本研究以化學氧化法將多壁奈米碳管(Multi-Walled Carbon nanotubes)進行純化，使奈米碳管表面接上羧基及羥基，提高在溶液中的分散性。隨後將奈米碳管以溶液混摻法製備不同重量組成的MWCNTs/PTT奈米複合材料。使用FTIR分析得知奈米碳管經純化後，具有(－COOH)與C－O伸縮振動吸收。以TGA分析聚對苯二甲酸丙二酯(Polytrimethylene Terephthalate)之熱穩定性測其T5為409.2℃，800℃之灰份殘餘量為4.3%。PTT加入奈米碳管可提高PTT的T5及灰份殘餘量，表示奈米碳管的添加可提高PTT的熱穩定性。由TMA分析測得PTT之熱膨脹係數(CTE)為276.70 μm/m℃，當奈米碳管加入後明顯降低PTT的CTE值，表示奈米碳管的添加可提高PTT的尺寸安定性；使用DSC分析等溫結晶與非等溫結晶行為，等溫結晶部分MWCNTs/PTT之Avrami指數n介於2~3之間，整體速率常數k隨著MWCNTs含量之增加而加快，表示MWCNTs扮演異質成核。非等溫結晶分析MWCNTs/PTT之Avrami指數n介於3~4之間，結晶溫度皆較純PTT低表示添加MWCNTs會阻礙PTT分子鏈之移動性異質成核較不明顯。使用Avrami-Ozawa方程式所得到的線性關係來瞭解非等溫結晶行為，MWCNTs/PTT之活化能比原PTT低，表示MWCNTs加入具有降低結晶活化能之效益。以SEM、POM觀察MWCNTs/PTT微觀形態。由POM觀測PTT屬於三維球晶形態。

Multiwalled carbon nanotubes (MWCNTs) was first treated with a mixing acid (H2SO4/HNO3=3/1) to produce carbonyl groups and hydroxyl groups on the surface of the MWCNTs. Then, the acid treated-MWCNTs was blended with poly(trimethylene terephthalate) (PTT) to prepare MWCNTs/PTT composites. FTIR results revealed that there are carboxylic groups (–COOH) and –CO stretching absorption in the acid-treated MWCNTs. Thermal stability of the MWCNTs/PTT composites was investigated by TGA. TGA analyses revealed that the 5% thermal decomposition temperature (T5) of the PTT was 409.2oC, and the ash content at 800oC was 4.3%. Both the T5 and ash content of the PTT increased after the MWCNTs addition to the PTT matrix. TMA results showed that the coefficient of thermal expansion (CTE) for the pure PTT was 276.70 ppm/ oC. The CTE value of the composites decreased after the addition of modified-MWCNTs into the PTT matrix. Isothermal and nonisothermal crystallization of PTT was investigated by DSC. From isothermal crystallization analysis, the Avrami index (n) of MWCNTs/PTT composites were between 2~3 and the overall crystallization rate (k) increased with increasing MWCNTs content. This result indicates that MWCNTs act as heterogeneous crystallization. From nonisothermal crystallization analysis, the Avrami exponent (n) of MWCNTs/PTT composites were between 3~4. The nonisothermal crystallization behaviors of the MWCNTs/PTT composites were analyzed with the Avrami-Ozawa equation. The activation energy of MWCNTs/PTT composites were lower than that of pure PTT. This result reveals that the addition of MWCNTs decreases the activation energy of PTT crystallization.

