CN111593335A - 一种用于金属表面处理的改良锆基转化膜及其制备方法与应用 - Google Patents

一种用于金属表面处理的改良锆基转化膜及其制备方法与应用 Download PDF

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CN111593335A
CN111593335A CN202010449531.4A CN202010449531A CN111593335A CN 111593335 A CN111593335 A CN 111593335A CN 202010449531 A CN202010449531 A CN 202010449531A CN 111593335 A CN111593335 A CN 111593335A
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zirconium
sodium
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马厚义
王岩
赫威
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Craftsman's Heart Surface Functionalization Technology Jinan Co ltd
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Abstract

本发明涉及一种基于传统锆化膜进行升级改良的锆基转化膜成膜液，原料组分及其以质量百分比100％计：成膜剂1‑10％，氧化剂0.1‑5％，螯合剂1‑10％，防锈剂0.1‑3％，分散剂0.01‑3％，中和剂0.1‑5％，余量为水(工业用水)。本发明优点在于无机螯合剂的加入络合了工业用水的杂离子，同时改良了锆转化液稳定性差、不能处理粗糙钢铁基材的缺陷。本发明不但提高膜层耐腐蚀性能，而且可以降低生产成本，同时处理液处理面积大，参数简单便于控制，适合大规模应用。

Description

一种用于金属表面处理的改良锆基转化膜及其制备方法与 应用
技术领域
本发明涉及一种在钢铁表面防腐转化膜的制备方法与应用，属于金属表面处理技术领域范畴。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
在金属表面前处理工艺中，传统上最常用的是磷化工艺，磷化工艺自发明之日起至今已有百年历史，因其具有裸膜耐腐蚀能力强、漆膜性能好、处理工件范围广等优点，一经发明便被广泛应用在金属表面前处理各个领域。但是随着如今社会对于环保要求的越来越高，磷化技术的弊端暴露无疑，磷化处理后沉渣多，重金属离子含量高，废液排放污染严重，对环境的伤害日益严重。
基于此背景，在金属表面前处理行业中，研发新型环保型前处理成膜剂迫在眉睫。目前市场上的一种主流的环保型产品为：锆基转化膜(又称陶化膜)。锆化液产品的优点是：(1)可在常温、低浓度和较短时间内完成操作；(2)转化处理液中不含重金属镍、亚硝酸盐、铬酸盐等污染物、无需表调，可减轻废水处理的负担；(3)溶液维护方便，在常温下使用，pH值控制在4.5～5.5，处理时间30-200秒，膜厚20-120nm；(4)转化膜的耐蚀性与涂膜的附着力与磷化处理相当；(5)总运作成本比磷化处理低(能耗和水耗也低)；(6)适用于多种金属材料(如钢铁、铝、锌、镁合金等)的涂装前处理(浸渍或喷淋)。
但发明人发现：该类锆基转化膜也存在着处理液稳定性较差，处理液中其他杂质离子副作用大，必须采用纯水，对于工艺流程要求较高，能处理的基材表面处理要求高等缺陷。
发明内容
针对现有锆化液的不足，本发明提供一种基于钢铁表面耐腐蚀、附着力性能优异的改良锆基成膜剂，可以采用工业用水配制溶液，可处理表面条件较差的钢铁基材，大大降低成本，可以大规模工业化应用。
为实现上述技术目的，本发明采用如下技术方案：
本发明的第一个方面，提供了一种钢铁表面改良锆基成膜液，由如下质量百分比的原料组成：成膜剂1-10％，氧化剂0.1-5％，螯合剂1-10％，防锈剂0.1-3％，分散剂0.01-3％，中和剂0.1-5％，余量为水。
