中空纤维担载无机分离膜的制备和表征
|
摘要
本论文采用溶胶凝胶法在氧化铝中空纤维支撑体上制备SiO_2介孔膜、SiO_2微孔膜、Al_2O_3：-SiO_2复合膜。通过扫描电镜、气体渗透装置对膜的微观结构、完整性及其对气体的选择性进行了研究；采用热重分析仪、差热分析仪、红外光谱、X射线衍射和等温N_2吸附考察了样品的稳定性、组成、晶相和孔径及其分布。结果表明：介孔SiO_2膜的比表面积可达919.75m~2／g，孔容达0.4346ml／g，最可几孔径小于3nm；膜较完整、无大缺陷，室温、0.12MPa下N_2的气体渗透通量为1.81×10~(-5)mol／(m~2·s·Pa)，H_2和N_2的分离因子为2.431。微孔SiO_2膜的气体渗透通量数量级为10~(-6)mol／(m~2·s·Pa)。不同比例的复合膜表面完整无针孔，在0.1MPa，条件下对氢／氮的分离因子为3.03，说明气体通过膜的扩散以Knudsen扩散传质为主，非担载Al_2O_3：-SiO_2复合膜的比表面积为294.85m~2／g，总孔容为0.2778mL／g，最可几孔径小于3nm。
Mesoporous silica membranes , microporous silica membranes and Al203,-Si02 composite membranes on hollow fiber alumina supports were prepared by a sol-gel process. The microstructure of the membranes was analyzed by sanning electro microscopy. Their permeability and gas separate ability were investigated by a gas separation installation. The thermal stability, composition, crystalline phase and pore size distribution of powder samples were studied by thermal gravimetric analysis, differential thermal analysis, FT-IR spectrograph, X-ray diffraction and isothermal nitrogen adsorption, respectively. The results showed that BET specific area of mesoporous silica membranes reached 919. 75m2/g and the total pore volume' was 0.4346ml/g. The most probable pore diameter was less than 3nm. Mesoporous silica membranes were free from large defects, the gas permeance of N2 and the separation factor of H2/N2 measured under room temperature and a pressure of 0.12MPa were 1.81Xl0-5mol/(m2 s Pa) and 2.431, respectively. For
the microporous silica membranes, gas permeance reached the order of lO-6mol/(m2 s'Pa). Different mole ratios of Al203-Si02 composite membranes were free from crack and distinct flaws. The separation factor of hydrogen to nitrogen measured at a pressure of 0. IMPa was 3.03. It was showed that the gas diffusion through the membrane is governed by Knudsen diffusion mechanism. The most probable pore diameter of an unsupported membrane after calcination at 600℃ was less than 3 nm, its specific surface area reached 294.85m2/g and .the total pore volume was 0. 2778mL/g.
Mesoporous silica membranes , microporous silica membranes and Al203,-Si02 composite membranes on hollow fiber alumina supports were prepared by a sol-gel process. The microstructure of the membranes was analyzed by sanning electro microscopy. Their permeability and gas separate ability were investigated by a gas separation installation. The thermal stability, composition, crystalline phase and pore size distribution of powder samples were studied by thermal gravimetric analysis, differential thermal analysis, FT-IR spectrograph, X-ray diffraction and isothermal nitrogen adsorption, respectively. The results showed that BET specific area of mesoporous silica membranes reached 919. 75m2/g and the total pore volume' was 0.4346ml/g. The most probable pore diameter was less than 3nm. Mesoporous silica membranes were free from large defects, the gas permeance of N2 and the separation factor of H2/N2 measured under room temperature and a pressure of 0.12MPa were 1.81Xl0-5mol/(m2 s Pa) and 2.431, respectively. For
the microporous silica membranes, gas permeance reached the order of lO-6mol/(m2 s'Pa). Different mole ratios of Al203-Si02 composite membranes were free from crack and distinct flaws. The separation factor of hydrogen to nitrogen measured at a pressure of 0. IMPa was 3.03. It was showed that the gas diffusion through the membrane is governed by Knudsen diffusion mechanism. The most probable pore diameter of an unsupported membrane after calcination at 600℃ was less than 3 nm, its specific surface area reached 294.85m2/g and .the total pore volume was 0. 2778mL/g.
