硅气凝胶的制备、表征及其性能研究
|
摘要
由于Si02气凝胶具有低密度、高比表面和高孔隙率的纳米多孔材料的优秀品质,使其在热学、力学、光学、电学、声学、催化剂及其药物载体等方面有着广阔的应用前景。
本文以正硅酸乙酯(TEOS)为硅源,以N,N-二甲基甲酰胺(DMF),丙三醇(GLY),聚乙二醇(PEG400)为干燥控制化学添加剂(DCCA),以无水乙醇(EtOH)/六甲基二硅氮烷(HMDZ)/正己烷(Hexane)为溶剂交换与表面改性试剂,对Si02气凝胶合成中的“一步溶剂交换与表面改性”新工艺,首次进行了探索。
实验中以气凝胶的稳定性、振实密度、接触角以及比表面(BET)等项目作为产品的性能指标；以傅立叶转换红外线光谱(FTIR)、X射线衍射(XRD)、热重-差示(TG-DSC)以及场发射扫描电镜(F-SEM)作为产品的结构指标；分别考察了DCCA的种类和用量、EtOH/HMDZ的摩尔比、HMDZ/Hexane的体积比等因素对产品的性能和结构的影响。并以产品对甲基橙和亚甲基蓝的吸附性能为标准,考察了Si02气凝胶的吸附应用性能。
结果表明,溶胶凝胶一步溶剂交换与表面改性制备Si02气凝胶的最佳工艺条件为：以DMF为DCCA, n(DMF)/n(TEOS)和n(EtOH)/n(HMDZ)的最佳摩尔比分别为0.2和0.8,V(HMDZ)/V(Hexane)的最佳体积比为0.1。所得产品Si02气凝胶的密度为130kg/m3,比表面积为842.63m2/g,产品粒径约为15nm,孔径分布在2-150nm,并具有良好的疏水性能。在45℃条件下,产品对甲基橙的最大吸收率为18.5%；产品对亚甲基蓝的最大吸附率为98.8%。
此外,本文还合成了六钛酸钾晶须掺杂Si02气凝胶,考察了不同掺杂量对产品结构和隔热性能的影响。结果表明,在不破坏Si02气凝胶原有微观结构掺杂量的前提下,随着掺杂量的增大,产品的隔热性能有所增强。
综上所述,用“一步法”制备的Si02气凝胶性能优越,与“多步法”相当,但将生产周期从原来的6天缩减到4天,在保证质量的前提下有效的降低了能耗,减少了污染,节约了成本。为解决传统气凝胶制备工艺周期长,条件复杂的难问题,实现节能减排,提供了重要的理论依据。
Silica aerogel has widely application prospects in thermology, mechanics, optics, electrics, acoustics and catalyst carriers, owning to its advantages of low density, high surface area and high porosity.
In this paper, the new method of "one-step acid-base sol-gel pr ocess" was firstly explored in the synthesis of Silica aerogel, when Tetraethoxysilane was used as precusor of silica, dimethyl formamid e, glycerol and polyethylene glycol were as DCCA. ethanol/hexmeth ydisilazane/hexane were the reagents of one-step solvent exchange and surface modification process.
The stability, tap density, contact angle and specific surface of aerogels were took as the main performance indexes of products. The structure and morphology of silica aerogels have been investigated by FTIR, XRD, TG-DSC, F-SEM, BET. The influence of the kinds and amounts of DCCA, EtOH/HMDZ molar ratio, HMDZ/Hexane volume ratio on the structures and properties of silica aerogels were also discussed, and the absorptivities of silica aerogels for were also investigated when took the adsorption performance of the product on methyl orange and methylene blue.
The results showed that the aerogels had high surface area of 842.63m2/g when the molar ratio of DMF and TEOS was 0.2, the optimal molar ratio of ETOH and HMDZ was 0.8, and the volume ratio of HMDZ and Hexane was 0.1. the density of the aerogels with the high surface area was 130kg/m3, the diameter was about 15nm and the diameter of the pore sizes was in the range of 2～150nm, the aerogels also showed an excellent hydrophobic feature.The maximum absorptivity of product on methyl orange was 18.5% and the maximum absorptivity of products on methylene blue was 98.8% when the temperature was 45℃.
Moreover, silica aerogels doped with K2Ti6O13 whiskers were also prepared, and the effects of doping amount on structure and heat-proof quality of product were also investigated. Results showed that the heat-proof quality of products was enhanced with doping amounts increasing on condition that the original microstructure of silica aerogel wasn't destroyed.
