CN111065761A - 用于无镍磷化金属表面的改进方法 - Google Patents
用于无镍磷化金属表面的改进方法 Download PDFInfo
- Publication number
- CN111065761A CN111065761A CN201880056072.4A CN201880056072A CN111065761A CN 111065761 A CN111065761 A CN 111065761A CN 201880056072 A CN201880056072 A CN 201880056072A CN 111065761 A CN111065761 A CN 111065761A
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- Prior art keywords
- composition
- ions
- water
- phosphating
- detergent composition
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 100
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 34
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 30
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- 239000003599 detergent Substances 0.000 claims abstract description 24
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 molybdenum ions Chemical class 0.000 claims description 38
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- 239000008139 complexing agent Substances 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 6
- 229940050410 gluconate Drugs 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 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 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 claims description 4
- 235000011180 diphosphates Nutrition 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 150000002826 nitrites Chemical class 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 31
- 235000021317 phosphate Nutrition 0.000 description 28
- 239000002253 acid Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 24
- 238000004140 cleaning Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 229920000768 polyamine Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 150000002222 fluorine compounds Chemical class 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 229920002873 Polyethylenimine Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite group Chemical group N(=O)[O-] IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical class [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 241000920033 Eugenes Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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
- C23C22/05—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
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Abstract
本发明涉及一种用于基本无镍磷化金属表面的方法,其中用以下组合物依次处理金属表面:i)包含至少一种水溶性硅酸盐的碱性含水清洁剂组合物,和ii)包含锌离子、锰离子和磷酸根离子的酸性含水且基本无镍的磷化组合物。本发明还涉及上述清洁剂组合物本身,并且涉及通过上述方法经磷酸盐涂覆的金属表面及其用途。
Description
本发明涉及一种使用特定清洁剂组合物基本无镍磷化金属表面的方法、该清洁剂组合物本身和通过该方法磷酸盐涂覆的金属表面以及所述表面的用途。
由现有技术已知位于金属表面上的磷酸盐涂层。该类涂层用于防止金属表面腐蚀,并且此外还用作后续涂膜的粘合促进剂。
该类磷酸盐涂层尤其用于汽车工业以及一般工业领域。
后续涂膜以及粉末涂层和湿漆尤其为阴极沉积的电涂层(CEC)材料。由于CEC的沉积需要金属表面和处理浴之间的电流流动,因此重要的是设置磷酸盐涂层中的限定电导率以确保有效且均匀的沉积。
因此,通常使用含镍的磷化溶液来施加磷酸盐涂层。在该方法中沉积的镍(元素或合金组分如Zn/Ni形式)在后续电涂程序的过程中提供涂层的适当导电性。
然而,由于镍离子的高毒性和环境有害性,所以镍离子不再为处理溶液的理想组分,且因此应尽可能避免或至少减少其量。
原则上确实已知使用无镍或低镍的磷化溶液。然而,其限于特定基材如钢。
此外,由于非理想的基材表面,在主导的CEC沉积条件下,所述无镍或低镍体系可能导致不良防腐值和涂层粘合值。
因此,本发明目的是提供一种方法,利用该方法可使金属表面经受基本无镍磷化,其中避免上述现有技术的缺点。
该目的通过根据权利要求1的方法、根据权利要求12的磷化组合物和根据权利要求14的经磷酸盐涂覆的金属表面来实现。
通过基本无镍磷化金属表面的本发明方法,用以下组合物依次处理金属表面:
i)包含至少一种水溶性硅酸盐的碱性含水清洁剂组合物,以及然后ii)包含锌离子、锰离子和磷酸根离子的酸性含水的基本无镍的磷化组合物。
定义:
本发明方法可用于处理未涂覆的金属表面或已经转化涂覆的金属表面。因此,在下文中提及“金属表面”总是还包括已经转化涂覆的金属表面。然而,优选所述金属表面是未涂覆的。
就本发明而言,“含水组合物”是其至少部分地,优选主要地,即以大于50重量%的程度包含水作为其溶剂/分散介质的组合物。除溶解的组分外,其还可包含粗分散的组分。因此,其可以是例如乳液。然而,优选地,其为溶液,换言之,其不含粗分散组分的组合物。
在下文中提及“水溶性硅酸盐”是指在25℃下的水溶解度(在完全软化水中)为至少1mg/l,优选至少10mg/l,更优选至少100mg/l,更优选至少1g/l,更优选至少10g/l,更优选至少100g/l,更优选至少200g/l,更优选至少300g/l,非常优选至少350g/l的硅酸盐。硅酸盐还可呈胶态溶液形式。
当组合物包含小于0.3g/l的镍离子时,就本发明而言,认为其是“基本无镍”的。磷化组合物优选包含小于0.1g/l,更优选小于0.01g/l的镍离子。
就本发明而言,“磷酸根离子”还是指磷酸氢根、磷酸二氢根和磷酸。此外,意欲包括焦磷酸和多磷酸及其所有部分和完全去质子化的形式。
就本发明而言,“金属离子”替换地是金属阳离子、络合金属阳离子或络合金属阴离子。
金属表面优选包括钢、钢合金、热浸镀锌体系、电解镀锌体系、锌合金如Zn/Fe或Zn/Mg、铝或铝合金。在热浸镀锌和电解镀锌体系的情况下,它们在每种情况下更特别地是在钢上的该种体系。金属表面更特别地至少部分镀锌。
