CN1477161A - 耐腐蚀的三价铬磷化化学转化型涂料 - Google Patents
耐腐蚀的三价铬磷化化学转化型涂料 Download PDFInfo
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Abstract
含有水溶性三价铬化合物的酸性水溶液，还含有改善抗腐蚀性和降低三价铬随着时间流逝而沉淀的添加剂。合适的添加剂是次氮基三(亚甲基)三膦酸(NTMP)。
Description
技术领域
本发明涉及一种耐腐蚀的三价铬磷化化学转化型涂料的制备方法。
背景技术
本发明涉及一种耐腐蚀的三价铬磷化学转化型涂料的制备方法，该涂料用于结构合金，优选地铝和航空器铝合金，和其它金属即铁/钢，锌或镀锌钢的防腐蚀。这种涂料其它不同的应用还包括在阳极氧化铝上的密封涂料，以及用于改善附着性结合的铝结构耐久性的涂料。
转化型涂料广泛地用于金属表面处理，改善腐蚀抑制作用与改善后续涂布漆层的附着性。通过金属与电解液(bath solution)之间的化学反应来涂布转化型涂料，该电解液可使金属表面转化或改性成具有所需要功能性质的薄膜。转化型涂料在金属表面处理中特别有用，金属例如是钢、锌、铝和镁。过去，曾证明铬酸盐转化型涂料是铝和镁最成功的转化型涂料。但是，过去使用的铬酸盐转化型涂料一般含有强毒性的六价铬。使用六价铬给生产操作者造成可能有害的工作环境，给废物处理增加非常高的成本。
为了克服与转化型涂料含有六价铬的相关问题，曾试图利用三价铬转化型涂料，从环境观点来看，这些转化型涂料还远不能为人们所接受。US 4 171 231、5 304 257和5 374 347公开了用于在金属上生成转化涂层的三价铬溶液。在这些专利中研制或描述的由三价铬涂料提供的防腐蚀性基本上归因于三价铬转化成六价铬，这种转化是通过在涂料电解液添加氧化剂，或用氧化剂后处理已显色的转化型涂料，或将腐蚀抑制粒种加入涂料电解液进行的。换句话说，这些三价铬方法的一个缺陷是防腐蚀性不如六价铬方法有效，无论哪一种方法的防腐蚀性基本上都归因于在涂料或涂料电解液中三价铬氧化成六价铬。但是，在本发明所描述的方法中，改善的防腐蚀性是归因于长链官能化有机氨基-膦酸化合物的膦酸根基团吸附在氧化铝表面上，生成Al-O-P共价键，接着在所有活性腐蚀点生成疏水层网。这些三价铬方法和酸性水溶液的另一个缺陷是随着时间流逝在处理电解液中生成含铬沉淀。该沉淀造成材料在溶液中的流失，并且当关键组分的浓度降低到所希望和所需要的水平以下时会影响涂料的质量。
因此，本发明的一个基本目的是提供防腐蚀性能与六价铬转化型涂料相近的三价铬化学转化型涂料，和有效稳定的涂料电解液，因为这些有机氨基-膦酸具有与三价金属离子，即Cr+3、Al+3等螯合生成络合物的能力是已知的。
发明内容
发明概述
根据本发明，容易达到下述目的。
根据本发明，向含有水溶性三价铬化合物的酸性水溶液中提供一种有效增加防腐蚀性，和还可降低三价铬随着时间流逝沉淀的添加剂。该添加剂包括螯合剂或多齿配位体，例如只由膦酸基团组成或与作为配位体的乙酸基团结合的配位体。优选的抑制腐蚀添加剂包括氨基-膦酸衍生物，例如盐与酯，像次氮基三(亚甲基)三膦酸(NTMP)、羟基-，氨基-烷基膦酸，乙基酰亚胺基(亚甲基)膦酸、二乙基氨基甲基膦酸等可以是一种或另一种或组合，只要该衍生物是基本溶于水的。
附图说明
通过下面详细的描述，本发明的特点将变得很清楚。
图1是在Al 2024上三价铬磷化涂料扫描电子显微照片(SEM)，放大倍数5000倍；
图2是在Al2024上NTMP-15涂料SEM的EDS1谱；
图3是在Al2024上NTMP-15涂料SEM的EDS2谱；
图4是在Al2024上NTMP-15涂料SEM的EDS3谱；
图5是在Al6061上三价铬磷化涂料扫描电子显微照片，放大倍数5000倍；
图6是在Al6061上NTMP-15涂料SEM的EDS1谱；
图7是在Al6061上NTMP-15涂料SEM的EDS2谱；