In conclusion, the performance of silica aerogel prepared with one-step method was superior than that prepared with multistep method, the production cycle was cut to four days from primary six days. The energy consumption was reduced, the pollution was decreased and the cost was saved in the premise of the guaranteeing quality. It also provided important theoretical basis for solving the problems of the long cycle and complex conditions of traditional aerogel preparation technology and realizing the advantages of energy saving and emission reduction.
本文以正硅酸乙酯(TEOS)为硅源,以N,N-二甲基甲酰胺(DMF),丙三醇(GLY),聚乙二醇(PEG400)为干燥控制化学添加剂(DCCA),以无水乙醇(EtOH)/六甲基二硅氮烷(HMDZ)/正己烷(Hexane)为溶剂交换与表面改性试剂,对Si02气凝胶合成中的“一步溶剂交换与表面改性”新工艺,首次进行了探索。
实验中以气凝胶的稳定性、振实密度、接触角以及比表面(BET)等项目作为产品的性能指标；以傅立叶转换红外线光谱(FTIR)、X射线衍射(XRD)、热重-差示(TG-DSC)以及场发射扫描电镜(F-SEM)作为产品的结构指标；分别考察了DCCA的种类和用量、EtOH/HMDZ的摩尔比、HMDZ/Hexane的体积比等因素对产品的性能和结构的影响。并以产品对甲基橙和亚甲基蓝的吸附性能为标准,考察了Si02气凝胶的吸附应用性能。
结果表明,溶胶凝胶一步溶剂交换与表面改性制备Si02气凝胶的最佳工艺条件为：以DMF为DCCA, n(DMF)/n(TEOS)和n(EtOH)/n(HMDZ)的最佳摩尔比分别为0.2和0.8,V(HMDZ)/V(Hexane)的最佳体积比为0.1。所得产品Si02气凝胶的密度为130kg/m3,比表面积为842.63m2/g,产品粒径约为15nm,孔径分布在2-150nm,并具有良好的疏水性能。在45℃条件下,产品对甲基橙的最大吸收率为18.5%；产品对亚甲基蓝的最大吸附率为98.8%。
此外,本文还合成了六钛酸钾晶须掺杂Si02气凝胶,考察了不同掺杂量对产品结构和隔热性能的影响。结果表明,在不破坏Si02气凝胶原有微观结构掺杂量的前提下,随着掺杂量的增大,产品的隔热性能有所增强。
综上所述,用“一步法”制备的Si02气凝胶性能优越,与“多步法”相当,但将生产周期从原来的6天缩减到4天,在保证质量的前提下有效的降低了能耗,减少了污染,节约了成本。为解决传统气凝胶制备工艺周期长,条件复杂的难问题,实现节能减排,提供了重要的理论依据。
Silica aerogel has widely application prospects in thermology, mechanics, optics, electrics, acoustics and catalyst carriers, owning to its advantages of low density, high surface area and high porosity.
In this paper, the new method of "one-step acid-base sol-gel pr ocess" was firstly explored in the synthesis of Silica aerogel, when Tetraethoxysilane was used as precusor of silica, dimethyl formamid e, glycerol and polyethylene glycol were as DCCA. ethanol/hexmeth ydisilazane/hexane were the reagents of one-step solvent exchange and surface modification process.
The stability, tap density, contact angle and specific surface of aerogels were took as the main performance indexes of products. The structure and morphology of silica aerogels have been investigated by FTIR, XRD, TG-DSC, F-SEM, BET. The influence of the kinds and amounts of DCCA, EtOH/HMDZ molar ratio, HMDZ/Hexane volume ratio on the structures and properties of silica aerogels were also discussed, and the absorptivities of silica aerogels for were also investigated when took the adsorption performance of the product on methyl orange and methylene blue.
The results showed that the aerogels had high surface area of 842.63m2/g when the molar ratio of DMF and TEOS was 0.2, the optimal molar ratio of ETOH and HMDZ was 0.8, and the volume ratio of HMDZ and Hexane was 0.1. the density of the aerogels with the high surface area was 130kg/m3, the diameter was about 15nm and the diameter of the pore sizes was in the range of 2～150nm, the aerogels also showed an excellent hydrophobic feature.The maximum absorptivity of product on methyl orange was 18.5% and the maximum absorptivity of products on methylene blue was 98.8% when the temperature was 45℃.
Moreover, silica aerogels doped with K2Ti6O13 whiskers were also prepared, and the effects of doping amount on structure and heat-proof quality of product were also investigated. Results showed that the heat-proof quality of products was enhanced with doping amounts increasing on condition that the original microstructure of silica aerogel wasn't destroyed.
