CN102227516A - 含锌表面的转化层 - Google Patents
含锌表面的转化层 Download PDFInfo
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- CN102227516A CN102227516A CN2009801474549A CN200980147454A CN102227516A CN 102227516 A CN102227516 A CN 102227516A CN 2009801474549 A CN2009801474549 A CN 2009801474549A CN 200980147454 A CN200980147454 A CN 200980147454A CN 102227516 A CN102227516 A CN 102227516A
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- Prior art keywords
- acid
- treatment solution
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- aqueous treatment
- chromium
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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
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23C22/17—Orthophosphates containing zinc cations containing also organic acids
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明涉及生产防止腐蚀的涂层的方法，其中需要处理的表面与水性处理溶液进行接触，该溶液含有至少一种铬(III)离子源以及在弱酸性或酸性溶液中作为锌的氧化剂的至少一种有机化合物。这里，表面的装饰效果和功能性能得以保留或改进。另外，与含铬(VI)的化合物的使用相关的已知问题得到避免。
Description
本发明的领域
本发明涉及金属材料、尤其具有转化层的金属材料的防腐蚀。
本发明的背景
为了保护金属材料的表面免受腐蚀性的环境影响，现有技术提供了各种方法。用另一种金属的涂层涂覆待保护的金属工件是现有技术中广泛采用和成熟的方法。与单独的工件基材金属相比，涂覆用金属能够是在腐蚀介质中在电化学方面更贵或更廉价的。如果涂覆用金属是更廉价的，则在腐蚀介质中的阴极腐蚀保护的意义上它用作相对于基材金属的牺牲阳极。虽然与涂覆用金属的腐蚀产物的形成相关的这一保护功能因此是所希望的，但是涂层的腐蚀产物本身常常导致不希望有的装饰性不利影响，并且不是罕见地还导致对工件的功能上不利的影响。为了减少涂覆用金属的腐蚀或尽可能长时间地延迟腐蚀，常常尤其在阴极保护用的非昂贵的涂覆金属如锌或其合金上使用所谓转化层。这些转化层是非昂贵的涂覆用金属与反应溶液的反应产物，这些反应产物在宽的pH范围内不溶于含水介质中。这些所谓转化层的例子例如是所谓磷酸盐处理层和铬酸盐处理层。对于磷酸盐处理层而言，需要保护的层被浸入到含有磷酸根离子的酸性溶液中。酸性介质会导致锌从涂层中的部分溶解。原则上，释放的Zn2+阳离子与反应溶液的磷酸根离子在表面上形成难溶的磷酸锌层。因为磷酸锌层本身仅仅构成较弱的腐蚀保护，但却是施涂到其上的漆和清漆的优异底涂层，它们在应用中的主要功能是作为漆和清漆的基础。
对于铬酸盐处理层，需要处理的表面被浸入到含有铬(VI)离子的酸性溶液中。如果该表面例如是锌表面，锌的一部分会溶解。在这里为主的还原条件下，铬(VI)还原为铬(III)，后者在由于氢气的放出已变得更高碱性的表面膜中尤其作为氢氧化铬(III)或作为难溶的μ-氧代-或μ-氢氧-桥连的铬(III)配合物而沉积。同时，形成难溶的铬酸锌(VI)。总结果是在锌表面上形成不渗透的转化涂层，它提供非常良好的防护作用，抵抗电解质的腐蚀侵蚀。
