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研究生: 陳宜姿
Chen, I-Tzu
論文名稱: 聚乳酸與聚氧化乙烯兩結晶型高分子混摻系統之相容性與結晶型態
Miscibility and Spherulite Morphology in Poly(L-lactic acid)/Poly(ethylene oxide) Blends
指導教授: 吳逸謨
Woo, Eamor M.
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 67
中文關鍵詞: 裂縫混摻相容性環狀帶球晶
外文關鍵詞: blends, cracks., miscibility, ring-banded spherulites
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  • 本研究使用微分掃描熱卡計(DSC)、偏光顯微鏡(POM)、掃描式電子顯微鏡(SEM)、原子力顯微鏡(AFM)以及廣角X光繞射儀(WAXD)來探討兩成份摻合系統poly(ethylene oxide)/low-molecular weight poly(L-lactic acid) (PEO/LMw-PLLA)的相容性以及球晶型態。此兩成份混摻系統,於熔融態呈現均勻相型態,此外,LMw-PLLA的平衡熔點隨PEO加入而下降且作用力參數(12)為-0.65,證明此摻合系統為一相容系統。
    相較於neat LMw-PLLA,當混系統中的PEO含量低於50 wt%時,且結晶溫度為105 oC~135 oC時,LMw-PLLA成長速率增加;然而,當混系統中的PEO含量大於80 wt%時,LMw-PLLA的球晶成長速率則降低。Neat LMw-PLLA於Tc=125~130 oC時會產生具有環狀消光環的球晶(ring-band spherulites),然而與PEO混摻後,形成環狀帶球晶的溫度範圍為Tc=110~130 oC。由AFM的結果,LMw-PLLA的環狀消光環球晶中的ridge 及valley處,主要分別由edge-on及flat-on的晶板構成。此外,neat LMw-PLLA及PEO/LMw-PLLA系統結晶後,於降溫過程中會產生裂縫(cracks),而其形貌主要受球晶型態、結晶溫度以及PEO的含量影響。

    Miscibility and spherulitic morphology of poly(ethylene oxide)/low-molecular-weight poly(L-lactic acid) (PEO/LMw-PLLA) blends were studied using differential scanning calorimeter (DSC), polarized-light microscopy (POM), scanning electron microscopy (SEM), atomic force microscopy (AFM), and wide-angle X-ray diffractometer (WAXD). The PEO/LMw-PLLA blend is a miscible blend with a interaction parameter (12) = -0.65.
    Compared with the growth rate of neat LMw-PLLA at crystallization temperature 105 oC~135 oC, that of LMw-PLLA in blend system increases with increasing PEO content up to 50 wt% and decreases when PEO content is higher than 80 wt%. Neat LMw-PLLA shows ring-banded spherulites at Tc=125~130 oC, but in the miscible PEO/LMw-PLLA blend, LMw-PLLA shows ring-banded ones at Tc’s (110 ~ 130 oC). In addition, the ring-banded patterns in the blend samples at the same Tc become regular. The AFM characterizations on the ring-banded spherulite of blend show that the ridge and valley regions of ring bands consist of edge-on and flat-on lamellae, respectively. After cooling from Tc to ambient temperature, the cracks are formed in the spherulite, and the crack patterns are influenced by spherulite morphology, crystallization temperature, and PEO content.

    中文摘要 I 英文摘要 II 誌謝 III 總目錄 表目錄 V 圖目錄 VI 第一章 簡介 1 第二章 原理 6 2.1 合系統混合熱力學 6 2.2 玻璃相轉移行為 9 2.3 平衡熔點下降 9 2.4 Keith-Padden Theory of Spherulitic Crystallization 11 2.5 球晶成長理論 14 2.6 聚合物的製備 16 第三章 實驗 17 3.1 實驗所用之高分子及試藥 17 3.2 實驗試樣之製備 17 3.3 實驗所用之儀器 18 第四章 結果與討論 21 4-1 合系統之相容性探討 21 4-2分子間作用力分析(平衡熔點分析) 26 4-3 合系統之球晶成長速率分析 34 4-4 球晶型態觀察 37 第五章 結論 60 參考文獻 62

    1.Paul, D. R.; Newman, S.; EDs. Polymer Blends; Academic Press: New York, 1978; Vols. 1, 2.
    2.Bank, M.; Leffingwell, J.; Thies, C. Macromolecules, 1971, 6, 43.
    3.Nishimoto, M.; Keskkula, H.; Paul, D. R. Polymer, 1991, 32, 272.
    4.Walsh, D. J.; Higgins, J. S.; Maconndchie, A.; “Polymer Blends and Mixtures”, Mijhoff Publishers, Boston, 1985.
