CN111455365A - 一种用于锌层的环保型三价铬无钴彩色钝化液及钝化工艺 - Google Patents

一种用于锌层的环保型三价铬无钴彩色钝化液及钝化工艺 Download PDF

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CN111455365A
CN111455365A CN202010487153.9A CN202010487153A CN111455365A CN 111455365 A CN111455365 A CN 111455365A CN 202010487153 A CN202010487153 A CN 202010487153A CN 111455365 A CN111455365 A CN 111455365A
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passivation
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chromium
trivalent chromium
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魏健
史晓峰
王鲁艳
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Dexin Chemical Shandong Co ltd
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Abstract

本发明公开了一种用于锌层的环保型三价铬无钴彩色钝化液及工艺，主要涉及金属表面处理与防护技术领域。钝化液，其原料按配比由以下组分组成：三价铬盐50‑500g/L；辅助成膜剂0.1‑100g/L；络合剂10‑200g/L；氧化剂10‑150g/L；pH调整剂10‑100g/L；溶剂为水。本发明具有无钴、低硝酸盐、耐铁杂质的优势，具有很好的耐腐蚀性，钝化膜艳丽鲜亮，钝化工艺操作简单。

Description

一种用于锌层的环保型三价铬无钴彩色钝化液及钝化工艺
技术领域
本发明涉及金属表面处理与防护技术领域，具体是一种用于锌层的环保型三价铬无钴彩色钝化液及钝化工艺。
背景技术
随着工业技术的发展，对材料表面的耐腐蚀性能提出了越来越高的要求。电沉积锌由于具有良好的耐蚀性和价格优势，广泛的运用于日用五金、汽车轮船、电子、航天等众多领域。由于锌的性质活泼，在湿热的环境条件下易被腐蚀，电沉积锌工件如果不进行后处理，表面很快就被腐蚀产生白渍状物质，时间久了基体继续发生腐蚀基材(铁)产生红锈，失去了防腐的效果。为了提高钢铁耐蚀性和改善表层外观，一般都会在电沉积锌结束后进行钝化处理，使其表面形成一层钝化膜。
铬酸盐彩色钝化由于色泽艳丽，耐蚀性优良而得到了广泛应用。但是因为六价铬毒性高，易致癌，对人的健康危害较大，已被三价铬钝化工艺所取代。现有的工艺主要以三价铬(通常为无机三价铬盐)为主成膜剂，添加辅助成膜剂(绝大多数为钴盐)，络合剂(含氟物质或者有机酸)、氧化剂(绝大多数为硝酸盐，双氧水用于六价铬钝化)等为主要成分配制而成的。
基于对生态环境和健康的保护，国内环保的形势越来越严峻。随着人们环保意识的加强，钴盐对环境的污染也被重视起来，人每当摄入钴超过500毫克就会中毒，钴在土壤溶液中浓度为10毫克/升时，可使农作物死亡。钴对鱼类和水生动物的毒性比较大，钴浓度达到10毫克/升，可使鲫鱼和丝鱼死亡。此外，硝酸盐对环境的污染也正式被人们提出来。高浓度的硝酸盐进入江河湖泊后会刺激藻类的疯长以致水体水质恶化、生物多样性减少、生态系统退化等。水源水中硝酸盐的污染也是一个困扰许多国家的难题，如长期饮用含有较高浓度硝酸盐的水会导致“高铁血红蛋白症”。所以降低各类污水、废水中的硝酸盐、钴盐浓度非常重要。
目前市面上彩色钝化普遍采用钴盐做辅助成膜剂来增加耐腐蚀性，用高浓度的硝酸盐作为氧化剂保持钝化液的持续性和稳定性，对水体环境的影响非常大。而且现有的钝化液普遍耐铁杂质能力差，铁离子浓度在50ppm以上时，钝化速度会明显加快，严重时会出现黄斑，对外观影响很大。如CN 201811379692中提到的三价铬彩色钝化技术，虽然没有采用钴盐，硝酸盐的用量也比较少，但是加入了很多硝酸，硝酸根的整体浓度很高；CN201810604760中提到的环保彩色钝化剂，其中不仅引入了硝酸还有大量的磷酸，对水体的影响较大；CN201210327002中用到重金属镍和硝酸盐，由于其成膜剂和辅助成膜剂浓度很低，耐腐蚀性能也相对较差；用双氧水等其他氧化剂来代替硝酸盐，主要应用在六价铬钝化中，在三价铬钝化液中使用会氧化三价铬为六价铬，造成六价铬超标，危害环境。
发明内容
本发明的目的在于提供一种用于锌层的环保型三价铬无钴彩色钝化液及钝化工艺，它具有无钴、低硝酸盐、耐铁杂质的优势，具有很好的耐腐蚀性，钝化膜艳丽鲜亮，钝化工艺操作简单。
本发明为实现上述目的，通过以下技术方案实现：
一种用于锌层的环保型三价铬无钴彩色钝化液，其原料按配比由以下组分组成：
Figure BDA0002519579350000031
作为一种优化，原料按配比由以下组分组成：
Figure BDA0002519579350000032
优选的，所述三价铬盐，包括硫酸铬、碱式硫酸铬、碳酸铬、乙酸铬、甲酸铬、氢氧化铬、硝酸铬、氯化铬、硫酸铬钾等中的任意一项或几项的组合。
优选的，所述辅助成膜剂，包括硅酸钠、钼酸钠、偏硅酸钠、氟锆酸、氟锆酸钾、氟锆酸铵、偏钒酸钠、偏钒酸铵、硫酸氧钒、硫酸铵、硫脲、甲基硫脲、乙基硫脲、苯基硫脲、缩氨基硫脲、乙撑硫脲等中的任意一项或几项的组合。
