CN1572904A - 用于镁合金的抗腐蚀、无铬酸盐转化涂层 - Google Patents

用于镁合金的抗腐蚀、无铬酸盐转化涂层 Download PDF

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CN1572904A
CN1572904A CNA2004100714667A CN200410071466A CN1572904A CN 1572904 A CN1572904 A CN 1572904A CN A2004100714667 A CNA2004100714667 A CN A2004100714667A CN 200410071466 A CN200410071466 A CN 200410071466A CN 1572904 A CN1572904 A CN 1572904A
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magnesium
chromate
phosphonic acids
phosphonic
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CN100339507C (zh
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X·唐
M·雅沃罗夫斯基
K·哈默施密德特
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Raytheon Technologies Corp
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C23C22/40—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 molybdates, tungstates or vanadates
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    • 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
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    • 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
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Abstract

一种在镁或镁合金底物上形成的有或无钒酸盐、无铬酸盐、磷酸盐－氟化物转化涂层，包括一种选自有机金属膦酸的活性阻蚀剂。膦酸基团与镁金属底物反应形成不溶性盐。

Description

用于镁合金的抗腐蚀、无铬酸盐转化涂层
发明背景
本发明涉及一种用于镁或镁合金所形成的产品上的有或无钒酸盐的抗腐蚀、无铬酸盐、磷酸盐-氟化物转化涂层，和一种在涂敷过程中使用的涂层溶液。
镁合金轻且坚硬，但是由于镁的活泼性，非常易受腐蚀的损坏。在所有的实际应用中镁合金需受到保护而不被腐蚀。一种对镁合金普遍使用的、低价的、抗腐蚀处理是基于重铬酸盐的转化涂层。虽然基于重铬酸盐的转化涂层提供了好的抗腐蚀保护，但是它们基于的化合物(六价铬)具有许多职业性曝露风险。需要无铬酸盐、抗腐蚀镁转化涂层以满足工业需求。
在Joesten等人的美国专利5,683,522中展示了另一种保护镁或镁合金产品的处理，在此作为参考文献。在这种处理中，油漆粘合和磷酸镁、氟化镁的抗腐蚀涂层用于由镁合金形成的产品上。施用涂层的过程包括在含有磷酸盐和氟化物离子的溶液中浸渍镁合金产品。这种处理虽然提供阻挡膜和非常好的油漆粘合，但不包括电化学活性成分来抑制腐蚀。于2002年2月11日提出的、并在此作为参考文献的共同未决的申请序列号10/073,688提出了一种改进的对镁的磷酸盐-氟化物抗腐蚀涂层，及施用这种涂层方法。
本发明的目的是提供一种用于镁和镁合金产品的改进的无铬酸盐抗腐蚀转化涂层。
本发明的另一个目的是提供一种形成无铬酸盐抗腐蚀涂层的涂层溶液。
发明概述
前述的目的通过本发明来实现。
根据本发明，在有或无钒酸盐下，在镁或镁合金底物上形成的无铬酸盐的、磷酸盐-氟化物转化涂层包括选自有机金属膦酸的活性阻蚀剂。膦酸基与底物上的镁金属反应，以形成不溶性盐。依据本发明所使用的作为阻蚀剂的有机金属膦酸优选自直链或支链的氨烷基膦酸、直链或支链的烷基膦酸和三膦酸特别是次氮基三(亚甲基)三膦酸(NTMP)。当阻蚀剂包含氨烷基膦酸时，胺基团可以在涂层溶液中与钒酸盐离子结合，以增加进入转化涂层的钒酸盐结合性。
本发明中镁-镁合金转化涂层的其它详情、目的和由此获得的优点在下面详细的描述中阐明。
详细描述
根据本发明，用于在镁或镁合金底物上形成无铬酸盐、抗腐蚀涂层的溶液包括含有磷酸盐和氟化物离子的溶液，和选自有机金属膦酸的活性阻蚀剂。
本发明中的溶液可以任选包括钒酸盐阴离子。活性阻蚀剂选自直链或支链的氨烷基膦酸、直链或支链的烷基膦酸、三膦酸和它们的混合物。特别适合的三膦酸包括次氮基三(亚甲基)三膦酸(NTMP)。
如前面所述，无铬酸盐溶液包括磷酸盐和氟化物离子。磷酸盐和氟化物离子的量分别在1g/L-50g/L之间和1g/L-10g/L之间，优选分别在10g/L-25g/L之间和3g/L-5g/L之间。在本发明中控制溶液的pH值是很重要的，这是通过溶液中磷酸盐离子和氟化物离子的数量来实现的。优选溶液的pH值在5-7之间。在形成适当pH值的溶液时所使用的具体的磷酸盐和氟化物化合物在2002年2月11日提出的共同未决的系列申请10/073,688中有详细记载，并且这个共同未决的申请和其内容在此引入作为参考。
根据本发明，溶液中阻蚀剂的量在1ppm-1wt％之间，优选在10ppm-0.5wt％之间。阻蚀剂以有机金属膦酸的形式存在。优选的有机金属膦酸包括直链的和支链的氨烷基膦酸、直链和支链的烷基膦酸和三膦酸。特别适合的三膦酸是次氮基三(亚甲基)三膦酸(NTMP)。
根据本发明，溶液可以包括钒酸盐阴离子。对于本发明的溶液，钒酸钠是适合的钒离子源。根据本发明，钒离子的量在约1.0g/l-5.0g/l之间。已发现钒酸盐阴离子与氨烷基膦酸中的胺基团结合可以增强钒酸盐到转化涂层的结合性，从而改善了涂层性能。另外，阻蚀剂中的膦酸基团与镁金属底物起反应形成可改善抗腐蚀性能的不溶性盐。
优选的无铬酸盐溶液包括量在10-25g/L之间的磷酸盐离子、量在3g/L-5g/L之间的氟化物离子、量在1g/L-5g/L之间的钒酸盐离子和量在10ppm-0.5wt％之间的阻蚀剂。
根据本发明，具有转化涂层的镁或镁合金底物主要包含磷酸镁和氟化镁。可认为氨烷基膦酸将形成作为转化涂层一部分的不溶性镁盐。这种成分将增加钒与转化涂层的相互作用，因而增加了涂层中钒的含量，钒也作为阻蚀剂使用
显然，本发明不局限于在此描述和展示的例子，这些只不过说明实施本发明的最佳方式，而且这些例子在部件的形式、大小、排列和操作的细节上允许改动。本发明的目的就是要包含在权利要求书所声明的它的精神和范围内的所有此类改动。

