CN111575693B - 一种热镀锌钢管用无铬预钝化液 - Google Patents

一种热镀锌钢管用无铬预钝化液 Download PDF

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CN111575693B
CN111575693B CN202010541826.4A CN202010541826A CN111575693B CN 111575693 B CN111575693 B CN 111575693B CN 202010541826 A CN202010541826 A CN 202010541826A CN 111575693 B CN111575693 B CN 111575693B
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詹洪
陆飚
罗晓锋
郭文勇
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Wuhan Desytek Environmental Protection New Material Co ltd
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Abstract

本发明属于金属表面处理与腐蚀防护技术领域，具体涉及到一种热镀锌钢管用无铬预钝化液。该无铬预钝化液包括以下重量百分含量的组分：成膜剂5%~10%、氧化剂2%~4%、有机缓蚀剂2%~4%、无机稀土缓蚀剂2%~4%、水质稳定剂0.5%~2%、基材润湿剂0.5%~2%，水余量。其制备方法为：将成膜剂、氧化剂、无机稀土缓蚀剂及水质稳定剂溶于水中，搅拌，再加入有机缓蚀剂、基材润湿剂，搅拌均匀即可。本发明的无铬预钝化液不含铬及其他有毒有害物质，其槽液高温稳定性好，预钝后的热镀锌钢管外观光亮、内壁抗白锈能力好，可以代替铬酸酐预钝。

