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論文名稱 Title |
聚對苯二甲酸二丙酯之平衡熔點
Equilibrium melting temperature of poly (trimethylene terephthalate) |
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系所名稱 Department |
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畢業學年期 Year, semester |
語文別 Language |
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學位類別 Degree |
頁數 Number of pages |
122 |
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研究生 Author |
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指導教授 Advisor |
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召集委員 Convenor |
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口試委員 Advisory Committee |
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口試日期 Date of Exam |
2002-07-30 |
繳交日期 Date of Submission |
2002-09-06 |
關鍵字 Keywords |
平衡熔點、聚對苯二甲酸二丙酯 Equilibrium melting temperature, Poly (trimethylene terephthalate) |
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統計 Statistics |
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中文摘要 |
以微差式掃瞄熱卡儀以及溫度調幅式微差掃描熱卡儀來研究不同分子量聚對苯二甲酸二丙酯之結晶動力以及熔融行為。樣品代號分別為PTT-1,PTT-2,PTT-4,PTT-6代表。觀察PTT-4以及PTT-6在182℃∼210℃的結晶範圍其主要結晶為二∼三維方向作成長之異質成核。而隨著過冷度的降低,其Avrami指數是在2.1∼3.0之間增加,且由於發現有 以及 的存在,故得知含有次要結晶。在等溫結晶部分,樣品的等溫結晶時間為結晶完成時間之4∼6倍,以確保結晶完成。從2、10和50或80 ℃/min加熱之熔融行為觀察到多熔融吸熱峰。 較低溫之熔融峰為次要結晶熔融峰,距結晶溫度Tc約10∼13℃,次高溫為主要結晶熔融峰,兩者皆會隨著結晶溫度的升高熔融峰往高溫移動。然而由於次要結晶之結晶度較差,且至高結晶溫度不易產生熔融再結晶的現象,與主要結晶峰相疊合而消失;主要結晶則是會隨著結晶溫度上升,其熱焓值變大,此趨勢是由於結晶溫度的升高,結晶層板變厚的緣故。最高溫之熔融峰部分是由於在微差式掃瞄熱卡儀的加熱過程中次要結晶的熔融而後隨即再結晶所造成,其雖有變動但似乎與結晶溫度無關,熔融再結晶峰隨著結晶溫度越高,其熱焓值相對於主要結晶熔融峰有逐漸減小的趨勢,而原因在於較高等溫結晶,熔融再結晶的現象趨減緩。然而, 在結晶溫度215℃以上,以80 ℃/min加熱觀察到雙熔融峰的現象。並以調幅式微差卡儀得可逆熱流熱分析圖觀察到比傳統微差掃描卡計多了一熔融峰,且在不可逆熱流熱分析圖發現在加熱過程中約在215℃另有一結晶放熱峰,並隨結晶溫度的升高,此一放熱現象越不明顯,研判在約215℃為一區型II-I 的轉移溫度。 以2℃/min以及50℃/min 加熱速率得到多熔融行為,將主要結晶之熔融峰溫度對結晶溫度作圖,以Hoffman-Weeks 外插方法所得平衡熔點,對樣品代號為PTT-1,PTT-2,PTT-4和PTT-6之平衡熔點分別為 ( (H-W)2, (H-W)50),分別為(237.0℃,240.6℃),(239.8℃,245.2℃),(240.4℃,243.7℃),(240.0℃,242.2℃),得知分子量的大小依序對平衡熔點之影響並不明顯。另外以結晶度完成一半所需的時間( ) 作分析,得PTT-4以及PTT-6的區型II→III轉移分別為187.2℃,191.0℃。PTT-4以在零結晶度情況下所得主要結晶之熔融峰溫度,以Marand-Xu 非線性外插法所得平衡熔點( (M-X) )為279.9℃。利用Thomson- Gibbs 方程式外插方式至結晶層板無限大時之平衡熔點 ( (T-G) ),PTT-4為287.3℃。 |
Abstract |
Differential scanning calorimeter (DSC) and temperature modulated differential scanning calorimeter (TMDSC) were used to study the isothermal crystallization kinetics and the melting behaviors at heating rates of 2, 10, 50, and 80 |
目次 Table of Contents |
目錄 I 表目錄 III 圖目錄 IV 摘要 X Abstract XII 第一章 緒論 1 第二章 簡介 3 第三章 文獻回顧及相關理論 5 3-1 聚對苯二甲酸酯類的結晶結構 5 3-2 高分子之結晶動力學 5 3-2.1 Avrami 方程式 6 3-2.2 區型轉移(Regime transition) 分析和結晶成長速率 7 3-2.3 多峰熔融之行為 9 3-2.4 平衡熔點 10 3-3 溫度調幅式微差掃描熱卡儀(TMDSC) 13 3-4 小角X光散射理論 14 第四章 實驗 18 4-1 實驗材料 18 4-2 實驗儀器與設備 18 4-3 樣品的製備 19 4-4 試片的製備及實驗條件 19 4-4.1 熱重分析儀(TGA) 19 4-4.2由微差掃描熱卡計找尋熱處理的最佳條件 19 4-4.3溫度調幅式微差掃描熱卡儀(TMDSC) 20 4-4.4小角X光散射 (small angle X-ray scattering,SAXS) 21 4-5 實驗流程圖 22 第五章 結果與討論 23 5-1. 熱分析 23 5-1.1 聚對苯二甲酸二丙酯之熱穩定分析 23 5-1.2 除核溫度與時間的決定 23 5-1.3 等溫結晶行為 24 5-1.3.1 PTT-4 24 5-1.3.2 PTT-6 25 5-1.4 升溫速率的影響 26 5-1.5 聚對苯二甲酸二丙酯之熔融行為 26 5-1.5.1 PTT-4 26 5-1.5.2 PTT-6 29 5-1.1.3 PTT-1 30 5-1.1.4 PTT-2 32 5-1.1.5 PTT-4之非線性平衡熔點 33 5-1.6 聚對苯二甲酸二丙酯之區型轉移(Regime) 分析 34 5-1.7 不同分子量之聚對苯二甲酸二丙酯差異性的比較 35 5-2 附錄 小角X光散射 36 第六章 結論 38 第七章 參考文獻 40 表目錄 表2-1 熱可塑性工程塑膠物性及電性比較表[8] 44 表2-2 玻璃補強纖維可塑性工程塑膠物性比較表[8] 44 表3-1 PTT結晶結構之晶格比較表 45 表4-1 PTT-1∼PTT-6的基本特性介紹 45 表5-1 TGA所得PTT之熱裂解溫度 46 表5-2 PTT-4 之Avrami 指數 1 和 2、整體速率常數 1和 2、熱焓值 |
參考文獻 References |
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