纳米多孔材料制备及力学相关问题的研究
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摘要
二氧化硅纳米多孔材料是由胶体粒子相互聚结构成纳米多孔网
络结构的一种高分散固体材料。具有高孔洞率、高比表面积和孔洞
尺寸在纳米量级的特点。由于结构的特异性，使其具有了许多奇特
的性质。但是在材料的制备上，一直存在着反应条件严格，容易开
裂的问题，这就限制了该材料的制备条件和应用。因此，我们在对
该材料进行了力学分析之后进行了材料的制备设计，采用了在常温
常压下的微分干燥法来制备该材料。
全文共分为两个部分：
1．材料干燥过程的力学分析和力学设计
对二氧化硅纳米多孔材料的干燥过程进行了初步的力学分析和
描述，将凝胶干燥过程分阶段来讨论。在干燥初期讨论了卸载波所
产生的动力学效应；在干燥中期分析了孔径分布不均匀对凝胶应力
场的影响，并在实验中得到证实，而且较好的解决了孔径分布不均
对纳米多孔材料干燥造成的影响问题；在干燥后期从宏观上对已经
产生微裂纹的材料分析了孔隙率和吸附效应对其裂纹扩展所产生的
影响。同时，力学分析对实验中控制反应条件以制备出性能良好的
材料并有效的防止开裂起了很大的指导作用。
2．掺Ni的二氧化硅纳米多孔材料和无机-高分子杂化材料的制备
实验中以正硅酸乙酯为硅源，以无水乙醇为溶剂，以稀盐酸和
稀氨水作为催化剂，采用溶胶凝胶法成功的制备了金属离子和二氧
化硅气凝胶的杂化材料；在电场下对其进行电学处理，使得Ni离子
在凝胶中呈梯度变化分布；通过实验选取合适的溶剂和催化剂，成
功的制取了无机高分子杂化材料。并对实验中所制备的各种材料的
结构、形态进行了一定的研究。
The nanoporous network structure of silicon dioxide nanoporous material which composed of colloid particles conglomerating together is a kind of highly dispersed non-crystalline solids. It has numerous particular properties for its unique structure of high porous, high area ratio and nano magnitude in porous' dimensions. In the synthesis of the material, however, it always exists the problems of rigorous reacting conditions and easily cracking, which confine the preparation and application of the material. Therefore, after mechanical analyzing of the material, we designed and adopted new method at normal temperature and pressure conditions of preparing the materials, differential drying method, to get intact specimens.
This paper mainly consists of two parts: 3. Mechanical analysis and designing of drying process
The drying process has been described and analyzed preliminarily in three periods. During the first period, the dynamical effects produced by unloading waves has been studied; During the medium period, it has been analyzed that the effects on stress field of gels are originated from the uneven distribution of porous, which has been proved and resolved by some chemical methods; Finally, during the last period, the materials with cracks have been studied for the effects of porous ratio and sorption on the crack developing. Under the guidance of mechanical analysis, new drying methods, differential drying method, which is useful in
controlling the reacting condition is designed.
4. Preparation of SiO2 nanoporous material
adulterated with Ni and inorganic-biomaterial hybrid
SiO2 nanoporous material adulterated with Ni has been synthesized successfully from tetraethoxysilicane as silicon resources, ethanol as solvent and watery HC1 or ammonia by sol-gel method; It is also dealt with in the electric field with Ni redistributed vertically; Organic-biomaterial hybrid has been prepared by choosing suitable solvent and catalyst ; Promising properties have been obtained after a series of experiments.
