CN105779988B - 一种电镀锌用无铬钝化溶液及其钝化工艺 - Google Patents
一种电镀锌用无铬钝化溶液及其钝化工艺 Download PDFInfo
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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
- 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
- C23C22/42—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 containing also phosphates
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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
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Abstract
本发明提供一种环保型无铬钝化液。其特殊之处在于包含钼酸铵、磷酸钠、硝酸铈、硫酸镍、浓硫酸或65％浓硝酸、有机类辅助剂、酸类络合剂。本发明还公开了一种采用该无铬钝化液生产钝化电镀锌的工艺。本发明的无铬钝化液不含铬等对环境和人体有重大危害的成分，减少了环境污染，属于环保型钝化液。钝化液组分简单、成本低廉。采用该无铬钝化液钝化后的电镀锌的耐腐蚀性接近六价铬的钝化效果。
Description
技术领域
本发明涉及一种无铬钝化体系中电镀锌所用的钝化溶液，及利用该溶液钝化电镀锌工艺，属于电镀工艺技术领域。
背景技术
钝化处理是指在一定的溶液中进行化学或电化学处理，在镀层上形成一层坚实致密的、稳定性高的薄膜的表面处理方法，钝化使镀层的耐腐蚀性能进一步的提高并增加表面光泽和抗污染的能力。如经过化学镀、电镀、酸洗、水洗等处理的工件表面非常活泼，所以要立即进行钝化处理，使处理后的金属表面形成一层保护膜，减缓腐蚀。对工件进行全面的钝化处理，可以提高其抗腐蚀性能，延长使用寿命。
钝化配方和工艺主要有有铬钝化和无铬钝化两类。其中研究比较成熟和应用较早的是铬酸盐钝化，但是由于Cr6+具有相当高的毒性且易致癌，随着人们环境保护意识的增强，越来越希望寻找可以代替铬酸钝化的新配方和新工艺。目前国内外研究较多的无铬钝化有：钼酸盐溶液、钨酸盐溶液、硅酸盐溶液、含锆溶液、含钴溶液、稀土金属盐溶液、钛盐钝化、三价铬溶液等无机盐钝化。
发明内容
本发明的目的在于针对传统电镀锌用无铬钝化体系的技术不足，提供一种环保型无铬钝化液。钝化液组分简单、成本低廉。采用该无铬钝化液钝化后的电镀锌的耐腐蚀性接近六价铬的钝化效果。
本发明是通过以下技术方案实现的：
首先，本发明环保型无铬钝化液主要包括以下组分：钼酸铵、磷酸钠、硝酸铈、硫酸镍、浓硫酸或65％浓硝酸、有机类辅助剂、酸类络合剂。
上述原料的用量为，每升钝化液分别包含：10.0～30.0g/L钼酸铵，15.0～35.0g/L磷酸钠，1.0～5.0g/L硝酸铈，1.0～3.0g/L硫酸镍，5.0～15.0mL/L 98％的浓硫酸或65％浓硝酸，0.5～10.0g/L有机类辅助剂,1.0～3.0g/L酸类络合剂。
上述原料的最佳用量为，每升钝化液分别包含：20.0～30.0g/L钼酸铵，25.0～35.0g/L磷酸钠，3.0～5.0g/L硝酸铈，2.0～3.0g/L硫酸镍，8.0～12.0mL/L 98％的浓硫酸或65％浓硝酸，0.5～4.0g/L有机类辅助剂,2.0～3.0g/L酸类络合剂。
上述钝化液的pH值为4.0～5.0，pH用磷酸或氨水调节。
其中所述的有机类辅助剂为羟基乙叉二磷酸、3-氨丙基三已氯基硅烷、硫酸羟胺、γ-缩水甘油醚氧丙基三甲氧基硅烷中的一种；
所述的酸类络合剂为单宁酸、柠檬酸或酒石酸中的一种。
其次，本发明还提供一种利用上述低成本无铬钝化液在电镀锌基体表面进行钝化处理的生产工艺。该生产工艺是在现有钝化生产工艺基础上，结合本发明的无铬钝化液，具体对生产工艺中一些参数进行了优化处理，从而得到的钝化体系稳定。使用该钝化液处理后的电镀锌工件表面成膜均匀致密，耐蚀时间长。
本发明可实施的镀件是电镀锌后的各类工件。其具体操作过程如下所示：
步骤(1)钝化液的配制
按照本发明提供的无铬钝化液配方进行配制，具体配制过程如下。本发明先将去离子水加热至30℃～60℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠或者硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入辅助剂、络合剂，调节溶液pH值至4.0～5.0，保温10min以上。
步骤(2)镀件预处理