优选的，所述络合剂包括苹果酸、酒石酸、柠檬酸、甘氨酸、5-磺基水杨酸、草酸、乙二酸、丙二酸、己二酸、丁二酸、甲酸、乙酸、氢氟酸、氟化氢铵、氟化钠、氟化铵等中的任意一项或几项的组合。
优选的，所述氧化剂包括过氧化氢、过硫酸钠、过硫酸铵、过硫酸钾、硝酸盐等中的任意一项或几项的组合。
优选的，所述pH调整剂包括氢氧化钠、氢氧化钾、氨水等中的任意一项或几项的组合。
通过以下方法制得：使用PH调整剂调节钝化液为碱性环境，加入三价铬盐，在温度60-90℃条件下缓慢加入络合剂，在80-120℃下搅拌反应2小时，冷却至室温，加入氧化剂和辅助成膜剂，搅拌均匀后即得。
作为本发明的另一方面，一种钝化工艺，使用上述钝化液，且钝化方法为，在PH值1.7-3.0，温度10-40℃，空气搅拌或机械搅拌条件下钝化30-90S，在温度60-80℃条件下烘干即可。
优选的，在PH值2.0-2.4，温度20-30℃，空气搅拌或机械搅拌条件下钝化50-70S，在温度70-75℃条件下烘干即可。
对比现有技术，本发明的有益效果在于：
本钝化液无钴、低硝酸盐、耐铁杂质，其中硝酸盐为现有常用钝化液中硝酸盐浓度的10％-30％解决现有的钝化液对水体环境的污染问题，同时，本钝化工艺操作简单，工艺易于控制，对环境友好，所获得的钝化膜具有很好的稳定性和持久性，具有很好的耐腐蚀性(白锈出现时间在72h以上)，钝化膜艳丽、鲜亮，外观亮新持久。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所限定的范围。
下述实施例中所涉及的仪器、试剂、材料等，若无特别说明，均为现有技术中已有的常规仪器、试剂、材料等，可通过正规商业途径获得。下述实施例中所涉及的实验方法，检测方法等，若无特别说明，均为现有技术中已有的常规实验方法，检测方法等。
以1L钝化液为例
实施例1：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000051
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为2.1，钝化温度为25℃，钝化时间为60s，获得艳丽鲜亮的黄绿彩色钝化膜。
实施例2：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000052
Figure BDA0002519579350000061
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为2.9，钝化温度为25℃，钝化时间为40s，获得鲜亮的红绿彩色钝化膜。
实施例3：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000062
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为1.8，钝化温度为28℃，钝化时间为50s，获得黄绿色彩色钝化膜。
实施例4：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000063
Figure BDA0002519579350000071
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为2.1，钝化温度为25℃，钝化时间为75s，获得鲜亮的粉色钝化膜。
实施例5：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000072
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为2.7，钝化温度为25℃，钝化时间为75s，获得鲜亮的黄绿色钝化膜。
实施例6：一种用于锌层的环保型三价铬无钴彩色钝化液及工艺
Figure BDA0002519579350000073
Figure BDA0002519579350000081
应用本实施例的三价铬彩色钝化剂，所述的钝化液的pH为2.6，钝化温度为25℃，钝化时间为75s，获得鲜亮的黄绿色钝化膜。
实施例7：对实施例1-6所获得的钝化膜进行验证试验
按照标准GB/T 10125-1997《人造气氛腐蚀试验盐雾试验》，分别对实施例1-6制得的电沉积锌工件进行中性盐雾试验。盐雾箱内温度为35℃，盐溶液为50g/L的氯化钠溶液(将分析纯的氯化钠固体溶于电导率不超过20μs/cm的蒸馏水中，pH为6.5-7.2)。实验结果如下表所示：
试验时间 实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
24h —— —— —— —— —— ——
48h —— —— —— —— 无白锈 无白锈
72h —— 无白锈 无白锈 无白锈 —— ——
96h 无白锈 —— —— —— —— ——
120h —— —— —— —— —— 无红锈
由以上结论可以看出，实施例1具有优秀的耐盐雾性能，实施例2,3,4耐盐雾性能达到要求，实施例5和5由于没有添加改善耐盐雾的组成，因此耐盐雾性能稍差。
实施例8：对实施例1-6所获得的钝化液进行溶铁试验
分别取1-6钝化液体积200mL置于相同的250ml烧杯中，各放一张铁片(从同一块无锌层铁片上平行剪下5×1cm的长条)形状、面积、质量基本一样，静置20h，消耗起始pH一样均调为2.0，中间过程同时补加相同量的硝酸维持钝化液的pH稳定在2.0-3.0之间。铁片质量变化如下表所示：
Figure BDA0002519579350000082
Figure BDA0002519579350000091
由以上数据可以看出，实施例2，3，4，6明显的抑制铁的溶解，溶铁前后质量几乎无变化，钝化液中没有溶解的铁离子，而实施例1，5中没有添加抑制铁溶解的成分，导致钝化液中溶入大量的铁离子。