Claims (8)

1、一种用于在镁或镁合金形成的产品上形成无铬酸盐、抗腐蚀涂层的溶液，包括：
含有磷酸盐和氟化物离子的溶液；和
选自有机金属膦酸的活性阻蚀剂。
2、如权利要求1所述的溶液，其中有机金属膦酸选自直链氨烷基膦酸、支链氨烷基膦酸、直链烷基膦酸、支链烷基膦酸、三膦酸和它们的混合物。
3、如权利要求2所述的溶液，其中三膦酸包括次氮基三(亚甲基)三膦酸(NTMP)。
4、如权利要求1所述的溶液，其中溶液包含钒酸盐。
5、如权利要求1所述的溶液，其中溶液包括1ppm-1wt％之间的阻蚀剂，优选为10ppm-0.5wt％之间。
6、如权利要求5所述的溶液，其中磷酸盐离子的量在1g/L-50g/L之间，优选在10g/L-25g/L之间，和氟化物离子的量在1g/L-10g/L之间，优选在3g/L-5g/L之间。
7、一种在镁或镁合金底物上制备抗腐蚀、无铬酸盐涂层的方法，包括用权利要求1-6的溶液处理底物，其中膦酸基团与镁金属反应形成不溶性盐。
8、一种制品，包括具有用权利要求7的方法制备的抗腐蚀涂层的镁或镁合金底物。
CNB2004100714667A 2003-06-20 2004-06-18 用于镁合金的抗腐蚀、无铬酸盐转化涂层 Expired - Fee Related CN100339507C (zh)

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US10/601,247 US20040256030A1 (en) 2003-06-20 2003-06-20 Corrosion resistant, chromate-free conversion coating for magnesium alloys

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CN102834364B (zh) * 2010-04-01 2016-03-16 法国原子能及替代能源委员会 用于调节镁金属的防蚀剂的应用、由此获得的调节材料和制备方法

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