铬(VI)化合物不仅具有急性毒性而且具有高的致癌潜力，因此需要替代采用这些化合物的工艺。使用三价铬化合物的各种配合物的许多工艺现在已确认为采用六价铬化合物的铬酸盐处理工艺的替代方法。在沉积过程中的关键步骤是反应，反应的结果是，在锌表面或含锌的表面与溶液之间的界面上的pH值提高到使得发生转化层沉积的程度。
在上述意义上铬(III)不适合作为锌的氧化剂。虽然由于氧化还原电位而导致还原成铬(II)是可能的，但是这不会导致在界面上pH值的提高。为了从铬(III)离子的酸性水溶液形成转化层，因此还需要添加合适的氧化剂，后者在锌或锌合金与溶液之间的界面上提高锌离子的浓度以及pH值，使得转化层的组分（它们在该溶液内部中的pH值下是可溶的）在金属表面上转化成难溶的水解形式。
为了获得不含铬(VI)的处理溶液，过氧化物如过氧化氢或过二硫酸盐已经建议作为氧化剂(US4,384,902，US4,349,392)。在酸性pH值下，过氧化氢不是足够强的氧化剂，无法将铬(III)氧化成铬(VI)。
硝酸盐发现可广泛地用作使锌发生氧化的氧化剂，以有助于提高pH值并且在处理溶液的条件下不会氧化铬(III)(EP 0 907 762 B1，EP 1 318 214 A1，WO 2004/072325 A1)。
在处理溶液的常规反应条件下，硝酸盐首先被还原成亚硝酸盐，
NO3 -+ Zn + 2 H3O+ 
NO2 -+ Zn2+ + 3 H2O，
并且以这一方式形成的亚硝酸盐用作更高活性的氧化剂进一步按照下面反应式氧化成一氧化氮：
2 NO2 -+ 4 H3O+ + Zn 
2 NO↑ + 6 H2O + Zn2+ 。
2 NO3 -+ 3 Zn + 8 H3O+ 
2 NO↑ + 3 Zn2+ + 12 H2O 。
此外，在处理溶液的酸性介质中（其pH值通常在pH 1到pH 3.5范围内），亚硝酸盐不是稳定的，而是倾向于歧化成硝酸盐和一氧化氮：
3 NO2 -+ 2 H3O+ 
NO3 -+ 2 NO↑ + 3 H2O 。
亚硝酸盐的还原和亚硝酸盐在酸性溶液中的歧化因此也导致一氧化氮的释放。氮氧化物是有毒气体，绝对必要的是在上述溶液表面上将它们抽出。
EP 1 816 234 A1描述水性反应溶液和钝化锌和锌合金的方法。反应溶液含有烟酸，它的盐或它的衍生物。在锌和锌合金上从此类反应溶液产生着色的钝化层。烟酸不适合作为在含铬(III)的处理溶液中的氧化剂，该溶液用于生产在含锌的表面上的转化层。
EP 1 970 470 A1描述了用于含锌的表面上的不含铬(VI)的黑色钝化层，其含有吡啶的羧酸衍生物作为络合剂。吡啶的此类羧酸衍生物不能在此类溶液中作为氧化剂。
EP 1 005 578 B1和GB 715,607描述了生产磷酸盐处理层的方法。有机硝基化合物和有机氮氧化物这里用作促进剂。这里所述的磷酸盐处理层是多孔的，因此没有提供腐蚀保护。
发明的叙述
本发明的目的是提供一种氧化剂，它符合了就锌氧化、氧鎓离子消耗和对铬(III)的反应性而言的上述标准，但是不会导致有毒气体的形成。这些标准通过选自于脂族硝基化合物、芳族硝基化合物、氮氧化物和醌中的本发明的有机氧化剂来满足。硝酸盐被水溶性有机氧化剂替代不会导致形成气态、毒性的反应产物。
硝酸根离子能够以低浓度存在于溶液中，而不使得负面性能成为问题。然而，该溶液优选不含有任何硝酸盐。
这一目的是通过用于在锌或锌合金层上产生基本上不含铬(VI)的黑色转化层的水性处理溶液来实现的，该溶液尤其含有下列组分：
- 至少一种Cr3+离子源，和
- 选自下组中的至少一种有机化合物：
其中R1到R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，其中甲基、乙基、正丙基和异丙基是特别优选的，
前提条件是0－2个基团R1－R5选自b)组。
