CN1978704A - Method for surface treatment of aluminum alloy - Google Patents
Method for surface treatment of aluminum alloy Download PDFInfo
- Publication number
- CN1978704A CN1978704A CNA200510125869XA CN200510125869A CN1978704A CN 1978704 A CN1978704 A CN 1978704A CN A200510125869X A CNA200510125869X A CN A200510125869XA CN 200510125869 A CN200510125869 A CN 200510125869A CN 1978704 A CN1978704 A CN 1978704A
- Authority
- CN
- China
- Prior art keywords
- chemical conversion
- zinc phosphate
- aluminium alloy
- ion
- aluminum alloy
- 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.)
- Pending
Links
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000004381 surface treatment Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 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 claims abstract description 52
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 31
- -1 iron ion Chemical class 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 15
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 239000003352 sequestering agent Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 10
- 150000002222 fluorine compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 8
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 125000002843 carboxylic acid group Chemical group 0.000 abstract 1
- 239000013522 chelant Substances 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001398 aluminium Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000007667 floating Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 229950006191 gluconic acid Drugs 0.000 description 1
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- AFYAQDWVUWAENU-UHFFFAOYSA-H nickel(2+);diphosphate Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O AFYAQDWVUWAENU-UHFFFAOYSA-H 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
-
- 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
- C23C22/07—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
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- 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
- C23C22/364—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 also manganese cations
- C23C22/365—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 also manganese cations containing also zinc and nickel cations
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
Abstract
A method for surface treatment of aluminum alloy to form a uniform and dense zinc phosphate coating, which has excellent corrosion resistance properties on the surface of the aluminum alloy. The method includes steps of surface adjusting the surface of the aluminum alloy by a surface adjustor containing a predetermined volume of zinc phosphate particles, copolymer containing carboxylic acid group, and natural hectorite and/or synthetic hectorite respectively, and chemical conversion treating the surface of the resultant aluminum alloy by a zinc phosphate treating agent containing a predetermined volume of chelating agent that can chelate bond with iron ion.
Description
Technical field
The present invention relates to a kind of surface treatment method of aluminium alloy, particularly on the surface of aluminium alloy, can form the surface treatment method of the aluminium alloy of good, the even and fine and close lithoform of erosion resistance.
Background technology
In each fields such as car body and automobile component, material of construction, furniture, utilize the metallic substance of steel plate, steel plate galvanized, aluminium alloy etc., apply after will these metallic substance being shaped, thereby make finished product.Coating is except the outward appearance that can improve these metallic substance, its main purpose is to prevent Corrosion of Metallic Materials, as the pre-treatment that applies, according to order implement degreasing, surface adjust, and chemical conversion handle the surface treatment of (conversion treatment, chemical method (metal) surface treatment) etc.
It is in the chemical conversion of next procedure is handled that the surface is adjusted, and evenly and promptly forms highdensity chemical conversion in the surperficial integral body of metallic substance and handles the needed processing of film.Specifically, by making the surface of surface conditioner contacting metal material, thereby make the surface adsorption upper surface of metallic substance adjust the agent particle, and then promote to form chemical conversion and handle film.
Yet in car body and trolley part, the local aluminium alloy that uses, its aluminium alloy are used for and cold-rolled steel sheet (below, be called SPC) or alloy molten steel plate galvanized (below, be called GA) contact.In such parts, because aluminium is easier comparatively speaking Ionized metal, so, aluminium excessive dissolving and situation of causing chemical conversion film normally not form in chemical conversion treating agent are often arranged.
Relative therewith, assemble car body etc. by clamping isolator between aluminium alloy and SPC or aluminium alloy and GA, the excessive dissolving of aluminium in chemical conversion treating agent can be suppressed, thereby good chemical conversion film can be on aluminium alloy, formed.
But, when adopting isolator, when the galvanic deposit of carrying out next procedure applies, do not have electric current to flow through in the aluminium alloy, thereby can not normally apply.Therefore, apply in the operation in galvanic deposit, need be by connection aluminium alloys such as other cables.And, curing in the operation after galvanic deposit applies, because isolator shrinks, so, need reinforcement.Thereby, need more than usual operation, and special production line is absolutely necessary also.
And the content of copper reduces as the erosion resistance of aluminium alloy, particularly rust-preventing characteristic and waterproof binding property for a long time in aluminium alloy.This be because, the potential difference of aluminium and copper is very big, under corrosive environment, the remarkable dissolved of aluminium.Therefore,, need to reduce the content of copper in the aluminium alloy for guaranteeing good erosion resistance, but because relate to the increase of cost, therefore, the solution that can not say so.
Therefore, developing a kind ofly on the surface of aluminium alloy, can form the surface treatment method that film is handled in good, the even and fine and close chemical conversion of erosion resistance, is the problem that urgency is to be solved that this area practitioner faces.In No. 3366826 communique of Japanese Patent (hereinafter referred to as patent documentation 1), the method that chemical conversion treating agent is improved for addressing this is that is disclosed.In this patent documentation 1, the zinc phosphate treatment agent that proposes is characterized in that, be the aqueous solution, and contain can chelating with iron ion sequestrant, be scaled 0.025g/l～0.45g/l with Fe, the main component of this aqueous solution is: zine ion 0.1g/l～2.0g/l, nickel ion 0.1g/l～4.0g/l, mn ion 0.1g/l～3.0g/l, phosphate anion 5g/l～40g/l, nitrate ion 0.1g/l～15g/l, nitrite ion 0.01g/l～0.5g/l, complex fluorides as fluorochemical, be scaled 0.5g/l～1.0g/l with F, and pure fluorochemical, be scaled 0.3g/l～0.5g/l according to this zinc phosphate treatment agent with F, at the content of copper is aluminum alloy surface smaller or equal to mass ratio 0.1%, or on its ground finish surface, it is good to form erosion resistance, even and fine and close lithoform.