    5.Landry, C. J. T.; Yang, H.; Machell, J. S. Polymer, 1991, 32, 44.
    6.Coleman, M. M.; Moskala, E. J. Polymer, 1983, 24, 251.
    7.Varnell, D. F. Moskala, E. J.; Painter, P. C.; Coleman, M. M. Polym. Eng. Sci. Phys. Ed., 1983, 23, 658.
    8.Eisenberg, A.; Hara, M. Polym. Eng. Sci., 1984, 24, 1306.
    9.Aubin, M.; Bedard, Y.; Morrissette, M. F.; Prud’homme, R. E. J. Polym. Sci. Phys. Ed., 1983, 21, 233.
    10.Rodriguez-Parada, J. M.; Percec, V. Macromolecules, 1986, 19, 55.
    11.Lu, J. M.; Qiu, Z. B.; Yang, W. T. Polymer, 2007, 48, 4196.
    12.Tokiwa Y.; Suzuki T.; J. Appl. Polym. Sci., 1981, 26, 441.
    13.Qiu, Z.; Ikehara,T.; Nishi, T. Macromolecules, 2002, 35, 8251.
    14.Urayama, H.; Kanamori, T.; Kimura, Y. Macromol. Mater. Eng., 2001, 286, 705
    15.Jorda, R.; Wilkes, G. L. Polym. Bull., 1988, 20, 479.
    16.Tsuji, H.; Ikada, Y. Macromolecules, 1992, 25, 5719.
    17.Tsuji, H.; Ikada, Y. J. Appl. Polym. Sci., 1995, 58, 1793.
    18.Tsuji, H.; Ikada, Y. Polymer, 1996, 37, 595.
    19.Tsuji, H.; Ikada, Y. J. Appl. Polym. Sci., 1997, 63, 855.
    20.Tsuji, H.; Ikada, Y. Polymer, 1999, 40, 6699.
    21.Yamane, H.; Sasai, K. Polymer, 2003, 44, 2569.
    22.Tsuji, H.; Fukui, I. Polymer, 2003, 44, 2891.
    23.Urayama, H.; Kanamori, T.; Fukushima, K.; Kimura, Y. Polymer, 2003, 44, 5635.
    24.Blmm, E.; Owen, A. J. Polymer, 1995, 36, 4077.
    25.Focarete, M. L.; Scandola, M.; Dobrzynski, P.; Kowalczuk, M. Macromolecules, 2002, 35, 8472.
    26.Nijenhuis, A. J.; Colstee, E.; Grijpma, D. W.; Pennings, A. J. Polymer, 1996, 37, 5849.
    27.Desai, N. P.; Hubbell, J. A. Biomaterials, 1991, 12, 144.
    28.Desai, N. P.; Hubbell, J. A. Macromolecules, 1992, 25, 226.
    29.Susan Budavari “The Merck index: an encyclopedia of chemicals, drugs, and biologicals”, 11th Ed, Merck & Co, Inc., Rahway, N.J., 1989.
    30.Nakafuku, C.; Sakoda, M. Polym. J., 1993, 25, 909.
    31.Rozema, F. R.; de Bruijn, W. C.; Bos, R. R. M.; Boering, G.; Nijenhuis, A. J.; Pennings, A. J. Adv. Biomaterials, 1992, 10, 349.
    32.Bergsma, J. E.; Rozema, F. R.; Bos, R. R. M.; de Bruijn, W. C.; Boering, G.; Pennings, A. J. Biomaterials, 1995, 16, 267.
    33.B. Morra; R. S. Stein J. Polym. Sci. B, 1982, 20, 2261.
    34.Nojima S.; Watanabe K.; Zheng Z.; Ashida T. Polym. J., 1988, 20, 823.
    35.Keith, H. D.; Padden, F. J., Jr.; Russell, T. P. Macromolecules, 1989, 22, 666.
    36.Wang, Z.; Jiang, B. Z. Macromolecules, 1997, 30, 6223.
    37.Wang, Z.; Wang, X.; Yu D.; Jiang. B. Z., Polymer, 1997, 38, 5897.
    38.Wang, Z.; Wang, X.; An L.; Jiang, W.; Jiang, B.; Wang, X. J Polym. Sci. Part B: Polym. Phys., 1999, 37, 2682.
    39.Li, W.; Yan, R.; Jiang, X.; Jiang, B. Macromol. Sci. Phys., 1992, B31, 227.
    40.Wang, Z.; An, L.; Jiang, B.; Wang, X. Macromol. Rapid Commun., 1998, 19, 131.
    41.Tanaka, H.; Hayashi, T.; Nishi, T.; J. Appl. Phys., 1986, 59, 3627.
    42.Keith, H. D.; Padden, F. J., Jr. Polymer, 1984, 25, 28.