In conclusion, the performance of silica aerogel prepared with one-step method was superior than that prepared with multistep method, the production cycle was cut to four days from primary six days. The energy consumption was reduced, the pollution was decreased and the cost was saved in the premise of the guaranteeing quality. It also provided important theoretical basis for solving the problems of the long cycle and complex conditions of traditional aerogel preparation technology and realizing the advantages of energy saving and emission reduction.
引文
[1]王英滨.常压干燥溶胶-凝胶法制备SiO2气凝胶：[博士学位论文].北京：中国地质大学.2002
[2]戴志成.硅化合物的生产与应用.成都：成都科技大学出版社,1994
[3]王珏.轻质纳米多孔性材料-气凝胶.材料导报,1993,2：36-38
[4]沈军,周斌,吴光明等.纳米孔超级绝热材料气凝胶的制备与热学特性.程工程学报,2002,2(4)：314～345
[5]Pierre A C, Pajonk G M. Chemistry of aerogels and their applications. Chemical Reviews,2002,102(11):4243-4265
[6]Hunt A J, Ayers M R, Cao W. Aerogel composites using chemical vapor infiltration. Journal of Non-Crystalline Solids,1995,185:227-232
[7]Hu S W, Willey R J, Notari B. An investigation on the catalytic properties of titania-silica materials. Journal of Catalysis,2003,220:240-248
[8]Beamish J, Herman T. Adsorption and desorption of helium in aerogels. Physica B: Condensed Matter,2003,329-333:340-341
[9]Lawrence W. Hrubesh. Aerogel applications. Journal of Non-Crystalline Solids, 1998,225:335-342
[10]黄娆,刘之景.新型低介电常数材料研究进展.纳米材料与结构.2003,09：11-15
[11]Berkutov I B, Babuin S, Golov A I. Transverse sound in aerogel with liquid 4He. Physica B:Condensed Matter,2003,329-333:337-339
[12]Danilyuk A F, Kirillov V L, Savelieva M D, et al. Recent results on aerogel development for use in Cherenkov counters. Nuclear Instruments and Methods in Physics Research A,2002,494:491-494
[13]Tsou P. Proceedings of the fourth international symposium on aerogels. Journal of Non-Crystalline Solids,1995,186:415-420
[14]Smirnova I, Suttiruengwong S, Arlt W. Feasibility study of hydrophilic and hydrophobic silica aerogels as drug delivery systems. Journal of Non-Crystalline Solids,2004,350:54-60
[15]王珏,沈军,J.Fricke高效隔热材料掺杂TiO2及玻璃纤维硅石气凝胶的研制。材料研究学报,1995,9(6)：568～572
[16]Kim G S, Hyun S H, Synthesis of window glazing coated with silica aerogel films via ambient drying. J. Non-Cryst. Solids,2003,320(1-3):125-132
[17]Shen Jun, Ouyang Ling, Lin Xuejing etal. Preparation of Low-K and Low-n Mesoporous Silica Film via Sol-Gel Process. Rare metal materials and engineering,2008, (5)37:76-79
[18]Cahill S A. Optical and electronic characterization of sol-gel-derived silica aerogels for display and imaging application:[Dissertation]. Davis:University of California,1999
[19]Akimov Y K. Fields of Application of Aerogels. Instruments and Experimental Techniques,2003,46(3):287-299
[20]邓忠生,王珏,陈玲艳.气凝胶应用进展.材料导报,1999,13(6)：47～49
[21]Cho W, Saxena R, Rodriguez O etal. Effects of sintering on dielectric constants of mesoporous silica. Journal of Non-Cryst. Solids,2004,350:336-344
[22]Kim G S, Sang H. Hyun. Synthesis and characterization of silica aerogel films for inter-metal dielectrics via ambient drying. Thin Solid Film,2004,460: 190-200