本发明方法尤其适合于多金属应用,特别适用于金属表面(其以及钢上的镀锌体系,优选热浸镀锌体系和电解镀锌体系包含铝和/或铝合金,优选铝合金)。
在用酸性含水且基本无镍的磷化组合物处理(步骤ii)之前,首先在碱性含水清洁剂组合物中清洁本发明的金属表面(步骤i),并且更特别地是脱脂。为此目的,任选地,还可额外使用酸性或中性酸洗组合物。
在该情况下,清洁剂组合物可通过用优选1.5-1000,更优选50-200倍的合适溶剂,优选用水稀释以及在必要时加入pH调节物质而由浓缩物获得。
清洁剂组合物中的至少一种水溶性硅酸盐的作用是改进清洁效果并减少清洁浴中的酸洗侵蚀(抑制作用)。
在此,至少一种水溶性硅酸盐优选包含至少一种水玻璃,更特别是锂水玻璃、钠水玻璃和/或钾水玻璃,更优选钠水玻璃和/或钾水玻璃,和/或至少一种偏硅酸盐如偏硅酸钠(Na2SiO3)。
特别优选至少一种水溶性硅酸盐包含钠水玻璃或钾水玻璃。
钠水玻璃优选为Na2O:SiO2摩尔比为1-4的钠水玻璃。钾水玻璃同样优选为K2O:SiO2摩尔比为1-4的钾水玻璃。
至少一种水溶性硅酸盐优选以0.01-15g/l,更优选0.2-13g/l,非常优选0.5-10g/l的总浓度存在。
除至少一种水溶性硅酸盐外,清洁剂组合物还可包含至少一种阳离子、非离子和/或阴离子表面活性剂和/或其他添加剂,尤其是络合剂、氧化剂、油和/或助剂如增溶剂、硼酸盐和/或碳酸盐。
已证明加入至少一种络合剂和/或至少一种氧化剂在所获得的防腐和涂层粘合值方面是有利的且因此是优选的。
络合剂在清洁剂组合物中的作用是引起水硬度和溶解的阳离子的络合,其由于酸洗侵蚀而存在于溶液中或进入清洁剂浴中的溶液。
在此,优选的络合剂一方面是含磷络合剂。
这些更特别是基于磷酸盐的络合剂-又优选缩合磷酸盐如焦磷酸盐、三聚磷酸盐和其他多磷酸盐,以及膦酸如1-羟基乙烷-(1,1-二膦酸)(HEDP)及其盐。
含磷,尤其是基于磷酸盐的络合剂以优选0.01-15g/l,更优选0.05-13g/l,非常优选0.1-10g/l(以焦磷酸四钾计)的总浓度存在。
另一方面,优选的络合剂是具有至少一个羟基以及至少一个羧基的羟基羧酸及其盐,特别是糖酸及其盐,更优选庚酸盐和葡糖酸盐。非常特别优选葡萄糖酸盐。该类络合剂优选以0.01-6g/l,更优选0.05-5g/l,非常优选0.1-4g/l的总浓度(以葡萄糖酸钠计)存在。
根据一个特别优选的实施方案,清洁剂组合物包含至少一种含磷络合剂,更特别是焦磷酸盐和/或三聚磷酸盐,以及至少一种羟基羧酸或其盐,更特别是葡萄糖酸盐。在此,尤其优选的组合如下:
i)焦磷酸四钾和葡萄糖酸盐,
ii)三聚磷酸五钠和葡萄糖酸盐。
一个优选的氧化剂是亚硝酸盐。氧化剂优选以10-100mg/l,更优选20-50mg/l的总浓度(以亚硝酸盐计)存在。
优选不向清洁剂组合物中加入铁离子,更特别地不加入铁(III)离子。在该情况下,清洁浴中存在的任何铁离子仅源自经处理的金属表面。
为了调节清洁剂组合物的碱度,一方面尤其可以使用氢氧化钠、氢氧化钾、苛性钠或苛性钾,且另一方面尤其可以使用磷酸。
在该情况下,清洁剂组合物的pH优选为9.5-13,更特别是10.5-12,更优选10.7-12.0,更优选11.0-12.0,更优选11.3-12.0,非常优选11.5-12.0。
清洁剂组合物的温度优选为35-70℃,更优选40-65℃,非常优选45-60℃。将金属表面用清洁剂组合物处理优选30-600秒,更优选60-480秒,非常优选90-360秒(优选通过浸渍或喷涂或二者的组合)。
根据一个优选实施方案,首先用清洁剂组合物喷涂金属表面30-90秒且随后浸入其中100-300秒。
在清洁/酸洗之后且在用磷化组合物处理金属表面之前,还有利的是至少用水冲洗金属表面,在该情况下,水还可任选地已与水溶解的添加剂如亚硝酸盐或表面活性剂混合。
此外,在用磷化组合物处理金属表面之前,有利的是额外用活化组合物处理金属表面。活化组合物的目的是在金属表面上沉积大量的超细磷酸盐颗粒作为晶种。这些晶体有助于在随后的方法步骤中与磷化组合物接触(优选其间无需冲洗)时,形成磷酸盐层,更特别地结晶磷酸盐层(其具有极大量的密集设置的细磷酸盐晶体)或基本不透的磷酸盐层。
在该情况下期望的活化组合物尤其包括基于磷酸钛或磷酸锌的碱性组合物。
