CN111019447B - 一种水性耐磨超双疏纳米复合涂层及其制备方法 - Google Patents

一种水性耐磨超双疏纳米复合涂层及其制备方法 Download PDF

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CN111019447B
CN111019447B CN201911048744.XA CN201911048744A CN111019447B CN 111019447 B CN111019447 B CN 111019447B CN 201911048744 A CN201911048744 A CN 201911048744A CN 111019447 B CN111019447 B CN 111019447B
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张友法
杨永玲
余新泉
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Abstract

一种水性耐磨超双疏纳米复合涂层及其制备方法,先制备超双疏二氧化硅纳米颗粒粉体的；再制备水性耐磨超双疏纳米复合涂料；最后制备超双疏涂层。本发明采用氟硅烷、水性硅溶胶、水性树脂等常规原料制备水性耐磨超双疏纳米复合涂层，无任何有毒的有机溶剂，从源头上避免了有毒物质的残留或处理不完全，满足环保要求，也降低了生产成本。在水性体系中制备的水性耐磨超双疏纳米复合涂层不燃、VOC低，适用于通风不畅、高温、有明火等多种苛刻场合，便于生产、储存、运输和施工作业，具有很好的应用前景。所述超双疏二氧化硅纳米颗粒粉体制备中，使用复配硅溶胶可以获得纳米尺度团聚纳米颗粒，增加纳米颗粒粗糙度，从而增加涂层粗糙度。

Description

一种水性耐磨超双疏纳米复合涂层及其制备方法
技术领域
本发明属于涂层制备领域，涉及一种水性耐磨超双疏纳米复合涂层及其制备方法。
背景技术
超疏水表面由于其特殊的表面润湿性使其在自清洁、防冰、防雾、防腐蚀、绿色打印、传感器以及油水分离等多个领域均有重要的应用前景。其中，水性超疏水涂料由于不使用乙醇、丙酮、氯仿等有机溶剂，制备工艺简单，成本较低，适合大面积制备等特点受到人们的广泛关注。但是目前水性超疏水领域存在的问题是：耐磨性差，不能超疏油，或者二者不能兼顾，这些缺点大大的限制了水性超疏水涂层的使用。
目前常用的提高水性超疏水涂层疏油性的方法通过用表面活性剂将低表面能物质溶在水中，制备出的涂层可以超疏油，但由于表面活性剂会存在极性反转问题导致涂层表面的氢氧键外翻，超疏油效果不稳定。常用的提高耐磨性的方法
是通过两步成膜法，以有机树脂为粘结剂将超疏水涂层与基底粘结起来，虽然其增韧效果非常明显，大大的拓展了其应用范围，但是，有机树脂会包埋低表面能颗粒，导致超疏油效果差。
受启发于荷叶表面微纳米结构，将经过超双疏改性的纳米二氧化硅加入到水溶液中，同时加入水性树脂提高基底粘附力，以达到耐磨超双疏效果。
发明内容
解决的技术问题：本发明为了拓展水性超疏水涂层在实际生活中应用，针对其耐磨性差、超疏油性和耐磨性不能兼顾等问题，提供一种水性耐磨超双疏纳米复合涂层及其制备方法。该方法工艺简单、可室温喷涂、绿色环保、对环境和人体无害，在自清洁、防冰抗结露等领域具有广泛的应用前景。
技术方案：一种水性耐磨超双疏纳米复合涂层的制备方法，步骤为：（1）超双疏二氧化硅纳米颗粒粉体的制备：将2-6份的氨水溶液分散于80份的无水乙醇溶液中，转速50-200rpm条件下，50℃下搅拌2-4min，随后加入10-15份复配硅溶胶，继续搅拌10min后加入0.1-1份正硅酸四乙酯，继续搅拌30min，加入0.1-1份低表面能物质，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发30-60min，再将所得颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