无机纳米粒子改性丙烯酸酯涂料的制备及其光老化性能的研究
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摘要
本论文拟研制新型高耐候无机纳米粒子改性水性丙烯酸酯外墙涂料。
在全面综述新型聚合物紫外光稳定剂的研究发展和应用状况的基础上，从材料的紫外光屏蔽性能出发，确定选用纳米TiO_2、SiO_2、ZnO作为涂料的光稳定材料。论文概括了无机纳米材料的各种制备技术，尤其着重介绍了湿化学方法制备纳米材料方面的最新进展，总结评述了当前无机纳米材料改性聚合物各种制备技术发展的现状及其问题。
在此基础上，为解决纳米粉体的团聚问题，使纳米粒子在涂料中有效分散与附聚，以实现纳米粒子改性的有效性，原创性地提出了原位生成纳米粒子改性涂料制备工艺的新思路：利用湿化学方法制备纳米材料的技术，在常规涂料制备的过程中加入所需引入纳米粒子的先驱物，直接在颜填料微粒的表面原位合成相应的纳米粒子。同时提出在位分散法纳米粒子改性涂料的制备技术：直接在涂料中引入采用湿化学方法制备的纳米粒子溶胶，而不是采用外加经过过滤和烧结等工艺制备的纳米粉体。原位生成纳米粒子改性法将纳米粒子的合成与分散一步完成；在位分散法纳米粒子改性工艺直接将纳米粒子溶胶与涂料进行分散，一定程度上避免了纳米粒子的团聚，保证了纳米粒子改性的有效性。
论文采用络合物水解法在常温下成功地制备了均匀分散的纳米TiO_2溶胶，并采用原位生成法制备了纳米TiO_2改性水性丙烯酸酯涂料。通过考查纳米TiO_2溶胶的紫外光吸收和散射性能发现纳米TiO_2溶胶对紫外光有很好的吸收屏蔽效果，在320nm以下紫外光波段的透过率几乎为零，且随着纳米二氧化钛粒径的变小，其紫外光吸收蓝移；研究了络合物水解法制备的工艺因素对纳米TiO_2紫外吸收和散射性能影响的相关规律；采用原位生成法制备的纳米TiO_2改性水性丙烯酸酯涂料的耐老化性能优异：人工老化1800小时后仍无粉化、起泡、剥落、裂纹等老化迹象，远远超过国标优等品要求的600小时粉化1级的标准，而相应的未改性涂料在人工老化1600小时时，粉化已达到1级。
用溶胶—凝胶法制备了稳定的纳米SiO_2溶胶，并采用在位分散法制备了纳
浙江大学硕士学位论文
米510:改性水性丙烯酸酷涂料。实验证明:纳米510:溶胶具有很强的紫外散射
屏蔽性能，对400nm以下的紫外光能屏蔽90%以上;在位分散法纳米510:改性
涂料的耐人工老化粉化时间比直接分散法纳米510:改性涂料提高了近1倍，耐
变色时间(达到色差2级的时间)是国标优等品要求的1.83倍，较相应的未改
性涂料提高了约25%。
通过原位生成法制备的纳米TIO:改性涂料和在位分散法制备的纳米510:改
性涂料具有超强的耐候性能，以人工老化100h大约相当于室外曝晒一年计算，
纳米改性的涂料在室外的使用寿命可超过18年。
The paper was intended to study a kind of waterborne acrylic resin exterior wall coatings with strong weatherability by the way of using inorganic nanoparticle as age-inhibiting addition.
Based on the comprehensive summary of the research and application of the modern ultraviolet radiation stabilizing agent, we began with the property of the UV shielding and chose the nano-TiO2, SiO2, ZnO as the UV shielding agent. In this thesis, we made a summary of the preparation technology of the nano-materials, especially of the latest development of preparing nano-materials by the way of the wet chemical method. The preparation methods of the nanocomposite materials were summarized too.