然而,还可能有利的是将活化剂,特别是磷酸钛或磷酸锌加入清洁组合物本身中,换言之,在一个步骤中进行清洁和活化。
酸性含水且基本无镍的磷化组合物包含锌离子、锰离子和磷酸根离子。
在此,磷化组合物可以通过用1.5-100倍,优选5-50倍的合适溶剂,优选用水稀释以及必要时加入pH调节物质而由浓缩物获得。
磷化组合物优选以以下优选和更优选的浓度范围包含以下组分:
Zn | 0.3-3.0g/l | 0.5-2.0g/l |
Mn | 0.3-2.0g/l | 0.5-1.5g/l |
磷酸盐(以P<sub>2</sub>O<sub>5</sub>计) | 8-25g/l | 10-18g/l |
游离氟化物 | 30-250mg/l | 50-180mg/l |
络合氟化物(以例如SiF<sub>6</sub><sup>2–</sup>和/或BF<sub>4</sub><sup>–</sup>计) | 0-5g/l | 0.5-3g/l |
然而,已证明有利的是就锰离子而言的浓度为0.3-2.5g/l,且就游离氟化物而言的浓度为10-250mg/l。
络合氟化物优选是四氟硼酸根(BF4 -)和/或六氟硅酸根(SiF6 2-)。
特别地在铝和/或镀锌材料的处理中,在磷化组合物中存在络合氟化物以及简单氟化物如氟化钠是有利的。
磷化体系中的Al3+是一种浴毒物且可以通过与氟络合(例如冰晶石形式)而由体系中移除。将络合氟化物作为“氟化物缓冲液”加入浴中,因为否则氟化物含量会快速下降并且不再进行涂覆。然后,氟化物支持磷酸盐层的形成且因此还间接导致涂层粘合性和防腐性的改进。此外,在镀锌材料上,络合氟化物有助于防止缺陷如斑点。
此外,特别是在处理铝的情况下,有利的是磷化组合物含有铁(III)离子。优选将铁(III)离子加入磷化组合物中。在该情况下,所加入的铁(III)离子的量优选为0.001-0.2g/l,更优选0.001-0.1g/l,更优选0.005-0.1g/l,非常优选0.005-0.05g/l,尤其优选0.005-0.02g/l。
磷化组合物进一步优选以以下优选和更优选的浓度范围包含至少一种选自以下化合物的促进剂:
然而,已证明有利的是就硝基胍而言的浓度为0.1-3.0g/l且就H2O2而言的浓度为5-200mg/l。
非常优选地,至少一种促进剂是H2O2。
然而,磷化组合物优选包含小于1g/l,更优选小于0.5g/l,非常优选小于0.2g/l,特别优选小于0.1g/l的硝酸盐。
这是因为在镀锌表面的情况下,磷化组合物中的硝酸盐尤其会导致涂层形成反应的额外加速,从而导致涂层重量降低,而且尤其锰掺入晶体减少。然而,如果磷酸盐涂层的锰含量过低,则其耐碱性变差。
耐碱性又在随后的阴极电涂层沉积中起关键作用。在该方法中,水在基材表面发生电离:形成氢氧根离子。由此,基材界面处的pH升高。实际上仅通过该方式,电涂层材料才能团聚和沉积。然而,升高的pH也可能损坏结晶磷酸盐层。
磷化组合物的温度优选为30-55℃。
此外,磷化组合物可以通过以下优选和更优选的参数范围来表征:
FA | 0.3-2.0 | 0.7-1.6 |
FA(稀释) | 0.5-8 | 1-6 |
TAF | 12-28 | 22-26 |
TA | 12-45 | 18-35 |
A值 | 0.01-0.2 | 0.03-0.15 |
温度 | 30-50℃ | 35-45℃ |
然而,已证明有利的是就FA参数而言的值为0.2-2.5且就温度而言的值为30-55℃。
在该列举中,“FA”代表游离酸,“FA(稀释)”代表游离酸(稀释),“TAF”代表总酸(费歇尔),“TA”代表总酸,且“A值”代表酸值。
确定这些参数作为磷化化学品分析检测的一部分进行且用于持续监测工作磷化浴(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8章,第332页及随后各页):
游离酸(FA):
(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8.1节,第333-334页)
为了测定游离酸,将10ml磷化组合物吸移至合适容器如300ml锥形瓶中。如果磷化组合物包含络合氟化物,则将额外的2-3g氯化钾加入样品中。然后使用pH计和电极以0.1MNaOH滴定至pH为3.6。该滴定中消耗的0.1M NaOH的量(以每10毫升磷化组合物毫升数计)得到游离酸(FA)的值(以点数计)。
