| 研究生: |
尤韻雯 Yun-wen You |
|---|---|
| 論文名稱: |
四氧化三鐵線/聚苯胺、銀線/聚苯胺複合材料之合成與分析研究 Preparation and characterization of Fe3O4 nanowire–polyaniline composites and Ag nanowire-polyaniline composites |
| 指導教授: |
楊思明
Sze-ming Yang |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 化學工程與材料工程學系 Department of Chemical & Materials Engineering |
| 畢業學年度: | 97 |
| 語文別: | 中文 |
| 論文頁數: | 108 |
| 中文關鍵詞: | 聚苯胺 、四氧化三鐵線 、銀線 |
| 外文關鍵詞: | nanowire, polyaniline, Fe3O4, Ag |
| 相關次數: | 點閱:16 下載:0 |
| 分享至: |
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本研究分為兩個部份,第一部分: 四氧化三鐵線/聚苯胺複合材料的合成和分析,產物同時擁有四氧化三鐵的磁性,以及導電高分子的導電性。本研究以十二烷基苯磺酸(C12H25C6H4SO3H)為界面活性劑,過硫酸胺( (NH4)2S2O8 )為氧化劑,鹽酸為摻雜酸,於2 ℃下化學聚合,並且改變四氧化三鐵線的含量比例作為變因,分別加入0.2、2、5、10、15 wt%,和苯胺單體的莫耳比分別為:1: 1340、1: 130、1: 51、1: 24、1: 15(此比例用熱重分析儀之重量百分比結果換算而得)。製備出的四氧化三鐵線/聚苯胺複合物分別製備出的四氧化三鐵線/聚苯胺複合物分別以SEM 觀察其表面形態;以TEM 作微細結構的觀察;以EDS 作成份分析;以FTIR 鑑定導電高分子結構;以TGA 分析無機物含量;以震動樣品磁度儀(VSM)測定飽和磁化率;以四點探針測量產物的導電率。含四氧化三鐵線的產物之熱穩定性和純聚苯胺相比明顯提昇。實驗結果發現加入10 wt% 四氧化三鐵線,和苯胺單體比例為1: 24時,四氧化三鐵線/聚苯胺複合材料的核殼結構最為完整,且導電率趨於穩定。
第二部份:在銀線/聚苯胺複合物部份,銀線外為包覆質地較軟的導電高分子,可使銀線能作成塗料,但又不減損太多銀線之導電率,本研究以藉由硫醇酸(HSCH2COOH)的和銀線之作用使聚苯胺包覆於銀線上,使用五種不同的方法去製備,其中四種於水相中製備,而一種於有機相中製備,製備出的銀線/聚苯胺複合物分別以SEM觀察其表面形態;以TEM 作微細結構的觀察;以EDS 作成份分析;以FTIR 鑑定導電高分子結構;以TGA 分析無機物含量;以半導體參數分析儀測量產物的導電率。實驗結果五種方法皆可成功製備出核殼結構之銀線/聚苯胺複合材料,於有機相中的產物熱穩定性明顯較差,而導電率和產物中銀的含量比例順序相符。其中以在水相中製備,聚乙烯吡咯烷酮為界面活性劑,乙硫醇酸摻雜酸之方法最佳,因其熱穩定性最良好。
In this thesis, we study two research topics: one is the composite of Fe3O4 nanowire and polyaniline, the other is the composite of silver nanowire and polyaniline. In the first part, the Fe3O4 nanowires (diameter: 50nm, aspect ratio: 150) were previously dispersed in the polyethylene glycols (PEG) solution obtained from Industrial Technology Research Institute. Fe3O4-polyaniline was prepared by polymerization of aniline in the presence of Fe3O4 nanowires, dodecylbenzenesulfonic acid (DBSA) and ammonium persulfate (APS). We varied the relative amount of Fe3O4 nanowires to aniline monomer. The morphology of core-shell structure was observed by SEM and TEM. FTIR spectra show functional groups of polyaniline synthesized. TGA was used to measure the content of Fe3O4 nanowires. Vibrating sample magnetometer (VSM) was used to measure the magnetic properties. Four-Point Probe method was used to measure the conductivity. The prepared composites show both properties of conductivity and magnetism. The thermal stability of the polymer can be enhanced by forming the composites.