In order to solve the problem of conglomeration of the nanoparticle and make the nanoparticle disperse evenly in the coatings. In this way, we could succeed in improving the effect of modification .We originally put forward the in-situ sythesising nanoparticle method to modify coatings. Through this method, we made use of the technology of the wet chemical method and added the precursor of nanoparticle during the preparation of coatings. Meanwhile, the nanoparticle was formed on the face of the pigment. We also put forward the technique of in-situ dispersion to modify coatings .The key of the technique was to add the nanoparticle sol prepared by the wet chemical method into coatings instead of dropping the nanoparticle powder prepared by the technics of filtration and calcinations in the coatings. The preparation and the dispersion of the nanoparticle were finished in the same step by the first method. The second method could also solve the problem of dispersion in some way. Thus the efficiency of the modifi
cation could be assured.
We succeeded in preparing the nano-TiO2 sol through the hydrolyzation of complex in the room temperature and preparing the nanoTiO2-modified coatings by the way of in-situ sythesising method. First, the UV absorbing and scattering characteristics of the nano-TO2 sol were studied. The sol of the nano-TiO2 had excellent shielding effect on UV radiation. UV transmittance below 320nm was nearly zero, and the absorbing
of UV radiation was moved to short wavelength when the granularity of the nano-TiO2 was becoming finer. The influence of the technics of the hydrolyzation of complex on the UV shielding was studied. Then, we examined the weatherability of nano-TiO2-modified coatings prepared by the way of in-situ sythesising method. There were no aging phenomena such as chalking , bubbly , crackling , peeling-off after 1800h of the artificial aging process, which went far beyond the national standard for the super coating(the first level chalking after 600h of the artificial aging process). The common coatings reached first-degree chalking after 1600h of the artificial aging process.
The stable nano-SiO2 sol was prepared by Sol-Gel method and the nano-SiO2-modified coatings were prepared by the way of in-situ dispersion method. The UV scattering characteristic of nanometer SiO2 sol was studied. The nano-SiO2 sol had excellent reflecting and absorbing effect on UV radiation. 90%UV below 400nm could be shielded by the nano-SiO2 sol. The time of the artificial aging of nano-SiO2-modified coatings prepared by the way of in-situ dispersion method was about twice as long as that of the nano-SiO2-modified coatings prepared by dispersing the nano-SiO2 powder in the coating directly. On the other hand, the fadeproof time (reaching the second level of color aberration) of the nano-SiO2-modified coatings was 1.83 times as long as that of the national standard for the super coatings. There was an increase in the fadeproof time of 25 percent over the common coatings.
Both the nano-TiO2-modified coatings prepared by the way of in-situ sythesising method and the nano-SiO2-modified coatings prepared by the way of in-situ dispersion were strong weatherability coatings, which could resist 18 years' weathering if we calculated the result with the standard which argued that 100h of the artificial aging process was equal
在全面综述新型聚合物紫外光稳定剂的研究发展和应用状况的基础上，从材料的紫外光屏蔽性能出发，确定选用纳米TiO_2、SiO_2、ZnO作为涂料的光稳定材料。论文概括了无机纳米材料的各种制备技术，尤其着重介绍了湿化学方法制备纳米材料方面的最新进展，总结评述了当前无机纳米材料改性聚合物各种制备技术发展的现状及其问题。
