CN1231705A - 用于磷化金属表面的水溶液和方法 - Google Patents
用于磷化金属表面的水溶液和方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 title claims description 19
- 239000011701 zinc Substances 0.000 claims abstract description 36
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 32
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 21
- 239000010959 steel Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 5
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 49
- 238000000576 coating method Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 48
- 239000000463 material Substances 0.000 description 20
- 239000002966 varnish Substances 0.000 description 18
- 230000002335 preservative effect Effects 0.000 description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 description 10
- 239000008397 galvanized steel Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005498 polishing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- SYNHCENRCUAUNM-UHFFFAOYSA-N Nitrogen mustard N-oxide hydrochloride Chemical compound Cl.ClCC[N+]([O-])(C)CCCl SYNHCENRCUAUNM-UHFFFAOYSA-N 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003599 detergent Substances 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- XIFJZJPMHNUGRA-UHFFFAOYSA-N n-methyl-4-nitroaniline Chemical compound CNC1=CC=C([N+]([O-])=O)C=C1 XIFJZJPMHNUGRA-UHFFFAOYSA-N 0.000 description 1
- -1 nitro amino ethyl Chemical group 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- CMUOJBJRZUHRMU-UHFFFAOYSA-N nitrourea Chemical compound NC(=O)N[N+]([O-])=O CMUOJBJRZUHRMU-UHFFFAOYSA-N 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 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
- 239000000758 substrate Substances 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [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 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/186—Orthophosphates containing manganese cations containing also copper cations
-
- 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
-
- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
- C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations
Abstract
