TW201632657A - 燃料槽用鋼板 - Google Patents
燃料槽用鋼板 Download PDFInfo
- Publication number
- TW201632657A TW201632657A TW105103301A TW105103301A TW201632657A TW 201632657 A TW201632657 A TW 201632657A TW 105103301 A TW105103301 A TW 105103301A TW 105103301 A TW105103301 A TW 105103301A TW 201632657 A TW201632657 A TW 201632657A
- Authority
- TW
- Taiwan
- Prior art keywords
- fuel tank
- steel sheet
- film
- layer
- chromate
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 67
- 239000010959 steel Substances 0.000 title claims abstract description 67
- 239000002828 fuel tank Substances 0.000 title claims abstract description 64
- 238000007747 plating Methods 0.000 claims abstract description 82
- 229910007567 Zn-Ni Inorganic materials 0.000 claims abstract description 68
- 229910007614 Zn—Ni Inorganic materials 0.000 claims abstract description 68
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 63
- 239000000956 alloy Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 18
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 16
- 239000005871 repellent Substances 0.000 claims description 15
- 230000002940 repellent Effects 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007739 conversion coating Methods 0.000 abstract 3
- 229910000859 α-Fe Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 97
- 230000007797 corrosion Effects 0.000 description 72
- 238000005260 corrosion Methods 0.000 description 72
- 238000000034 method Methods 0.000 description 36
- 239000000446 fuel Substances 0.000 description 28
- 239000003502 gasoline Substances 0.000 description 27
- 239000000126 substance Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 8
- 238000003466 welding Methods 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002739 metals Chemical class 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
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 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
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- RVUXIPACAZKWHU-UHFFFAOYSA-N sulfuric acid;heptahydrate Chemical compound O.O.O.O.O.O.O.OS(O)(=O)=O RVUXIPACAZKWHU-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000036962 time dependent Effects 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