    43.Keller, A. J. Polym. Sci. 1955, 17, 291.
    44.Keller, A. .J Polym. Sci. 1959, 39, 151.
    45.Keith, H. D.; Padden, F. J., Jr. Macromolecules 1996, 29, 7776
    46.Keith, H. D. Polymer 2001, 42, 9987.
    47.Vasanthakumari, R.; Penning, A. J. Polymer 1983, 24, 175.
    48.Sarasua, J. R.; Prud’homme, R. E.; Wisniewski, M.; Le Borgne, A.; Spassky, N. Macromolecules 1998, 31, 3895.
    49.Gazzano, M.; Forcarete, M. L.; Riekel, C.; Scandola, M. Biomacromolecules 2004, 5, 553.
    50.Xu, J.; Guo, B. H.; Zhou, J. J.; Li, L.; Wu, J.; Kowalczuk, M. Polymer 2005, 46, 9176.
    51.Yasuniwa, M.; Tsubakihara, S.; Iura, K.; Ono, Y.; Dan, Y.; Takahashi, K. Polymer 2006, 47, 7554.
    52.Wang, Y.; Funari, S. S.; Mano, J. F. Macromol. Chem. Phys. 2006, 207, 1262.
    53.Barham, P. J.; Keller, A. J. Polym. Sci., Polym. Phys. Ed., 1986, 24, 69.
    54.Martinez-Salazar, J.; Sanchez-Cuesta, M.; Barham, P. J.; Keller, A. J. Mater. Sci. Lett., 1989, 8, 490.
    55.Hobbs, J. K.; McMaster, T. J.; Miles, M. J.; Barham, P. J. Polymer, 1996, 37, 3241.
    56.Xu, J.; Guo, B. H.; Chen, G. Q.; Zhang, Z. M. J. Polym. Sci., Part B: Polym. Phys., 2003, 41, 2128.
    57.Kuboyama, K.; Ougizawa, T. Polym. J., 2008, 40, 1005.
    58.Fraschini, C.; Plesu, R.; Sarasua, J. R.; Prud’homme, R. E. J. Polym. Sci., Part B: Polym. Phys., 2005, 43, 3308.
    59.He, Y.; Fan, Z.; Wei, J.; Li, S. Polym. Eng. Sci., 2006, 46, 1583.
    60.Rameau, A.; Gallot, Y.; Farnoux, P. M. B. Polymer, 1989, 30, 386.
    61.Stoelting, J.; Karasz, F. E.; MacKnight, W. J. Polym. Eng. Sci., 1970, 10, 133.
    62.Flory, P. J. J. Am. Chem. Soc., 1965, 86, 1833.
    63.Flory, P. J. Discuss Faraday Soc., 1970, 49, 7.
    64.Jo, W. H.; Lee, S. C. Macromolecules, 1990, 23, 2261.
    65.Sperling, L. H. “ Introduction to Physical Polymer Science 2nd ed.”, John Wiley & Sons, Inc., New York, 1992.
    66.Hudson, S. D.; Davies, D. D.; Lovinger, A. J. Macromolecules, 1992, 25, 1759.
    67.Di Lorenzo, M. L. Prog. Polym. Sci., 2003, 28, 663.
    68.Nakafuku, C. Polym. J., 1996, 28, 568.
    69.Minakov, A. A.; Mordvintsev, D. A.; Schick, C. Polymer, 2004, 45, 3755.
    70.Papageorgiou, G. Z.; Bikiaris, D. N. Polymer, 2005, 46, 12081.
    71.Pan P.; Kai W.; Zhu B.; Dong, T.; Inoue, Y. Macromolecules, 2007, 40, 6898.
    72.Alfonso, G. C.; Russel, T. P. Macromolecules, 1986, 19, 1143.
    73.Martuscelli, E.; Silvestre, C.; Gismondi, C. Makromol. Chem., 1985, 186, 2161.
    74.Keith, H. D.; Padden, F. J., Jr. J. Appl. Phys., 1964, 35, 1270.
    75.Keith, H. D.; Padden, F. J., Jr. J. Appl. Phys., 1964, 35, 1286.
    76.Keith, H. D.; Padden, F. J., Jr. J. Appl. Phys., 1963, 34, 2409.
    77.Kawai, T.; Rahman, N.; Matsuba, G.; Nishida, K.; Kanaya, T.; Nakano, M.; Okamoto, H., Kawada, J.; Usuki, A.; Honma, N.; Nakajima, K.; Mastsuda, M. Macromolecules, 2007, 40, 9463.
    78.Zhang, J.; Tashiro, K.; Tsuji, H.; Domb, A. J. Macromolecules, 2008, 41, 1352.

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