臺灣博碩士論文加值系統

本研究利用PEO-b-PCL、PEO、PCL與PVPh來製作單分子膜。將溫度及濃度設為變數，觀察單分子膜在氣/液界面，表面壓力(π)隨著每分子佔據面積(A)的變化(π-A等溫線)以及鬆弛曲線的行為。將PVPh分別加入PEO-b-PCL、PEO及PCL形成混合單分子膜，再與純成份系統比較，藉由熱力學分析了解組成與溫度兩者對單分子膜穩定性的影響，進一步利用Vollhardt動力學方程式作模擬，來探討單分子膜的成核及成長機制。
等溫線及過剩面積分析中，PEO-b-PCL在低溫及常溫下，特性較類似PEO，高溫下則偏向PCL主導，而過剩面積的正負偏差值可知混合系統偏離理想狀態，為可混合性系統。由鬆弛曲線實驗得知，溫度的增加會造成單分子膜穩定性的下降。利用Vollhardt模擬方程式模擬出kx與x值，可得知xkx乘積值與單分子膜穩定性密切相關。由於部份混合系統中，單分子膜穩定性在時間接近零時或是面積鬆弛過程中急遽下降以及面積突然的提升，導致模擬情形不符合物理意義而無法進行討論，但大部份可使用Vollhardt 動力學方程式描述PEO-b-PCL、PEO、PCL與PVPh混合系統的成核及成長機制。

This study investigated the mixed monolayers containing polyethylene oxide-block-polycaprolactone(PEO-b-PCL)、polyethylene oxide(PEO)、polycaprolactone(PCL) and polyvinylphenol(PVPh). Use temperature and concentration as the variables to observe the behavior of the monolayers by measuring surface pressure-area per molecule(π-A) isotherm and relaxation curve. Add PVPh into PEO-b-PCL、PEO and PCL respectively,to form the mixed monolayers and compared with pure component monolayers. The relationship of temperature、composition and stability of these monolayers were analyzed by thermodynamics. Furthermore, nucleation and growth model for relaxation of monolayers were simulated the via Vollhardt kinetics equation.
The analysis of π-A isotherm and excess area showed that the character of PEO-b-PCL was similar to PEO at low temperature and normal temperature, but like PCL at higher temperature. Furthermore, we can know the system deviates from the deal condition. By relaxation curve, the increase of temperature will decreases the stability of the monolayers. We obtain the constant x and kx from the Vollhardt kinetics equation and the product of x and kx are closely related to the stability of the monolayers.

目錄
摘要 I
Abstract II
目錄 III
表目錄 VI
圖目錄 VIII
附錄圖目錄 XV
第一章 緒論 1
1.1 前言1
1.2 研究目的與動機 4
第二章 文獻資料 6
2.1 Langmuir單分子膜 6
2.2 Langmuir 單分子膜的等溫線行為 9
2.3 單分子膜相變化 12
2.4 單分子膜的鬆弛行為 14
2.5 熱力學理論分析 15
2.6 鬆弛曲線模擬的探討 16
第三章 實驗 18
3.1 實驗藥品及配製 18
3.2 實驗器材 22
3.3 實驗步驟 24
3.3.1 π-A等溫線測量 24
3.3.2 鬆弛曲線測量 25
第四章 結果與討論 26
Part 1. PEO、PCL、PEO-b-PCL、PVPh純成份系統 26
4.1 單分子膜π-A等溫線 26
4.2 單分子膜之鬆弛行為 35
4.3 鬆弛曲線之模擬 39
Part 2. PEO、PCL、PEO-b-PCL與PVPh混合單分子膜之系統 42
4.4 單分子膜π-A等溫線 42
4.4.1 PEO與PVPh混合系統 42
4.4.2 PCL與PVPh混合系統 45
4.4.3 PEO-b-PCL與PVPh混合系統 48
4.5 混合單分子膜過剩面積之探討 51
4.6 混合單分子膜之鬆弛行為 .62
4.7 鬆弛行為之模擬 70
4.8 lnkx對1/T及濃度 74
4.9 lnx對1/T及濃度 78
4-10 模擬常數kx及x對A∞/A0效應 81
第五章 結論 87
參考文獻 89
附錄 93

