研究生: |
林福仁 Fu-jen Lin |
---|---|
論文名稱: |
以不同高分子碳源及觸媒合成奈米碳管之研究及其純化效果之討論 The Study of Synthesis Carbon Nanotubes from Difference Carbon Sources and Catalysts and the Effect of Purification Processes |
指導教授: |
顏怡文
Yee-wen Yen |
口試委員: |
吳子嘉
Albert T. Wu 陳志銘 Chih-Ming Chen 郭俞麟 Yu-Lin Kuo 鄭偉鈞 Wei-Chun Cheng |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 材料科學與工程系 Department of Materials Science and Engineering |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 108 |
中文關鍵詞: | 奈米碳管 、流體化床 、化學氣相沉積 |
外文關鍵詞: | carbon nanotubes, fluidized bed, CVD |
相關次數: | 點閱:356 下載:8 |
分享至: |
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
奈米碳管具有優異的機械、電性、光學和化學等特殊性質特性,在目前的材料研究領域上站有重要的地位。以目前的商業生產技術,主要包括了雷射蒸發法(laser vaporization)以及化學氣相沉積法(chemical vapor deposition,CVD),Wei等人更藉由化學氣相沉積法以及流體化床的結合產生新式的化學氣相沉積-流體化床法(Chemical Vapor Deposition-Fluidized Bed, CVD-FB),以此方法增加化學氣相沉積法的產率。
奈米碳管具有優異的機械、電性、光學和化學等特殊性質特性,在目前的材料研究領域上站有重要的地位。以目前的商業生產技術,主要包括了雷射蒸發法以及化學氣相沉積法,Wei等人更藉由化學氣相沉積法以及流體化床的結合產生新式的化學氣相沉積-流體化床法,以此方法增加化學氣相沉積法的產率。
在相關文獻中已經有提到利用CVD-FB以高分子為原料進行反應,在通入H2/Ar混合氣體進行反應之後,可成功獲得奈米碳管。本實驗利用在型設計的三段式CVD-FBR為反應器,PE、PP以及PET做為碳源,並且以Fe(NO3)3、FeCl3、NiCl2觸媒進行反應,在反應過後經由讓氧化、酸洗以及退火的純化步驟,得到提純的奈米碳管,以SEM, TEM以及Raman等儀器做分析,將自備的奈米碳管以及各種參數做比之後,發現高分子的種類並不影響碳管的微結構,而是影響整體樣品的雜質程度,此種因素尚且牽涉到高分子的化學結構、熱穩定性以及粒徑大小;而金屬觸媒的種類才是影響碳管結構的主要因素,以鐵為觸媒的系統,其碳管直徑較為粗大,且容易有粗大的碳管出現,而以鎳為觸媒的系統則的管徑較為細小,另外在鹽類基上的差異,以硝基為主的系統可生成較為筆直的碳管,而以氯基為主的系統所生成的碳管則皆為扭曲。
Carbon nanotubes (CNTs) is special empty tube structure composed of single or multi-layer graphite. Due to CNTs’ machinic, electric conduction, thermal conduction chemical and magnetic properties, it is one of most significant studies in material science. Arc discharge, laser vaporization and CVD are three main produce ways at present. In order to increase the production efficiency, Wei al. introduce CVD-FBR to synthesize CNTs and generated CNTs successfully.
In this study, different carbon sources (PE, PP and PET) and catalysts (Fe(NO3)3, FeCl3 and NiCl2) were used to synthesize CNTs by CVD-FBR. after reaction for 1 Hr, as growth CNTs were obtained. For purification process, a serious steps such as thermal oxidizing, acidic washing, annealing were needed.
Under SEM and TEM examining, CNTs can be observed easily in all samples. And the effect of purification process is significant by comparison the Raman spectrums between different purification stages. In a overall discussion. It was founded that carbon sources do not influence the morphology of CNTs but affect purity of CNTs mainly. And catalysts are the most important key for the morphology of CNT in microstructure. When using Fe as catalyst, CNTs are more thick using Ni as catalyst. And using NO3- salt as catalyst, CNTs are more curved then using Cl- salt as catalyst.
1. T. A. Edison, US Patent 470,925 (1892).
2. S. Iijima , “Helical microtubules of graphitic carbon”, Nature, Vol. 354, PP. 56-58 (1991).
3. H. W. Kroto, J. R. Heath, S. C. O’Brien, R.F. Curl, R.E. Smalley,“C60: Buckminsterfullerene”, Nature, Vol. 318, pp.162(1985).
