实施方式的无机系无铬化学转化覆膜可以通过公知的方法而形成。例如,调整含有上述那样的成分的涂布液,利用棒涂机、辊涂机等公知的方法,在Zn-Ni合金镀层的上层涂布调整后的涂布液。之后,使所得涂布膜以规定的加热温度进行加热·干燥即可。
针对本实施方式的Zn-Ni合金镀层的裂纹,以下对更优选的方式进行说明。
上述裂纹的存在可以如下进行确认:将样品进行树脂填埋后,进行截面垂直研磨,进行截面SEM观察,从而确认。此时,以1000倍左右的倍率、观察100μm的视野,更优选从镀层表层至铁基体为止的裂纹存在有5个以上且50个以下。例如如100μm的视野中的裂纹数低于5个那样,裂纹数量少的情况下,有燃料耐腐蚀性降低的倾向。另一方面,例如如100μm的视野中的裂纹数超过50个那样,裂纹数量过多的情况下,有盐水环境那样的一般的耐腐蚀性降低的倾向。本实施方式的Zn-Ni合金镀层中,100μm的视野中的裂纹的个数更优选为10个以上且40个以下。
另外,利用上述方法观察裂纹,以10000倍左右的倍率观察从镀层的表层至铁基体为止的裂纹中开口幅度最大的裂纹,求出其最大宽度的情况下,所得最大宽度期望低于0.5μm。裂纹的最大宽度为0.5μm以上的情况下,有盐水环境那样的一般的耐腐蚀性降低的倾向。
为了得到最佳的劣化汽油耐腐蚀性,也考虑前述裂纹数与覆膜表面的水接触角的关系是重要的。具体而言,裂纹数少的情况下,重要的是,将水接触角管理为更高,另一方面,裂纹数多的情况下,可以在较宽的水接触角的范围内得到良好的燃料耐腐蚀性。进行了详细的研究,结果具体而言,裂纹的个数X个(每100μm的视野中)与覆膜表面的水接触角Y(度)只要满足以下(I)式的关系,就可以得到最佳的劣化汽油耐腐蚀性。
Y≥-0.18X+56.5···(I)
以图1为参照,对(I)式的关系进行说明。如图1所示那样,如果裂纹的个数X少,则钢板受到加工时,Zn-Ni合金镀层中产生较多新的裂纹(由于加工而新产生的新生裂纹),伴随着Zn-Ni合金镀层的破坏,无机系无铬化学转化覆膜也被破坏。因此,为了得到良好的燃料耐腐蚀性,必须提高覆膜表面的水接触角Y。
另一方面,裂纹的个数X多的情况下,钢板受到加工时,原本具有的裂纹使应力缓和,因此不易产生新生裂纹。因此,无机系无铬化学转化覆膜也不易被破坏,燃料耐腐蚀性的降低小。另外,沿着裂纹的内表面形成无机系无铬化学转化覆膜的情况下,无机系无铬化学转化覆膜的表面积增加,进而燃料耐腐蚀性提高。推定这是由于,裂纹的个数X越多,无机系无铬化学转化覆膜的表面积越增大,因此,即使为接触角Y较小的覆膜,保护镀层、铁基体免受燃料中的腐蚀因子、特别是亲水性的腐蚀因子的效果也变大。
劣化汽油耐腐蚀性与盐水环境那样的一般的耐腐蚀性这两者中为了得到最佳的特性,在满足上述(I)式的基础上,将从镀层表层至铁基体为止的裂纹的个数设为5个以上且低于50个(每100μm视野)、且裂纹的最大宽度设为低于0.5μm。
本实施方式的Zn-Ni合金镀层的每单面的附着量优选为5~40g/m2。Zn-Ni合金镀层的每单面的附着量低于5g/m2时,有劣化汽油耐腐蚀性容易不足的倾向。另外,Zn-Ni合金镀层的每单面的附着量超过40g/m2时,虽然赋予了劣化汽油耐腐蚀性,但在成本上是不利的,故不优选。需要说明的是,从涂装性的观点出发,Zn-Ni合金镀层的每单面的附着量优选为0.01~0.5g/m2。需要说明的是,Zn-Ni合金镀层的Ni含有率没有特别限定,优选为9~14质量%,在该范围内,特别是劣化汽油耐腐蚀性变得良好。另外,Zn-Ni合金镀层可以含有公知的第三成分、例如Fe、Co、Sn、Cr等金属,或者在Zn-Ni合金镀层的下层上可以具有公知的预镀层、例如Fe、Ni等的预镀层。