[23]Ayers M R, Hunt A J, molecular oxygen sensors based on photoluminescent silica aerogels, J. of Non-Cryst. Solids,2001,285:79-83
[24]Alain C, Pierret, Ge'rard M, et al. Chemistry of aerogels and their applications. Chemistry Review,2002,102:4243-4265
[25]Forest L, Gibiat V, Hooley A. Impedance matching and acoustic absorption in granular layers of silica aerogels. Journal of Non-Crystalline Solids,2001,285: 230-235
[26]Akimov Y K. Fields of Application of Aerogels. Instruments and Experimental Techniques,2003,46(3):287-299
[27]Forest L, Gibiat V, Hooley A. Impedance matching and acoustic absorption in granular layers of silica aerogels. J. Non-Cryst. Solids,2001,285(1-3): 230-235
[28]武志刚,赵永祥,许临萍等.气凝胶制备进展及其在催化方面的应用.化学研究与应用,2003,15(1)：17-20
[29]何飞.Si02和SiO2-Al2O3复合干凝胶超级隔热材料的制备与表征：[博士学位论文].哈尔滨：哈尔滨工业大学,2006
[30]王亚权.催化剂表面分形结构对催化反应的影响.燃料化学学报,1999,27(2)：110～115
[31]郝利锋,高志华,阴丽华等.气凝胶的制备及其在催化领域的应用.天然气 化工,2005,30(1)：49～53
[32]甘礼华,郝志显,王玉栋等TiO2/SiO2气凝胶的非超临界干燥法制备及其对吡啶降解的光催化活性.中国化学工程学报(英文版),2005,13(6)：1002～1005
[33]王承学,齐国帧,李然.在改性M/SiO2催化剂在甲烷部分氧化,长春工业大学学报,2002,8(23)：90～94
[34]Buisson P, Hernandez C, Pierre M, et al. Encapsulation of lipases in aerogel. Journal of Non-Crystalline Solids,2001,285:295-302
[35]胡巧开.粉煤灰对甲基橙的吸附研究.上海化工,2004,8：10-12
[36]John G. Reynolds, Paul R. Coronado, Lawrence W. Hrubesh. Hydrophobic aerogels for oil-spill clean up synthesis and characterization. Journal of Non-Crystalline Solids,2001, (292):127-137
[37]Reynes J, Woignier T, Phalippou J. Permeability measurement in composity aerogels:application to nuclear waste storage. J.Non-Cryst. Solid,2001,285(1-3):323-327
[38]Woignier T, Reynes J, Phalippou J, Dussossoy J L etal. Sintered silica aerogel:a host matrix for long life nuclear wastes. J. Non-cryst. Solids,1998,225(1): 353-327
[39]Kraume I M. Synthesis of silica aerogels and their application as a drug delivery system:[Dissertation]. Berlin:Technischen Universitat Berlin,2002
[40]Buisson P, Hernandez C, Pierre M, et al. Encapsulation of lipases in aerogel. Journal of Non-Crystalline Solids,2001,285:295-302
[41]Jang K Y, Kim K. Study of sol-gel processing for fabrication of hollow silica-aerogel spheres. Journal of Vacuum Science and Technoloy,1989, A8: 1732-1735
[42]Golob P. Current status and future perspetives for inert dusts for control of stored product insect. Journal of Stored Produncts Research,1997,33:69-79
[43]丁星兆,何怡贞,董远达.溶胶-凝胶工艺在材料科学中的应用.材料科学与工程,1994,12(2)：1-8
[44]赵文珍.溶胶-凝胶科学技术的发展.材料导报,1996,6：12-15
[45]田明原,施尔畏.纳米陶瓷与纳米陶瓷粉末.无机材料学报,1998,2：129～137
[46]Mosing K, Jacobs T, Brennan K, et al. Integration challenges of porous ultra low-k spin-on dielectrics. Microelectronic Engineering,2002,64:11-24
[47]Scherer G W, Nisen E, Einarsrud M A, et al. Shrinkage of silica gels aged in TEOS. Journal of Non-Crystalline Solids,1996,202:42-52
[48]Scherer G W. Effect of drying on properties of silica gel. Journal of Non-Crystalline Solids,1997,215:155-168