In the second part, the Ag nanowires were previously dispersed in polyvinylpyrrolidone solution obtained from Industrial Technology Research Institute. Ag nanowires -polyaniline was prepared by five different methods. Four methods were prepared in aqueous solution, and one of the methods was prepared in chloroform solution. We use thioglycolic acid to modify the surface of Ag nanowire, and then polymerization of aniline occurs near the surface of Ag nanowires. The morphology of core-shell structure was observed by SEM and TEM. FTIR spectra show functional groups of polyaniline synthesized. TGA was used to measure the content of Ag nanowires. Semiconductor parameter analyzer was used to measure the conductivity. The composites prepared by using thioglycolic acid as dopant, and ammonium persulfate (APS) as the oxidant were the best.
參考文獻
1. 陳壽安,「導電高分子:新世代光電材料」,物理雙月刊, 23-2,312-321(2001)。
2. H. Letherby, “J. chem. Soc.” , 15, 16 (1962).
3. M. Josefowicz, In: “Thesis”, University of Paris , (1963).
4. A. G. MacDiarmid, J. C. Chiang, M. Halpern, W. S. Huang, S. L. Mu, N. L. D. Somasir, “Mol. Cryst. Liq. Cryst.”, 121, 173(1985).
5. J. P. Travers, J. Chroboczek, F. Derreux, F. Genoud, M. Nechtscheim, A. M. Sayed, E. M. Genies, C. Tsintavis, “Mol. Cryst. Liq. Cryst.”, 121, 195 (1985).
6. E. M. Genies, A. M. Sayed, C. Tsintavis, “Mol. Cryst. Liq. Cryst.”,121, 181(1985)
7. T. Ohsaka, Y. Ohnuki, N. Oyama, G. Katagiri, K. Kamisako, “J. Elec- troanal. Chem. Interf. Electrochem.”, 161, 399 (1984).
8. J. C. Chang, A. G. MacDiarmid, “Synth. Met.”, 13, 193(1986).
9. W. S. Huang, B. D. Humphrey and A. G. MacDiarmid, “J. Chem. Soc. Faraday Trans.”, 82, 2385(1986).
10. A. G. Green, and A. E. Woodhead, “J. Chem. Soc. Trans.”, 97, 2388(1910).
11. C. R. Martin, “Science”, 266, (1994).
12. B. L. Brinda, K. D. Peter, R. M. Charles, “Chem. Mater.”, 9, 857–862(1997).
13. W. Liang, C. R. Martin, J. Am. “Chem. Soc.”, 112, 9666(1990).
14. M. S. Yun and D. P. Kang, “Synth. Met.”, 29, 343 (1989).
15. A. G. MacDiarmid, J. C. Chiang, M. Halpern, W. S. Huang, S. L. Mu,
N. L. D.Somasiri, W. Wu and S. I. Yaniger, “Mol. Cryst., Liq.
Cryst.”, 121-174(1985).
16. A. G. MacDiarmid, N. L. D. Somasiri, W. R. Salaneck, I. LundstrSrn,
B. Liedberg, M.A. Hasan, R. Erlandsson and P. Konrasson, “Springer
Series in Solid State Sciences”,Vol. 63, Springer, Berlin, 218 (1985).
17. Ft. Patent No. EN 8 307958 (1983); U.S. Patent No. 698 183 (1985).
18. L. T. Yu, M. S. Borredon, M. Jozefowicz, G. Belorgey and R. Buvet,
“J. Polym. Sci.”,10, 2931(1987).
19. Asturias, G. E., MacDiarmid, A.G, McCall, R.P. and Epstein, A.J.,
“Synth. Met.”, 29.E 157(1989).
20. D. Vachon, R. 0. Angus, F. L. Lu, M. Nowak, Z. X. Liu, H. Schaffer,
F. Wudl and A.J. Heeger, “Synth. Met.”, 18, 297 (1987).
21. E.M. Genie`s and C. Tsintavis, “J. Electroanal. Chem.”, 195, 109
(1985).
22. E. M. Genie`s and C. Tsintavis, “J. Electroanal. Chem.”, 200, 127
(1986).
23. E.M. Genie`s and M. Lapkowski, “J. Electroanal. Chem.”, 220, 67
(1987).