Description

一种热镀锌钢管用无铬预钝化液
技术领域
本发明属于金属表面处理与腐蚀防护技术领域，具体涉及到一种热镀锌钢管用无铬预钝化液。
背景技术
热镀锌技术是目前世界上钢材防腐蚀方法中一种最基本、最广泛的方法，热镀锌技术已广泛用于冶金、建材、电力、交通、农业等国民经济的各个领域。其中钢管热镀锌是将经加工过的表面洁净的钢管浸渍到锌液中进行热浸镀锌加工，得到表面性能优良的金属管件。热镀锌钢管已经应用到国民经济的各个方面，主导产业包括消防用管、建筑用管、生产物料传输用管、农业大棚支架用管等。据不完全统计，目前我国已有热镀锌钢管生产线170条以上，年生产能力超过6000万吨，我国已成为世界上最大的热镀锌钢管生产国。
热镀锌钢管的生产工序流程为：黑管上料→酸洗→水漂洗→浸助镀溶剂→烘干→热浸镀锌→外吹、内吹→水冷/预钝化→钝化→喷码、检查、包装。钢管在外吹、内吹完成后浸入水冷工序，水冷工序的目的是让钢管尽快冷却，避免钢管热镀锌层长时间处于高温导致氧化变暗。目前有部分钢管生产企业的水冷工序的水冷槽装的是纯净水，但更多的钢管生产企业会在水冷槽的冷却水中加入约0.1～0.5％的铬酐对热镀锌钢管进行预钝化。预钝化的目的有几点：一是防止钢管表面出现水纹、水斑；二是防止钢管在水冷至终钝工序这段时间出现锈蚀；更重要的一点是防止钢管在储存期间内壁出现腐蚀(因为热镀锌钢管的吹镀生产线终钝的喷淋钝化无法对钢管内壁进行钝化保护)。
含有铬酐的冷却水在循环运行过程中会产生大量的铬酸雾和含铬废水，严重危害作业工人的身体健康，同时含铬废水的跑冒滴漏会严重污染环境。所以热镀锌钢管企业急需一种具有良好耐蚀性能的、但不含铬及其他有毒有害物质的环保预钝化液来替代铬酐进行预钝化。
而由于热镀锌钢管水冷工序的工况的特殊性(预钝化液的高温稳定性、预钝化槽液必须对铁质槽体无腐蚀、预钝化液需对锌离子有较高容忍度、预钝化液对锌层须有一定的耐蚀保护能力)，相关的研究几乎未见报道，市面上也没有能够替代铬酐的预钝化液可供热镀锌生产企业使用。
发明内容
本发明的目的是：提供一种满足热镀锌钢管工艺工况要求、可以替代铬酐的无铬预钝化液。该无铬预钝化液不含铬及其他有毒有害物质，其槽液高温稳定性好，预钝后的热镀锌钢管外观光亮、耐蚀性能好、内壁抗白锈能力好，可以代替铬酸酐预钝。
为实现本发明的目的，本发明的发明人针对无铬预钝化的使用工况及热镀锌钢管企业的要求，确定如下技术开发思路：
①预钝化槽液长时间保持在70℃～90℃之间，局部瞬时温度达到100℃以上，要求预钝化的高温稳定性要好，所以预钝化液的配方中不宜使用有机树脂；
②预钝化槽液中钝化剂的浓度极低，且必须要保证一定的耐蚀性能，所以预钝化液的配方中需要有成膜剂及缓蚀剂。
③由于水质的波动，预钝化槽液中会渐渐富集一部分的钙镁离子。另外，槽液中会有锌、铁离子的富集，这就要求预钝化对这些金属离子有一定的容忍度，且要保证这些离子的富集不影响预钝化液性能，所以预钝化液的配方中需要有水质稳定剂。
根据以上技术开发思路，经过发明人的无数次实验和测试，发现采用如下技术方案可以完成本发明的发明目的：
一种热镀锌钢管用无铬预钝化液，其由以下重量百分含量的原料组成：
成膜助剂5％～10％、氧化剂2％～4％、有机缓蚀剂2％～4％、无机稀土缓蚀剂2％～4％、水质稳定剂0.5％～2％、基材润湿剂0.5％～2％、水余量。
进一步的，所述的成膜助剂选自植酸、磷酸或磷酸二氢锌中的一种或几种。
进一步的，所述的氧化剂选自硝酸钾、硝酸钠、硝酸钙、硝酸铝、硝酸镁、硝酸锌、硝酸镍、硝酸钴中的一种或几种。
进一步的，所述的有机缓蚀剂选自三乙醇胺硼酸酯、聚乙二醇硼酸酯、油酸二乙醇酰胺硼酸酯中的一种或几种。
进一步的，所述的无机稀土缓蚀剂为硝酸铈或硝酸镧。
进一步的，所述的水质稳定剂选自EDTA-2Na、柠檬酸、酒石酸中的一种或几种。
进一步的，所述的基材润湿剂为阴离子表面活性剂或非离子表面活性剂。
进一步的，所述阴离子表面活性剂选自十二烷基苯磺酸钠或二(2-乙基己基)磺基琥珀酸酯钠。
进一步的，所述非离子表面活性剂为聚氧乙烯辛基苯酚醚-10(OP-10)。
本发明还提供了一种上述的热镀锌钢管用无铬预钝化液的制备方法，具体操作为：先将成膜助剂、氧化剂、无机稀土缓蚀剂及水质稳定剂溶于水中，搅拌分散均匀，再向其中加入有机缓蚀剂、基材润湿剂，搅拌均匀即可。
本发明的热镀锌钢管用无铬预钝化液中，成膜助剂的作用是构成预钝化膜的骨架，其在预钝化液中占主要部分。氧化剂的作用是促进成膜助剂在热镀锌层表面迅速成膜。有机缓蚀剂和无机稀土缓蚀剂共同协同作用，提供钝化膜良好的耐蚀性能。水质稳定剂提高预钝化液对钙、镁、锌、铁离子的容忍度，提高预钝化液的寿命。基材润湿剂提高预钝化液对热镀锌钢管的润湿能力，保证预钝化液在基材表面成膜的均匀性。
与现有技术相比，本发明的优点和有益效果如下：
本发明的无铬预钝化液不含铬及其他有毒有害物质，属于环保钝化液；本发明的无铬预钝化液配制的槽液高温稳定性好(在80℃以上使用依然稳定，而且耐蚀性能好)，盐雾试验的结果表明使用本发明的预钝化液预钝后的热镀锌钢管外观光亮、耐蚀性能好、内壁抗白锈能力好；本发明的无铬预钝化液可以代替铬酸酐预钝，有望在热镀锌钢管企业得到广泛应用，具有非常大的工业价值和社会价值。
具体实施方式
通过下述实施例对本发明的技术方案再进行具体说明，但本发明不受这些实施例限定。
以下实施例中，所有原料均为市购普通原料。以下实施例中，预钝化的钢管耐蚀性检验采用中性盐雾加速腐蚀试验，采用JH-60型盐雾腐蚀试验箱，按GB/T10125-2012《人造气氛腐蚀试验盐雾试验》执行。
对比例
以质量百分浓度为0.5％的铬酸酐水溶液作为预钝化槽液，将其加热至80℃后，将刚制备的热镀锌管浸入到预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达3h无腐蚀。
实施例1：
一种热镀锌钢管用无铬预钝化液，包括的原料及各个原料的量为：成膜助剂10g、氧化剂4g、有机缓蚀剂2g、无机稀土缓蚀剂2g、水质稳定剂1g、基材润湿剂1g、水80g。
其制备方法为：在80g水中加入10g成膜助剂、4g氧化剂、2g无机稀土缓蚀剂和1g水质稳定剂，搅拌10min使其分散均匀，再向其中加入2g有机缓蚀剂和1g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为植酸，氧化剂为六水合硝酸锌，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为EDTA-2Na，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到无铬预钝槽液中60秒，然后将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达3h无腐蚀。
实施例2：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂5g、氧化剂2g、有机缓蚀剂4g、无机稀土缓蚀剂4g、水质稳定剂2g、基材润湿剂2g、水81g。
其制备方法为：在81g水中加入5g成膜助剂、2g氧化剂、4g无机稀土缓蚀剂和2g水质稳定剂，搅拌10min让其分散均匀，再向其中加入4g有机缓蚀剂和2g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为磷酸(浓度为85wt％，以下实施例同，不赘述)、氧化剂为六水合硝酸锌，有机缓蚀剂为油酸二乙醇酰胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为柠檬酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达2h无腐蚀。