摘要 Ⅰ
ABSTRACT Ⅱ
誌謝 Ⅲ
目錄 Ⅳ
圖目錄 Ⅶ
表目錄 Ⅹ
第一章 緒論 1
1.1 前言 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 聚對苯二甲酸丙二酯 3
2.1.1 聚對苯二甲酸丙二酯之介紹 3
2.1.2 聚對苯二甲酸丙二酯之特性 6
2.1.3 聚對苯二甲酸丙二酯之市場分析 8
2.2 利用1,3-丙二醇製備聚對苯二甲酸丙二酯 9
2.2.1 1,3-丙二醇的製備 9
2.2.2 聚對苯二甲酸丙二酯的製備 11
2.2.2.1 DMT法合成聚對苯二甲酸丙二酯 11
2.2.2.2 PTA 法合成聚對苯二甲酸丙二酯 11
2.3 奈米碳管 11
2.3.1 奈米碳管 11
2.3.2 奈米碳管的合成方式 13
2.3.3 奈米碳管之熱性質 16
2.3.4 奈米碳管純化 16
2.4 高分子結晶 18
2.5 結晶動力學 19
2.5.1 Avrami等溫結晶動力學 19
2.5.2 Modified Avrami非等溫結晶動力學 21
2.5.3 Modified Ozawa非等溫結晶動力學 21
2.5.4 Modified Avrami/Ozawa非等溫結晶動力學 22
2.5.5 Modified Kissinger結晶活化能 23
2.6 結晶度 23
2.7 高分子結晶形態 23
第三章 實驗 26
3.1 實驗流程 26
3.2 實驗藥品 27
3.3 奈米碳管純化 28
3.4 MWCNTs/PTT混摻 29
3.5 實驗儀器 30
3.5.1 傅立葉轉換紅外光光譜 30
3.5.2 拉曼光譜 30
3.5.3 微差掃描熱卡計 31
3.5.4 熱重分析儀 32
3.5.5 熱機械分析儀 32
3.5.6 偏光顯微鏡 33
3.5.7 掃描式電子顯微鏡 35
第四章 結果與討論 37
4.1 奈米碳管改質之鑑定 37
4.2 MWCNTs/PTT複合材料之鑑定 39
4.3 MWCNTs/PTT複合材料之等溫結晶 42
4.4 MWCNTs/PTT複合材料Avrami等溫結晶動力學 45
4.5 MWCNTs/PTT複合材料之非等溫結晶 53
4.6 MWCNTs/PTT複合材料Avrami等溫結晶動力學 62
4.7 MWCNTs/PTT複合材料Ozawa非等溫結晶動力學 66
4.8 MWCNTs/PTT複合材料合併Avrami/Ozawa非等溫結晶動力學 69
4.9 MWCNTs/PTT複合材料非等溫結晶活化能 73
4.10 MWCNTs/PTT複合材料等溫結晶形態觀察 74
4.11 MWCNTs/PTT複合材料之形態分析 77
第五章 結論 78
第六章 參考文獻 79

1.L. Jiang. ; M. P. Wolcott. ; J. Zhang. Biomacromlecules 2006, 7, 199.
2.W. J. Lambert. ; K. D. Peck. J.Controlled release 1995, 33, 189.
3.H. Tsuji. ; S. Miyauchi. Biomacromlecules 2001, 2, 597.
4.C. S. Ha. ; J. A. G. Jr, Chem.Rev. 2005, 105, 4205.
5.C. S. Wu. ; J. Appl. Polym. Sci. 2003, 89, 2888.
6.D. Bikiaris. ; Panayiotu. J Appl. Plym. Sci. 1998, 70, 1503.
7.Y. Zhihong. ; B. Mrinal. ; R. V. Utpal. Polymer 1996, 37, 2137.
8.C. S. Wu. Polymer 2005, 46, 147.
9.J. W. Hill. ; W. H. Carothers. J. Am. Chem. Soc 1933, 55, 5031.
10.J. R. Whinfield. ; J. T. Dickson. US. Patent 2465319 1949.
11.C. Schick. ; E. Donth. Phys Scripta 1991, 43, 423.
12.C. Schick. ; J. Wigger. ; W. Mischok. Acta Polym 1990, 41, 137.
13.R. Pan. ; B. Wunderlich. Makromol Chem 1988, 189, 2443.
14.Ritter SK. Chem. News 2003, 81, 30.
15.A. Scott. Chem. Week 2002, 164, 35.
