4.3 質導陶瓷薄膜
4.3.7 塗布於多孔氧化鋁管型基材
圖 4.23：BaCe0.4Zr0.4Gd0.1Dy0.1O3使用方法一塗布混和 PVA(比例為 6wt%)的漿料於多孔的 氧化鋁管型基材在空氣中於 1000oC 鍛燒 5 小時的 SEM 圖 (a）未經過塗布的氧化鋁管型 基材（b）塗布兩次在 1000oC 鍛燒的俯視圖（c）塗布兩次在 1000oC 鍛燒的剖面圖 從圖 4.23 可看出在原有的氧化鋁基材上，表面粗糙度相當之大，預期對所鍍上的膜會使 膜的連續性不佳．而在鍍膜兩次後的俯視圖中可看出雖有形成一陶瓷膜，然而在剖面圖 的觀察下，卻觀察到因為表面粗糙度太大而使膜的連續性不佳．
(a) (b)
(c)
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第5章 結論與未來展望
本研究利用溶膠凝膠法的前驅物溶液，製作管型質導陶瓷複合薄膜的陶瓷膜層．並 所選用新組成 BaCe0.4Zr0.4Gd0.1Dy0.1O3-x做為質導陶瓷材料．
在陶瓷粉體部分：以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 操作溫度下，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和 PVA 後（混和比例為 6wt%）配置 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 陶瓷膜形成且裂痕的大小與裂痕出現的機率也較其他鍛燒溫度小且低．藉由重差法 計 算膜厚為 500~600nm．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．
將陶瓷膜鍍於氧化鋁管型基材上，發現因表面粗糙太大而使薄膜連續性受到限制，
所以未來將在管型基材上結合先前研究之氧化鋁緩衝層製成．預先鍍上氧化鋁緩衝層以 增加其表面平坦性．雖然在平板基材上，我們觀察到陶瓷層依然會有裂痕產生，但是可 在未來的無電鍍製程中，將金屬鍍於陶瓷膜之上，將此裂痕做填補，形成陶瓷金屬腹膜 薄膜．再經由封裝與氣體測試，測試其 permeability．
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第6章 參考文獻
[1] 林有銘. 化學工廠中新能源之利用. 化工技術. 1998;6(3):136-41.
[2] Zuo CD, Dorris SE, Balachandran U, Liu ML. Effect of Zr-doping on the chemical stability and hydrogen permeation of the Ni-BaCe0.8Y0.2O3- mixed protonic-electronic conductor. Chemistry of Materials. 2006;18(19):4647-50.
[3] Zuo CD, Lee TH, Dorris SE, Balachandran U, Liu ML. Composite Ni-BaCe0.7Zr0.1Y0.2O3- cermet on the hydrogen permeation performance. Journal of Alloys and Compounds. 2010;508(1):L5-L8.
[6] Yan L, Sun W, Bi L, Fang S, Tao Z, Liu W. Effect of Sm-doping on the hydrogen permeation of Ni–La2Ce2O7mixed protonic–electronic conductor. International Journal of Hydrogen Energy. 2010;35(10):4508-11.
[7] Jeon SY, Lim DK, Choi MB, Wachsman E, Song SJ. Hydrogen separation by Pd-CaZr0.9Y0.1O3- cermet composite membranes. Separation and Purification Technology.
2011:337-41.
[8] Zhu Z, Sun W, Yan L, Liu W. Synthesis and hydrogen permeation of Ni-Ba(Zr0.1Ce0.7Y0.2)O3- metal-ceramic asymmetric membranes. International Journal of Hydrogen Energy. 2011:6337-42.
[9] 胡蒨傑, 魏大欽. 21 世紀的新森林-薄膜氣體分離. 薄膜科技. 2008;429:29-37.
[10] Phair J, Badwal SPS. Review of proton conductors for hydrogen separation. Ionics.
2006;12(2):103-15.
[11] Bose AC. Inorganic membranes for energy and fuel applications: Springer Verlag; 2008.
[12] Islam MS. Ionic transport in ABO3 perovskite oxides: a computer modelling tour. J Mater Chem. 2000;10(4):1027-38.
[13] Wu J. Defect chemistry and proton conductivity in Ba-based perovskites California Institute of Technology 2005.
[14] Weber G, Kapphan S, Wöhlecke M. Spectroscopy of the OH and OD stretching vibrations in SrTiO3 under applied electric field and uniaxial stress. Physical Review B.
1986;34(12):8406.
56
[15] Eurenius KEJ. Proton conductivity in acceptor-doped lanthanide based pyrochlore oxides.
Göteborgs universitet, 2009.
[16] Chen F, Sørensen OT, Meng G, Peng D. Chemical stability study of BaCe0.9Nd0.1O3-α
high-temperature proton-conducting ceramic. J Mater Chem. 1997;7(3):481-5.
[17] Ryu KH, Haile SM. Chemical stability and proton conductivity of doped BaCeO3–BaZrO3
solid solutions. Solid State Ionics. 1999;125(1):355-67.
[18] Cherry M, Islam MS, Gale JD, Catlow CRA. Compuatational studies of protons in perovskite-structured oxides. J Phys Chem. 1995;99(40):14614-8.
[19] Iwahara H. Proton conducting ceramics and their applications. Solid State Ionics.
1996;86-8:9-15.
[20] Bonanos N. Oxide-based protonic conductors: point defects and transport properties.
Solid State Ionics. 2001;145(1-4):265-74.
[21] Wang W, Liu J, Li Y, Wang H, Zhang F, Ma G. Microstructures and proton conduction behaviors of Dy-doped BaCeO3 ceramics at intermediate temperature. Solid State Ionics.
2010;181(15):667-71.
[22] 張天益. 利用溶膠-凝膠法製備鋯鈦酸鉛陶瓷塊材與薄膜之研究 國立成功大學 博士, 2003.
[23] Brinker CJ, Scherer GW. Sol gel science: the physics and chemistry of sol gel processing academic press; 1990.
[24] Okubo T, Haruta K, Kusakabe K, Morooka S, Anzai H, Akiyama S. Preparation of a sol-gel derived thin membrane on a porous ceramic hollow fiber by the filtration technique.
Journal of Membrane Science. 1991;59(1):73-80.
[25] Smid J, Avci C, Günay V, Terpstra R, Van Eijk J. Preparation and characterization of microporous ceramic hollow fibre membranes. Journal of Membrane Science.
1996;112(1):85-90.
[26] Oyama. ST, Gu. Y, kee. D, inventors; Hydrogen-selective silica-based membrane patent US 7,179,325 B2. 2007.
[27] Morilla-Santos C, Schreiner WH, Lisboa-Filho PN. Chemical deposition of La0.7Ca0.3MnO3±δ films on ceramic substrates. Materials Research. 2011;14(2):217-21.
[28] Weber IT, Audebrand N, Bouquet V, Guilloux-Viry M, Perrin A. KTaO3 powders and thin films prepared by polymeric precursor method. Solid State Sciences. 2006;8(6):606-12.
[29] Roberts G. Langmuir-Blodgett films. Contemporary Physics. 1984;25(2):109-28.
[30] Gu Y, Meng G. A model for ceramic membrane formation by dip-coating. Journal of the European Ceramic Society. 1999;19(11):1961-6.
[31] Schmidt H, Mennig M. Wet Coating Technologies for Glass. 2000 [cited 2012 7/10];
Available from: http://www.solgel.com/articles/nov00/mennig.htm