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- 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
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Abstract
一種燃料槽用鋼板，具備：鍍Zn-Ni合金層，其係位於基鐵的一面或兩面；及無機系無鉻酸鹽化成皮膜，其係位於前述鍍Zn-Ni合金層的上層；前述鍍Zn-Ni合金層具有龜裂，且所述龜裂係從該鍍Zn-Ni合金層與前述無機系無鉻酸鹽化成皮膜之界面起至到達前述鍍Zn-Ni合金層與前述鋼板之界面，而且在前述無機系無鉻酸鹽化成皮膜的表面之水接觸角為50度以上。
Description
本發明係有關於一種燃料槽用鋼板。
從對於最近環境規則之動向而言，對不使用有害金屬的材料之市場需求提高。例如在汽車領域，從燃料槽的主流材料之鉛-錫合金鍍敷鋼板，轉換成為無鉛素材係進展中。在此，對於被要求在封入有燃料的環境下的內面耐蝕性(以下，亦稱為燃料耐蝕性)之燃料槽獨特的要求性能，係有揭示許多具有實績的鋅系鍍敷鋼板作為汽車的內外板(例如，參照以下的專利文獻1~3等)。
因為如上述之利用鋅系鍍敷鋼板的技術，係將鉻酸鹽處理設作前提者，與要求不使用有害金屬之近年來的市場需求不相容。因此，如以下的專利文獻4~專利文獻9所記載，有提案揭示不使用鉻之無鉻酸鹽的燃料槽用鍍鋅系鋼板。
專利文獻1：日本特開平5-106058號公報
專利文獻2：日本特開平9-324279號公報
專利文獻3：日本特開平9-324281號公報
專利文獻4：日本特開2004-169122號公報
專利文獻5：日本特開2007-186745號公報
專利文獻6：日本特開2013-133527號公報
專利文獻7：日本特開2013-227646號公報
專利文獻8：日本特開2011-38139號公報
專利文獻9：WO2007/011008
但是，相較於先前利用鉻酸鹽處理之鋅系鍍敷鋼板的燃料耐蝕性，上述專利文獻4~專利文獻9所揭示之無鉻酸鹽的燃料槽用鍍鋅系鋼板的燃料耐蝕性，在較嚴格的條件下之燃料耐蝕性(例如，較長期間的耐蝕性和因加工而產生皮膜損傷時的耐蝕性等)係不充分而必須進一步改良。
例如，在上述專利文獻4及專利文獻5，係揭示一種有機樹脂主體的無鉻酸鹽皮膜。但是，此種有機樹脂主體的無鉻酸鹽皮膜，長期間被暴露在燃料環境中時，有機樹脂因燃料而膨潤致使鍍敷界面的密著性低落。推定此種有機樹脂的膨潤係成為耐蝕性不足之主要原因。
在上述專利文獻6及專利文獻7，係揭示一種磷酸系的無機無鉻酸鹽皮膜。但是，磷酸系無機無鉻酸鹽皮膜之耐水性係未必充分，在燃料中存在結露水時，特別是耐
蝕性不足。
在上述專利文獻8，係記載一種在具有龜裂之鋅-鎳合金鍍敷層形成無鉻酸鹽的化成處理層。但是，因為該化成處理層係以胺甲酸酯系水性樹脂作為主體，雖然耐蝕性提升，但是未賦予對劣化汽油之耐蝕性。又，如後述，該化成處理膜中的磷酸、釩、鈦、鋯，係對劣化汽油所賦予耐蝕性為不充分。
在上述專利文獻9，係記載一種使用含有有機矽化合物之水系金屬表面處理劑在鋅系鍍敷鋼板形成皮膜而成之鋼板。但是，雖然該鋼板之耐蝕性提升，但是未賦予對劣化汽油之耐蝕性。
因此，本發明係鑒於上述問題所完成者，本發明之目的係提供一種燃料槽用鋼板，其在含有如劣化汽油的有機酸、甚至亦含有結露水的各種燃料環境下，不必使用鉛、鉻等的環境負荷物質就能夠實現優異的耐蝕性。
本發明者等進行研討改善無鉻酸鹽鋅系鍍敷鋼板的燃料耐蝕性之結果，得到以下的見解：將鋅系鍍敷層作為鍍Zn-Ni合金層之同時，使此種鍍敷層形成預定的龜裂，而且，藉由使無鉻酸鹽化成皮膜成為無機物主體之後，賦予皮膜表面撥水性，從而能夠得到顯著的改善效果。
基於如上述的見解而完成之本發明的要旨係如以下。
(1)一種燃料槽用鋼板，具備：鍍Zn-Ni合金層，其係位於基鐵的一面或兩面且係形成於至少一面；及無機系無
鉻酸鹽化成皮膜，其係位於前述鍍Zn-Ni合金層的上層；前述鍍Zn-Ni合金層具有龜裂，且所述龜裂係從該鍍Zn-Ni合金層與前述無機系無鉻酸鹽化成皮膜之界面起至到達前述鍍Zn-Ni合金層與前述鋼板之界面，而且在前述無機系無鉻酸鹽化成皮膜的表面之水接觸角為50度以上。
(2)如(1)之燃料槽用鋼板，其中前述基鐵的一面係具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜；與前述一面相反的面係不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜。
(3)如(2)之燃料槽用鋼板，其中在不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜之面之水接觸角為小於10度。
(4)如(2)或(3)之燃料槽用鋼板，其中在不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜之面之Zn及/或Ni的附著量為0.01~0.5g/m2。
(5)如(1)至(4)項中任一項之燃料槽用鋼板，其中前述無機系無鉻酸鹽化成皮膜係含有：選自矽烷偶合劑、矽烷偶合劑的聚縮合物、氧化矽、矽酸鹽、磷酸、磷酸鹽之一種以上；及選自Ti、Zr、V、Mo、W之一種以上的金屬之化合物。
(6)如(1)至(5)項中任一項之燃料槽用鋼板，其中前述無機系無鉻酸鹽化成皮膜係含有撥水劑。
(7)如(6)之燃料槽用鋼板，其中前述撥水劑係選自聚烯烴蠟、矽系樹脂、氟系樹脂之1種以上。
