CN113088160B - 一种具有耐磨性的超疏水涂层及其制备方法 - Google Patents

一种具有耐磨性的超疏水涂层及其制备方法 Download PDF

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CN113088160B
CN113088160B CN202110343583.8A CN202110343583A CN113088160B CN 113088160 B CN113088160 B CN 113088160B CN 202110343583 A CN202110343583 A CN 202110343583A CN 113088160 B CN113088160 B CN 113088160B
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张达威
张帆
徐迪
马菱薇
王金科
黄尧
李晓刚
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University of Science and Technology Beijing USTB
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Abstract

本发明公开了一种具有耐磨性的超疏水涂层及其制备方法。该涂层由质量分数为20％～30％的二氧化硅‑碳纳米管杂化体和余量的树脂组成，涂层厚度为40μm～120μm。该涂层的制备首先是对纳米二氧化硅和多壁碳纳米管分别进行表面修饰，然后制备二氧化硅‑碳纳米管杂化体，接着将杂化体颗粒加入树脂并均匀分散，最后喷涂于金属表面，固化后得到耐磨超疏水涂层。制备出的二氧化硅‑碳纳米管杂化体通过缠绕互锁作用提高了复合涂层的耐磨性；当涂层表面受到摩擦磨损等损伤时，可以保持超疏水性能，从而有效阻隔溶液与基体的接触，起到保护基体材料的作用。本发明制备工艺简单，生产成本低，涂层的耐磨性和超疏水性能良好，具有广阔的应用前景。