体；（2）水性耐磨超双疏纳米复合涂料的制备：将1-2份的超双疏二氧化硅颗粒粉体分散于1-2份的异构十六烷或航空煤油中，转速50-200rpm条件下，室温搅拌2-4min，随后加入10-15份去离子水，再加入0.1-0.5份水性阴离子氟碳表面活性剂，搅拌5-10min后加入3-9份水性树脂，继续搅拌30min，既得水性超双疏复合涂料；（3）超双疏涂层制备：对于硬质基底材料，将水性超双疏复合涂料倒入喷枪，0.2-0.8MPa压力下，沿45°方向对基底材料喷涂1-2道次，间隔10s后继续喷涂，重复上述步骤3-5次，接着喷涂1-2道次氟硅烷溶液，而后在80℃烘箱中固化10-120min，即可获得水性耐磨纳米复合涂层；对于软质多孔材料，即将基材浸渍在水性超双疏复合涂料中，浸渍时间3-5min，1浸1轧处理，接着喷涂1-2道次质量浓度0.5%的氟硅烷水溶液，而后在80℃烘箱中固化24h，即可获得超双疏多孔材料，所述氟硅烷溶液是先将1份氟硅烷滴入1份乙醇中，超声5min后再倒入100份去离子水超声10min获得的混合溶液。
上述复配硅溶胶是pH值2-4、尺寸20-100nm、固含15%酸性硅溶胶，和pH值8-9、尺寸5-10nm、固含15%硅溶胶按照1:1重量比混合而成。
上述低表面能物质为碳链长度大于6的长链烷基硅氧烷或含氟烷基硅氧烷。
上述水性树脂为水性含氟丙烯酸树脂、水性氟碳树脂、水性三聚氰胺甲醛树脂、水性聚氨酯树脂或水性丙烯酸树脂中的至少一种。
上述硬质基底为玻璃、水泥、陶瓷、金属或木材，软质多孔材料为纤维编织物或纸张。
上述制备方法制得的水性耐磨超双疏纳米复合涂层，所述水性耐磨超双疏纳米复合涂层的水滴和油滴静态接触角均大于150°，滚动角均小于10°。
上述水性耐磨超双疏纳米复合涂层具有如下特性：（1）经1500目金相砂纸100 g砝码负重9.8Kpa压力下滑动距离90米下打磨1000次后、磨耗仪1kg负载橡胶轮材质下打磨1000转、30°倾斜角度50mm高度800mL连续水滴撞击后，涂层仍能保持超双疏性；（2）经划圈法测量涂层在硬质基底上的的附着力等级是一级，涂层与基底的结合力好。
有益效果：（1）本发明采用氟硅烷、水性硅溶胶、水性树脂等常规原料制备水性耐磨超双疏纳米复合涂层，无任何有毒的有机溶剂，从源头上避免了有毒物质的残留或处理不完全，满足环保要求，也降低了生产成本。（2）本发明在水性体系中制备的水性耐磨超双疏纳米复合涂层不燃、VOC低，适用于通风不畅、高温、有明火等多种苛刻场合，便于生产、储存、运输和施工作业，具有很好的应用前景。（3）本发明所述超双疏二氧化硅纳米颗粒粉体制备中，使用复配硅溶胶可以获得纳米尺度团聚纳米颗粒，增加纳米颗粒粗糙度，从而增加涂层粗糙度。（4）本发明所述超双疏二氧化硅纳米颗粒粉体可均匀分散在异构十六烷或航空煤油中， 15天以上不沉降，且在阴离子表面活性剂作用下，混有纳米超双疏粉体的异构十六烷或航空煤油可很好的分散于水中，形成乳化液，便于后期分散在树脂中。（5）本发明所述超双疏涂层的制备中，在喷涂水性超双疏纳米复合涂料后再在表面喷涂氟硅烷溶液，可诱发纳米颗粒自迁移到表面，同时可诱发氟碳表面活性剂含氟官能团朝外，从而增强涂层超疏油效果。（6）本发明所述水性耐磨超双疏纳米复合涂层具有超双疏性能，水滴接触角大于160°、滚动角小于5°；油滴接触角大于150°、滚动角小于10°。（7）本发明所述水性耐磨超双疏纳米复合涂层在聚酯、玻纤、棉等材质的滤料、布料等纤维上浸渍轧制后，不仅不影响其柔软性、透气率等性能，而且还能防水透气、防潮、防污、防油、防霉抗菌。（8）传统的两步法制备耐磨超疏水涂层要求底漆树脂半固化后再及时喷涂面漆超疏水涂料，干燥后获得超疏水涂层，但不利于大面积整体施工，本发明提出的水性耐磨超双疏纳米复合涂层通过一步法喷涂超双疏树脂复合涂料，室温喷涂，中低温固化后即可获得稳定的耐磨超双疏涂层，有利于大面积整体施工。
附图说明
图1.实施例1中水性耐磨超双疏纳米复合涂层超双疏光学图和接触角光学图（左图为水滴，右图为油滴）。