本发明公开了一种水性含磷酸盐溶液,用于在由铁、钢、锌、锌合金、铝或铝合金制成的金属表面上产生磷酸盐涂层。该溶液含有0.3至5gZn2+/l和0.1至3g硝基胍/l,S值为0.03至0.3,Zn：P2O5的重量比等于1∶5至1∶30。本发明还公开了一种磷化方法,所述磷化方法包括,清洁金属表面,随后在15至70℃的温度下用所述磷化液处理5秒至10分钟,最后用水漂洗。
Description
本发明涉及一种用于在铁、钢、锌、锌合金、铝或铝合金的金属表面上产生磷酸盐涂层的水性含磷酸盐溶液。本发明另外还涉及使用水性磷化液进行磷化处理的方法。
从DE-PS750957已经知道一种提高金属、尤其是铁和钢的防腐性的方法，即将它们在溶液中进行处理以形成磷酸盐涂层，所述溶液含有促进剂，并且其中硝基甲烷、硝基苯、苦味酸、硝基苯胺、硝基苯酚、硝基苯甲酸、硝基间苯二酚、硝基脲、硝基氨基甲酸乙酯或硝基胍被用作促进剂。对每种促进剂而言，其最佳浓度各不相同，但在磷化液中通常的范围为0.01-0.4％(重量)。对于促进剂硝基胍，最佳浓度据说为0.2％(重量)。
从DE-OS3800835已经知道一种磷化金属表面，尤其是铁、钢、锌及其合金以及铝表面的方法，作为其中不在30-70℃的温度范围内进行活化的冷加工的预处理，将表面与水溶液接触，水溶液含有10-40gCa2+/l、20-40g Zn2+/l、10-100g PO4 3-/l和作为促进剂的10-100g NO3 -/l和/或0.1-2.0g有机硝基化合物/l，其中溶液的pH值为2.0至3.8，游离酸与总酸的比为1∶4至1∶100。作为促进剂，可以使用间硝基苯磺酸盐和/或硝基胍。根据已知方法产生的磷酸盐涂层的涂层量为3至9g/m2。
尽管磷化金属表面时用硝基胍作为促进剂本身已经公知，但在实际使用这种促进剂时会遇到一些困难，因为所获得的磷化结果常常不令人满意。很显然这是由于促进剂硝基胍的作用很大程度上依赖于磷化液中的无机成分和磷化液中无机成分的浓度，以致仅仅当硝基胍能成功地得到这样一种磷化液时，使用硝基胍产生的磷酸盐涂层才具有良好的作用性能，该磷化液中每种成分得以相互调节，使得当使用硝基胍作为促进剂时、在连续操作中仍能获得良好稳定质量的磷酸盐涂层。而且，磷化液中硝基胍和其它成分之间的相互作用不能通过理论研究或简单实验进行预测或确定，而必须对不同的磷化体系通过广泛实验进行确定。这种常见的不令人满意的结果也是由于硝基胍不好的水溶性和不均匀的分散性造成的。
因此，本发明的目的是发明一种用于磷化金属表面的水溶液，该水溶液含有硝基胍作为促进剂，并其它成分得以相互调节，使磷化过程中形成的磷酸盐涂层精细结晶，并具有低的涂层量，该涂层可提供良好的清漆粘结性，并确保具有良好的防腐性。本发明的另一目的是，发明一种使用本发明磷化液进行磷化的方法，其中该方法在尽可能低的温度下进行操作，可用于磷化不同的金属表面，而且使用简单的技术方式进行操作，并且操作安全。
通过发明一种在铁、钢、锌、锌合金、铝或铝合金的金属表面上产生磷酸盐涂层的水性含磷酸盐溶液，可实现本发明目的，所述溶液含有0.3至5g Zn2+/l和0.1至3g硝基胍/l，其中酸值为0.03至0.3，Zn∶P2O5的重量比等于1∶5至1∶30，该溶液可产生精细结晶的磷酸盐涂层，其中晶体的最大棱边长＜15μm。令人惊奇地发现，本发明的磷化液可产生非常精细结晶的磷酸盐涂层，该涂层具有良好的清漆粘结性和良好的防腐性。晶体为层状长方体形或立方体形，并且最大棱边长＜15μm，通常平均＜10μm。而且，本发明的磷化液非常适合磷化型腔。从本发明的磷化液沉积在金属制品上磷酸盐涂层的涂层量为1.5至4.5g/m2，优选1.5至3g/m2，因此对清漆粘结性产生良好影响。如果锌含量＞5g/l，防腐性和清漆粘结性将明显变差。
Zn∶P2O5的比是基于总P2O5量计的。确定总P2O5是基于磷酸和/或伯式磷酸盐的滴定结果，它是从伯式磷酸盐的等当点滴定到仲式磷酸盐的等当点。酸值表示游离酸(按游离P2O5计算)与总P2O5的比值。总P2O5和游离P2O5的定义和测定方法在W.Rausch的出版物“金属的磷化处理”，1988，第299-304页中有详细描述。
根据本发明，当水性含磷酸盐的溶液含有0.3至3g Zn2+/l和0.1至3g硝基胍/l，其中酸值为0.03至0.3，Zn∶P2O5的重量比等于1∶5至1∶30时，是尤其有益的。对于本发明，由于锌含量为0.3至3g/l，因此适合进行低锌磷化，尤其可获得总体上良好的结果。
根据本发明，水溶液含有0.5至20g NO3 -/l。本发明的硝酸盐含量有益地影响到最佳涂层量，使之保持为1.5至4.5g/m2。以碱金属硝酸盐的形式将硝酸盐添加到磷化液中，和/或通过阳离子的方式使硝酸盐存在于系统中，例如作为硝酸锌和/或作为HNO3。由于无硝酸盐的水溶液也可以提供良好的磷化效果，公知的硝酸盐的促进作用在目前情况下多半是不重要的。
本发明另外还提供含有0.01至3g Mn2+/l和/或0.01至3g Ni2+/l和/或1至100mg Cu2+/l和/或10至300mg Co2+/l的磷化液。这些金属离子掺合在磷酸盐涂层中，提高涂层的清漆粘结性和防腐性。