需要说明的是,Zn-Ni合金镀层的每单面的附着量例如可以通过应用电镀法时的电量(库仑量)来控制,也可以事后进行测定。上述Zn-Ni合金镀层的每单面的附着量的测定方法没有特别限定,可以通过公知的测定方法来测定,例如,可以通过重量法、荧光X射线法来测定。此处的重量法是指如下方法:测定面积一定的镀覆样品的重量后,用盐酸等仅使镀层溶解,根据与溶解后的重量的差值求出附着量。另外,荧光X射线法是指如下方法:预先通过重量法等手段,用附着量已知的样品制成标准曲线,根据目标试样的荧光X射线强度算出附着量。
本实施方式的Zn-Ni合金镀层的裂纹的形成方法没有任何限定,适合使用镀覆后的酸水溶液处理。特别适合使用如下方法:在酸性镀液中进行电镀从而形成Zn-Ni合金镀层的情况下,镀覆后切断通电,在镀液中进行无通电浸渍。裂纹的数量、最大宽度可以根据处理浴的浓度、温度、以及处理时间来调整。使用酸性镀浴进行处理的情况下,裂纹的数量特别是温度的依赖性高,越高温,数量越容易增加。另一方面,裂纹宽度的时间依赖性高,想要抑制裂纹宽度的情况下,可以缩短处理时间。在高温下进行短时间处理时,裂纹数量多,裂纹宽度不会变得那么大。另一方面,在低温下进行长时间处理时,裂纹数量不会变多,但裂纹宽度容易增大。
以上的本发明的特征涉及燃料耐腐蚀性成为问题的成为燃料罐内表面的面。对于成为燃料罐的外表面的面没有特别限定,Zn-Ni合金镀层可以存在,Zn-Ni合金镀层也可以不存在,进而,可以在Zn-Ni合金镀层的上层具有无铬化学转化覆膜。
实施例
接着,列举实施例和比较例,对本发明的燃料罐用钢板进一步进行具体说明。需要说明的是,以下所示的实施例只不过是本发明的燃料罐用钢板的一例,本发明的燃料罐用钢板不限定于下述例子。
<实验例1>
(实施例1~28和比较例1~2)
以极低碳钢板为原板,使用硫酸酸性镀浴,通过电镀,形成每单面的附着量为20g/m2、Ni 10质量%的Zn-Ni合金镀层,在镀浴中切断通电保持3秒,从而形成规定的镀层裂纹。需要说明的是,使用的硫酸酸性镀浴是由硫酸Zn七水合物:200g/L、硫酸Ni六水合物:380g/L、硫酸Na:80g/L、硫酸:10g/L形成的50℃的浴。之后,在得到的Zn-Ni合金镀层的上层形成规定量的表1所示的各种组成的无铬化学转化覆膜。无铬化学转化覆膜的形成通过利用棒涂机的涂布和利用热风干燥炉的干燥(达到板温100℃)来进行。需要说明的是,无铬化学转化覆膜的附着量通过上述荧光X射线法来测定。
[表1]
此处,上述表1中,为:
*1:3-环氧丙氧基丙基三甲氧基硅烷
*2:3-环氧丙氧基丙基三甲氧基硅烷与3-氨基丙基三乙氧基硅烷的3:2缩聚物(分子量约3000)
*3:1-羟基乙叉基-1,1’-二膦酸
*4:酯系氨基甲酸酯树脂
*5:Na中和离聚物树脂
*6:四氟乙烯·全氟烷基乙烯基醚的共聚物。
(比较例3)
不形成化学转化覆膜,除此之外,与上述同样地进行制作。
(比较例4~7)
Zn-Ni合金镀覆后,在镀浴中不进行无通电浸渍处理,除此之外,与上述同样地进行制作。
(比较例8)
使用电镀锌代替Zn-Ni合金镀覆,除此之外,与前述同样地进行制作。
[镀层裂纹的观察]
将制作好的样品进行树脂填埋后,实施截面垂直研磨,进行截面SEM观察。以1000倍的倍率,观察100μm的视野,测量从镀层表层至铁基体为止的裂纹的数量。另外,在上述视野中,以10000倍,对从镀层表层至铁基体为止的裂纹中开口幅度最大的裂纹进行SEM观察,测量最大宽度。