(8)如(1)至(7)項中任一項之燃料槽用鋼板，其中剖面觀察前
述鍍Zn-Ni合金層時，前述龜裂係每100μm的視野存在5個以上且50個以下。
(9)如(8)之燃料槽用鋼板，其中剖面觀察前述鍍Zn-Ni合金層而得到之每100μm的視野的前述龜裂的個數X個與前述水接觸角Y(度)，係滿足以下的(I)式表示之關係，Y≧-0.18X+56.5···(I)。
(10)如(9)之燃料槽用鋼板，其中剖面觀察前述鍍Zn-Ni合金層時，前述龜裂係每100μm的視野存在5個以上且小於50個，並且龜裂的最大寬度為小於0.5μm。
如以上說明，依照本發明能夠提供一種燃料槽用鋼板，其在含有如劣化汽油的有機酸、甚至亦含有結露水的各種燃料環境下，不必使用鉛、鉻等的環境負荷物質就能顯示優異的耐蝕性。
圖1係將龜裂的個數較少時(龜裂少)、及龜裂的個數較多時(龜裂多)進行比較而顯示之(I)式的關係之說明圖。
以下，詳細地說明本發明之適合的實施形態。
以下所詳述的本發明，係有關於一種燃料槽用鋼板，其對各種燃料具有優異的耐蝕性，不使用鉛和鉻酸鹽處理而利用對環境友善之鋅系鍍敷鋼板。又，本發明係有
關於一種使用在以汽車、兩輪車、產業機械、建築機械為首、以及封入有燃料之燃料槽或該燃料槽的零件之鋼板。
本發明的實施形態之燃料槽用鋼板，係具有：鍍Zn-Ni合金層，其係位於基鐵的一面或兩面；及無機系無鉻酸鹽化成皮膜(以下，亦簡稱「化成皮膜」)，其位於該鍍Zn-Ni合金層(以下，亦簡稱「鍍敷層」)的上層。
將本發明的實施形態之燃料槽用鋼板利用在燃料槽用鋼板時，具有鍍Zn-Ni合金層、及位於該鍍Zn-Ni合金層的上層之無機系無鉻酸鹽化成皮膜之面(一面)係成為燃料槽內面(以下，稱為內面)。此時，與該一面為相反的面，係成為燃料槽外面(以下，稱為外面)。
本發明的鋼板亦可為兩面均具有鍍Zn-Ni合金層。但是，為了使鋼板的熔接性良好，成為燃料槽外面之面，係以不具有鍍敷層為佳。又，例如鋼板係使用在如兩輪車用燃料槽之重視燃料槽外面塗裝的美觀之用途時，為了使塗裝外觀成為良好，燃料槽外面以不具有鍍敷層為佳。另一方面，鋼板係使用在燃料槽外面亦被要求高度的耐蝕性之用途時，燃料槽外面係以具有鍍敷層為佳。本發明的鋼板，係能夠按照用途而控制有無外面及內面的鍍敷層。
為了使外面成為不具有鍍敷層的狀態，能夠採用在進行電鍍時，不對非鍍敷面側進行通電之方法。或是在進行鍍敷之後，將非鍍敷面側藉由電化學式(例如陽極電解處理)或機械式(例如毛刷磨削)方法除去鍍敷層之方法。又，亦能夠組合前述的方法。
使用前述記載的方法所形成的非鍍敷面(成為外面的面)之接觸角，較佳是水接觸角為小於10度，更佳為小5度。藉此能夠改善塗裝性。為了使前述的接觸角確實，抑制鋼板的表面氧化係有效的，就該點而言，以在非鍍敷面側亦存在極微量的Zn及或Ni為佳。較佳是其附著量為0.01~0.3g/m2，較佳為0.01~0.1g/m2。
在此，本實施形態之燃料槽用鋼板的母材，係沒有特別限定，只要是作為鋅系鍍敷鋼板的母材通常被使用的鋼板，就能夠適當地利用眾所周知者。
形成在此種鋼板的至少一面且係形成於至少一面之鍍Zn-Ni合金層，係至少含有由鋅及鎳所構成的合金之合金鍍敷層。此種鍍Zn-Ni合金層，係例如能夠使用電鍍法等眾所周知的鍍敷法來形成。
此種鍍Zn-Ni合金層，其特徵在於：具有從鍍敷層的表層(換言之，鍍Zn-Ni合金層與無機系無鉻酸鹽化成皮膜之界面)起至到達基鐵(換言之，母材之鋼板與鍍Zn-Ni合金層之界面)之龜裂。又，形成在鍍Zn-Ni合金層的上層之無機系無鉻酸鹽化成皮膜，其特徵在於：在皮膜表面的水接觸角為50度以上。
在鍍Zn-Ni合金層存在龜裂時燃料耐蝕性提升，以鉻酸鹽處理作為前提的情況係已被熟知的現象。此種現象係能夠由以下的情形來說明：藉由進入龜裂內的鉻酸鹽皮膜之錨固效果來提升皮膜密著性、和預先在鍍敷層存在龜裂來抑制壓製加工時產生新的龜裂之效果等。推測此種
效果，在專利文獻8所記載的鋼板亦能夠觀察到。
另一方面，近年來被研討之無鉻酸鹽化成皮膜，係即便在鍍敷層存在龜裂亦無法期待顯著地提升燃料耐蝕性之效果，不如說是燃料耐蝕性反而變差。這被認為是不存在如鉻酸鹽皮膜中所存在的Cr6+之強力的腐蝕抑制劑之緣故。
燃料耐蝕性，係特別是為了在含有如劣化汽油的有機酸、甚至亦含有如結露水的燃料環境下，而且皮膜的一部分在壓製加工等的過程受到損傷的條件下亦發揮良好的耐蝕性，必須下列的全部均齊全：必須在鍍Zn-Ni合金層存在龜裂；無鉻酸鹽化成皮膜必須為無機系；及在化成皮膜表面的水接觸角必須為50度以上。
本實施形態之鍍Zn-Ni合金層的龜裂，係指從鍍敷表層起至到達基鐵為止。推定龜裂的作用機構係除了如前述的錨固效果、及抑制加工時新產生的龜裂以外，亦藉由以下的效果：使顯示撥水性之無機系的化成皮膜的表面積，藉由此種表面積的増加而保護鍍敷層和基鐵避免受到燃料中的腐蝕因素、特別是親水性的腐蝕因素的影響。又，此種龜裂的存在，係能夠藉由從剖面使用掃描型電子顯微鏡(Scanning Electron Microscope：SEM)等進行觀察來確認。
本實施形態之無鉻酸鹽化成皮膜，必須是無機系的皮膜。所謂無機系的皮膜，係指不是以有機樹脂作為主體之皮膜，而不是將含有有機樹脂除外，但是有機樹脂的