在此基础上，为解决纳米粉体的团聚问题，使纳米粒子在涂料中有效分散与附聚，以实现纳米粒子改性的有效性，原创性地提出了原位生成纳米粒子改性涂料制备工艺的新思路：利用湿化学方法制备纳米材料的技术，在常规涂料制备的过程中加入所需引入纳米粒子的先驱物，直接在颜填料微粒的表面原位合成相应的纳米粒子。同时提出在位分散法纳米粒子改性涂料的制备技术：直接在涂料中引入采用湿化学方法制备的纳米粒子溶胶，而不是采用外加经过过滤和烧结等工艺制备的纳米粉体。原位生成纳米粒子改性法将纳米粒子的合成与分散一步完成；在位分散法纳米粒子改性工艺直接将纳米粒子溶胶与涂料进行分散，一定程度上避免了纳米粒子的团聚，保证了纳米粒子改性的有效性。
论文采用络合物水解法在常温下成功地制备了均匀分散的纳米TiO_2溶胶，并采用原位生成法制备了纳米TiO_2改性水性丙烯酸酯涂料。通过考查纳米TiO_2溶胶的紫外光吸收和散射性能发现纳米TiO_2溶胶对紫外光有很好的吸收屏蔽效果，在320nm以下紫外光波段的透过率几乎为零，且随着纳米二氧化钛粒径的变小，其紫外光吸收蓝移；研究了络合物水解法制备的工艺因素对纳米TiO_2紫外吸收和散射性能影响的相关规律；采用原位生成法制备的纳米TiO_2改性水性丙烯酸酯涂料的耐老化性能优异：人工老化1800小时后仍无粉化、起泡、剥落、裂纹等老化迹象，远远超过国标优等品要求的600小时粉化1级的标准，而相应的未改性涂料在人工老化1600小时时，粉化已达到1级。
用溶胶—凝胶法制备了稳定的纳米SiO_2溶胶，并采用在位分散法制备了纳
浙江大学硕士学位论文
米510:改性水性丙烯酸酷涂料。实验证明:纳米510:溶胶具有很强的紫外散射
屏蔽性能，对400nm以下的紫外光能屏蔽90%以上;在位分散法纳米510:改性
涂料的耐人工老化粉化时间比直接分散法纳米510:改性涂料提高了近1倍，耐
变色时间(达到色差2级的时间)是国标优等品要求的1.83倍，较相应的未改
性涂料提高了约25%。
通过原位生成法制备的纳米TIO:改性涂料和在位分散法制备的纳米510:改
性涂料具有超强的耐候性能，以人工老化100h大约相当于室外曝晒一年计算，
纳米改性的涂料在室外的使用寿命可超过18年。
The paper was intended to study a kind of waterborne acrylic resin exterior wall coatings with strong weatherability by the way of using inorganic nanoparticle as age-inhibiting addition.
Based on the comprehensive summary of the research and application of the modern ultraviolet radiation stabilizing agent, we began with the property of the UV shielding and chose the nano-TiO2, SiO2, ZnO as the UV shielding agent. In this thesis, we made a summary of the preparation technology of the nano-materials, especially of the latest development of preparing nano-materials by the way of the wet chemical method. The preparation methods of the nanocomposite materials were summarized too.
In order to solve the problem of conglomeration of the nanoparticle and make the nanoparticle disperse evenly in the coatings. In this way, we could succeed in improving the effect of modification .We originally put forward the in-situ sythesising nanoparticle method to modify coatings. Through this method, we made use of the technology of the wet chemical method and added the precursor of nanoparticle during the preparation of coatings. Meanwhile, the nanoparticle was formed on the face of the pigment. We also put forward the technique of in-situ dispersion to modify coatings .The key of the technique was to add the nanoparticle sol prepared by the wet chemical method into coatings instead of dropping the nanoparticle powder prepared by the technics of filtration and calcinations in the coatings. The preparation and the dispersion of the nanoparticle were finished in the same step by the first method. The second method could also solve the problem of dispersion in some way. Thus the efficiency of the modifi
cation could be assured.
We succeeded in preparing the nano-TiO2 sol through the hydrolyzation of complex in the room temperature and preparing the nanoTiO2-modified coatings by the way of in-situ sythesising method. First, the UV absorbing and scattering characteristics of the nano-TO2 sol were studied. The sol of the nano-TiO2 had excellent shielding effect on UV radiation. UV transmittance below 320nm was nearly zero, and the absorbing
of UV radiation was moved to short wavelength when the granularity of the nano-TiO2 was becoming finer. The influence of the technics of the hydrolyzation of complex on the UV shielding was studied. Then, we examined the weatherability of nano-TiO2-modified coatings prepared by the way of in-situ sythesising method. There were no aging phenomena such as chalking , bubbly , crackling , peeling-off after 1800h of the artificial aging process, which went far beyond the national standard for the super coating(the first level chalking after 600h of the artificial aging process). The common coatings reached first-degree chalking after 1600h of the artificial aging process.