Description

一种具有耐磨性的超疏水涂层及其制备方法
技术领域
本发明涉及一种具有耐磨性的超疏水涂层及其制备方法，属于微/纳米材料技术领域。
背景技术
在“生物仿生学”启发下，超疏水表面受到广泛的关注。超疏水表面应用于金属的腐蚀防护领域是一项重要的突破，通过提高材料表面的疏水性，来有效的阻隔水或腐蚀性离子对金属材料的表面侵蚀，降低金属的腐蚀速率，从而延长金属材料的使用寿命。然而，涂层在服役过程中会受到沙石磨损、人为挤压等物理损伤，使疏水性能下降，腐蚀介质易与金属基体接触，造成防腐性能的降低。因此，亟需开发具有优异耐磨性能的超疏水涂层。
通过制备表面具有微/纳米结构的复合涂层，提高涂层的表面粗糙度，可以使涂层表面具有超疏水性和耐磨性能。现有的用于提高涂层表面粗糙度的方法有化学转换膜法、刻蚀法、水热法、阳极氧化法、电沉积法、溶胶-凝胶法、模板法、纳米复合涂层等。其中，通过在树脂中添加纳米颗粒来制备耐磨超疏水涂层的方法具有简单、高效、成本低等特点。常用的纳米颗粒包括石墨烯、ZnO纳米棒、纳米TiO2等，但基于这些物质的复合涂层存在成本高、制备效率低等问题。所以在实际应用中需要选用价格更为低廉的物质来替代，纳米二氧化硅属于价格低廉的、常见的用来制备超疏水涂层的纳米颗粒。现有的使用纳米二氧化硅制备复合涂层的方法中，为了提高涂层的耐磨性能，通过添加硅橡胶、硫橡胶或其它橡胶来提高涂层的耐磨性能，但添加橡胶后由于纳米二氧化硅表面存在羟基，易吸水聚集，从而与有机物的相容性较差，使得二氧化硅的附着力较低，磨损后涂层很快失去超疏水能力；其次，有实验采用双连续相乳液法/双相分层法或与其它聚合物相结合使用来改善涂层和基底之间的附着力，但这些方法在使用过程中需要使用大量的有机溶剂，会产生大量的污染性气体，对环境污染较严重，且成本较高。因此亟需开发基于二氧化硅的新型超疏水涂层制备技术，提高涂层的耐磨性和实用性。
发明内容
本发明的目的是提供一种具有耐磨性能的超疏水涂层及其制备方法，选用价格低廉的纳米二氧化硅和多壁碳纳米管构筑杂化纳米颗粒，在涂层表面形成微/纳米结构实现超疏水性能，利用二者之间的缠绕互锁作用提高涂层的耐磨性，得到具有优异耐磨性的超疏水涂层。
为了达到上述目的，本发明采用的技术方案如下：
一种具有耐磨性的超疏水涂层，该涂层具有由纳米二氧化硅和多壁碳纳米管组成的杂化体颗粒以及与树脂基体组成的复合结构。
所述纳米二氧化硅-多壁碳纳米管杂化体的质量占树脂质量的20％～30％。
所述树脂为环氧树脂、聚氨酯、不饱和聚酯树脂、丙烯酸树脂中的任一种。
所述杂化体-树脂复合涂层的厚度为40μm～120μm。
所述多纳米二氧化硅颗粒的尺寸为20nm～200nm，多壁碳纳米管直径为10nm～50nm。
上述具有耐磨性的超疏水涂层的制备方法，包括如下步骤：
(1)制备纳米二氧化硅-多壁碳纳米管杂化体颗粒，在多壁碳纳米管表面修饰氨基，在纳米二氧化硅表面修饰环氧基；将表面带有氨基的多壁碳纳米管和表面带有环氧基的纳米二氧化硅放入丙酮溶剂中混合，制备纳米二氧化硅-多壁碳纳米管杂化体颗粒；
(2)将步骤(1)制备出的杂化体颗粒均匀分散于丙酮溶液中，然后与树脂均匀混合形成均质液体；
(3)将杂化体-树脂复合溶液通过喷涂的方式均匀喷涂于基材的表面，并在40℃～80℃的温度下固化12h～24h，得到具有优异耐磨性能的超疏水涂层。
步骤(1)所述在多壁碳纳米管表面修饰氨基，首先是将多壁碳纳米管均匀分散于浓度比为1:1的盐酸和硝酸的混合溶液中，回流使表面羧基化，然后在其表面接枝质量分数为0.5％～1.5％的硅烷偶联剂KH550。
步骤(1)所述在纳米二氧化硅表面修饰环氧基，是使用硅烷偶联剂KH560改性纳米二氧化硅，硅烷偶联剂KH560的质量分数为0.5％～1.5％。
步骤(1)所述将表面带有氨基的多壁碳纳米管和表面带有环氧基的纳米二氧化硅放入丙酮溶剂混合过程中，磁力搅拌64h～80h，控制两者质量比例为1:1～5:1，得到纳米二氧化硅-多壁碳纳米管杂化体颗粒。
本发明具有以下优点及突出性的技术效果：本发明制备了一种具有优异耐磨性能的超疏水涂层，首先制备纳米二氧化硅-多壁碳纳米管杂化体，之后将杂化体与树脂混合形成均质液体；接着将杂化体-树脂复合溶液均匀喷涂于基材的表面，最终得到具有耐磨性能的超疏水涂层。杂化体-树脂复合涂层表面的微/纳米结构提高了涂层的表面粗糙度，有助于实现超疏水性能；涂层和液体之间形成的气膜可以减小腐蚀介质与涂层表面的接触面积，使金属基体免受腐蚀损害。其次，杂化体-树脂复合涂层具有良好的耐磨性能，当涂层表面发生摩擦磨损时，缠绕互锁的杂化体使涂层表面具有良好的抗剥离能力，使涂层保持超疏水性能。本发明的制备工艺简单，成本低，涂层的耐磨性和超疏水性优异，具有广阔的应用前景。
附图说明
图1a为实施例1中制备的纳米二氧化硅-多壁碳纳米管杂化体的透射电镜照片；图1b为实施例1中制备的杂化体-树脂复合涂层扫描电镜图片；图1c为实施例1中制备的杂化体-树脂复合涂层的水接触角图片。
图2a为实施例2中制备的杂化体-树脂复合涂层粘接前的扫描电镜图片；图2b为实施例2中制备的杂化体-树脂复合涂层粘接后的扫描电镜图片。
图3为实施例3中制备的杂化体-树脂复合涂层循环粘接后涂层表面水接触角的变化曲线，以及多壁碳纳米管-树脂复合涂层循环粘接后涂层表面水接触角的变化曲线。
具体实施方式
下面结合实施例及附图对本发明做进一步的说明。下述实施例是说明性的，不是限定性的，不能以下述实施例来限定本发明的保护范围。