图8是在Al6061上NTMP-15涂料SEM的EDS3谱；
具体实施方式
发明详述
本发明涉及在一种金属，优选在铝和航空器铝合金上使用的耐腐蚀三价铬涂料的制备方法，以及在该方法中使用的改性酸性水溶液。
在铝和铝合金基体上耐腐蚀三价铬涂料的制备方法包括用无六价铬的酸性水溶液处理基体，该溶液含有水溶性三价铬化合物、水溶性氟化合物以及改善腐蚀的添加剂，该添加剂也可以降低三价铬沉淀。根据本发明，该添加剂包括螯合剂或双-或多齿配位体。一般地，添加剂的量是以总涂料溶液计为5-100ppm(百万分之一)，优选地是以总涂料溶液计为15-30ppm。优选的抑制腐蚀添加剂包括氨基-膦酸衍生物，例如盐和酯，像次氮基三(亚甲基)三膦酸(NTMP)、羟基-、氨基-烷基膦酸、乙基酰亚胺基(亚甲基)膦酸、二乙基氨基甲基膦酸等，可以是一种或另一种或组合，只要该衍生物在水中是基本可溶的即可。特别适合用作腐蚀抑制剂的添加剂和溶液稳定性添加剂是次氮基三(亚甲基)三膦酸(NTMP)。
稀的酸性水溶液含有水溶性三价铬化合物、水溶性氟化合物和氨基-膦酸化合物。三价铬化合物在溶液中的量是0.2-10.0克/升(优选地，0.5-8.0克/升)，氟化合物的量是0.2-20.0克/升优选地，0.5-18.0克/升)。以这样一种方式制备的稀三价铬涂料溶液的pH可以是2.5-4.0。
曾发现，使用三价铬量为100-300ppm，氟化合物量为200-400ppm，抑制腐蚀的氨基-膦酸化合物量为10-30ppm的涂料溶液时，如下面实施例所证明的，与无氨基-膦酸化合物相比，防腐蚀作用达到优异，随着时间流逝三价铬的沉淀也减少了。
实施例
制备下述三种主要原料溶液：
部分A溶液：8.0克/升在去离子水中的Cr(III)盐；
部分B溶液：18.0克/升在去离子水中的含氟化物的盐；NTMP溶液：在去离子水中1000ppm次氮基三(亚甲基)三膦酸，即NTMP。
根据下面给出的方法制备这些溶液：
部分A，即硫酸铬(III)原料溶液制备如下：8.0克从Fluka(Milwaukee，WI)购买的硫酸铬(III)化合物溶于1升去离子(DI)水中。让该溶液平衡后再使用。部分B，即氟锆酸钾原料溶液制备如下：18.0克从Aldruch(Milwaukee，WI)购买的这种化合物溶于1升去离子水中。让该溶液充分溶解与稳定。NTMP原料溶液制备如下：0.1毫升从Sigma-Aldrich(St.Louis，MO)购买的50重量％NTMP水溶液溶于100毫升去离子水中。根据表I中列出的组成制备了不同稀释的涂料电解液。一种涂料电解液不用NTMP制备，其溶液用作评价NTMP对腐蚀性能影响的对照涂料。所有电解液的pH是3.5-4.0。
表I涂料电解液组成
| 溶液ID | 部分A(毫升) | 部分B(毫升) | DI水(毫升) | NTMP(毫升) |
| 对照，无NTMP | 100 | 100 | 1800 | - |
| NTMP-5 | 100 | 100 | 1800 | 10 |
| NTMP-10 | 100 | 100 | 1800 | 20 |
| NTMP-15 | 100 | 100 | 1800 | 30 |
| NTMP-20 | 100 | 100 | 1800 | 40 |
| NTMP-25 | 100 | 100 | 1800 | 50 |
| NTMP-30 | 100 | 100 | 1800 | 60 |
所有这些溶液都是在加工样板时制备的。3″×3″Al 2024-T3和Al 6061-T6合金涂布两次。经下述方法使涂料显色：
1)所有测试试样用斯柯奇brite机械摩擦两面，然后在流动的自来水下用Kimwipes轻擦进行清洗。这种试样最后用去离子水漂洗，用纸巾吸干，然后浸没在涂布的电解液中。
2)测试试样在室温下浸没在涂料电解液中10分钟。
3)涂布的测试试样再用去离子水漂洗，空气干燥至少24小时。