对于新鲜刚镀出来的电镀锌工件可直接钝化。而对于放置了一段时间的电镀锌工件，一般可进行如下处理。镀件表面可用400目、600目、1000目砂纸依次打磨。之后用稀酸溶液中酸洗、自来水冲洗、乙醇清洗去除表面有机物、去离子水清洗，最后吹干待用。
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温30℃～60℃。根据所需钝化膜厚度决定钝化时间为30～90s，空停5～20s。
步骤(4)镀件后处理
钝化结束后用温水、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件。注意温水的水温不可高于钝化过程中钝化液的温度。
下面结合具体实施方式对本发明作进一步的说明。
具体实施方式
下面结合本发明的具体实施方案，进一步说明本发明的技术方案，但本发明的实施方式不限于以下具体实施方案。
实施例一：
步骤(1)钝化液的配制
按照本发明提供的无铬钝化液配方进行配制，具体配方如下：10.0g/L钼酸铵，15.0g/L磷酸钠，5.0g/L硝酸铈，1.0g/L硫酸镍，5.0mL/L 98％的浓硫酸，5.0g/L羟基乙叉二磷酸,1.0g/L单宁酸。本发明先将去离子水加热至50℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠或者硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入辅助剂、络合剂。pH用磷酸调节为4.0。保温10min以上。
步骤(2)镀件预处理
采用新鲜刚镀出来的电镀锌工件，用自来水冲洗之后直接钝化。
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温50℃。根据所需钝化膜厚度决定钝化时间为60s，空停5s。
步骤(4)镀件后处理
钝化结束后用温水45℃、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件。注意温水的水温不可高于钝化过程中钝化液的温度。
采用本发明制造的钝化膜表面均匀致密，钝化膜有浅蓝色金属光泽，钝化液稳定性好。按照GB/T10125-1997测试96h后，参照GB/T6461-2002进行等级评价，保护等级达8级以上；同时用5％的NaCl溶液浸泡25天后白锈面积百分比小于5％。
实施例二：
步骤(1)钝化液的配制
按照本发明提供的无铬钝化液配方进行配制，具体配方如下：20.0g/L钼酸铵，25.0g/L磷酸钠，3.0g/L硝酸铈，3.0g/L硫酸镍，15.0mL/L的5％浓硝酸，0.5g/L的3-氨丙基三已氯基硅烷,1.0g/L柠檬酸。pH用磷酸调节为4.5。本发明先将去离子水加热至30℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠或者硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入辅助剂、络合剂。pH用磷酸调节为4.0。保温10min以上。
步骤(2)镀件预处理
采用新鲜刚镀出来的电镀锌工件，用自来水冲洗之后直接钝化。
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温30℃。根据所需钝化膜厚度决定钝化时间为90s，空停20s。
步骤(4)镀件后处理
钝化结束后用温水30℃、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件。注意温水的水温不可高于钝化过程中钝化液的温度。
采用本发明制造的钝化膜表面均匀致密，钝化膜有浅灰色金属光泽，钝化液稳定性好。按照GB/T10125-1997测试96h后，参照GB/T6461-2002进行等级评价，保护等级达8级以上；同时用5％的NaCl溶液浸泡25天后白锈面积百分比小于3％。
实施例三：
步骤(1)钝化液的配制
按照本发明提供的无铬钝化液配方进行配制，具体配方如下：30.0g/L钼酸铵，35.0g/L磷酸钠，2.0g/L硝酸铈，2.0g/L硫酸镍，10.0mL/L 98％的浓硫酸，10.0g/L硫酸羟胺,2.0g/L单宁酸。pH用氨水调节为4.5。本发明先将去离子水加热至60℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠或者硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入辅助剂、络合剂。pH用磷酸调节为4.0。保温10min以上。
步骤(2)镀件预处理
放置了一段时间的电镀锌工件，一般可进行如下处理。镀件表面可用400目、600目、1000目砂纸依次打磨。之后用稀酸溶液中酸洗、自来水冲洗、乙醇清洗去除表面有机物、去离子水清洗，最后吹干待用。
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温60℃。根据所需钝化膜厚度决定钝化时间为30s，空停15s。
