碳纳米管的修饰及应用
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摘要
上世纪末，纳米技术在高科技领域里异军突起。科学家们认为，它将引起一场产业革命，对于21世纪的信息科学、生命科学、分子生物学、新材料科学、生态系统以及军事领域等的发展提供一个新的技术基础。为抢占这一新的制高点，各发达国家正在人力，财力和物力上增加投入，展开竞争。
纳米是一种几何尺寸的量度单位，它的长度为一米的十亿分之一，它正好处于以原子、分子为代表的微观世界和以人类活动空间为代表的宏观世界的中间地带，也是物理、化学、材料科学、生命科学以及信息科学发展的新领地。一般说来把组成相或晶体结构控制在100纳米(nm)以下的长皮尺寸的材料称为纳米材料。在这个研究领地，即不同于原子和分子这样的微观起点，又不同于现实宏观物质领域，它正好介于微观和宏观之间，科学家们把它称之为“介观物理”或“介观”。介观物理历经四十多年的发展，已有长足进展，特别是近十几年来的高速发展，已形成了新兴的科学技术，即纳米科技(Nano-ST)。这是人类对现实物质世界认识的深层次的回归和把握。这也是人们对“微观”和“宏观”的深究和远探以后的现实回应。实现回归的“介观”将会引导人们采用技术手段师法自然，像天然植物那样，把存在于自然界的空气、水、无机物质自组装成人类生活所需要的各种各样的物品，如粮食、纤维、各种微型机器人、计算机等等。被认为爱因斯坦之后最杰出的量子物理学家理查德·费曼，在1959年的美国物理学年会上发表《底部有很大空间》的演讲，这被公认为是纳米科学技术思想的来源。他在这篇演讲中所做的惊世预言“至少依我来看，物理学的规律不排除一个原子一个原子地制造物品的可能性”，将会变成现实。
本文对纳米材料的结构、特性、在实际中的应用及发展状况等方面进行了比较全面的介绍；对碳纳米管的制备作了较详尽的阐述；特别是对碳纳米管的修饰作了一些研究。论文的主要内容如下：
1 聚乙烯醇用于碳纳米管的开口及修饰研究并对开口及修饰的机理作了初步探讨。
2 多壁碳纳米管球磨后的结构表征，采用低速球磨机，使碳纳米管变短，
澎器掀蕊
研究了球磨时间对碳纳米管的影响，对其断裂机制作了定性分析。
3研究了碳纳米管对一二氧化锰的吸附，分析了碳纳米管吸附二氧化锰后的
形貌和吸附机理。
4利用碳纳米管覆盖层为模板，对使化学反应限制在纳米级范围进行，将
样品压成片状，采用化学气相沉积法生成纳米级的二硫化钨，并探讨了其在
纳米陶瓷中应用的可能性。
At the end of last century, nano-technology as a new force suddenly rises.The scientists think it will cause a industrial revolution and provide a new technique foundation of development in information of 21st centuries science, life science, molecular biology, new material science, ecosystem the system and military field etc. Because it is a chance, the developed countries are increasing input on manpower and financial power for the competition in the field.
Nanometer is a measure of geometry dimension, the length is billonth of a meter. It is happened in the zone between the microcosmic which is represented by atoms and molecules and the macro world which is delegated by humans' movement space, so it is a new field for the development of physics, chemistry, materials science, life sciences and info science and so on. Commonly, those material which the crystal sizds are less than 100 nanometers in one dimension are called nano-materials. This field,which is named 'mesoscopic physics' by scientists, differs from microcosm and macrocosm. But It is between microcosm and macrocosm . The mesoscopic physics has made great progress through 40 years development. Especially in recent ten years, it has been newly arisen science technique, namely , 'Nano-ST'.It is the conclusion of the deep understanding of the material world . It is also the embodiment of the researching and discussion of the microcosm and macrocosm. The reali
zation of the 'mesoscopic physics' will lead the mankind to study and imitate the nature as the plants. Then all kinds of production which mankind need, was produced with the air, water, inorganic materials in the nature, such as foodstuff, fibre, all sorts of micro-robots, computers. Richard Fayman, a outsanding quantum physicist after Einstein, made a speech whose title was 'There is Plenty of Room at the Bottom' in the American annual symposium about physics in 1959. It is considered as resource of the thought of Nano-ST. In his speech, the prediction, 'as for my opinion,the principle of physics don'texceed the probility of produce something whith atoms one by one.' will be in
reality.
In this thesis,the author give full-scale introduction about the nanomaterial's structure and traits,the application in practice and the present progress in our country; expatiate the preparation of CNTs in detail; do some researching on the decoration of CNTs. The contents of the thesis is as follows:
1 A chemical method of opening and decorating CNTs by PVA and put forward possible mechanism.
2 Structure measurement of multi-wall carbon nanotubes after ball milling.The long CNTs has been shorted by commen ball milling and effect of time on CNTs has researched. The mechanism of cut has been analyzed.