兰-粉红色-紫色化学转化性涂料有混合的铬和磷的氧化物，该涂料在Al2024和Al 6061合金表面上显色。评价这些涂料的涂布重量和腐蚀性能。还用SEM/EDAX研究了NTMP-15涂料的形态特征。
所有显色涂层的涂料重量测定值是0.15-0.5毫克/平方英寸。
根据ASTM B 117，让样板暴露于盐雾喷淋试验器，评价耐腐蚀性能。这些结果汇集于下表II中。
表II盐雾喷淋试验结果
| 涂料ID | 小时数 | 观察结果 | |
| Al 2024 | Al 6061 | ||
| 对照，无NTMP | 240 | 腐蚀斑点，15-20％总面积 | 腐蚀斑点，10-15％总面积 |
| NTMP-5 | 400 | 无腐蚀斑点，在不多的地方有锈斑 | 无腐蚀 |
| NTMP-10 | 400 | 无腐蚀斑点，在不多的地方有锈斑 | 无腐蚀 |
| NTMP-15 | 400 | 无腐蚀斑点，在不多的地方有锈斑 | 无腐蚀 |
| NTMP-20 | 400 | 无腐蚀 | 无腐蚀 |
| NTMP-25 | 336 | 在不多地方到一些地方无规则的腐蚀麻坑，集中在边缘周围，黑色锈斑类腐蚀 | 无腐蚀除在边缘周围发现2个麻坑外 |
| NTMP-30 | 336 | 在不多地方发现无规则的腐蚀麻坑，集中在边缘周围，黑色锈斑类腐蚀 | 无腐蚀 |
采用SEM/EDAX研究了在Al 2024和Al 6061上显色的NTMP-15三价铬涂料。在Al 2024上的涂料扫描电子显微照片(SEM)示于图1，在Al 2024上的相同涂料的EDS谱示于图2-4。同样地，在Al 6061上显色的NTMP-15扫描电子显微照片示于图5，EDS谱示于图6-8。显微照片和EDAX谱两者显示出在转化型涂料中磷随同铬一起存在。认为氨基膦酸的膦酸根吸附在氧化铝表面上，生成Al-O-P化学键。
本发明还可以采用没有超出本发明精神实质和基本特征的其它方式具体化或其它途径实施。因此，该具体实施方式被认为是说明而非限制各个方面，权利要求书指出了本发明的范围，试图将等效性的含意和范围内的所有变化都包括在其中。
Claims (23)
1、一种无六价铬的酸性水溶液，它含有水溶性的三价铬化合物、水溶性氟化合物，以及改善抗腐蚀性的添加剂。
2、根据权利要求1所述的酸性水溶液，其中添加剂是次氮基三(亚甲基)三膦酸(NTMP)。
3、根据权利要求1所述的酸性水溶液，其中添加剂的量是以总酸性溶液计为5-100ppm(百万分之一)。
4、根据权利要求2所述的酸性水溶液，其中添加剂的量是以总酸性溶液计为5-100ppm。
5、根据权利要求1所述的酸性水溶液，其中添加剂的量是以总酸性溶液计为5-30ppm。
6、根据权利要求2所述的酸性水溶液，其中添加剂的量是以总酸性涂料溶液计为5-30ppm。
7、根据权利要求3所述的酸性水溶液，其中三价铬化合物在溶液中的量是0.2-8.0克/升，氟化合物的量是0.2-18.0克/升，其中溶液的pH是3.5-4.0。
8、根据权利要求4所述的酸性水溶液，其中三价铬化合物在溶液中的量是0.5-8.0克/升，氟化合物的量是0.5-18.0克/升，其中溶液的pH是3.5-4.0。
9、根据权利要求5所述的酸性水溶液，其中三价铬化合物在溶液中的量是0.2-10.0克/升，氟化合物的量是0.2-20.0克/升，其中溶液的pH是2.5-4.0。
10、根据权利要求6所述的酸性水溶液，其中三价铬化合物在溶液中的量是0.5-8.0克/升，氟化合物的量是0.5-18.0克/升，其中溶液的pH是3.5-4.0。
11、根据权利要求1所述的酸性水溶液，其中添加剂是螯合剂或多齿配位体。
12、在基体上耐腐蚀三价铬涂料的制备方法，该方法包括用无六价铬的酸性水溶液处理基体，该溶液含有水溶性三价铬化合物，水溶性氟化合物以及改善耐腐蚀的添加剂。
13、根据权利要求12所述的方法，其中添加剂是螯合剂或多齿配位体。
14、根据权利要求12所述的方法，其中添加剂是NTMP。