优选的有机化合物选自通式I、III、IV和V的化合物，其中R1－R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，其中甲基、乙基、正丙基和异丙基是特别优选的，
前提条件是0－2个基团R1－R5是选自b)组。
特别优选的有机化合物选自通式I的化合物，其中R1－R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，其中甲基、乙基、正丙基和异丙基是特别优选的，
前提条件是0－2个基团R1－R5选自b)组。
合适种类的化合物的例子是，例如，硝基苯甲酸，硝基水杨酸，硝基酚，二硝基酚，三硝基酚，硝基丙酸，吡啶N-氧化物，吗啉N-氧化物以及苯醌。用于本发明的合适化合物因此是，例如，间硝基苯甲酸，2-羟基-5-硝基苯甲酸，3,5-二硝基水杨酸，2,4-二硝基苯酚，间硝基苯磺酸，N-甲基吗啉-N-氧化物，吡啶N-氧化物和对苯醌。
此外，已经吃惊地发现，当使用有机氧化剂如醌、N-氧化物和芳族硝基化合物如硝基苯甲酸、硝基酚（尤其硝基苯磺酸，如间硝基苯磺酸）时，所产生的转化层的腐蚀保护作用显著高于能够由相应的含硝酸盐的钝化层所实现的作用。这尤其适用于通过铁、钴或镍的金属微粒或所提及金属的黑色或变黑的金属化合物的颗粒的引入已经变成黑色或深色的转化层。
高度可能的是这不仅归因于锌氧化的其它动力学和因此该转化层的生长，而且还归因于已经沉积或吸附在钝化层中的有机氧化剂的还原产物（它们进而是良好的还原剂）的腐蚀抑制性能。可能的还原反应的例子示于反应式1。
反应式1：合适的有机氧化剂在酸性介质中的还原反应的例子。
根据本发明的组分的另一优点是，它们不具有任何游离的硝酸根，并且因此能够用于含有具有氨基的染料、用于产生转化层的溶液中。现有技术中已知的硝酸根离子用于生产转化层的用途的缺点是硝酸盐还原成亚硝酸盐。在用于形成转化层的强酸性溶液中，该亚硝酸盐能够与含氨基的染料发生重氮化反应，导致不明确的染料产品，后者不再得到转化层的所希望的表面颜色。根据反应式I-III的有机基键接的NO基团不发生此类反应。
根据本发明的水性处理溶液含有0.2 g/l－20 g/l的铬(III)，优选0.5 g/l－15 g/l的铬(III)离子和特别优选1 g/l－5 g/l的铬(III)离子。没有Cr(VI)盐添加到溶液中。所存在的阴离子能够是，例如，甲磺酸根，硫酸根，硫酸氢根，硼酸根以及酸性硼酸酯的阴离子，磷酸根，磷酸氢根，磷酸二氢根，硝酸根，亚硝酸根，氯离子，碘离子，氟离子，六氟硅酸根，六氟钛酸根，四氟硼酸根，六氟锑酸根，六氟磷酸根，磷酸根，磷酸氢根，磷酸二氢根和磷酸酯的合适阴离子。铬(III)能够以铬(III)盐的形式添加到溶液中，如碱性硫酸铬(III)，氢氧化铬(III)，磷酸二氢铬(III)，氯化铬(III)，硫酸钾铬(III)或有机酸的铬(III)盐，例如甲磺酸铬(III)，柠檬酸铬(III)。
另外，有可能使用络合剂如多羧酸，羟基羧酸，羟基多羧酸，氨基羧酸或羟基膦酸。可能的羧酸类的例子是草酸，丙二酸，琥珀酸，戊二酸，己二酸，庚二酸，辛二酸，壬二酸，癸二酸，马来酸，邻苯二甲酸，对苯二甲酸，酒石酸，柠檬酸，苹果酸，抗坏血酸，乙二胺四乙酸，四氢呋喃-2-甲酸，马来酸，乙二胺四乙酸，二亚乙基二胺五乙酸，次氮基三乙酸，乳酸，己二酸，4-氨基马尿酸，4-氨基苯甲酸，5-氨基间苯二甲酸，L-天冬氨酸，L-谷氨酰胺，L-谷氨酸，丙氨酸，β-丙氨酸，L-精氨酸，L-阿斯巴特，L-丙氨酸，N,N-双(2-羟乙基)甘氨酸，L-半胱氨酸，L-胱氨酸，谷胱甘肽，甘氨酸，甘氨酰替甘氨酸，L-组氨酸，L-羟基脯氨酸，L-异白氨酸，L-亮氨酸，L-赖氨酸，L-蛋氨酸，L-鸟氨酸，L-苯基丙氨酸，L-脯氨酸，L-丝氨酸，L-酪氨酸，L-色氨酸，L-苏氨酸，L-缬氨酸，N-[三(羟甲基)甲基]甘氨酸，L-瓜氨酸，N-乙酰基-L-半胱氨酸，N-(2-乙酰胺基)亚氨基二乙酸，1,2-亚环己基二氮川四乙酸，D(+)-生物素，L-正亮氨酸，5-氨基左旋酸，DL-蛋氨酸，3-氨基苯甲酸，6-氨基己酸，乙炔二甲酸，吡啶-2,3-二甲酸，(-)