EP1439243B1 - Method of non-chromate pretreatment for metal alloys - Google Patents
Method of non-chromate pretreatment for metal alloys Download PDFInfo
- Publication number
- EP1439243B1 EP1439243B1 EP03001023A EP03001023A EP1439243B1 EP 1439243 B1 EP1439243 B1 EP 1439243B1 EP 03001023 A EP03001023 A EP 03001023A EP 03001023 A EP03001023 A EP 03001023A EP 1439243 B1 EP1439243 B1 EP 1439243B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- organic
- alloy
- organic acid
- alloy surface
- 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 - Lifetime
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- 238000000034 method Methods 0.000 title claims abstract description 36
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001092 metal group alloy Inorganic materials 0.000 title abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 78
- 239000000956 alloy Substances 0.000 claims abstract description 78
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 150000007524 organic acids Chemical class 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 238000003618 dip coating Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000007522 mineralic acids Chemical group 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 5
- 238000007761 roller coating Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 125000002521 alkyl halide group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 4
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 4
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 claims description 3
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 3
- -1 aryl alcohol Chemical compound 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005237 degreasing agent Methods 0.000 claims description 3
- 239000013527 degreasing agent Substances 0.000 claims description 3
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- SKWZHINXPDOQDF-UHFFFAOYSA-N disilanyl(ethenyl)silane Chemical compound [SiH3][SiH2][SiH2]C=C SKWZHINXPDOQDF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 238000009501 film coating Methods 0.000 abstract description 4
- 239000007888 film coating Substances 0.000 abstract description 3
- 150000001455 metallic ions Chemical class 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 20
- 239000010409 thin film Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007797 corrosion 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
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
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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
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- This invention relates to a method of non-chromate pretreatment for magnesium alloys, particularly to one in which film treatment is carried out after an alloy surface is degreased and cleaned.
- the process of film treatment is to have the alloy surface coated with coating liquid which will bond with the alloy surface to form a film thereon, impossible to produce industrial waste water with heavy metallic ion, reducing environmental pollution to the minimum, simple in handling, and able to elevate producing efficiency and lower producing cost.
- a conventional process for treating an alloy surface acid conversion or anodizing in acid liquid has to be carried out in order to produce a rough and porous oxidized layer on the alloy surface for facilitating gluing or lacquering.
- the process of treating the alloy surface is to have an alloy surface degreased and cleaned first and then water washed through two stages to ensure its cleanness and then pickled to remove dissociative agent, and then water rinsing again so as to remove pickling liquid from the alloy surface for carrying out sequent film forming. Subsequently, the alloy has its surface treated with dip coating, spray coating or roll coating with film forming agent, which will react to the alloy surface for preventing corrosion and sequent lacquering with excellent physical adhesion.
- EP 0 358 338 A2 discloses a method of pretreatment for metals like titanium, copper, zinc, aluminium and their alloys. This method includes the steps of degreasing and water rinsing. Afterwards the surface is treated by a pretreatment solution which is an aqueous composition comprising an inorganic hydrous oxide sol in order to form a protective coating.
- This aqueous composition may contain an adhesion promoter, for instance one or more silane coupling agents.
- JP 57023057 A discloses a method of treating the surface of magnesium or magnesium alloys by a coating composition containing a silane coupling agent like vinyl trichlorosilane.
- JP 02034790 A discloses a method for treating steel sheets by applying a solution containing one or more of (1) an alkoxide of Al, Zr, Ti, (2) monomethyl alkoxide of the metals, and (3) one or more of acetylacetonate salts, and an amount of silane coupling agent.
- One objective of the invention is to offer a method of non-chromate pretreatment for metal alloys, impossible to produce heavy metallic waste water to pollute environment and able to reduce producing cost.
- Another objective of the invention is to offer a method of non-chromate pretreatment for metal alloys, able to let a treated alloy surface have high adhesion, high conductivity, and anti-rust, anti-corrosion, anti-finger, anti-dust and water repellence functions.
- the main feature of the invention is a treating process including degreasing, water rinsing acid pretreatment and film treatment as specified in claim 1.
