Preparation and modification of nano-TiO2 and its application in polymer matrix composites research progress
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摘要: 基于纳米二氧化钛 (TiO2) 作为添加剂制备的复合材料具有优异的耐温性、抗老化性等，而且由于其特殊的光催化活性，在通过吸收紫外光能量后具有较强的抗菌杀菌能力，因此在涂料、化妆品和医学等领域具有广泛的应用。然而，受纳米尺寸效应影响，纳米TiO2在聚合物基体中存在易团聚、难分散的缺点，使其应用受到限制。因此，需要通过多种表面改性方法调控纳米TiO2的表面性质，增强其与聚合物基体相容性。本论文首先详细阐述了纳米TiO2的制备、表面改性方法及机制，并综述了近期纳米TiO2改性聚合物基复合材料方面的研究进展。最后，讨论了纳米TiO2聚合物复合材料研究中存在的主要问题，并展望了其未来的发展方向。Abstract: The composite materials prepared based on the titanium dioxide (TiO2) nanoparticles as additives have excellent heat resistance, aging resistance, etc. The TiO2 nanoparticles have special photocatalytic activity, such as, it has strong antibacterial and bactericidal ability after absorbing ultraviolet energy. Currently, TiO2 nanoparticles have a wide range of applications in various fields of coatings, cosmetics and medicine. However, affected by the nano-dimensional effect, the TiO2 nanoparticles in the polymer matrix have the disadvantages of being easy to agglomerate and difficult to disperse, which limits its application. Therefore, it is necessary to regulate the surface properties of nano-TiO2 by various surface modification methods to enhance its compatibility with the polymer matrix. This paper first described the preparation, surface modification method and mechanism of TiO2 nanoparticles in detail, subsequently, and the research progress on the TiO2 nanoparticles modified polymer compound composite material is reviewed in the recent years. Finally, this paper discussed the TiO2 nanoparticles exist problems in the research of polymer composites, and prospected its development direction in the future.
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Key words:
- nano-TiO2 /
- surface modification /
- aggregation /
- polymers /
- nanocomposites
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图 1 ((a)~(e)) 乙醇体积占比为0.1、0.3、0.5、0.7、0.85时制备纳米TiO2粒径为100、65、50、40、30 nm的TEM图像; (f) 50 nm TiO2的低放大TEM图像; ((g), (h)) 50 nm和 65 nm TiO2选定区域电子衍射 (SAED) 图像[45]
Figure 1. ((a)-(e)) TEM images of ethanol volume ratio of 0.1, 0.3, 0.5, 0.7, 0.85 were prepared with 100, 65, 50, 40, 30 nm particle size; (f) Low magnification TEM images of 50 nm TiO2; ((g), (h)) Electron diffraction patterns of selected regions (SAED) of 50 nm TiO2 and 65 nm TiO2[45]
图 2 含有不同颗粒样品的消光光谱 (a)、反射光谱 (b) 和吸收光谱 (c)；(d) 测量人造皮肤表面温度装置图；模拟阳光照射300 s后，人造皮肤达到最高平衡温度 (e) 和未进行任何处理/使用含有TiO2@Al(OH)3胶体和混合空心粒子的化妆品配方后人造皮肤外观 (f)[54]
Figure 2. Extinction (a), reflectance (b) and absorption spectra of the cosmetic formulations containing various particles (c); (d) Diagram of device for measuring surface temperature of artificial skin; Maximum equilibrium temperatures of the artificial skin reached after 300 s illumination of the simulated sunlight (e) and artificial skin appearances under no treatment, and after applying the cosmetic formulations containing TiO2@Al(OH)3 colloids and hybrid hollow particles (f)[54]
AM 1.5 G—Global spectrum; T—Temperature; Tmax—Maximum equilibrium temperatures of the artificial skin reached after 300 s illumination of the simulated sunlight
图 3 样品改性前后在紫外光((a), (c))和可见光((b), (d))照射下降解亚甲基蓝的反应活性图[56]
Figure 3. Reaction activity of powder samples under UV ((a), (c)) and visible light ((b), (d)) irradiation grafted film for methylene blue degradation[56]
PMMA—Poly(methyl methacrylate); P25—Average particle size is 25 nm; c0—Concentration of methylene blue at initial time; c—Concentration of methylene blue at t time
图 5 (a) 接触角 (CA) 与UV辐照时间的关系；(b)复合材料表面CA随加热时间的变化；(c)复合材料表面在紫外线照射和加热下可逆的超疏水-超亲水性切换[69]
Figure 5. (a) Relationship between contact angle (CA) and UV irradiation time; (b) Variations in the CA of the composite surface with heating time; (c) Reversible superhydrophobicity-superhydrophilicity switching of the composite surface under UV irradiation and heating[69]
表 1 全氟化膜(Nafion-117)为基准测试膜的拉伸强度、吸水率、氧化稳定性、离子电导率和BH4–渗透性[59]
Table 1. Tensile strength, water uptake, oxidative stability, ionic conductivity and BH4– permeability of the prepared membranes and benchmark Nafion macromolecule (Nafion-117)[59]
Membrane Tensile
strength/MPaWater
uptake/%Oxidative
stability/%Ionic conductivity/
(mS·cm−1)BH4– permeability/(cm2·s−1) PVA-PEO-PVP 2.7 >100 81 13.1 2.10×10−5 PVA-PEO-PVP/SPTO-1.0wt% 10.6 47 81 14.4 6.30×10−6 PVA-PEO-PVP/SPTO-2.5wt% 12.3 14 99 15.6 0.41×10−6 PVA-PEO-PVP/SPTO-5wt% 17.2 11 98 16.0 0.12×10−6 Nafion-117 25.0 15 92 45.0 0.40×10−6 Notes: PVA—Poly(vinyl alcohol); PEO—Ethylene oxide; PVP—Vinyl pyrrolidone; SPTO—Sulphated and phosphated titanium dioxide; SPTO-1.0wt%, SPTO-2.5wt%, SPTO-5wt%—Amount of SPTO added is 1wt%, 2.5wt% and 5wt%. 
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