含量(相對於皮膜全體的固體含量質量之含量)為小於50%，以30%以下為佳，較佳為10%以下(包含零)。無鉻酸鹽化成皮膜係以有機樹脂作為主體時(亦即，有機系的皮膜時)，有機樹脂受到燃料中的烴引起的膨潤作用，致使鍍敷層與化成皮膜之間的密著性低落之同時，以鍍敷層的龜裂作為起點而進行腐蝕。如本實施形態之化成皮膜，藉由設作無機系的皮膜而能夠抑制此種膨潤現象。
在本實施形態之化成皮膜表面的水接觸角，必須為50度以上。藉由水接觸角為50度以上，藉由與在前述的鍍敷層的龜裂效果之相乘效果，來保護鍍敷層和基鐵避免受到燃料中的腐蝕因素、特別是親水性的腐蝕因素之影響，而能夠得到良好的耐蝕性。在本實施形態之化成皮膜的表面之水接觸角，係以55度以上為佳，更佳為60度以上。又，針對此種水接觸角，其上限係沒有特別規定，以具有接近理論界限的180度之值為佳，但是在本實施形態之鍍敷鋼板上能夠到達之水接觸角係以120度左右為界限。此種水接觸角係能夠利用接觸角計且藉由眾所周知方法來測定。
本實施形態之無機系無鉻酸鹽化成皮膜，係以含有選自矽烷偶合劑、矽烷偶合劑的聚縮合物、氧化矽、矽酸鹽、磷酸、磷酸鹽之一種以上、及選自Ti、Zr、V、Mo、W之一種以上的金屬化合物為佳。又，本實施形態之無機系無鉻酸鹽化成皮膜，係以含有撥水劑為佳。
在此，所謂本實施形態之撥水劑，係指具有添加在無機系的化成皮膜而使水接觸角增大的作用之物質。作
為此種撥水劑的具體例，能夠舉出具有C-H鍵或C-F鍵之有機樹脂。作為撥水劑的較佳具體例，能夠舉出聚烯烴蠟、矽系樹脂、氟系樹脂等。因為該等撥水劑係藉由添加少量(例如相對於化成皮膜的固體含量質量全體，為10%以下)而能夠得到預定的水接觸角，所以本實施形態之化成皮膜，係沒有變成非無機系的皮膜之可能性。
在本實施形態之無機系無鉻酸鹽化成皮膜，以在化成皮膜表面的水接觸角成為50度以上之方式調整前述的撥水劑係重要的。
具體而言，化成皮膜係以選自矽烷偶合劑、矽烷偶合劑的聚縮合物之一種以上作為主成分而含有時，因為該等成分具有C-H鍵，所以即便不添加撥水劑亦能夠容易地得到比較高的水接觸角，但是以添加撥水劑為較佳。作為此時的撥水劑，係相對於固體含量質量全體，以使用選自聚烯烴蠟、矽系樹脂、氟系樹脂之1種以上且添加0.1%以上為佳。
又，化成皮膜係以選自氧化矽、矽酸鹽、磷酸、磷酸鹽之一種以上作為主成分而含有時，因為通常不添加撥水劑時，係難以得到預定的水接觸角，以含有撥水劑為佳。作為此時的撥水劑，係相對於固體含量質量全體，以使用選自聚烯烴蠟、矽系樹脂、氟系樹脂之1種以上且添加1%以上為佳。
本實施形態之無機系無鉻酸鹽化成皮膜的每一面之附著量，係以0.1~2g/m2為佳，較佳為0.3~1g/m2。化成
皮膜的每一面之附著量小於0.1g/m2時，對劣化汽油之耐蝕性有低落之情形，化成皮膜的每一面之附著量大於2g/m2時，成本較高之同時，依照熔接條件亦有熔接性低落之情形。此種化成皮膜的每一面之附著量的測定方法係沒有特別限定，能夠使用眾所周知的測定方法來測定，例如能夠藉由重量法和螢光X射線法來測定。在此，所謂重量法，係指測定規定面積的試樣之重量之後，形成化成皮膜且從與隨後重量的差異來求取附著量之方法。又，所謂螢光X射線法，係指預先藉由重量法等的手段且使用已知附著量的試樣製作校正曲線，且從所著眼的試料之螢光X射線強度算出附著量之方法。
在此，本實施形態之無機系無鉻酸鹽化成皮膜，係能夠使用眾所周知方法來形成。例如，調製含有如上述的成分之塗佈液，使用桿塗佈器、輥塗佈機等眾所周知方法，將所調製的塗佈液塗佈在鍍Zn-Ni合金層的上層。隨後，使所得到的塗佈膜在預定加熱溫度加熱．乾燥即可。
針對本實施形態之鍍Zn-Ni合金層的龜裂，以下說明較佳的形態。
此種龜裂的存在，係能夠藉由將試樣進行樹脂填埋之後，進行剖面垂直研磨且進行剖面SEM觀察來確認。此時，以1000倍左右的倍率進行觀察100μm的視野，從鍍敷層表層起到達基鐵之龜裂，係以存在5個以上且50個以下為較佳。例如在100μm視野的龜裂數目小於5個之龜裂數目較少的情況，有燃料耐蝕性低落之傾向。另一方面，例如在100μ
m視野的龜裂數目大於50個之龜裂數目太多的情況，如鹽水環境之通常的耐蝕性有低落之傾向。在本實施形態之鍍Zn-Ni合金層，在100μm的視野之龜裂的個數，係以10個以上且40個以下為較佳。
又，使用上述的方法觀察龜裂，以10000倍左右的倍率觀察從鍍敷層表層起至到達基鐵之龜裂之中開口寬度最大的龜裂而求取其最大寬度時，所得到的最大寬度，係以小於0.5μm為佳。龜裂的最大寬度為0.5μm以上時，如鹽水環境之通常的耐蝕性有低落之傾向。
為了得到最佳劣化汽油耐蝕性，亦考慮前述的龜裂數目與皮膜表面的水接觸角之關係為重要的。具體而言，龜裂數目較少時，將水接觸角管理成為更提高係重要的，另一方面，龜裂數目較多時，能夠在比較廣濶的水接觸角範圍得到良好的燃料耐蝕性。進行詳細的研討之結果，具體而言，龜裂的個數X個(每100μm的視野)與皮膜表面的水接觸角Y(度)為滿足以下(I)式的關係時，能夠得到最佳的劣化汽油耐蝕性。
Y≧-0.18X+56.5···(I)
參照圖1而說明(I)式的關係。如圖1所顯示，龜裂的個數X較少時，在鋼板接受加工時，在鍍Zn-Ni合金層係大量地產生新的龜裂(因加工而新產生的新生龜裂)，隨著鍍Zn-Ni合金層的破壞致使無機系無鉻酸鹽化成皮膜亦被破壞。因此，為了得到良好的燃料耐蝕性，必須提高皮膜表面的水接觸角Y。