4. 維基百科,http://en.wikipedia.org/wiki/Carbon_nanotube#Discovery (2006)
5. K. T. Lau, D. Hui, “The revolutionary creation of new advanced materials—carbon nanotube composites”, Composites: Part B, Vol. 33, pp. 263-277(2002).
6. 匡元生化科技,http://www.cbt.com.tw/0300.html (2006)
7. 彭志維,“雜亂方向的多層奈米碳管薄膜之場發射特性”,國立清華大學物理學系碩士論文 (2003)。
8. 成會明,”奈米碳管”,五南圖書出版股份有限公司。
9. 美國密歇根州立大學, http://www.pa.msu.edu/cmp/csc/nanotube.html (2008)
10. http://physicsworld.com/cws/article/print/19746/1/pwpia1_07-04 (2008)
11. 黃明德,”利用化學氣相沉積法在流體化床反應器中以高分子合成奈米碳管”,國立台灣科技大學碩士論文(2006)。
12. D. He, T. Zhao, Y. Liu, J. Zhu, G. Y. and L. Ge,” he effect of electric current on the synthesis of single-walled carbon nanotubes by temperature controlled arc discharge”, Diamond and Related Materials, Vol. 16, PP. 1722-1726 (2007).
13. F. Kokai, K. Takahashi, D. Kasuya, T. Ichihashi, M. Yudasaka and S. Iijima,” Synthesis of single-wall carbon nanotubes by millisecond-pulsed CO2 laser vaporization at room temperature”, Chemical Physics Letters, Vol. 332, PP. 449-454 (2000).
14. N. Braidy, M. A. El Khakani and G. A. Botton, ” Effect of laser intensity on yield and physical characteristics of single wall carbon nanotubes produced by the Nd:YAG laser vaporization method”, Carbon, Volume 40, PP. 2835-2582 (2002).
15. D. Nishide, H. Kataura, S. Suzuki, S. Okubo and Y. Achiba, ” Growth of single-wall carbon nanotubes from ethanol vapor on cobalt particles produced by pulsed laser vaporization”, Chemical Physics Letters, Vol. 392, PP. 309-313 (2004).
16. N. Inami, M. A. Mohamed, E. Shikoh and A. Fujiwara,” Synthesis-condition dependence of carbon nanotube growth by alcohol catalytic chemical vapor deposition method”, Science and Technology of Advanced Materials, Vol. 8, PP. 292-295 (2007).
17. T. H. Fang, W. J. Chang, D. M. Lu and W. C. Lien,” Effects of gas composition on the growth of multi-walled carbon nanotube”, Applied Surface Science, Vol. 253, PP.8749-8753 (2007).
18. T. Inoue, I. Gunjishima and A. Okamoto,” Synthesis of diameter-controlled carbon nanotubes using centrifugally classified nanoparticle catalysts”, Carbon, Vol. 45, PP. 2164-2170 (2007).
19. 台南科技大學,http://elearning.stut.edu.tw/m_facture/Nanotech/Web/ ch8.htm (2008)
20. W .Kratschmer, L. D. Lamb, K . Fostiropoulos, “C60: a new form of carbon”, Nature, Vol. 347, PP. 354-358 (1990).
21. Y. Wang, F. Wei, G. S. Gu, H. Yu, “Agglomerated carbon nanotubes and its mass production in a fluidized-bed reactor”, Physica B: Condensed Matter, Vol. 323, PP. 327-329 (2002).
22. F. Wei, C. Huang, Y. Wang, “Fluidization of carbon nanotubes”, China Particuology, Vol.3, PP.40-41 (2005).
23. H. Yu, Q. Zhang, Q. F. Zhang, Q. Wang, G. Q. Ning, G. H. Luo, F. Wei, “Effect of the reaction atmosphere on the diameter of single-walled carbon nanotubes produced by chemical vapor deposition”, Carbon, Vol. 44, PP. 1706-1712 (2006).
24. H. Yu, Z. F. Li, G. H. Luo, F. Wei, “Growth of branch carbon nanotubes on carbon nanotubes as support”, Diamond and Related Materials, Vol.15, PP. 1447-1451 (2006).