-金鸡纳酸，4-氨基-2-羟基苯甲酸，吡啶-2,6-二甲酸，吡啶-2-甲酸，吡嗪-2,3-二甲酸，吡嗪-2-甲酸，吡啶-4-甲酸，3,5-二羟基苯甲酸，2,4-二羟基苯甲酸，癸二酸，苯-1,3,5-三甲酸，呋喃-2-甲酸，衣康酸，DL-苦杏仁酸，DL-α-氨基苯基乙酸，DL-托品酸，2,2’-硫代二乙酸，3,3’-硫代二丙酸，3-(2-呋喃基)丙烯酸，哌啶-4-甲酸，4-胍基苯甲酸，L-高丝氨酸，反-丙烯-1,2,3-三甲酸，(R)-(-)-柠苹酸，(3-羟苯基)乙酸，4-羟基喹啉-2-甲酸，N-乙酰基-L-谷氨酸，N-乙酰基-DL-缬氨酸，4-氨基马尿酸，2,6-二羟基苯甲酸，4-(二甲基氨基)苯甲酸，葡糖醛酸，柠嗪酸，吲哚-3-甲酸，吲哚-5-甲酸，丁烷-1,2,3,4-四甲酸，DL-亮氨酸，2,2-双(羟甲基)丙酸，喹啉-2,4-二甲酸，2-氨基吡啶-3-甲酸，5-氨基-2-羟基苯甲酸，邻氨基苯甲酸，苯-1,2,4-三甲酸，3,5-二氨基苯甲酸，4,8-二羟基喹啉-2-甲酸，3,3-二甲基戊二酸，反,反-2,4-己二烯酸，3-羟丁酸，邻羟基马尿酸，(4-羟苯基)乙酸，咪唑-4-丙烯酸，吲哚-2-甲酸，吲哚-3-丙酸，巯基琥珀酸，3-酮戊二酸，吡啶-2,4-二甲酸，吡啶-3,5-二甲酸，2-甲基丙氨酸，2-磺基苯甲酸，吡啶-2,5-二甲酸，葡糖酸，4-氨基苯甲酸，(-)-莽草酸，喹哪啶酸，5-羟基间苯二酸，吡唑-3,5-二甲酸，吡啶-3,4-二甲酸，1,2-二氨基丙烷四乙酸，2-吡啶基乙酸，D-正缬氨酸，2-甲基戊二酸，2,3-二溴琥珀酸，3-甲基戊二酸，(2-羟苯基)乙酸，3,4-二羟基苯甲酸，二羟乙酸，丙烷-1,2,3-三甲酸，2,3-二甲基氨基丙酸，2,5-二羟基苯甲酸，2-羟基异丁酸，苯基丁二酸，N-苯基甘氨酸，1-氨基环己烷甲酸，肌氨酸，托品酸，壬二酸，糠酸和半乳糖二酸。除所述酸之外，还有可能使用全部的酸酐，盐，腈和在酸性介质中用作羧酸类的来源的其它化合物。手性化合物的例子不局限于所指明的构型；还有可能使用所指明化合物的非对映异构体，对映异构体或外消旋物。
可能的络合剂的这一列举仅仅给出了合适化合物的例子，但是这没有将本发明能够使用的物质组限制到所提及的物质。在处理溶液中络合剂的浓度能够是在0.05 g/l至络合剂的溶解度极限的范围内。
此外，该处理溶液也能够含有一种或多种表面活性物质，如羰基合成醇乙氧基化物(例如Lugalvan ON110，BASF)，脂肪醇乙氧基化物(例如Ethylan CPG 660，Julius Hoesch GmbH)，或具有氟化基团的表面活性剂(例如Novec FC-4432，3M)以及0.01 g/l到10 g/l的其它金属离子或类金属离子如Sc、Y、Ti、Zr、Mo、W、Mn、Fe、Co、Ni、Zn、B、Al、Si、P。
实施例
一般的实验规程
配制水性处理溶液，它含有3.0 g/l的Cr3+(来自氯化铬(III)六水合物)，2 g/l的Co2+(来自硫酸钴七水混合物)和8 g/l的PO4 3-(来自正磷酸)和2.5 g/l的Fe2+(来自硫酸铁(III)七水合物)以及在表1中的根据本发明的化合物或根据对比例的硝酸盐。该处理溶液通过使用硝酸/氢氧化钠调节至1.6的pH。低合金钢的片材在碱性镀锌过程(Protolux 3000，Atotech Deutschland GmbH)中涂覆10μm的锌。该片材在0.3重量%强度的硝酸中活化10秒，用软化水漂洗三次，然后在上述处理溶液中浸泡60秒。该溶液在这一程序中进行搅拌。在取出该片材后，用软化水漂洗三次，然后在对流烘箱中于80℃下干燥10分钟。根据DIN EN ISO 9227，黑色片材在中性盐喷雾试验中的6小时之后显示出锌腐蚀的第一迹象。按照类似方式生产的片材利用含有有机硅酸酯的密封组合物(例如Corrosil Plus 501，Atotech Deutschland GmbH)进行处理，然后在对流烘箱中于80℃下干燥10分钟。根据DIN EN ISO 9227，片材在中性盐喷雾试验中进行试验。直至锌腐蚀的第一迹象能够辨别为止的时间（小时）报道在表1中。