The stable nano-SiO2 sol was prepared by Sol-Gel method and the nano-SiO2-modified coatings were prepared by the way of in-situ dispersion method. The UV scattering characteristic of nanometer SiO2 sol was studied. The nano-SiO2 sol had excellent reflecting and absorbing effect on UV radiation. 90%UV below 400nm could be shielded by the nano-SiO2 sol. The time of the artificial aging of nano-SiO2-modified coatings prepared by the way of in-situ dispersion method was about twice as long as that of the nano-SiO2-modified coatings prepared by dispersing the nano-SiO2 powder in the coating directly. On the other hand, the fadeproof time (reaching the second level of color aberration) of the nano-SiO2-modified coatings was 1.83 times as long as that of the national standard for the super coatings. There was an increase in the fadeproof time of 25 percent over the common coatings.
Both the nano-TiO2-modified coatings prepared by the way of in-situ sythesising method and the nano-SiO2-modified coatings prepared by the way of in-situ dispersion were strong weatherability coatings, which could resist 18 years' weathering if we calculated the result with the standard which argued that 100h of the artificial aging process was equal
引文
[1] 张贻鑫，建筑物外墙装饰应以涂料为主，新型建筑材料，1998. 1，17～20。
[2] B.Ranby, J F Rabek, Photodegradation photo-oxidation and photo-stabilization of polymers[M], John wiley & sons, 1975, 379-381.
[3] Norman S.Allen, Michele Edge, Teresa Corrales, Aileen Childs, Christopher M Liauw, Fernando Catalina, C.Peinado, Alan Minihan, Derek aldcroft, Ageing and stabilisation of filled polymers: an overview, Polyer Degradation and Stability, 1998, Volume: 61, Issue: 2;183-199.
[4] Vesa P S Judin, Influence of titanium dioxide pigments on the photodegradation of poly (vinyl chloride) [J] , Chem in Bri, 1993, 29(6) :574～577.
[5] 张立德，牟季美著，纳米材料和纳米结构，科学出版社，第一版，2001
[6] Jose Aldana, Y. Andrew Wang, Xiaogang Peng, Photochemical Instability of CdSe Nanocrystals Coated by Hydrophilic Thiols, J.Am.Chem.Soc, 2001, 123: 8844-8850.
[7] Fujishima A, Honda K, Electrochemical photolysis of water at a semiconductor electrode, Nature ,1972,238:37～38.
[8] Wang R, Hashimoto K, Fujishima, Light-induced amphiphilic Surface, Nature, 1997, 388:431～432.
[9] 黄志杰，刘景春，黄海，左美祥，纳米SiO_2-x抗老化性研究及其应用，化学建材2001年，第01期：46-47。
[10] Zhou Shuxue, Wu Limin , Sun Jian Shen, Weidian, The change of the properties of acrylic-based polyurethane via addition of nano-silica, Progress in Organic Coatings, 2002, 45: 33-42.
[11] 关振铎，张中太，焦金生 编著，无机材料物理性能，清华大学出版社，第1版，1992。
[12] Clayton J,Ultrafine titanium dioxide for wood finishs,Am Paint coatings J,1994:49.
[13] Vignolo CE, Some applications of ultrafine titanium dioxide, Eur Coat J,1995,
5：359。
[14] 曹鹏军，范培耕，仵海东，周安若，利用纳米材料TiO2提高漆膜老化性能的研究，重庆工业高等专科学校学报，2002，17(4)：34-38。
[15] 陈彩凤，陈志刚，陈雪梅，郝臣，纳米粉体的制备技术，江苏理工大学学报(自然科学版)，2000，21(6)：98-102。
[16] 陈洪龄，王延儒，时钧，四氯化钛络合法制备单分散纳米二氧化钛，无机材料学报2002，17(1)，149—153。
[17] 陈小泉，古国榜，钛氧有机化合物常压低温液相合成纳米二氧化钛晶体的研究，无机化学学报，2002，18(7)：749—752
[18] 王子忱，王莉玮，赵敬哲，杨广丽，杨烨，赵慕愚，沉淀法合成高比表面积超细SiO_2，无机材料学报，1997年03期，391～396。
[19] Werner Stober, Arthur Fink,Ernst Bohn, Controlled growth of monodisperse silica spheres in the micron size range, Journal of colloid and interface science 1968, 26,62～69.