引文
1. Burggraaf A J. Key Points in Understanding and Development of Ceramic Membrane, in Proceeding of the Third Inter. Conf. on Inorganic Membr. ed. by Ma Y H. Worcestere, Massachusetts, 1994, 1-16
2. Bonekamp B C. Preparation of Asymmetric Ceramic Membrane supports by dip-coating, in Fundamentals of Inorganic Membrane Science and Technology., ed. by Burgraaf A J. and Cot Ⅰ. Elsevier, Amsterdam, 1996,144-221
3． 霍明亮，李世光等．多孔陶瓷膜．化学工业与工程，1996，13(4)：25-28
4. Lin Y S, J. Mem. Sci., 1993, 79:55
5． 李健生．[学位论文]，南京：南京理工大学，2001
6. Uhlhorn R J R, Burggraaf A J. Gas separation with Inorganic membranes, in inorganic membranes synthesis, characteristics and applications, ed. By Bhave R R, New York, Van Nostrand Reinhold, 1991,155-176
7. Van Veen H M, Tol J P B M, Engelen C W R, et al. High Temperature Gas separation with Alumina membranes, key Eng. Mater., 1991,61-62:593-598
8. Alami-Younssi S, Larbort A, Persin, et al. Gamma Alumina Nanofiltration Membrane Application to the Rejection of Metallic Cations. J. Mem. Sci., 1994,9:87-95
9. Mynin V.N. and Terpugov G.V., Purification of wastewater from heavy metals by using ceramic membrane and natural ployeletrolytes. Desalination, 1998, 119:361-362
10. Vercanteren S, Keizer K. Process ceramic membranes: preparation, transport properties and applications. J. Porous Mater. 1998,5:241-258
11．黄仲涛，曾昭槐，钟邦克等．无机膜技术及其应用．中国石化出版社，1999，1-2
12. Adikane H.A., Singh R.K. and Nene S.N., recovery of penicillin G from fermentation Broth by microfiltration. J. Mem. Sci.,1999,162:119-123
13. Larbot A., Fabra J.P. and Guizard C. et al Inorganic membranes oriented by sol-gel techniques. J. Meme. Sci.,1988,39:203-212
14. Zarzycki J, Past and present of sol-gel scienceand technology. J. Sol-gel Sci. Tech.,1997,8:17-22
15. Anderson Marc A, Gieselmann Mary J, Xu Qunyin. Titania and Alumina Ceramic membrane. J. Mem. Sci., 1998,39:243-258
16. Larbot A., jube A. and Guizard C. et al, silica membranes by the sol-gel process. J. Mem. Sci., 1989.44:289-303
17．奚红霞，黄仲涛．氧化锆膜的制备和表征．无机材料学报，1996，11(4)：627-632
18．曾智强，萧小月，桂治轮等．溶胶—凝胶制备Al_2O_3—SiO_2陶瓷薄膜的研究．膜科学与技术，1997，17(5)：16-20
19. Saraeco G, Versteeg G F, Van Swaij W P M. Current hurdles to the success of'high-temperature membranes reactors. J. Mem. Sci.,1994,95:105-123
