氣體測試

在氣體測試部份，我們先在室溫下用純二氧化碳測試其氣密性，由圖 4.38 可知 GC 之結果顯示，可以觀察到非常明顯的二氧化碳波峰，研判是由膜之部份 漏氣，其結果我們也由 SEM 可以得到，因為孔洞太大，以至二氧化碳可經孔洞 作 Knudsen diffusion，我們也對過檢量線，其二氧化碳漏氣量超過 50%以上，尚 未有效的做氫氣及二氧化碳分離。

圖 4.38 二氧化碳漏氣測試圖

72

在氫氣滲透測試部份，我們也是經過計算發現，絕大部份之氫氣都是經由孔 洞作 Knudsen diffusion，因此如何降低膜表面孔隙大小是未來研究重點。

73 比 74:26、鈀銀銅比 67:11:21 及鈀銀銅鎳比 56:5:27:12，分析之前可先用秤重減 重法粗估其成份。

74

第6章 未來方向

基材的解決，可以在粗糙之氧化鋁管表面先鍍上一層氧化鋁緩衝層，氧化鋁 顆粒由大至小依序鍍上，將可以大幅降低表面粗糙度，一方面可以減少前驅鹽的 使用量，另一方面也可以將膜厚降低而提高整體的氫氣通量，在基材改質過後，

確定其表面粗糙度到預期時，再搭配抽真空製程，這樣才可以讓膜更緊密，否則 在粗糙度大的基材上抽真空，只會破壞膜之表面，造成漏氣。

另一方面，緩衝層除了使用氧化鋁製作之外，未來也可嘗試利用本研究團隊 另一方向所製備之陶瓷膜作為緩衝層，利用新穎金屬合金薄膜與新穎陶瓷材料做 結合，在靠金屬合金膜傳導氫原子、電子，以及陶瓷材料傳導氫離子之雙管齊下 之導氫機制下，預估可以大幅提升整體的氫滲透率，再搭配國際知名理論模擬大 師 Goddard 經理論計算得到氫氣分離複合膜最佳組成，未來無論是花費成本、理 論驗證及氫氣滲漏率都能大幅改善。

75

第7章 參考文獻

[1] Ratafia-Brown JA, Manfredo LM, Hoffmann JW, Ramezan M, Stiegel GJ. An environmental assessment of IGCC power systems. p. 23- 7

[2] Wang L, Yoshiie R, Uemiya S. Fabrication of novel Pd-Ag-Ru/Al2O3 ternary alloy composite membrane with remarkably enhanced H2 permeability. Journal of Membrane Science. 2007;306(1-2):1-7.

[3] Ryi SK, Park JS, Kim SH, Kim DW, Moon JW. Long-term hydrogen permeation tests of Pd-Cu-Ni/PNS with temperature cycles from room temperature to 773 K.

Journal of Membrane Science. 2007;306(1-2):261-6.

[4] Samhun Y, Oyama ST. Correlations in palladium membranes for hydrogen separation: A review. Journal of Membrane Science. 2011;375(1-2).

[5] Adhikari S, Fernando S. Hydrogen membrane separation techniques. Industrial

& Engineering Chemistry Research. 2006;45(3):875-81.

[6] Paglieri S, Way J. Innovations in palladium membrane research. Separation &

Purification Reviews. 2002;31(1):1-169.

[7] Buxbaum RE, Kinney AB. Hydrogen transport through tubular membranes of palladium-coated tantalum and niobium. Industrial & Engineering Chemistry Research. 1996;35(2):530-7.

[8] Gryaznov V. Membrane catalysis. Catalysis Today. 1999;51(3–4):391-5.

[9] Hatlevik O, Gade SK, Keeling MK, Thoen PM, Davidson AP, Way JD.

Palladium and palladium alloy membranes for hydrogen separation and production:

History, fabrication strategies, and current performance. Separation and Purification Technology. 2010;73(1):59-64.

[10] Lewis FA. The palladium hydrogen system. Academic, London and New York;

1967.

[11] Barrer RM. Diffusion in and through solids. Cambridge University Press, London; 1951.

