本研究係以聚醯胺酸(polyamic acid, PAA)為前驅物，以旋轉塗佈成膜於多孔性氧化鋁基材上，並經環化形成聚醯亞胺(polyimide, PI)後，再以熱裂化法製備碳分子篩/氧化鋁複合膜(CMS/Al2O3)，以供氣體透過之用。文中針對所合成之PI膜進行特性分析，並探討不同裂化溫度對所得碳分子篩膜特性與其氣體透過之影響。
　　
　　關於PAA之製備，係以純化後之BTDA與ODA在低溫氮氣環境下合成。經FTIR與EA分析顯示此法所得之PAA可成功製備出PI膜。TGA分析結果顯示，在氮氣氣氛下，此PI膜自500℃才開始有重量損耗，至800℃時損耗約達40％，並形成一穩定碳膜，此膜之碳含量約為 86.72％，且表面均勻、緻密性佳。XRD分析顯示各裂化溫度所得之碳膜皆為非晶態。

　　由N2與CO2於碳膜上之吸附實驗可知，兩氣體之吸附行為符合Langmuir恆溫吸附模式。碳膜之BET比表面積值約為200∼500 m2/g，且隨裂化溫度增加而增大，其平均孔徑則由18.6 Å(600℃)減至7.9 Å(900℃)。另由CO2之吸附來分析碳膜微孔結構結果。700℃裂化之CMS具有最大之微孔洞體積。但當裂化溫度達到900℃時，由於孔洞之收縮，導致CO2亦難以進入，故吸附量下降，由此估計孔徑應與CO2之動力學直徑(3.3 Å)相當或更小。

　　以碳分子篩膜進行氣體透過實驗，結果顯示當裂化溫度為600℃時，由於碳膜孔洞過大，氣體透過機制主要受Knudsen diffusion控制，其N2及CO2之透過速率隨透過溫度之增加而下降，不具分子篩之分離能力；裂化溫度在700℃以上所得之碳膜，由於微孔收縮，故呈現分子篩特性，但其氣體透過量亦減小。當透過溫度增加時，由於活化擴散(activated diffusion)機制，氣體透過量隨之增加。裂化溫度為700℃所得碳分子篩/氧化鋁複合膜具有最佳之CO2/N2分離能力，在50℃、500 kPa條件下，CO2、N2之透過係數分別為0.25×10-10 mole/m2 sec Pa、3.0×10-10 mole/m2 sec Pa，其分離係數高達12。

　　In this study, the carbon molecular sieve/alumina (CMS/Al2O3) composite membranes were prepared from the polyamic acid (PAA)-derived polyimide (PI) /Al2O3 membranes by pyrolysis. The properties of CMS membranes as well as the PI membranes were characterized by FT-IR, EA, TGA, SEM and AFM techniques. Moreover, the effects of pyrolysis temperature on characteristics of CMS composite membranes and the permeations of N2 and CO2 were also investigated.

　　Firstly, the PAA synthesized from BTDA and ODA at 0oC under N2 atmosphere was successfully used to obtain the PI. The result of TGA showed that the PI was thermally stable below 500 oC at N2 atmosphere. Up to 800 oC, a stable carbon membrane was achieved with weight loss of about 40 % and carbon content of 86.72 %, which was amorphous structure from XRD analysis.

　　From the results of gas adsorption experiments, it was found that the adsorptions of N2 and CO2 on CMS membranes follow the Langmuir model. The BET surface area of CMS membrane, estimated about 200~500 m2/g based on the N2 adsorption at 77 K, was increased with increasing the pyrolysis temperature, whereas the average pore size decreased from 18.6 Å (600 oC) to 7.9 Å (900 oC). From the result of CO2 adsorption at 273 K, it revealed that the CMS membrane pyrolyzed at 700 oC exhibited the largest total volume of micropores. However, as the pyrolysis temperature increased to 900℃, the adsorption amount of CO2 was dramatically decreased due to the shrinkage of micropores. Accordingly, it was inferred that the pore diameter was approximate to or less than the kinetic diameter of CO2 (3.3 Å).

　　From the result of gas permeation experiments, it showed that permeabilities of N2 and CO2 in the CMS membrane pyrolyzed at 600 oC were decreased with increasing the permeating temperature, indicating that the gas permeation rate was dominantly controlled by Knudsen diffusion and was without molecular sieving effect. For the CMS membranes pyrolyzed at temperature above 700 oC, due to the shrinkage of pore, the gas permeability was decreased with increasing pyrolysis temperature. However, due to the activated diffusion effect, the gas permeability was increased with elevating the permeating temperature.