根据本发明的另一方面，所提供的水性磷化液含有0.01至3g F-/l和/或0.05至3.5g/l配位的氟化物，优选(SiF6)2-或(BF4)-。当由铝或铝合金构成的金属表面需要磷化时，将氟化物添加到磷化液中。将配位的氟化物添加到磷化液中起稳定作用，因此可使磷化浴获得较长的停留时间。
通过本发明磷化方法可进一步实现本发明目的，所述磷化方法包括清洁金属表面，随后在15至70℃的温度下用水性含磷酸盐的磷化液处理5秒至10分钟，再最后用水漂洗。本方法可以用简单的技术方式完成，并且操作安全。由本方法的方式得到的磷酸盐涂层具有稳定良好的质量，并且甚至不会随着磷化浴操作时间的延长而降低其质量。本发明方法中最短的磷化时间比公知的、使用常用促进剂的低锌法的磷化时间短。最短的磷化时间是指表面覆盖100％磷酸盐涂层的时间。
根据本发明，用磷化液处理金属表面是通过喷涂、浸涂、喷淋浸渍或辊涂来实现的。这些加工技术为本发明的方法提供了广泛和不同的应用范围。当用于喷涂的磷化液中Zn∶P2O5的重量比等于1∶10至1∶30，和当用于浸涂的磷化液中Zn∶P2O5的重量比等于1∶5至1∶18时，本发明被证明是尤其有益的。
根据本发明，清洁后金属表面用含有含钛磷酸盐的活化剂进行处理通常是有益的。这有利于紧密、精细的晶体磷酸锌涂层的形成。
最后，在磷化处理之后的漂洗操作后，本发明还提供用钝化剂对金属表面进行后处理。所使用的钝化剂可含Cr和不含Cr。
根据本发明的方法在对金属表面进行清洁时，将机械杂质和粘附的油都从待磷化表面除去。金属表面的清洁属于公知的现有技术，可有益地用水性-碱性清洁剂进行清洁。方便地，金属表面清洁后再用水漂洗。或者用自来水或者用去离子水漂洗清洁过的或磷化过的金属表面。
本发明的磷化液这样制备，即将含有磷化液无机成分以及水的约30至90g浓缩物用水稀释到1升。随后，将给定量的硝基胍以悬浮液的形式或作为粉末引入到磷化液中。然后准备好该溶液以备用，磷化过程中消耗的物质可通过连续添加浓缩物和硝基胍进行补充。
为避免硝基胍作为粉末时其配料难的问题，本发明提出将硝基胍以稳定的悬浮液的形式引入到水溶液中。根据本发明，悬浮液用片状硅酸盐进行稳定。悬浮液含有100至300g硝基胍/1、10至30g片状硅酸盐/l和剩余量的水。该悬浮液可以用泵容易地进行输送，并且经过12个月仍然是稳定的，即甚至在延长的存放时间内硝基胍不会沉淀。悬浮液可这样制得，将片状硅酸盐悬浮在1升完全去离子的水中，然后在其中搅拌加入硝基胍。磷化液中的pH值为2至3时，悬浮液被破坏，硝基胍以微细分散体形式析出。根据本发明，片状硅酸盐[Mg6(Si7.4Al0.6)O20(OH)4]Na0.6.xH2O和[(Mg5.4Lio.6)Si8O20(OH3F)4]Na0.6.xH2O被证明是尤其有用的。这些是合成的蒙脱石型三层硅酸盐。片状硅酸盐对磷酸盐涂层的形成没有不利的影响。除了其实际有益的效果外，它们还可改善磷酸盐浆的沉积作用，并提高其固含量。
随后将参考实施例详细解释本发明的主题要点。
实施方案1和2按以下工艺步骤进行：
a)用弱碱性清洁剂(2％的水溶液)于60℃的温度下对由钢板制成的金属制品表面清洁5分钟，并特别进行脱脂。
b)然后，室温下用自来水漂洗0.5分钟。
c)随后，室温下用含有磷酸钛的活化剂(3g/lH2O)活化0.5分钟。
d)然后，通过在约55℃的温度下浸渍3分钟，进行磷化。
e)最后，室温下用自来水漂洗0.5分钟。
f)用压缩空气干燥磷化过的表面。
用于磷化的水溶液组合物和磷酸盐涂层的性能列于表1中。
根据实施方案1和2，用本身已知的但含有不同促进剂的磷化液(比较试验A和B)进行比较试验。另外，用就Zn∶P2O5比而言不属于本发明范围、但含有硝基胍作为促进剂的磷化液(比较试验C)进行比较试验。在比较试验A、B、C中进行步骤a)至f)。用于比较试验的磷化液组合物和磷酸盐涂层的性能列于表2中。
实施方案1和2与比较试验A、B、C的比较表明，将本发明的磷化液与已知的并经多次试验证明有用的磷化液进行对照，获得良好的结果，但硝基胍与促进剂NO2 -相比具有好得多的作用性能。比较试验C表明，仅仅使用本发明的参数可获得良好的实用的磷化结果。
实施方案3和4使用以下操作条件进行处理，在这种场合尤其可以验证是否本发明适合于磷化型腔：根据操作步骤a)至e)(实施方案1和2也使用了这些步骤)在模拟型腔的盒中处理钢板。室温下不用压缩空气在型腔(盒)中干燥磷化过的钢板。用于磷化型腔的水性溶液组合物和磷酸盐涂层的性能列于表3中。
对涂层量、晶体棱边长度和最小磷化时间而言，实施方案3和4的磷酸盐涂层与实施方案1和2的磷酸盐涂层具有大致相同的性能。
根据实施方案3和4进行比较试验D和E，其中每个操作步骤相同。用于比较试验D和E的磷化液本身是公知的，含有羟胺作为促进剂。用于进行比较试验D和E的溶液组合物和和磷酸盐涂层的性能列于表4中。
实施方案3和4与比较试验D和E的比较表明，本发明可获得非常好的型腔磷化，根据本发明可得到完整、紧密的磷酸盐涂层，没有形成闪锈。术语“形成闪锈”指在干燥过程中不具有完整、紧密的磷酸盐涂层的金属表面形成锈层，这是非常不利的。在有些情况下，由于磷化液对金属表面的钝化，尽管没有完整、紧密的磷酸盐涂层，也没有形成闪锈。
为验证根据本发明磷化过的各种金属基材上的防腐性和清漆粘结性，测定清漆粘结性值。
