CN1250769C - 用于铝合金的复合无铬转化镀层 - Google Patents

用于铝合金的复合无铬转化镀层 Download PDF

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CN1250769C
CN1250769C CNB011456019A CN01145601A CN1250769C CN 1250769 C CN1250769 C CN 1250769C CN B011456019 A CNB011456019 A CN B011456019A CN 01145601 A CN01145601 A CN 01145601A CN 1250769 C CN1250769 C CN 1250769C
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chromium
aluminium alloy
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CN1381614A (zh
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M·R·亚沃罗夫斯基
M·A·克里茨曼
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Raytheon Technologies Corp
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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
    • 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
    • C23C22/40—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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/73—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 characterised by the process

Abstract

本发明涉及一种用于由铝合金制成的零件的复合无铬转化镀层。该镀层的形成方法是：提供含有阳极抑制剂物质的第一种溶液，提供含有阴极腐蚀抑制剂物质的第二种溶液，将待镀覆的零件浸渍在第一种溶液和第二种溶液的第一种溶液中，然后浸渍在第一种溶液和第二种溶液的第二种溶液中。合适的阳极抑制剂物质包括钨酸盐、高锰酸盐、钒酸盐、钼酸盐、及其混合物。合适的阴极腐蚀抑制剂包括钴、铈、其它镧系元素、及其混合物。在一个实施方案中，转化镀层是用含有铈的溶液和含有钨酸盐的溶液形成的。