游离酸(稀释)(FA(稀释)):
(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8.1节,第333-334页)
为了测定游离酸(稀释),将10ml磷化组合物吸移至合适容器如300ml的锥形瓶中。然后加入150ml完全软化水。使用pH计和电极以0.1M NaOH滴定至pH 4.7。该滴定中消耗的0.1M NaOH的量(以每10毫升稀释的磷化组合物的毫升数计)得到游离酸(稀释)(FA(稀释))的值(以点数计)。可由相对于游离酸(FA)的差确定络合氟化物的量。如果将该差乘以0.36的系数,则结果为络合氟化物如SiF6 2–的量(以g/l计)。
总酸(费歇尔)(TAF):
(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8.2节,第334-336页)
在确定游离酸(稀释)之后,在加入草酸钾溶液之后,使用pH计和电极以0.1M NaOH滴定稀释的磷化组合物至pH为8.9。在该程序中0.1M NaOH的消耗量(以每10毫升稀释的磷化组合物的毫升数计)得到总酸(费歇尔)(TAF)(以点数计)。如果将该值乘以0.71,则结果为磷酸根离子总量(以P2O5计)。
总酸(TA):
(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8.3节,第336-338页)
总酸(TA)是存在的二价阳离子以及游离和键合的磷酸(后者是磷酸盐)的总和。其使用pH计和电极通过消耗0.1M NaOH来测定。为此目的,将10ml磷化组合物吸移至合适容器如300ml的锥形瓶中并用25ml完全软化水稀释。随后用0.1M NaOH滴定至pH为9。该程序中的消耗量(以每10毫升稀释的磷化组合物的毫升数计)对应于总酸(TA)的点数。
酸值(A值):
(参见W.Rausch“Die Phosphatierung von Metallen”,Eugen G.Leuze Verlag,第3版,2005,第8.4节,第338页)
酸值(A值)代表比率FA:TAF且通过将游离酸(FA)的值除以总酸(费歇尔)(TAF)的值而获得。
由于将酸值设定为0.03-0.065,更特别是0.04-0.06,尤其是在热浸镀锌的表面上,涂层粘合性的进一步改进是令人惊讶的。
令人惊讶地发现,特别是在钢或热浸镀锌体系作为金属表面的情况下,小于45℃,优选35-45℃的磷化组合物温度导致进一步改进的腐蚀和涂层粘合值。
将金属表面用磷化组合物处理优选30-480秒,更优选60-300秒,非常优选90-240秒(优选通过浸渍或喷涂)。
取决于所处理的表面,用磷化组合物处理金属表面会在金属表面上产生以下优选和更优选的磷酸锌涂层重量(由X射线荧光分析(XRF)测定):
在用磷化组合物处理之后,优选冲洗,更优选用完全软化水或城市水冲洗金属表面。
有利的是将已用磷化组合物处理并因此经磷酸盐涂覆的金属表面进一步用含水后冲洗组合物处理。在该情况下,金属表面任选地在用后冲洗组合物处理之前干燥。
在此,后冲洗组合物可以通过用1.5-1000倍,优选5-700倍的合适溶剂,优选用水稀释以及必要时加入pH调节物质而由浓缩物获得。
用后冲洗组合物的处理允许通过在磷酸盐层中产生限定的孔以靶向方式调节磷酸盐涂覆的金属表面的电导率。在该情况下,电导率可以大于、等于或小于提供有含镍磷酸盐涂层的相应金属表面的电导率。
在此,可通过后冲洗组合物中的给定金属离子和/或聚合物的浓度变化来影响经磷酸盐涂覆的金属表面的调节的电导率。
根据一个实施方案,后冲洗组合物以以下优选、更优选和非常优选的浓度范围包含至少一种选自以下金属的离子的金属离子(均以相应金属计):
Mo | 1-500mg/l | 10-250mg/l | 20-150mg/l |
Cu | 1-1000mg/l | 100-500mg/l | 150-225mg/l |
Ag | 1-500mg/l | 5-300mg/l | 20-150mg/l |
Au | 1-500mg/l | 10-300mg/l | 20-200mg/l |
Pd | 1-200mg/l | 5-100mg/l | 15-60mg/l |