- the film treatment is to have an alloy surface coated with coating liquid to carry out continuously a coating reaction on the alloy surface until the coating liquid bonds with the alloy surface and forms a film thereon.
- the film coating liquid applies aluminum sec-butoxide or a combination freely composed of more than one of the following chemicals: vinyltrimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ⁇ -methacryloxypropyl-trimethoxysilane, ⁇ -chloropropyl-trimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, isobutyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tert-butyldimethylchlorosilane, vinyltrichlorosilane, ⁇ -mercaptopropyl-trimethoxysilane, diphenyldichlorosilane, hexamethyldisilane, vinyltrisilane, zirconiumpropoxide, ethylsilicate, 1,1,2,2-tetrahydroct
- the invention is a method of non-chromate pretreatment especially for magnesium alloy.
- the treating step is to have the magnesium alloy surface degreased and water rinsed first and then acid treatment before carrying out film coating.
- the alloy surface is treated with a mixed solution of organic and inorganic acid to let the alloy surface present metal original color or gray or black and become activated to form a thin film afterward.
- the treatment on metal surface with a mixed solution of organic and inorganic acid can remove oxidization layer from the metal surface and form hydroxyl group thereon to facilitate sequent film treatment.
- a method of non-chromate pretreatment for metal alloys, inclusive of aluminum alloy, titanium alloy, zinc alloy or copper alloy as shown in Fig. 2 is to have the alloy surface degreased and cleaned first and then carry out spray coating, dip coating or roller coating and then bake it for five to thirty minutes at a temperature 150°C ⁇ 200°C to get a film with a thickness around 0.5 ⁇ 1 ⁇ m.
- the steps of treating the alloy surface are as follows.
- a preferred embodiment of a method of non-chromate pretreatment for magnesium alloy in the present invention includes the following steps:
- the modes of the film treatment in the steps of the preferred embodiment mentioned above may have the following processes.
- the alloy surface formed with a thin film and treated through the above-mentioned processes is tested by salt spraying for twenty four hours, The result is that less than 5% corrosion area of the alloy surface that means the treated alloy performming well in quality.
- the alloy treated through the foresaid processes passes the adhesion tested per ASTM D3359-97 by over coat on the treated alloy surface. Further, the alloy treated through the foresaid processes is tested in conductivity by means of a HP milliohmer (HP4338) and the result is less than 0.3 m ⁇ , it means that the alloy surface has good conductivity.
- HP milliohmer HP4338
- the method of non-chromate pretreatment for magnesium alloys in the invention has the following advantages.
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Abstract
Description
- This invention relates to a method of non-chromate pretreatment for magnesium alloys, particularly to one in which film treatment is carried out after an alloy surface is degreased and cleaned. The process of film treatment is to have the alloy surface coated with coating liquid which will bond with the alloy surface to form a film thereon, impossible to produce industrial waste water with heavy metallic ion, reducing environmental pollution to the minimum, simple in handling, and able to elevate producing efficiency and lower producing cost.
- For the present, communication electronic products, such as portable computers, mobile phones, radars and the like, have a tendency to become comparatively light, thin and small. An alloy which is thin and light and has great strength (unit weight), high vibration-resisting force, good conductivity and a function of isolating EMI, most meet the requirements of the foresaid products, including magnesium alloy, aluminum alloy, titanium alloy, zinc alloy or copper alloy.
- In a conventional process for treating an alloy surface, acid conversion or anodizing in acid liquid has to be carried out in order to produce a rough and porous oxidized layer on the alloy surface for facilitating gluing or lacquering. The process of treating the alloy surface, as shown in
Fig. 1 , is to have an alloy surface degreased and cleaned first and then water washed through two stages to ensure its cleanness and then pickled to remove dissociative agent, and then water rinsing again so as to remove pickling liquid from the alloy surface for carrying out sequent film forming. Subsequently, the alloy has its surface treated with dip coating, spray coating or roll coating with film forming agent, which will react to the alloy surface for preventing corrosion and sequent lacquering with excellent physical adhesion. Although this conventional method has been employed for many years and proved effective, yet it is too complicated and acid used for treating an alloy surface is mostly inclusive of chromium ion (six valence chromium), phosphorous ion vanadium ion, manganese ion of heavy metal, seriously polluting environment, wasting much water and increasing producing cost. -
EP 0 358 338 A2 discloses a method of pretreatment for metals like titanium, copper, zinc, aluminium and their alloys. This method includes the steps of degreasing and water rinsing. Afterwards the surface is treated by a pretreatment solution which is an aqueous composition comprising an inorganic hydrous oxide sol in order to form a protective coating. This aqueous composition may contain an adhesion promoter, for instance one or more silane coupling agents. -
JP 57023057 A -
JP 02034790 A - One objective of the invention is to offer a method of non-chromate pretreatment for metal alloys, impossible to produce heavy metallic waste water to pollute environment and able to reduce producing cost.