[49]Smith D M, Scherer G W, Anderson J M. Shrinkage during drying of silica gel. Journal of Non-Crystalline Solids,1995,188:191-206
[50]陈武龙,张宇星,甘礼华等.气凝胶的非超临界干燥制备技术.实验室研究与探索,2001,20(6)：54～57
[51]相宏伟,钟炳,彭少逸.超临界流体干燥理论、技术及应用.材料科学与工程,1995,13(2)：38～53
[52]李文翠,郭树才,赵旭东.超临界流体干燥法制备炭气凝胶.碳素技术,2000,3：7-9
[53]陈龙武,甘礼华,岳天仪等.超临界干燥法制备Si02气凝胶的研究.高等学校化学学报,1995,16(6)：840～843
[54]陈龙武,甘礼华,侯秀红.气凝胶的非超临界干燥法制备及其形成过程.物理化学学报,2003,19(9)：819～823
[55]沈军,王珏,吴翔.气凝胶-一种结构可控的新型材料功能材料.材料科学与工程,1994,12(3)：1-6
[56]Jima AN, Hashimoto K, Watanabe T. Recent studies on super-hyrophobic films. Monatshefte fur Chemie,2001, (132):31-34
[57]同小刚,王芬,冯海涛等.二氧化硅气凝胶的制备和应用研究.材料导报,2006.20：24～26
[58]陈龙武.二氧化硅气凝胶介孔大孔材料研究：[硕士学位论文].上海：同济大学,2003
[59]李伟,王霞瑜,张平等.溶胶-凝胶法制备疏水型Si02气凝胶.材料科学与工程,2002,20(1)：58-60
[60]甘礼华,张宇星,陈龙武等.干燥控制化学添加剂在制备硅气凝胶中的应用.同济大学学报(自然科学版),2003,31：1131～1134
[61]Uchida N, Ishiyama N, Kato Z, et al. Chemical effects of DDCA to the sol-gel process. Journal of Materials Sciences,1994,29:5188-5192
[62]Amato G, Brunetto N, Parisini A. Characterization of freeze-dried porous silicon. Thin Solid Films,1997,297:73-78
[63]Mathieu B, Blacher S, Pirard R, et al. Freeze-dried resorcinol-formaldehyde gels. Journal of Non-Crystalline Solids,1997,212:250-261
[64]Tamon H, Ishizaka H, Yamamoto T. Preparation of mesoporous carbon by freeze drying. Carbon,1999,37:2049-2055
[65]陈一民,谢凯,盘毅等.钴/Si02纳米复合气凝胶的制备表征.功能材料,2011,32(1)：91～92
[66]甘礼华,李光明,岳天仪等.超临界干燥法制备Fe2O3/SiO2气凝胶.物理化学学报,1999,15(7)：588～592
[67]武志刚,赵永祥,许临萍等.镍含量对NiO/SiO2气凝胶性能的影响.无机化学学报,2002,18(9)：949～952
[68]何文,张旭东,韩丽.A12O3/SiO2气凝胶纳米粉的制备与表征.中国陶瓷,2000,36(6)：4-6
[69]Yao L Z, Ye C H, Mo C M etal. Study of crystallization and spectral properties of PbS nanocrystals doped in SiO2 aerogel matrix. J Cryst,2000,216:147-151
[70]甘礼华,王小兰,郝志显等.TiO2-SiO2气凝胶对亚甲基蓝降解的光催化活性.同济大学(自然科学版),2005,33(8)：1078～1082
[71]Kim G S, Hyun S H. Effect of mixing on thermal and mechanical properties of aerogel-PVB composites. J. Mater. Sci,2003,38:1961-1966
[72]Ayers M R, Hunt A J, Synthesis and properties of chitosan-silica hybrid aerogels. J.Non-Crystal. Solids,2001,285:123-127
[73]邱坚,李坚,超临界干燥制备木材-Si02气凝胶复合材料及其纳米结构.东北林业大学学报,2005,33(3)：3-5
[74]Pradip B. Sarawada, Jong-Kil Kim, Ho-Kun Kim, et al. High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure. Applied Surface Science,2007,254:574-579
[75]邓忠生,魏建东,王珏等.由多聚硅氧烷制备二氧化硅气凝胶.功能材料,2000,31(3)：296～298
[76]Sharad D. Bhagat, Yong-Ha Kim, Myung-Jun Moon, et al. A cost-effective and fast synthesis of nanoporous SiO2 aerogel powders using water-glass via ambient pressure drying route. Solid State Science,2007,9:628-635
[77]董志军,李轩科,袁冠明.莫来石纤维增强Si02气凝胶隔热材料的制备工艺研究.应用化工,2006,35(6)：440～442
[78]许岗,杨觉明,杨平等.疏水复合薄膜接触角的测定.西安工业学院学报,2004,24(1)：65～69
[79]王寅生.纳米孔超级绝热材料基础研究：[硕士学位论文].北京：北京科技大学,2003
[80]沈军,王珏,吴翔.气凝胶-一种结构可控的新型材料功能材料.材料科学 与工程,1994,12(3)：1-6
[81]高朋召,王红洁,金志浩.Si02溶胶-凝胶转变过程的动力学研究及应用.复合材料学报,2003,20(4)：122～126
[82]张锐,秦丹丹,王海龙等.溶胶凝胶法制备Si02工艺.郑州大学学报(工学版).2006,27(4)：119～122
[83]Rao A V, Kuldarni M M, Amalnerkar D P, et al. Superhydrophobic silica aerogels based on methyltrimethoxysilane precursor. Journal of Non-Crystalline Solids, 2003,330:187-195