16.Iijima, S. Nature, 1991, 354, 56.
17.Kroto, H. W. ; Heath, J. R. ; O’Brien, S. C. ; Curl, R. F. ; Smalley, R. E. Nature, 1985,318, 162.
18.Iijima, S. ; Ichihashi, T. Nature 1993, 363, 603.
19.Bethune, D. S. ; Kiang, C. H. ; Devries, M. S. Nature 1993, 363, 605.
20.Harris. Carbon Nanotubes and R elated Structure, Cambridge Press, Cambridge, London, 1999.
21.Ebbesen, T. W. CRC Press, Inc., New Yor, (1997)1-293.
22.Lange, H. ; Huczko, A. ; Byszewski, P.; Mizera, E. ; Shinohara, H. Chemical Physics Letters 1998, 289, 174.
23.Saito, Y. ; Uemura, S. ; Hamaguchi, K. Japanese Journal of Applied Physics 37, Part 2, 3B, L346-L348 (1998).
24.Colbert, D. T. ; Zhang, J. ; Mcclure, S. M. ; Nikolaev, P.; Chen, Z. ; J. H. Hafner, ; Owens,D. W. ; Kotula, P. G. ; Carter, C. B. ; Weaver, J. H.; Rinzler, A. G.; Smalley, R. E. Science 1994, 266, 1218.
25.Chang, B. H. ; Zhang, H. ; Zhou, W. Y. ; Qian, L. X. ; Pan, Z. W. ; Mao, J. M. ; Li, W. Z. Acta Physica Sinica 1998, 47, 2, 340.
26.Ando, Y. ; Xinluozhao ; Ohkohchi, M. Japanese of Journal Applied Physics 37, Part 2, 1, L61-L63 (1998).
27.Thess, A. ; Lee, R. ; Nikolaev, P. Science 1996, 273, 483.
28.Smally, R. E. Chem. Phys. Lett. 1995, 243, 49
29.Guo, T. ; Nikolaev, P. ; Thess, A. ; Chem. Phys. Lett. 1995, 243, 49.
30.Galiotis, C. ; Melanitis, N. ; Vlattas, C. ; Wall, A. The Manchester Conference Centre 1993, 29. UMIST,Manchester, UK.
31.Cornwell, C. F. ; Wille, L. T. Solid State Communications 1997, 101, 555.
32.Terrones, M. ; Hsu, W. K. ; Kroto, H. W. ; Walton, D. R. M. Topics in Current Chemistry 1998, 199, 1.
33.Hone, J. ; Whitney, M. ; Piskoti, C. ; Zettl, A. Phys. Rev. B 1999, 59, 2514.
34.Osman, M. A. ; Srivastava, D. Nanotechnology 2001, 12, 21.
35.Vaccarini, L. ; Goze, C. ; Aznar, R. ; Micholet, V. ; Journet, C. ; Bernier, P. Synthetic Metals 1999, 103, 2492.
36.Pang, L. S. K. ; Saxby, J. D. ; Chatfield, S. P. Journal of Physical Chemistry 1993, 97, 6941.
37. Tsang, S. C. ; Harris, P. J. ; Green, M. L. Nature 1993, 362, 520.
38.Hu, H. ; Zhao, B.; Itkis, M. E. ; Haddon, R. C. Journal of the American Chemical Society 2001, 123, 11673.
39.Harutyunyan, A. R. ; Pradhan, B. K. ; Chang, J. ; Chen, G. ; Eklund, P. C. Journal of Physical Chemistry B 2002, 106, 8671.
40.Hernadi, K. ; Siska, A. ; Thie-Nga, L. ; Forro, L. ; Kiricsi, Solid State Ionics 2001, 141, 203.
41.Li, Y. H. ; Wang, S. ; Wei, J. ; Zhang, X. ; Xu, C. ; Luan, Z. ; Wu, D. ; Wei, B. Chem. Phys.Lett. 2002, 357, 263.