络结构的一种高分散固体材料。具有高孔洞率、高比表面积和孔洞
尺寸在纳米量级的特点。由于结构的特异性，使其具有了许多奇特
的性质。但是在材料的制备上，一直存在着反应条件严格，容易开
裂的问题，这就限制了该材料的制备条件和应用。因此，我们在对
该材料进行了力学分析之后进行了材料的制备设计，采用了在常温
常压下的微分干燥法来制备该材料。
全文共分为两个部分：
1．材料干燥过程的力学分析和力学设计
对二氧化硅纳米多孔材料的干燥过程进行了初步的力学分析和
描述，将凝胶干燥过程分阶段来讨论。在干燥初期讨论了卸载波所
产生的动力学效应；在干燥中期分析了孔径分布不均匀对凝胶应力
场的影响，并在实验中得到证实，而且较好的解决了孔径分布不均
对纳米多孔材料干燥造成的影响问题；在干燥后期从宏观上对已经
产生微裂纹的材料分析了孔隙率和吸附效应对其裂纹扩展所产生的
影响。同时，力学分析对实验中控制反应条件以制备出性能良好的
材料并有效的防止开裂起了很大的指导作用。
2．掺Ni的二氧化硅纳米多孔材料和无机-高分子杂化材料的制备
实验中以正硅酸乙酯为硅源，以无水乙醇为溶剂，以稀盐酸和
稀氨水作为催化剂，采用溶胶凝胶法成功的制备了金属离子和二氧
化硅气凝胶的杂化材料；在电场下对其进行电学处理，使得Ni离子
在凝胶中呈梯度变化分布；通过实验选取合适的溶剂和催化剂，成
功的制取了无机高分子杂化材料。并对实验中所制备的各种材料的
结构、形态进行了一定的研究。
The nanoporous network structure of silicon dioxide nanoporous material which composed of colloid particles conglomerating together is a kind of highly dispersed non-crystalline solids. It has numerous particular properties for its unique structure of high porous, high area ratio and nano magnitude in porous' dimensions. In the synthesis of the material, however, it always exists the problems of rigorous reacting conditions and easily cracking, which confine the preparation and application of the material. Therefore, after mechanical analyzing of the material, we designed and adopted new method at normal temperature and pressure conditions of preparing the materials, differential drying method, to get intact specimens.
This paper mainly consists of two parts: 3. Mechanical analysis and designing of drying process
The drying process has been described and analyzed preliminarily in three periods. During the first period, the dynamical effects produced by unloading waves has been studied; During the medium period, it has been analyzed that the effects on stress field of gels are originated from the uneven distribution of porous, which has been proved and resolved by some chemical methods; Finally, during the last period, the materials with cracks have been studied for the effects of porous ratio and sorption on the crack developing. Under the guidance of mechanical analysis, new drying methods, differential drying method, which is useful in
controlling the reacting condition is designed.
4. Preparation of SiO2 nanoporous material
adulterated with Ni and inorganic-biomaterial hybrid
SiO2 nanoporous material adulterated with Ni has been synthesized successfully from tetraethoxysilicane as silicon resources, ethanol as solvent and watery HC1 or ammonia by sol-gel method; It is also dealt with in the electric field with Ni redistributed vertically; Organic-biomaterial hybrid has been prepared by choosing suitable solvent and catalyst ; Promising properties have been obtained after a series of experiments.
引文
1．张立德，纳米材料，化学工业出版社，北京，2000，2
2. Gleiter H. Nanostructured Material: State of the art and perspectives. Nanostructured Materials, 1995, 16:3～14
3. Andres RP et al. Research apportunities on clusters and clusters-assembled materials [J]. J Mater Res, 1989, 4: 704～712
4. Gleiter H. On the structure of grain boundaries in metals [J]. Mater Sci&Eng, 1982, 52: 91～102
5．张立德，纳米材料研究的现状、特点和发展趋势，2000
6．逄杰斌，非表面活性剂摸板法中孔二氧化硅材料的制备及表征研究，北京大学，19810839，2001
7. George W. Scherer, Stress and fracture during of gels, Journal of Non-crystalline solids 121, 1990, 104～109
8．张立德，纳米材料，化学工业出版社，北京，2000，96～97