表5列出了清漆粘结性和防腐性值，它们是通过对不同的片材(基材)测定得到的，其中根据实施例5、6和7的每个基材通过浸渍在本发明的溶液中进行磷化，根据比较试验F和G的基材通过浸渍在公知的溶液中进行磷化。根据上述操作步骤a)至f)，对每个基材进行浸渍。用于实施例5、6和7的磷化液组合物列于表7中。该表还列出了用于比较试验F和G的公知的磷化液组合物。通过浸渍对基材进行磷化后，再涂覆电泳漆、填孔涂层和面漆。随后，进行户外耐候性试验，6个月后进行评估，交替气候试验12个循环后，进行盐雾试验和飞石试验。表5列出每个试验测定的、用mm表示的清漆涂层表面下腐蚀情况，对于飞石试验，清漆的片状剥落用百分比表示。
表6列出了通过喷涂而磷化的各种基材的清漆粘结性和防腐性值。根据本发明，使用以下操作步骤对基材进行喷涂磷化：
g)用弱碱性清洁剂(2％的水溶液)于60℃的温度下对基材表面清洁5分钟并特别进行脱脂。
h)随后，室温下用自来水漂洗0.5分钟。
i)然后，在约55℃的温度下喷涂磷化3分钟。
k)随后，在室外用含(ZrF6)2-的无铬漂洗剂漂洗1分钟，使磷化过的基材钝化。
l)最后，室温下用完全去离子水漂洗1分钟。
m)在80℃的烘箱中干燥磷化过的基材10分钟。
用于实施例8、9和10的本发明水性磷化液组合物列于表8。用于完成比较试验H的公知的磷化液组合物也列于表8。在通过喷涂而磷化的基材上，再涂覆电泳漆、填孔涂层和面漆。然后对磷化过和涂漆基材进行6个月户外耐候性试验、盐雾试验、划格法附着力试验和12个循环的交替气候试验，随后进行飞石试验。表6列出每个基材的测定值，表中列出了划格法附着力试验的等级，对于户外耐候性试验、盐雾试验和交替气候试验，表中列出清漆涂层的下表面腐蚀情况，用mm表示。对于飞石试验，列出用百分比表示的清漆剥落情况。
由本发明的磷化方法获得的防腐性可以与使用经试验证明有用的公知的磷化方法(该方法用亚硝酸盐作为促进剂)获得的防腐性进行比较。本发明的磷化方法避免使用促进剂亚硝酸盐，使用亚硝酸盐会遇到不允许的情况，因为磷化过程中从亚硝酸盐形成的反应产物对环境有害并且部分对人有害。由本发明的磷化方法的方式获得的清漆粘结性和防腐效果必须被评估为非常好到好。
表1
| 实施例1 | 实施例2 | |
| Zn2+ | 1.4g/l | 1.4g/l |
| Mn2+ | 1.0g/l | 1.0g/l |
| Ni2+ | 1.0g/l | - |
| Cu2+ | - | 8mg/l |
| NO3 - | 3.0g/l | 3.0g/l |
| PO4 3-(总) | 18.0g/l | 18.0g/l |
| =P2O5(总) | 13.5g/l | 13.5g/l |
| 硝基胍 | 0.5g/l | 0.g/l |
| Na+ | 对于调整滴定数据所需的量 | |
| 酸值 | 0.09 | 0.09 |
| 涂层量 | 2.4g/m2 | 2.6g/m2 |
| 晶体棱边长度 | 2.8μm | 2.8μm |
| 最小磷化时间 | ＜60秒 | ＜60秒 |
表2
| 比较试验A | 比较试验B | 比较试验C | |
| Zn2+ | 1.4g/l | 1.4g/l | 3.5g/l |
| Ni2+ | 1.0g/l | 1.0g/l | - |
| Mn2++ | 1.0g/l | 1.0g/l | - |
| P2O5(总) | 12.0g/l | 12.0g/l | 5.5g/l |
| 酸值 | 0.07 | 0.09 | 0.35g/l |
| NO3 - | 3.0g/l | 3.0g/l | 3.0g/l |
| H2O2 | 30mg/l | - | - |
| NO2 - | - | 170mg/l | - |
| 硝基胍 | - | - | 2.0g/l |
| Na+ | 对于调整滴定数据所需的量 | ||
| 涂层量 | 1.3g/m2 | 2.2g/m2 | 4.9g/m2 |
| 晶体棱边长度 | 40μm | 10μm | 20-25μm |
| 最小磷化时间 | 120秒 | 60秒 | 60秒 |
表3
| 实施例3 | 实施例4 | |
| Zn2+ | 1.4g/l | 1.9g/l |
| Ni2+ | 1.0g/l | 1.0g/l |
| Mn2+ | 1.0g/l | 1.0g/l |
| P2O5(总) | 12.0g/l | 12.0g/l |
| 酸值 | 0.09 | 0.09 |
| NO3 - | 3.0g/l | 3.0g/l |
| 硝基胍 | 0.5g/l | 0.9g/l |
| Na+ | 对于调整滴定数据所需的量 | |
| 完整的、紧密的磷酸盐涂层 | 有 | 有 |
| 形成闪锈 | 无 | 无 |
表4
| 比较试验D | 比较试验E | |
| Zn2+ | 1.4g/l | 1.9g/l |
| Ni2+ | 1.0g/l | 1.0g/l |
| Mn2+ | 1.0g/l | 1.0g/l |
| P2O5(总) | 12.0g/l | 12.0g/l |
| 酸值 | 0.09 | 0.09 |
| NO3 - | 3.0g/l | 3.0g/l |
