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研究生： 陳怡如
Chen, Yi-Ru
論文名稱： 熱電材料Bi2Te3區域重熔之長晶凝固及微組織模擬研究
Thermal and Microstructure Simulation of Thermoelectric Material Bi2Te3 by Zone-melting Technique
指導教授： 黃文星
Hwang, Weng-Sing
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2014
畢業學年度： 102
語文別： 中文
論文頁數： 116
中文關鍵詞： 碲化鉍 、區域重熔 、方向性生長 、微組織 、數值模擬 、CA法
外文關鍵詞： Bi2Te3, zone-melting, directional growth, microstructure, numerical simulation, CA method
相關次數： 點閱：100  下載：5 
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    • 藉由公式ZT=S2σT/κ可知提升電導率σ並降低熱導率κ可提升ZT值，進而提高熱電轉換效率。由於熱電材料碲化鉍的電性質及熱性質具有高異向性，因此碲化鉍的熱電轉換效率深受其微組織影響，若能長成柱狀晶，就能達到提升電導率及降低熱導率的效果。區域重熔製程中，固體鑄件周圍環繞著移動式加熱器，為一方向性凝固法，所以此製程有利於長成柱狀晶。
    本研究利用電腦數值模擬技術建立區域重熔凝固長晶系統的模型，並模擬區域重熔長晶製程的溫度分布隨時間之變化及碲化鉍的微組織。此外，將模擬結果與實驗作比對，驗證數值模型，進一步進行區域重熔凝固長晶系統的最佳化。
    為了達到量產的目的，碲化鉍鑄件的尺寸必須增大，因此製程參數必須做調整才能保持柱狀晶的品質。本研究改變的製程參數為加熱器的溫度，以及加熱器與冷卻裝置的移動速度。另外還探討了不同製程參數下凝固長晶介面的型態，因為凝固長晶介面的型態會影響晶粒的生長方向及晶粒大小。模擬結果顯示，當30 φ碲化鉍的加熱器溫度設定在770℃、加熱器及冷卻裝置的移動速度為0.75 cm/hr時，長晶凝固介面呈現凸面，即可生長出最長且最粗的大尺寸柱狀晶，橫截面的平均晶粒直徑可高達6.9 mm。且此製程條件下可得到穩定的熔融區，熔融區長度為6 cm 。

    The thermoelectric conversion efficiency of thermoelectric material Bi2Te3 is significantly affected by its microstructure. Considering of the effect of anisotropy on the electrical and thermal properties, the columnar crystal structure can improve the thermoelectric conversion efficiency by raising the electrical conductivity σ and reduce the thermal conductivity κ, because of ZT=S2σT/κ. Zone-melting process is a method which can directionally solidify and purify the ingot by a moving heater along the solid ingot.
    In this study, a zone-melting model is setup and numerical simulation techniques are used to simulate temperature variation/distribution of crystallization process and the microstructure of Bi2Te3. Besides, the results of simulation are compared with experimental measurements and verify the numerical model. Furthermore, the verified numerical model is used to investigate the optimal process parameters.
    To achieve the goal of mass production, the size of Bi2Te3 ingot should be increased. Then the process parameters, the temperature of heater and the moving speed of heater and cooling device, are adjusted in order to maintain the quality of columnar crystals. The shapes of the solidification interface are compared, which has great impact on the direction of grain growth and the grain size, with different simulation parameters. Summarizing the simulation result, it indicate that there is a maximum cross grain size, 6.9mm, for 30 φ Bi2Te3 at high heater temperature 770℃ and low moving speed 0.75 cm/hr. In these process conditions, the solidification interface is convex. On the other hand, the melting zone is stable and the length of melting zone is 6 cm in this case.

    中文摘要 I Abstract III 誌謝 V 目錄 VII 表目錄 X 圖目錄 XI 符號表 XV 第一章 前言 1 第二章 文獻回顧 7 2-1 熱電原理 7 2-1-1 熱電現象 7 2-1-1-1 Seebeck效應 8 2-1-1-2 Peltier效應 10 2-1-1-3 Thomson效應 11 2-1-2 電阻率 13 2-1-3 熱電力 15 2-1-4 熱導度 18 2-1-5 霍爾效應 20 2-2 熱電材料的種類 21 2-2-1 Bi-Te系列 21 2-2-2 Pb-Te系列 22 2-2-3 Si-Ge系列 22 2-3 熱電材料的主要製備方式 23 2-3-1 Bridgman法 24 2-3-2 Czochralski法 25 2-3-3 區域重熔法 26 2-3-4 粉末冶金法 27 2-3-5 火花電漿燒結法 28 2-4 提升熱電優值的方式 28 2-4-1 調整能帶結構 30 2-4-2 晶界效應 30 第三章 數值方法及理論基礎 44 3-1 數值模擬流程 44 3-2 理論基礎 44 3-2-1 熱傳模組 44 3-2-1-1熱傳及凝固控制方程式 45 3-2-1-2熱輻射模式 45 3-2-2 長晶模組CAFE 47 3-2-2-1 成核模式 48 3-2-2-2 成長模式 51 第四章 實驗方法及步驟 56 4-1 研究流程 56 4-1-1 實際區域重熔長晶製程 56 4-1-2 溫度曲線量測 57 4-2 數值模擬 58 4-2-1 溫度場及凝固模擬解析 59 4-2-2 微組織模擬解析 59 第五章 結果與討論 72 5-1 17 φ及25 φ碲化鉍之溫度場驗證 72 5-2 25 φ碲化鉍之微組織驗證 73 5-3 30 φ碲化鉍溫度場及微組織模擬 74 5-3-1 溫度場及凝固場模擬 74 5-3-2 微組織模擬 77 5-4 碲化鉍SEM及EDS分析 79 第六章 結論 106 參考文獻 108

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