[84]Rao A V, Kuldarni D P, Seth T. Surface chemical modification of silica aerogels using various alkyl-alkoxy/chloro silanes. Applied Surface Science,2003,206: 262-270
[85]张志华,倪星远,沈君等.疏水型Si02气凝胶的常压制备及吸附性能研究.同济大学自然科学版.2005,33(12)：1641～1645
[2]戴志成.硅化合物的生产与应用.成都：成都科技大学出版社,1994
[3]王珏.轻质纳米多孔性材料-气凝胶.材料导报,1993,2：36-38
[4]沈军,周斌,吴光明等.纳米孔超级绝热材料气凝胶的制备与热学特性.程工程学报,2002,2(4)：314～345
[5]Pierre A C, Pajonk G M. Chemistry of aerogels and their applications. Chemical Reviews,2002,102(11):4243-4265
[6]Hunt A J, Ayers M R, Cao W. Aerogel composites using chemical vapor infiltration. Journal of Non-Crystalline Solids,1995,185:227-232
[7]Hu S W, Willey R J, Notari B. An investigation on the catalytic properties of titania-silica materials. Journal of Catalysis,2003,220:240-248
[8]Beamish J, Herman T. Adsorption and desorption of helium in aerogels. Physica B: Condensed Matter,2003,329-333:340-341
[9]Lawrence W. Hrubesh. Aerogel applications. Journal of Non-Crystalline Solids, 1998,225:335-342
[10]黄娆,刘之景.新型低介电常数材料研究进展.纳米材料与结构.2003,09：11-15
[11]Berkutov I B, Babuin S, Golov A I. Transverse sound in aerogel with liquid 4He. Physica B:Condensed Matter,2003,329-333:337-339
[12]Danilyuk A F, Kirillov V L, Savelieva M D, et al. Recent results on aerogel development for use in Cherenkov counters. Nuclear Instruments and Methods in Physics Research A,2002,494:491-494
[13]Tsou P. Proceedings of the fourth international symposium on aerogels. Journal of Non-Crystalline Solids,1995,186:415-420
[14]Smirnova I, Suttiruengwong S, Arlt W. Feasibility study of hydrophilic and hydrophobic silica aerogels as drug delivery systems. Journal of Non-Crystalline Solids,2004,350:54-60
[15]王珏,沈军,J.Fricke高效隔热材料掺杂TiO2及玻璃纤维硅石气凝胶的研制。材料研究学报,1995,9(6)：568～572
[16]Kim G S, Hyun S H, Synthesis of window glazing coated with silica aerogel films via ambient drying. J. Non-Cryst. Solids,2003,320(1-3):125-132
[17]Shen Jun, Ouyang Ling, Lin Xuejing etal. Preparation of Low-K and Low-n Mesoporous Silica Film via Sol-Gel Process. Rare metal materials and engineering,2008, (5)37:76-79
[18]Cahill S A. Optical and electronic characterization of sol-gel-derived silica aerogels for display and imaging application:[Dissertation]. Davis:University of California,1999
[19]Akimov Y K. Fields of Application of Aerogels. Instruments and Experimental Techniques,2003,46(3):287-299
[20]邓忠生,王珏,陈玲艳.气凝胶应用进展.材料导报,1999,13(6)：47～49
[21]Cho W, Saxena R, Rodriguez O etal. Effects of sintering on dielectric constants of mesoporous silica. Journal of Non-Cryst. Solids,2004,350:336-344
[22]Kim G S, Sang H. Hyun. Synthesis and characterization of silica aerogel films for inter-metal dielectrics via ambient drying. Thin Solid Film,2004,460: 190-200
[23]Ayers M R, Hunt A J, molecular oxygen sensors based on photoluminescent silica aerogels, J. of Non-Cryst. Solids,2001,285:79-83
[24]Alain C, Pierret, Ge'rard M, et al. Chemistry of aerogels and their applications. Chemistry Review,2002,102:4243-4265
