中空TiO2微球的制备及其对聚丙烯酸酯薄膜保温性能的影响

doi:10.15541/jim20160488

摘要/Abstract

摘要：

以阳离子PS微球为模板, 钛酸四丁酯为钛源, 氨水为催化剂制备中空TiO₂微球, 通过物理共混法将中空TiO₂微球引入到聚丙烯酸酯薄膜中, 考察了中空TiO₂微球的空心粒径及用量对复合薄膜光反射性、导热系数及力学性能的影响。结果表明: 中空TiO₂微球的引入可显著提升聚丙烯酸酯薄膜的各项性能, 中空TiO₂微球的空心粒径和用量对复合薄膜的性能有不同程度的影响, 随着中空TiO₂微球空心粒径和用量的增加, 复合薄膜的性能基本呈现先提升后降低的趋势, 其中当中空TiO₂微球空心粒径为300 nm、用量为1%时, 所制备的复合薄膜保温性能和力学性能最优。

关键词: 中空二氧化钛微球, 聚丙烯酸酯, 复合薄膜, 保温性能, 力学性能

Abstract:

Hollow TiO₂ microspheres were fabricated with PS as template, tetrabutyl titanate as titanium resource and ammonium as catalyst. Then, hollow TiO₂ microspheres were introduced into polyacrylate emulsion by physical blending method. The effect of hollow size and dosage of hollow TiO₂ microspheres on light reflection, thermal conductivity and mechanical property of composite film were investigated. The results show that hollow TiO₂ microspheres can significantly improve the properties of polyacrylate film. The hollow size and dosage of hollow TiO₂ microspheres have different degree influence on properties of composite film. The properties of composite film firstly increase and then decrease with increasing of hollow size and dosage of hollow TiO₂ microspheres. When the hollow diameter and the dosage of hollow TiO₂ microspheres is 300 nm and 1%, respectively, the thermal insulation properties and mechanical properties of the composite membrane are optimal.

Key words: Hollow TiO₂ spheres, polyacrylate, composite film, thermal insulation, mechanical property

中图分类号:

TB34

鲍艳, 康巧玲. 中空TiO₂微球的制备及其对聚丙烯酸酯薄膜保温性能的影响[J]. 无机材料学报, 2017, 32(6): 581-586.

BAO Yan, KANG Qiao-Ling. Fabrication of Hollow TiO₂ Spheres and Their Effect on Thermal Insulation Property of Polyacrylate Film[J]. Journal of Inorganic Materials, 2017, 32(6): 581-586.

图/表 10

图1 中空TiO2微球的SEM及TEM照片

Fig. 1 SEM and TEM images of hollow TiO2 spheres(a, b) SEM images; (c, d) TEM images

图2 中空TiO2微球的XRD谱图

Fig. 2 XRD pattern of hollow TiO2 spheres

图3 中空TiO2微球空心粒径对聚丙烯酸酯薄膜导热系数的影响

Fig. 3 Effect of hollow cavity of hollow TiO2 spheres on thermal conductivity of polyacrylate film(a) Pure polyacrylate film; (b-f) Composite films containing hollow TiO2 spheres with hollow diameter of 150, 200, 300, 400, and 500 nm, respectively

图4 (a)纯聚丙烯酸酯薄膜(b)聚丙烯酸酯/中空TiO2微球复合薄膜的截面SEM照片

Fig. 4 SEM images of (a) polyacrylate thin films and (b) composite thin films

表1 中空TiO2微球的比表面积、孔体积及平均孔径

Table1 Specific surface area, pore volume, average pore size of hollow TiO2 spheres samples

Sample	S_BET/(m²·g^-1)	Pore volume / (cm³·g^-1)	Pore size / nm
150 nm	58.2790	0.005458	33.2
500 nm	50.9239	0.002651	14.5

图5 中空TiO2微球空心粒径对聚丙烯酸酯薄膜光反射率的影响

Fig. 5 Effect of hollow cavity of hollow TiO2 spheres on light reflectivity of polyacrylate film(a) Pure polyacrylate film; (b-f) Composite films containing hollow TiO2 spheres with hollow diameter of 150, 200, 300, 400, and 500 nm, respectively

图6 中空TiO2微球空心粒径对聚丙烯酸酯薄膜力学性能的影响

Fig. 6 Effect of hollow cavity of hollow TiO2 spheres on tensile strength and elongation at break of polyacrylate film(a) Pure polyacrylate film; (b-f) Composite films containing hollow TiO2 spheres with hollow diameter of 150, 200, 300, 400, and 500 nm, respectively

图7 中空TiO2微球用量对聚丙烯酸酯薄膜导热系数的影响

Fig. 7 Effect of hollow TiO2 spheres content on thermal conductivity of polyacrylate film(a) Pure polyacrylate film; (b-e) Composite films containing hollow TiO2 spheres of 1%, 2%, 3% and 4%, respectively