实施例3：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂6g、氧化剂3g、有机缓蚀剂4g、无机稀土缓蚀剂3g、水质稳定剂0.5g、基材润湿剂1.5g、水82g。
其制备方法为：在82g水中加入6g成膜助剂、3g氧化剂、3g无机稀土缓蚀剂和0.5g水质稳定剂，搅拌10min让其分散均匀，再向其中加入4g有机缓蚀剂和1.5g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为植酸和磷酸二氢锌的混合物，且植酸和磷酸二氢锌的重量比为1:1，氧化剂为硝酸钠，有机缓蚀剂为聚乙二醇硼酸酯(购自平顶山市华宇助剂厂，为分子量400的聚乙二醇和硼酸以3：1的摩尔比进行酯化反应所得)，无机稀土缓蚀剂为硝酸镧(La(NO3)3·6H2O)，水质稳定剂为酒石酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达3h无腐蚀。
实施例4：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂7g、氧化剂3g、有机缓蚀剂3g、无机稀土缓蚀剂4g、水质稳定剂1g、基材润湿剂2g、水80g。
其制备方法为：在80g水中加入7g成膜助剂、3g氧化剂、4g无机稀土缓蚀剂和1g水质稳定剂，搅拌10min让其分散均匀，再向其中加入3g有机缓蚀剂和2g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为磷酸和磷酸二氢锌的混合物、且磷酸和磷酸二氢锌的重量比为1:1，氧化剂为硝酸钾，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为柠檬酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达2.5h无腐蚀。
实施例5：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂8g、氧化剂4g、有机缓蚀剂3g、无机稀土缓蚀剂3g、水质稳定剂1.5g、基材润湿剂0.5g、水80g。
其制备方法为：在80g水中加入8g成膜助剂、4g氧化剂、3g无机稀土缓蚀剂和1.5g水质稳定剂，搅拌10min让其分散均匀，再向其中加入3g有机缓蚀剂和0.5g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为植酸和磷酸的混合物，且植酸和磷酸的重量比为1:1，氧化剂为硝酸镍，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为酒石酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到上述无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达3h无腐蚀。
实施例6：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂9g、氧化剂4g、有机缓蚀剂3g、无机稀土缓蚀剂2g、水质稳定剂1g、基材润湿剂1g、水80g。
其制备方法为：在80g水中加入9g成膜助剂、4g氧化剂、2g无机稀土缓蚀剂和1g水质稳定剂，搅拌10min让其分散均匀，再向其中加入3g有机缓蚀剂和1g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为植酸，氧化剂为硝酸钴(Co(NO3)2·6H2O)，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸镧，水质稳定剂为柠檬酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到上述无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达4h无腐蚀。
实施例7：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂8g、氧化剂4g、有机缓蚀剂2g、无机稀土缓蚀剂4g、水质稳定剂1g、基材润湿剂1g、水80g。
其制备方法为：在80g水中加入8g成膜助剂、4g氧化剂、4g无机稀土缓蚀剂和1g水质稳定剂，搅拌10min让其分散均匀，再向其中加入2g有机缓蚀剂和1g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为磷酸，氧化剂为六水合硝酸锌，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为EDTA-2Na，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，加热至80℃，此时预钝槽液为清澈透明，将刚制备的热镀锌管浸入到上述无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达3.5h无腐蚀。
实施例8：
一种热镀锌钢管用无铬预钝化液，其包括的原料及各个原料的量为：成膜助剂8g、氧化剂4g、有机缓蚀剂4g、无机稀土缓蚀剂2g、水质稳定剂1g、基材润湿剂1g、水80g。
其制备方法为：在80g水中加入8g成膜助剂、4g氧化剂、2g无机稀土缓蚀剂和1g水质稳定剂，搅拌10min让其分散均匀，再向其中加入4g有机缓蚀剂和1g基材润湿剂，搅拌均匀即得到热镀锌管用无铬预钝化液。
上述成膜助剂为磷酸和磷酸二氢锌混合物、且磷酸和磷酸二氢锌的重量比为1:1，氧化剂为六水合硝酸锌，有机缓蚀剂为三乙醇胺硼酸酯，无机稀土缓蚀剂为六水合硝酸铈，水质稳定剂为酒石酸，基材润湿剂为OP-10。
将该热镀锌钢管用无铬预钝化液10g加入到2000g水中搅拌均匀配成无铬预钝槽液，此时加热至80℃，预钝槽液为清澈透明，将刚制备的热镀锌管浸入到上述无铬预钝槽液中60秒，将预钝化后的热镀锌管取出，自然放置30min后，观察热镀锌管的表面光亮，盐雾实验达4h无腐蚀。
实施例9实际工业应用案例
于河北唐山某大型热镀锌钢管厂，在镀锌8线(镀锌钢管管径为3～4寸，壁厚为2～4mm，每24h产量平均为350吨)上使用本发明实施例1的热镀锌钢管用无铬预钝化液，初始配比为：100吨的水冷槽中加入实施例1制备的无铬预钝化液150kg，后续添加量为每日10kg，截止到2020年5月已运行9个月，期间槽液高温稳定好(在60～90℃下运行，槽液无沉淀或浑浊等异常情况发生)，生产出的预钝化钢管表面光亮，盐雾实验稳定在3h以上，预钝后钢管在实际室外储存过程中6个月以上(2019年8月～2020年2月)，其内、外壁均没有产生腐蚀，无铬预钝化液的综合消耗量为0.030kg/吨钢管。
于河北唐山某大型热镀锌钢管厂，在镀锌5线和6线(管径为1寸，壁厚为1～3mm，每条生产线每24h产量平均为300吨)上使用本发明实施例1的热镀锌钢管用无铬预钝化液，初始配比为：100吨的水冷槽中加入实施例1制备的无铬预钝化液加入150kg，后续添加量为每日10kg，截止到2020年5月已运行7个月，期间槽液高温稳定好，生产出的预钝化钢管表面光亮，盐雾实验稳定在2.5h以上，预钝的钢管在实际室外储存过程中6个月以上(2019年10月～2020年4月)内外壁均没有产生腐蚀，无铬预钝化液的综合消耗量为0.035kg/吨钢管。
本发明的热镀锌钢管用无铬预钝化液实际上线使用效果良好，预钝的钢管各项性能完全满足要求，消耗量较低，客户使用满意，完全可代替铬酐预钝，具有非常大的工业价值和社会价值。