表1：针对转化层的实验
| 实验No. | 根据本发明的化合物 | 量/g/l | 腐蚀试验 |
| 1 | 硝基苯磺酸(钠盐) | 9.3 | 96 h |
| 2 | 吡啶N-氧化物 | 10.0 | 96 h |
| 3 | 苯醌 | 6.0 | 96 h |
| 4 (对比) | 硝酸钠 | 3.5 | 48 h |
Claims (13)
1.用于在锌或锌合金层上生产基本上不含铬(VI)的转化层的水性处理溶液，其中该溶液含有：
- 至少一种Cr3+离子源，和
- 选自下组中的至少一种有机化合物：
其中R1－R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，
前提条件是，0－2个基团R1到R5选自b)组。
2.根据权利要求1的水性处理溶液，特征在于所述有机化合物选自：
其中R1－R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，
前提条件是，0－2个基团R1到R5选自b)组。
3.根据权利要求1的水性处理溶液，特征在于所述有机化合物选自：
其中R1－R5各自彼此独立地是：
a) 氢原子或具有1－10个碳原子的线性或支化的烷基，或
b) -NR2，-NO2，-COOR，-OR，-SO3R基团，其中R =-H或具有1－5个碳原子的线性或支化的烷基，
前提条件是，0－2个基团R1到R5选自b)组。
4.根据权利要求1的水性处理溶液，特征在于所述有机化合物选自间硝基苯甲酸，2-羟基-5-硝基苯甲酸，3,5-二硝基水杨酸，2,4-二硝基酚，间硝基苯磺酸，N-甲基吗啉-N-氧化物，吡啶-N-氧化物和对苯醌。
5.根据前述权利要求中任何一项的水性处理溶液，特征在于所述有机化合物I-V的浓度是在30 mg/l到30 g/l的该物质的范围内。
6.根据前述权利要求中任何一项的水性处理溶液，特征在于该处理溶液含有0.2 g/l到20 g/l的铬(III)离子。
7.根据前述权利要求中任何一项的水性处理溶液，其特征在于该处理溶液含有选自下列这些中的至少一种阴离子：甲磺酸根，硫酸根，硫酸氢根，硼酸根，酸式硼酸酯，磷酸根，磷酸氢根，磷酸二氢根，氯离子，碘离子，氟离子，硝酸根，六氟硅酸根，六氟钛酸根，四氟硼酸根，六氟锑酸根，六氟磷酸根，磷酸根，磷酸氢根，磷酸二氢根和磷酸酯的阴离子。
8.根据前述权利要求中任何一项的水性处理溶液，特征在于该处理溶液另外含有0.01－10 g/l浓度的选自下列这些当中的至少一种金属或类金属：Sc、Y、Ti、Zr、Mo、W、Mn、Fe、Co、Ni、Zn、B、Al、Si、P。
9.根据前述权利要求中任何一项的水性处理溶液，特征在于该处理溶液含有0.05 g/l到20 g/l的至少一种络合剂，后者选自多羧酸，羟基羧酸，羟基多羧酸，氨基羧酸和羟基膦酸。
10.根据前述权利要求中任何一项的水性处理溶液，特征在于该处理溶液具有在pH 0.1到pH 7范围内的pH值。
11.处理具有转化层的表面的方法，特征在于将需要处理的表面浸入到根据权利要求1-10中任何一项的处理溶液中。
12.根据权利要求11的方法，特征在于在处理溶液中的处理时间是在0.5秒至180秒的范围内。
13.根据权利要求11和12的方法，特征在于所述处理溶液具有在10-90℃范围内的温度。
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| DE102008044143A DE102008044143B4 (de) | 2008-11-27 | 2008-11-27 | Wässrige Behandlungslösung und Verfahren zur Erzeugung von Konversionsschichten für zinkhaltige Oberflächen |
| DE102008044143.0 | 2008-11-27 | ||