本发明是在锆基转化膜的基础上引入精选螯合剂来改良锆基转化膜的适用性范围窄的缺点，而且进一步增强耐腐蚀效果与漆膜附着力性能。通过螯合剂结合溶液中多种游离金属离子在金属基体表面杂化沉积，形成多维层状结构的坚实转化膜层。可以处理表面粗糙度较大的钢铁表面，可以大大提高处理液适用范围。
本发明的第二个方面，提供了一种钢铁表面改良锆基成膜液的制备方法，包括：
向工业水中依次加入成膜剂、氧化剂、螯合剂、防锈剂、分散剂、中和剂，混合均匀后，调节pH为1.8～2.2；
所述加入过程中，待前一试剂溶解均匀后再加入后一试剂。
本发明采用工业用水作为原料，改良了相比传统的锆化处理液必须要用纯水，大大降低原料成本，但是在钢铁表面的膜层性能并没有显著降低，各项指标均能满足国标要求。
本发明的第三个方面，提供了任一上述的钢铁表面改良锆基成膜液在钢铁表面处理中的应用。
本发明的有益效果在于：
(1)螯合剂的引入可以与无机锆转化膜结合在钢铁表面成三维网状膜，膜层相比传统锆化膜更厚，耐腐蚀性能更强；改良了锆化膜只能处理表面粗糙度较小的钢铁基材；
(2)采用工业用水作为原料，改良了相比传统的锆化处理液必须要用纯水，大大降低原料成本；
(3)虽然采用工业用水，但是在钢铁表面的膜层性能并没有显著降低，依然可以满足裸膜测试，漆膜测试等，各项指标均能满足国标要求；
(4)本发明成膜液无污染、无重金属离子，对环境没有损害。
(5)本发明的方法简单、成本低、实用性强，易于推广。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1是实施例1至实施例4的阻抗结果图。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
一种钢铁表面改良锆基成膜液，原料组分及其以质量百分比100％计：成膜剂1-10％，氧化剂0.1-5％，螯合剂1-10％，防锈剂0.1-3％，分散剂0.01-3％，余量为水(自来水)。
本发明的成膜剂相较于众多学者研究的锆化膜的优势在于，出发点在于工业中的生产应用，解决众多企业目前磷化膜，铬酸盐转化膜等高污染产品被禁用而现有产品有局限性无法完全替代磷化膜等的困境，满足国家新时代对环境保护的要求。
优选的，所述钢铁表面改良锆基成膜液由成膜剂，螯合剂，氧化剂组成。
根据发明优选的，成膜剂包括氟钛酸、氟硼酸、氟硅酸、氢氟酸、氟锆酸、中的一种或几种；更优选的，所述成膜剂为氟锆酸或氟钛酸。
与现有论文研究的锆化膜体系相比，本发明研究了更宽泛的体系如氟锆酸、氟钛酸、氟硼酸、氟硼酸+硝酸钠、氧氯化锆、双氧水、六偏磷酸钠、三聚磷酸钠、酒石酸钠、植酸、柠檬酸钠、氨基三羧酸等，且可以采工业用水，不需纯水，成本降低，各原料及处理液条件工业应用上均能满足要求。而目前的论文所做的测试是关于理论研究的电化学数据，不够接近工业应用实际。
根据发明优选的，氧化剂包括氧氯化锆、硝酸钠、硝酸锌、双氧水、氯酸钠等；更优选的，所述氧化剂为硝酸钠，硝酸锌，氧氯化锆。
根据发明优选的，螯合剂包括柠檬酸钠、酒石酸钠、硼酸、植酸、六偏磷酸钠、醋酸钠、乙二酸、氨基三羧酸、氨基三羧酸钠中的一种或几种；更优选的，所述螯合剂为柠檬酸钠，六偏磷酸钠，酒石酸钠，植酸。
本发明研究发现：通过多种无机螯合剂复配，如六偏磷酸钠、三聚磷酸钠等将工业用水中的钙镁离子等螯合沉降，降低钙镁杂离子对锆化液产生的干扰，既改良了传统的锆化处理液必须要用纯水的缺点，又大大降低原料成本，而且钢铁表面的膜层性能并没有显著降低，因此，可采用工业用水作为原料。
根据发明优选的，防锈剂包括苯甲酸钠、钼酸钠、钨酸钠、海藻酸钠、硫脲中的一种或几种；更优选的，所述防锈剂为钼酸钠，硫脲，苯甲酸钠，以提高金属的防锈时间。
根据发明优选的，分散剂包括水性聚氨酯、纳米二氧化钛溶胶、聚丙烯酸酯、纳米氧化锌溶胶、十二烷基苯磺酸钠中的一种或几种；更优选的，所述分散剂为聚丙烯酸酯，纳米氧化锌溶胶，以改善各组分在成膜液中的分散效果，增强成膜性能。
根据发明优选的，中和剂包括氢氧化钠、碳酸钠、氢氧化钾、氨水中的一种或几种。更优选的，所述中和剂为氢氧化钠，以调节成膜液的pH，提高成膜性能。