[12] Dembovský V. Thermodynamics of dissolution and liberation of gases in the atomization of molten metals by plasma-induced expansion. Journal of Materials Processing Technology. 1997;64(1–3):65-74.

[13] Okazaki J, Ikeda T, Tanaka DAP, Sato K, Suzuki TM, Mizukami F. An investigation of thermal stability of thin palladium-silver alloy membranes for high temperature hydrogen separation. Journal of Membrane Science.

76

2011;366(1-2):212-9.

[14] Holleck GL. Diffusion and solubility of hydrogen in palladium and palladium--silver alloys. The Journal of Physical Chemistry. 1970;74(3):503-11.

[15] Hurlbert R, Konecny J. Diffusion of hydrogen through palladium. The Journal of Chemical Physics. 1961;34:655.

[16] Ilias S, Su N, Udo-Aka U, King F. Application of electroless deposited thin-film palladium composite membrane in hydrogen separation. Separation Science and Technology. 1997;32(1-4):487-504.

[17] Steward S. Review of hydrogen isotope permeability through materials:

Lawrence Livermore National Lab., CA (USA); 1983.

[18] Ye J, Dan G, Yuan Q. The preparation of ultrathin palladium membrane. Key Engineering Materials. 1992;61:437-42.

[19] Itoh N, Akiha T, Sato T. Preparation of thin palladium composite membrane tube by a CVD technique and its hydrogen permselectivity. Catalysis Today.

2005;104(2):231-7.

[20] Xiong L, Liu S, Rong L. Fabrication and characterization of Pd/Nb40Ti30Ni30/Pd/porous nickel support composite membrane for hydrogen separation and purification. International Journal of Hydrogen Energy.

2010;35(4):1643-9.

[21] Xomeritakis G, Lin Y. Fabrication of thin metallic membranes by MOCVD and sputtering. Journal of Membrane Science. 1997;133(2):217-30.

[22] Hsieh H. Inorganic membranes for separation and reaction: Elsevier Science;

1996.

[23] Nam SE, Lee KH. A study on the palladium/nickel composite membrane by vacuum electrodeposition. Journal of Membrane Science. 2000;170(1):91-9.

[24] Samingprai S, Tantayanon S, Ma YH. Chromium oxide intermetallic diffusion barrier for palladium membrane supported on porous stainless steel. Journal of Membrane Science. 2010;347(1-2):8-16.

[25] Guazzone F, Engwall EE, Ma YH. Effects of surface activity, defects and mass transfer on hydrogen permeance and n-value in composite palladium-porous stainless steel membranes. Catalysis Today. 2006;118(1):24-31.

[26] Ayturk M, Ma YH. Electroless Pd and Ag deposition kinetics of the composite Pd and Pd/Ag membranes synthesized from agitated plating baths. Journal of Membrane Science. 2009;330(1-2):233-45.

[27] Yolcular S, Olgun Ö . Pd/Al2O3 composite membranes for the production of pure hydrogen. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects.

2010;32(15):1437-45.

77

[28] Pomerantz N, Ma YH. Novel method for producing high H2 permeability Pd membranes with a thin layer of the sulfur tolerant Pd/Cu fcc phase. Journal of Membrane Science. 2011:97-108.

[29] Oyama ST, Gu Y, Lee D. Hydrogen-selective silica-based membrane. Google Patents 2007.

[30] Pomerantz N, Ma YH. Effect of H2S on the performance and long-term stability of Pd/Cu membranes. Industrial & Engineering Chemistry Research.

2009;48(8):4030-9.

[31] Ohira K, Sakamoto Y, Flanagan T. Thermodynamic properties for solution of hydrogen in Pd-Ag-Ni ternary alloys. Journal of Alloys and Compounds.

1996;236(1):42-9.

[32] Rogers H. Hydrogen embrittlement of metals. Science. 1968;159(3819):1057.

[33] Collins JP, Schwartz RW, Sehgal R, Ward TL, Brinker C, Hagen GP, et al.

Catalytic dehydrogenation of propane in hydrogen permselective membrane reactors.

Industrial & Engineering Chemistry Research. 1996;35(12):4398-405.