9．张弜，李宗全，纳米复合材料力学性能的研究，材料科学与工程，2001，122～125
10．姬相玲，姜炳政，有机／无机纳米杂化功能材料，创新者的报告(6)，科学出版社，2001，144～148
11．易昌凤，有机／无机复合材料的制备技术，材料导报，2000，
37～42
12．符连社，张洪杰等，溶胶-凝胶法制备无机／有机杂化材料研究进展，材料科学与工程，1999，84～88
13. Sing K S W, Everett D H, Haul R A W, M oscou L, Pierootti R A, Rouquerol J, Siemieniewska T. Reporting physisorption data for gas solid systems with special reference to the determination of surface-area and porosity. Pure Appl. Chem., 1985, 603～619
14. Kistler S S, J. Phys. Chem., 1932, 36:52
15．沈军，王珏等，气凝胶——一种结构可控制的新型材料，材料科学与工程，1994，1～37
16. S. Henning, L. Svensson, Phys. Scr., 1981; 23:697
17. G. M. Pajonk, Applied Catalysis, 191; 72:217
18．沈军，王珏等，二氧化硅气凝胶的纳米结构与分形特性，同济大学学报，1996，76～80
19. T. Woignier, J. Phalippou, J. Non-crystalline solids, 1988, 100:404
20. J. Gross et al, Proceedings of the 2nd Int. Symposium on Aerogels. 1989, 185～190
21. J. Fricke et al, Thermal conductivity, 1990, 21～235
22. J. Fricke ed: Aerogel, Springer-Verlag, Berliu, Heide, 1986
23．莫红军，王宁飞等，低密度SiO_2气凝胶的制备及性质表征，化学世界，1999，12～16
24．潘群雄，潘晖华，陈建华，溶胶-凝胶技术与纳米材料的制备，材料导报，2001，40～42
25. Pope E J A. Mackenzie J D, Ed.Sol-gel optics Ⅱ,Proc SPIE Washington DC, 1992
26．王家芳，章文贡，溶胶-凝胶法合成有机／无机杂化材料进展，高分子通报，2001，30～36
27. Woignier T, Phalippu J, et al. J Noncryst Solids, 1992, 25～145
28. Scherer G W. J Noncrystalline Solids, 1992, 33～145
29. Laudise B A, Johnson D W. J Noncrystalline, 1986, 79～155
30．秦国彤等，气凝胶结构控制，功能材料，2000，116～121
31. Scherer G B. J Am Ceram Soc, 1990, 3～73
32. Hench L L, Wilson M J R. J Noncrystalline Solids, 1990, 121～234
33. Mujumder A S. Advances in Drying. Hemisphere, Newyork, 1981,11
34. J. Zarzyckl, M. Prassas, J. Phalippou, Synthesis of glasses from gels: the problem of monolithic gels, J. Materials Science 17, 1982, 3371～3379
35. George W. Scherer, effect of shrinkage on the modulus of silicagel, J. Noncrystalline Solids 109, 1989, 183～190
36．切列帕诺夫，脆性断裂力学，科学出版社，北京，1990，42
37．B．R．劳恩，T．R．威尔肖，脆性固体断裂力学，地震出版社，北京，1985
38．张平，刘祖武等，硅气凝胶破坏的研究，1998
39. S-I Nishimura, H kai, K Shinada, et al. Regioselective syntheses of sulfated polysaccharides: specific anti-HIV-1 activity of novel chitin sulfates [J]. Macromolecules, 1998,427～433
40. Keisuke Kurita, Taku Kojima, Yasuhiro Nishyama, et al. Synthesis and some properties of nonnatrual polysaccharides: branched chitin and chitosan [J]. Macromolecules, 2000, 4711～4716
41．吴人洁，植入型生物医用聚合物基复合材料[C]，’99高分子学术论文报告会议论文集，上海：e-8
42. Fwu-Long Mi, Shin-Shing Shyu. Yu-Bey Wu, et al. The effect of PVA/Chitosan/Fibroin (PCF)-blended spongy sheets on wound healing in rats[J]. Biomaterials, 2001, 165～173
43. Seong-Bae Park, Jin-Oh You, Ham-Yong Park, et al. A novel pH-sensitive membrane from chitosan TEOS IPN; preparation and its drug permeation characteristics [J]. Biomaterials, 2001, 323～330
44. T Koyano, N Koshizaki, H Umchara, et al. Surface states of PVA/chitosan blended hydrogels [J]. Polymer, 2000, 4461～4465
45．魏建东，邓忠生等，亚临界干燥制备SiO_2气凝胶，同济大学学报，2000，575～578
46．相宏伟，钟炳等，超临界流体干燥理论、技术及应用，材料科学与工程，1995，38～53
47．邓忠生，魏建东等，疏水型SiO_2气凝胶，无机材料学报，2000，381～383
2. Gleiter H. Nanostructured Material: State of the art and perspectives. Nanostructured Materials, 1995, 16:3～14
3. Andres RP et al. Research apportunities on clusters and clusters-assembled materials [J]. J Mater Res, 1989, 4: 704～712
4. Gleiter H. On the structure of grain boundaries in metals [J]. Mater Sci&Eng, 1982, 52: 91～102