[20] Morris C A,Anderson M L, Stroud P M, Silica sol as a nanoglue:Flexible synthesis of composite aerogels.Science, 1999,284:622-624.
[21] Ju C S, Lee M G, Hong S S. Effect of precipitation Conditions on the Shapes and Size Distributions of Zinc Oxide Particles Prepared by Homogeneous Preciptation[J]. Hwahak Konghak,1997,35(5): 655-660.
[22] 祖庸，刘超峰，李晓娥，均匀沉淀法合成纳米氧化锌，现代化工，1997，17(9)：33—35。
[23] Roy R, Kormarneni, Cation-exchange propertyes of hydrated cements, Mater Res Soc Symp Proc, 1984,32: 347.
[24] 生瑜，朱德钦，陈建定，聚合物基无机纳米复合材料的制备方法，高分子通报，2001年，第4期：9—14。
[25] Tasoula Kyprianidou-Leodidou, Walter Caseri, Ulrich W. Suter, Size Variation of PbS Particles in High-Refractive-Index Nanocomposites, J Phys Chem,1994, 98(36): 8992-8997.
[26] 陈祖耀，郝凌云，周勇，朱玉瑞，合成聚丙酰胺一硫属半导体复合纳米材料
的新技术，化学物理学报，2000年，第01期：95—98。
[27] 黄惠忠编著，纳米材料分析，化学工业出版社，2003年第1版。
[28] 殷晓梅，宋建华，李庆娟，左文才，关于涂料漆膜人工加速老化的研究，化学建材，2000年，第3期：23—24。
[29] 吴孟强，张其翼，陈艾，马银铃，凝胶-水热法制备纺锤形TiO_2粉体，硅酸盐学报，2002，30(1)：108-111。
[30] 关振铎，张中太，焦金生 编著，无机材料物理性能，清华大学出版社，1992年3月，第一版
[31] Overbeek J Th C, Advance in Colloid & Inteerface Sci, 1982,15:251-277.
[32] Claudius Kormann; Detlef W.Bahnemann and Michacl R.Hoffmann.Preparation and characterization of quantum-size titanium dioxide, J. Phys Chem 1988, 92: 5196-5201.
[33] Louis Brug, Electron wave functions in semiconductor clusters:experiment and theory, J. phys. chem, 1986, 90: 2555-2560.
[34] 王训，祖庸，李晓娥，纳米TiO_2表面改性，化工进展，2000年，第1期：67-71。
[35] 蒋莉，张鑫，赵石林，纳米TiO_2生产及其在涂料中的应用，新型建筑材料，2003年，第2期：19—21。
[36] P. Salvador, M. L. Garcia Gonzalez, F. Munoz, Catalytic role of lattice defects in the photoassisted oxidation of water at (001) n-titanium(Ⅳ) oxide rutile J. Phys. Chem. 1992, 96(25), 10349-10353.
[37] 王玲玲，方小龙，唐芳琼，杨传芳，刘会洲，单分散二氧化硅超细颗粒的制备，过程工程学报，2001，1(2)：167-172。
[38] Thometzek P, Ludwig A, Karbach A, Khler K, Effects of morphology and surface treatment of inorganic pigments on waterborne coating properties, Progress in Organic Coatings, 1999, 36: 201-209.
[39] Frings, S, Meinema, H.A, van Nostrum, C.F, van der Linde, R, Organic-inorganic hybrid coatings for coil coating application based on polyesters and tetraethoxysilan, Progress in Organic Coatings, 1998, 33 (2): 126-130.
