CN116179001A - 一种水性无铬复合涂料及其涂料的制备方法、使用方法 - Google Patents
一种水性无铬复合涂料及其涂料的制备方法、使用方法 Download PDFInfo
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Abstract
一种水性无铬复合涂料及其涂料的制备方法、使用方法，涉及防腐蚀涂层技术领域，其包括以下组分的原料：锌铝粉、防污剂、粘接剂、缓蚀剂、分散剂、保护剂、增稠剂、消泡剂、去离子水。本发明制备的涂料涂覆到基体得到的涂层可具有良好的附着力和耐腐蚀性能，同时由于避免了六价铬的使用，因此对环境的污染影响更低。
Description
技术领域
本发明涉及防腐蚀涂层技术领域，尤其指一种水性无铬复合涂料及其涂料的制备方法、使用方法。
背景技术
在海洋基建、轮船运行等人类海洋活动中，面临着严峻的金属腐蚀和生物污损问题。这些问题会导致降低航行效率、影响船舶及基站的垫声学仪器、造成管道堵塞、各类仪器及机械的运转失灵、加速集体腐蚀。
目前常用的防治海洋生物污损以降低金属腐蚀的方法主要有物理防污法、电解法、使用防污金属或者合金、涂覆防污涂层。通过实践证明，涂覆防污涂层来防污损是最经济有效的方法，其主要是在基体表面涂覆一层防污涂料，让涂层涂料在海水中慢慢的把毒性物质释放出去，从而抑制污损生物的生长。但现有防污涂料涂层都存在污染环境等问题。
发明内容
本发明的目的之一在于提供一种水性无铬复合涂料，用于在金属表面涂覆形成耐污损、防腐蚀复合涂层，同时以降低对环境的污染。
为了解决上述技术问题，本发明采用如下技术方案：一种水性无铬复合涂料，包括以下组分的原料：锌铝粉、防污剂、粘接剂、缓蚀剂、分散剂、保护剂、增稠剂、消泡剂、去离子水。
优选地，所述原料中的组分配比为：锌铝粉3.5g、防污剂1.5g、粘接剂2g、缓蚀剂0.35g、分散剂0.40g、保护剂1.6g、增稠剂0.1g、消泡剂3-4滴、余量的去离子水；其中，防污剂为铜粉；粘接剂为AC-66，即γ-缩水甘油醚丙基三甲氧基硅烷，该粘接剂可提高聚合物涂层或粘合剂对金属或其它聚合物表面的粘附性；缓蚀剂为Mo12Na3O40P；分散剂为吐温20以及（CH2OH）2，两种组分混合形成分散剂，具体的混合比例则不作限定；增稠剂为羟乙基纤维素；而保护剂和消泡剂的具体选用可以是常规的，因此不对其做出限定。
制备上述水性无铬复合涂料的方法包括以下步骤：
在容器内加入适量的粘接剂、分散剂、保护剂、消泡剂、去离子水，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入锌铝粉和防污剂，待锌铝粉和防污剂润湿后加入适量的缓蚀剂和增稠剂，最后搅拌3个小时左右直至各组分混合均匀，得到外层水性无铬复合涂料；
在容器内加入适量的粘接剂、分散剂、保护剂、消泡剂、去离子水，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入锌铝粉，待锌铝粉润湿后加入适量的缓蚀剂和增稠剂，最后搅拌3个小时左右直至各组分混合均匀，得到内层水性无铬复合涂料。
上述水性无铬复合涂料的使用方法则包括以下步骤：
预处理：采用砂纸将基体表面磨平除锈后，再放入碱性溶液中浸泡40分钟除油，然后用酒精清洗干净并吹干待用；
一次涂覆：将基体浸涂至内层水性无铬复合涂料中，然后去除基体表面多余的溶液，使得制得的涂层表面均匀，然后烘干及烧结，再于室温下冷却，得到涂覆有内层水性无铬复合涂料涂层的基体；
二次涂覆：将一次涂覆后得到的基体浸涂至外层水性无铬复合涂料中，然后去除基体表面多余的溶液，使得制得的涂层表面均匀，然后烘干及烧结，再于室温下冷却，即可得到涂覆有复合涂层的基体。
优选地，在一次涂覆和二次涂覆步骤中，均是通过将基体旋转来甩出表面多余的溶液。
