CN105951083B - 镀锌钢板用水性复合钝化液及其制备方法 - Google Patents
镀锌钢板用水性复合钝化液及其制备方法 Download PDFInfo
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Classifications
-
- 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
- C23C22/40—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
- C23C22/44—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 fluorides or complex fluorides
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开了一种镀锌钢板用水性复合钝化液及其制备方法，组分及各组分质量份数如下：钒酸锌3~8份，钨酸钠5~15份，硝酸铈2~8份，钛盐1~5份，偏钒酸钾1~6份，酒石酸2~10份，氟化氢铵2~6份，硅烷偶联剂5~15份，氨基三亚甲基膦酸2~8份，丙二酸2~8份，二氨基二氮杂茂1~5份，稳定剂2~10份，聚乙烯醇0.1~2份，水20~50份。钝化液采用磷酸‑钛盐体系配合改性水解性硅烷偶联剂及填充物组成，不含铬酸盐，符合环保要求，有效地增强了钝化液的耐蚀性能，钝化及烘干固化时间短，稳定性高，膜层质量好，72小时盐雾实验白绣面积低于5%；同时基本不影响导电性能，增强了镀锌板的涂装性能。
Description
技术领域
本发明属于金属表面处理化学品技术领域，具体涉及一种镀锌钢板用水性复合钝化液及其制备方法。
背景技术
金属材料以其优良的性能广泛的应用于生产和生活的各个方面，但是大多数金属材料在一定条件下很容易遭到腐蚀，从而造成巨大的损失。据报道，腐蚀造成的直接经济损失占其国民生产总产值的比重，美国为3.5%，英国为4.2%。严重的金属腐蚀甚至造成巨大的灾难性事故，妨碍了正常的工农业生产、国防建设和环境保护等。因此金属材料的腐蚀和防护，是关系国计民生的重要课题，也是科技工作者的研究重点之一。
镀锌是提高钢铁抗大气腐蚀的有效方法,广泛应用于航空、电力、交通、建筑、机械等行业。通常采用的方法有电镀、浸镀和喷镀三种。在多种环境下,锌的腐蚀电位比较低相对于大多数金属材料,当钢铁基体受到腐蚀时,锌镀层作为阳极优先溶解,从而保护了钢铁基体。金属锌的化学性质相当活泼,虽然在大气中的腐蚀速率比较低,但在潮湿环境中,裸露的镀锌层表面很快变暗,形成白色疏松的腐蚀产物称为白锈,且腐蚀产物基本上对基体无保护性,因此,镀锌后通常对其表面进行防蚀处理。如何防腐蚀是金属表面处理科学的主攻方向。
为了降低锌的化学活性,往往采用铬酸盐溶液来钝化处理,使其表面形成一层铬酸盐转化膜。这层膜正式的名称叫做“铬酸盐转化膜”,电镀行业称为“镀锌层钝化膜”,或简称“镀锌钝化”。锌合金层表面的铬酸盐膜在侵蚀性环境中表现出了良好的耐蚀性,并且是有剧毒的锅的合适替代。锌的铬酸盐钝化发展到今天已经有上百年的历史,其成膜机理及生产工艺都已相当成熟。膜层的物理化学性能非常好,因而在镀件上的应用极其广泛。历史上应用最普遍的钝化处理工艺是铬酸盐钝化处理,铬酸盐钝化液性能稳定,成本低廉,钝化工艺简单,钝化膜光泽性和抗蚀性能好,得到广泛应用,因此对铬酸盐钝化膜的研究也最多。传统的铬酸盐钝化液通常是由六价铬化合物、三价铬化合物、导电盐、络合剂等组成。在钝化膜形成的过程中发生锌的溶解、铬酸根还原以及三价铬凝胶的析出,这些反应形成了钝化膜的骨架,随后铬酸盐以碱式盐的形式吸附于凝胶上形成面层,至此生成了完整的六价铬钝化层。当钝化层因外力而刮伤后,在潮湿的空气中六价铬化合物溶于水并与露出的锌层起反应—即再次进行钝化处理,从而使钝化膜得到修复,亦被称作六价铬钝化的自愈能力。由于铬酸盐膜较薄,在高强度下易破裂,影响抗蚀性,而且六价铬对人体及环境都有一定的危害,随着人们环境意识的增强,近年来逐渐采用无铬或低铬与有机物相结合的钝化液进行热镀锌后处理,达到良好效果,对这种钝化膜的研究也较多。目前在生产中广泛使用的钝化剂中主要含有铬酸酐,磷酸根、硝酸根,少量柠檬酸和极少量的氟硅酸,pH值约3-4。德国Chemtall公司生产的钝化剂Chemtall因性能稳定、钝化效果后,在国际上具有很高的市场占有率和知名度,很长一段时期内令大多数厂家只能望其项背。