- Another objective of the invention is to offer a method of non-chromate pretreatment for metal alloys, able to let a treated alloy surface have high adhesion, high conductivity, and anti-rust, anti-corrosion, anti-finger, anti-dust and water repellence functions.
- The main feature of the invention is a treating process including degreasing, water rinsing acid pretreatment and film treatment as specified in claim 1. The film treatment is to have an alloy surface coated with coating liquid to carry out continuously a coating reaction on the alloy surface until the coating liquid bonds with the alloy surface and forms a film thereon. The film coating liquid applies aluminum sec-butoxide or a combination freely composed of more than one of the following chemicals: vinyltrimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, γ-methacryloxypropyl-trimethoxysilane, γ-chloropropyl-trimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, isobutyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tert-butyldimethylchlorosilane, vinyltrichlorosilane, γ-mercaptopropyl-trimethoxysilane, diphenyldichlorosilane, hexamethyldisilane, vinyltrisilane, zirconiumpropoxide, ethylsilicate, 1,1,2,2-tetrahydroctyl-1-triethoxysilane, titanium( IV )propoxide, titanium( IV )isopropoxide, titanium( IV )butoxide, titanium(IV)sec-butoxide, or titanium(IV)tert-butoxide.
- The invention is a method of non-chromate pretreatment especially for magnesium alloy. The treating step is to have the magnesium alloy surface degreased and water rinsed first and then acid treatment before carrying out film coating. The alloy surface is treated with a mixed solution of organic and inorganic acid to let the alloy surface present metal original color or gray or black and become activated to form a thin film afterward. In reality, the treatment on metal surface with a mixed solution of organic and inorganic acid can remove oxidization layer from the metal surface and form hydroxyl group thereon to facilitate sequent film treatment.
- This invention will be better understood by referring to the accompanying drawings, wherein:
-
Fig.1 is a block diagram of a flowing process of a conventional method for treating the surface of magnesium alloy; -
Fig.2 is a block diagram of a flowing process of a method of non-chromate pretreatment for metal alloys; and, -
Fig.3 is a block diagram of a flowing process of a method of non-chromate pretreatment for magnesium alloy in the present invention. - A method of non-chromate pretreatment for metal alloys, inclusive of aluminum alloy, titanium alloy, zinc alloy or copper alloy as shown in
Fig. 2 , is to have the alloy surface degreased and cleaned first and then carry out spray coating, dip coating or roller coating and then bake it for five to thirty minutes at a temperature 150°C ~200°C to get a film with a thickness around 0.5~1 µm. The steps of treating the alloy surface are as follows. - 1. Degreasing: A primary alloy is treated with degreasing agent to remove superficial oily dirt from the alloy surface.
- 2. Water rinsing: The degreased alloy surface is rinsed to keep it clean.
- 3. Thin film treatment: The alloy surface is treated with dip coating, spray coating or roller coating with coating liquid which will bond with the alloy surface and form a film on the alloy surface.
The coating liquid employs aluminum sec-butoxide or a compound freely composed of more than one of the following chemicals: vinyltrimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, γ-methacryloxypropyl-trimethoxysilane, γ-chloropropyl-trimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, isobutyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tert-butyldimethylchlorosilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane,diphenyldichlorosilane, hexamethyldisilane, vinyltrisilane, zirconiumpropoxide, ethylsilicate, 1,1,2,2-tetrahydroctyl-1-triethoxysilane, titanium( IV )propoxide, titanium( IV )isopropoxide, titanium( IV )butoxide, titanium(IV)sec-butoxide, or titanium(IV)tert-butoxide. - 4. Painting: apply lacquer or adhesives to the surface of the film formed on the alloy surface, but whether this step is necessary or not depends on forming quality of the film and requirement of the product.