Summary of the invention
The present invention is as the method that addresses the aforementioned drawbacks, start with from the improvement of surface conditioner and improvement two aspects of chemical conversion treating agent, its purpose is, is provided at the aluminium alloy surface treatment method that can form good, the even and fine and close lithoform of erosion resistance on the surface of aluminium alloy.
The present inventor has carried out repeatedly for addressing the aforementioned drawbacks, unremitting research, consequently, by containing the zinc phosphate particle that is respectively predetermined amount, carboxylic multipolymer, and the surface conditioner of natural hectorite and/or synthetic li-montmorillonite, aluminum alloy surface is carried out after the surface adjusts, by contain predetermined amount with iron ion can chelating the zinc phosphate chemical conversion treating agent of sequestrant carry out chemical conversion and handle, thus, it is good to form erosion resistance on the surface of aluminium alloy, even and fine and close lithoform, thus the present invention finished.More particularly, the invention provides following method.
The aluminium alloy surface treatment method of first embodiment of the present invention comprises following operation: the surface of degreasing and washing aluminium alloy; By surface conditioner described aluminum alloy surface of carrying out degreasing and washing is carried out surface adjustment; And by the zinc phosphate chemical conversion treating agent described aluminum alloy surface of having carried out surperficial adjustment is carried out chemical conversion and handle, the PH of described surface conditioner is 7 to 12, it contains: D
50Smaller or equal to the zinc phosphate particle 50ppm of 3 μ m to 2000ppm; Carboxylic multipolymer 2ppm is to 200ppm, this multipolymer forms by copolyreaction by containing less than the vinylformic acid of mass ratio 50% with greater than the monomer composition of the 2-acrylamido-2-methyl propane sulfonic acid of mass ratio 50%, and natural hectorite and/or synthetic li-montmorillonite 3ppm are to 200ppm, described zinc phosphate chemical conversion treating agent is formed by acidic aqueous solution, and this acidic aqueous solution contains: zine ion 0.1g/l is to 2.0g/l; Nickel ion 0.1g/l is to 4.0g/l; Mn ion 0.1g/l is to 3.0g/l, and phosphate anion 5g/l is to 40g/l; Fluorine in the complex fluorides (converting with F) 0.5g/l is to 1.0g/l; Fluorine in the pure fluorochemical (converting with F) 0.3g/l is to 0.5g/l; And can with iron in the sequestrant of iron ion chelating (converting) 0.025g/l with Fe to 0.45g/l.
Second embodiment of the present invention is that the content of copper is smaller or equal to mass ratio 0.2% in the described aluminium alloy according to the described aluminium alloy surface treatment method of (1) (first embodiment).
Can provide a kind of aluminium alloy surface treatment method according to the present invention, utilize this method can on the surface of aluminium alloy, form good, the even and fine and close lithoform of erosion resistance.
Description of drawings
Fig. 1 illustrates SPC contacts the process object raw material of conducting with aluminium alloy synoptic diagram.
Embodiment
Below, describe about embodiments of the present invention.
(surface conditioner)
Employed in the present invention surface conditioner is the surface conditioner that contains the zinc phosphate particle that is respectively predetermined amount, carboxylic multipolymer and natural hectorite and/or synthetic li-montmorillonite.More particularly, the pH value of surface conditioner is 7 to 12, and it contains: D
50Smaller or equal to the zinc phosphate particle 50ppm of 3 μ m to 2000ppm (more than or equal to 500ppm and smaller or equal to 2000ppm, down with); Carboxylic multipolymer 2ppm is to 200ppm, this multipolymer forms by copolyreaction by containing less than the vinylformic acid of mass ratio 50% with greater than the monomer composition of the 2-acrylamido-2-methyl propane sulfonic acid of mass ratio 50%, and natural hectorite and/or synthetic li-montmorillonite 3ppm are to 200ppm.
Utilize the known in the prior art surface conditioner that contains divalence or tervalent phosphate particle, on the surface of aluminium alloy, can not form the chemical conversion film of sufficient quantity, relative therewith, use surface conditioner of the present invention just can form the chemical conversion film of sufficient quantity.Therefore, according to surface treatment method involved in the present invention, can make aluminium alloy have enough erosion resistancies.
The zinc phosphate particle that comprises in the surface conditioner of Shi Yonging in the present invention, D
50Smaller or equal to 3 μ m, less than the particle diameter of the zinc phosphate particle that in the surface conditioner of prior art, uses.Therefore, can suppress the sedimentation of zinc phosphate particle in surface conditioner, improve stability.And, adsorbable a large amount of surface conditioner particle on the surface of aluminium alloy, thereby the formation of promotion chemical conversion film.In addition, as the D of zinc phosphate particle
50For smaller or equal to 0.01 μ m the time, disperse owing to cross, might cause the zinc phosphate particle coacervation, therefore, not preferred.Be preferably 0.05 μ m to 1 μ m.