步骤(4)镀件后处理
钝化结束后用温水50℃、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件。注意温水的水温不可高于钝化过程中钝化液的温度。
采用本发明制造的钝化膜表面均匀致密，钝化膜有金色金属光泽，钝化液稳定性好。按照GB/T10125-1997测试96h后，参照GB/T6461-2002进行等级评价，保护等级达8级以上；同时用5％的NaCl溶液浸泡25天后白锈面积百分比小于5％。
实施例四：
步骤(1)钝化液的配制
按照本发明提供的无铬钝化液配方进行配制，具体配方如下：25.0g/L钼酸铵，30.0g/L磷酸钠，1.0g/L硝酸铈，2.5g/L硫酸镍，10.0mL/L的65％浓硝酸，3.0g/Lγ-缩水甘油醚氧丙基三甲氧基硅烷,1.0g/L酒石酸。pH用氨水调节为5.0。本发明先将去离子水加热至40℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠或者硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入辅助剂、络合剂。pH用磷酸调节为4.0。保温10min以上。
步骤(2)镀件预处理
放置了一段时间的电镀锌工件，一般可进行如下处理。镀件表面可用400目、600目、1000目砂纸依次打磨。之后用稀酸溶液中酸洗、自来水冲洗、乙醇清洗去除表面有机物、去离子水清洗，最后吹干待用。
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温40℃。根据所需钝化膜厚度决定钝化时间为80s，空停10s。
步骤(4)镀件后处理
钝化结束后用温水35℃、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件。注意温水的水温不可高于钝化过程中钝化液的温度。
采用本发明制造的钝化膜表面均匀致密，钝化膜有彩色金属光泽，钝化液稳定性好。按照GB/T10125-1997测试96h后，参照GB/T6461-2002进行等级评价，保护等级达8级以上；同时用5％的NaCl溶液浸泡25天后白锈面积百分比小于3％。
Claims (4)
1.一种环保型无铬钝化液，组分为：钼酸铵、磷酸钠、硝酸铈、硫酸镍、浓硫酸或65％浓硝酸、有机类辅助剂、酸类络合剂；上述原料的用量为，每升钝化液的组分为：10.0～30.0g/L钼酸铵，15.0～35.0g/L磷酸钠，1.0～5.0g/L硝酸铈，1.0～3.0g/L硫酸镍，5.0～15.0mL/L98％的浓硫酸或65％浓硝酸，0.5～10.0g/L有机类辅助剂，1.0～3.0g/L酸类络合剂；
所述的有机类辅助剂为3-氨丙基三已氯基硅烷、硫酸羟胺和γ-缩水甘油醚氧丙基三甲氧基硅烷中的一种；
所述的钝化液的pH值为4.0～5.0，pH用磷酸或氨水调节。
2.按照权利要求1所述一种环保型无铬钝化液，其特征在于上述原料的用量为，每升钝化液的组分为：20.0～30.0g/L钼酸铵，25.0～35.0g/L磷酸钠，3.0～5.0g/L硝酸铈，2.0～3.0g/L硫酸镍，8.0～12.0mL/L 98％的浓硫酸或65％浓硝酸，0.5～4.0g/L有机类辅助剂，2.0～3.0g/L酸类络合剂。
3.按照权利要求1所述一种环保型无铬钝化液，其特征在于所述的酸类络合剂为单宁酸、柠檬酸或酒石酸中的一种。
4.一种采用权利要求1所述环保型无铬钝化液在电镀锌基体表面进行钝化处理的生产工艺，其特征在于，所述生产工艺的流程依次是钝化液的配制、镀件预处理、镀件钝化、镀件后处理；所述生产工艺实施的镀件是电镀锌后的各类工件；所述生产工艺的具体操作过程如下
所示：
步骤(1)钝化液的配制
按照提供的无铬钝化液配方进行配制，具体配制过程如下：先将去离子水加热至30℃～60℃，加入钼酸铵搅拌直到完全溶解，然后再依次加入磷酸钠、硝酸铈、硫酸镍搅拌溶解后，继续加入浓硫酸或浓硝酸搅拌均匀，最后依次加入有机类辅助剂、酸类络合剂，调节溶液pH值至4.0～5.0，保温10min以上；
步骤(2)镀件预处理
对于新鲜刚镀出来的电镀锌工件可直接钝化，而对于放置了一段时间的电镀锌工件，进行如下处理：镀件表面用400目、600目、1000目砂纸依次打磨，之后依次用稀酸溶液中酸洗、自来水冲洗、乙醇清洗去除表面有机物，再用去离子水清洗，最后吹干待用；
步骤(3)镀件钝化
将镀件放入钝化液中浸置，恒温30℃～60℃，根据所需钝化膜厚度决定钝化时间为30～90s，空停5～20s；
步骤(4)镀件后处理
钝化结束后依次用温水、常温自来水清洗镀件，最后烘干，即得到表面有钝化膜的电镀锌工件，温水的水温不高于钝化过程中钝化液的温度。
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