臺灣博碩士論文加值系統

本論文研究以鈉金屬、二氯二甲基矽烷（DCDMS）和二氯二茂鈦（TiCp2Cl2）為反應物，以單一反應器、單一合成步驟的新型方法來製備碳化矽（SiC）纖維的前驅體聚合物—聚甲基碳矽烷（PMCS）。此係在〜100 ℃，0.1 MPa氮氣氣氛下進行反應，合成之初得產物經純化程序後，以傅立葉轉換紅外線光譜儀、紫外線/可見光分光光譜儀、29Si 核磁共振光譜儀、凝膠滲透層析儀和同步熱分析儀等儀器進行精製產物的特性分析。結果顯示，此法可以成功製備分子量分佈窄的直鏈PMCS。精製產物經靜電紡絲及熟化後，在氮氣氣氛下以1100 ℃煅燒2小時，所得之生成物經X光繞射分析、電子顯微鏡觀察和能量分散光譜確認為具SiC-TiC立方晶相複合陶瓷纖維。另外，本研究亦探討反應物TiCp2Cl2與DCDMS莫耳比對轉化率和產物特性（熱穩定性、重量平均分子量及聚合分散度）的影響。根據實驗結果，我們也提出了可能的非均勻相反應機構。

In this work, polymethylcarbosyilane (PMCS), which is referred as a novel polymeric precursor for manufacturing silicon carbide (SiC) fiber, was synthesized via an one-pot approach by using sodium, dimethyldicholoromsilane (DMDCS) and titanocene dichloride (TiCp2Cl2) as reactants. The reaction was conducted at ~100 ℃ under nitrogen atmosphere of 0.1 MPa. After synthesis and purification procedures, characterization of the as-prepared product was performed with FT-IR spectroscopy, 29Si NMR spectroscopy, GPC, and TG-DSC analysis. The results showed that Ti-containing PMCS with narrow molecular distribution could be successfully prepared via this approach. The fibers, derived from the electrospinning of the as-synthesized product, calcined at 1100 ℃ under N2, was identified to be a composite of SiC and TiC by XRD. The effects of the TiCp2Cl2-to -DMDCS molar ratio on the reaction conversion and the product 's characteristics such as thermal stability, molecular weight, and polydispersity were investigated. Based on the experimental results, a possible heterogeneous reaction mechanism was also proposed.

目錄

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 v
表目錄 viii
圖目錄 ix
1. 緒論 1
1.1 概述 1
1.2 研究動機 4
1.3 研究目的 4
1.4 研究流程 4
2. 文獻回顧 7
2.1 碳化矽纖維的應用 7
2.1.1 碳化矽的由來 7
2.1.2 碳化矽的合成方法 7
2.1.3 碳化矽纖維的發展 9
2.1.4 碳化矽纖維的合成方法 12
2.2 靜電紡絲介紹 13
2.2.1 靜電紡絲的由來 13
2.2.2 靜電紡絲的原理 14
2.2.3 影響靜電紡絲的參數 15
2.3 聚碳矽烷的製程發展 15
2.3.1 聚碳矽烷的製程研究 15
2.3.2 聚碳矽烷現行製程方法 17
2.3.3 聚碳矽烷製程的未來目標 21
3. 實驗 22
3.1 實驗藥品 22
3.2 實驗機儀器設備 22
3.3 儀器分析原理與測試方法 23
3.3.1 旋轉蒸發儀（Rotary Evaporator） 23
3.3.2 熱分析儀（Thermal Analyzer） 24
3.3.3 傅立葉轉換式紅外線光譜儀（FT-IR） 24
3.3.4 X光繞射分析儀（XRD） 25
3.3.5 掃描式電子顯微鏡（SEM） 26
3.3.6 靜電紡絲機（Electrospinning Machine） 27
3.4實驗程序 28
3.4.1 實驗流程 28
3.4.2 實驗條件規劃 34
4. 結果與討論 36
4.1 PMCS產物分析 36
4.1.1 PMCS產物之轉化率 36
4.1.2 PMCS產物之FT-IR分析 37
4.1.3 PMCS產物之UV-Vis光譜分析 38
4.1.4 PMCS產物之NMR分析 39
4.1.5 PMCS產物之GPC分析 40
4.1.6 PMCS產物之轉化率和熱安定性分析 41
4.1.7 PMCS莫耳比與聚合分散度之影響 43
4.1.8 PMCS產物之TGA分析 44
4.1.9 PMCS產物濃度對黏度之影響 45
4.1.10 PMCS產物接觸角量測 46
4.2 PMCS纖維分析 48
4.2.1 PMCS纖維表面形貌分析 48
4.2.2 PMCS纖維SEM分析 49
4.3 碳化矽纖維分析 53
4.3.1 碳化矽纖維之XRD分析 53
4.3.2 碳化矽纖維之SEM表面形貌 54
4.4 產物分析結果討論 55
5. 結論 58
參考文獻 59
發表著作 66
自傳 67

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