20. IUPAC manual of symbols and termeinology. Pure Appl. Chem, 1972,31:578-680
21．齐凯，牛忠伟，容建华等．有序孔材料的发展现状．材料导报，2001，15(6)：47-53
22．谢永贤，陈文，徐庆有序介孔材料的合成及机理．材料导报，2002，16(1)：51-53
23．吴越，刘持泳．介孔无机固体材料的合成、特性和应用前景．石油化工，1998，27(3)：212-220
24．王连洲，施剑林，禹剑等．介孔氧化硅材料的研究进展．无机材料学报，1999，14(3)：333-341
25. Kresge C T, Leonowicz M E, Roth W J, et al. Nature, 1992,359:710-712
26. Huo Q, Margoliese D I, Clesla U, et al. Chem. Mater.,1994,6:1176-1191
27, Tanev P T, Pinnavaia T J. Science, 1995,267:865-867
28. Wang L Z, YU J, Shi J L, Yan D S. J. Mater. Sci. Lett., revised.
29. Davis M E. Organizing for better synthesis. Nature, 1993:391
30. Corma A. From microporous to molecular sieve materials and their use in catalysis. Chem. Rev.,1997,97:2373-2382
31. Yang H, Kuperman A, Coombs N, Maniche-Afara S et al. Synthesis of oriented films of mesoporous silica on mica. Nature, 1996,379:703-705
32. Aksay, T, Trau M, Manne S, et al. Biominetic pathways for assembling inorganic thin films. Science, 1996,273(5277):892-898
33. Nishiyama N, Koide A, Egashira Y, Ueyama K. Mesoporous MCM-48 membrane synthesized on a porous stainless steel support. J. chem. Soc. Chem. Commun., 1998,19:2147-2148
34. Ogawa M. Preparation of transparent thin films of silica-surfactant mesostructured materials. Supramol Sci, 1998,5:247-251
35. Berquier J M, Teyssedre L, Jacquiod C. Synthesis of transparent mesoporous and mesostructured thin silica films. J sol-gel Sci Technol, 1998, 13: 739
-742
36. Martin j E, Anderson M T, Odinek J, Newcomer P. Synthesis of periodic mesoporous silica thin films. Langmuir, 1997,13:4133-4141
37. Huang M H, Funn B S, Soyez H, Zink J I. In situ probing by fluorescence spectroscopy of the formation of continuous highly-ordered lamellar-phase mesostructured thin films. Langmuir, 1998,14:7331-7333
38. Vlasoula B, Maria-Luisa Ferret, Panagiotis Llanos. Time-resolved fluor-escence quenching studies in nanocomposite materials made of silica and cetyltrimethylammonium bromide. J Phys. Chem. B, 1999,103
39. Alan Sellinger, Pilar M Weiss, Anh Nguyen, Yunfeng Lu. Continuous self-asse-mbly of organic-inorganic nanocomposite coatings that mimic nacre. Nature, 1998,394:173-175
40. Ryong Ryoo, Chang HyunKo, Sung June Cho, JiMan Kim. Optically transparent, single-crystal-like oriented mesoporous silica films and plates. J Phys Chem B, 1997,101:10610-10613
41. Miyata H, Kuroda K. Formation of a continuous mesoporous silica film with fully aligned mesochannedls on a glass substrate. Chem Mater, 2000,12:49-54
42. Miyata H, Kuroda K. Alignment of mesoporous silica on a glass substrate by a bubbing method. Chem Mater, 1999,11:1448-1452
43. Chung-yi Tsai, Siu-Yue Tam, Yunfeng Lu, C. Jeffrey Brinker. Dual-layer asymm-etric microporous silica membranes. Journal of Membrane Science, 2000, 169: 255-268