图8 中空TiO2微球用量对聚丙烯酸酯薄膜光反射率的影响

Fig. 8 Effect of hollow TiO2 spheres content on light reflectivity of polyacrylate film(a) Pure polyacrylate film; (b-e) Composite films containing hollow TiO2 spheres of 1%, 2%, 3% and 4%, respectively

图9 中空TiO2微球用量对聚丙烯酸酯薄膜抗张强度与断裂伸长率的影响

Fig. 9 Effect of hollow TiO2 spheres content on tensile strength and elongation at break of polyacrylate film(a) Pure polyacrylate film; (b-e) Composite films containing hollow TiO2 spheres of 1%, 2%, 3% and 4%, respectively

参考文献 40

[1]	YIN L W, BANDO Y, LI M S, et al.Growth of semiconducting GaN hollow spheres and nanotubes with very thin shells via a controllable liquid gallium-gas interface chemical reaction.Small, 2005, 1(11): 1094-1099.
[2]	WANG W S, ZHEN L, XU C Y, et al.Aqueous solution synthesis of Cd(OH)2 hollow microspheres via Ostwald ripening and their conversion to CdO hollow microspheres.The Journal of Physical Chemistry C, 2008, 112(37): 14360-14366.
[3]	ZHOU L, ZHAO D, LOU X W.Double-shelled CoMn2O4 hollow microcubes as high-capacity anodes for lithium-ion batteries.Advanced Materials, 2012, 24(6): 745-748.
[4]	JOO J B, ZHANG Q, LEE I, et al.Mesoporous anatase titania hollow nanostructures though silica-protected calcination.Advanced Functional Materials, 2012, 22(1): 166-174.
[5]	GAO T, JELLE B P, SANDBERG L I C, et al. Monodisperse hollow silica nanospheres for nano insulation materials: synthesis, characterization, and life cycle assessment.ACS Applied Materials & Interfaces, 2013, 5(3): 761-767.
[6]	HAN L, LIU R, LI C, et al.Controlled synthesis of double-shelled CeO2 hollow spheres and enzyme-free electrochemical bio-sensing properties for uric acid. Journal of Materials Chemistry, 2012, 22(33): 17079-17085.
[7]	ZENG Y, WANG X, WANG H, et al.Multi-shelled titania hollow spheres fabricated by a hard template strategy: enhanced photocatalytic activity.Chemical Communications, 2010, 46(24): 4312-4314.
[8]	ZHANG H, DU G, LU W, et al.Porous TiO2 hollow nanospheres: synthesis, characterization and enhanced photocatalytic properties.CrystEngComm, 2012, 14(10): 3793-3801.
[9]	XI G, YAN Y, MA Q, et al.Synthesis of multiple-shell WO3 hollow spheres by a binary carbonaceous template route and their applications in visible-light photocatalysis.Chemistry-A European Journal, 2012, 18(44): 13949-13953.
[10]	WANG B, CHEN J S, WU H B, et al.Quasiemulsion-templated formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties.Journal of the American Chemical Society, 2011, 133(43): 17146-17148.
[11]	YAO Y, MCDOWELL M T, RYU I, et al.Interconnected silicon hollow nanospheres for lithium-ion battery anodes with long cycle life.Nano letters, 2011, 11(7): 2949-2954.
[12]	JIN L, XU L, MOREIN C, et al.Titanium containing γ-MnO2 (TM) hollow spheres: one-step synthesis and catalytic activities in Li/air batteries and oxidative chemical reactions.Advanced Functional Materials, 2010, 20(19): 3373-3382.
[13]	ZHOUJ K, LV L, YU J, et al.Synthesis of self-organized polycrystalline F-doped TiO2 hollow microspheres and their photocatalytic activity under visible light.The Journal of Physical Chemistry C, 2008, 112(14): 5316-5321.
[14]	CHEN J S, LOU X W D. SnO2-based nanomaterials: synthesis and application in lithium-ion batteries.small, 2013, 9(11): 1877-1893.
[15]	CHEN Y, CHEN H R, SHI J L.Construction of homogenous/heterogeneous hollow mesoporous silica nanostructures by silica-etching chemistry: principles, synthesis, and applications.Accounts of Chemical Research, 2013, 47(1): 125-137.
[16]	WU D, ZHU F, LI J, et al.Monodisperse TiO2 hierarchical hollow spheres assembled by nanospindles for dye-sensitized solar cells.Journal of Materials Chemistry, 2012, 22(23): 11665-11671.
[17]	AGRAWAL M, PICH A, ZAFEIROPOULOS N E, et al.Fabrication of hollow titania microspheres with tailored shell thickness.Colloid and Polymer Science, 2008, 286(5): 593-601.
[18]	ZHANG K, ZHANG X, CHEN H, et al.Hollow titania spheres with movable silica spheres inside.Langmuir, 2004, 20(26): 11312-11314.
[19]	LI Y, KUNITAKE T, FUJIKAWA S.Efficient fabrication and enhanced photocatalytic activities of 3D-ordered films of titania hollow spheres.The Journal of Physical Chemistry B, 2006, 110(26): 13000-13004.