发明内容
本发明的目的是提供一种镀锌钢板用水性复合钝化液及其制备方法，钝化液采用磷酸-钛盐体系配合改性水解性硅烷偶联剂及填充物组成，不含铬酸盐，符合环保要求，有效地增强了钝化液的耐蚀性能，钝化及烘干固化时间短，稳定性高，膜层质量好，72小时盐雾实验白绣面积低于5%；同时基本不影响导电性能，增强了镀锌板的涂装性能。
为了实现上述目的，本发明采用的技术手段为：
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 3~8份，钨酸钠 5~15份，硝酸铈 2~8份，钛盐 1~5份， 偏钒酸钾1~6份，酒石酸2~10份，氟化氢铵 2~6份，硅烷偶联剂5~15份，氨基三亚甲基膦酸2~8份，丙二酸 2~8份，二氨基二氮杂茂1~5份，稳定剂 2~10份，聚乙烯醇0.1~2份，水 20~50份。
所述钛盐为硫酸钛、硫酸氧钛或者钛酸钠中的至少一种。
所述稳定剂为三盐基硫酸铅或者二盐基亚磷酸铅。
所述镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 4~6份，钨酸钠 8~12份，硝酸铈 4~6份，钛盐 2~4份， 偏钒酸钾2~5份，酒石酸4~8份，氟化氢铵3~5份，硅烷偶联剂7~13份，氨基三亚甲基膦酸4~6份，丙二酸3~5份，二氨基二氮杂茂2~4份，稳定剂4~8份，聚乙烯醇0.4~1.2份，水 30~40份。
所述镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 5份，钨酸钠 10份，硝酸铈 5份，钛盐 3份， 偏钒酸钾3份，酒石酸6份，氟化氢铵4份，硅烷偶联剂10份，氨基三亚甲基膦酸5份，丙二酸4份，二氨基二氮杂茂3份，稳定剂6份，聚乙烯醇0.8份，水35份。
所述镀锌钢板用水性复合钝化液的制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌10~30min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
步骤1）中搅拌20min
得到的镀锌钢板用水性复合钝化液主要用于镀锌钢板表面的钝化处理，处理方法为：将镀锌板除油、出光，采用喷淋或辊涂的方法将所述的钝化液涂覆在镀锌板上，之后经过辊干、热风烘干制成成品；钝化时间10~20s，烘干温度100~150℃，烘干时间10~40s。
有益效果：本发明提供的一种镀锌钢板用水性复合钝化液，采用磷酸-钛盐体系配合改性水解性硅烷偶联剂及填充物组成，不含铬酸盐，符合环保要求，通过在钝化液体系中复配氟酸盐、有机磷酸、稳定剂等，有效地增强了钝化液的耐蚀性能，钝化及烘干固化时间短，稳定性高，膜层质量好，72小时盐雾实验白绣面积低于5%；同时基本不影响导电性能，增强了镀锌板的涂装性能。制备工艺简单，价格低廉，使用工艺简单，烘干固化快速，采用本发明钝化液处理过的镀锌板具有更好的耐蚀性，超过目前的市售产品，且具有优异的涂装性，外观和导电性能良好。
具体实施方式
实施例1
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 3份，钨酸钠 5份，硝酸铈 8份，钛酸钠 5份， 偏钒酸钾1份，酒石酸10份，氟化氢铵 2份，硅烷偶联剂15份，氨基三亚甲基膦酸8份，丙二酸 2份，二氨基二氮杂茂1份，稳定剂二盐基亚磷酸铅 10份，聚乙烯醇2份，水 20份。
制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌20min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
实施例2
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 8份，钨酸钠 15份，硝酸铈 2份，钛盐 硫酸钛 1份， 偏钒酸钾6份，酒石酸2份，氟化氢铵6份，硅烷偶联剂5份，氨基三亚甲基膦酸2份，丙二酸8份，二氨基二氮杂茂5份，稳定剂三盐基硫酸铅 2份，聚乙烯醇0.1份，水 50份。