- A preferred embodiment of a method of non-chromate pretreatment for magnesium alloy in the present invention, as shown in
Fig.3 , includes the following steps: - 1. Degreasing: Primary magnesium alloy is degreased with a degreasing agent to remove superficial oily dirt from its surface.
- 2. Water rinsing: The degreased magnesium alloy is rinsed to keep its surface clean.
- 3. Acid treatment: The alloy surface is treated with a mixed solution of organic and inorganic acid to let the alloy surface present metal original color or gray or black and become activated to enhance forming a thin film afterward. The mixed solution of organic-inorganic acid can be an inorganic acid or an organic acid singly, or a mixed solution of both. The organic acid in the solution can be selected from more than one of the followings: acid, alcoholic acid, diacid and phosphonic acid, while the inorganic acid can be selected from more than one of the followings: hydrochloric acid, phosphoric acid, boric acid or nitric acid.
The general formula of the organic acid is R-(COOH):- when R is alkyl, the organic acid is alkanoic acid;
- when R is alkenyl, the organic acid is alkene acid;
- when R is aryl, the organic acid is aromatic acid;
- when R is alkylhalide, the organic acid is halidealkanoic acid;
- when R is hydrogen, the organic acid is formic acid; and,
- when R is alkynyl, the organic acid is alkyne acid.
The general formula of the organic alcohol acid is (HO)-R-(COOH):- when R is alkyl, the organic acid is hydroxyalkanoicacid;
- when R is alkenyl, the organic acid is hydroxyalkenoicacid;
- when R is aryl, the organic acid is aryl alcoholic acid; and,
- when R is alkynyl, the organic acid is hydroxyalkynoicacid.
The general formula of the organic diacid is (HOOC)-R-(COOH):- when R is alkyl, the organic acid is alkyl diacid;
- when R is alkenyl, the organic acid is alkene diacid;
- when R is aryl, the organic acid is aryl diacid; and,
- when R is alkynyl, organic acid is alkyne diacid.
The general formula of the organic phosphoric acid is (R1O), (R2O)-(POOH):- when R is alkyl, the organic acid is dialkylphosphoric acid;
- when R is alkenyl, the organic acid is dialkene phosphoric acid;
- when R is alkylhalide, the organic is halidedialkylphosphoric acid;
- when R is hydrogen, the organic is phosphoric acid; and,
- when R is alkynyl, the organic is dialkyne phosphoric acid.
- 4. Water rinsing: All acid residuals are removed from alloy surface by water rinsing.
- 5. Removing of oxide on the alloy surface: After acid treatment, the alloy is put in a solution of acidity or alkalinity to remove oxide from the alloy surface. Meanwhile in this process, the alloy surface produces hydroxyl.
- 6. The acidic or alkaline solution left on the alloy surface is cleaned up by water.
- 7. Thin film treatment: The alloy surface formed with hydroxyl group is treated by dip coating, spray coating or roller coating with coating liquid which will bond with the hydroxyl group on the alloy surface and form a film thereon. The coating liquid employs aluminum sec-butoxide or a compound freely composed of more than one of the ingredients listed in the first preferred embodiment of the invention.
- 8. Curing: The alloy formed with a film on the surface is cured for five to thirty minutes at a temperature around 150°C~200°C to finish thin film coating on the alloy surface.
- In addition, the modes of the film treatment in the steps of the preferred embodiment mentioned above may have the following processes.
- (A). Dip coating with coating liquid:
The ingredient of the coating liquid forms an extremely thin film on an alloy surface, and then the alloy is centrifugated by a centrifugal machine. Then, the alloy formed with a film on the surface is cured for about five to thirty minutes at a temperature around 150°C~200°C to obtain a film with a thickness around 0.5~1 µm, thus finishing coating a film on the alloy surface. - (B). Heat the alloy with coating liquid: The coating liquid is first reacts with the alloy surface which immersed in the liquid, and also the nano-particle ingredients in the coating liquid will penetrate into the alloy surface to make up an extremely thin film thereon and then cured. The thin film thickness is around 0.5~1µm.