图2. 实施例2中水性耐磨超双疏纳米复合涂层打磨前后光学照片。其中：（a）为水性耐磨超双疏纳米复合涂层摩擦前的显微形貌照片；（b）为水性耐磨超双疏纳米复合涂层摩擦后的显微形貌照片；（c）为水性耐磨超双疏纳米复合涂层摩擦前的水接触角；（d）为水性耐磨超双疏纳米复合涂层摩擦后的水接触角。
图3. 实施例3中水性耐磨超双疏纳米复合涂层耐磨性表征图。其中图（a）为涂层经手指压力15Kpa摩擦1000次后的水接触角；（b）为涂层经1500目金相砂纸100 g砝码负重9.8Kpa压力下滑动距离90米下打磨1000次后水接触角；（c）为涂层经磨耗仪1kg负载橡胶轮材质下打磨1000转后水接触角；（d）为涂层经30°倾斜角度50mm高度800mL连续水滴撞击后水接触角。
图4. 实施例3中水性耐磨超双疏纳米复合涂层划圈法光学图。
图5. 实施例4中水性耐磨超双疏纳米复合涂层在不同基底上的水滴和油滴接触角光学图（左图为水滴，右图为油滴）。
具体实施方式
复配硅溶胶是pH值2-4、尺寸20-100nm、固含15%酸性硅溶胶，和pH值8-9、尺寸5-10nm、固含15%硅溶胶按照1:1重量比混合而成
实施例1
（1）超双疏二氧化硅纳米颗粒粉体的制备：将6份的氨水溶液分散于80份的无水乙醇溶液中，转速200rpm条件下，50℃下搅拌4min，随后加入10份复配硅溶胶，继续搅拌10min后加入0.2份正硅酸四乙酯，继续搅拌30min，加入0.2份十三氟辛基三甲氧基硅烷，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发60min，再将该颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体；
（2）水性耐磨超双疏纳米复合涂料的制备：将1份的超双疏二氧化硅颗粒粉体分散于1份的异构十六烷中，转速200rpm条件下，室温搅拌4min，随后加入15份去离子水，再加入0.1份水性阴离子氟碳表面活性剂，搅拌10min后加入3份水性氟碳树脂，继续搅拌30min，既得水性超双疏复合涂料；
（3）超双疏涂层制备：将水性超双疏复合涂料分散在0.2MPa压力下的喷枪中，沿45°方向向玻璃片喷涂2道次，间隔10s后继续喷涂，重复上述步骤5次，接着喷涂2道次氟硅烷溶液，而后在80℃烘箱中固化24h，即可获得水性耐磨纳米复合涂层，所述氟硅烷溶液是先将1份氟硅烷滴入1份乙醇中，超声5min后再倒入100份去离子水超声10min获得的混合溶液。
经过该方法制备的水性耐磨超双疏纳米复合涂层，水滴接触角大于160°、滚动角小于5°；油滴接触角大于150°、滚动角小于10°。
实施例2
（1）超双疏二氧化硅纳米颗粒粉体的制备：将6份的氨水溶液分散于80份的无水乙醇溶液中，转速200rpm条件下，50℃下搅拌4min，随后加入10份复配硅溶胶，继续搅拌10min后加入0.2份正硅酸四乙酯，继续搅拌30min，加入0.2份十三氟辛基三甲氧基硅烷，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发60min，再将该颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体；
（2）水性耐磨超双疏纳米复合涂料的制备：将1份的超双疏二氧化硅颗粒粉体分散于1份的航空煤油中，转速200rpm条件下，室温搅拌4min，随后加入20份去离子水，再加入0.1份水性阴离子氟碳表面活性剂，搅拌10min后加入2份水性聚氨酯树脂，继续搅拌30min，既得水性超双疏复合涂料；
（3）超双疏涂层制备：将水性超双疏复合涂料分散在0.2MPa压力下的喷枪中，沿45°方向向铝片喷涂2道次，间隔10s后继续喷涂，重复上述步骤5次，接着喷涂2道次氟硅烷溶液，而后在80℃烘箱中固化24h，即可获得水性耐磨纳米复合涂层。