24. M. Musiani, G. Mengoli and F. Furlaneto, “J. Appl. Polym. Sci.”, 29,
4433(1984).
25. D. W. DeBerry, “J. Electrochem. Sac.”, 132, 1022 (1985).
26. G. Mengoli, M. T. Munari and C. Folonari, “J. Electroanal. Chem.”, 124, 237 (1981).
27. E. M. Genie`s and C. Tsintavis, unpublished work.
28. E. W. Paul, A. J. Ricco and M. S. Wrighton, “J. Phys. Chem.”, 89,
1441 (1981).
29. B. Pfeiffer, A. Thyssen, M. Wolff and J. W. Schultze, “Int.Workshop
- Electrochemistry of Polymer Layers, Duisburg”, F.R.G., Sept. 15 –
17(1986).
30. C. M. Carlin, L. J. Kepley and A. J. Bard, “J. Electrochem. Soc.”,
132, 353(1985).
31. N. Oyama, Y. Ohnuki, K. Chiba and T. Ohsaka, “Chem. Lett.”,
1759(1983).
32. B. Aurian-Blajeni, I. Taniguchi and J. O''M. Boekris, “J. Electroanal. Chem.“ , 149, 291 (1983).
33. A. Thyssen, A. Hochfeld, R. Kessel, A. Meyer and J. W. Schulzte, “Synth. Met.”, 29, E357(1989).
34. B. Villeret and M. Nechtschein, “Solid State Commun.”, 64,
435(1988).
35. C. Tsintavls, “Thesis”, Grenoble University, (1986)
36. MacDiarmid, A. G., Yang, L. S., Huang, W. S. and Humphrey, B. D., “Synth. Met.”, 18, 393(1987).
37. M. Millard, “Synthesis of Organic Polymer Films in Plasmas”, in J. R. Hollahan and A. T. Bell (eds.), “Techniques and Applications of PlasmaChemistry”, Wiley, New York, Ch 5(1974).
38. M. Shen, “Plasma Chemistry of Polymers”, Marcel Dekker, New
York, (1976).
39. R. Hernandez, A. F. Diaz, R. Waltman and J. Bargon, “ISE Meeting,
July 1984,Berkeley, CA, U.S.A.; J. Phys. Chem.”, 88, 3333 (1984).
40. B. Nayak and R. C. Bhakta, “J. Appl. Electrochem.”, 13, 105(1983).
41. P. A. K. Nedungati, A. Gupta and K. Zutshi, “J. Electrochem. Soc.”
Sept. 15 - 17(1986).
42. K. Uvdal, M. Loglund, P. Danneton, L. Bertilsson, S. Strafstrom, W.
R. Salaneck,A. G. MacDiarmid, A. Ray, E. M. Scherr, T. Hjertberg
and A. J. Epstein, “Synth. Met.” ,29, E451(1989).
43. Tang, J.,Jing, X., Wang, B. and Wang, F., “Synth. Met.”, 24 , 231(1988).
44. Kang, E. T., Neoh, K.G, Tan, T. C., Khor, S. H. and Tan, K. L., “Macromolecules”, 23, 2918(1990).
45. Somasiri, N. L. D. and MacDiarmid, A. G., “J. Appl. Electrochem.”, 18, 92-95(1988).
46. Koga, K., Yamasaki, S., Narimatsu, K. and Takayanagi, M., “Polym.
J.”, 9, 733-738(1989).
47. Desilvestro, J., Scheifele, W. and Haas, O., “J.Electrochem.Soc.”, 139, 2727-2736(1992).
48. Mu, S. L., Ye, J. H. and Wang, Y. H., “J. Power Sources”, 45, (1993).
49. Kaminaga, A., Tatsuma, T., Sotomura, T. and Oyama, N., “J.
Electrochem.Soc.”, 142, L47-L49(1995).
50. Genie`s, E. M. and Picart, S., “Synth. Met.”, 69, 165-166(1995).
51. Oyama, N., Tatsuma, T., Sato, T. and Sotomura, T., “Nature”, 373,
98-600(1995).
52. Racicot, R., Brown, R., Yang, S. C., “Synth. Met.” , 85, 1263(1997).
53. Kin, P. J., Silverman, D. C., Jeffreys, C. R., “Synth. Met”., 85, 1327
(1997).