42.Lkazaki, F. ; Ohshima, S. ; Uchida, K. ; Kuriki, Y. ; Hayakawa, H. ; Yumura,M. ; Takahashi, K. ; Tojima, K. Carbon 1994, 32, 1539.
43.Duesberg, G. S. ; Burghard, M. ; Muster, J. ; Philipp, G. ; Roth, S. Chem. Commum.1998, 10, 584.
44.Ko, F. H. ; Lee, C. Y. ; Ko, C. J. ; Chu, T. C. Carbon 2005, 43, 727.
45.蔡銘豐，Polybenzoxazine/多壁奈米碳管(MWNT)奈米複合材料之製備及性質之研究，萬能科技大學碩士論文.
46.王昱翔，熱穩定性Polybenzoxazine混成材料之研究，國立勤益科技大學碩士論文.
47.莊宴惠，奈米碳管表面改質與複合材料合成之電性和導熱性量測，國立成功大學碩士論文.
48. 王仕漢，多壁奈米碳管/導電型碳黑應用於複合型導電高分子之電性研究，國立交通大學碩士論文.
49.石立節，奈米碳管純化前後表面特性之變化，國立中央大學碩士論文.
50.高嘉蔆，官能化多壁奈米碳管/Polybenzoxazine奈米複合材料之製備鑑定及性研究，萬能科技大學碩士論文.
51.林江珍、林嵩祚，奈米碳管之有機分散性改質及應用，中華民國九十四年，石油季刊， 4, 47.
52.Sperling, L. H. Introduction to physical polymer science 2001.
53.B. P. Improvements Relating to the Manufacture of Highly Polymeric Substances 1942.
54.M. C. Kuo. ; J. C. Huang. ; M. Chen. ; M. H. Jen. Materials Transactions 2003,
44, 1613.
55.Yao-Chi Shu. ; Keven Hsiao. Journal of Applied Polymer Science 2007, 106,664.
56.Shaffer, M. S. P.; Windle, A. H. Adv. Mater. 1999, 11, 937.
57.Pyda, M. ; B. Wunderlich. Journal of Polymer Science, Part B: Polymer Physics 2000, 38, 622.
58.Yao-Chi, Shu. Keven Hsiao. Journal of Applied Polymer Science 2007, 106, 644.
59.H. J. Chiu. ; W. J. Shu. ; J. M. Huang. Polymer Engineering and Science 2006,46, 89.
60.Deschamps, A. A. Biomaterials 2004, 25, 247.
61.J. W. You. ; H. J. Chiu. ; W. J. Shu. ; T. M. Don. J. Polym. Res. 2003, 10, 47.
62.Avrami, M. Journal of chemical physics 1940, 9, 177.
63.Avrami, M. Journal of chemical physics 1939, 7, 1103.
64.Jeziorny, A. Polymer 1978, 19, 1142.
65.Freeman E. S. ; Carroll B. J Phys. Chem 1958, 62, 394.
66.Ozawa T. Polymer 1971, 12, 150.
67.Ozawa T. J Therm Anal 1976, 9, 369.
68.Di Lorenzo ML. ; Silvestre C. Prog Polym Sci 1999, 24, 917.
69.Liu T. ; Mo Z. ;Wang S. ; Zhang H. Polym Eng Sci 1997, 37, 568.
70.Kissinger HE. J Therm Aanal 1957, 9, 369.
71.伍碧玲，聚酯類高分子系之熔融行為、結晶型態及多晶態機制，國立成功大學，博士論文.
72.羅志明，無規共聚酯之序列排列、結晶形態、結晶熱力學、和結晶動力學之探討，逢甲大學，博士論文.
73.董佳欣，ET與EB共聚酯等溫結晶結構之研究，逢甲大學，碩士論文.
74.朱文亞，聚已內酯結晶機制之研究，國立台灣科技大學，碩士論文.
75.郭育孝，聚酯類高分子摻合物之不定型區相容性與結晶區相型態之探討，國立成功大學，碩士論文.