參考文獻

1.陳唯欣，“鈀-咪銼錯合物Langmuir-Blodgett 薄膜之製備與鑑定”，國立東華大學化學系碩士論文，2004.
2.黃文峰，“ZnTPP之Langmuir-Blodgett薄膜製備及其光電效應之研究”，國立台灣科技大學化學工程系碩士 論文，2006.
3.Blodgett,K.B., “Monomolecular Films of Fatty Acids on Glass”, J. Am. Chem. Soc.,56(2),495,1934.
4.李威達，“利用原子力顯微鏡分析DPPC/Albumin Langmuir-Blodgett與Langmuir-Schaefer膜的研究”，國立成功大學化學工程學系碩士論文，2004.
5.陳琛、袁立麗，LB膜的應用综述，“Journal of Hefei Teachers College”，230061，2009.
6.Chuan Qin, Alfredo T. N. Pires, Laurence A. Belfiore, “Spectroscopic investigations of specific interactions in amorphous polymer-polymer blends: poly(vinylphenol) and poly(vinyl methyl ketone)”, Macromolecules,24,666,1991.
7.Neumann, A.W., and Good, P. J., Surface and Colloid Science Vol.II, Plenum, New York, 1979.
8.Jones, M. N. and Chapman, D., “Micelles, Monolayers and Biomembranes”, Wiley-Liss, Inc.：New York, 1995； Chapter 2.
9.Roberts, G., Ed.； Langmuir-Blodgett Films； Plenum Press：NewYork, 1990.
10.Ter Minassian-Saraga, L., “Adsorption and Desorption at Liquid Surface. III. Desorption of Unimolecular Layers ”, J. Chem. Phys., 52, 181, 1995.
11.Gaines, G. L., Jr., “Insoluble Monolayers at Liquid –Gas Interface”, Wiley Press：New York, 1966, Chapter 6.
12.Girard-Egrot, A. P., Morelis, R. M. and Coulet, P. R., “ Dependence of Langmuir-Blodgett Films Deposition”, Langmuir, 9, 3107, 1993.
13.Smith, T., “Monolayers on Water. III. Kinetics and Mechanism of the Reaction of Erucic Acid with Copper Ions ”, J. Chem. Phys., 95, 3723, 1991.
14.陳凱斌，“氣液界面上雙成分混合單分子層性質之研究”，成功大學化學工程系碩士論文，1996.
15.陳凱斌，“在氣液界面上DDPPC/長碳鏈醇類混合單分子層的行為”，成功大學化學工程系博士論文，2002.
16.Vollhardt, D. and Retter, U., “Nucleation in Insoluble Monolayers.1：Nucleation and Growth Model for Relaxation of Metastable Monolayers”, J. Phys. Chem., 95, 3723, 1991.
17.Vollhardt, D., Retter, U. and Siegel, S., “Nucleation in Insoluble Monolayers. 2：Constant Pressure Relaxation of Octadecanoic Acid Monolayers”, Thin Solid Films, 199, 189, 1991.
18.Vollhardt, D., Retter, U. and Siegel, S., “Nucleation in Insoluble Monolayers. 3：Overlapping Effects of The Growing Centers”, Langmuir, 8, 309, 1992.
19.Thomas J., Kristina M., Claire Mathieu, Michael A. R., Ulrich S., and Randolph S., “Langmuir and Langmuir-Blodgett Films of Poly(ethylene oxide)-b-Poly(ε-caprolactone) Star-Shaped Block Copolymers”, Langmuir, 22, 9264, 2006.
20.Bingbing Li, Yitian Wu, Minghua Liu, and Alan R. Esker, “Brewster Angle Microscopy Study of Poly(ɛ-caprolactone) Crystal Growth in Langmuir Films at the Air/Water Interface”, Langmuir, 22, 4903, 2006.
21.Bingbing Li and Alan R. Esker, “ Blends of Poly(ε-caprolactone) and Intermediate Molar Mass Polystyrene as Langmuir Films at the Air/Water Interface”, Langmuir, 23, 574, 2007.
22.Nisa V. Salim, Tracey Hanley, and Qipeng Guo, “Microphase Separation through Competitive Hydrogen Bonding in Double Crystalline Diblock Copolymer/Homopolymer Blends”, Macromolecules, 43, 7695, 2010.
23.Wen-Ping Hsu, “A closed-loop behavior of ternary polymer blends composed of three miscible binaries”, Thermochimica Acta, 454, 50, 2007.
24.Kai-Teng Jheng, Wen-Ping Hsu, “Characteristics and Iso-Baric Relaxation Phenomenon of PMMA Monolayers with Different Molecular Weights at Different Temperatures”, Journal of Applied Polymer Science, 120, 2615, 2011.
25.Yuh-Lang Lee, Wen-Ping Hsu, “Relaxation phenomena of stereoregular poly(methyl methacrylate) monolayers at the air/water interface”, Journal of Applied Polymer Science, 37, 2008.
26.上海聯勝化工股份有限公司http：//www.liansheng-chemical.com/
27.沂慶貿易股份有限公司http：//www.achemc.com.tw/
28.黃春輝，李富友，黃岩誼，“光電功能超薄膜”， 曉園出版社，2006；第一章 超薄膜的製備