更优选地，在一次涂覆和二次涂覆步骤中，烘干及烧结的方式均是先预烘8-10分钟，再高温烧结25-30分钟。
更优选地，预烘温度为100℃，烧结温度为280℃。
本发明制备的涂料涂覆到基体得到的涂层可具有良好的附着力和耐腐蚀性能，同时由于避免了六价铬的使用，因此对环境的污染影响更低。
附图说明
图1为本发明实施例中涂层截面的SEM示意图；
图2为本发明实施例中涂层表面的SEM示意图。
具体实施方式
为了便于本领域技术人员的理解，下面结合实施例与附图对本发明作进一步的说明，实施方式提及的内容并非对本发明的限定。
实施例1
取粘接剂（AC-66）1g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉和1.5g铜粉，待锌铝粉和铜粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到外层水性无铬复合涂料。
取粘接剂（AC-66）1g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉，待锌铝粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到内层水性无铬复合涂料。
采用砂纸将基体表面磨平除锈后，再放入碱性溶液中浸泡40分钟除油，然后用酒精清洗干净并吹干待用。
将基体浸涂至内层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到涂覆有内层水性无铬复合涂料涂层的基体。
接着，将涂覆有内层水性无铬复合涂料涂层的基体浸涂至外层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到最终的涂覆有水性无铬复合涂料涂层的基体。
实施例2
取粘接剂（AC-66）2g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉和1.5g铜粉，待锌铝粉和铜粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到外层水性无铬复合涂料。
取粘接剂（AC-66）2g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉，待锌铝粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到内层水性无铬复合涂料。
采用砂纸将基体表面磨平除锈后，再放入碱性溶液中浸泡40分钟除油，然后用酒精清洗干净并吹干待用。
将基体浸涂至内层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到涂覆有内层水性无铬复合涂料涂层的基体。
接着，将涂覆有内层水性无铬复合涂料涂层的基体浸涂至外层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到最终的涂覆有水性无铬复合涂料涂层的基体。
实施例3
取粘接剂（AC-66）4g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉和1.5g铜粉，待锌铝粉和铜粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到外层水性无铬复合涂料。
取粘接剂（AC-66）4g、分散剂（吐温20以及（CH2OH）2）0.40g、保护剂1.6g、消泡剂3-4滴、余量的去离子水加入到容器内，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入3.5g锌铝粉，待锌铝粉润湿后加入0.35g的 Mo12Na3O40P和0.1g的羟乙基纤维素、最后搅拌3个小时直至各组分混合均匀，得到内层水性无铬复合涂料。