25. Q. Zhang, W. Z. Qian, Q. Wen, Y. Liu, D. Z. Wang, F. Wei, “The effect of phase separation in Fe/Mg/Al/O catalysts on the synthesis of DWCNTs from methane”Carbon, Vol. 45, PP. 1645-1650 (2007).
26. F. Wei, Q. Zhang, W. Z. Qian, H. Yu, Y. Wang, G. H. Luo, G. H. Xu, D.Z. Wang,” The mass production of carbon nanotubes using a nano-agglomerate fluidized bed reactor: A multiscale space–time analysis”, Powder Technology, Vol. 183, PP. 10-20(2008).
27. W. Z. Qian, T. Liu, Z. W. Wang, F. Wei, Z.F. Li, G. H. Luo, Y. D. Li, “Production of hydrogen and carbon nanotubes from methane decomposition in a two-stage fluidized bed reactor”, Vol. 260, PP. 223-226 (2004)
28. Y. W. Yen, M. D. Huang, F. J. Lin, ” Synthesize carbon nanotubes by a novel method using chemical vapor deposition-fluidized bed reactor from solid-stated polymers”, Diamond and Related Materials, vol. 17, pp. 567-570(2008).
29. R. Xiang, G. H. Luo, W. Z. Qian, Q. Zhang, Y. Wang, F. Wei, Q. Li, A.Y. Cao, “Encapsulation, compensation, and substitution of catalyst particles during continuous growth of carbon nanotubes”, Adv. Mater. Vol. 19,PP.2360–2363 (2007).
30. Q. Zhang, W. P. Zhou,W .Z. Qian, R. Xiang, J. Q. Huang, D. Z. Wang, F.Wei, “Synchronous growth of vertically aligned carbon nanotubes with pristine stress in the heterogeneous catalysis process”, J. Phys. Chem.Vol. 110, PP. 14638–14643 (2007).
31. Y. Hao, Q.F. Zhang, F. Wei, W.Z. Qian, G.H. Luo, “Agglomerated CNTs synthesized in a fluidized bed reactor: agglomerate structure and formation mechanism”, Carbon, Vol. 41, PP. 2855–2863 (2003).
32. 徐逸明,“化學氣相沉積法及電漿輔助化學氣相沉積法於低溫合成奈米碳管之研究”,國立成功大學化學工程研究所博士論文 (2001)。
33. G. Z. Chen, X. Fan, A. Luget, Milo S. P. Shaffer, D. J. Fray and A. H. Windle,” Electrolytic conversion of graphite to carbon nanotubes in fused salts”, Journal of Electroanalytical Chemistry, Vol. 446, PP. 1-6 (1998).
34. A. T. Dimitrov, G. Z. Chen, I. A. Kinloch and D. J. Fray,” A feasibility study of scaling-up the electrolytic production of carbon nanotubes in molten salts”, Electrochimica Acta, Vol. 48, PP. 91-102 (2002).
35. Li YL, Yu YD,Liang Y.,” A navel method for synthesis of carbon nanotubes:low temperature solid pyrolysis”, Journal of Materials Research, Vol. 12, PP. 1687 (1997).
36. Li WZ, Xie SS, Qian LX,” Large-scale synthesis of aligned carbon nanotubes ” , Science, Vol. 271, PP.1701-1703 (1996).
37. J. Y. Huang, H. Yasuda, H. Mori, ”Highly curved carbon nanostructures produced by ball-milling”, Chem Phys Lett, Vol. 303, PP. 130-134 (2000).
38. Y. Chen, J. F. Gerald, L. T. CHadderton, et al, ” Nanoporous carbon produced by ball milling” appl phys lett, Vol. 74, PP. 2782 (1999).
39. Vander Wal RL, Ticich TM, Curtis VE, “Diffusion flame synthesis of single-walled carbon nanotubes”, Chem Phys Lett, Vol. 323, PP. 271 (2000).
40. F. H. Ko, C. Y. Lee, C. J. Ko, T. C. Chu, ” Purification of multi-walled carbon nanotubes through microwave heating of nitric acid in a closed vessel”, Carbon, Vol.43, PP. 727-733 (2005).
41. C. M. Chen, M. Chen, Y. W. Peng, C. H. Lin, L. W. Chang, C. F. Chen, “Microwave digestion and acidic treatment procedures for the purification of multi-walled carbon nanotubes”, Diamond and Related Materials, Vol.14, PP. 793-803 (2005).