实施例1
1.将不锈钢片用砂纸打磨，再用丙酮、酒精、去离子水顺序超声清洗并用冷风吹干。
2.将直径为10nm的多壁碳纳米管分散于浓度比为1:1的盐酸和硝酸的混合液中，80℃回流12h，使表面羧基化；然后添加0.5％的硅烷偶联剂KH550，保持80℃，在300rpm的转速下搅拌24h，甲苯、去离子水依次清洗3次后，真空干燥得到带有氨基的多壁碳纳米管。
3.在20ml去离子水中加入0.5％的硅烷偶联剂KH560，在300rpm的转速下磁力搅拌30min，使其充分水解；加入粒径为20nm的纳米二氧化硅，在室温下超声2h；然后在60℃下干燥24h，得到表面带有环氧基的二氧化硅。
4.将改性纳米二氧化硅和带有氨基的多壁碳纳米管按1:1的比例加入到丙酮溶液中，在600rpm转速下室温搅拌64h，然后用去离子水抽滤清洗3次，80℃下干燥得到改性纳米二氧化硅-多壁碳纳米管杂化体。
5.将0.4g杂化体颗粒分散于丙酮溶液中，在600rpm的转速下，磁力搅拌30min。
6.将2g环氧树脂溶于含有杂化体颗粒的溶液中，在300rpm的转速下室温溶解成为均质溶液。
7.将杂化体-树脂复合溶液喷涂于不锈钢片表面。
8.在40℃下固化干燥24h，固化后涂层厚度为40μm。
图1a为实施例1中制备的改性纳米二氧化硅-多壁碳纳米管杂化体的透射电镜照片；图1b为实施例1中制备的杂化体-树脂复合涂层表面扫描电镜图片；图1c为实施例1中制备的杂化体-树脂复合涂层的水接触角图片。改性纳米二氧化硅和多壁碳纳米管通过化学键结合后，在涂层表面形成具有微/纳米结构的聚集体，复合涂层的水接触角达到159.2°。
实施例2
1.将铝片用砂纸打磨，再用丙酮、酒精、去离子水顺序超声清洗并用冷风吹干。
2.将直径为30nm的多壁碳纳米管分散于盐酸和硝酸的混合液中，80℃回流12h，使表面羧基化；然后添加1.0％的硅烷偶联剂KH550，保持80℃，在300rpm的转速下搅拌24h，甲苯、去离子水依次清洗3次后，真空干燥得到带有氨基的多壁碳纳米管。
3.在20ml去离子水中加入1.0％的硅烷偶联剂KH560，在300rpm的转速下磁力搅拌30min，使其充分水解；加入粒径为100nm的纳米二氧化硅，在室温下超声2h；然后在60℃下干燥24h，得到表面带有环氧基的二氧化硅。
4.改性纳米二氧化硅和带有氨基的多壁碳纳米管按3:1的比例加入到丙酮溶液中，在600rpm转速下室温搅拌70h，然后用去离子水抽滤清洗3次，80℃下干燥得到改性纳米二氧化硅-多壁碳纳米管杂化体。
5.将0.75g杂化体颗粒分散于丙酮溶液中，在600rpm的转速下，磁力搅拌30min。
6.将3g聚氨酯溶于含有杂化体颗粒的溶液中，在300rpm的转速下室温溶解成为均质溶液。
7.将杂化体-树脂复合溶液采用喷涂法喷涂于铝片表面。
8.在60℃下固化干燥18h，固化后涂层厚度为80μm。
9.采用3M胶带粘接杂化体-树脂复合涂层的表面，粘接次数为200次。
图2a为实施例2中制备的杂化体-树脂复合涂层表面粘接前的扫描电镜图片；图2b为实施例2中制备的杂化体-树脂复合涂层表面粘接200次后的扫描电镜图片。杂化体-树脂复合涂层表面的微/纳米结构提高了涂层的表面粗糙度，缠绕互锁的杂化体结构使涂层表面具有良好的抗剥离能力，即使涂层经过200次的循环粘接后，表面依旧保留微/纳米分层结构，有助于保持涂层的超疏水性能。
实施例3
1.将低合金钢用砂纸打磨，再用丙酮、酒精、去离子水顺序超声清洗并用冷风吹干。
2.将直径为50nm的多壁碳纳米管分散于盐酸和硝酸的混合液中，80℃回流12h，使表面羧基化；然后添加1.5％的硅烷偶联剂KH550，保持80℃，在300rpm的转速下搅拌24h，甲苯、去离子水依次清洗3次后，真空干燥得到带有氨基的多壁碳纳米管。
3.在20ml去离子水中加入1.5％的硅烷偶联剂KH560，在300rpm的转速下，磁力搅拌30min，使其充分水解；加入粒径为200nm的纳米二氧化硅，在室温下超声2h；然后在60℃下干燥24h，得到表面带有环氧基的二氧化硅。
4.改性纳米二氧化硅和带有氨基的多壁碳纳米管按5:1的比例加入到丙酮溶液中，在600rpm转速下，室温搅拌80h，然后用去离子水抽滤清洗3次，80℃下干燥得到改性纳米二氧化硅-多壁碳纳米管杂化体。
5.将0.6g杂化体颗粒分散于丙酮溶液中，在600rpm的转速下，磁力搅拌30min。
6.将2g丙烯酸树脂溶于含有杂化体颗粒的溶液中，在室温下，300rpm的转速下溶解成为均质溶液。
7.将杂化体-树脂复合溶液采用喷涂法喷涂于低合金钢表面。
8.在80℃下固化干燥12h，固化后涂层厚度为120μm。
9.采用3M胶带粘接杂化体-树脂复合涂层的表面，每循环10次，测试涂层的水接触角，循环以上工作，直至涂层水接触角低于150°。
图3为实施例3中制备的杂化体-树脂复合涂层循环粘接后涂层表面水接触角变化曲线，以及多壁碳纳米管-树脂复合涂层循环粘接后涂层表面水接触角的变化曲线。杂化体-树脂复合涂层在循环粘接300次后，水接触角仍然保持在150°，这是由于多壁碳纳米管和改性纳米二氧化硅之间的缠绕互锁作用，使涂层表面具有良好的抗剥离能力，涂层在摩擦过程中不易损坏。对于多壁碳纳米管-树脂复合涂层，由于多壁碳纳米管在涂层表面的附着能力较低，涂层的耐磨性能较差，在粘接80次后，水接触角便降到150°。以上研究证明了纳米二氧化硅-多壁碳纳米管的缠绕互锁结构在提高涂层耐磨性上的关键作用。