44. Guliants V V, Carreon Y S, Lin Y S. Ordered mesoporous and macroporous inorganic films and membranes. J. Mem. Sci.,2004,235:53-72
45. Makoto Ogawa, Takanori Igarashi, Kazuyuki Kuroda. Preparation of transpare-nt silica-surfactant nano-composite films with controlled microstruc-tures. Bull them Soc Jpn, 1997,70(11):2833-2837
46．李健生，孙秀云，刘晓东．过滤成膜制备氧化铝中空纤维超滤膜．催化学报，2002，23(5)：453-456
47．S．J．格雷格，K．S．W．辛．吸附、比表面积与孔隙率，北京：化学出版社．1989，231-244
48. De Vos R M, Verweij H. Improved performance of silica membranes of gas separation.J. Mem. Sci.,1998,143:37-51
49．李传风，钟顺和．无机膜的气体传递机理和模型．膜科学与技术，2000，20(3)．33-37
50. Yunfeng Lu, Rahul Ganguli, Celeste A. Drewlen, et al. Continuous formation of
supported cubic and hexagonal mesoporous films by sol-gel, dip -coating. Nature, 1997,389:364-368
51. Sotirchos Straitis V, Burganos Vasilis N, Transport of Gases in Porous Membranes, MRS, 1999, March, 41-45
52．丁祥金．[学位论文]，上海：中国科学院上海硅酸盐研究所，2001
53. Tomanos R E, Steriotis T A et al. Innovative methods for preparation and testing of Al_2O_3 supported silicate-1 membranes. J. Euro. Ceram. Soc, 2000, 21:119-126
54．韦奇，李健林等．微孔二氧化硅膜的制备、氢气分离以及水热稳定性对于二氧化硅的水热稳定性．无机材料学报，2004，19(1)：133-139
55. VanVeen H M, Bracht M, et al. Feasibility of the application of porous inorganic gas separation membranes in some large-scale chemical processes(J), in:Burggraaf A J, Cot. Fundamentals of Inorganic Membrane Science and Technology, Membrane Science and Technology Series, 1996, 4: 641-676
56. Klaus J W, Seneho, et al. Growth of SiO_2 at room temparature with the use of catalyzed sequential half-rections. Science, 1997, 278:1934-1936
57. Tsuru T, Izumi S, et al. Temparature effect on transport performance by inorganic nanofilteration membranes ALCHEJ., 2000, 46:565-574
58. De Vos R M, Maier W F, et al. Hydrophobic silica membranes for gas separation. J. membr. Sci., 1999, 158:277-288
59. Castro R P, Cohen Y, Monbouquettr H G. Thepermeability behavior of poly vinyl-pyrrolidone modified porous silica membraned. Journal of Membrane Science, 1993, 84:151
60．芦贻春，李再耕．pH值对硅溶胶凝胶化过程的影响．耐火材料，1995，29(6)，326-328
61．王自新，赵冰．硅溶胶制备与应用．化学推进剂与高分子材料，2003，1(5)：34-39
62．李安武，赵宏宾等．γ-Al_2O_3复合膜的制备及顶膜完整性检验．中国科学(B辑)，1996，26(6)，502-508
63. Lin Y S. Experimental studies on pore size change of porous ceramic membrane after modification. Journal of membrane Science, 1993, 79:55
64. Sheng Guangyao, Chulixin, Zelltner W A, et al. Nanoparticulate Alumina, sili-ca and aluminosilicate membranes. Journal of Non-Crystalline Solids, 1992, 147&148:548
65. Zeng Zhi qiang, Xiaoxiaoyue, Gui Zhilun, et al. Preparation of alunmina
-silica membranes supported on α-alumina substrates. In:ICECM-ICSA' 95, Procedding of International Conference on Electronic Components and Materials, Sensors and Actuators. Beijing: International Academic Publishe-rs, 1995.1211