3 The research of adsorption of MnOa by CNTs ,the TEM micrograph of CNTs and mechanism were analyzed.
4 The nano-bulk WS2 was synthesized by CVD with the carbon nanotubes as template and analyzed its appearance and mechanism ;also discuss its application in nano-ceramics.
纳米是一种几何尺寸的量度单位，它的长度为一米的十亿分之一，它正好处于以原子、分子为代表的微观世界和以人类活动空间为代表的宏观世界的中间地带，也是物理、化学、材料科学、生命科学以及信息科学发展的新领地。一般说来把组成相或晶体结构控制在100纳米(nm)以下的长皮尺寸的材料称为纳米材料。在这个研究领地，即不同于原子和分子这样的微观起点，又不同于现实宏观物质领域，它正好介于微观和宏观之间，科学家们把它称之为“介观物理”或“介观”。介观物理历经四十多年的发展，已有长足进展，特别是近十几年来的高速发展，已形成了新兴的科学技术，即纳米科技(Nano-ST)。这是人类对现实物质世界认识的深层次的回归和把握。这也是人们对“微观”和“宏观”的深究和远探以后的现实回应。实现回归的“介观”将会引导人们采用技术手段师法自然，像天然植物那样，把存在于自然界的空气、水、无机物质自组装成人类生活所需要的各种各样的物品，如粮食、纤维、各种微型机器人、计算机等等。被认为爱因斯坦之后最杰出的量子物理学家理查德·费曼，在1959年的美国物理学年会上发表《底部有很大空间》的演讲，这被公认为是纳米科学技术思想的来源。他在这篇演讲中所做的惊世预言“至少依我来看，物理学的规律不排除一个原子一个原子地制造物品的可能性”，将会变成现实。
本文对纳米材料的结构、特性、在实际中的应用及发展状况等方面进行了比较全面的介绍；对碳纳米管的制备作了较详尽的阐述；特别是对碳纳米管的修饰作了一些研究。论文的主要内容如下：
1 聚乙烯醇用于碳纳米管的开口及修饰研究并对开口及修饰的机理作了初步探讨。
2 多壁碳纳米管球磨后的结构表征，采用低速球磨机，使碳纳米管变短，
澎器掀蕊
研究了球磨时间对碳纳米管的影响，对其断裂机制作了定性分析。
3研究了碳纳米管对一二氧化锰的吸附，分析了碳纳米管吸附二氧化锰后的
形貌和吸附机理。
4利用碳纳米管覆盖层为模板，对使化学反应限制在纳米级范围进行，将
样品压成片状，采用化学气相沉积法生成纳米级的二硫化钨，并探讨了其在
纳米陶瓷中应用的可能性。
At the end of last century, nano-technology as a new force suddenly rises.The scientists think it will cause a industrial revolution and provide a new technique foundation of development in information of 21st centuries science, life science, molecular biology, new material science, ecosystem the system and military field etc. Because it is a chance, the developed countries are increasing input on manpower and financial power for the competition in the field.
Nanometer is a measure of geometry dimension, the length is billonth of a meter. It is happened in the zone between the microcosmic which is represented by atoms and molecules and the macro world which is delegated by humans' movement space, so it is a new field for the development of physics, chemistry, materials science, life sciences and info science and so on. Commonly, those material which the crystal sizds are less than 100 nanometers in one dimension are called nano-materials. This field,which is named 'mesoscopic physics' by scientists, differs from microcosm and macrocosm. But It is between microcosm and macrocosm . The mesoscopic physics has made great progress through 40 years development. Especially in recent ten years, it has been newly arisen science technique, namely , 'Nano-ST'.It is the conclusion of the deep understanding of the material world . It is also the embodiment of the researching and discussion of the microcosm and macrocosm. The reali
zation of the 'mesoscopic physics' will lead the mankind to study and imitate the nature as the plants. Then all kinds of production which mankind need, was produced with the air, water, inorganic materials in the nature, such as foodstuff, fibre, all sorts of micro-robots, computers. Richard Fayman, a outsanding quantum physicist after Einstein, made a speech whose title was 'There is Plenty of Room at the Bottom' in the American annual symposium about physics in 1959. It is considered as resource of the thought of Nano-ST. In his speech, the prediction, 'as for my opinion,the principle of physics don'texceed the probility of produce something whith atoms one by one.' will be in
reality.
In this thesis,the author give full-scale introduction about the nanomaterial's structure and traits,the application in practice and the present progress in our country; expatiate the preparation of CNTs in detail; do some researching on the decoration of CNTs. The contents of the thesis is as follows:
1 A chemical method of opening and decorating CNTs by PVA and put forward possible mechanism.
2 Structure measurement of multi-wall carbon nanotubes after ball milling.The long CNTs has been shorted by commen ball milling and effect of time on CNTs has researched. The mechanism of cut has been analyzed.