At this, D
50Be called as volume 50% diameter, expression when whole volumes of zinc phosphate particle are asked for summation curve as 100%, becomes the particle diameter of 50% point according to the size-grade distribution in the dispersion liquid on its summation curve.This D
50Can be by for example using, laser-Doppler formula sreen analysis meter (Ri Machine dress society produces, trade(brand)name " Microtrac (マ イ Network ロ ト ラ Star Network) UPA150 ") etc. the particle size measurement device measure.
Usually, the zinc phosphate particle can obtain by the zinc phosphate that uses as raw material.Though zinc phosphate comprises tetrahydrate, dihydrate, monohydrate, reaches no hydrate, in the surface conditioner that the present invention relates to, can use any one zinc phosphate.Usually, can directly use the tetrahydrate of facile white powder.These zinc phosphates also can be to have carried out various surface-treated zinc phosphates.For example, can be that metal alkoxide by silane coupling agent, rosin, silicone compounds, silicon alkoxide or aluminium-alcohol salt etc. has carried out the surface-treated zinc phosphate.And, do not limit the shape of zinc phosphate, can use the zinc phosphate of arbitrary shapes such as tabular, flakey.These zinc phosphates by dispersing method commonly known in the art, for example, are used dispersion machines such as bead mill (bead mill), high-pressure homogenizer (homogenizer), ultrasonic dispersing machine to carry out miniaturization, thereby can obtain D
50Be zinc phosphate particle smaller or equal to 3 μ m.
The content of zinc phosphate particle be 50ppm to 2000ppm, more preferably 60ppm is to 1500ppm.When the content of zinc phosphate particle is during less than 50ppm, on aluminum alloy surface, only adsorb a spot of surface conditioner particle, can not promote the formation of chemical conversion film.And, even greater than 2000ppm, neither just can obtain adjusting effect, and cause waste with the corresponding surface of the increase of its amount.
Comprise in the surface conditioner that the present invention uses: carboxylic multipolymer, it forms by copolyreaction by containing less than the vinylformic acid of mass ratio 50% with greater than the monomer composition of the 2-acrylamido-2-methyl propane sulfonic acid of mass ratio 50%.When this carboxylic multipolymer plays a role as dispersion agent, has the film formed effect of the chemical conversion of promotion.Therefore, in the chemical conversion of next procedure is handled, can form even and fine and close chemical conversion and handle film, make aluminium alloy have good erosion resistance.
Carboxylic multipolymer is by method commonly known in the art, carry out copolyreaction by monomer composition under the catalysis of superoxide etc. and obtain simply, this monomer composition contains less than the vinylformic acid of mass ratio 50% with greater than the 2-acrylamido-2-methyl propane sulfonic acid of mass ratio 50%.At acrylic acid content is during more than or equal to mass ratio 50%, or the content of 2-acrylamido-2-methyl propane sulfonic acid is during smaller or equal to mass ratio 50%, can not form good chemical conversion in aluminum alloy surface and handle film.The lower limit of acrylic acid content is preferably mass ratio 20%, and more preferably mass ratio 25%.And the upper limit of content is preferably mass ratio 45%, and more preferably mass ratio 40%.On the other hand, the lower limit of the content of 2-acrylamido-2-methyl propane sulfonic acid is preferably mass ratio 55%, and more preferably mass ratio 60%.And the upper limit of content is preferably mass ratio 80%, and more preferably mass ratio 75%.
Above-mentioned monomer composition can comprise other monomer in the scope that does not influence effect of the present invention.As other monomer, can enumerate, for example methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, vinylformic acid hydroxy pentane ester, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, methacrylic acid hydroxy pentane ester, vinyl acetate between to for plastic etc.These monomers use can be mixed with above-mentioned monomer composition separately, also the monomer more than two kinds use can be mixed with above-mentioned monomer composition.
The content of carboxylic multipolymer be 2ppm to 200ppm, be preferably 4ppm to 100ppm.The content of carboxylic multipolymer is during less than 2ppm, the dispersion force deficiency, and when the particle diameter of zinc phosphate particle became big, the stability of surface conditioner also descended, and might cause sedimentation.In addition, content is during greater than 200ppm, can not obtain and effect is adjusted on the corresponding surface of increase of its amount, and be waste.
And the surface conditioner that uses among the present invention contains natural hectorite and/or synthetic li-montmorillonite.Natural hectorite, synthetic li-montmorillonite can be used separately respectively, also can be used in combination more than two kinds.Contain natural hectorite and/or synthetic li-montmorillonite in the surface conditioner by making, thereby can have better dispersion stabilization, prevent the sedimentation of zinc phosphate particle.
Natural hectorite is the clay mineral of the trioctahedron type (trioctahedral) of the montmorillonite family that belongs to represented in the chemical formula one.As the natural hectorite commercially available prod, can enumerate, for example BENTONEW, BENTON AD (production of ELEMENTIS society) etc.
Chemical formula one
[Si
8(Mg
5.34Li
0.66)O
20(OH)
4M
+ 0.66·nH
2O]
Synthetic li-montmorillonite has the crystal three-decker, and the trioctahedral hectorite of unrestricted crystal layer expanded polystyrene veneer with expansion character is close with belonging to, with chemical formula two expressions.As the commercial goods of synthetic li-montmorillonite, for example: Laporte Industries Ltd produces, and commodity are called Laponite (ラ Port Na イ ト) B, S, RD, RDS, XLG, XLS etc.These are white powder, just easily form colloidal sol or gel in case add water.And, as other commercial goods, can enumerate the LUCENTITE SWN of Co-op Chemical (コ one プ ケ ミ カ Le) society.