| 羟基胺 | 1.0g/l | 1.0g/l |
| Na+ | 对于调整滴定数据所需的量 | |
| 完整的、紧密的磷酸盐涂层 | 无 | 无 |
| 形成闪锈 | 有 | 有 |
表5清漆粘结性值，浸渍涂覆
| 基材 | 实施例 | 比较试验 | |||
| 5 | 6 | 7 | F | G | |
| 户外老化6个月，mm表面下腐蚀，从擦痕面单面测量 | |||||
| 钢 | ＜1 | ＜1 | 1.5 | ＜1 | 2.5 |
| 镀锌钢 | 1 | 1 | 1 | 1.5 | 2.5 |
| 热法镀锌钢 | 0 | ＜1 | 1 | 0 | ＜1 |
| 有Fe-Zn涂层的钢 | ＜1 | ＜1 | ＜1 | ＜1 | ＜1 |
| AlMgSi，未抛光 | 3 | 0 | 0 | ＜1-3 | - |
| AlMgSi，抛光 | 5 | ＜1 | 0 | 4 | - |
| 盐雾试验，1008h，根据DIN50021SS，mm表面下腐蚀 | |||||
| 钢 | ＜1 | ＜1 | 1.5 | ＜1 | 1 |
| 根据VDA 621-415交替气候试验12个循环，用mm表示表面下腐蚀，从擦痕面单面测量，随后根据VW AG的规格进行飞石试验，清漆片状剥落％表示在()内 | |||||
| 钢 | ＜1(0.5) | ＜1(0.5) | 1.5(0.5) | ＜1(1) | 2(2) |
| 镀锌钢 | 6.5(1.5) | 7(8.5) | 7(5) | 5.5(2) | 8(40) |
| 热法镀锌钢 | 1.5(0.5) | 2(7) | 2(2) | 1(0.5) | 2.5(15) |
| 有Fe-Zn涂层的钢 | 1(0.5) | 1(0.5) | 1(0.5) | 1(0.5) | 1(0.5) |
表6清漆粘结性值，喷涂涂覆
| 基材 | 实施例 | 比较试验 | ||
| 8 | 9 | 10 | H | |
| 户外老化6个月，mm表面下腐蚀，从擦痕面单面测量 | ||||
| 钢 | ＜1 | 1 | ＜1 | ＜1 |
| 镀锌钢 | ＜1 | 1.5 | 1.5 | 1.5 |
| 热法镀锌钢 | 0 | 0 | 0 | 0 |
| 有Fe-Zn涂层的钢 | 0 | ＜1 | ＜1 | ＜1 |
| AlMgSi，未抛光 | 0 | 0 | 0 | 2 |
| AlMgSi，抛光 | 0 | 0 | 2.5 | 5 |
| 盐雾试验，1008h，根据DIN50021SS，mm表面下腐蚀 | ||||
| 钢 | ＜1 | ＜1 | ＜1 | ＜1 |
| 240小时后划格法附着力试验，根据DIN 50017kk和DIN/ISO 2409，等级 | ||||
| 钢 | 1 | 2 | 1 | 1 |
| 镀锌钢 | 1 | 2 | 1-2 | 1 |
| 热法镀锌钢 | 1 | 2 | 2 | 1 |
| 有Fe-Zn涂层的钢 | 1 | 1 | 1 | 1 |
| AlMgSi，未抛光 | 1 | 0 | 3 | 1 |
| AlMgSi，抛光 | 1 | 0-1 | 3 | 1 |
| 根据VDA 621-415交替气候试验12个循环，用mm表示表面下腐蚀，从擦痕面单面测量，随后根据VW AG的规格进行飞石试验，清漆片状剥落％表示在()内 | ||||
| 钢 | ＜1(2) | 1(5) | ＜1(2) | ＜1(2) |
| 镀锌钢 | 5(5.5) | 5.5(9) | 6(14) | 5.5(4) |
| 热法镀锌钢 | 1.5(1) | 2.5(2) | 2.5(1.5) | 1.5(1) |
| 有Fe-Zn涂层的钢 | 1(1) | 1(2) | 1(1) | 1(1) |
表7
| 物质/值 | 实施例 | 比较试验 | |||
| 5 | 6 | 7 | F | G | |
| Zn2+ | 1.4g/l | 1.4g/l | 1.4g/l | 1.4g/l | 3.5g/l |
| Mn2+ | 1.0g/l | 1.0g/l | 1.0g/l | 1.0g/l | - |
| Ni2+ | 1.0g/l | - | - | 1.0g/l | - |
| Cu2+ | - | 8mg/l | - | - | - |
| NO3 - | 3.0g/l | 3.0g/l | 3.0g/l | 3.0g/l | 3.0g/l |
| P2O5(总) | 13.5g/l | 13.5g/l | 13.5g/l | 12.0g/l | 5.5g/l |
| 硝基胍 | 0.5g/l | 0.5g/l | 0.5g/l | - | 2g/l |
| NO2 - | - | - | - | 170mg/l | - |
| 酸值 | 0.09 | 0.09 | 0.09 | 0.09 | 0.35 |
表8
| 物质/值 | 实施例 | 比较试验 | ||
| 8 | 9 | 10 | H | |
| Zn2+ | 0.9g/l | 0.9g/l | 0.9g/l | 0.9g/l |
| Mn2+ | 1.0g/l | 1.0g/l | 1.0g/l | 1.0g/l |