[40] 欧玉春，杨锋，庄严，漆宗能，在位分散聚合聚甲基丙烯酸甲酯／二氧化硅纳米复合材料研究，高分子学报，1997年，第2期：199-205。
[41] 刘景春，韩建成，跨世纪高新科技纳米材料一员——纳米SiO_2，中国陶瓷，1997，33(03)：39-40。
[42] 夏正斌，涂伟萍，外墙涂料的老化与降解，现代涂料与涂装，2003年，第05期：20—22。
[43] 柯博，黄志杰，左美祥，马全利，纳米SiO_2在涂料中的应用，涂料工业，1998年，第12期：29-30。
[2] B.Ranby, J F Rabek, Photodegradation photo-oxidation and photo-stabilization of polymers[M], John wiley & sons, 1975, 379-381.
[3] Norman S.Allen, Michele Edge, Teresa Corrales, Aileen Childs, Christopher M Liauw, Fernando Catalina, C.Peinado, Alan Minihan, Derek aldcroft, Ageing and stabilisation of filled polymers: an overview, Polyer Degradation and Stability, 1998, Volume: 61, Issue: 2;183-199.
[4] Vesa P S Judin, Influence of titanium dioxide pigments on the photodegradation of poly (vinyl chloride) [J] , Chem in Bri, 1993, 29(6) :574～577.
[5] 张立德，牟季美著，纳米材料和纳米结构，科学出版社，第一版，2001
[6] Jose Aldana, Y. Andrew Wang, Xiaogang Peng, Photochemical Instability of CdSe Nanocrystals Coated by Hydrophilic Thiols, J.Am.Chem.Soc, 2001, 123: 8844-8850.
[7] Fujishima A, Honda K, Electrochemical photolysis of water at a semiconductor electrode, Nature ,1972,238:37～38.
[8] Wang R, Hashimoto K, Fujishima, Light-induced amphiphilic Surface, Nature, 1997, 388:431～432.
[9] 黄志杰，刘景春，黄海，左美祥，纳米SiO_2-x抗老化性研究及其应用，化学建材2001年，第01期：46-47。
[10] Zhou Shuxue, Wu Limin , Sun Jian Shen, Weidian, The change of the properties of acrylic-based polyurethane via addition of nano-silica, Progress in Organic Coatings, 2002, 45: 33-42.
[11] 关振铎，张中太，焦金生 编著，无机材料物理性能，清华大学出版社，第1版，1992。
[12] Clayton J,Ultrafine titanium dioxide for wood finishs,Am Paint coatings J,1994:49.
[13] Vignolo CE, Some applications of ultrafine titanium dioxide, Eur Coat J,1995,
5：359。
[14] 曹鹏军，范培耕，仵海东，周安若，利用纳米材料TiO2提高漆膜老化性能的研究，重庆工业高等专科学校学报，2002，17(4)：34-38。
[15] 陈彩凤，陈志刚，陈雪梅，郝臣，纳米粉体的制备技术，江苏理工大学学报(自然科学版)，2000，21(6)：98-102。
[16] 陈洪龄，王延儒，时钧，四氯化钛络合法制备单分散纳米二氧化钛，无机材料学报2002，17(1)，149—153。
[17] 陈小泉，古国榜，钛氧有机化合物常压低温液相合成纳米二氧化钛晶体的研究，无机化学学报，2002，18(7)：749—752
[18] 王子忱，王莉玮，赵敬哲，杨广丽，杨烨，赵慕愚，沉淀法合成高比表面积超细SiO_2，无机材料学报，1997年03期，391～396。
[19] Werner Stober, Arthur Fink,Ernst Bohn, Controlled growth of monodisperse silica spheres in the micron size range, Journal of colloid and interface science 1968, 26,62～69.
[20] Morris C A,Anderson M L, Stroud P M, Silica sol as a nanoglue:Flexible synthesis of composite aerogels.Science, 1999,284:622-624.