5．张立德，纳米材料研究的现状、特点和发展趋势，2000
6．逄杰斌，非表面活性剂摸板法中孔二氧化硅材料的制备及表征研究，北京大学，19810839，2001
7. George W. Scherer, Stress and fracture during of gels, Journal of Non-crystalline solids 121, 1990, 104～109
8．张立德，纳米材料，化学工业出版社，北京，2000，96～97
9．张弜，李宗全，纳米复合材料力学性能的研究，材料科学与工程，2001，122～125
10．姬相玲，姜炳政，有机／无机纳米杂化功能材料，创新者的报告(6)，科学出版社，2001，144～148
11．易昌凤，有机／无机复合材料的制备技术，材料导报，2000，
37～42
12．符连社，张洪杰等，溶胶-凝胶法制备无机／有机杂化材料研究进展，材料科学与工程，1999，84～88
13. Sing K S W, Everett D H, Haul R A W, M oscou L, Pierootti R A, Rouquerol J, Siemieniewska T. Reporting physisorption data for gas solid systems with special reference to the determination of surface-area and porosity. Pure Appl. Chem., 1985, 603～619
14. Kistler S S, J. Phys. Chem., 1932, 36:52
15．沈军，王珏等，气凝胶——一种结构可控制的新型材料，材料科学与工程，1994，1～37
16. S. Henning, L. Svensson, Phys. Scr., 1981; 23:697
17. G. M. Pajonk, Applied Catalysis, 191; 72:217
18．沈军，王珏等，二氧化硅气凝胶的纳米结构与分形特性，同济大学学报，1996，76～80
19. T. Woignier, J. Phalippou, J. Non-crystalline solids, 1988, 100:404
20. J. Gross et al, Proceedings of the 2nd Int. Symposium on Aerogels. 1989, 185～190
21. J. Fricke et al, Thermal conductivity, 1990, 21～235
22. J. Fricke ed: Aerogel, Springer-Verlag, Berliu, Heide, 1986
23．莫红军，王宁飞等，低密度SiO_2气凝胶的制备及性质表征，化学世界，1999，12～16
24．潘群雄，潘晖华，陈建华，溶胶-凝胶技术与纳米材料的制备，材料导报，2001，40～42
25. Pope E J A. Mackenzie J D, Ed.Sol-gel optics Ⅱ,Proc SPIE Washington DC, 1992
26．王家芳，章文贡，溶胶-凝胶法合成有机／无机杂化材料进展，高分子通报，2001，30～36
27. Woignier T, Phalippu J, et al. J Noncryst Solids, 1992, 25～145
28. Scherer G W. J Noncrystalline Solids, 1992, 33～145
29. Laudise B A, Johnson D W. J Noncrystalline, 1986, 79～155
30．秦国彤等，气凝胶结构控制，功能材料，2000，116～121
31. Scherer G B. J Am Ceram Soc, 1990, 3～73
32. Hench L L, Wilson M J R. J Noncrystalline Solids, 1990, 121～234
33. Mujumder A S. Advances in Drying. Hemisphere, Newyork, 1981,11
34. J. Zarzyckl, M. Prassas, J. Phalippou, Synthesis of glasses from gels: the problem of monolithic gels, J. Materials Science 17, 1982, 3371～3379
35. George W. Scherer, effect of shrinkage on the modulus of silicagel, J. Noncrystalline Solids 109, 1989, 183～190
36．切列帕诺夫，脆性断裂力学，科学出版社，北京，1990，42
37．B．R．劳恩，T．R．威尔肖，脆性固体断裂力学，地震出版社，北京，1985
38．张平，刘祖武等，硅气凝胶破坏的研究，1998
39. S-I Nishimura, H kai, K Shinada, et al. Regioselective syntheses of sulfated polysaccharides: specific anti-HIV-1 activity of novel chitin sulfates [J]. Macromolecules, 1998,427～433
40. Keisuke Kurita, Taku Kojima, Yasuhiro Nishyama, et al. Synthesis and some properties of nonnatrual polysaccharides: branched chitin and chitosan [J]. Macromolecules, 2000, 4711～4716
41．吴人洁，植入型生物医用聚合物基复合材料[C]，’99高分子学术论文报告会议论文集，上海：e-8
42. Fwu-Long Mi, Shin-Shing Shyu. Yu-Bey Wu, et al. The effect of PVA/Chitosan/Fibroin (PCF)-blended spongy sheets on wound healing in rats[J]. Biomaterials, 2001, 165～173
43. Seong-Bae Park, Jin-Oh You, Ham-Yong Park, et al. A novel pH-sensitive membrane from chitosan TEOS IPN; preparation and its drug permeation characteristics [J]. Biomaterials, 2001, 323～330
44. T Koyano, N Koshizaki, H Umchara, et al. Surface states of PVA/chitosan blended hydrogels [J]. Polymer, 2000, 4461～4465
45．魏建东，邓忠生等，亚临界干燥制备SiO_2气凝胶，同济大学学报，2000，575～578
46．相宏伟，钟炳等，超临界流体干燥理论、技术及应用，材料科学与工程，1995，38～53
47．邓忠生，魏建东等，疏水型SiO_2气凝胶，无机材料学报，2000，381～383