| Ni2+ | 1.0g/l | - | - | 1.0g/l |
| Cu2+ | - | 5mg/l | - | - |
| NO3 - | 3.0g/l | 3.0g/l | 3.0g/l | 3.0g/l |
| P2O5(总) | 11g/l | 11g/l | 11g/l | 11g/l |
| 硝基胍 | 0.5g/l | 0.5g/l | 0.5g/l | - |
| NO2 - | - | - | - | 150mg/l |
| 酸值 | 0.07 | 0.07 | 0.07 | 0.07 |
Claims (17)
1、一种用于在铁、钢、锌、锌合金、铝或铝合金的金属表面上产生磷酸盐涂层的水性含磷酸盐溶液，该溶液含有0.3至5g Zn2+/l和0.1至3g硝基胍/l，其中酸值为0.03至0.3，Zn∶P2O5的重量比等于1∶5至1∶30，该溶液可产生精细结晶的磷酸盐涂层，层中晶体的最大棱边长＜15μm。
2、权利要求1的水性溶液，该溶液含有0.3至3g Zn2+/l。
3、权利要求1至2的水性溶液，该溶液含有0.5至20g NO3 -/l。
4、权利要求l至3的水性溶液，该溶液含有0.01至3g Mn2+/l和/或0.01至3g Ni2+/l和/或1至100mg Cu2+/l和/或10至300mg Co2+/l。
5、权利要求1至4的水性溶液，该溶液含有0.01至3g F-/l和/或0.05至3.5g至少一种配位的氟化物/l。
6、权利要求5的水性溶液，该溶液含有(SiF6)2-或(BF4)-作为配位的氟化物。
7、一种磷化方法，所述磷化方法包括，清洁金属表面，随后在15至70℃的温度下用权利要求1至6的水性含磷酸盐的溶液处理5秒至10分钟，最后用水漂洗。
8、权利要求7的方法，其中用磷化液处理金属表面是通过喷涂、浸涂、喷淋浸渍或辊涂来实现的。
9、权利要求8的方法，其中用于喷涂的磷化液中Zn∶P2O5的重量比等于1∶10至1∶30。
10、权利要求8的方法，其中用于浸涂的磷化液中Zn∶P2O5的重量比等于1∶5至1∶18。
11、权利要求7至10的方法，其中清洁后金属表面用含有含钛磷酸盐的活化剂进行处理。
12、权利要求7至11的方法，其中磷化处理之后的漂洗操作后，金属表面用钝化剂进行处理。
13、权利要求7的方法，其中硝基胍以稳定的、水性悬浮液的形式引入到水溶液中。
14、权利要求13的方法，其中稳定的、水性悬浮液含有片状硅酸盐作为稳定剂。
15、权利要求14的方法，其中将片状硅酸盐[Mg6(Si7.4Al0.6)O20(OH)4]Na0.6.xH2O和[(Mg5.4Li0.6)Si8O20(OH3F)4]Na0.6.xH2O用作稳定剂，其用量是10至30g/l硝基胍悬浮液。
16、将权利要求1至6的水性含磷酸盐溶液和权利要求7至15的磷化方法用于涂层前处理工件的用途。
17、权利要求16的用途，用于电浸涂前处理工件。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19634685.1 | 1996-08-28 | ||
| DE19634685A DE19634685A1 (de) | 1996-08-28 | 1996-08-28 | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231705A true CN1231705A (zh) | 1999-10-13 |
| CN1080325C CN1080325C (zh) | 2002-03-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198243A Expired - Lifetime CN1080325C (zh) | 1996-08-28 | 1997-08-11 | 用于磷化金属表面的水溶液和方法 |
Country Status (25)
| Country | Link |
|---|---|
| US (1) | US6261384B1 (zh) |
| EP (1) | EP0922123B1 (zh) |
| JP (1) | JP3940174B2 (zh) |
| KR (1) | KR100473779B1 (zh) |
| CN (1) | CN1080325C (zh) |
| AR (1) | AR009336A1 (zh) |
| AT (1) | ATE195005T1 (zh) |
| AU (1) | AU720551B2 (zh) |
| BR (1) | BR9713177A (zh) |
| CA (1) | CA2264568C (zh) |
| CZ (1) | CZ294673B6 (zh) |
| DE (2) | DE19634685A1 (zh) |
| DK (1) | DK0922123T3 (zh) |
| ES (1) | ES2150791T3 (zh) |
| GR (1) | GR3034297T3 (zh) |
| HU (1) | HU228330B1 (zh) |
