功能化超疏水织物的设计、制备及应用研究

人们通常将表面水接触角θ＞150°，滚动接触角α＜10°的材料称为超疏水材料，近年来这类材料成为研究热点之一。超疏水材料最初的设计理念来源于自然界，随着表面科学和纳米技术的发展，研究人员能够制备出各种具有超疏水性能的材料，在自清洁、减阻、防冰、防雾、抗细菌黏附等领域展现出良好的应用前景。但是，现有超疏水材料制备工艺还存在巨大挑战，例如制备工艺复杂、成本高、受外界环境影响材料疏水性能下降（即稳定性差）等，严重阻碍了超疏水材料的广泛应用。

为解决这些问题，本论文从以下两种思路开展研究，一是通过材料表面涂覆高分子或纳米材料涂层来增强超疏水织物的稳定性，二是直接制备具有表面可自修复功能的超疏水织物。我们分别通过浸渍法和水热法制备了超疏水织物，重点研究了纳米材料尺寸和添加剂添加量对超疏水稳定性能的影响，以及基于磷酸锆原位生长过程超疏水自修复机理，在此基础上探讨了超疏水织物的应用场景，主要研究结果如下：

为制备具有良好稳定性的超疏水织物，本论文通过两步浸渍法在织物表面涂覆了TiO2@PVDF-g-FAS，当TiO2纳米粒子为500 nm、TiO2/PVDF 质量比为0.01/1时，织物表现出优异的超疏水性能（接触角：161°，滚动角：1.7°），良好的热稳定性（180℃）、耐紫外性（可在紫外光照下600 h仍保持超疏水性能）、耐酸碱腐蚀性（在不同酸碱条件下浸泡48 h仍保持超疏水性能）和机械稳定性（砂纸摩擦600次）。涂覆TiO2@PVDF-g-FAS的超疏水织物还表现出很强的抗菌性能，对于革兰氏阴性菌（大肠杆菌）和革兰氏阳性菌（金葡萄球菌）的杀菌率分别达到84％和99％。此超疏水织物的制备方法简单，反应条件温和，可实现大批量生产，具有较好的实际应用前景。

为制备可自修复的超疏水织物，本论文设计了以氧氯化锆、磷酸、吐温-80为原料，通过原位生长法在织物表面生成了α-磷酸锆纳米片，并通过十八烷基胺（ODA）改性，制备了超疏水织物（接触角：163°，滚动角：3.7°）。使用Plasma辐照法验证了超疏水涂层的自修复性能，在氧Plasma处理1分钟后，织物的水接触角降为0°，通过100℃热处理4 h后，内部的ODA扩散至表面实现自修复，织物重新恢复超疏水性能。使用该超疏水织物进行油水分离，对于不同种类油的油水分离率皆可达到95% 以上，并可在多种应用条件下实现油水分离。织物循环25次油水分离后，性能仍可保持稳定。织物具有较高的膜通量及截留率，且当超疏水性能被破坏-修复后仍表现出良好的油水分离效果。

综上所述，本论文分别通过制备高分子/纳米复合材料涂层和具有自修复功能纳米涂层的方式来提升超疏水织物（表面）的稳定性，这些制备方法简单可行，可以扩展到其它材料或基底表面，为超疏水现象更广泛的实际应用提供了新的解决方案。

人们通常将表面水接触角θ＞150°，滚动接触角α＜10°的材料称为超疏水材料，近年来这类材料成为研究热点之一。超疏水材料最初的设计理念来源于自然界，随着表面科学和纳米技术的发展，研究人员能够制备出各种具有超疏水性能的材料，在自清洁、减阻、防冰、防雾、抗细菌黏附等领域展现出良好的应用前景。但是，现有超疏水材料制备工艺还存在巨大挑战，例如制备工艺复杂、成本高、受外界环境影响材料疏水性能下降（即稳定性差）等，严重阻碍了超疏水材料的广泛应用。

为解决这些问题，本论文从以下两种思路开展研究，一是通过材料表面涂覆高分子或纳米材料涂层来增强超疏水织物的稳定性，二是直接制备具有表面可自修复功能的超疏水织物。我们分别通过浸渍法和水热法制备了超疏水织物，重点研究了纳米材料尺寸和添加剂添加量对超疏水稳定性能的影响，以及基于磷酸锆原位生长过程超疏水自修复机理，在此基础上探讨了超疏水织物的应用场景，主要研究结果如下：

为制备具有良好稳定性的超疏水织物，本论文通过两步浸渍法在织物表面涂覆了TiO2@PVDF-g-FAS，当TiO2纳米粒子为500 nm、TiO2/PVDF 质量比为0.01/1时，织物表现出优异的超疏水性能（接触角：161°，滚动角：1.7°），良好的热稳定性（180℃）、耐紫外性（可在紫外光照下600 h仍保持超疏水性能）、耐酸碱腐蚀性（在不同酸碱条件下浸泡48 h仍保持超疏水性能）和机械稳定性（砂纸摩擦600次）。涂覆TiO2@PVDF-g-FAS的超疏水织物还表现出很强的抗菌性能，对于革兰氏阴性菌（大肠杆菌）和革兰氏阳性菌（金葡萄球菌）的杀菌率分别达到84％和99％。此超疏水织物的制备方法简单，反应条件温和，可实现大批量生产，具有较好的实际应用前景。

为制备可自修复的超疏水织物，本论文设计了以氧氯化锆、磷酸、吐温-80为原料，通过原位生长法在织物表面生成了α-磷酸锆纳米片，并通过十八烷基胺（ODA）改性，制备了超疏水织物（接触角：163°，滚动角：3.7°）。使用Plasma辐照法验证了超疏水涂层的自修复性能，在氧Plasma处理1分钟后，织物的水接触角降为0°，通过100℃热处理4 h后，内部的ODA扩散至表面实现自修复，织物重新恢复超疏水性能。使用该超疏水织物进行油水分离，对于不同种类油的油水分离率皆可达到95% 以上，并可在多种应用条件下实现油水分离。织物循环25次油水分离后，性能仍可保持稳定。织物具有较高的膜通量及截留率，且当超疏水性能被破坏-修复后仍表现出良好的油水分离效果。

综上所述，本论文分别通过制备高分子/纳米复合材料涂层和具有自修复功能纳米涂层的方式来提升超疏水织物（表面）的稳定性，这些制备方法简单可行，可以扩展到其它材料或基底表面，为超疏水现象更广泛的实际应用提供了新的解决方案。

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