Sn | 1-500mg/l | 2-200mg/l | 3-100mg/l |
Sb | 1-500mg/l | 2-200mg/l | 3-100mg/l |
Ti | 20-500mg/l | 50-300mg/l | 50-150mg/l |
Zr | 20-500mg/l | 50-300mg/l | 50-150mg/l |
Hf | 20-500mg/l | 50-300mg/l | 50-150mg/l |
后冲洗组合物中所包含的金属离子以盐的形式沉积在待处理的表面(例如铜、银、金或钯)上,该盐包含相应金属阳离子(例如钼或锡),优选以至少两种氧化态,更特别地羟基氧化物、氢氧化物、尖晶石或缺陷尖晶石,或以元素形式包含相应的金属阳离子(例如钼或锡)。
根据一个优选实施方案,金属离子是钼离子。它们优选以钼酸盐,更优选七钼酸铵,非常优选七钼酸铵×7H2O的形式加入后冲洗组合物中。钼离子还可以钼酸钠的形式加入。
钼离子可替换地例如以至少一种包含钼阳离子的盐,例如氯化钼的形式加入后冲洗组合物中且然后通过合适氧化剂氧化成钼酸盐,其中实例是上文较早描述的促进剂。在该情况下,后冲洗组合物本身包含相应氧化剂。
进一步优选后冲洗组合物包含与铜离子、锡离子或锆离子组合的钼离子。
特别优选其包含与锆离子组合的钼离子,并且还任选地包含更特别选自以下聚合物类别的聚合物或共聚物:聚胺、聚乙烯胺、聚苯胺、聚亚胺、聚乙烯亚胺、聚噻吩和聚吡咯及其混合物和其共聚物以及聚丙烯酸,其中钼离子和锆离子的含量在每种情况下为10-500mg/l(以金属计)。
在此,钼离子的含量优选为20-150mg/l,更优选25-100mg/l,非常优选30-75mg/l,且锆离子的含量优选为50-300mg/l,更优选50-150mg/l。
根据另一优选实施方案,金属离子是铜离子。在该情况下,其优选以100-500mg/l,更优选150-225mg/l的浓度存在于后冲洗溶液中。
根据另一实施方案,本发明的后冲洗组合物包含至少一种选自以下聚合物类别的聚合物:聚胺、聚乙烯胺、聚苯胺、聚亚胺、聚乙烯亚胺、聚噻吩和聚吡咯及其混合物和其共聚物。
在此,所包括的至少一种聚合物的浓度优选为0.1-5g/l,更优选0.1-3g/l,更优选0.3-2g/l,非常优选0.5-1.5g/l(以纯聚合物计)。
所用聚合物优选是阳离子聚合物,特别是聚胺、聚乙烯胺、聚亚胺和/或聚乙烯亚胺。特别优选使用的是聚胺和/或聚亚胺,非常优选聚胺。
根据第三实施方案,本发明的后冲洗组合物在每种情况下以以下优选、更优选和非常优选的浓度范围(聚合物以纯聚合物计且金属离子以相应金属计)包含至少一种选自以下的离子的金属离子:钼、铜、银、金、钯、锡、锑、钛、锆和铪以及至少一种选自以下聚合物类别的聚合物:聚胺、聚乙烯胺、聚苯胺、聚亚胺、聚乙烯亚胺、聚噻吩和聚吡咯及其混合物和其共聚物。
Mo | 1-500mg/l | 10-250mg/l | 20-150mg/l |
Cu | 1-1000mg/l | 100-500mg/l | 150-225mg/l |
Ag | 1-500mg/l | 5-300mg/l | 20-150mg/l |
Au | 1-500mg/l | 10-300mg/l | 20-200mg/l |
Pd | 1-200mg/l | 5-100mg/l | 15-60mg/l |
Sn | 1-500mg/l | 2-200mg/l | 3-100mg/l |
Sb | 1-500mg/l | 2-200mg/l | 3-100mg/l |
Ti | 20-500mg/l | 50-300mg/l | 50-150mg/l |
Zr | 20-500mg/l | 50-300mg/l | 50-150mg/l |
Hf | 20-500mg/l | 50-300mg/l | 50-150mg/l |
聚合物 | 0.1-3g/l | 0.3-2g/l | 0.5-1.5g/l |
根据一个优选实施方案,至少一种聚合物是阳离子聚合物,更特别是聚胺和/或聚亚胺,且金属离子是铜离子、钼离子和/或锆离子,在每种情况下在优选、更优选和非常优选的浓度范围内(聚合物以纯聚合物计且金属离子以相应金属计)。
Mo | 1-500mg/l | 10-250mg/l | 20-150mg/l |
Cu | 1-1000mg/l | 100-500mg/l | 150-225mg/l |