- Subsequently, the alloy surface formed with a thin film and treated through the above-mentioned processes is tested by salt spraying for twenty four hours, The result is that less than 5% corrosion area of the alloy surface that means the treated alloy performming well in quality.
- Besides, the alloy treated through the foresaid processes passes the adhesion tested per ASTM D3359-97 by over coat on the treated alloy surface. Further, the alloy treated through the foresaid processes is tested in conductivity by means of a HP milliohmer (HP4338) and the result is less than 0.3 mΩ, it means that the alloy surface has good conductivity.
- As can be noted from the above description, the method of non-chromate pretreatment for magnesium alloys in the invention has the following advantages.
- 1. Promotion of anti-corrosion : In the process of thin film forming, chemical bonding takes the place of physical engagement, able to make up a strong adhesion and extreme thin film with anti-corrosion performance.
- 2. Increasing adhesion in coating or gluing: By adhesion test, it is proved that the paint on the alloy surface treated through the process of this invention is performing well. Besides, there is a variety of coating liquids, so chemical ingredients for coating on an alloy surface can be freely selected and adjusted for use, able to acquire different capacities in adhesion, anti-rust, anti-corrosion, anti-finger, anti-dust conductivity and in water repellence.
- 3. Having good conductivity: The conductivity of the treated alloy, tested by a HP milliohmer (HP4338), is less than 0.3mΩ, indicating that the alloy treated through the process of this invention has excellent conductibility.
- 4. The alloy surface treated by the method of this invention is able to reduce adherence of fingerprint and dust.
- 5. No water rinsing process is used after thin film formed on the alloy surface and no heavy metallic ion in the agents employed for treating the alloy surface, impossible to waste and pollute water.
- 6. The film is formed on the alloy surface by means of dip coating, spray coating or roller coating, simple and easy in handling, greatly lowering cost in equipment and able to produce products with high throughput.
- While the preferred embodiments of the invention have been described above, it will be recognized and understood that various modifications may be made therein and the appended claims are intended to cover all such modifications that may fall within the scope of said claims.
Claims (3)
- Method of non-chromate pretreatment for magnesium alloys comprising:(a) a first step of degreasing: an alloy is primarily treated with a degreasing agent to remove superficial oily dirt from the surface of said alloy:(b) a second step of water rinsing: said alloy surface finished in step (a) is rinsed with water to make it clean;(c) a third step of acid pretreatment: a mixed solution of organic-inorganic acid is applied on the surface of said magnesium alloy to let the surface of said magnesium alloy present its original color or gray or black and make its surface activated to enhance a film's formation; using said mixed solution of said organic-inorganic acid for acid pretreatment on an alloy surface can activate a metal and remove oxide from its surface and form hydroxyl group thereon so as to enhance sequent film treatment;(d) a fourth step of film treatment: said alloy surface is coated with coating liquid, said coating liquid carrying out reaction on said alloy surface, said coating liquid bonding with said alloy surface and forming a film on said alloy surface, said coating liquid using aluminium sec-butoxide or a compound freely composed of more than one of the following chemicals: vinyltrimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, γ-methacryloxypropyl-trimethoxysilane, γ-chloropropyl-trimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, decyltrimethoxysilane, isobutyltrimethoxysilane, 3-aminopropyltrimethoxysilane, tert-butyldimethylchlorosilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, diphenyldichlorosilane, hexamethyldisilane, vinyltrisilane, zirconiumpropoxide, ethylsilicate, 1,1,2,2-tetrahydroctyl-1-triethoxysilane, titanium(IV)propoxide, titanium(IV)isopropoxide, titanium(IV)butoxide, titanium(IV)sec-butoxide, or titanium(IV)tert-butoxide.
