臺灣博碩士論文加值系統

摘要
本研究利用微分掃描熱卡計(DSC)和X-ray繞射分析(WAXD)描述其加入不定形的聚苯乙烯(atactic polystyrene,a-PS)及熱處理條件的改變對間規排向(syndiotactic polystyrene,s-PS)聚苯乙烯的多熔峰行為和多晶態之相關性探討。由DSC結果顯示在熔融結晶的s-PS(Mw=241,000)試樣中，至少存在四個熔融峰，分別為熔融峰一、二、三和四(結晶溫度240℃)。而由X-ray繞射分析結果，在低溫恆溫結晶或由熔融態慢速冷卻非恆溫結晶同時形成α(α”)晶態(熔融峰2和4)和β(β’)晶態(熔融峰1和3)，隨著結晶溫度愈高或是冷卻速度愈慢，則β(β’)晶態組成愈高，當結晶溫度高於260℃，分子堆積只形成β(β’)晶態。另外，由不定形的s-PS升溫結晶中，在低溫結晶(150℃)形成α’晶態(單一寬廣的熔融峰)，而在高溫結晶(225~260℃)分子堆積形成α”晶態。再者，在DSC升溫掃描中多熔峰現象分別為不同晶態(雙熔峰)及不同厚度晶板(三熔峰)的熔融行為。除此之外，摻合a-PS也會影響s-PS的結晶行為，當a-PS摻合組成愈高(s-PS/a-PS=25/75)且冷結晶溫度愈高(250~260℃)則結晶形成β’晶態。由偏光觀察，冷結晶和熔融結晶球晶形態大不相同，且同時存在球狀、棒狀和盤狀等多種形態。
對於低分子量(Mw=63,000)的s-PS而言，熔融恆溫結晶只形成β’晶態(結晶溫度230~260℃)，而冷結晶的結晶行為，在低溫結晶(150℃)或由不定形玻璃態s-PS慢速(10℃/min)升溫至245℃非恆溫結晶，分子堆積形成α’晶態，而在高溫結晶(225~260℃)形成α”晶態。由偏光觀察，熔融結晶球晶形態隨著結晶溫度不同而有所改變。至於冷結晶形態和熔融結晶球晶形態大不相同，同時存在球狀、棒狀和盤狀等多種形態。

Abstract
Unique thermal treatments were performed and differential scanning calorimeter (DSC), X-ray diffraction analysis and optical microscopy were used to characterize the multiple melting behavior and dominating crystal form(s) being developed in cold-crystallized syndiotactic polystyrene (s-PS, Mw=241,000) and its miscible blends with atactic polystyrene (a-PS) in comparison with melt-crystallized polystyrene. The DSC results revealed that there are four melting sharp peaks (Peak-1, -2, -3 and —4) for the melt-crystallized s-PS samples. The X-ray result suggested that melt-crystallization at lower than 260℃ produced a combination ofα—type (Peak-2 and Peak—4) and β—type crystals, or majority of β—type if at temperatures higher than 260℃.
In addition, the s-PS samples cold-crystallized produced only α-type (α’-type produced for s-PS annealing at 150℃ andα”-type produced for s-PS annealing at 225~260℃ ) crystal forms. DSC traces show only one peak (broad-base) for the s-PS cold-crystallized at 150℃ (or slow-heated from liquid-nitrogen quenched glass to 245℃) and multiple melting peaks if at temperatures at than 175℃. The multiple melting peaks for cold-crystallized s-PS samples are attributed to different lamellar thickness and crystal forms. For low a-PS content of the blend (s-PS/a-PS=75/25), there are onlyα-type (α’-type andα”-type) crystal forms in cold-crystallized sPS-base blends, but a combination ofα—type and β—type crystal forms are produced for high a-PS content (s-PS/a-PS=50/50,25/75).
For low molecular weight s-PS (Mw=63,000) samples, there is only β(β’)-type crystal in melt-crystallization and α-type crystal in cold-crystallization. By using optical microscopy, sheaf-like spherulites for s-PS samples melt-crystallized at higher temperatures (250~260℃) were observed and fully spherulites were observed if at low temperatures (230~240℃). In comparison with melt-crystallized s-PS, there are only tiny spherulites in cold-crystallized s-PS samples.

總目錄
頁數
中文摘要 I
英文摘要 II
總目錄 III
表目錄 IV
圖目錄 V
第一章、簡介 1
第二章、原理 4
2-1. Keith-Padden theory of Spherulitic Crystallization 4
2-2. Hoffman’s Nucleation Theory 7
第三章、實驗 9
3-1. 試樣名稱 9
3-2. 高分子摻合體製備 9
3-3. 儀器及樣品製備 9
第四章、結果與討論 11
4-1. 半結晶性間規排向聚苯乙烯多晶態與多熔融峰相關性 11
4-2. 間規排向聚苯乙烯之冷結晶系統探討 29
4-3. s-PS/a-PS 摻合體對冷結晶之影響 46
4-4. 低分子量(MW=63,000)s-PS對熔融結晶和冷結晶的影響 58
第五章、結論 86
參考文獻 89
附錄 92

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