Zr | 20-500mg/l | 50-300mg/l | 50-150mg/l |
阳离子聚合物 | 0.1-3g/l | 0.3-2g/l | 0.5-1.5g/l |
特别是如果金属表面是铝或铝合金,则后冲洗组合物优选进一步包含20-500mg/l,更优选50-300mg/l,非常优选50-150mg/l的络合形式的Ti、Zr和/或Hf(以金属计)。所述配合物优选是氟配合物。此外,后冲洗组合物优选包含10-500mg/l,更优选15-100mg/l,非常优选15-50mg/l的游离氟化物。
特别优选后冲洗组合物包含络合形式的Zr(以金属计)和至少一种选自钼、铜、银、金、钯、锡和锑,优选钼的离子的金属离子。
后冲洗组合物的pH优选在酸性范围内,更优选为3-5,非常优选为3.5-5。
令人惊讶地发现降低pH值促进钼离子在经磷酸盐涂覆的金属表面上沉积。因此,在后冲洗溶液包含钼离子的情况下,pH优选为3.5-4.5,更优选3.5-4.0。
后冲洗组合物基本无镍。其优选包含小于0.1g/l,更优选小于0.01g/l的镍离子。
后冲洗组合物的温度优选为15-40℃。用后冲洗组合物将金属表面处理优选10-180秒,更优选20-150秒,非常优选30-120秒(优选通过浸渍或喷涂)。
然后,可将电涂层材料阴极沉积在经磷酸盐涂覆的金属表面上-其任选地还用后冲洗组合物处理,并施加涂覆体系。
在该情况下,在用后冲洗组合物处理之后,任选地首先冲洗金属表面,优选用完全软化水冲洗,并且任选地干燥。
本发明额外涉及包含至少一种水溶性硅酸盐的上述碱性含水清洁剂组合物和在相应点描述的浓缩物,由该浓缩物可获得该清洁剂组合物。
此外,本发明涉及一种可通过本发明方法获得的经磷酸盐涂覆的金属表面。
最后,本发明还涉及用本发明方法涂覆的金属表面在汽车、汽车部件供应商或一般工业领域中的用途。
在下文中,意欲通过工作实施例(其应理解为不施加限制)和对比例来说明本发明。
实施例
i)清洁和磷化浴的制备:
将各组分在完全软化水中混合,任选地用磷酸调节pH值(清洁浴A),然后将混合物稀释50-70倍,以制备以下清洁浴:
额外地,制备清洁浴F和清洁浴G。清洁浴F除pH为10.5外与清洁浴B相同,而清洁浴G除pH为10.5外与清洁浴E相同。在清洁浴F和清洁浴G的情况下,使用磷酸调节pH。
将各组分在完全软化水中混合(以硝酸盐和/或磷酸盐的形式加入锌、镍和锰),并通过用氢氧化钠降低游离酸(FA)来调节A值,以制备以下无镍的磷化浴:
将H2ZrF6和七钼酸铵在完全软化水中混合,并使用稀氨水调节pH值,以制备以下后冲洗浴:
组分 | 量(mg/l) |
Zr | 130 |
Mo | 50 |
pH | 4 |
ii)测试板的处理:
将热浸镀锌钢(EA)、电解镀锌钢(G)以及铝合金AA 6014(Al)的测试板在60℃下浸入清洁浴A-D之一中300秒,随后在25℃下浸入包含0.6g/l磷酸锌的活化浴中30秒。然后将测试板在45℃下浸入磷化浴A'-C'之一中180秒,随后在25℃下浸入上述后冲洗浴中30秒。用完全软化水彻底冲洗后,将测试板进一步用阴极电涂以及标准汽车涂覆体系(填料、底涂层、透明涂层)涂覆。
iii)防腐和涂层粘合性测试:
随后使以此方式预处理和涂覆的测试板经受DIN EN ISO 2409划格测试。在每种情况下测试的是在暴露于冷凝水中240小时前后的3个板(DIN EN ISO 6270-2CH)。相应结果(平均值)见于表1。在这些结果中,划格结果0是最好的,其中结果5是最差的结果。在此,0和1的结果具有相当品质。
表1
此外,使电解镀锌和热浸镀锌钢的测试板经受VDA测试(VDA 621-415;10轮),该测试测定了膜降低(U)(以mm计)以及碎石后的膜分离(DIN EN ISO20567-1,方法C)。在此,发生碎石之后,结果0是最好的,其中结果5是最差的。认为至多1.5的结果是良好的。表2中同样概括了结果(三个板的平均值)。
表2
相反,使由铝合金制成的测试板经受240小时的根据DIN EN ISO 9227的CASS测试和根据DIN EN 3665的丝状测试。结果(三个板的平均值)概括于表3中。
表3
iv)结果和讨论:
表1的划格结果清楚地显示了在热浸镀锌和电解镀锌钢上无镍磷化而非含镍磷化的情况下涂层粘合性的劣化(参见VB2与VB1;VB4与VB3)。通过使用本发明的清洁浴,在无镍变体的情况下,可以实现几乎对应于含镍变体的涂层粘合性(参见B1与VB1和B2与VB3)。
对于表2的结果,适用相似评述。在此在无镍磷化中使用本发明的清洁浴还实现了防腐值的显著改进。通过向清洁浴中加入葡萄糖酸盐和亚硝酸盐进一步改进(参见B1与B4)。
表3中的CASS和丝状结果显示在铝合金上的无镍磷化中使用本发明的清洁浴得到防腐值的显著改进(参见B3与VB5和VB6)。在CASS以及丝状的情况下,所实现的防腐性实际上要好于含镍变体。
实施例B6和B7的比较(参见表1和表2)表明在每种情况下通过选择pH为11.6(B6)而非pH为10.5(B7)进一步改进所实现的结果。
实施例B8和B9的比较(参见表1和表2)表明在每种情况下通过选择pH为11.3(B8)而非pH为10.5(B9)进一步改进所实现的结果。
Claims (15)
1.一种用于基本无镍磷化金属表面的方法,其包括用以下组合物依次处理金属表面:
i)包含至少一种水溶性硅酸盐的碱性含水清洁剂组合物,以及然后
ii)包含锌离子、锰离子和磷酸根离子的酸性含水且基本无镍的磷化组合物。
2.根据权利要求1的方法,其中清洁剂组合物的pH为10.7-12.0,优选11.0-12.0,更优选11.3-12.0,非常优选11.5-12.0。
3.根据权利要求1或2的方法,其中金属表面为至少部分镀锌的。
4.根据前述权利要求中任一项的方法,其中至少一种水溶性硅酸盐包括至少一种水玻璃和/或至少一种偏硅酸盐。
5.根据权利要求4的方法,其中至少一种水溶性硅酸盐包括至少一种钠水玻璃和/或钾水玻璃。
6.根据前述权利要求中任一项的方法,其中至少一种水溶性硅酸盐以0.01-15,优选0.2-13,更优选0.5-10g/l的总浓度存在。
7.根据前述权利要求中任一项的方法,其中清洁剂组合物包含至少一种含磷络合剂和/或至少一种羟基羧酸或其盐。
8.根据权利要求7的方法,其中至少一种含磷络合剂包括焦磷酸盐和/或三聚磷酸盐。
9.根据权利要求7或8的方法,其中至少一种羟基羧酸或其盐包括葡萄糖酸盐。
10.根据前述权利要求中任一项的方法,其中清洁剂组合物包含亚硝酸盐。
11.根据前述权利要求中任一项的方法,其中将经磷化组合物处理的金属表面进一步用包含钼离子和锆离子的含水后冲洗组合物处理。
12.一种碱性含水清洁剂组合物,包含至少一种根据前述权利要求中任一项的水溶性硅酸盐。
13.一种浓缩物,可由其通过用合适溶剂稀释并在必要时加入pH调节物质获得根据权利要求12的清洁剂组合物。
14.一种经磷酸盐涂覆的金属表面,可通过根据权利要求1-11中任一项的方法获得。
15.根据权利要求14的金属表面在汽车、汽车部件供应商或一般工业领域中的用途。
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US11643731B2 (en) * | 2017-08-31 | 2023-05-09 | Chemetall Gmbh | Method for nickel-free phosphating metal surfaces |
TW202330890A (zh) | 2021-09-27 | 2023-08-01 | 德商開麥妥公司 | 用於清潔及處理金屬基材之無硼酸鹽水性組合物 |
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JP2021501829A (ja) | 2021-01-21 |
MX2020002343A (es) | 2020-07-13 |
US20200199758A1 (en) | 2020-06-25 |
RU2020111711A3 (zh) | 2022-02-02 |
JP7279019B2 (ja) | 2023-05-22 |
WO2019042951A1 (de) | 2019-03-07 |
KR20200045487A (ko) | 2020-05-04 |
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US11643731B2 (en) | 2023-05-09 |
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