[34] O'Brien CP, Gellman AJ, Morreale BD, Miller JB. The hydrogen permeability of Pd4S. Journal of Membrane Science. 2011:263-7.

[35] Jun CS, Lee KH. Palladium and palladium alloy composite membranes prepared by metal-organic chemical vapor deposition method (cold-wall). Journal of Membrane Science. 2000;176(1):121-30.

[36] Bryden KJ, Ying JY. Nanostructured palladium–iron membranes for hydrogen separation and membrane hydrogenation reactions. Journal of Membrane Science.

2002;203(1):29-42.

[37] Uemiya S, Endo T, Yoshiie R, Katoh W, Kojima T. Fabrication of thin palladium-silver alloy film by using electroplating technique. Materials transactions.

2007;48(5):1119.

[38] Uemiya S, Matsuda T, Kikuchi E. Hydrogen permeable palladium-silver alloy membrane supported on porous ceramics. Journal of Membrane Science.

1991;56(3):315-25.

[39] Timofeev N, Berseneva F, Gromov V. Influence of preliminary hydrogen impregnation on the mechanical properties of palladium and its alloys with silver.

Materials Science. 1982;17(5):417-9.

[40] Miller JB, Morreale BD, Gellman AJ. The effect of adsorbed sulfur on surface segregation in a polycrystalline Pd70Cu30 alloy. Surface Science.

2008;602(10):1819-25.

[41] O'Brien CP, Howard BH, Miller JB, Morreale BD, Gellman AJ. Inhibition of hydrogen transport through Pd and Pd47Cu53 membranes by H2S at 350°C. Journal of

78

Membrane Science. 2010;349(1-2):380-4.

[42] Peters T, Stange M, Klette H, Bredesen R. High pressure performance of thin Pd-23% Ag/stainless steel composite membranes in water gas shift gas mixtures;

influence of dilution, mass transfer and surface effects on the hydrogen flux. Journal of Membrane Science. 2008;316(1-2):119-27.

[43] Decaux C, Ngameni R, Solas D, Grigoriev S, Millet P. Time and frequency domain analysis of hydrogen permeation across PdCu metallic membranes for hydrogen purification. International Journal of Hydrogen Energy.

2010;35(10):4883-92.

[44] Charbonnier M, Romand M, Harry E, Alami M. Surface plasma functionalization of polycarbonate: Application to electroless nickel and copper plating. Journal of Applied Electrochemistry. 2001;31(1):57-63.

[45] Chen WD, Hu XJ, Wang RX, Huang Y. On the assembling of Pd/ceramic composite membranes for hydrogen separation. Separation and Purification Technology. 2010;72(1):92-7.

[46] Tarditi AM, Braun F, Cornaglia LM. Novel PdAgCu ternary alloy: Hydrogen permeation and surface properties. Applied Surface Science. 2011;257(15):6626-35.

[47] Roa F, Way JD, McCormick RL, Paglieri SN. Preparation and characterization of Pd-Cu composite membranes for hydrogen separation. Chemical Engineering Journal.

2003;93(1):11-22.

[48] Acha E, van Delft YC, Overbeek J, Arias PL, Cambra JF. Copper deposition on Pd membranes by electroless plating. International Journal of Hydrogen Energy.

2011;36(20):13114-21.

[49] Tarditi AM, Cornaglia LM. Novel PdAgCu ternary alloy as promising materials for hydrogen separation membranes: Synthesis and characterization. Surface Science.

2011;605(1-2):62-71.

[50] Bulasara VK, Thakuria H, Uppaluri R, Purkait MK. Nickel-ceramic composite membranes: Optimization of hydrazine based electroless plating process parameters.

Desalination. 2011;275(1-3):243-51.

[51] Bulasara VK, Abhimanyu MS, Pranav T, Uppaluri R, Purkait MK. Performance characteristics of hydrothermal and sonication assisted electroless plating baths for nickel-ceramic composite membrane fabrication. Desalination. 2012;284:77-85.

[52] Rohan JF, O’Riordan G, Boardman J. Selective electroless nickel deposition on copper as a final barrier/bonding layer material for microelectronics applications.

Applied Surface Science. 2002;185(3–4):289-97.