本发明的改良锆基成膜剂的制备方法如下：
(1)在工业用水中逐渐加入成膜剂，搅拌；
(2)再加入氧化剂，搅拌溶解；
(3)加入螯合剂，搅拌溶解；
(4)加入防锈剂，搅拌溶解；
(5)最后加入分散剂、中和剂，搅拌，调节pH为2.0左右；
本发明的改良锆基成膜剂在钢铁表面处理的应用过程步骤如下：
(1)将待处理的钢铁表面先进行脱脂处理，待钢铁表面油污除尽后再用自来水冲洗；
(2)然后将钢铁放置在用中和剂调节至pH＝4.0的成膜液中浸泡5-10分钟；
(3)然后取出，水洗，并在自然环境中晾干或烘干，即可在表面得到一层耐腐蚀的薄膜，膜层呈现暗黄色。
下面结合具体的实施例，对本发明做进一步的详细说明，应该指出，所述具体实施例是对本发明的解释而不是限定。
以下实施例中，所述纳米二氧化钛溶胶为纳米二氧化钛透明分散液，购自杭州智钛净化科技有限公司。
实施例1：
一种钢铁表面改良锆基成膜液，原料质量百分比如下：氟钛酸、氟硼酸2％(比例为3：11)，硝酸钠、硝酸锌、双氧水1％(比例为9：7：1)，柠檬酸钠、酒石酸钠、六偏磷酸钠、硼酸4％(比例为1：3：7：5)，苯甲酸钠、钼酸钠、钨酸钠0.5％(3：5：1)，水性聚氨酯、纳米二氧化钛溶胶0.1％(比例为5：7)，氢氧化钠0.5％，余量为水。
按照上面所描述的方法按顺序依次添加溶剂配制处理液，利用中和剂氢氧化钠将处理液pH值调整至4.0；随后将已配置好的改良锆基成膜液对钢铁表面进行处理，步骤如下：
(1)对钢铁表面进行脱脂，水洗，再水洗；
(2)常温下将步骤(1)处理后的钢铁板置于上述调节好pH＝4.0的成膜液中5分钟；
(3)将步骤(2)处理后的钢铁表面用水冲洗，自然晾干或烘干即可完成成膜过程。随后将样板分别进行硫酸铜点滴试验和环氧干粉喷塑盐雾试验。
实施例2：
一种钢铁表面改良锆基成膜液，原料质量百分比如下：氟硼酸、氟硅酸、氢氟酸3％(比例为1：1：2)，氧氯化锆、硝酸钠、硝酸锌、双氧水1.5％(比例为2：3：1：1.5)，硼酸、植酸、三聚磷酸钠、醋酸钠、乙二酸5％(比例为1：0.5：5：3：7)，钨酸钠、海藻酸钠1％(比例为1：3)，聚丙烯酸酯、纳米氧化锌溶胶0.5％(比例为3：5)，碳酸钠0.7％，余量为水。
按照上面所描述的方法按顺序依次添加溶剂配制处理液，利用中和剂碳酸钠将处理液pH值调整至4.0；随后将已配置好的改良锆基成膜液对钢铁表面进行处理，步骤如下：
(1)对钢铁表面进行脱脂，水洗，再水洗；
(2)常温下将步骤(1)处理后的钢铁板置于上述调节好pH＝4.0的成膜液中5分钟；
(3)将步骤(2)处理后的钢铁表面用水冲洗，自然晾干或烘干即可完成成膜过程。随后将样板分别进行硫酸铜点滴试验和环氧干粉喷塑盐雾试验。
实施例3：
一种钢铁表面改良锆基成膜液，原料质量百分比如下：氟硅酸、氢氟酸、氟锆酸4％(比例为5：7：1)，氯酸钠、硝酸锌2％(比例为1：5)，酒石酸钠、硼酸、植酸、六偏磷酸钠、醋酸钠6％(比例为1：3：7：5：7.5)，钨酸钠、海藻酸钠1.5％(比例为3：7)，纳米氧化钛溶胶、十二烷基苯磺酸钠0.8％(比例为2：5)，氢氧化钾0.8％，余量为水。
按照上面所描述的方法按顺序依次添加溶剂配制处理液，利用中和剂氢氧化钾将处理液pH值调整至4.0；随后将已配置好的改良锆基成膜液对钢铁表面进行处理，步骤如下：
(1)对钢铁表面进行脱脂，水洗，再水洗；
(2)常温下将步骤(1)处理后的钢铁板置于上述调节好pH＝4.0的成膜液中5分钟；
(3)将步骤(2)处理后的钢铁表面用水冲洗，自然晾干或烘干即可完成成膜过程。随后将样板分别进行硫酸铜点滴试验和环氧干粉喷塑盐雾试验。
实施例4：
一种钢铁表面改良锆基成膜液，原料质量百分比如下：氟锆酸、氟钛酸、氢氟酸5％(比例为2：5：7.5)，氧氯化锆、硝酸钠、硝酸锌、双氧水2.5％(比例为5：1：7：1.5)，醋酸钠、乙二酸、氨基三羧酸、三聚磷酸钠、氨基三羧酸钠7％(比例为3.5：2：5：1.75：6)，钼酸钠、硫脲、钨酸钠0.9％(比例为3：5：1)，聚丙烯酸酯、纳米氧化锌溶胶1％(比例为1：3)，氢氧化钠0.8％，余量为水。
按照上面所描述的方法按顺序依次添加溶剂配制处理液，利用中和剂氢氧化钾将处理液pH值调整至4.0；随后将已配置好的改良锆基成膜液对钢铁表面进行处理，步骤如下：