42. H. Jia, Y. Lian, M. O. Ishitsuka, T.Nakahodo, Y. Maeda, T. Tsuchiya, T. Wakahara, T. Akasaka, “Centrifugal purification of chemically modified single-walled carbon nanotubes”, Science and Technology of Advanced Materials, Vol. 6, PP.571-581 (2005)
43. Y. Yang, L. Xie, Z. Chen, M. Liu, T. Zhu, Z. Liu,” Purification and length separation of single-walled carbon nanotubes using chromatographic method” Synthetic Metals, Vol. 155, PP. 155-160 (2005)
44. P. Chungchamroenkit, S. Chavadej, U. Yanatatsaneejit, B. Kitiyanan, “Residue catalyst support removal and purification of carbon nanotubes by NaOH leaching and froth flotation”, Separation and Purification Technology, Vol. 60 PP. 206-214 (2008).
45. T. Suzuki, S. Inoue, Y. Ando, “Purification of single-wall carbon nanotubes by using high-pressure micro reactor”, Diamond and Related Materials, Available online (2008).
46. S. H. Su, W. T. Chiang, Chun-Chang Lin, Meiso Yokoyama, ” Multi-wall carbon nanotubes: Purification, morphology and field emission performance”, Physica E: Low-dimensional Systems and Nanostructures, Available online (2007).
47. X. Liu, J. L. Spencer, A. B. Kaiser, W. M. Arnold,” Selective purification of multiwalled carbon nanotubes by dielectrophoresis within a large array “, Current Applied Physics, Vol.6, PP. 427-431 (2006).
48. N. Shah, S. Ma, Y. Wang, G. P. Huffman,” Semi-continuous hydrogen production from catalytic methane decomposition using a fluidized-bed reactor”, International Journal of Hydrogen Energy, Vol. 30, PP. 3315-3319 (2007)
49. F. R. García-García, M. Pérez-Cabero, D. M. Nevskaia, I. Rodríguez-Ramos, A. Guerrero-Ruiz, “Improving the synthesis of high purity carbon nanotubes in a catalytic fluidized bed reactor and their comparative test for hydrogen adsorption capacity”, Catalysis Today, Vol. 133-135, PP. 815-821 (2008)
50. L. E. Murr, K. F. Soto, “A TEM study of soot, carbon nanotubes, and related fullerene nanopolyhedra in common fuel-gas combustion sources”, Materials Characterization, Vol. 55, PP. 50-65 (2005).
51. 陳立俊,”材料電子顯微鏡學”,國家實驗研究院儀器科技研究中心,台北(1990)。
52. K. Yang, H. Han, Xifeng Pan, Na Chen, Mingyuan Gu, ” The effect of chemical treatment on the crystallinity of multi-walled carbon nanotubes”, Journal of Physics and Chemistry of Solids, Vol. 69, PP. 222-229 (2008).
53. L. Henrard, A. Loiseau, C. Journet and P. Bernier, “Study of the symmetry of single-wall nanotubes by electron diffraction”, Vol. 13, PP. 661-669 (2000).
54. 蔡淑慧,”奈米通訊”,第十二卷第二期,47-51頁(2005)。
55. Y. Ouyang, L. M. Cong, L. Chen, Q. X. Liu, Y. Fang, ”Raman study on single-walled carbon nanotubes and multi-walled carbon nanotubes with different laser excitation energies”, Physica E: Low-dimensional Systems and Nanostructures, Available online (2007).
56. X. Gui, J. Wei, K. Wang, W. Wang, R. Lv, J. Chang, F. Kang, J. Gu, D. Wu, “Improved filling rate and enhanced magnetic properties of Fe-filled carbon nanotubes by annealing and magnetic separation”, Materials Research Bulletin, Available online (2008).
57. C. M. Chen, Y. M. Dai, J. G. Huang, J. M. Jehng, “Intermetallic catalyst for carbon nanotubes (CNTs) growth by thermal chemical vapor deposition method”, Carbon, Vol. 44, 2006, PP. 1808-1820(2006).
58. Kong Bee Hong, Aidawati Azlin Binti Ismail, Mohamed Ezzaham Bin Mohd Mahayuddin, Abdul Rahman Mohamed, Sharif Hussein Sharif Zein,” Production of High Purity Multi-Walled Carbon Nanotubes from Catalytic Decomposition of Methane”, Journal of Natural Gas Chemistry, Vol. 15, PP. 266-270 (2006).