采用砂纸将基体表面磨平除锈后，再放入碱性溶液中浸泡40分钟除油，然后用酒精清洗干净并吹干待用。
将基体浸涂至内层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到涂覆有内层水性无铬复合涂料涂层的基体。
接着，将涂覆有内层水性无铬复合涂料涂层的基体浸涂至外层水性无铬复合涂料中，然后通过将基体旋转来甩出表面多余的溶液，使得制得的涂层表面均匀，然后以100℃烘干10分钟，再以280℃烧结30分钟，再于室温下冷却，得到最终的涂覆有水性无铬复合涂料涂层的基体。
涂料指标测试分析
（1）使用涂-4杯粘度计，对3组实施例所制得的外层水性无铬复合涂料分别进行粘度测试，每个涂料都进行四次测试，然后取平均值，最终测出涂液的粘度结果为分别为实施例1-3：39S、37S、35S。结果证明均属于涂液粘度的正常范围。
（2）细度测试分析：使用国际规定设计的刮板细度计，分别对3组实施例制得的外层水性无铬复合涂料进行细度测试，测试结果为均在15um左右，误差范围较小，结果表明涂液的颗粒较小，涂液覆盖的均匀性和涂层的致密性较好。
涂层性能测试分析
（1）附着力测试：采用胶带法和划格法结合来对3组实施例中的基体表面的涂层进行测试，其测试结果均为0级，也就是ISO等级0，为最高等的附着力水平。
（2）厚度测试分析：对3组实施例中的基体表面的涂层进行电镜扫描，通过观察可以看出涂层鳞片状的金属粉层层铺垫而成，结构非常紧密，涂层总厚度大约为：实施例1厚度48um，实施例2厚度50um，实施例3厚度47um。
（3）外观测试分析：3组实施例的涂层均呈现灰色的金属光泽，涂层连续且平整，厚度均匀。
涂层耐腐蚀性能测试分析
（1）耐盐水（5wt.%NaCl）性能测试分析：
实施例1：50天无明显锈蚀、涂层的表面仍较为平整，没有出现不平现象；100天试样表面出现明显的白锈和不平整现象，涂层结构已经受到盐水腐蚀破坏，但未出现明显的红锈，说明涂层此时对基体有一定的保护作用；150天后出现大面积红锈，涂层已经完全破坏，基体收到大面积的腐蚀。
实施例2：50天无明显锈蚀、涂层的表面仍较为平整，没有出现不平现象；120天试样表面出现明显的白锈和不平整现象，涂层结构已经受到盐水腐蚀破坏，但未出现明显的红锈，说明涂层此时对基体有一定的保护作用；180天后出现大面积红锈，涂层已经完全破坏，基体收到大面积的腐蚀。
实施例3：50天无明显锈蚀、涂层的表面仍较为平整，没有出现不平现象；110天试样表面出现明显的白锈和不平整现象，涂层结构已经受到盐水腐蚀破坏，但未出现明显的红锈，说明涂层此时对基体有一定的保护作用；140天后出现大面积红锈，涂层已经完全破坏，基体收到大面积的腐蚀。
（2）电化学测试分析：对经过盐水腐蚀100天后的涂层样件（制成电化学样件）与裸钢样件浸泡在3.5%NaCl溶液中进行动电位极化曲线测试，试验结果表明经过腐蚀处理后的实施例1的涂层样件电位为-1.010V，实施例2的涂层样件电位为-1.016V，实施例3的涂层样件电位为-1.012V。而Q235钢的电位为-0.667V，各实施例的结果明显比基体电位低得多，说明涂层为基体提供阴极保护作用。
（3）中性盐雾测试分析：在中性盐雾连续试验下，实施例1在95天后出现红锈，实施例2在100天后出现红锈，实施例3在90天后出现红锈。
（4）复合涂层的SEM表面形貌及CRD物相分析：特殊致密的表面结构，赋予涂层优异的性能，能为基体提供良好的物理屏蔽。腐蚀产物主要由锌铝的碱性化合物和铜氯化合物，其中铜氯化合物对海洋污损生物生长起到抑制作用。