3 The research of adsorption of MnOa by CNTs ,the TEM micrograph of CNTs and mechanism were analyzed.
4 The nano-bulk WS2 was synthesized by CVD with the carbon nanotubes as template and analyzed its appearance and mechanism ;also discuss its application in nano-ceramics.
引文
1 Iijima, S. Nature, 1991, 354: 56
2 Iijima, S. and Ichihashi, T. Nature, 1993, 363: 603
3 wang, M. W.; Li, J.Y.; Peng, N.C. New Carbon Materials, 2002, 17(3): 75
4 Ajayan, P. M. Chemical Reviews, 1999, 99: 1787.
5 Stepanek, I. Maurin, G. Chemical Physics Letters, 2000, 331: 125
6 Service, R. F. Science, 1998, 281: 940
7 Yang, Z.Q. Xie, Z.L. He, Y.S. New Carbon Materials, 2003, 18(1): 75
8 Mao, Z.Q. Xu, C.L. Yan, J. New Carbon Materials, 2000, 15(1): 64
9 Clare, B. W. Kepert, D. L. Inorganica Chimica Acta, 2003, 343: 1
10 Tsang, S.C. Chert, Y.K. Harris ,P.J.F. Green, M.L.H. Nature 1994, 372: 159
11 Pierard, N. Fonseca, Konya, Z. Willems, I. Tendeloo,G.V. Nagy, J.B. A. Chemical Physics Letters, 2001, 335: 1
12 Mothioux, M. Carbon, 2002, 40:1809
13 YANG, K.X. J. Magn Mater Devices, 2002, 33(4): 40
14 Liu, L.Q. Guo, Z.X. Chinese Science Bulletin, 2001, 19:1590
15 Li, L.X. Li, F. Ying, Z. Yang, Q.H. Cheng, H.M. New Carbon Materials, 2003, 18(1): 69
16 Dalton, A.B. Collins, S. Munoz, E. Razal, J.M. Ebrow, V.H. Ferraris, J.P. Coleman, J.N. Rim, B.G. Baughman, R.H. Nature, 2003, 423: 703
17 王太宏等 纳米器件的制备、表征及其应用 物理 2001 20
18 Carbon 39 (2001) 1273-1278
19 王世敏 须租勋 傅晶．纳米材料制备技术 化学工业出版社 2002．12
20 Chen Y, Gerald JF, Chadderton LT, et al. Appl Phys Lett. 1996, 262:161
21 J. Y. Huang H. Yasuda H. Mori Chemical Physics Letters 303 1999 130-134
22 "Introduction to Carbon Materials Research" Department of Electrical Engineering and Computer Science and Department of Physics MIT Cambridge, Massachusetts. IBM Research Division, T. J. Watson Research Laboratory Yorktown Heights, NY
23 吕德义、陈万喜．化学通报．2000．10：5
24 Ebbesen TW, Ajayan PM, Hiura H, et al. Nature. 1994, 265: 1850
25 Chemical Physics Letters 335(2001) 1-8
26 成会明 纳米碳管制备、结构、物性及应用．化学工业出版社 2002．8
27 张立德、牟季美．纳米材料和纳米结构 北京 科学出版社 2001
28 顾书英、吴琪琳．碳纳米管应用研究的现状和未来 同济大学学报 2002．2
29 邓玉荣，丁晓夏，甘仲维等．化学气相沉积法合成ZnS纳米球[J]．华中师范大学学报，2002，36(3)：305-307
30 H. J. Kai, E.W. Wong, and C.M. Lieber [J]. Nature, 375 (1997): 769-771
31 Niihara K. New design concept of structural ceramics-cera micnanocomposites[J]. J Ceram Soc Jpn, 1991, 99(10):974-982
32 Li J. G. , Sun X. D. Synthesis and sintering behavior of a nanocrystalli α-Alumina powder [J]. Acta mater, 2000, 48: 3103-3112
33 Li J.G., Sun X. D., et al. Effect of seed on phase transformation of AACH upon heating and sintering reactivity of ultrafine Alumina powder[J]. Acta metallurgica sinica, 1999, 35(10): 1099-1102
34 Zhang F., Sun X. D., You J., et al. Production of ultra-fine α-Al_2O_3 powders from ammonium aluminum carbonate hydroxide[J], Acta
metallurgica Sinica, 1999, 12(5): 1194-1197
35 Jia Y Q, Li J. G., Wang Y. M., et al. Effect of precipitant on the properties of ultrafine yttria powder produced by precipitation method [J]. Acta metallurgica Sinica, 1999, 12 (5): 1188-1193
36 Ohji T., Jeong Y. K., Choa Y. H., et al. Strengthening and toughening mechanics of ceramic nanocomposites[J]. J Mater Sci, 1998, 81 (6): 1453-1460