54. Bernard, M. C., Goff, H. L., Joiret, S., Dinh, N. N., Toan, N. “J.
Electrochem. Soc.”, 146, 995(1999).
55. Wessling, B., Posdorfer., “J. Electrochim. Acta”, 44, 2139(1999).
56. Malik, M. A.; Galkowski, M. T.; Bala, H.; Grzybowska, B.; Kulesza, P. “J. Electrochim Acta”, 44, 2157(1999).
57. 李翌翠,張育雯,「防蝕專家-聚苯胺」,中華民國第四十一屆科展,應用科學科,91.7.23。
58. Morita, M., “J. Poly. Sci., Part B: Polymer Phys.”, 32, 231 (1994).
59. Bernard, M. C., Goff, H. L., Wen, Z., “Synth. Met.”, 85, 1347(1997).
60. Bernard, M. C., Goff, H. L., Bich, V. T., Wen, A. Z., “Synth. Met.” , 81, 5(1996).
61. Tsamouras, D., Dalas, E., Sakkopoulocos, S. and Vitoratos, E., “Appl. Surface Sci”., 65-66, 388-393(1993).
62. Mu, S. L. and Xia, C. F., “Synth. Met.”,59, 243-247(1993).
63. Yuan, R. K., Liu, Y. X., Yuan, H., Wang, Y. B., Zheng, X. Q., Xu, J. and Shen, X. C., “Synth. Met.”, 55-57, 4087-4092 (1993).
64. Dalas, E., Sakkopoulocos, S. and Vitoratos, E., Maroulis, G. and Kobotiatis, L., “J. Mater. Sci.”, 28, 5456-5460 (1993).
65. Wang, Y. Z., Gebler, D. D., Lin, L. B., Blatchford, J. W., Jessen, S. W., Wang, H. L., Epstein, A. J., “ Appl. Phys. Lett.”, 68, 894(1996).
66. Chen, S. A., Chuang, K. R., Chao, C. I., Lee, H. T., “Synth. Met.” ,
82, 207(1996).
67. Gaponik, N. P., Talapin, D. V., Dmitri, V., Rogach, A. L., “Phys. Chem. ”, 1, 787( 1999).
68. Joo, J. Epstein, A. J.; Yue, “J. Appl Phys Lett”, 65, 2278( 1994)
69. Makela, T.; Pienimaa, S.; Taka, T.; Jussila, S.; Isotalo, H., “Synth. Met.”, 85, 1335(1997).
70. Chikazumi, S. 著; 張喣、李學養合譯,磁性物理學,聯經公司
出版(1981).
71. 張文成,唐敏注,張慶瑞、劉如熹,科學月刊,32, 286-317(2001).
72. 莊萬發,超微粒子理論應用,復漢出版社出版(1994)
73. G. F. Goya, T. S. Berquo, and F. C. Fonseca. “ J. Appl. Phys.” 5, 3520(2003).
74. 周更生,李賢學,高振裕,盧育杰,「功能性粉末-奈米銀」,科
學發展第四零八期,32~39頁,2006年12月
75. A. A. Setlur, and J. M. Lauerhaas , “ Appl. Phys. Lett.” , 345-347(1996)
76. Y. C. Kong, “Appl. Phys. Lett.” , 78, 407-409(2001).
77. S.-Z. Chu, K. W., “Chem. Mater.” , 14, 266-272 (2002)
78. A. Z. Jim, “J. Cryst.” , 252 , 167-173(2003)
79. Y. Zhou, “Mater. Sci. Eng.”, A335, 260-267(2002).
80. Xiao Han, Yuan-Sheng Wang. “Phys. Scr.”, 129, 335-339(2007)
81. Jianguo Deng, Xiaobing Ding. “Polymer”, 43, 2179-2184(2002)
82. Aihua Chen, Haiqao Wang, “Synth. Met.”, 139, 411-415(2003)
83. J. Stejskal, M. Trchova,“Reactive & Functional Polymer” ,69, 86-90(2008)
84. Mohammad Rezaul Karim, Kwon Taek Lim, “Polymer Chemistry” , 45, 5741-5747(2007)