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博碩士論文 etd-0721107-174437 詳細資訊
Title page for etd-0721107-174437
論文名稱
Title
對排聚苯乙烯晶相穩定之探討
Phase stability in bulk crystallized syndiotactic polystyrene
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
66
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2007-06-26
繳交日期
Date of Submission
2007-07-21
關鍵字
Keywords
多晶態、結晶、對排聚苯乙烯、相穩定、平衡熔點
Equilibrium melting temperature, Syndiotactic polystyrene, Crystallization, Phase stability, Polymorphism
統計
Statistics
本論文已被瀏覽 5729 次,被下載 951
The thesis/dissertation has been browsed 5729 times, has been downloaded 951 times.
中文摘要
本研究以同步的微差掃描卡計、寬角X光散射、與小角X光散射之技術詳細分析對排聚苯乙烯之結晶行為,以Kratky-Porod近似法分析小角X光散射數據,求得接近完全熔解時之晶板厚度與溫度之關係。此一方法應用於低溫範圍時,與傳統之一維相關函數法所求得的晶板厚度相同,顯示其具有相當可靠度而又能應用於一維相關函數法無法適用之晶板於高溫瀕臨完全熔解時之特殊要求。基於實驗所得晶態與熔融態接近平衡時之晶板厚度與溫度之關係,我們以Gibbs-Thomson分析求得a相與b相的平衡熔點及折鏈表面自由能,並進一步推論屬於三角晶系之a相實為高溫穩定晶相,其平衡熔點約為355度,但具較高之折鏈表面自由能,因而不易於高溫孕核。屬於正交晶系之b相則為低溫穩定晶相,其平衡熔點約為314度,但其折鏈表面自由能較低,有利於高溫孕核。此結果不但符合高溫相通常具有高對稱性之晶體結構及較低之密度的基本原則,同時也解釋了先前文獻中有關此二晶相之結晶與熔解程序之各項觀察。
Abstract
Simultaneous differential scanning calorimetry (DSC), small-angle (SAXS) and wide-angle X-ray scattering (WAXS) measurements were adopted for more precise determination of the equilibrium melting temperatures (Tm*) of a and b phases in bulk-crystallized syndiotactic polystyrene. On the basis of Kratky-Porod approximation, a new method for determining crystalline lamellar thickness from SAXS profiles obtained at high temperatures where there are only limited number of discrete crystalline lamellae dispersed in the melt matrix was developed. This method is shown to be reliable as it gave comparable results obtained from the conventional 1D correlation function method for SAXS profiles obtained at lower temperatures where lamellae are closely stacked. Results of the subsequent Gibbs-Thomson analysis indicated that the trigonal a phase is the entropically favored high temperature phase with Tm* = 355 oC whereas the b phase is enthalpically favored at lower temperatures, with Tm* = 314 oC. Compared to previous held contention in the temperature-dependent phase stability of these two phases, the current phase stability assignment is more consistent with both the density and the symmetry of the corresponding crystal structures. It also explains various observations reported previously on the competition between the two polymorphs during crystallization and during melting.
目次 Table of Contents
摘要.........................................................................................II
Abstract.................................................................................III
Acknowledgement..............................................................IV
Table of Contents................................................................V
List of Tables......................................................................VI
List of Figures....................................................................VII
1. Background......................................................................1
1.1. Introduction...................................................................1
1.1.1. Polymorphism...........................................................1
1.1.2. Phase stability...........................................................4
1.1.3. Equilibrium melting temperature...........................7
1.1.3.1. Gibbs-Thomson approach..................................8
1.1.3.2. Linear Hoffman-Weeks extrapolation................9
1.1.3.3. Nonlinear Hoffman-Weeks extrapolation.......10
1.2. Unresolved Issues ....................................................12
1.3. Objectives and Approaches.....................................14
1.3.1. 1-D correlation function.........................................14
1.3.2. Kratky-Porod approximation.................................16
2. Experimental Details ....................................................18
2.1. Materials......................................................................18
2.2. Instruments.................................................................18
2.3. Sample Preparation..................................................20
3. Simultaneous SAXS/WAXS/DSC Study of sPS........22
3.1. Equilibrium melting temperatures of a phase.....22
3.2. Equilibrium melting temperatures of b phase.....41
3.3. Comparison of Tm* and se of a and bphases....48
4. Conclusion.....................................................................51
5. Possible Extensions and Follow-up Studies..........52
6. References....................................................................53
List of Refereed Publications.........................................56
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