臺灣博碩士論文加值系統

本研究利用溶膠凝膠法製作管型質導陶瓷複合薄膜的陶瓷膜層．並所選用之組成為BaCe0.4Zr0.4Gd0.1Dy0.1O3-x做為質導陶瓷材料．在陶瓷粉體部分：已成功利用溶膠凝膠法在1350oC製備陶瓷粉末．並經由XRD確認之燒結成相情形．再經由TGA確認，其在30~600oC操作溫度及二氧化碳環境下的化學穩定性，在測試結果中顯示，BaCe0.4Zr0.4Gd0.1Dy0.1O3-x粉體未與CO2反應，在薄膜部分：利用溶膠凝膠法將前驅物溶液混合PVA後（混合比例為6wt%）配製成漿料，並利用沉浸塗布法(Dip-coating)將此前驅物塗布於片狀基材上，以便於於觀察其表面形貌與薄膜成相情形．在1000oC下鍛燒．並經由SEM觀察下發現基材表面已經一層陶瓷膜形成且並未看到明顯裂痕．藉由XRD看出perovskite已成相且並無雜相並與所合成之粉末繞射峰位置相同．而根據粉體的TGA測試，此薄膜不會與CO2反應，推論此新組成可用於CO2-H2分離膜之用．

A sol-gel method is adopted to prepare proton conducting ceramics in tubular thin films and powder forms. The targeted composition for the proton conducting ceramics is BaCe0.4Zr0.4Gd0.1Dy0.1O3-xand the as-synthesized samples undergo characterizations including XRD, TGA, SEM. The XRD patterns indicate a perovskite structure after sintering at elevated temperature. In addition, TGA analysis confirms that the sample is chemically stable against CO2 at temperatures of 30 to 600oC. The ceramic thin film is deposited on a tubular alumina substrate by multiple steps of dip coating and sintering. We have successfully prepared uniform ceramic thin film at reduced thickness without noticeable cracks.

摘要 i
Abstract ii
致謝 iii
目錄 v
表目錄 viii
圖目錄 viii
第1章 緒論 1
1.1 研究背景 1
1.2 研究動機 2
第2章 文獻回顧 3
2.1 薄膜氣體分離 3
2.1.1 薄膜氣體分離技術 3
2.1.1.1 高分子薄膜 3
2.1.1.2 奈米孔洞陶瓷薄膜 4
2.1.2 緻密型陶瓷薄膜 4
2.1.2.1 質導陶瓷材料Perovskite介紹 4
2.1.2.2 質導陶瓷導氫原理 5
2.1.2.3 摻雜元素與本研究所選用組成 6
2.2 陶瓷粉體與薄膜製備方法 8
2.2.1 固態反應法 8
2.2.2 氣相反應法 8
2.2.3 液態反應法 8
2.2.4 溶膠凝膠法 9
2.2.4.1 溶膠凝膠法簡介 9
2.2.4.2 溶膠凝膠法原理與應用 10
2.2.4.3 利用溶膠凝膠法製備氧化鋁薄膜緩衝層 12
2.2.4.4 利用溶膠凝膠法製備質導陶瓷薄膜 13
2.3 沉浸法 14
第3章 實驗方法與步驟 16
3.1 實驗流程 16
3.2 實驗藥品列表 17
3.3 氧化鋁薄膜(Buffer layer) 18
3.3.1 製備boehmite sol 18
3.3.2 利用沉浸法將boehmite sol塗布於管型基材 18
3.4 製備質導陶瓷薄膜 19
3.4.1 製備BaCe0.4Zr0.5Gd0.1O3-x 的前驅物 19
3.4.2 製備BaCe0.4Zr0.4Gd0.1Dy0.1O3-x的前驅物 19
3.4.3 利用沉浸法將氧化物之前驅物塗布於管型基材 20
3.5 製備質導陶瓷粉末 21
3.6 氣體測試線路圖 21
3.6.1 氣體測試線路圖 21
3.6.2 檢量線測試 22
3.6.3 薄膜漏氣測試 23
3.6.4 氣體分離測試 24
3.7 實驗儀器 25
第4章 結果與討論 28
4.1 氧化鋁薄膜 (Buffer layer) 28
4.1.1 Boemite sol粒徑分佈分析 28
4.1.2 光學顯微鏡 29
4.1.3 SEM 30
4.1.4 氣泡測試 (Bubbling test) 31
4.2 質導陶瓷氧化物粉體 32
4.2.1 氧化物粉體XRD 分析 32
4.2.2 氧化物粉體TGA分析 33
4.3 質導陶瓷薄膜 35
4.3.1 塗布於平滑氧化鋁片狀基材陶瓷薄膜SEM 表面分析 35
4.3.2 塗布於平滑氧化鋁片狀基材陶瓷薄膜XRD分析 39
4.3.3 塗布於粗糙氧化鋁片狀基材陶瓷薄膜SEM 表面分析 40
4.3.3.1 塗布混和PVA(比例為4wt%)漿料於粗糙氧化鋁基材40
4.3.3.2 塗布混和PVA(比例為6wt%)漿料於粗糙氧化鋁基材42
4.3.4 塗布於粗糙氧化鋁片狀基材陶瓷薄膜XRD分析 46
4.3.5 質導陶瓷前軀物溶液與氧化鋁粉末共燒 47
4.3.6 塗布於粗糙氧化鋁片狀基材陶瓷薄膜在較低溫鍛燒之結果 48
4.3.6.1 在800~1000oC鍛燒之SEM圖 48
4.3.6.2 在1000oC鍛燒之EDX分析 50
4.3.6.3 在800~1000oC鍛燒之XRD分析 51
4.3.6.4 利用重量差計算膜厚 52
4.3.7 塗布於多孔氧化鋁管型基材 53
第5章 結論與未來展望 54
第6章 參考文獻 55

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