Claims (10)

1.一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，其原料按配比由以下组分组成：
Figure FDA0002519579340000011
2.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，其原料按配比由以下组分组成：
Figure FDA0002519579340000012
3.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，所述三价铬盐，包括硫酸铬、碱式硫酸铬、碳酸铬、乙酸铬、甲酸铬、氢氧化铬、硝酸铬、氯化铬、硫酸铬钾等中的任意一项或几项的组合。
4.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，所述辅助成膜剂，包括硅酸钠、钼酸钠、偏硅酸钠、氟锆酸、氟锆酸钾、氟锆酸铵、偏钒酸钠、偏钒酸铵、硫酸氧钒、硫酸铵、硫脲、甲基硫脲、乙基硫脲、苯基硫脲、缩氨基硫脲、乙撑硫脲等中的任意一项或几项的组合。
5.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，所述络合剂包括苹果酸、酒石酸、柠檬酸、甘氨酸、5-磺基水杨酸、草酸、乙二酸、丙二酸、己二酸、丁二酸、甲酸、乙酸、氢氟酸、氟化氢铵、氟化钠、氟化铵等中的任意一项或几项的组合。
6.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，所述氧化剂包括过氧化氢、过硫酸钠、过硫酸铵、过硫酸钾、硝酸盐等中的任意一项或几项的组合。
7.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，所述pH调整剂包括氢氧化钠、氢氧化钾、氨水等中的任意一项或几项的组合。
8.根据权利要求1所述一种用于锌层的环保型三价铬无钴彩色钝化液，其特征在于，通过以下方法制得：使用PH调整剂调节钝化液为碱性环境，加入三价铬盐，在温度60-90℃条件下缓慢加入络合剂，在80-120℃下搅拌反应2小时，冷却至室温，加入氧化剂和辅助成膜剂，搅拌均匀后即得。
9.一种钝化工艺，其特征在于，使用如权利要求1-8任一项所述的钝化液，且钝化方法为，在PH值1.7-3.0，温度10-40℃，空气搅拌或机械搅拌条件下钝化30-90S，在温度60-80℃条件下烘干即可。
10.根据权利要求9所述一种钝化工艺，其特征在于，在PH值2.0-2.4，温度20-30℃，空气搅拌或机械搅拌条件下钝化50-70S，在温度70-75℃条件下烘干即可。
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