Claims (5)

1.一种具有耐磨性的超疏水涂层，其特征在于，涂层具有由纳米二氧化硅和多壁碳纳米管组成的杂化体颗粒以及与树脂基体组成的复合结构，纳米二氧化硅-多壁碳纳米管杂化体的质量占树脂质量的20%~30%，纳米二氧化硅颗粒的尺寸为20nm~200nm，多壁碳纳米管直径为10nm~50nm；
所述涂层的制备方法包括如下步骤：
（1）制备纳米二氧化硅-多壁碳纳米管杂化体颗粒，在多壁碳纳米管表面修饰氨基，在纳米二氧化硅表面修饰环氧基；将表面带有氨基的多壁碳纳米管和表面带有环氧基的纳米二氧化硅放入丙酮溶剂中混合，制备纳米二氧化硅-多壁碳纳米管杂化体颗粒；
所述在多壁碳纳米管表面修饰氨基，首先是将多壁碳纳米管均匀分散于浓度比为1:1的盐酸和硝酸的混合溶液中，回流使表面羧基化，然后在其表面接枝质量分数为0.5%~1.5%的硅烷偶联剂KH550；
所述在纳米二氧化硅表面修饰环氧基，是使用硅烷偶联剂KH560改性纳米二氧化硅，硅烷偶联剂KH560的质量分数为0.5%~1.5%；
（2）将步骤（1）制备出的杂化体颗粒均匀分散于丙酮溶液中，然后与树脂均匀混合形成均质液体；
（3）将杂化体-树脂复合溶液通过喷涂的方式均匀喷涂于基材的表面，并在40℃~80℃的温度下固化12h~24h，得到具有耐磨性的超疏水涂层。
2.根据权利要求1所述的具有耐磨性的超疏水涂层，其特征在于，所述树脂为环氧树脂、聚氨酯、不饱和聚酯树脂、丙烯酸树脂中的任一种。
3.根据权利要求1所述的具有耐磨性的超疏水涂层，其特征在于，所述杂化体-树脂复合涂层的厚度为40μm~120μm。
4.权利要求1-3任一项所述的具有耐磨性的超疏水涂层的制备方法，其特征在于，包括如下步骤：
（1）制备纳米二氧化硅-多壁碳纳米管杂化体颗粒，在多壁碳纳米管表面修饰氨基，在纳米二氧化硅表面修饰环氧基；将表面带有氨基的多壁碳纳米管和表面带有环氧基的纳米二氧化硅放入丙酮溶剂中混合，制备纳米二氧化硅-多壁碳纳米管杂化体颗粒；
所述在多壁碳纳米管表面修饰氨基，首先是将多壁碳纳米管均匀分散于浓度比为1:1的盐酸和硝酸的混合溶液中，回流使表面羧基化，然后在其表面接枝质量分数为0.5%~1.5%的硅烷偶联剂KH550；
所述在纳米二氧化硅表面修饰环氧基，是使用硅烷偶联剂KH560改性纳米二氧化硅，硅烷偶联剂KH560的质量分数为0.5%~1.5%；
（2）将步骤（1）制备出的杂化体颗粒均匀分散于丙酮溶液中，然后与树脂均匀混合形成均质液体；
（3）将杂化体-树脂复合溶液通过喷涂的方式均匀喷涂于基材的表面，并在40℃~80℃的温度下固化12h~24h，得到具有耐磨性的超疏水涂层。
5.根据权利要求4所述的具有耐磨性的超疏水涂层的制备方法，其特征在于，步骤（1）所述将表面带有氨基的多壁碳纳米管和表面带有环氧基的纳米二氧化硅放入丙酮溶剂混合过程中，磁力搅拌64h~80h，控制两者质量比例为1:1~5:1，得到纳米二氧化硅-多壁碳纳米管杂化体颗粒。
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