Chemical formula two
[Si
8(Mg
aLi
b)O
20(OH)
cF
4-C]
X-M
X+
In chemical formula two, 0＜a≤6,0＜b≤6,4＜a+b＜8,0≤c＜4 and x=12-2a-b.And M is almost Na.Synthetic li-montmorillonite by as the magnesium of main component, silicon, sodium, and lithium, the fluorine of trace form.
The content of natural hectorite and/or synthetic li-montmorillonite be 3ppm to 200ppm, be preferably 20ppm to 100ppm.When the content of natural hectorite and/or synthetic li-montmorillonite during, might cause to prevent effectively the sedimentation of zinc phosphate particle less than 3ppm.And content is during greater than 200ppm, can not obtain and effect is adjusted on the corresponding surface of increase of its amount, and cause waste.
The pH value of the surface conditioner of Shi Yonging is 7 to 12 in the present invention.When the pH value less than 7 the time, the zinc phosphate particle easily dissolves, and might cause instability.And, when the pH value greater than 12 the time, in the chemical conversion of next procedure is handled, might cause the pH value of chemical conversion treating agent to rise, become the bad factor of chemical conversion processing.
In addition, in the surface conditioner of Shi Yonging, in the scope that does not influence effect of the present invention, can further mix other dispersion agent, dispersion medium or thickening material etc. in the present invention.When using this surface conditioner that aluminium alloy is carried out the surface adjustment, be to be undertaken by the surface that makes surface conditioner contact aluminium alloy.But be not to be defined in contact method especially, can adopt pickling process commonly known in the art or spraying method etc.
(zinc phosphate chemical conversion treating agent)
The zinc phosphate chemical conversion treating agent of Shi Yonging is made up of acidic aqueous solution in the present invention, and this acidic aqueous solution contains: zine ion 0.1g/l is to 2.0g/l; Nickel ion 0.1g/l is to 4.0g/l; Mn ion 0.1g/l is to 3.0g/l, and phosphate anion 5g/l is to 40g/l; Fluorine in the complex fluorides (converting with F) 0.5g/l is to 1.0g/l; Fluorine in the pure fluorochemical (converting with F) 0.3g/l is to 0.5g/l; And can with iron (converting) 0.025g/l in the sequestrant of iron ion chelating with Fe to 0.45g/l.
As everyone knows, in the zinc phosphate chemical conversion is handled, contain divalence or tervalent iron ion in the chemical conversion treating agent, thereby can obtain on iron class surface or zinc class surface, forming the effect of even and fine and close lithoform by making.In the present invention the zinc phosphate chemical conversion treating agent of Shi Yonging be mixed with can with the sequestrant of iron ion chelating, this sequestrant will carry out sequestering action from the iron ion of iron class surface dissolved.Therefore, in chemical conversion treating agent, a certain amount of iron ion can be stably kept, the effect of aforesaid iron ion can be when forming the lithoform on aluminium class surface, manifested.
The concentration of zine ion be 0.1g/l to 2.0g/l, be preferably 0.3g/l to 1.5g/l.During less than 0.1g/l, on aluminium class surface, can not form uniform lithoform, and the space is many at zinc ion concentration, the local film that forms blue (blue colored) shape.And, when zinc ion concentration during, can form uniform lithoform greater than 2.0g/l, but dissolving easily in alkali, particularly when the cationic electrodeposition of next procedure applies, because of being exposed under the alkaline environment, so situation is bad.If lithoform dissolving, then heatproof salt water-based (high temperature resistant, salt tolerant, water resistance) reduces, particularly when the time for iron class surface, and erosion resistance (that is, preventing to generate the performance of the rust of scab shape) reduction, the performance that can not obtain wishing.
Nickel concentration be 0.1g/l to 4.0g/l, be preferably 0.1g/l to 2.0g/l.When nickel ion concentration during less than 0.1g/l, the erosion resistance of iron reduces, and when greater than 4.0g/l, the erosion resistance of aluminium reduces.
Manganese ion concentration be 0.1g/l to 3.0g/l, be preferably 0.6g/l to 3.0g/l.When manganese ion concentration during less than 0.1g/l, the raising effect of zinc class surface and binding property of filming and heatproof salt water-based is insufficient.And, when greater than 3.0g/l, can not obtain the increase corresponding effects with its amount, and cause waste.
The concentration of phosphate anion be 5g/l to 40g/l, be preferably 10g/l to 30g/l.When the concentration of phosphate anion during less than 5g/l, easily form uneven lithoform, when greater than 40g/l, can not obtain the increase corresponding effects with its amount, and cause waste.
In the fluorochemical, the concentration of complex fluorides with fluorine in the complex fluorides convert (converting) with F be 0.5g/l to 1.0g/l when the concentration of complex fluorides with complex fluorides in fluorine when being scaled (with the F conversion) less than 0.5g/l, can not form uniform lithoform on aluminium class surface, thereby can not get good erosion resistance.And when greater than 1.0g/l, iron class surface is by excessive corrosion, and the lithoform amount reduces, thereby can not obtain good erosion resistance.