[25]Forest L, Gibiat V, Hooley A. Impedance matching and acoustic absorption in granular layers of silica aerogels. Journal of Non-Crystalline Solids,2001,285: 230-235
[26]Akimov Y K. Fields of Application of Aerogels. Instruments and Experimental Techniques,2003,46(3):287-299
[27]Forest L, Gibiat V, Hooley A. Impedance matching and acoustic absorption in granular layers of silica aerogels. J. Non-Cryst. Solids,2001,285(1-3): 230-235
[28]武志刚,赵永祥,许临萍等.气凝胶制备进展及其在催化方面的应用.化学研究与应用,2003,15(1)：17-20
[29]何飞.Si02和SiO2-Al2O3复合干凝胶超级隔热材料的制备与表征：[博士学位论文].哈尔滨：哈尔滨工业大学,2006
[30]王亚权.催化剂表面分形结构对催化反应的影响.燃料化学学报,1999,27(2)：110～115
[31]郝利锋,高志华,阴丽华等.气凝胶的制备及其在催化领域的应用.天然气 化工,2005,30(1)：49～53
[32]甘礼华,郝志显,王玉栋等TiO2/SiO2气凝胶的非超临界干燥法制备及其对吡啶降解的光催化活性.中国化学工程学报(英文版),2005,13(6)：1002～1005
[33]王承学,齐国帧,李然.在改性M/SiO2催化剂在甲烷部分氧化,长春工业大学学报,2002,8(23)：90～94
[34]Buisson P, Hernandez C, Pierre M, et al. Encapsulation of lipases in aerogel. Journal of Non-Crystalline Solids,2001,285:295-302
[35]胡巧开.粉煤灰对甲基橙的吸附研究.上海化工,2004,8：10-12
[36]John G. Reynolds, Paul R. Coronado, Lawrence W. Hrubesh. Hydrophobic aerogels for oil-spill clean up synthesis and characterization. Journal of Non-Crystalline Solids,2001, (292):127-137
[37]Reynes J, Woignier T, Phalippou J. Permeability measurement in composity aerogels:application to nuclear waste storage. J.Non-Cryst. Solid,2001,285(1-3):323-327
[38]Woignier T, Reynes J, Phalippou J, Dussossoy J L etal. Sintered silica aerogel:a host matrix for long life nuclear wastes. J. Non-cryst. Solids,1998,225(1): 353-327
[39]Kraume I M. Synthesis of silica aerogels and their application as a drug delivery system:[Dissertation]. Berlin:Technischen Universitat Berlin,2002
[40]Buisson P, Hernandez C, Pierre M, et al. Encapsulation of lipases in aerogel. Journal of Non-Crystalline Solids,2001,285:295-302
[41]Jang K Y, Kim K. Study of sol-gel processing for fabrication of hollow silica-aerogel spheres. Journal of Vacuum Science and Technoloy,1989, A8: 1732-1735
[42]Golob P. Current status and future perspetives for inert dusts for control of stored product insect. Journal of Stored Produncts Research,1997,33:69-79
[43]丁星兆,何怡贞,董远达.溶胶-凝胶工艺在材料科学中的应用.材料科学与工程,1994,12(2)：1-8
[44]赵文珍.溶胶-凝胶科学技术的发展.材料导报,1996,6：12-15
[45]田明原,施尔畏.纳米陶瓷与纳米陶瓷粉末.无机材料学报,1998,2：129～137
[46]Mosing K, Jacobs T, Brennan K, et al. Integration challenges of porous ultra low-k spin-on dielectrics. Microelectronic Engineering,2002,64:11-24
[47]Scherer G W, Nisen E, Einarsrud M A, et al. Shrinkage of silica gels aged in TEOS. Journal of Non-Crystalline Solids,1996,202:42-52
[48]Scherer G W. Effect of drying on properties of silica gel. Journal of Non-Crystalline Solids,1997,215:155-168
[49]Smith D M, Scherer G W, Anderson J M. Shrinkage during drying of silica gel. Journal of Non-Crystalline Solids,1995,188:191-206
[50]陈武龙,张宇星,甘礼华等.气凝胶的非超临界干燥制备技术.实验室研究与探索,2001,20(6)：54～57
[51]相宏伟,钟炳,彭少逸.超临界流体干燥理论、技术及应用.材料科学与工程,1995,13(2)：38～53
[52]李文翠,郭树才,赵旭东.超临界流体干燥法制备炭气凝胶.碳素技术,2000,3：7-9