66. Keizer K. Kumar K P, Lijzenga C, et al. Stress development during the formation of ceramic membranes. Stressrelaxation in alumina-titania compowite membranes during drying. Key Engineering Materials, 1991, 61-62:43313
67．夏长荣，唐晔，杨萍华．PVA修饰的溶胶凝胶法制备γ氧化铝超滤膜．材料研究学报，1999，13(3)：279～283
68. Uhlhorn, M H B, Husiln' T V et al. High permselectiveties of microporous silica-modified gama alunimna membranes. J. Mate. Sci. Lett.,1990,8(10):41
69. Haruhiko Ohya, Nakajima Hidehiko, et al. Separation of hydrogen from thermochemical processes uning zirconia-silica composite membranes. J. Mem. Sci, 1994,97:91
70. Galan M, Llorens J, Gulierrez J M, et al. Ceramic membranes from sol-gel technology. Journal of Non-Crystalline Solids, 1992,147-148:518
2. Bonekamp B C. Preparation of Asymmetric Ceramic Membrane supports by dip-coating, in Fundamentals of Inorganic Membrane Science and Technology., ed. by Burgraaf A J. and Cot Ⅰ. Elsevier, Amsterdam, 1996,144-221
3． 霍明亮，李世光等．多孔陶瓷膜．化学工业与工程，1996，13(4)：25-28
4. Lin Y S, J. Mem. Sci., 1993, 79:55
5． 李健生．[学位论文]，南京：南京理工大学，2001
6. Uhlhorn R J R, Burggraaf A J. Gas separation with Inorganic membranes, in inorganic membranes synthesis, characteristics and applications, ed. By Bhave R R, New York, Van Nostrand Reinhold, 1991,155-176
7. Van Veen H M, Tol J P B M, Engelen C W R, et al. High Temperature Gas separation with Alumina membranes, key Eng. Mater., 1991,61-62:593-598
8. Alami-Younssi S, Larbort A, Persin, et al. Gamma Alumina Nanofiltration Membrane Application to the Rejection of Metallic Cations. J. Mem. Sci., 1994,9:87-95
9. Mynin V.N. and Terpugov G.V., Purification of wastewater from heavy metals by using ceramic membrane and natural ployeletrolytes. Desalination, 1998, 119:361-362
10. Vercanteren S, Keizer K. Process ceramic membranes: preparation, transport properties and applications. J. Porous Mater. 1998,5:241-258
11．黄仲涛，曾昭槐，钟邦克等．无机膜技术及其应用．中国石化出版社，1999，1-2
12. Adikane H.A., Singh R.K. and Nene S.N., recovery of penicillin G from fermentation Broth by microfiltration. J. Mem. Sci.,1999,162:119-123
13. Larbot A., Fabra J.P. and Guizard C. et al Inorganic membranes oriented by sol-gel techniques. J. Meme. Sci.,1988,39:203-212
14. Zarzycki J, Past and present of sol-gel scienceand technology. J. Sol-gel Sci. Tech.,1997,8:17-22
15. Anderson Marc A, Gieselmann Mary J, Xu Qunyin. Titania and Alumina Ceramic membrane. J. Mem. Sci., 1998,39:243-258
16. Larbot A., jube A. and Guizard C. et al, silica membranes by the sol-gel process. J. Mem. Sci., 1989.44:289-303
17．奚红霞，黄仲涛．氧化锆膜的制备和表征．无机材料学报，1996，11(4)：627-632
18．曾智强，萧小月，桂治轮等．溶胶—凝胶制备Al_2O_3—SiO_2陶瓷薄膜的研究．膜科学与技术，1997，17(5)：16-20
19. Saraeco G, Versteeg G F, Van Swaij W P M. Current hurdles to the success of'high-temperature membranes reactors. J. Mem. Sci.,1994,95:105-123