[21] Ju C S, Lee M G, Hong S S. Effect of precipitation Conditions on the Shapes and Size Distributions of Zinc Oxide Particles Prepared by Homogeneous Preciptation[J]. Hwahak Konghak,1997,35(5): 655-660.
[22] 祖庸，刘超峰，李晓娥，均匀沉淀法合成纳米氧化锌，现代化工，1997，17(9)：33—35。
[23] Roy R, Kormarneni, Cation-exchange propertyes of hydrated cements, Mater Res Soc Symp Proc, 1984,32: 347.
[24] 生瑜，朱德钦，陈建定，聚合物基无机纳米复合材料的制备方法，高分子通报，2001年，第4期：9—14。
[25] Tasoula Kyprianidou-Leodidou, Walter Caseri, Ulrich W. Suter, Size Variation of PbS Particles in High-Refractive-Index Nanocomposites, J Phys Chem,1994, 98(36): 8992-8997.
[26] 陈祖耀，郝凌云，周勇，朱玉瑞，合成聚丙酰胺一硫属半导体复合纳米材料
的新技术，化学物理学报，2000年，第01期：95—98。
[27] 黄惠忠编著，纳米材料分析，化学工业出版社，2003年第1版。
[28] 殷晓梅，宋建华，李庆娟，左文才，关于涂料漆膜人工加速老化的研究，化学建材，2000年，第3期：23—24。
[29] 吴孟强，张其翼，陈艾，马银铃，凝胶-水热法制备纺锤形TiO_2粉体，硅酸盐学报，2002，30(1)：108-111。
[30] 关振铎，张中太，焦金生 编著，无机材料物理性能，清华大学出版社，1992年3月，第一版
[31] Overbeek J Th C, Advance in Colloid & Inteerface Sci, 1982,15:251-277.
[32] Claudius Kormann; Detlef W.Bahnemann and Michacl R.Hoffmann.Preparation and characterization of quantum-size titanium dioxide, J. Phys Chem 1988, 92: 5196-5201.
[33] Louis Brug, Electron wave functions in semiconductor clusters:experiment and theory, J. phys. chem, 1986, 90: 2555-2560.
[34] 王训，祖庸，李晓娥，纳米TiO_2表面改性，化工进展，2000年，第1期：67-71。
[35] 蒋莉，张鑫，赵石林，纳米TiO_2生产及其在涂料中的应用，新型建筑材料，2003年，第2期：19—21。
[36] P. Salvador, M. L. Garcia Gonzalez, F. Munoz, Catalytic role of lattice defects in the photoassisted oxidation of water at (001) n-titanium(Ⅳ) oxide rutile J. Phys. Chem. 1992, 96(25), 10349-10353.
[37] 王玲玲，方小龙，唐芳琼，杨传芳，刘会洲，单分散二氧化硅超细颗粒的制备，过程工程学报，2001，1(2)：167-172。
[38] Thometzek P, Ludwig A, Karbach A, Khler K, Effects of morphology and surface treatment of inorganic pigments on waterborne coating properties, Progress in Organic Coatings, 1999, 36: 201-209.
[39] Frings, S, Meinema, H.A, van Nostrum, C.F, van der Linde, R, Organic-inorganic hybrid coatings for coil coating application based on polyesters and tetraethoxysilan, Progress in Organic Coatings, 1998, 33 (2): 126-130.
[40] 欧玉春，杨锋，庄严，漆宗能，在位分散聚合聚甲基丙烯酸甲酯／二氧化硅纳米复合材料研究，高分子学报，1997年，第2期：199-205。
[41] 刘景春，韩建成，跨世纪高新科技纳米材料一员——纳米SiO_2，中国陶瓷，1997，33(03)：39-40。
[42] 夏正斌，涂伟萍，外墙涂料的老化与降解，现代涂料与涂装，2003年，第05期：20—22。
[43] 柯博，黄志杰，左美祥，马全利，纳米SiO_2在涂料中的应用，涂料工业，1998年，第12期：29-30。