[水接触角]
使用接触角计(协和界面科学株式会社制DM901),在25℃的气氛中,滴加离子交换水3μL,测定60秒后的静态接触角。
[劣化汽油耐腐蚀性]
对于制作好的样品,模拟燃料罐而成形为内径50mm、深度35mm的圆筒状,用脱脂处理去除油后,在内表面底,用切割机赋予达到至铁基体的瑕疵(模拟利用加压加工的瑕疵引入)。之后,封入模拟劣化汽油的试验液(含有甲酸100ppm、乙酸300ppm、氯化物离子100ppm、水1.0体积%的汽油),在40℃下保持2个月后,进行锈去除,测定腐蚀所导致的最大板厚减少值(mm)。
以下的表2中一并示出各样品的镀层裂纹状态、使用化学转化覆膜种类、化学转化附着量、水接触角和劣化汽油耐腐蚀性评价结果。需要说明的是,以下的表2中,劣化汽油耐腐蚀性评价结果如下:最大板厚减少值低于0.05mm的情况下,可以判断为良好。
[表2]
由上述表2表明,比较例1中,水接触角小且不在本发明范围内,因此,劣化汽油耐腐蚀性不良。比较例2中,虽然水接触角高,但是为本发明范围外的有机系的覆膜,因此,劣化汽油耐腐蚀性不良。比较例4和比较例5中,虽然水接触角在本发明范围内,但是镀层中不具有裂纹,因此,劣化汽油耐腐蚀性不良。
对比较例1与比较例6进行比较时可知,不在本发明范围内的水接触角小的覆膜中,由于形成镀层裂纹而耐腐蚀性劣化。同样地,对比较例2与比较例7进行比较时可知,对于不在本发明范围内的有机系覆膜而言,由于形成镀层裂纹而耐腐蚀性劣化。
如以上那样可知,通过组合镀层裂纹与无机系的覆膜与水接触角,全部满足这些的本发明的实施例中,可以得到良好的特性。
<实验例2>
(实施例29~81)
以极低碳钢板为原板,使用硫酸酸性镀浴,通过电镀,形成每单面的附着量为20g/m2、Ni 10质量%的Zn-Ni合金镀层,在镀浴中切断通电,分别变更进行浸渍时的温度、时间,形成规定的镀层裂纹。镀浴使用与上述实验例1相同的镀浴,温度在50~65℃、浸渍时间在1秒~5秒之间变更。之后,与上述实验例1同样地,形成规定量的上述表1所示的各种组成的无铬化学转化覆膜。另外,无铬化学转化覆膜的附着量通过上述荧光X射线法来测定。
评价与上述实验例1同样地进行,但本实验例中,也一并对以下的SST耐腐蚀性进行了评价。
[SST耐腐蚀性]
密封制作好的样品的背面和边缘,进行JISZ2371中规定的盐水喷雾试验72小时,测量白锈发生面积率(%)。
以下的表3中一并示出各样品的镀层裂纹状态、使用的化学转化覆膜种类、化学转化附着量、水接触角、以及劣化汽油耐腐蚀性和SST耐腐蚀性评价结果。需要说明的是,劣化汽油耐腐蚀性评价结果如下:最大板厚减少值低于0.05mm的情况下,可以判断为良好。另外,SST耐腐蚀性如下:白锈发生率低于5%的情况下,可以判断为良好。
[表3]
由上述表3表明,本发明的实施例中,均显示出良好的特性。
特别是,关于劣化汽油耐腐蚀性,满足(I)式时,劣化汽油耐腐蚀性试验中的板厚减少为0,显示出特别优异的劣化汽油耐腐蚀性。另外,裂纹宽度低于0.5μm时,SST耐腐蚀性中的白锈发生率低于1%,显示出优异的SST耐腐蚀性。特别是,裂纹宽度低于0.5μm、且裂纹数低于50个时,在任意条件下SST耐腐蚀性中的白锈发生率均为零,是特别优异的。
由以上,满足(I)式、且裂纹数为5个以上且低于50个、进而裂纹宽度低于0.5μm时,劣化汽油耐腐蚀性和SST耐腐蚀性这两者中均是特别优异的。
<实验例3>
(实施例82~89)