20. IUPAC manual of symbols and termeinology. Pure Appl. Chem, 1972,31:578-680
21．齐凯，牛忠伟，容建华等．有序孔材料的发展现状．材料导报，2001，15(6)：47-53
22．谢永贤，陈文，徐庆有序介孔材料的合成及机理．材料导报，2002，16(1)：51-53
23．吴越，刘持泳．介孔无机固体材料的合成、特性和应用前景．石油化工，1998，27(3)：212-220
24．王连洲，施剑林，禹剑等．介孔氧化硅材料的研究进展．无机材料学报，1999，14(3)：333-341
25. Kresge C T, Leonowicz M E, Roth W J, et al. Nature, 1992,359:710-712
26. Huo Q, Margoliese D I, Clesla U, et al. Chem. Mater.,1994,6:1176-1191
27, Tanev P T, Pinnavaia T J. Science, 1995,267:865-867
28. Wang L Z, YU J, Shi J L, Yan D S. J. Mater. Sci. Lett., revised.
29. Davis M E. Organizing for better synthesis. Nature, 1993:391
30. Corma A. From microporous to molecular sieve materials and their use in catalysis. Chem. Rev.,1997,97:2373-2382
31. Yang H, Kuperman A, Coombs N, Maniche-Afara S et al. Synthesis of oriented films of mesoporous silica on mica. Nature, 1996,379:703-705
32. Aksay, T, Trau M, Manne S, et al. Biominetic pathways for assembling inorganic thin films. Science, 1996,273(5277):892-898
33. Nishiyama N, Koide A, Egashira Y, Ueyama K. Mesoporous MCM-48 membrane synthesized on a porous stainless steel support. J. chem. Soc. Chem. Commun., 1998,19:2147-2148
34. Ogawa M. Preparation of transparent thin films of silica-surfactant mesostructured materials. Supramol Sci, 1998,5:247-251
35. Berquier J M, Teyssedre L, Jacquiod C. Synthesis of transparent mesoporous and mesostructured thin silica films. J sol-gel Sci Technol, 1998, 13: 739
-742
36. Martin j E, Anderson M T, Odinek J, Newcomer P. Synthesis of periodic mesoporous silica thin films. Langmuir, 1997,13:4133-4141
37. Huang M H, Funn B S, Soyez H, Zink J I. In situ probing by fluorescence spectroscopy of the formation of continuous highly-ordered lamellar-phase mesostructured thin films. Langmuir, 1998,14:7331-7333
38. Vlasoula B, Maria-Luisa Ferret, Panagiotis Llanos. Time-resolved fluor-escence quenching studies in nanocomposite materials made of silica and cetyltrimethylammonium bromide. J Phys. Chem. B, 1999,103
39. Alan Sellinger, Pilar M Weiss, Anh Nguyen, Yunfeng Lu. Continuous self-asse-mbly of organic-inorganic nanocomposite coatings that mimic nacre. Nature, 1998,394:173-175
40. Ryong Ryoo, Chang HyunKo, Sung June Cho, JiMan Kim. Optically transparent, single-crystal-like oriented mesoporous silica films and plates. J Phys Chem B, 1997,101:10610-10613
41. Miyata H, Kuroda K. Formation of a continuous mesoporous silica film with fully aligned mesochannedls on a glass substrate. Chem Mater, 2000,12:49-54
42. Miyata H, Kuroda K. Alignment of mesoporous silica on a glass substrate by a bubbing method. Chem Mater, 1999,11:1448-1452
43. Chung-yi Tsai, Siu-Yue Tam, Yunfeng Lu, C. Jeffrey Brinker. Dual-layer asymm-etric microporous silica membranes. Journal of Membrane Science, 2000, 169: 255-268
44. Guliants V V, Carreon Y S, Lin Y S. Ordered mesoporous and macroporous inorganic films and membranes. J. Mem. Sci.,2004,235:53-72
45. Makoto Ogawa, Takanori Igarashi, Kazuyuki Kuroda. Preparation of transpare-nt silica-surfactant nano-composite films with controlled microstruc-tures. Bull them Soc Jpn, 1997,70(11):2833-2837
46．李健生，孙秀云，刘晓东．过滤成膜制备氧化铝中空纤维超滤膜．催化学报，2002，23(5)：453-456