另一方面，龜裂的個數X較多時，因為在鋼板接受加工時原來具有的龜裂係將應力緩和，而不容易產生新生龜裂。因此，亦不容易將無機系無鉻酸鹽化成皮膜破壞，燃料耐蝕性的降低較小。又，沿著龜裂的內面形成有無機系無鉻酸鹽化成皮膜時，無機系無鉻酸鹽化成皮膜的表面積増加，使得燃料耐蝕性進一步提升。推定龜裂的個數X越多，無機系無鉻酸鹽化成皮膜的表面積越増大，即便接觸角Y比較小的皮膜，保護鍍敷層和基鐵避免受到燃料中的腐蝕因素、特別是親水性的腐蝕因素的影響之效果亦變大之緣故。
為了在劣化汽油耐蝕性與如鹽水環境之通常的耐蝕性之雙方得到最佳特性，在滿足上述(I)式之後，使從鍍敷表層起至到達基鐵之龜裂的個數成為5個以上且小於50個(每100μm視野)，而且使龜裂最大寬度成為小於0.5μm為佳。
本實施形態之鍍Zn-Ni合金層的每一面之附著量，係以5~40g/m2為佳。鍍Zn-Ni合金層的每一面之附著量小於5g/m2時，劣化汽油耐蝕性有容易不足之傾向。又，鍍Zn-Ni合金層的每一面之附著量大於40g/m2時，雖然能夠賦予劣化汽油耐蝕性，但是在成本上不利，乃是不佳。又，從塗裝性的觀點而言，鍍Zn-Ni合金層的每一面之附著量，係以0.01~0.5g/m2為佳。又，鍍Zn-Ni合金層的Ni含有率係沒有特別限定，以9~14質量%為佳，藉由在該範圍，特別是劣化汽油耐蝕性係變為良好。又，鍍Zn-Ni合金層亦可含有眾所周知第三成分、例如Fe、Co、Sn、Cr等的金屬，亦可在
鍍Zn-Ni合金層的下層具有眾所周知預鍍敷層、例如Fe、Ni等的預鍍敷層。
又，鍍Zn-Ni合金層的每一面之附著量，例如能夠藉由應用電鍍法時的電量(庫侖量)來控制，亦可在事後的進行測定。此種鍍Zn-Ni合金層的每一面之附著量之測定方法係沒有特別限定，能夠使用眾所周知測定方法來測定，例如能夠使用重量法和螢光X射線法來測定。在此，所謂重量法，係指測定規定面積的鍍敷試樣的重量之後，使用鹽酸等只有使鍍敷層溶解，而從與溶解後的重量之異差來求取附著量之方法。又，所謂螢光X射線法，係指預先藉由重量法等的手段且使用已知附著量的試樣製作校正曲線，且從所著眼的試料之螢光X射線強度算出附著量之方法。
本實施形態之鍍Zn-Ni合金層的龜裂形成方法，係不被任何限定，能夠適合使用鍍敷後的酸水溶液處理。特別是藉由使用酸性鍍敷液進行電鍍來形成鍍Zn-Ni合金層時，能夠適合使用在鍍敷後斷電且在鍍敷液進行無通電浸漬之方法。龜裂數目和最大寬度係能夠藉由處理浴的濃度、溫度、以及處理時間來調整。使用酸性鍍敷浴進行時，龜裂數目係特別是溫度依存性較高，而且越高溫，數目越容易増加。另一方面，龜裂寬度係時間依存性較高，欲抑制龜裂寬度時，係以使處理時間縮短為佳。在高溫進行短時間處理時，龜裂數目為較多，而龜裂寬度不怎麼變大。另一方面，在低溫進行長時間處理時，龜裂數目不變多，但是龜裂寬度容易増大。
以上的本發明構成，係有關於燃料耐蝕性成為問題之燃料槽內面之面。針對燃料槽的外面之面係沒有特別限定，可以不存在鍍Zn-Ni合金層，亦可以存在鍍Zn-Ni合金層，而且，亦可以在鍍Zn-Ni合金層的上層具有無鉻酸鹽化成皮膜。
其次，舉出實施例及比較例而更具體地說明本發明之燃料槽用鋼板。又，在以下所揭示的實施例，係到底只不過是本發明之燃料槽用鋼板的一個例子，本發明之燃料槽用鋼板不被下述的例子限定。
將極低碳鋼板設作母板，使用硫酸酸性鍍敷浴且藉由電鍍形成每一面的附著量為20g/m2，Ni10質量%的鍍Zn-Ni合金層，藉由在鍍敷浴中斷電且保持3秒鐘而形成預定鍍敷層龜裂。又，所使用的硫酸酸性鍍敷浴，係由硫酸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所構成之50℃的鍍敷浴。隨後，在所得到的鍍Zn-Ni合金層的上層，預定量形成在表1所顯示之各種組成的無鉻酸鹽化成皮膜。無鉻酸鹽化成皮膜的形成，係藉由使用桿塗佈器之塗佈、及使用熱風乾燥爐之乾燥(到達板溫100℃)來進行。又，無鉻酸鹽化成皮膜的附著量係使用上述的螢光X射線法來測定。
在此，上述在表1，
*1：3-環氧丙氧基丙基三甲氧基矽烷
*2：3-環氧丙氧基丙基三甲氧基矽烷與3-胺丙基三乙氧基矽烷之3：2聚縮合物(分子量約3000)
*3：1-羥基亞乙基-1,1’-二膦酸
*4：酯系胺甲酸乙酯樹脂
*5：Na中和離子聚合物樹脂
*6：四氟乙烯．全氟烷基乙烯醚的共聚物。
(比較例3)
除了不形成化成皮膜以外，係與上述同樣地進行而製成。
(比較例4~7)
除了在Zn-Ni合金鍍敷後，不進行鍍敷浴中無通電浸漬處理以外，係與上述同樣地進行而製成。
(比較例8)
除了使用電鍍鋅代替鍍Zn-Ni合金以外，係與前述同樣地製成。
[鍍敷層龜裂的觀察]
將所製成的試樣進行樹脂填埋之後，進行剖面垂直研磨且進行剖面SEM觀察。以1000倍左右的倍率進行觀察100μm的視野，計量從鍍敷層的表層起至到達基鐵之龜裂數目。又，在上述視野中從鍍敷層的表層起至到達基鐵之龜裂之中，以10000倍進行SEM觀察開口寬度的最大龜裂且計量最大寬度。
[水接觸角]
使用接觸角計(協和界面科學製DM901)在25℃的環境下滴下離子交換水3μl(微升)且測定60秒後的靜態接觸角。
[劣化汽油耐蝕性]
將製成的試樣模擬燃料槽而成形為內徑50mm、深度35mm的圓筒狀，使用脫脂處理將油除去之後，在內面底使用切刀產生達到基鐵為止之傷痕(模擬在壓製加工的傷痕)。隨後，將模擬劣化汽油之試驗液(含有甲酸100ppm、乙酸300ppm、氯化物離子100ppm、水1.0容量%之汽油)封入且在40℃保持2個月之後，進行將鏽除去且測定因腐蝕引起的最大板厚減少值(mm)。