37 Lee H. Y., Riehemann W., Mordike B1[J], J. the Europ. Ceram. Soc,1992., 10: 245
2 Iijima, S. and Ichihashi, T. Nature, 1993, 363: 603
3 wang, M. W.; Li, J.Y.; Peng, N.C. New Carbon Materials, 2002, 17(3): 75
4 Ajayan, P. M. Chemical Reviews, 1999, 99: 1787.
5 Stepanek, I. Maurin, G. Chemical Physics Letters, 2000, 331: 125
6 Service, R. F. Science, 1998, 281: 940
7 Yang, Z.Q. Xie, Z.L. He, Y.S. New Carbon Materials, 2003, 18(1): 75
8 Mao, Z.Q. Xu, C.L. Yan, J. New Carbon Materials, 2000, 15(1): 64
9 Clare, B. W. Kepert, D. L. Inorganica Chimica Acta, 2003, 343: 1
10 Tsang, S.C. Chert, Y.K. Harris ,P.J.F. Green, M.L.H. Nature 1994, 372: 159
11 Pierard, N. Fonseca, Konya, Z. Willems, I. Tendeloo,G.V. Nagy, J.B. A. Chemical Physics Letters, 2001, 335: 1
12 Mothioux, M. Carbon, 2002, 40:1809
13 YANG, K.X. J. Magn Mater Devices, 2002, 33(4): 40
14 Liu, L.Q. Guo, Z.X. Chinese Science Bulletin, 2001, 19:1590
15 Li, L.X. Li, F. Ying, Z. Yang, Q.H. Cheng, H.M. New Carbon Materials, 2003, 18(1): 69
16 Dalton, A.B. Collins, S. Munoz, E. Razal, J.M. Ebrow, V.H. Ferraris, J.P. Coleman, J.N. Rim, B.G. Baughman, R.H. Nature, 2003, 423: 703
17 王太宏等 纳米器件的制备、表征及其应用 物理 2001 20
18 Carbon 39 (2001) 1273-1278
19 王世敏 须租勋 傅晶．纳米材料制备技术 化学工业出版社 2002．12
20 Chen Y, Gerald JF, Chadderton LT, et al. Appl Phys Lett. 1996, 262:161
21 J. Y. Huang H. Yasuda H. Mori Chemical Physics Letters 303 1999 130-134
22 "Introduction to Carbon Materials Research" Department of Electrical Engineering and Computer Science and Department of Physics MIT Cambridge, Massachusetts. IBM Research Division, T. J. Watson Research Laboratory Yorktown Heights, NY
23 吕德义、陈万喜．化学通报．2000．10：5
24 Ebbesen TW, Ajayan PM, Hiura H, et al. Nature. 1994, 265: 1850
25 Chemical Physics Letters 335(2001) 1-8
26 成会明 纳米碳管制备、结构、物性及应用．化学工业出版社 2002．8
27 张立德、牟季美．纳米材料和纳米结构 北京 科学出版社 2001
28 顾书英、吴琪琳．碳纳米管应用研究的现状和未来 同济大学学报 2002．2
29 邓玉荣，丁晓夏，甘仲维等．化学气相沉积法合成ZnS纳米球[J]．华中师范大学学报，2002，36(3)：305-307
30 H. J. Kai, E.W. Wong, and C.M. Lieber [J]. Nature, 375 (1997): 769-771
31 Niihara K. New design concept of structural ceramics-cera micnanocomposites[J]. J Ceram Soc Jpn, 1991, 99(10):974-982
32 Li J. G. , Sun X. D. Synthesis and sintering behavior of a nanocrystalli α-Alumina powder [J]. Acta mater, 2000, 48: 3103-3112
33 Li J.G., Sun X. D., et al. Effect of seed on phase transformation of AACH upon heating and sintering reactivity of ultrafine Alumina powder[J]. Acta metallurgica sinica, 1999, 35(10): 1099-1102
34 Zhang F., Sun X. D., You J., et al. Production of ultra-fine α-Al_2O_3 powders from ammonium aluminum carbonate hydroxide[J], Acta
metallurgica Sinica, 1999, 12(5): 1194-1197
35 Jia Y Q, Li J. G., Wang Y. M., et al. Effect of precipitant on the properties of ultrafine yttria powder produced by precipitation method [J]. Acta metallurgica Sinica, 1999, 12 (5): 1188-1193
36 Ohji T., Jeong Y. K., Choa Y. H., et al. Strengthening and toughening mechanics of ceramic nanocomposites[J]. J Mater Sci, 1998, 81 (6): 1453-1460
37 Lee H. Y., Riehemann W., Mordike B1[J], J. the Europ. Ceram. Soc,1992., 10: 245