成为燃料罐的内表面的面与实施例1同样地制作,但成为燃料罐的外表面的面进行各种变更。实施例82中,对外表面不实施覆膜。实施例83、84中,利用刷子磨削完全去除成为外表面的面的镀层。之后涂布实施例83中规定的覆膜。实施例85~89中,再次通过电镀使规定的附着量的Zn、Ni附着于利用前述方法完全去除了镀层的外表面。
评价如以下进行。
(涂装性)
对成为燃料罐的外表面的面的涂装性进行评价。与通常的汽车或二轮车用的燃料罐外表面同样地,进行涂装前处理(磷酸锌处理)和电沉积涂装,对其外观进行目视判定。将允许水平的情况评价为○、极均匀美观的情况评价为“◎”。
(保管后涂装性)
将防锈油(Parker Industries,Inc.的Noxrust530)极薄涂油(约0.1g/m2)于制作好的样品上后,模拟线圈状态,成为内表面的面与成为外表面的面相接触地重叠并包装。使用在50℃、98%RH环境下保管1个月的样品,与前述涂装性评价同样地进行涂装,以相同的基准进行评价。
(焊接性)
将成为燃料罐的内表面的面彼此以成为内侧的方式重叠并进行缝焊,改变焊接电流,求出得到适当的熔核的电流的范围。条件如以下所述。
·电极:Cu-Cr合金、具有中央部为15mmR的4.5mm宽、端部为4mmR的宽8mm的截面的圆盘状电极
·焊接方法:二重重叠、重叠缝焊
·加压力:400kgf(需要说明的是,1kgf为约9.8N)
·通电时间:2/50秒通电on(开)、1/50秒通电off(关)
·冷却:内部水冷和外部水冷
·焊接速率:2.5m/分钟
将结果示于表4。由表4表明,本发明的实施例中,均显示出良好的特性。而且发现:Zn与Ni的总计附着量为0.01~0.5g/m2的情况下(实施例85~88),钢板的涂装性、保管后涂装性和焊接性特别提高。
[表4]
以上,对本发明的优选实施方式进行了详细说明,但本发明不限定于上述例子。对于本发明所述的技术领域中的现有技术人员,显而易见的是,在权利要求书中记载的技术构思的范围内,可以想到各种变更例或修正例,应了解,对于这些,当然属于本发明的保护范围。
产业上的可利用性
根据本发明,可以提供:在劣化汽油那样的含有有机酸、进而还含有凝结水那样的各种燃料环境下,显示出优异的耐腐蚀性的燃料罐用钢板,因此,在产业上是有用的。
本发明提供:使成为燃料罐外表面的面为基底金属、使成为燃料罐内表面的面为无铬化学转化覆膜,在内外表面形成状态不同的表面的钢板。这样的本发明的钢板具备如下从燃料罐的制造至使用为止所需的一切性能:(i)对钢板进行加工并焊接形成罐形状时所需的加工性优异;(ii)将加工后的罐进行涂装提高外观的美观时所需的涂装性优异;(iii)长年使用制造后的罐时所需的耐腐蚀性优异。
本发明的钢板在内外表面状态不同的表面彼此发挥作用、可以更进一步发挥内外表面的性能的差异的方面,也具有以往没有的效果。具体而言,在燃料罐外表面的基底金属上涂布的涂料(油)的剩余量被燃料罐内表面的无铬化学转化覆膜吸附,因此,外表面的涂装性提高。
Claims (8)
1.一种燃料罐用钢板,其具备:
在成为燃料罐内表面的铁基体的单面上形成的附着量为5g/m2~40g/m2的Zn-Ni合金镀层;和,
位于所述Zn-Ni合金镀层的上层的水接触角为50度以上的无机系无铬化学转化覆膜,所述无机系无铬化学转化覆膜的相对于覆膜整体的固体成分质量的有机树脂的含量低于50%,
所述Zn-Ni合金镀层具有从该Zn-Ni合金镀层与所述无机系无铬化学转化覆膜的界面至所述Zn-Ni合金镀层与所述铁基体的界面为止的裂纹,
成为所述燃料罐外表面的所述铁基体的另一单面至少不具备所述无机系无铬化学转化覆膜,并且水接触角低于10度。