| PCT/EP2009/065646 WO2010060883A1 (de) | 2008-11-27 | 2009-11-23 | Konversionsschichten für zinkhaltige oberflächen |
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| EP (1) | EP2358922B1 (zh) |
| JP (1) | JP5562347B2 (zh) |
| KR (1) | KR20110089304A (zh) |
| CN (1) | CN102227516B (zh) |
| DE (1) | DE102008044143B4 (zh) |
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| CN107109659A (zh) * | 2014-12-26 | 2017-08-29 | 迪普索股份公司 | 锌或锌合金基材用3价铬化成处理液和化成被膜 |
| CN108291316A (zh) * | 2015-10-14 | 2018-07-17 | 亥姆霍兹中心盖斯特哈赫特材料及海岸研究中心有限公司 | 用于镁或镁合金的腐蚀抑制剂组合物 |
| CN114592186A (zh) * | 2022-04-27 | 2022-06-07 | 上海库曜新材料有限公司 | 一种锌粉的无铬钝化方法 |
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| US9499700B2 (en) * | 2010-09-14 | 2016-11-22 | Yuken Industry Co., Ltd. | Finishing agent for chemical conversion coating and method for producing same |
| US20160348245A1 (en) * | 2015-05-28 | 2016-12-01 | Macdermid, Incorporated | Method of Pretreatment for Electroless Plating |
| KR101998606B1 (ko) * | 2018-11-21 | 2019-07-10 | 주식회사 지에스켐텍 | 아연-니켈 도금용 3가 크로메이트계 흑색 내식성 향상제 및 이를 이용한 아연-니켈 도금층의 표면처리방법 |
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Also Published As
| Publication number | Publication date |
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| EP2358922B1 (de) | 2016-01-27 |
| PL2358922T3 (pl) | 2016-07-29 |
| JP5562347B2 (ja) | 2014-07-30 |
| KR20110089304A (ko) | 2011-08-05 |
| EP2358922A1 (de) | 2011-08-24 |
| JP2012509994A (ja) | 2012-04-26 |
| DE102008044143A1 (de) | 2010-06-02 |
| DE102008044143B4 (de) | 2011-01-13 |
| WO2010060883A1 (de) | 2010-06-03 |
| US20110217476A1 (en) | 2011-09-08 |
| CN102227516B (zh) | 2015-07-22 |
| ES2565839T3 (es) | 2016-04-07 |
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