15、根据权利要求13所述的方法，其中螯合剂或多齿配位体选自氨基酸、氨基(亚甲基)、亚烷基膦酸、乙基酰亚胺基(亚甲基)膦酸、二乙基氨基甲基膦酸、二乙三胺五乙酸、N，N′-二(2-羟基苄基)乙二胺-N，N′-二乙酸及其混合物。
16、根据权利要求12所述的方法，其中螯合添加剂的量是以总酸性水溶液计5-100ppm。
17、根据权利要求12所述的方法，其中螯合添加剂的量是以总酸性水溶液计5-30ppm。
18、根据权利要求12所述的方法，其中三价铬化合物在溶液中的量是0.2-10.0克/升，氟化合物的量是0.2-20.0克/升，其中溶液的pH是2.5-4.0。
19、根据权利要求14所述的方法，其中三价铬化合物在溶液中的量是0.5-8.0克/升，氟化合物的量是0.5-18.0克/升，其中溶液的pH是3.5-4.0。
20、一种制品，该制品包括金属基体和在该金属基体上的含三价铬的转化型涂料，该含三价铬的转化型涂料是根据权利要求12所述方法制备的。
21、根据权利要求20所述的制品，其中金属是铝。
22、根据权利要求20所述的制品，其中金属基体是阳极氧化铝。
23、一种制品，该制品包括铝基体、在铝基体上的阳极氧化层和在阳极氧化层上的密封涂料，其中密封涂料含有三价铬、磷酸盐和次氮基三(亚甲基)三膦酸(NTMP)。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534598A (zh) * | 2012-03-16 | 2012-07-04 | 广西民族大学 | 一种铝合金高性能三价铬杂化转化膜的制备方法及其成膜液 |
| CN102534598B (zh) * | 2012-03-16 | 2013-12-18 | 广西民族大学 | 一种铝合金高性能三价铬杂化转化膜的制备方法及其成膜液 |
| CN105695973A (zh) * | 2016-03-16 | 2016-06-22 | 深圳市鑫鸿达清洗技术有限公司 | 一种铝合金三价铬钝化液 |
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| PL360927A1 (en) | 2003-12-29 |
| US20050178475A9 (en) | 2005-08-18 |
| SG114620A1 (en) | 2005-09-28 |
| BR0302051A (pt) | 2004-09-08 |
| DE60322792D1 (de) | 2008-09-25 |
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| JP4261264B2 (ja) | 2009-04-30 |
| RU2248409C1 (ru) | 2005-03-20 |
| IL156537A0 (en) | 2004-01-04 |
| CN100357492C (zh) | 2007-12-26 |
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| CA2433122A1 (en) | 2003-12-27 |
| AU2003204821A1 (en) | 2004-01-15 |
| EP1378585A1 (en) | 2004-01-07 |
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| IL156537A (en) | 2006-10-31 |
| US7018486B2 (en) | 2006-03-28 |
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| CA2433122C (en) | 2007-02-20 |
| KR20040002633A (ko) | 2004-01-07 |
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