中文摘要
碳化矽（SiC）為具有高度共價鍵特性的陶瓷材料，具有高度的安定性、高機械強度、耐腐蝕性、質輕、熔點高的特性，無機氣體分離膜的應用著眼於高分子膜無法使用的惡劣環境，使用過程保持其透選特性不變，氣體分離膜在高溫時必須要有充份的安定性，耐高溫，耐腐蝕，不變質，所以碳化矽是相當適合氣體分離膜的合成物質。
化學氣相沉積以SiH4/C2H2/Ar反應系進行，在孔洞內沉積固體的改質法，需在透過率與選擇率間做妥協。 縮小孔徑有助於提升選擇率，但將會犧牲透過率，將兩只透過率相近的支撐材，一置於體積/表面積比值大的環境，一置於體積/表面積比值小的環境，同樣的孔徑縮小的效果，後者犧牲之透過率較小。 因此改質在體積/表面積受控制的小室中進行，改質的效果可用量測所得之氣相反應速率常數與表面反應速率常數代入數學模式中，預測多孔材孔徑的移動，從而計算平均孔徑下降與透過率之下降，其中塗覆兩層非對稱支撐材08hd11樣品的流動平均孔徑由297 nm縮小至14 nm，而透氣率亦減少93％。
陶瓷先驅高分子改質研究在自製的碳化矽多孔支撐材上進行，支撐材骨幹是以注漿成型，再以次微米的粉末覆於內側，進行二次燒結得到非對稱性的改質支撐材。 陶瓷先驅高分子的構想，基本上是承襲碳分子篩的原理，高分子的碳氫元素在裂解時，以小分子的形態脫離高分子主鍊，這些小分子破片穿過分離膜產生分子級尺寸的管道，這些小於1 nm的管道是氣體分離機制的關鍵。聚二甲基矽烷（polydimethylsilane）先驅高分子塗覆改質後經熱轉化反應（thermolytic reaction），部分轉化成聚碳矽烷（polycarbosilane），再經氧熟化反應交鏈固定，最後熱裂解成膜。裂解溫度對透過性有很大的影響，573 K裂解所得到的氣體分離膜於473 K時其H2/N2選擇率為100，而氫氣透過率為8.9×10-8 mol/Pa sec m2，在873 K裂解所產生的氣體分離膜在473 K時其H2/N2選擇率為40，氫氣透過率為4.9×10-9 mol/Pa sec m2，轉化熟化過程以TGA與DTA熱分析瞭解之，膜孔洞分佈以BET量測分析。

Abstract
Silicon carbide is a ceramic material of high covalency. It possesses attractive characteristics, such as light, high stability, high mechanical strength, corrosion resistance, and high melting point. The inorganic membrane is targeted on the applications under hostile environment, which the polymeric membrane is not accessible, for instance, high temperature. The inorganic membrane for gas separation is supposed to be sufficiently stable under high temperature and resistant to acid and base. It permeation properties should be enduring for reasonable working time. Therefore, silicon carbide is an ideal candidate for synthesis of the inorganic membrane.
The modification of chemical vapor deposition is carried out in the SiH4/C2H2/Ar reaction system. The modification, by depositing solid in fine pores, often needs to compromise between the permeation rate and selectivity. Reduction in pore size enhances the selectivity of membrane, yet the permeance is sacrificed for pore narrowing. If two porous supports of similar permeance are placed in two environments of different volume/surface V/S ratios, the one in the environment of small V/S suffers less reduction in permeance than the one modified in large V/S for the same pore narrowing effect. Therefore, a better modification is achieved in a chamber of designed V/S ratio. The modification effect of chemical vapor deposition can be predicted by the mathematical model, which calculates the shifting of pore size distribution of support from the experimental gas-phase and surface reaction constants, subsequently the reduction in pore size and the permeance. The flow-average pore radius of one modified specimen 08hd11, is reduced from 297 to 14 nm for a price of 93% reduction in permeance.
The modification of preceramic polymer is carried out on the home-made silicon carbide porous support. The asymmetric support is made by slip casting and sintering of a ceramic tube, then using submicron powder to carry out another casting and sintering to form an inner layer of finer pores. The basic idea behind the preceramic polymer modification is from the fabrication of carbon molecular sieve. Elements of hydrogen and carbon, in form of small molecules, escape from the backbone of polymer, and channel through the polymer matrix. Channeling of these molecular debris creates pores of molecular sizes. These minute pores (< 1nm) are crucial to the gas separation mechanism.
The polydimethylsilane (PMS) coating undergoes thermolytic reaction, which converts part of PMS into polycarbosilane. The subsequent oxygen curing further crosslinks the preceramics. Finally the preceramic is pyrolyzed into a membrane capable of gas separation. The pyrolysis temperatures has a significant influence on membrane permeance and permselectivity. For the membrane pyrolyzed at 573 K, H2 permeance of is 8.9×10-8mol/Pa sec m2 and permselectivity of H2/N2 is 100 at permeation temperature of 473 K. For the membrane pyrolyzed at 873 K, H2 permeance is 4.9×10-9 mol/Pa sec m2, and H2/N2 selectivity is 40 at permeation temperature of 473 K. Thermal treament of preceramics are analyzed, using TGA and DTA. The pore size distribution of the pyrolyzed preceramic is measured by BET.

封面
中文摘要
英文摘要
誌謝
目錄
圖目錄
表目錄
第一章 碳化矽性質與合成
1.1 碳化矽材料基本性質
1.2 碳化矽的合成方法
1.3 非晶或微晶碳化矽之發展、應用、與性質
第二章 陶瓷多孔膜的發展
2.1 碳分子篩膜
2.2 氧化矽氣體分離膜
2.3 沸路氣體分離膜
2.4 碳化矽氣體分離膜
2.5 多孔氣體分離膜之透過率與透選率
2.6 多孔膜中氣體輸送的機構
2.7 氣體分離之緻密鈀膜
2.8 陶瓷多孔膜之應用
理論分析
第三章 低壓化學氣相沉積改質碳化矽多孔膜理論分析
3.1 擴散機構與孔洞構造數學模式
3.2 沉積固體對孔徑分佈的影響
3.3 沉積對氣體通過多孔膜影響
實驗步驟與藥品
第四章 SiH/CH/Ar低壓化學氣相沉積改質碳化矽多孔膜與陶瓷先驅高分子改質碳化矽支撐材
4.1 化學氣相沉積改質部份
4.2 實驗藥品與氣體
4.3 實驗設備與儀器
4.4 流動平均孔徑之計算
陶瓷先驅高分子改質碳化矽支撐材
4.5 實驗步驟
4.6 實驗藥品與氣體
4.7 實驗設備與儀器
理論研究
第五章 化學氣相沉積改質之理論分析
5.1 單一孔徑多孔膜之改質深度
5.2 具有孔徑分佈的多孔膜改質
第六章 化學氣相沉積改質碳化矽技撐材
6.1 SiH/CH/Ar 低壓化學氣相沉積動力
6.2 碳化矽多孔膜的改質
第七章 陶瓷先驅高分子改質碳化矽支撐材
7.1 碳化矽中間層製備與孔洞分佈
7.2 陶瓷先驅高分子改質-聚二甲基矽烷(PMS)
7.3 熟化的先驅高分子裂解殘餘物之 BET 量測
7.4 陶瓷先驅高分子IR分析
7.5 陶瓷先驅高分子的外觀
7.6 碳化矽多孔膜經二甲基矽烷改質後氣體透過率
7.7 乙醯丙酮酸酯鋁與聚二甲矽烷之液改質
結論
參考文獻
附錄
符號索引
作者簡介及論文著作

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