[53]陈龙武,甘礼华,岳天仪等.超临界干燥法制备Si02气凝胶的研究.高等学校化学学报,1995,16(6)：840～843
[54]陈龙武,甘礼华,侯秀红.气凝胶的非超临界干燥法制备及其形成过程.物理化学学报,2003,19(9)：819～823
[55]沈军,王珏,吴翔.气凝胶-一种结构可控的新型材料功能材料.材料科学与工程,1994,12(3)：1-6
[56]Jima AN, Hashimoto K, Watanabe T. Recent studies on super-hyrophobic films. Monatshefte fur Chemie,2001, (132):31-34
[57]同小刚,王芬,冯海涛等.二氧化硅气凝胶的制备和应用研究.材料导报,2006.20：24～26
[58]陈龙武.二氧化硅气凝胶介孔大孔材料研究：[硕士学位论文].上海：同济大学,2003
[59]李伟,王霞瑜,张平等.溶胶-凝胶法制备疏水型Si02气凝胶.材料科学与工程,2002,20(1)：58-60
[60]甘礼华,张宇星,陈龙武等.干燥控制化学添加剂在制备硅气凝胶中的应用.同济大学学报(自然科学版),2003,31：1131～1134
[61]Uchida N, Ishiyama N, Kato Z, et al. Chemical effects of DDCA to the sol-gel process. Journal of Materials Sciences,1994,29:5188-5192
[62]Amato G, Brunetto N, Parisini A. Characterization of freeze-dried porous silicon. Thin Solid Films,1997,297:73-78
[63]Mathieu B, Blacher S, Pirard R, et al. Freeze-dried resorcinol-formaldehyde gels. Journal of Non-Crystalline Solids,1997,212:250-261
[64]Tamon H, Ishizaka H, Yamamoto T. Preparation of mesoporous carbon by freeze drying. Carbon,1999,37:2049-2055
[65]陈一民,谢凯,盘毅等.钴/Si02纳米复合气凝胶的制备表征.功能材料,2011,32(1)：91～92
[66]甘礼华,李光明,岳天仪等.超临界干燥法制备Fe2O3/SiO2气凝胶.物理化学学报,1999,15(7)：588～592
[67]武志刚,赵永祥,许临萍等.镍含量对NiO/SiO2气凝胶性能的影响.无机化学学报,2002,18(9)：949～952
[68]何文,张旭东,韩丽.A12O3/SiO2气凝胶纳米粉的制备与表征.中国陶瓷,2000,36(6)：4-6
[69]Yao L Z, Ye C H, Mo C M etal. Study of crystallization and spectral properties of PbS nanocrystals doped in SiO2 aerogel matrix. J Cryst,2000,216:147-151
[70]甘礼华,王小兰,郝志显等.TiO2-SiO2气凝胶对亚甲基蓝降解的光催化活性.同济大学(自然科学版),2005,33(8)：1078～1082
[71]Kim G S, Hyun S H. Effect of mixing on thermal and mechanical properties of aerogel-PVB composites. J. Mater. Sci,2003,38:1961-1966
[72]Ayers M R, Hunt A J, Synthesis and properties of chitosan-silica hybrid aerogels. J.Non-Crystal. Solids,2001,285:123-127
[73]邱坚,李坚,超临界干燥制备木材-Si02气凝胶复合材料及其纳米结构.东北林业大学学报,2005,33(3)：3-5
[74]Pradip B. Sarawada, Jong-Kil Kim, Ho-Kun Kim, et al. High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure. Applied Surface Science,2007,254:574-579
[75]邓忠生,魏建东,王珏等.由多聚硅氧烷制备二氧化硅气凝胶.功能材料,2000,31(3)：296～298
[76]Sharad D. Bhagat, Yong-Ha Kim, Myung-Jun Moon, et al. A cost-effective and fast synthesis of nanoporous SiO2 aerogel powders using water-glass via ambient pressure drying route. Solid State Science,2007,9:628-635
[77]董志军,李轩科,袁冠明.莫来石纤维增强Si02气凝胶隔热材料的制备工艺研究.应用化工,2006,35(6)：440～442
[78]许岗,杨觉明,杨平等.疏水复合薄膜接触角的测定.西安工业学院学报,2004,24(1)：65～69
[79]王寅生.纳米孔超级绝热材料基础研究：[硕士学位论文].北京：北京科技大学,2003
[80]沈军,王珏,吴翔.气凝胶-一种结构可控的新型材料功能材料.材料科学 与工程,1994,12(3)：1-6
[81]高朋召,王红洁,金志浩.Si02溶胶-凝胶转变过程的动力学研究及应用.复合材料学报,2003,20(4)：122～126
[82]张锐,秦丹丹,王海龙等.溶胶凝胶法制备Si02工艺.郑州大学学报(工学版).2006,27(4)：119～122
[83]Rao A V, Kuldarni M M, Amalnerkar D P, et al. Superhydrophobic silica aerogels based on methyltrimethoxysilane precursor. Journal of Non-Crystalline Solids, 2003,330:187-195
[84]Rao A V, Kuldarni D P, Seth T. Surface chemical modification of silica aerogels using various alkyl-alkoxy/chloro silanes. Applied Surface Science,2003,206: 262-270
[85]张志华,倪星远,沈君等.疏水型Si02气凝胶的常压制备及吸附性能研究.同济大学自然科学版.2005,33(12)：1641～1645