制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌20min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。实施例3
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 4份，钨酸钠 12份，硝酸铈 4份，钛酸钠 4份， 偏钒酸钾2份，酒石酸8份，氟化氢铵3份，硅烷偶联剂7份，氨基三亚甲基膦酸6份，丙二酸3份，二氨基二氮杂茂4份，稳定剂二盐基亚磷酸铅 4份，聚乙烯醇1.2份，水 30份。
制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌20min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
实施例4
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 6份，钨酸钠 8份，硝酸铈 6份，硫酸氧钛 2份， 偏钒酸钾5份，酒石酸4份，氟化氢铵5份，硅烷偶联剂13份，氨基三亚甲基膦酸4份，丙二酸5份，二氨基二氮杂茂2份，稳定剂 三盐基硫酸铅8份，聚乙烯醇0.4份，水 40份。
制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌20min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
实施例5
一种镀锌钢板用水性复合钝化液，组分及各组分质量份数如下：钒酸锌 5份，钨酸钠 10份，硝酸铈 5份，硫酸氧钛 3份， 偏钒酸钾3份，酒石酸6份，氟化氢铵4份，硅烷偶联剂10份，氨基三亚甲基膦酸5份，丙二酸4份，二氨基二氮杂茂3份，稳定剂二盐基亚磷酸铅 6份，聚乙烯醇0.8份，水 35份。
制备方法，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌20min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
对比例1
本实施例与实施例5的区别仅在于组分中不包含氨基三亚甲基膦酸和二氨基二氮杂茂，其他组分及其制备方法同实施例5。
对比例2
本实施例与实施例5的区别仅在于组分中不包含氟化氢铵和偏钒酸钾，其他组分及其制备方法同实施例5。
将镀锌板除油、出光，采用喷淋或辊涂的方法，采用实施例1~5及对比例1-2的镀锌钢板水性复合钝化液涂覆在镀锌板上，之后经过辊干、热风烘干制成成品；钝化时间15s，烘干温度120℃，烘干时间20s，然后进行性能测试，结果见表1。
参照机械行业标准 JB/T 6073-1992，采用全浸腐蚀试验测定超低温金属钝化磷化液在铝合金表面形成涂层的耐蚀性能：取样品浸入 5% NaCl 溶液中浸泡，试样用塑料绳悬挂，上端距液面大于 2cm，溶液 pH 值为 6.5，每隔六天更换一次盐水，敞口放置，温度10±2℃，记录每个样品出现第一个红锈的时间，耐蚀时间作为耐蚀性评价结果。
中性盐雾试验：
试验箱内的温度保持在25℃，压缩空气要预热到35℃之间并调节到足够的压力。氯化纳溶液的质量浓度为5%±1%，冷凝后溶液的pH值在6.5-7.2之间。在盐雾试验过程中，降雾量应控制在如下范围:每80cm2水平面内，每小时收集的降雾量平均为1.0~2.0ml之间，将试样放置在试验箱中进行连续喷雾72小时，测定平面部腐蚀程度。
涂膜附着力实验：
在试验片的涂膜上间隔1mm刻画横竖垂直的线，根据断开处裂痕扩展的大小判定涂膜的脆性及对本材质的附着性能是否良好。
表1：
| 耐蚀时间 | 30℃成膜时间 | 72h平面腐蚀度 | 附着力 | |
| 实施例1 | 319h | 8min | 4.8% | 一级 |
| 实施例2 | 327h | 7min | 4.3% | 一级 |
| 实施例3 | 356h | 6min | 3.1% | 一级 |
| 实施例4 | 371h | 5min | 3.6% | 一级 |
| 实施例5 | 436h | 2min | 2.5% | 一级 |
| 对比例1 | 257h | 12min | 9.6% | 二级 |
| 对比例2 | 262h | 16min | 12.5% | 二级 |
Claims (7)