| IN (1) | IN192301B (zh) |
| PL (1) | PL192285B1 (zh) |
| PT (1) | PT922123E (zh) |
| SI (1) | SI0922123T1 (zh) |
| SK (1) | SK283857B6 (zh) |
| TR (1) | TR199900426T2 (zh) |
| TW (1) | TW363089B (zh) |
| WO (1) | WO1998008999A1 (zh) |
| ZA (1) | ZA977706B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314836C (zh) * | 2004-08-02 | 2007-05-09 | 吉林大学 | 镁合金磷化溶液及其磷化工艺 |
| CN101693993B (zh) * | 2009-09-27 | 2011-03-30 | 上海大学 | 碳钢表面磷化处理液及镀镍封闭方法 |
| CN109518176A (zh) * | 2018-12-14 | 2019-03-26 | 上海大学 | 碱性磷化液、制备方法及磷化处理工艺 |
| CN110699681A (zh) * | 2019-10-24 | 2020-01-17 | 河南北方红阳机电有限公司 | 一种高强度钢和硬铝合金组合体喷淋磷化工艺 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19808440C2 (de) | 1998-02-27 | 2000-08-24 | Metallgesellschaft Ag | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens |
| DE19834796A1 (de) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung |
| DE19857799A1 (de) | 1998-12-15 | 2000-06-21 | Henkel Kgaa | Verfahren zum Steuern einer Behandlungslinie |
| DE19911843C2 (de) * | 1999-03-17 | 2001-05-10 | Metallgesellschaft Ag | Verfahren für den Korrosionsschutz von Aluminium und Aluminiumlegierungen sowie Verwendung des Verfahrens |
| CN100374620C (zh) | 2002-07-10 | 2008-03-12 | 坎梅陶尔股份有限公司 | 金属表面的涂层方法 |
| US20040118483A1 (en) * | 2002-12-24 | 2004-06-24 | Michael Deemer | Process and solution for providing a thin corrosion inhibiting coating on a metallic surface |
| US20040188323A1 (en) * | 2003-03-24 | 2004-09-30 | Tzatzov Konstantin K. | Active coating system for reducing or eliminating coke build-up during petrochemical processes |
| DE10320313B4 (de) * | 2003-05-06 | 2005-08-11 | Chemetall Gmbh | Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes |
| DE10323305B4 (de) * | 2003-05-23 | 2006-03-30 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände |
| CN107338428B (zh) * | 2017-06-02 | 2019-01-11 | 余卫民 | 钴、锌、铁三元体系磷酸盐金属表面处理剂、制备方法及复合沉积物 |
| RU2690876C1 (ru) * | 2018-06-14 | 2019-06-06 | Закрытое Акционерное общество "ФК" (ЗАО " ФК") | Способ получения фосфатного покрытия |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2375468A (en) * | 1938-02-04 | 1945-05-08 | Parker Rust Proof Co | Phosphate coating of metals |