Claims (4)

1.一种热镀锌钢管用无铬预钝化液，其特征在于，包括的原料组分及各个原料组分的重量百分比为：
成膜剂5%~10%、氧化剂2%~4%、有机缓蚀剂2%~4%、无机稀土缓蚀剂2%~4%、水质稳定剂0.5%~2%、基材润湿剂0.5%~2%，水余量；
所述的有机缓蚀剂选自三乙醇胺硼酸酯、聚乙二醇硼酸酯、油酸二乙醇酰胺硼酸酯中的一种或几种；
所述的无机稀土缓蚀剂选自硝酸铈或硝酸镧，
所述的成膜剂为植酸、磷酸或磷酸二氢锌中的一种或几种；
所述的氧化剂为硝酸钾、硝酸钠、硝酸钙、硝酸铝、硝酸镁、硝酸锌、硝酸镍、硝酸钴中的一种或几种。
2.根据权利要求1所述的热镀锌钢管用无铬预钝化液，其特征在于，所述的水质稳定剂选自EDTA-2Na、柠檬酸、酒石酸中的一种或几种。
3.根据权利要求1所述的热镀锌钢管用无铬预钝化液，其特征在于，所述的基材润湿剂为阴离子表面活性剂或非离子表面活性剂。
4.权利要求1所述的热镀锌钢管用无铬预钝化液的制备方法，其特征在于，步骤如下：先将成膜剂、氧化剂、无机稀土缓蚀剂及水质稳定剂溶于水中，搅拌分散均匀，再加入有机缓蚀剂、基材润湿剂，搅拌均匀即可。
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