本发明所提供的水性无铬复合涂料，在制备得到内层涂料和外层涂料后分别涂覆到基体表面，相较于无铬的锌铝涂层，加入铜使其耐污损能力更好，而由于只在外层涂料中含有铜粉组分，因此在很大程度上节约了成本，同时又保证了所形成的涂层具备足够的厚度和耐腐蚀性能，如图1所示，内层主要为Zn-AI结构，外层主要为Cu-Zn-AI结构。其次，通过图2可以看出，涂层形成了迷宫式的结构，这种结构可延长腐蚀介质向基体渗透的路径，从而进一步起到腐蚀产物的屏蔽作用，配合牺牲阳极保护的机制，涂层腐蚀产物堆积至涂层表面继续给基体提供保护作用和抑制海洋生物的生长，从而起到了双重屏蔽的效果，让本发明的涂层结构能够具备优异的综合防腐蚀性能。
而之所以能够形成迷宫式结构，主要是因为选用了适量的AC-66作为粘接剂，在烧结后，本身的多层次结构能够在该粘接剂的作用下很好的实现堆叠，进而形成多回路的迷宫式结构。不仅如此，内层加外层式的涂层涂覆方式，又进一步加大了这种迷宫式结构的复杂性，因为在内层涂料完成烧结后形成内层涂层后，再涂覆外层涂料，外层涂料中的一部分也会渗入到内层涂层的迷宫式结构中去，从而对腐蚀介质的进入形成了更大程度的阻挡效果。
为了让本领域普通技术人员更方便地理解本发明相对于现有技术的改进之处，本发明的一些附图和描述已经被简化，并且上述实施例为本发明较佳的实现方案，除此之外，本发明还可以其它方式实现，在不脱离本技术方案构思的前提下任何显而易见的替换均在本发明的保护范围之内。
Claims (7)
1.一种水性无铬复合涂料，其特征在于，包括以下组分的原料：锌铝粉、防污剂、粘接剂、缓蚀剂、分散剂、保护剂、增稠剂、消泡剂、去离子水。
2.根据权利要求1所述的水性无铬复合涂料，其特征在于，所述原料中的组分配比为：
锌铝粉3.5g、防污剂1.5g、粘接剂2g、缓蚀剂0.35g、分散剂0.40g、保护剂1.6g、增稠剂0.1g、消泡剂3-4滴、余量的去离子水；
其中，防污剂为铜粉，粘接剂为AC-66，缓蚀剂为Mo12Na3O40P，分散剂为吐温20以及（CH2OH）2，增稠剂为羟乙基纤维素。
3.如权利要求1-2所述的水性无铬复合涂料的制备方法，其特征在于，包括以下步骤：
在容器内加入适量的粘接剂、分散剂、保护剂、消泡剂、去离子水，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入锌铝粉和防污剂，待锌铝粉和防污剂润湿后加入适量的缓蚀剂和增稠剂，最后搅拌2.5-3.5小时直至各组分混合均匀，得到外层水性无铬复合涂料；
在容器内加入适量的粘接剂、分散剂、保护剂、消泡剂、去离子水，然后在集热式恒温加热磁力搅拌器搅拌下缓慢加入锌铝粉，待锌铝粉润湿后加入适量的缓蚀剂和增稠剂，最后搅拌2.5-3.5小时直至各组分混合均匀，得到内层水性无铬复合涂料。
4.一种水性无铬复合涂料的使用方法，该水性无铬复合涂料采用权利要求3所述的制备方法制备得到，其特征在于，包括以下步骤：
预处理：采用砂纸将基体表面磨平除锈后，再放入碱性溶液中浸泡40分钟除油，然后用酒精清洗干净并吹干待用；
一次涂覆：将基体浸涂至内层水性无铬复合涂料中，然后去除基体表面多余的溶液，使得制得的涂层表面均匀，然后烘干及烧结，再于室温下冷却，得到涂覆有内层水性无铬复合涂料涂层的基体；
二次涂覆：将一次涂覆后得到的基体浸涂至外层水性无铬复合涂料中，然后去除基体表面多余的溶液，使得制得的涂层表面均匀，然后烘干及烧结，再于室温下冷却，即可得到涂覆有复合涂层的基体。
5.根据权利要求4所述的水性无铬复合涂料的使用方法，其特征在于：在一次涂覆和二次涂覆步骤中，均是通过将基体旋转来甩出表面多余的溶液。
6.根据权利要求4所述的水性无铬复合涂料的使用方法，其特征在于：在一次涂覆和二次涂覆步骤中，烘干及烧结的方式均是先预烘8-10分钟，再高温烧结25-30分钟。
7.根据权利要求6所述的水性无铬复合涂料的使用方法，其特征在于：预烘温度为100℃，烧结温度为280℃。
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