| BE432557A (zh) * | 1938-02-04 | |||
| DE821907C (de) * | 1943-06-07 | 1951-11-22 | Pyrene Co Ltd | Mittel fuer die Herstellung von Phosphatueberzuegen auf Metallen |
| DE977633C (de) * | 1950-07-06 | 1967-11-02 | Galvapol Ges Fuer Galvanotechn | Verfahren zur Herstellung von Phosphatueberzuegen auf eisenhaltigen Metallgegenstaenden |
| US3855147A (en) * | 1972-05-26 | 1974-12-17 | Nl Industries Inc | Synthetic smectite compositions, their preparation, and their use as thickeners in aqueous systems |
| GB2080835B (en) * | 1980-07-25 | 1984-08-30 | Pyrene Chemical Services Ltd | Prevention of sludge in phosphating baths |
| DE3800835A1 (de) * | 1988-01-14 | 1989-07-27 | Henkel Kgaa | Verfahren zur phosphatierung von metalloberflaechen |
| US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
-
1996
- 1996-08-28 DE DE19634685A patent/DE19634685A1/de not_active Withdrawn
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- 1997-08-11 CN CN97198243A patent/CN1080325C/zh not_active Expired - Lifetime
- 1997-08-11 BR BR9713177-6A patent/BR9713177A/pt not_active IP Right Cessation
- 1997-08-11 ES ES97943803T patent/ES2150791T3/es not_active Expired - Lifetime
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- 1997-08-11 WO PCT/EP1997/004360 patent/WO1998008999A1/de active IP Right Grant
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- 1997-08-11 DE DE59702088T patent/DE59702088D1/de not_active Expired - Lifetime
- 1997-08-20 IN IN1531CA1997 patent/IN192301B/en unknown
- 1997-08-26 AR ARP970103872A patent/AR009336A1/es unknown
- 1997-08-27 ZA ZA977706A patent/ZA977706B/xx unknown
- 1997-08-28 TW TW086112378A patent/TW363089B/zh not_active IP Right Cessation
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314836C (zh) * | 2004-08-02 | 2007-05-09 | 吉林大学 | 镁合金磷化溶液及其磷化工艺 |
| CN101693993B (zh) * | 2009-09-27 | 2011-03-30 | 上海大学 | 碳钢表面磷化处理液及镀镍封闭方法 |
| CN109518176A (zh) * | 2018-12-14 | 2019-03-26 | 上海大学 | 碱性磷化液、制备方法及磷化处理工艺 |
| CN110699681A (zh) * | 2019-10-24 | 2020-01-17 | 河南北方红阳机电有限公司 | 一种高强度钢和硬铝合金组合体喷淋磷化工艺 |
| CN110699681B (zh) * | 2019-10-24 | 2021-12-14 | 河南北方红阳机电有限公司 | 一种高强度钢和硬铝合金组合体喷淋磷化工艺 |
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