[20]	LI H, HA C S, KIM I.Facile fabrication of hollow silica and titania microspheres using plasma-treated polystyrene spheres as sacrificial templates.Langmuir, 2008, 24(19): 10552-10556.
[21]	LI X, XIONG Y, LI Z, et al.Large-scale fabrication of TiO2 hierarchical hollow spheres.Inorganic Chemistry, 2006, 45(9): 3493-3495.
[22]	NAKASHIMA T, KIMIZUKA N.Interfacial synthesis of hollow TiO2 microspheres in ionic liquids.Journal of the American Chemical Society, 2003, 125(21): 6386-6387.
[23]	BALA H, YU Y, ZHANG Y.Synthesis and photocatalytic oxidation properties of titania hollow spheres.Materials Letters, 2008, 62(14): 2070-2073.
[24]	SHANG S, JOAO X, CHEN D.Template-free fabrication of TiO2 hollow spheres and their photocatalytic properties.ACS Applied Materials & Interfaces, 2012, 4(2): 860-865.
[25]	REN L, LI Y, HOU J, et al.Preparation and enhanced photocatalytic activity of TiO2 nanocrystals with internal pores.ACS Applied Materials & Interfaces, 2014, 6(3): 1608-1615.
[26]	LI D, QIN Q, DUAN X, et al.General one-pot template-free hydrothermal method to metal oxide hollow spheres and their photocatalytic activities and lithium storage properties.ACS Applied Materials & Interfaces, 2013, 5(18): 9095-9100.
[27]	ZHUANG Y, SUN J, GUAN M.Template free preparation of TiO2/C core-shell hollow sphere for high performance photocatalysis.Journal of Alloys and Compounds, 2016, 662: 84-88.
[28]	VAZ F A S, DE CASTRO P M, MOLINA C, et al. External polyacrylate-coating as alternative material for preparation of photopolymerized Sol-Gel monolithic column.Talanta, 2008, 76(1): 226-229.
[29]	BAO Y, SHI C, YANG Y, et al.Effect of hollow silica spheres on water vapor permeability of polyacrylate film.RSC Advances, 2015, 5(15): 11485-11493.
[30]	BAO Y, YANG Y, MA J.Fabrication of monodisperse hollow silica spheres and effect on water vapor permeability of polyacrylate membrane.Journal of Colloid and Interface Science, 2013, 407: 155-163.
[31]	YUE Q, LI Y, KONG M, et al.Ultralow density, hollow silica foams produced through interfacial reaction and their exceptional properties for environmental and energy applications.Journal of Materials Chemistry, 2011, 21(32): 12041-12046.
[32]	LI B, YUANG J, AN Z, et al.Effect of microstructure and physical parameters of hollow glass microsphere on insulation performance. Materials Letters, 2011, 65(12): 1992-1994.
[33]	QIAN BO ZHANG, ZHU JIAN FANG.Technology progress of thermal insulation materials of building energy efficiency.Journal of Building Energy Efficiency, 2009, 37(2): 56-60.
[34]	TACHIBANA Y, HARA K, SAYAMA K, et al.Quantitative analysis of light-harvesting efficiency and electron-transfer yield in ruthenium-dye-sensitized nanocrystalline TiO2 solar cells.Chemistry of Materials, 2002, 14(6): 2527-2535.
[35]	T LI H, BIAN Z, ZHU J, et al. Mesoporous titania spheres with tunable chamber stucture and enhanced photocatalytic activity. Journal of the American Chemical Society, 2007, 129(27): 8406-8407.
[36]	LEE J, HWANG S H, YUN J, et al.Fabrication of SiO2/TiO2 double-shelled hollow nanospheres with controllable size via Sol-Gel reaction and sonication-mediated etching.ACS Applied Materials & Interfaces, 2014, 6(17): 15420-15426.
[37]	BAO Y, LI MIAO, MA J.The effect of hollow SiO2 spheres on thermal insulation property of polyacrylate film.Journal of Functional Materials, 2016, 47(7): 7022-7027.
[38]	LEI ZHUO YAN, WANG ZHI, FAN HENG BING.Effect of B2O3 doping and phosphate impregnation on oxidation resistance and mechanical properties of mesocarbon microbead composites.Journal of Inorganic Materials. 2015, 30(7): 769-773.
[39]	ZHU PING, SUI SHU YING, LI JING.Study on performance of Nano-Far-Infrared PET Fiber.Nannoscience&Nanotechnology. 2007, 4(4): 17-21.
[40]	WANG F, LIANG J, TANG Q, et al.Preparation and performance of thermal insulation energy saving coating materials for exterior wall.Journal of Nanoscience and Nanotechnology, 2014, 14(5): 3861-3867.

中空TiO₂微球的制备及其对聚丙烯酸酯薄膜保温性能的影响

Fabrication of Hollow TiO₂ Spheres and Their Effect on Thermal Insulation Property of Polyacrylate Film

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