在以下的表2，係將各試樣的鍍敷層龜裂狀態、所使用的化成皮膜種、化成附著量、水接觸角及劣化汽油耐蝕性評價結果一併顯示。又，在以下的表2，劣化汽油耐蝕性評價結果，最大板厚減少值為小於0.05mm時，係能夠判定為良好。
從上述表2能夠清楚明白，比較例1係因為水接觸角較小而脫離本發明範圍，所以劣化汽油耐蝕性不良。比較例2係雖然水接觸角較高，但是因為是本發明範圍外的
有機系皮膜，所以劣化汽油耐蝕性不良。比較例4及比較例5，雖然水接觸角為本發明範圍內，但是因為在鍍敷層不具有龜裂，所以劣化汽油耐蝕性不良。
將比較例1與比較例6進行比較時，得知從本發明脫離之水接觸角較小的皮膜，由於形成鍍敷層龜裂致使耐蝕性劣化。同樣地，將比較例2與比較例7進行比較時，得知從本發明脫離之有機系皮膜，由於形成鍍敷層龜裂致使耐蝕性劣化。
如以上，得知藉由鍍敷層龜裂、無機系皮膜、及水接觸角之組合且滿足該等全部之本發明的實施例，係能夠得到良好的特性。
將極低碳鋼板設作母板，使用硫酸酸性鍍敷浴且藉由電鍍形成每一面的附著量為20g/m2，Ni10質量%的鍍Zn-Ni合金層，藉由在鍍敷浴中斷電且將浸漬時的溫度、時間進行各種變更而形成預定鍍敷層龜裂。鍍敷浴係使用與上述實驗例1相同者，溫度為50~65℃，浸漬時間係在1秒~5秒之間變更。隨後，與上述實驗例1同樣地進行而預定量形成在上述表1所顯示之各種組成的無鉻酸鹽化成皮膜。又，無鉻酸鹽化成皮膜的附著量係使用上述的螢光X射線法來測定。
評價係與上述實驗例1同樣地進行，但是在本實驗例，亦一併進行評價以下的SST耐蝕性。
將所製成的試樣之背面尾部及邊緣進行密封，進行依據JISZ2371所規定的鹽水噴霧試驗72小時且計量白鏽產生面積率(%)。
在以下的表3，將各試樣的鍍敷層龜裂狀態、使用的化成皮膜種、化成附著量、水接觸角、以及劣化汽油耐蝕性及SST耐蝕性評價結果一併顯示。又，劣化汽油耐蝕性評價結果，係在最大板厚減少值小0.05mm時，能夠判定為良好。又，SST耐蝕性係白鏽產生率小於5%小於時，能夠判定為良好。
從上述表3能夠清楚明白，本發明的實施例係任一者均顯示良好的特性。
特別是有關於劣化汽油耐蝕性，滿足(I)式者係在劣化汽油耐蝕性試驗的板厚減少為0，而顯示特別優異的劣化汽油耐蝕性。又，龜裂寬度小於0.5μm者，係在SST耐蝕性的白鏽產生率小於1%，而顯示優異的SST耐蝕性。特別是龜裂寬度小於0.5μm且龜裂數目小於50個時，在任一條件下均是SST耐蝕性的白鏽產生率為零，乃是特別優異。
從以上情形，滿足(I)式且龜裂數目為5個以上且小於50個，而且龜裂寬度小於0.5μm者，在劣化汽油耐蝕性及SST耐蝕性之雙方，均是特別優異。
成為燃料槽的內面之面係與實施例1同樣地製造，但是成為燃料槽的外面之面係進行各種變更。在實施例82係不在外面施加皮膜。實施例83、84係藉由毛刷磨削將成為外面之面的鍍敷層完全除去。隨後，在實施例83塗佈預定皮膜。實施例85~89係在使用前述方法將鍍敷層完全除去後之外面，再次藉由電鍍使預定附著量的Zn、Ni附著。
評價係如以下進行。
進行評價成為外面之面的塗裝性。與通常汽車或兩輪車用的燃料槽外面同樣地進行塗裝前處理(磷酸鋅處理)及電著塗裝，且目視判定其外觀。將容許水準者判定為○，
將非常均勻美麗者評判為「◎」。
在所製成的試樣，將防鏽油(Parker興產Noxrust530)進行極薄塗油(約0.1g/m2)之後，模擬鋼捲狀態而以成為內面之面與成為外面之面接觸的方式進行重疊捆包。使用在50℃98%RH環境下保管1個月後之試樣，進行與前述的塗裝性評價相同塗裝且基於相同基準進行評價。
以成為燃料槽的內面之面之間係成為內側的方式合在一起而進行接縫熔接，使熔接電流變化而求取能夠得到適當的熔核(nugget)之電流範圍。條件係如以下。
．電極：Cu-Cr合金且具有中央部為15mmR的4.5mm寬度、端部為4mmR的寬度8mm的剖面之圓盤狀電極
．熔接方法：雙層重疊、搭接縫熔接(lap seam welding)
．加壓力：400kgf(又，1kgf係約9.8N)
．通電時間：2/50秒通電on、1/50秒通電off
．冷卻：內部水冷、及外部水冷
．熔接速度：2.5m/分鐘
將結果顯示在表4。從上述表4能夠清楚明白，本發明的實施例係任一者均顯示良好的特性。而且，發現Zn與Ni的合計附著量為0.01~0.5g/m2時(實施例85~88)，鋼板的塗裝性、保管後塗裝性及熔接性係特別地提升。
以上，詳細地說明了本發明的適合實施形態，但是本發明係不被如此的例子限定。只要具有屬於本發明技術的領域之通常的知識者，係清楚明白在申請專利範圍所記載的技術思想範疇內，能夠創造出各種的變更例或修正例，應了解該等當然係屬於本發明的技術範圍。
依照本發明，因為能夠供一種在含有如劣化汽油的有機酸、甚至亦含有結露水的各種燃料環境下，顯示優異的耐蝕性之燃料槽用鋼板，所以在產業上係有用的。
本發明係提供一種使成為燃料槽外面之面成為裸金屬(bare metal)，使成為燃料槽內面之面成為無鉻酸鹽化成皮膜，而使內外面成為不同狀態的表面之鋼板。此種本發明的鋼板係具備從燃料槽的製造開始至使用為止所必要的所有性能，包括：(i)將鋼板加工且熔接而成為槽形狀時所必要的加工性優異；(ii)將加工後的燃料槽進行塗裝且
必須提高外觀的美觀時具有優異的塗裝性；以及(iii)製造後長年使用燃料槽時所必要的耐蝕性優異。