In the fluorochemical, the concentration of pure fluorochemical is that 0.3g/l is to 0.50g/l with fluorine conversion (converting with F) in the pure fluorochemical.When the concentration of pure fluorochemical with pure fluorochemical in fluorine convert (converting) with F be during less than 0.3g/l, on aluminium class surface, can not form lithoform fully, thereby can not obtain good erosion resistance.And during greater than 0.5g/l, the etching extent on aluminium class surface increases, and promoting thus to generate with Al, F, Na on aluminium class surface is the by product of main component, thereby can not obtain good erosion resistance and waterproof binding property.
At this,, for example can enumerate zinc oxide, zinc carbonate, zinc nitrate etc. as the supply source of zine ion.And, as the supply source of nickel ion, for example can exemplify, nickelous carbonate, nickelous nitrate, nickelous chloride, nickelous phosphate, nickel hydroxide etc. as the supply source of mn ion, for example can be enumerated, manganous carbonate, manganous nitrate, Manganous chloride tetrahydrate, manganous phosphate etc.And,, for example can enumerate phosphoric acid, zinc phosphate, manganous phosphate etc. as the supply source of phosphate anion.
In addition, as complex fluorides, for example can enumerate SiF
6, BF
4Deng.As SiF
6Supply source for example can enumerate silicofluoric acid, nickelous fluosilicate, zine fluosilicate, manganese fluosilicate, silicofluoric acid iron, magnesium silicofluoride, calcium silicofluoride etc.As BF
4Supply source, for example can enumerate fluoroboric acid, nickel fluoborate, zinc fluoroborate, fluoroboric acid manganese, ferric fluoborate, fluoroboric acid magnesium, fluoroboric acid calcium etc.
In the fluorochemical,, for example can enumerate hydrofluoric acid, Potassium monofluoride, Sodium Fluoride, Neutral ammonium fluoride, potassium hydrogen fluoride, sodium bifluoride, Neutral ammonium fluoride, ammonium bifluoride etc. as the pure fluorochemical that the fluorine free ion is provided.From the aluminum ion of aluminium alloy dissolved, combine with fluorine free ion in the chemical conversion treating agent, form complexing ion, thereby promote the formation of lithoform.
And, the zinc phosphate chemical conversion treating agent that the present invention relates to contain can with the sequestrant of iron ion chelating, iron in this sequestrant (converting with Fe) is that 0.025g/l is to 0.45g/l.Like this, but the sequestrant with the iron ion chelating is added in the zinc phosphate chemical conversion treating agent, thus, the iron ion from iron class surface dissolved can be remained on the chemical conversion treating agent, thereby form lithoform even and fine and close, that spreadability is high.As concrete sequestrant, for example can enumerate citric acid, tartrate, EDTA, glyconic acid, succsinic acid, Weibull, oxysuccinic acid and these sour compound or derivative.
When the content of iron is less than 0.025g/l in sequestrant, reduce, can not form lithoform even and fine and close, high spreadability in the spreadability of the lithoform on aluminium class surface.And greater than 0.45g/l the time, the lithoform amount reduces, and can not obtain good rust-preventing characteristic.
The pH value of zinc phosphate chemical conversion treating agent is 2.0 to 5.0, preferred 3.0 to 4.0.The adjustment of pH value can be waited by NaOH, ammonia soln, nitric acid to be carried out.When the chemical conversion of carrying out aluminium alloy is handled, undertaken by making zinc phosphate treatment agent contact aluminium alloy.The contact temperature is preferably 40 ℃ to 60 ℃, more preferably 42 ℃ to 48 ℃.As contact method, can enumerate spraying method or pickling process, spray treatment time and dipping time all are 1 minute to 10 minutes, more preferably 1.5 minutes to 3 minutes.As other contact method, also can pass through flow coat method, rolling method, make zinc phosphate treatment agent contact aluminium alloy.In addition, carry out the aluminium alloy that chemical conversion is handled, after washing, be provided to drying process.Drying temperature is 80 ℃ to 120 ℃.
(aluminium alloy)
Copper content in the aluminium alloy that uses among the present invention is smaller or equal to mass ratio 0.2%.Copper content in aluminium alloy for a long time, then erosion resistance reduces, so, for example, even the content that also needs to make copper in patent documentation 1 is for smaller or equal to mass ratio 0.1%.Relative therewith, in surface treatment method according to the present invention,, but still have good erosion resistance though the content of copper is mass ratio 0.2%.
Embodiment
Below, according to embodiment, the present invention is further elaborated, but the present invention not only is defined in this.
(implementation column 1～7, comparison array 1～5)
(process object raw material)
In arbitrary example of embodiment 1～7 and comparative example 1～5, all be to use identical aluminium alloy as the process object raw material.Specifically, the content that is to use copper is for smaller or equal to mass ratio 0.01%, mass ratio 0.1%, and the aluminium alloy of mass ratio 0.2%.The size of aluminium alloy is 70mm * 150mm, and thickness is 0.8mm.With the sandpaper of these aluminium alloys, use double-acting sander (Double Action Sander) (" 905B4D " that Compact Tool (コ Application パ Network ト Star one Le) society produces) to carry out after comprehensive grinding as the process object raw material by #180.And in these aluminium alloys that integral grinding is crossed, as the process object raw material, this SPC has identical size, thickness with aluminium alloy with the aluminium alloy that makes SPC contact conducting.That is, about three kinds of different aluminium alloys of copper content, with make SPC contact conducting with do not make SPC contact conducting as the process object raw material.