该水性耐磨纳米复合涂层的表面显微形貌如图2：a所示，其水接触角为167.3°（图2：c），滚动角为2.8°，该涂层经手指摩擦500次后（图2：b）的水接触角为154.3°（图2：d），滚动角为7.6°。
实施例3
（1）超双疏二氧化硅纳米颗粒粉体的制备：将6份的氨水溶液分散于80份的无水乙醇溶液中，转速200rpm条件下，50℃下搅拌4min，随后加入10份复配硅溶胶，继续搅拌10min后加入0.2份正硅酸四乙酯，继续搅拌30min，加入0.2份十六烷基三甲氧基硅烷，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发60min，再将该颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体；
（2）水性耐磨超双疏纳米复合涂料的制备：将1份的超双疏二氧化硅颗粒粉体分散于1份的异构十六烷中，转速200rpm条件下，室温搅拌4min，随后加入15份去离子水，再加入0.1份水性阴离子氟碳表面活性剂，搅拌10min后加入1.5份水性三聚氰胺甲醛树脂，继续搅拌30min，既得水性超双疏复合涂料；
（3）超双疏涂层制备：将水性超双疏复合涂料分散在0.2MPa压力下的喷枪中，沿45°方向向铝片喷涂2道次，间隔10s后继续喷涂，重复上述步骤5次，接着喷涂2道次氟硅烷溶液，而后在120℃烘箱中固化12h，即可获得水性耐磨纳米复合涂层。
将上述制备的水性耐磨超双疏纳米复合涂层用于涂层的耐磨性表征：
（1）手指打磨操作方法为：用单根手指指腹(戴塑胶手套)均匀打磨水性耐磨超双疏纳米复合涂层处理的玻璃片，手指摩擦压力约为15 kPa，每打磨50次测打磨涂层处去离子水和大豆油的接触角和滚动角；（2）砂纸打磨操作方法为：将水性耐磨超双疏纳米复合涂层处理的玻璃片倒扣于1500目砂纸上，并在100 g砝码负重9.8Kpa压力的条件下进行打磨试验，打磨距离为10 cm，纵横两次为一个周期，每打磨100次测打磨涂层处去离子水和大豆油的接触角和滚动角；（3）磨耗仪打磨操作方法为：将水性耐磨超双疏纳米复合涂层处理的玻璃片固定在平台上，橡胶轮负载为1Kg，每打磨100次测打磨涂层处去离子水和大豆油的接触角和滚动角；（4）连续水滴撞击试验操作方法为：将水性耐磨超双疏纳米复合涂层处理的玻璃片30°倾斜固定在平台上，采用梨形分液漏斗来实现连续水滴撞击试验，漏斗底部距倾斜样品距离30mm，出水速度4m/s，每撞击100mL后测撞击涂层处去离子水和大豆油的接触角和滚动角。
该涂层经手指压力15Kpa摩擦1000次后的水接触角为154.3°（图3：a），滚动角为7.6°，油滴接触角为152.3°，滚动角为10°；经1500目金相砂纸100 g砝码负重9.8Kpa压力下滑动距离90米下打磨1000次后水接触角为155.3°（图3：b），滚动角为8.6°，油滴接触角为150.3°，滚动角为8.6°; 磨耗仪1kg负载橡胶轮材质下打磨1000转后水接触角为153.5°（图3：c），滚动角为8.6°，油滴接触角为151.5°，滚动角为6.8°; 30°倾斜角度50mm高度800mL连续水滴撞击后水接触角为155.5°（图3：d），滚动角为4.6°，油滴接触角为154.5°，滚动角为5.8°。
将上述制备的水性耐磨超双疏纳米复合涂层用于涂层的附着力表征：
将样品固定在台上，有涂膜面朝上，将划针压头的针尖紧压在涂膜上，摇动旋转手柄，使针尖在涂膜土划出依次重叠的、连续的圆圈，测试3块样品。用4倍放大镜观察划痕，与标准涂膜评定等级对比， 3块样品涂膜等级均为1级。
实施例4
（1）超双疏二氧化硅纳米颗粒粉体的制备：将6份的氨水溶液分散于80份的无水乙醇溶液中，转速200rpm条件下，50℃下搅拌4min，随后加入10份复配硅溶胶，继续搅拌10min后加入0.2份正硅酸四乙酯，继续搅拌30min，加入0.2份十三氟辛氧丙基甲基二氯硅烷，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发60min，再将该颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体；