Description

用于铝合金的复合无铬转化镀层
                           发明背景
本发明涉及一种在由铝合金制成的零件上制备复合无铬转化镀层的方法。
铬酸盐转化镀层用于保护由铝合金制成的零件免遭腐蚀。这些镀层是通过用含六价铬的溶液处理零件的铝表面形成的。六价铬被国际癌症研究机构(IARC)认定为第一类或证实的人类致癌物质。因此，应尽可能避免使用这样的镀层。
                           发明概述
因此，本发明的一个目的是提供一种用于铝合金零件上的复合无铬转化镀层。
本发明的另一个目的是提供一种在由铝合金制成的零件上沉积不含铬的镀层的方法。
根据本发明，复合无铬转化镀层施用在由铝合金制成的零件上的方法是：首先将零件浸渍在含阳极抑制剂的溶液中，然后将零件浸渍在含阴极腐蚀抑制剂的溶液中。阳极抑制剂在酸性还原条件下沉积，理想地是进行价态变化到还原态。可以用于形成本发明镀层的阳极抑制剂的例子包括钨酸盐、高锰酸盐、钒酸盐、钼酸盐物质、及其混合物。阴极抑制剂在碱性还原条件下沉积，理想地是进行价态变化。阴极抑制剂的例子包括钴、铈、其他诸如镨的镧系元素、及其混合物。
在本发明的一个实施方案中，阴极腐蚀抑制剂包括在去离子水中是约10g/L至约30g/L的硝酸铈(III)，阳极抑制剂溶液是在氢氧化铵中包括10g/L的钨酸的溶液。
本发明的复合无铬转化镀层包括厚度是约0.96μm至约1.51μm的Ce2(WO4)3。
本发明的复合无铬转化镀层的其他细节和其他目的及优点将在下面的详述部分说明。
                           优选实施方案详述
本发明涉及基于通过浸渍方法使阳极和阴极腐蚀抑制化合物顺序沉积在由铝合金制成的零件上而形成的转化镀层，铝合金的例子是基本上由1.0wt％的镁、0.25wt％的铜、0.6wt％的硅、0.25wt％的铬和平衡量的铝及不可避免的杂质组成的铝合金6061。已经发现：用本发明的方法得到的镀层重量可以与用铬酸盐转化镀层方法得到的镀层重量相类似。镀层重量是约4305.56-8611.13mg/m2(400-800mg/ft2)。
在待涂覆的铝合金零件表面上施加本发明的镀层之前，用200-400粒度的砂纸将铝合金零件的一个表面或多个表面磨光。磨光后，用柔性洗涤剂洗涤待镀覆的表面，然后顺序用自来水、去离子水和乙醇漂洗。
将零件磨光、洗涤和漂洗后，首先在室温下将其浸渍在含有阳极抑制剂物质的溶液中，不要进行任何搅拌。阳极抑制剂物质选自于钨酸盐、高锰酸盐、钒酸盐、钼酸盐、及其混合物。适用的一种溶液是在氢氧化铵中含有约10g/L至约20g/L的钨酸，其pH是约11至约12。例如，一种合适的溶液是在氢氧化铵中含有10g/L的钨酸，其pH是11.82。优选将铝合金零件在含有阳极抑制剂的溶液中浸渍约3分钟至约15分钟。其它适用的溶液是含有约1.0g/L至约100g/L的阳极抑制剂物质的溶液。
在含有阳极抑制剂物质的溶液中浸渍后，将铝合金零件浸渍在含有阴极腐蚀抑制剂物质的溶液中，也是在室温下将零件浸渍在溶液中，不要进行任何搅拌。适用的溶液包括钴、铈、其他诸如镨的镧系元素、及其混合物。可以使用在去离子水中含有约10g/L至约50g/L、优选约10g/L至约30g/L的硝酸铈(III)且其pH是约3.5至约3.6的溶液。将铝合金零件在阴极抑制剂溶液中浸渍约3分钟至约15分钟。其他含有其他阴极腐蚀抑制剂物质的溶液也可含有约10g/L至约50g/L的阴极腐蚀抑制剂物质，在其使用过程中的浸渍时间与上述相同。
已经发现：根据本发明处理后的铝合金6061零件与未处理的铝合金6061相比，其阻透性和自然腐蚀速度都改进了10倍。
用下述实施例说明本发明的方法。
                           实施例
用三种溶液将转化镀层施加在6061铝腐蚀试片上。这三种溶液是：
溶液#1：在去离子水中的10g/L的硝酸铈(III)，pH＝3.60；
溶液#2：在去离子水中的30g/L的硝酸铈(III)，pH＝3.5；和
溶液#3：在氢氧化铵中的10g/L的钨酸，pH＝11.82。
用220和400粒度的砂纸将腐蚀试片磨光，用柔性洗涤剂洗涤，用自来水、去离子水和乙醇漂洗。用三种不同的方法但都是在室温下和不搅拌的条件下将试片浸渍。这三种方法描述在下表中。
 方法   #1第一次浸渍：溶液#3(3分钟)第二次浸渍：溶液#1(3分钟)   #2第一次浸渍：溶液#3(15分钟)第二次浸渍：溶液#1(15分钟)   #3第一次浸渍：溶液#2(3分钟)第二次浸渍：溶液#3(3分钟)
 Ce的峰高   103点   82点   137点
 Ce的覆盖层   990.28mg/m2(92mg/ft2)   785.77mg/m2(73mg/ft2)   1313.20mg/m2(122mg/ft2)
 W的峰高   192点   174点   262点
 W的覆盖层   2497.23mg/m2(232mg/ft2)   2271.19mg/m2(211mg/ftu)   3412.16mg/m2(317mg/ft2)
 Ce2(WO4)3的厚度   1.12μm   0.96μm   1.51μm
用X射线荧光光谱仪分析铝合金零件并测定镀层重量。该方法测定的一般镀层组成列举在上表中。
用电化学阻抗光谱法评价转化镀层的质量。上面所示的镀层的阻抗谱图证实了该镀层具有抗腐蚀性，并且先用阳极抑制剂物质(钨酸盐)处理然后用阴极抑制剂物质(铈)处理可以得到最佳效果。但是，如果需要，铝合金零件可以先浸渍在含有阴极抑制剂物质的溶液中然后浸渍在含有阳极抑制剂物质的溶液中。
根据本发明的一个实施方案形成的镀层包括厚度是约0.96μm至约1.51μm的Ce2(WO4)3。
很明显，本发明提供了一种能够达到上述目的、方法和优点的用于铝合金的复合无铬转化镀层。虽然本发明是用其具体实施方案来说明的，但是，对于阅读过上述说明的本领域普通技术人员来说，其他的一些替换、改进和变化是显而易见的。因此，所附的权利要求书的保护范围应当包括那些替换、改进和变化。

Claims (1)

1、一种在铝合金零件上形成无铬转化镀层的方法，其包括下述步骤：
提供含有阳极抑制剂物质的第一种溶液；
提供含有阴极腐蚀抑制剂物质的第二种溶液；
将所说的铝合金零件浸渍在所说的第一种溶液和第二种溶液中的第一种溶液中，然后浸渍在所说的第一种溶液和第二种溶液中的第二种溶液中；
所说的提供第二种溶液的步骤包括提供含有浓度是10g/L至50g/L的选自于钴、铈、镧系元素、及其混合物的阴极腐蚀抑制剂物质的溶液，其中所说的提供第一种溶液的步骤包括提供pH是11-12且含有在氢氧化铵中浓度是10g/L至20g/L的钨酸的溶液，并且其中所说的铝合金零件在所说的第一种溶液中的浸渍时间是3分钟至15分钟。
CNB011456019A 2000-12-19 2001-12-18 用于铝合金的复合无铬转化镀层 Expired - Fee Related CN1250769C (zh)

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ATE291107T1 (de) 2005-04-15
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IL147090A0 (en) 2002-08-14
CA2364964A1 (en) 2002-06-19
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