1.一种镀锌钢板用水性复合钝化液，其特征在于，组分及各组分质量份数如下：钒酸锌3~8份，钨酸钠 5~15份，硝酸铈 2~8份，钛盐 1~5份， 偏钒酸钾1~6份，酒石酸2~10份，氟化氢铵 2~6份，硅烷偶联剂5~15份，氨基三亚甲基膦酸2~8份，丙二酸 2~8份，二氨基二氮杂茂1~5份，稳定剂 2~10份，聚乙烯醇0.1~2份，水 20~50份。
2.根据权利要求1所述镀锌钢板用水性复合钝化液，其特征在于：所述钛盐为硫酸钛、硫酸氧钛或者钛酸钠中的至少一种。
3.根据权利要求1所述镀锌钢板用水性复合钝化液，其特征在于：所述稳定剂为三盐基硫酸铅或者二盐基亚磷酸铅。
4.根据权利要求1所述镀锌钢板用水性复合钝化液，其特征在于，组分及各组分质量份数如下：钒酸锌 4~6份，钨酸钠 8~12份，硝酸铈 4~6份，钛盐 2~4份， 偏钒酸钾2~5份，酒石酸4~8份，氟化氢铵3~5份，硅烷偶联剂7~13份，氨基三亚甲基膦酸4~6份，丙二酸3~5份，二氨基二氮杂茂2~4份，稳定剂4~8份，聚乙烯醇0.4~1.2份，水 30~40份。
5.根据权利要求1所述镀锌钢板用水性复合钝化液，其特征在于，组分及各组分质量份数如下：钒酸锌 5份，钨酸钠 10份，硝酸铈 5份，钛盐 3份， 偏钒酸钾3份，酒石酸6份，氟化氢铵4份，硅烷偶联剂10份，氨基三亚甲基膦酸5份，丙二酸4份，二氨基二氮杂茂3份，稳定剂6份，聚乙烯醇0.8份，水 35份。
6.权利要求1所述镀锌钢板用水性复合钝化液的制备方法，其特征在于，包括如下步骤：
1）将钒酸锌、钨酸钠、硝酸铈、钛盐、偏钒酸钾、酒石酸和水加入反应釜中搅拌溶解，搅拌10~30min；
2）将硅烷偶联剂加入到酒石酸、丙二酸和聚乙烯醇中，搅拌形成硅烷溶液，然后加入氟化氢铵，混合均匀加入到步骤1）的反应釜中；
3）最后加入余下组分，搅拌均匀后装罐得到镀锌钢板用水性复合钝化液。
7.根据权利要求6所述的镀锌钢板用水性复合钝化液的制备方法，其特征在于：步骤1）中搅拌20min。
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| CN1615375A (zh) * | 2002-01-11 | 2005-05-11 | 日本帕卡濑精株式会社 | 处理基材的含水试剂、基材处理方法和已处理的基材 |
| CN101542018A (zh) * | 2006-11-21 | 2009-09-23 | 日本帕卡濑精株式会社 | 环保型预涂金属材料用水性表面处理剂、以及表面处理金属材料和环保型预涂金属材料 |
| CN102378828A (zh) * | 2009-03-31 | 2012-03-14 | 杰富意钢铁株式会社 | 镀锌系钢板 |
| CN103069046A (zh) * | 2010-09-29 | 2013-04-24 | 杰富意钢铁株式会社 | 镀锌系钢板的制造方法和镀锌系钢板 |
| CN103797157A (zh) * | 2011-09-14 | 2014-05-14 | 杰富意钢铁株式会社 | 镀锌系钢板用表面处理液和镀锌系钢板及其制造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1615375A (zh) * | 2002-01-11 | 2005-05-11 | 日本帕卡濑精株式会社 | 处理基材的含水试剂、基材处理方法和已处理的基材 |
| CN101542018A (zh) * | 2006-11-21 | 2009-09-23 | 日本帕卡濑精株式会社 | 环保型预涂金属材料用水性表面处理剂、以及表面处理金属材料和环保型预涂金属材料 |
| CN102378828A (zh) * | 2009-03-31 | 2012-03-14 | 杰富意钢铁株式会社 | 镀锌系钢板 |
| CN103069046A (zh) * | 2010-09-29 | 2013-04-24 | 杰富意钢铁株式会社 | 镀锌系钢板的制造方法和镀锌系钢板 |
| CN103797157A (zh) * | 2011-09-14 | 2014-05-14 | 杰富意钢铁株式会社 | 镀锌系钢板用表面处理液和镀锌系钢板及其制造方法 |
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