就內外面不同狀態的表面互相作用而能夠進一步發揮內外面的性能差異而言，本發明的鋼板係具有先前所沒有的效果。具體而言，係因為在燃料槽外面的裸金屬所塗佈的塗料(油)的剩餘部分，係被燃料槽內面的無鉻酸鹽化成皮膜吸附，所以外面的塗裝性塗佈提升。
Claims (10)
- 一種燃料槽用鋼板，具備：鍍Zn-Ni合金層，其係位於基鐵的一面或兩面且係形成於至少一面；及無機系無鉻酸鹽化成皮膜，其係位於前述鍍Zn-Ni合金層的上層；前述鍍Zn-Ni合金層具有龜裂，且所述龜裂係從該鍍Zn-Ni合金層與前述無機系無鉻酸鹽化成皮膜之界面起至到達前述鍍Zn-Ni合金層與前述鋼板之界面，而且在前述無機系無鉻酸鹽化成皮膜的表面之水接觸角為50度以上。
- 如請求項1之燃料槽用鋼板，其中前述基鐵的一面係具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜；與前述一面相反的面係不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜。
- 如請求項2之燃料槽用鋼板，其中在不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜之面之水接觸角為小於10度。
- 如請求項2或3之燃料槽用鋼板，其中在不具有前述鍍Zn-Ni合金層及前述無機系無鉻酸鹽化成皮膜之面之Zn及/或Ni的附著量為0.01~0.5g/m2。
- 如請求項1至4項中任一項之燃料槽用鋼板，其中前述無機系無鉻酸鹽化成皮膜係含有：選自矽烷偶合劑、矽烷 偶合劑的聚縮合物、氧化矽、矽酸鹽、磷酸、磷酸鹽之一種以上；及選自Ti、Zr、V、Mo、W之一種以上的金屬之化合物。
- 如請求項1至5項中任一項之燃料槽用鋼板，其中前述無機系無鉻酸鹽化成皮膜係含有撥水劑。
- 如請求項6之燃料槽用鋼板，其中前述撥水劑係選自聚烯烴蠟、矽系樹脂、氟系樹脂之1種以上。
- 如請求項1至7項中任一項之燃料槽用鋼板，其中剖面觀察前述鍍Zn-Ni合金層時，前述龜裂係每100μm的視野存在5個以上且50個以下。
- 如請求項8之燃料槽用鋼板，其中剖面觀察前述鍍Zn-Ni合金層而得到之每100μm的視野的前述龜裂的個數X個與前述水接觸角Y(度)，係滿足以下的(I)式表示之關係，Y≧-0.18X+56.5···(I)。
- 如請求項9之燃料槽用鋼板，其中剖面觀察前述鍍Zn-Ni合金層時，前述龜裂係每100μm的視野存在5個以上且小於50個，並且龜裂的最大寬度為小於0.5μm。
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| MX2017008628A (es) * | 2015-01-21 | 2017-11-15 | Nippon Steel & Sumitomo Metal Corp | Lamina de acero de superficie tratada para tanque de combustible. |
| KR102071515B1 (ko) * | 2015-09-29 | 2020-01-30 | 닛폰세이테츠 가부시키가이샤 | 방향성 전자 강판 및 방향성 전자 강판의 제조 방법 |
| JP7368712B2 (ja) * | 2019-10-21 | 2023-10-25 | 日本製鉄株式会社 | 熱間プレス成形用めっき鋼板 |
| WO2024111158A1 (ja) * | 2022-11-24 | 2024-05-30 | Ｊｆｅスチール株式会社 | 表面処理鋼板およびその製造方法 |
| WO2024111159A1 (ja) * | 2022-11-24 | 2024-05-30 | Ｊｆｅスチール株式会社 | 表面処理鋼板およびその製造方法 |
| JP7435924B1 (ja) | 2022-11-24 | 2024-02-21 | Ｊｆｅスチール株式会社 | 表面処理鋼板およびその製造方法 |
| JP7435925B1 (ja) | 2022-11-24 | 2024-02-21 | Ｊｆｅスチール株式会社 | 表面処理鋼板およびその製造方法 |
| EP4397786A1 (en) * | 2023-01-03 | 2024-07-10 | Henkel AG & Co. KGaA | Conversion coating composition for coloured layers on aluminium |
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| DE69122212T2 (de) | 1990-10-25 | 1997-01-30 | Matsushita Electric Industrial Co., Ltd., Kadoma, Osaka | Durch chemische Adsorption laminierter monomolekularer Film und Verfahren zu seiner Herstellung |
| JP2981040B2 (ja) * | 1990-10-25 | 1999-11-22 | 松下電器産業株式会社 | 化学吸着単分子累積膜及びその製造方法 |
| JPH0525679A (ja) * | 1991-07-20 | 1993-02-02 | Sumitomo Metal Ind Ltd | 耐衝撃密着性に優れた高耐食性表面処理鋼板 |