- Method according to claim 1, characterized in that after film treatment, said film formed on said alloy surface can be lacquered or stuck thereon with adhesives, and the way of applying said coating liquid on said alloy surface is dip coating, spray coating or roller coating.
- Method according to claim 1 or 2, characterized in that activation treatment is carried out after said alloy surface finishes acid treatment; said activation treatment is to have said alloy dipped in an acidic or alkaline solution to let said alloy surface produce hydroxyl group, and said mixed solution of said organic-inorganic acid used for acid treatment is inorganic acid or organic acid singly, or a mixed solution of both; said organic acid can be selected from more than one of the followings, acid, alcohol acid, diacid and phosphonic acid, while said inorganic acid can be selected from more than one of the followings, hydrochloric acid, phosphoric acid, boric acid or nitric acid; and,
the general formula of said organic acid being R-(COOH):when R is alkyl, said organic acid being alkanoic acid;when R is alkenyl, said organic acid being alkene acid;when R is aryl, said organic acid being aromatic acid;when R is alkylhalide, said organic acid being halidealkanoic acid;when R is hydrogen, said organic acid being formic acid;when R is alkynyl, said organic acid being alkyne acid; and,the general formula of organic alcohol acid being (HO)-R-(COOH):when R is alkyl, said organic acid being hydroxyalkanoic acid;when R is alkenyl, said organic acid being hydroxyalkenoic acid;when R is aryl, said organic acid being aryl alcohol acid;when R is alkynyl, said organic acid being hydroxyalkynoic acid; andthe general formula of organic diacid being (HOOC)-R-(COOH):when R is alkyl, said organic acid being alkyl diacid;when R is alkenyl, said organic acid being alkene diacid;when R is aryl, said organic acid being aryl diacid;when R is alkynyl, said organic acid being alkyne diacid; and,the general formula of organic phosphoric acid being (R1O), (R2O)-(POOH):when R is alkyl, said organic acid being dialkyl phosphoric acid;when R is alkenyl, said organic acid being dialkene phosphoric acid;when R is alkylhalide, said organic acid being halidedialkyl phosphoric acid;when R is hydrogen, said organic acid being phosphoric acid;when R is alkynyl, said organic acid being dialkyne phosphoric acid.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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AT03001023T ATE389738T1 (en) | 2003-01-17 | 2003-01-17 | CHROMATE-FREE PRETREATMENT PROCESS FOR METAL ALLOYS |
DE60319795T DE60319795T2 (en) | 2003-01-17 | 2003-01-17 | Chromate-free pretreatment process for metal alloys |
EP03001023A EP1439243B1 (en) | 2003-01-17 | 2003-01-17 | Method of non-chromate pretreatment for metal alloys |
ES03001023T ES2302873T3 (en) | 2003-01-17 | 2003-01-17 | METHOD OF PRE-TREATMENT WITHOUT CHROMATE FOR METAL ALLOYS. |
Applications Claiming Priority (1)
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EP03001023A EP1439243B1 (en) | 2003-01-17 | 2003-01-17 | Method of non-chromate pretreatment for metal alloys |
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EP1439243B1 true EP1439243B1 (en) | 2008-03-19 |
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AT (1) | ATE389738T1 (en) |
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CN107739929A (en) * | 2017-11-29 | 2018-02-27 | 西华大学 | A kind of high-weatherability aluminium alloy and preparation method thereof |
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US8916020B2 (en) | 2007-12-05 | 2014-12-23 | 3M Innovative Properties Company | Assembly bonded to a structural adhesive and method and applicator for making it |
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JPS5723057A (en) * | 1980-07-17 | 1982-02-06 | Hitachi Ltd | Surface treatment of magnesium or magnesium alloy |
JPH0234790A (en) * | 1988-07-21 | 1990-02-05 | Nisshin Steel Co Ltd | Production of surface-treated steel sheet having superior durability and adhesion to organic resin |
IN176027B (en) * | 1988-08-12 | 1995-12-23 | Alcan Int Ltd |
-
2003
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CN107739929A (en) * | 2017-11-29 | 2018-02-27 | 西华大学 | A kind of high-weatherability aluminium alloy and preparation method thereof |
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DE60319795T2 (en) | 2009-04-16 |
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