（2）水性耐磨超双疏纳米复合涂料的制备：将1份的超双疏二氧化硅颗粒粉体分散于1份的航空煤油中，转速200rpm条件下，室温搅拌4min，随后加入15份去离子水，再加入0.1份水性阴离子氟碳表面活性剂，搅拌10min后加入3份水性丙烯酸树脂，继续搅拌30min，既得水性超双疏复合涂料；
（3）超双疏涂层制备：对于硬质基底材料，将步骤二所述涂料倒入喷枪，0.2MPa压力下，沿45°方向向基底材料喷涂2道次，间隔10s后继续喷涂，重复上述步骤3次，接着喷涂2道次氟硅烷溶液，而后在80℃烘箱中固化80min，即可获得水性耐磨纳米复合涂层；对于软质多孔材料，即将基材浸渍在步骤二所述涂料中，浸渍时间5min，1浸1轧处理，接着喷涂2道次质量浓度0.5%氟硅烷水溶液，而后在80℃烘箱中固化24h，即可获得超双疏多孔材料，所述氟硅烷溶液是先将1份氟硅烷滴入1份乙醇中，超声5min后再倒入100份去离子水超声10min获得的混合溶液。
Figure 815655DEST_PATH_IMAGE001
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下还可以做出若干改进，这些改进也应视为本发明的保护范围。

Claims (3)

1.一种水性耐磨超双疏纳米复合涂层的制备方法，其特征在于步骤为：
（1）超双疏二氧化硅纳米颗粒粉体的制备：将2-6份的氨水溶液分散于80份的无水乙醇溶液中，转速50-200rpm条件下，50℃下搅拌2-4min，随后加入10-15份复配硅溶胶，继续搅拌10min后加入0.1-1份正硅酸四乙酯，继续搅拌30min，加入0.1-1份低表面能物质，搅拌2h后置于旋转蒸发器中，在60℃条件下旋转蒸发30-60min，再将所得颗粒置于冷冻干燥机中-80℃冷冻干燥6 h，即可得到超双疏二氧化硅纳米颗粒粉体，所述复配硅溶胶是pH值2-4、尺寸20-100nm、固含15%酸性硅溶胶，和pH值8-9、尺寸5-10nm、固含15%硅溶胶按照1:1重量比混合而成，所述低表面能物质为碳链长度为6-10的碳氟长链有机硅氧烷、碳链长度大于6的长链烷基硅氧烷和碳链长度大于6的长链烷基氯硅烷；
（2）水性耐磨超双疏纳米复合涂料的制备：将1-2份的超双疏二氧化硅颗粒粉体分散于1-2份的异构十六烷或航空煤油中，转速50-200rpm条件下，室温搅拌2-4min，随后加入10-15份去离子水，再加入0.1-0.5份水性阴离子氟碳表面活性剂，搅拌5-10min后加入3-9份水性树脂，继续搅拌30min，既得水性超双疏复合涂料，所述水性树脂为水性含氟丙烯酸树脂、水性氟碳树脂、水性三聚氰胺甲醛树脂、水性聚氨酯树脂或水性丙烯酸树脂中的至少一种；
（3）超双疏涂层制备：对于硬质基底材料，将水性超双疏复合涂料倒入喷枪，0.2-0.8MPa压力下，沿45°方向对基底材料喷涂1-2道次，间隔10s后继续喷涂，重复上述步骤3-5次，接着喷涂1-2道次氟硅烷溶液，所述氟硅烷溶液是先将1份氟硅烷滴入1份乙醇中，超声5min后再倒入100份去离子水超声10min获得的混合溶液，而后在80℃烘箱中固化10-120min，即可获得水性耐磨纳米复合涂层；对于软质多孔材料，即将基材浸渍在水性超双疏复合涂料中，浸渍时间3-5min，1浸1轧处理，接着喷涂1-2道次质量浓度0.5%的氟硅烷水溶液，而后在80℃烘箱中固化24h，即可获得超双疏多孔材料。
2.根据权利要求1所述水性耐磨超双疏纳米复合涂层的制备方法，其特征在于所述硬质基底为玻璃、水泥、陶瓷、金属或木材，软质多孔材料为纤维编织物或纸张。
3.根据权利要求1-2任一所述制备方法制得的水性耐磨超双疏纳米复合涂层，其特征在于所述的水性耐磨超双疏纳米复合涂层的水滴和油滴静态接触角均大于150°，滚动角均小于10°。
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