2.根据权利要求1所述的燃料罐用钢板,其中,成为所述燃料罐外表的面的Zn和/或Ni的总附着量为0.01~0.5g/m2。
3.根据权利要求1或2所述的燃料罐用钢板,其中,所述无机系无铬化学转化覆膜含有:选自硅烷偶联剂、硅烷偶联剂的缩聚物、二氧化硅、硅酸盐、磷酸、磷酸盐中的一种以上;和,选自Ti、Zr、V、Mo、W中的一种以上金属的化合物。
4.根据权利要求1或2所述的燃料罐用钢板,其中,所述无机系无铬化学转化覆膜含有拒水剂。
5.根据权利要求4所述的燃料罐用钢板,其中,所述拒水剂为选自聚烯烃蜡、硅系树脂、氟系树脂中的1种以上。
6.根据权利要求1或2所述的燃料罐用钢板,其中,对所述Zn-Ni合金镀层进行截面观察的情况下,所述裂纹在每100μm的视野中存在有5个以上且50个以下。
7.根据权利要求6所述的燃料罐用钢板,其中,对所述Zn-Ni合金镀层进行截面观察而得到的、每100μm的视野中的所述裂纹的个数X个与所述水接触角Y(度)满足以下的(I)式所示的关系,
Y≥-0.18X+56.5···(I)。
8.根据权利要求7所述的燃料罐用钢板,其中,对所述Zn-Ni合金镀层进行截面观察的情况下,所述裂纹在每100μm的视野中存在有5个以上且低于50个、且裂纹的最大宽度低于0.5μm。
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2016
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- 2016-02-01 BR BR112017012657A patent/BR112017012657A2/pt not_active IP Right Cessation
- 2016-02-01 JP JP2016533732A patent/JP6066019B2/ja active Active
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BR112017012657A2 (pt) | 2017-12-26 |
CN107208277A (zh) | 2017-09-26 |
WO2016125740A1 (ja) | 2016-08-11 |
TWI586836B (zh) | 2017-06-11 |
PL3231896T3 (pl) | 2020-08-24 |
KR101941806B1 (ko) | 2019-01-23 |
EP3231896A4 (en) | 2018-04-25 |
EP3231896A1 (en) | 2017-10-18 |
TW201632657A (zh) | 2016-09-16 |
EP3231896B9 (en) | 2020-08-12 |
MX2017008941A (es) | 2017-12-07 |
EP3231896B1 (en) | 2020-04-01 |
JPWO2016125740A1 (ja) | 2017-04-27 |
KR20170098308A (ko) | 2017-08-29 |
ES2800478T3 (es) | 2020-12-30 |
JP6066019B2 (ja) | 2017-01-25 |
US20170361571A1 (en) | 2017-12-21 |
US10688755B2 (en) | 2020-06-23 |
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