Fig. 1 illustrates the process object raw material that makes SPC contact conducting with aluminium alloy.This process object raw material is to make by following operation.At first, the interval of about 20mm is set in the left and right sides of aluminium alloy 10 and disposes SPC20, these are hung up with hanger 40.Then, the hole is set, and these holes are linked with aluminum steels 30,, thus, make and make SPC 20 contact the process object raw material of conducting with aluminium alloy 10 by aluminium alloy 10 and SPC 20 are linked on the top of aluminium alloy 10 and SPC 20.
(treatment process)
In arbitrary example of embodiment 1～7 and comparative example 1～5, all according to (a) degreasing, (b) washing, (c) surface adjust, (d) chemical conversion is handled, (e) washing, (f) pure water are washed, (g) is dry, and (h) order of applying of galvanic deposit handle.In (b) and washing step (e), at room temperature,, wash in the operation at (f) pure water to 15 seconds tap water of process object raw material spray, at room temperature, to 15 seconds deionized waters of process object raw material spray.And, in (g) drying process, under 80 ℃, made the process object raw material drying 5 minutes.In addition, about (a) degreasing, (c) surface adjust, (d) chemical conversion is handled and (h) galvanic deposit apply and then undertaken by following.
(degreasing)
In arbitrary example of embodiment 1～7 and comparative example 1～5, carry out identical skimming treatment respectively about above-mentioned process object raw material.Specifically, in the A agent that contains the alkali degreasing treatment agent (trade(brand)name " SurfCleaner (サ one Off Network リ one Na one) SD250 ") that Nippon Paint Co., Ltd. (Japanese ペ イ Application ト Co., Ltd.) produces is that mass ratio 1.5%, B agent are in the aqueous solution of mass ratio 0.9%, above-mentioned process object raw material was flooded 2 minutes down at 43 ℃, carry out skimming treatment.
(surface is adjusted)
In embodiment 1～7, use the surface conditioner contain the zinc phosphate particle of predetermined amount, carboxylic multipolymer and natural hectorite and/or synthetic li-montmorillonite respectively (below, as surface conditioner 1) to carry out surface adjustment.Specifically, at first, as the adjustment of surface conditioner 1, in water 87.7 mass parts, add natural hectorite " BENTONEW " (production of ELEMENTIS society) 0.3 mass parts, use dispersion machine (dispersingmachine) to stir 30 minutes, obtain pre-gelled with 3000rpm.On the pre-gelled that obtains, add commercially available " Aron (ア ロ Application) A-6020 " (vinylformic acid mass ratio 40%, and the synthetic society of carboxylic multipolymer East Ami of 2-acrylamido-2-methyl propane sulfonic acid mass ratio 60% produce) 2 mass parts and zinc phosphate particle 50 mass parts, adjusting the pH value by alkaline carbonic acid sodium is 9.0, obtains surface conditioner (zinc phosphate particle concentration 1500ppm, carboxylic copolymer concentration 60ppm, natural hectorite concentration 45ppm).Then, in the surface conditioner 1 that obtains, at room temperature, dip treating object raw material 30 seconds carries out surface adjustment.
In comparative example 1～5, be not to use the surface conditioner of the zinc phosphate class as among the embodiment, and be to use the surface conditioner of titanium colloidal type to carry out surface adjustment.Specifically, contain that the surface treatment agent that Nippon Paint Co., Ltd. produces (trade(brand)name " Surf Fine (サ one Off Off ア イ Application) 5N-10 " build bathe with) mass ratio is 0.1%, the pH value is 9.0 the aqueous solution (below, as surface conditioner 2) in, at room temperature, the process object raw material was flooded 30 seconds, carry out surface adjustment.In addition, in surface conditioner 1 and surface conditioner 2, solids component is set at about equally.
But, about embodiment 7 and comparative example 5, after having carried out degreasing and having washed, do not containing zine ion, nickel ion, reaching in the chemical conversion treating agent of magnesium ion, after 60 seconds, carry out the surface adjustment at dipping under 43 ℃.It is described to carry out the reasons are as follows of this operation.When using surface conditioner 1 in the surface is adjusted, even carry out the chemical conversion processing in that SPC contact with aluminum feedstock under the state of conducting, the reduction of lithoform is also not obvious.Therefore, for determining to keep the ultimate value of performance, and implement such operation in low film amount side.Being immersed in reason in the chemical conversion treating agent that does not contain metal ion and being etching extent for aluminum feedstock is set to and carries out equating when chemical conversion is handled in that aluminum feedstock is contacted with SPC under the state of conducting.That is, in order to obtain low film amount, use normal chemical conversion treating agent, when handling at short notice, the film amount is few but etching extent is also little.This operation is because can not can simulate aluminum feedstock contacts conducting with SPC state certainly, so control etching extent with the chemical conversion treating agent that does not contain metal ion.In addition, as target, etching extent is controlled to be about 0.5g/m
2
(chemical conversion processing)
In arbitrary example in embodiment 1～7 and comparative example 1～5, use identical chemical conversion treating agent, flooded 2 minutes and carry out the chemical conversion treatment reason down at 43 ℃.Specifically, contain as chemical conversion treating agent: fluorine (converting) 0.35g/l in (converting) 0.5g/l of fluorine in zine ion 1.0g/l, nickel ion 1.0g/l, magnesium ion 1.3g/l, phosphate anion 20g/l, the complex fluorides and the pure fluorochemical with F with F, and, can be (converting) 0.025g//l with iron in the sequestrant of iron ion chelating with Fe.And the total acidity of adjusting chemical conversion treating agent is that 22.2pt, free acidity are 0.5pt.In addition, as mentioned above,, chemical conversion then is set shortly handles the time embodiment 7 and comparative example 5.Specifically, in embodiment 7, be set to 10 seconds, in comparative example 5, be set to 20 seconds.
