韋文誠臺灣大學：材料科學與工程學研究所陳右儒Chen, Yu-JuYu-JuChen2007-11-262018-06-282007-11-262018-06-282007http://ntur.lib.ntu.edu.tw//handle/246246/55191封裝玻璃在燃料電池的單電池組中，扮演著一個重要的角色。製造一妥適性的封裝玻璃系統（compliant sealing glass），其玻璃轉換溫度需小於燃料電池操作溫度，在材料設計上可說是一大挑戰。因為要考慮到玻璃轉換溫度、材料熱膨脹係數、高溫導電性與化學穩定度。因此本研究主要分為兩部分，第一部份在討論以氧化物與合金當做靶材，使用離子束濺鍍法 (IBSD) 進行鍍膜，選擇Si (100) 晶圓與NiO/YSZ 燒結體作為基材，討論靶材對於薄膜的影響、薄膜成長機制與微結構的觀察。第二部份則為封裝玻璃的合成，選用Pb- 與Bi-Zn-Si-B 氧化物玻璃，透過熱處理了解其結晶行為與物理特性的變化。並與8Y-YSZ塊材和薄膜在600-650oC 進行接合，研究其界面反應；以SEM與TEM進行為結構分析，XRD進行結晶相分析。無鉛的Bi系玻璃因為結晶產生而導致熱膨脹係數變化，使得玻璃系統在長時間使用上呈現負面結果。最後依循玻璃封裝的實驗結果設計一玻璃適用性評分表，可對其他封裝玻璃系統進行一系列的評估。A complient sealing glass-ceramic with the following properties is needed for the preparation of solid oxide fuel cell (SOFC), The design of the sealing material to have a glass transition temperature (Tg) slightly lower than operation temperature (To), good match of the coefficient of thermal expansion (CTE) with SOFC components, chemically inert at To, non-electrical conductive and good wetting for gas tight is tough and a great challenge in engineering aspects. This study included tow major subjects. One is used ion-beam sputtering deposition (IBSD), sputtered oxide or metal targets on various ZrO2 substrates, which included Si (100) wafer and porous NiO/YSZ composite disk. The other is preparation of two sealing glasses, Pb- and Bi-Zn-Si-B-oxides, and analyze the crystallization behaviors have been conducted. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM) with energy dispersive spectroscopy (EDS) were employed to study the best performance is contact with YSZ at 600-650oC for at least 10 hr, but the microstructural and phase evolution of the films and glasses. The results show that porous YSZ thin films with columnar crystalline structure on NiO/YSZ substrate or in amorphous state on Si wafer were observed. One Pb-free glass (B4 glass) has the microcracks induced by crystallization and CTE mismatch may play a negative role for the sealing. The discussion on the influence by different targets, substrates, phase transformation. Electric conductivity will be discussed.Chapter 1 Introduction .................................................................- 1 - 1.1 Objectives of This Research..............................................................- 2 - Chapter 2 Literature Survey .........................................................- 5 - 2.1. Thin Electrolyte Films......................................................................- 5 - 2.1.1 Synthesis Methods ......................................................................- 5 - 2.1.2. Developments of Thin Electrolyte Film ..................................- 10 - 2.2 The Sealing Glass............................................................................- 13 - 2.2.1 Rules of Sealing Glass in SOFC...............................................- 13 - 2.2.2 Function Requirement for SOFC..............................................- 16 - 2.2.3 Characteristics of Sealing Glass ...............................................- 20 - 2.2.4 Effect Coefficient of Thermal Expansion (CTE) of the Sealing Glass...................................................................................................- 22 - 2.2.5 Electrical Resistance of Sealing Glass......................................- 32 - 2.2.6 Chemical Stability under Operation Conditions.......................- 37 - Chapter 3 Experimental Procedure..............................................- 42 - 3.1 Materials ..........................................................................................- 43 - 3.1.1 Materials for IBSD Method ......................................................- 43 - 3.1.2 Glass Selection for Sealing.......................................................- 43 - 3.2 Sample Preparation..........................................................................- 44 - 3.2.1 YSZ Thin Film for IBSD Method ............................................- 44 - 3.2.2 Glass Ceramics..........................................................................- 44 - 3.3 Characterization...............................................................................- 46 - 3.3.1 X-ray diffraction .......................................................................- 46 - 3.3.2 Thermal properties analysis ......................................................- 46 - 3.3.3 Microstructural and Elemental Analysis ..................................- 46 - VI 3.3.4 Electrical Properties..................................................................- 47 - 3.3.5 Density and Porosity.................................................................- 47 - Chapter 4 Results .......................................................................- 55 - 4.1 Formation of YSZ thin film by IBSD and analysis ........................- 55 - 4.1.1 Microstructure of Targets .........................................................- 55 - 4.1.2 Properties of Sputtered Films ...................................................- 55 - 4.1.3 TEM Observation Results.........................................................- 69 - 4.1.4 Microstructure of Films by Thermal Treatment .......................- 70 - 4.2 Thermal Properties and Interfacial Reaction of Pb-glass System...- 79 - 4.3 Bi2O3-ZnO-SiO2-B2O3 Oxide Glass System ...................................- 86 - 4.3.1 Thermal Properties of Bi2O3-glass System...............................- 86 - 4.3.2 Crystalline Phase Analysis in B4-glass System .......................- 87 - 4.3.3 Effect of 900oC Wetting Treatment ..........................................- 90 - 4.3.4 Ionic Conductivity of glass .......................................................- 91 - 4.4 The Interface Reaction of B4-glass/YSZ ......................................- 114 - 4.4.1 The Interface Reaction at Intermediate temperature ..............- 114 - 4.4.2 Interfacial Reaction of High Temperature Wetting Sample...- 116 - 4.4.3 Interfacial Reaction of B4-glass and YSZ Thin Film.............- 117 - Chapter 5 Discussions ...............................................................- 126 - 5.1 Methods of Sealing Materials Selection .......................................- 126 - 5.2 Composition ..................................................................................- 126 - 5.3 Thermal Properties ........................................................................- 127 - 5.4 Crystalline Phases and Crystallization ..........................................- 128 - 5.5 Interfacial Reactions......................................................................- 128 - 5.6 Interfacial Diffusion Analysis .......................................................- 130 - 5.7 Electrical Conductivity..................................................................- 131 - VII Chapter 6 Conclusions ..............................................................- 135 - Chapter 7 Future work .............................................................- 138 - Reference .................................................................................- 139 - Appendix..................................................................................- 145 -11593212 bytesapplication/pdfen-US燃料電池薄膜封裝玻璃無鉛玻璃Bi-Zn-Si-B 氧化物玻璃相變化SOFCthin filmsealing glassPb-freeglass ceramicsthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/55191/1/ntu-96-R93527005-1.pdf