　　In addition, it showed that the CMS membrane pyrolyzed at 700 oC exhibited the best separation efficiency for CO2/N2 among all. This result was in accordance with those obtained from gas adsorption. At permeation conditions of 50 oC and 500 kPa, the CO2 and N2 permeabilities were 3.0×10-10, and 0.25×10-10 mole/m2 sec Pa, respectively, with the high CO2/N2 selectivity of 12.

中文摘要
英文摘要
總目錄 Ⅰ
表目錄 Ⅴ
圖目錄 Ⅵ
符號說明 Ⅸ

第一章 緒論……………………………………………… 1
1.1 無機薄膜……………………………………………… 1
1.1.1 無機薄膜之簡介…………………………………….. 1
1.1.2 無機薄膜之分類…………………………………….. 2
1.1.3 無機薄膜之應用…………………………………….. 3
1.2 碳分子篩薄膜…………………………………………… 3
1.2.1 碳分子篩薄膜之簡介………………………………... 3
1.2.2 碳分子篩膜之製備………………………………….. 4
1.3 文獻回顧……………………………………………….. 5
1.4 研究動機與目的………………………………………… 7

第二章 原理………………………………………………….. 11
2.1 聚醯亞胺之合成………………………………………… 11
2.2 薄膜製備程序…………………………………………… 12
2.3 碳材料之製程…………………………………………… 13
2.4 吸附理論……………………………………………….. 14
2.4.1 吸附現象……………………………………………. 14
2.4.2 吸附理論……………………………………………. 15
2.4.2.1 Langmuir equation………………………………… 15
2.4.2.2 BET equation……………………………………… 16
2.4.2.3 Dubinin-Radushkevich equation…………………… 17
2.4.2.4 Dubinin-Astahov equation…………………………. 17
2.5 氣體透過理論…………………………. ………………. 18
2.5.1 氣體透過機制…………………………. …………… 18
2.5.2 氣體透過性質之量測…………………………. ……. 19

第三章 實驗部分…………………………………………….. 28
3.1 藥品及材料……………………………………………... 28
3.2 分析儀器……………………………………………… 29
3.2.1 分析儀器…………………………………………. 29
3.2.2 普通儀器…………………………………………. 30
3.3 實驗方法及步驟………………………………………… 31
3.3.1 擔體之製備………………………………………….. 31
3.3.2 聚醯胺酸溶液之合成………………………………... 32
3.3.3 聚醯亞胺膜之製備及性質分析……………………… 32
3.3.4 碳分子篩膜之製備………………………………….. 33
3.3.5 薄膜之特性分析…………………………………….. 34
3.3.6 氣體吸附之測定…………………………………….. 34
3.3.7氣體透過之測定……………………………………… 34

第四章 結果與討論…………………………………………... 39
4.1預備實驗………………………………………………… 39
4.1.1二酸酐之純化………………………………………… 39
4.1.2複合膜之製備…………………………………………… 39
4.2聚醯亞胺膜之特性分析…………………………………….. 40
4.2.1分子結構……………………………………………... 40
4.2.2表面型態與晶態……………………………………… 41
4.2.3元素分析…………………………………………….. 41
4.3碳分子篩膜之特性分析………………………………….. 42
4.3.1分子結構、表面型態與晶態…………………………. 42
4.3.2熱性質……………………………………………….. 43
4.3.3元素分析……………………………………………... 44
4.4氣體在碳分子篩膜上之吸附行為…….......................... 45
4.4.1氮氣在碳分子篩膜之吸附情形………………………… 45
4.4.2二氧化碳在碳分子篩膜之吸附情形…………………… 45
4.4.3氮氣與二氧化碳之吸附比較…………………………… 47
4.5氣體在碳分子篩膜上之透過行為………………………….. 48
4.5.1氮氣在碳分子篩膜之透過情形………………………… 49
4.5.2二氧化碳在碳分子篩膜之透過情形…………………… 50
4.5.3氮氣/二氧化碳之選擇性………………………………... 50

第五章結論……………………………………………………….. 90
5.1結論……………………………………………………. 90
5.2建議及展望…………………………………………….. 91

參考文獻……………………………………………………… 92
自述…………………………………………………………... 99

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