(galvanic deposit coating)
In arbitrary example in embodiment 1～7 and comparative example 1～5, carry out identical galvanic deposit and apply.Specifically, the cation electrodeposition coating (trade(brand)name " Power Top V50 Gray (パ ワ one ト Star プ V5 0 グ レ one) ") that uses Nippon Paint Co., Ltd. to produce carries out the cationic electrodeposition coating.It is 25 μ m that coated conditions is set to cure dried coating thick.Galvanic deposit was cured under 170 ℃ 25 minutes after applying, and forms cationic electrodeposition and film on the aluminum alloy surface of carrying out surface adjustment, chemical conversion processing.
(floating coat coating)
The floating coat coating (trade(brand)name " Orga (オ Le ガ) P-5A N-2.0 ") that spraying Nippon Paint Co., Ltd. produces on electrodeposition coating cured 20 minutes under 140 ℃ of temperature.The floating coat that forms is filmed and cured dried thickness is 35 μ m.
(going up coating applies)
Coated coating (trade(brand)name " superlac (ス one パ one ラ Star Network) M-95HB YR-511P ") on spraying Nippon Paint Co., Ltd. produces on the filming of floating coat cured 20 minutes under 140 ℃ of temperature.Being coated with coating film on forming, to cure dried thickness be 15 μ m.
(assessment)
(rust-preventing characteristic)
On the filming of three paint sheets, use sharp cutter crosscut (incision length is 20cm), carrying out with JIS-Z2371 is the salt spray 24 hours of standard.Then, under 40 ℃ of temperature, relative humidity is that placing 240 hours is one-period under 70～75% the moist environment, and the expansion situation of the crosscut portion of four all after dates is confirmed in range estimation, according to following criterion evaluation.
Zero ... almost do not have expansion.
△ ... a small amount of expansion is arranged.
* ... obvious expansion is arranged.
(waterproof binding property)
The test board that forms lithoform and cationic electrodeposition film is cooled to room temperature at dipping under 40 ℃ the warm water after 240 hours.Afterwards, draw lattice bonding (cross-cutadhesion) test, situation is peeled off in range estimation, and by following criterion evaluation.
Zero ... do not have and peel off.
△ ... there is disappearance at the cutting part edge.
* ... peel off.
(chemical conversion film weight)
The weight of chemical conversion film is tried to achieve like this: the test board that will carry out the chemical conversion processing flooded 1 minute in 30% aqueous nitric acid at normal temperatures, made the chemical conversion film dissolving, measured the weight of its dissolving front and back, and calculated.
Table 1 illustrates the rust-preventing characteristic and the fusible assessment result of waterproof of carrying out about embodiment 1～7 and comparative example 1～5.
Table 1:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |||
| Surface conditioner | 1 | Concentration (wt%) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | - | - | - | - | - |
| pH | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | - | - | - | - | - | ||
| 2 | Concentration (wt%) | - | - | - | - | - | - | - | .01 | 0.1 | 0.1 | 0.1 | 0.1 | |
| pH | - | - | - | - | - | - | - | 9.0 | 9.0 | 9.0 | 9.0 | 9.0 | ||
| The content of Cu (%) in the aluminium alloy | ≤0.01 | ≤0.01 | 0.1 | 0.1 | 0.2 | 0.2 | ≤0.01 | ≤0.01 | ≤0.01 | 0.1 | 0.2 | ≤0.01 | ||
| Aluminium-SPC contacts conducting | Do not have | Have | Do not have | Have | Do not have | Have | Do not have | Do not have | Have | Do not have | Do not have | Do not have | ||
| Aluminum chemistry conversion film weight (g/m 2) | 1.8 | 1.5 | 1.9 | 1.6 | 2.0 | 1.6 | 0.3 | 2.0 | 0.7 | 2.1 | 2.3 | 0.3 | ||
| Galvanic deposit applies back aluminum feedstock erosion resistance | Rust-preventing characteristic | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | × | × | |
| The waterproof binding property | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | × | ||
The assessment result of conclusive table 1 is as described below.The first, when making aluminium alloy contact conducting with SPC, can not obtain good erosion resistance in comparative example, relative therewith, in an embodiment, the content of copper is in the scope smaller or equal to mass ratio 0.2%, can obtain good erosion resistance in aluminium alloy.When the second, the content of copper is mass ratio 0.2% in aluminium alloy, good erosion resistance can not be obtained in the comparative example, but in an embodiment, all good erosion resistance can be obtained no matter whether aluminium alloy contacts conducting with SPC.And, the 3rd, when lithoform be 0.3g/m
2Low film amount the time, in comparative example, can not obtain good erosion resistance, relative therewith, then can obtain good erosion resistance in an embodiment.Therefore, can determine, on the surface of aluminium alloy, can form good, the even and fine and close lithoform of erosion resistance according to the present invention.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Symbol description
10 aluminium alloys
20 SPC
30 aluminum steels
40 hangers
Claims (2)
1. the surface treatment method of an aluminium alloy, comprise following operation: degreasing is also washed aluminum alloy surface; Described aluminum alloy surface with surface conditioner degreasing and washing is carried out surface adjustment; And carry out chemical conversion with the described aluminum alloy surface that the zinc phosphate chemical conversion treating agent will carry out adjusting on the surface and handle, wherein,
The pH value of described surface conditioner is more than or equal to 7 smaller or equal to 12, and it comprises: D
50For smaller or equal to 3 microns zinc phosphate particle 50ppm to 2000ppm; Carboxylic multipolymer 2ppm is to 200ppm, and it is formed less than the monomer composition copolymerization greater than the 2-acrylamido-2-methyl propane sulfonic acid of mass ratio 50% of the vinylformic acid of mass ratio 50% and content by content; And natural hectorite and/or synthetic li-montmorillonite 3ppm be to 200ppm,
Described zinc phosphate chemical conversion treating agent is made up of acidic aqueous solution, and described acidic aqueous solution comprises: zine ion 0.1g/l is to 2.0g/l; Nickel ion 0.1g/l is to 4.0g/l; Mn ion 0.1g/l is to 3.0g/l; Phosphate anion 5g/l is to 40g/l; Fluorine in the complex fluorides (converting with F) 0.5g/l is to 1.0g/l; Fluorine in the pure fluorochemical (converting with F) 0.3g/l is to 0.5g/l; And can with iron (converting) 0.025g/l in the sequestrant of iron ion chelating with Fe to 0.45g/l.