| JPH05106058A (ja) | 1991-10-18 | 1993-04-27 | Kawasaki Steel Corp | 燃料容器用高耐食性表面処理鋼板 |
| DE69625365T2 (de) * | 1996-06-06 | 2003-09-11 | Sumitomo Metal Ind | Oberflächenbehandeltes stahlblech mit hervorragenden korrosionseigenschaften nach der bearbeitung |
| JP2985767B2 (ja) | 1996-06-06 | 1999-12-06 | 住友金属工業株式会社 | 加工後耐食性に優れた表面処理鋼板 |
| JP2985768B2 (ja) * | 1996-06-06 | 1999-12-06 | 住友金属工業株式会社 | 加工後耐食性に優れた表面処理鋼板 |
| JP2985770B2 (ja) * | 1996-06-06 | 1999-12-06 | 住友金属工業株式会社 | 加工後耐食性に優れた表面処理鋼板 |
| JP2985769B2 (ja) | 1996-06-06 | 1999-12-06 | 住友金属工業株式会社 | 溶接性、加工後耐食性に優れた表面処理鋼板 |
| JPH11350186A (ja) * | 1998-06-02 | 1999-12-21 | Nkk Corp | 化成処理性とプレス加工性に優れたＺｎ−Ｎｉ系合金めっき鋼板の製造方法 |
| JP2004084499A (ja) * | 2002-08-23 | 2004-03-18 | Toyota Motor Corp | ディーゼルエンジン用燃料噴射ノズル及び燃料用タンク |
| JP2004169122A (ja) * | 2002-11-20 | 2004-06-17 | Nippon Steel Corp | 亜鉛系燃料容器用鋼板 |
| JP2005068511A (ja) * | 2003-08-26 | 2005-03-17 | Sumitomo Metal Ind Ltd | プレコート鋼板 |
| JP4776458B2 (ja) | 2005-07-22 | 2011-09-21 | 新日本製鐵株式会社 | 耐食性、耐熱性、耐指紋性、導電性、塗装性および加工時の耐黒カス性に優れたクロメートフリー表面処理金属材 |
| JP2007186745A (ja) | 2006-01-12 | 2007-07-26 | Jfe Steel Kk | 燃料タンク用鋼板 |
| CN100480428C (zh) * | 2007-01-12 | 2009-04-22 | 北京化工大学 | 超疏水高粘附复合金属氧化物薄膜及其制备方法 |
| WO2010061964A1 (ja) * | 2008-11-28 | 2010-06-03 | 新日本製鐵株式会社 | クロメートフリー表面処理金属材 |
| JP5369986B2 (ja) * | 2009-08-07 | 2013-12-18 | 新日鐵住金株式会社 | 塗装金属材とそれを用いてなる筐体 |
| JP5715556B2 (ja) | 2011-12-27 | 2015-05-07 | 新日鐵住金株式会社 | 加工後耐食性と耐劣化燃料性とに優れた亜鉛系めっき鋼板 |
| JP5701268B2 (ja) | 2012-03-27 | 2015-04-15 | 朝日化学工業株式会社 | 耐食性などに優れた亜鉛系めっき鋼板用の表面処理剤および該表面処理剤で被覆された亜鉛系めっき鋼板 |
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| CN107208277A (zh) | 2017-09-26 |
| EP3231896A4 (en) | 2018-04-25 |
| EP3231896A1 (en) | 2017-10-18 |
| TWI586836B (zh) | 2017-06-11 |
| KR20170098308A (ko) | 2017-08-29 |
| ES2800478T3 (es) | 2020-12-30 |
| CN107208277B (zh) | 2019-06-21 |
| MX2017008941A (es) | 2017-12-07 |
| BR112017012657A2 (pt) | 2017-12-26 |
| JP6066019B2 (ja) | 2017-01-25 |
| US20170361571A1 (en) | 2017-12-21 |
| JPWO2016125740A1 (ja) | 2017-04-27 |
| US10688755B2 (en) | 2020-06-23 |
| EP3231896B9 (en) | 2020-08-12 |
| KR101941806B1 (ko) | 2019-01-23 |
| WO2016125740A1 (ja) | 2016-08-11 |
| EP3231896B1 (en) | 2020-04-01 |
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