(1)对钢铁表面进行脱脂，水洗，再水洗；
(2)常温下将步骤(1)处理后的钢铁板置于上述调节好pH＝4.0的成膜液中5分钟；
(3)将步骤(2)处理后的钢铁表面用水冲洗，自然晾干或烘干即可完成成膜过程。随后将样板分别进行硫酸铜点滴试验和环氧干粉喷塑盐雾试验。
试验结果：
对实施例1-4进行处理后的钢铁表面进行性能检测，测试项目及结果如下：
1)外观
Figure BDA0002507172970000091
2)硫酸铜点滴与氯化钠浸泡实验
Figure BDA0002507172970000092
参照QB/T 3824－1999，将40mL 0.5mol/L硫酸铜(CuSO4·5H2O)溶液、20mL 10％氯化钠(NaCl)溶液、0.8mL 0.1mol/L盐酸(HCl)混合配制成所需溶液，从硫酸铜滴到试样表面开始计时，试样表面出现玫瑰色斑点为止，即为该试样耐硫酸铜腐蚀时间。
实施例结果证明本发明制备的改良锆转化膜，其致密度、耐蚀性都有很大提高。
3)电化学测试
采用CHI660E电化学工作站进行极化曲线测定，将试样作为工作电极，饱和甘汞电极为参比电极，以铂电极为辅助电极。取制备面为工作面，其余用704硅胶封装绝缘；室温；溶液为3.5％NaCl去离子水溶液。
阻抗曲线：
开路时间：1200s
扫描频率：1000kHz-0.1mHz
由图1可以看出，改良锆基成膜的阻抗值远远高于空白裸铁，耐腐蚀能力显著提高。
4)漆膜测试结果
Figure BDA0002507172970000101
漆膜测试结果表明：本发明改良锆基转化膜性能优异，有大规模应用的潜力。
最后应该说明的是，以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。上述虽然对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (10)

1.一种钢铁表面改良锆基成膜液，其特征在于，由如下质量百分比的原料组成：成膜剂1-10％，氧化剂0.1-5％，螯合剂1-10％，防锈剂0.1-3％，分散剂0.01-3％，中和剂0.1-5％，余量为水。
2.如权利要求1所述的钢铁表面改良锆基成膜液，其特征在于，由如下质量百分比的原料组成：成膜剂1-5％，氧化剂0.1-2.5％，螯合剂1-5％，防锈剂0.1-1.5％，分散剂0.01-1.5％，中和剂0.1-5％，余量为水。
3.如权利要求1所述的钢铁表面改良锆基成膜液，其特征在于，由如下质量百分比的原料组成：成膜剂5-10％，氧化剂2.5-5％，螯合剂5-10％，防锈剂1.5-3％，分散剂1.5-3％，中和剂0.1-5％，余量为水。
4.如权利要求1-3任一项所述的钢铁表面改良锆基成膜液，其特征在于，所述成膜剂包括氟钛酸、氟硼酸、氟硅酸、氢氟酸、氟锆酸中的一种或几种。
5.如权利要求1-3任一项所述的钢铁表面改良锆基成膜液，其特征在于，所述氧化剂包括氧氯化锆、硝酸钠、硝酸锌、双氧水、氯酸钠。
6.如权利要求1-3任一项所述的钢铁表面改良锆基成膜液，其特征在于，所述螯合剂包括柠檬酸钠、酒石酸钠、六偏磷酸钠、三聚磷酸钠、硼酸、植酸、醋酸钠，乙二酸，氨基三羧酸，氨基三羧酸钠中的一种或几种。
7.如权利要求1-3任一项所述的钢铁表面改良锆基成膜液，其特征在于，所述防锈剂包括苯甲酸钠、钼酸钠、钨酸钠、海藻酸钠、硫脲中的一种或几种。
8.如权利要求1-3任一项所述的钢铁表面改良锆基成膜液，其特征在于，所述分散剂包括水性聚氨酯、纳米二氧化钛溶胶、聚丙烯酸酯、纳米氧化锌溶胶、十二烷基苯磺酸钠中的一种或几种。
9.一种钢铁表面改良锆基成膜液的制备方法，其特征在于，包括：
向工业用水中依次加入成膜剂、氧化剂、螯合剂、防锈剂、分散剂，混合均匀后，加入中和剂调节pH为1.8～2.2；
所述加入过程中，待前一试剂溶解均匀后再加入后一试剂。
10.权利要求1-8任一项所述的钢铁表面改良锆基成膜液在钢铁表面处理中的应用。
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Application publication date: 20200828