47．S．J．格雷格，K．S．W．辛．吸附、比表面积与孔隙率，北京：化学出版社．1989，231-244
48. De Vos R M, Verweij H. Improved performance of silica membranes of gas separation.J. Mem. Sci.,1998,143:37-51
49．李传风，钟顺和．无机膜的气体传递机理和模型．膜科学与技术，2000，20(3)．33-37
50. Yunfeng Lu, Rahul Ganguli, Celeste A. Drewlen, et al. Continuous formation of
supported cubic and hexagonal mesoporous films by sol-gel, dip -coating. Nature, 1997,389:364-368
51. Sotirchos Straitis V, Burganos Vasilis N, Transport of Gases in Porous Membranes, MRS, 1999, March, 41-45
52．丁祥金．[学位论文]，上海：中国科学院上海硅酸盐研究所，2001
53. Tomanos R E, Steriotis T A et al. Innovative methods for preparation and testing of Al_2O_3 supported silicate-1 membranes. J. Euro. Ceram. Soc, 2000, 21:119-126
54．韦奇，李健林等．微孔二氧化硅膜的制备、氢气分离以及水热稳定性对于二氧化硅的水热稳定性．无机材料学报，2004，19(1)：133-139
55. VanVeen H M, Bracht M, et al. Feasibility of the application of porous inorganic gas separation membranes in some large-scale chemical processes(J), in:Burggraaf A J, Cot. Fundamentals of Inorganic Membrane Science and Technology, Membrane Science and Technology Series, 1996, 4: 641-676
56. Klaus J W, Seneho, et al. Growth of SiO_2 at room temparature with the use of catalyzed sequential half-rections. Science, 1997, 278:1934-1936
57. Tsuru T, Izumi S, et al. Temparature effect on transport performance by inorganic nanofilteration membranes ALCHEJ., 2000, 46:565-574
58. De Vos R M, Maier W F, et al. Hydrophobic silica membranes for gas separation. J. membr. Sci., 1999, 158:277-288
59. Castro R P, Cohen Y, Monbouquettr H G. Thepermeability behavior of poly vinyl-pyrrolidone modified porous silica membraned. Journal of Membrane Science, 1993, 84:151
60．芦贻春，李再耕．pH值对硅溶胶凝胶化过程的影响．耐火材料，1995，29(6)，326-328
61．王自新，赵冰．硅溶胶制备与应用．化学推进剂与高分子材料，2003，1(5)：34-39
62．李安武，赵宏宾等．γ-Al_2O_3复合膜的制备及顶膜完整性检验．中国科学(B辑)，1996，26(6)，502-508
63. Lin Y S. Experimental studies on pore size change of porous ceramic membrane after modification. Journal of membrane Science, 1993, 79:55
64. Sheng Guangyao, Chulixin, Zelltner W A, et al. Nanoparticulate Alumina, sili-ca and aluminosilicate membranes. Journal of Non-Crystalline Solids, 1992, 147&148:548
65. Zeng Zhi qiang, Xiaoxiaoyue, Gui Zhilun, et al. Preparation of alunmina
-silica membranes supported on α-alumina substrates. In:ICECM-ICSA' 95, Procedding of International Conference on Electronic Components and Materials, Sensors and Actuators. Beijing: International Academic Publishe-rs, 1995.1211
66. Keizer K. Kumar K P, Lijzenga C, et al. Stress development during the formation of ceramic membranes. Stressrelaxation in alumina-titania compowite membranes during drying. Key Engineering Materials, 1991, 61-62:43313
67．夏长荣，唐晔，杨萍华．PVA修饰的溶胶凝胶法制备γ氧化铝超滤膜．材料研究学报，1999，13(3)：279～283
68. Uhlhorn, M H B, Husiln' T V et al. High permselectiveties of microporous silica-modified gama alunimna membranes. J. Mate. Sci. Lett.,1990,8(10):41
69. Haruhiko Ohya, Nakajima Hidehiko, et al. Separation of hydrogen from thermochemical processes uning zirconia-silica composite membranes. J. Mem. Sci, 1994,97:91
70. Galan M, Llorens J, Gulierrez J M, et al. Ceramic membranes from sol-gel technology. Journal of Non-Crystalline Solids, 1992,147-148:518
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |