摘 要

超双亲自清洁涂层即为涂层表面对水和油都表现出超亲和性，可以使水滴和油滴在其表面的接触角都小于10°。这样就可以使涂层与空气中的水分或油液相结合，并在涂层表面形成水膜或者油膜，从而隔绝外部污染物与基底表面相接触，在重力、风力或下雨等自然条件下使污染物脱落来达到自清洁的目的。目前制备一种可以用于建筑外墙或者玻璃幕墙的超双亲自清洁涂层已成为研究热点。

本文主要探究在建筑物玻璃上涂敷一层二氧化钛薄膜，使其既具有优良的超双亲性，可以形成水膜或油膜来隔绝外部污染物；同时又具有优异的光催化性能，可以降解一部分无法脱落的有机污染物，通过以上两方面的共同作用来达到自清洁的目的。本文一方面通过钛溶胶制备二氧化钛薄膜，另一方面则通过有机无机复合制备PVDF/TiO₂薄膜，以下为两方面的内容：

（1）以PVDF为连接剂，以二氧化钛粉末（P25）为双亲材料。将纳米二氧化钛粉末加入到溶胶中，从而得到成分均匀的涂层。通过改变二氧化钛粉末的含量、PVDF的含量、紫外处理时间以及PVP的添加，同时进行接触角测量来探究不同条件下PVDF/TiO₂涂层的双亲性能。从PVDF/TiO₂薄膜经过紫外处理后对水的接触角数值可以得到，二氧化钛粉末用量增加，紫外光照时间延长都可以提高PVDF/TiO₂薄膜的亲水性。然而由于PVDF本身就具有亲油性，PVDF/TiO₂薄膜无法具有亲水性。通过向PVDF溶胶中接枝PVP来改善其亲水性，但是二氧化钛粉末在接枝PVP之后的溶胶中无法很好的分散。通过降低PVDF的含量可以使薄膜的亲水性能提高，并在一段时间的紫外光照后使薄膜获得超亲水性。此外，油滴在薄膜上接触角小于10°，此时的薄膜具有超双亲性。

（2）选择硫酸氧钛为制备TiO₂薄膜的原料，将钛溶胶在不同温度热处理1 h，得到二氧化钛薄膜。通过改变pH值、KH570的用量、载玻片的刻蚀时间以及热处理温度，同时采用接触角测试，扫描电镜分析来探究不同条件下二氧化钛薄膜的成膜性以及双亲性。从已得数据可知，随着热处理温度的升高，水在二氧化钛薄膜表面的接触角减小，油在薄膜表面的接触角增大。当热处理温度为500℃时，二氧化钛薄膜具有超亲水性能，且在该温度下薄膜仍具有亲油性，从而表现出双亲性。此外由SEM图可知，经过热处理之后的薄膜弥补了热处理之前薄膜的裂纹，产生了许多微孔和颗粒，增加了薄膜和玻璃片表面的结合，使薄膜的成膜性提高。

关键词：超双亲 二氧化钛 接触角 成膜性

Preparation and property study of superamphiphilic

self-cleaning coating

Abstract

The superamphiphilic self-cleaning coating means that the surface of the coating exhibits superoleophilicity and superhydrophilicity, so that the contact angle of water droplets and oil droplets on the surface is less than 10°. This allows the coating to combine with moisture or oil in the air and form a water film or oil film on the surface of the coating to isolate external contaminants from contact with the substrate surface under natural conditions such as gravity, wind or rain. The contaminants are shed to achieve self-cleaning purposes. At present, the preparation of a superamphiphilic self-cleaning coating that can be used for building exterior walls or glass curtain walls has become a research hotspot.

This paper mainly explores the application of a layer of titanium dioxide film on the building glass, it has both excellent superamphiphilic property and can form water film or oil film to isolate external pollutants. At the same time, it has excellent photocatalytic performance, which can degrade part of the organic pollutants that cannot be shed, and achieve the purpose of self-cleaning through the combined action of the above two aspects. In this paper, on the one hand, titanium dioxide thin films are prepared by titanium sol; on the other hand, PVDF/TiO₂ thin films are prepared by organic and inorganic composite. The following are two aspects:

（1）Sols were prepared by soluting PVDF in DMF and adding nanometer titanium dioxide powder. Nanometer titanium dioxide powder was added to the sol to obtain uniform coating. The parent properties of PVDF/TiO₂ coating under different conditions were investigated by changing the content of titanium dioxide powder，PVDF content，UV treatment time and the addition of PVP, as well as by measuring the CA. According to the contact Angle of PVDF/TiO₂ films to water after UV treatment，the hydrophilicity of PVDF/TiO₂ films can be improved by increasing the amount of titanium dioxide powder and extending the UV treatment time. However, PVDF/TiO₂ films cannot be hydrophilic due to PVDF inherent oleophilicity. The hydrophilicity was improved by grafting PVP into PVDF sol, but the titanium dioxide powder could not be well dispersed in the sol after grafting PVP. By reducing the content of PVDF, the hydrophilicity of the film can be improved, and the film can obtain super hydrophilicity after a period of ultraviolet light. In addition, CA of the oil droplets in the thin film is less than 10 °，film has superamphiphilicity at this time.

（2）TiO₂ thin films were prepared from TiOSO₄，and Titanium dioxide films were obtained by heat treatment of titanium sol at different temperatures for 1h. By changing pH value, KH570 dosage, etching time of the glass slide and heat treatment temperature, as well as using contact Angle test and SEM analysis, the film-forming and amphiphilic properties of titanium dioxide thin film under different conditions were explored. It can be seen from CA data of water and oil of the titanium dioxide film prepared with PTA sol that the hydrophilicity of the titanium dioxide film can be improved and the oleophilicity can be decreased with the increase of heat treatment temperature. When the heat treatment temperature of 500 ℃, the titanium dioxide thin film has a superhydrophilic, and under the heat treatment temperature film still has the oleophilicity，so as to show the amphiphilicity. In addition, it can be seen from the SEM figure that the film after heat treatment makes up for the cracks of the film before heat treatment, and many micropores and particles are generated, which increases the combination of the film and the surface of the glass sheet and improves the film-forming property of the film.

Key words：superamphiphilic; Titanium dioxide; CA; film-forming property

目 录

摘要 I

Abstract III

第一章 文献综述 1

1.1 研究背景 1

1.2 超双亲性原理 2

1.2.1 二氧化钛薄膜的超双亲性原理 2

1.2.2 介孔二氧化硅的超双亲性原理 3

1.3 制备方法 3

1.3.1 溶胶-凝胶法 3

1.3.2聚合物/纳米粒子法 4

1.3.3 自组装法 4

1.4 应用及展望 4

1.5 选题的目的、意义及主要研究内容 4

1.5.1 选题的目的、意义 4

1.5.2 选题的主要研究内容 5

第二章 实验研究方法 6

2.1 实验原料 6

2.2实验仪器 6

2.3 实验过程 6

2.4 样品分析与表征 7

第三章 PVDF/TiO₂涂层的双亲性 9

3.1引言 9

3.2 纳米二氧化钛粉末含量及紫外光照时间对膜亲水性影响 9

3.3 PVP对膜亲水性影响 12

3.4 PVDF对膜亲水性的影响 12

3.5 本章小结 13

第四章 钛溶胶制备TiO₂薄膜的双亲性 15

4.1 引言 15

4.2 硅烷偶联剂及pH值对TiO₂薄膜成膜性的影响 15

4.3 TiO₂薄膜的双亲性 16

4.4 TiO₂薄膜的表面形貌 18

4.5 本章小结 19

第五章 结论 20

参考文献 21

致谢 23

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