2. the surface treatment method of aluminium alloy according to claim 1, wherein, the content of the copper in the described aluminium alloy is smaller or equal to mass ratio 0.2%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004347244 | 2004-11-30 | ||
| JP2004347244 | 2004-11-30 |
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| CN1978704A true CN1978704A (en) | 2007-06-13 |
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| US (1) | US20060113005A1 (en) |
| CN (1) | CN1978704A (en) |
| CA (1) | CA2528275A1 (en) |
| GB (1) | GB2420565A (en) |
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| CN104099600A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Surface treating agent for polysilicate aluminum alloy |
| CN104099593A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Surface treating agent for trace rare earth aluminum alloy |
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| CN106380900A (en) * | 2016-08-31 | 2017-02-08 | 立邦涂料（重庆）化工有限公司 | Liquid surface adjusting agent and preparing method thereof |
| CN106521475A (en) * | 2016-11-11 | 2017-03-22 | 武汉钢铁股份有限公司 | Liquid surface conditioning agent for coating and preparation method thereof |
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| CN101233261B (en) * | 2005-07-29 | 2010-11-24 | 日本油漆株式会社 | Surface conditioners and method of surface condition |
| US20100031851A1 (en) * | 2006-04-07 | 2010-02-11 | Toshio Inbe | Surface conditioning composition, method for producing the same, and surface conditioning method |
| DE102010030697A1 (en) * | 2010-06-30 | 2012-01-05 | Henkel Ag & Co. Kgaa | Process for the selective phosphating of a composite metal construction |
| CN101982564B (en) * | 2010-09-25 | 2015-04-29 | 湖南立发釉彩科技有限公司 | Rust-removing and anti-rusting agent for iron and steel |
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| DE102014119472A1 (en) * | 2014-12-22 | 2016-06-23 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Process for the preparation of anisotropic zinc phosphate particles and zinc metal mixed phosphate particles and their use |
| US11355697B2 (en) * | 2019-11-25 | 2022-06-07 | The Board Of Trustees Of The Leland Stanford Junior University | Nanometer scale nonvolatile memory device and method for storing binary and quantum memory states |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3366826B2 (en) * | 1997-04-30 | 2003-01-14 | 本田技研工業株式会社 | Zinc phosphate treatment agent for aluminum alloy |
| CA2368445C (en) * | 1999-03-26 | 2008-02-12 | Calgon Corporation | Rust and scale removal composition and process |
| TW587096B (en) * | 2000-08-11 | 2004-05-11 | Nihon Parkerizing | Greases component containing in aqueous composition for forming protective membranes |
| EP1378586B1 (en) * | 2002-06-13 | 2007-02-14 | Nippon Paint Co., Ltd. | Zinc phosphate-containing conditioning agent for phosphate conversion-treatment of steel plate and corresponding product |
| JP3733372B2 (en) * | 2004-02-20 | 2006-01-11 | 日本ペイント株式会社 | Surface conditioning agent and surface conditioning method |
| DE602005027279D1 (en) * | 2004-02-20 | 2011-05-19 | Chemetall Gmbh | Surface conditioning agents and methods |
-
2005
- 2005-11-29 US US11/288,798 patent/US20060113005A1/en not_active Abandoned
- 2005-11-29 GB GB0524293A patent/GB2420565A/en not_active Withdrawn
- 2005-11-29 CA CA002528275A patent/CA2528275A1/en not_active Abandoned
- 2005-11-30 CN CNA200510125869XA patent/CN1978704A/en active Pending
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| CN104099600A (en) * | 2014-06-19 | 2014-10-15 | 锐展(铜陵)科技有限公司 | Surface treating agent for polysilicate aluminum alloy |
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Also Published As
| Publication number | Publication date |
|---|---|
| GB0524293D0 (en) | 2006-01-04 |
| US20060113005A1 (en) | 2006-06-01 |
| CA2528275A1 (en) | 2006-05-30 |
| GB2420565A (en) | 2006-05-31 |
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