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研究生：	王茹立 Wang, Ju-Li
論文名稱：	不同熱處理與鋇鈦比對鈦酸鋇粉末粒徑大小、結晶相、相轉換溫度及介電常數之影響 Effects of Heat Treatment and Ba/Ti Ratio on Particle Size, Crystalline Phase, Curie Temperature and Dielectric Constant of BaTiO3 Powder
指導教授：	黃啟原 Huang, Chi-Yuang
學位類別：	碩士 Master
系所名稱：	工學院 - 資源工程學系 Department of Resources Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	中文
論文頁數：	94
中文關鍵詞：	鋇鈦比、粒徑、結晶相、居禮溫度、介電常數
外文關鍵詞：	crystalline phase, particle size, Ba/Ti ratio, curie temperature, dielectric constant
相關次數：	點閱：92 下載：10
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鈦酸鋇因具有良好的介電性質，而被廣泛地運用在多層陶瓷電容器、熱敏電阻等電子產品。鈦酸鋇的微結構、結晶相、相轉換溫度以及介電性質等，容易因 Ba/Ti 比以及粒徑的改變而有不同的表現，因此了解 Ba/Ti 比和粒徑對鈦酸鋇性質的影響為相當重要的課題。故本研究將設計不同 Ba/Ti 比之起始粉末，搭配不同的熱處理條件，合成單一相並具有相同粒徑之不同 Ba/Ti 比的非計量比鈦酸鋇粉末，以了解兩者對粉末結晶相、相轉換溫度以及介電常數的影響。
由實驗結果得知，Ti-excess 之鈦酸鋇粉末，其固溶極限範圍較 Ba-excess 之鈦酸鋇粉末大，原因為形成 Ti-O Schottky defect所需之活化能較大，故單一相之 Ba-excess 鈦酸鋇粉末較難合成。觀察粉末之微結構發現，Ba-excess 之鈦酸鋇粉末約在 1050℃ 開始有 necking 現象發生，而 Ti-excess 之鈦酸鋇粉末開始發生 necking 之溫度更高，約在 1300℃ 左右，此結果証實非計量比鈦酸鋇鈦粉末之粒徑成長，控制於鈦空缺及鈦原子之擴散速率，而鈦原子所需之擴散活化能更高，故Ti-excess 之鈦酸鋇粉末需於更高之溫度下進行熱處理，其粒徑才有明顯之變化。
本研究控制 Ba-excess 與 Ti-excess 之粉末於低溫下合成粒徑大小相似之鈦酸鋇粉末，發現其正方性與相轉換所需能量，隨著鋇鈦比偏離計量比而有降低之趨勢，相轉換溫度往低溫偏移；於高溫下合成時，因不同 Ba/Ti 比之鈦酸鋇粉末粒徑差異較大，故Ba-excess 之鈦酸鋇粉末之正方性與相轉換所需能量隨著粒徑變大而有增加之趨勢，相轉換溫度往高溫偏移。此結果顯示，粉末之正方性、相轉換溫度及相轉換能量皆受到鋇鈦比及粒徑大小影響，但因熱處理溫度不同，影響程度並不相同。
選擇於 1000℃-2 h 熱處理後粒徑相似之粉末進行介電常數量測。由實驗結果推測，鈦酸鋇粉末之介電常數應到受粉末之正方性與粉末之成分影響。由於 Ba/Ti 比 = 0.9985 之粉末其正方性較高，亦較接近計量比，故於常溫下之介電常數較高。
選擇粒徑相似之粉末經過造粒並加壓成型後，進行燒結測試並量測介電常數。由實驗結果推測，非計量比鈦酸鋇陶瓷體之介電常數應受起使粉之粒徑與燒結後之晶粒大小影響較為明顯，故 Ba/Ti 比 = 0.9837 之陶瓷體因晶粒分布均勻，故介電常數較高。

Barium titanate is a dielectric and ferroelectric material that used widely in electrical applications, including multilayer ceramics capacitors (MLCCs), PTCR thermistors, etc. Moreover, the microstructure, crystalline phase, Curie temperature and dielectric constant of barium titanate are affected easily by Ba/Ti ratio and particle size. In order to realize the effects of Ba/Ti ratio on BaTiO3 powder, high purity BaCO3 and TiO2 were used to synthesize non-stoichiometric BaTiO3 via solid state reaction, and tried different heating parameters to control the BaTiO3 powder with similar particle size in this study.
After analyzing the powder with similar particle size, the tetragonality decreases and the Curie temperature shifts to lower temperature when Ba/Ti ratio strays from 1. The dielectric constant of BaTiO3 powder is also measured in this study. The dielectric constant shows higher when Ba/Ti ratio is closed to stoichiometry.
The dielectric constant of bulk is measured. The dielectric constant of bulk with Ba/Ti ratio = 0.9837 is higher than each other just because that with grain size about 0.7 ~1 m, moreover, the distribution of grain size is quit homogeneous.

摘要....................................................................................................................................... I
Abstract............................................................................................................................. III
致謝.................................................................................................................................... IV
圖目錄................................................................................................................................VII
圖目錄................................................................................................................................VII
表目錄..................................................................................................................................X
第一章 緒論......................................................................................................................... 1
1-1 前言........................................................................................................................ 1
1-2 研究目的................................................................................................................ 1
第二章 前人文獻回顧及理論基礎..................................................................................... 3
2-1 鈦酸鋇晶體結構及性質........................................................................................ 3
2-2 鈦酸鋇的粒徑大小及表面效應........................................................................... 3
2-3 鋇鈦比的改變對鈦酸鋇性質之影響................................................................... 8
2-3-1 鋇鈦比對固溶極限之影響........................................................................ 8
2-3-2 鋇鈦比對居禮溫度及相轉換能量之影響.............................................. 13
2-4 拉曼光譜分析...................................................................................................... 19
2-4-1 拉曼光譜原理.......................................................................................... 19
2-4-2 拉曼光譜於鈦酸鋇之應用...................................................................... 19
2-5 鈦酸鋇之介電常數.............................................................................................. 24
2-5-1 晶粒大小對鈦酸鋇介電常數之影響...................................................... 24
2-5-2 鋇鈦比對鈦酸鋇陶瓷體介電常數之影響.............................................. 26
2-5-3 粒徑大小對鈦酸鋇介電常數之影響...................................................... 26
第三章 實驗方法與實驗步驟........................................................................................... 33
3-1 起始原料.............................................................................................................. 33
3-2 實驗方法及實驗流程.......................................................................................... 33
3-2-1 實驗方法.................................................................................................. 33
3-2-2 粉末製備.................................................................................................. 33
3-2-3 DTA/TGA 分析....................................................................................... 35
3-3-4 燒結體製備及燒結條件測試.................................................................. 35
3-3 材料分析.............................................................................................................. 38
3-3-1 粉末之定量分析...................................................................................... 38
3-3-2 相鑑定...................................................................................................... 38
3-3-3 晶格常數分析.......................................................................................... 42
3-3-4 掃描式電子顯微鏡.................................................................................. 42
3-3-5 粉末粒徑大小之計算及其分布.............................................................. 42
3-3-6 粉末比表面積分析.................................................................................. 43
3-3-7 拉曼光譜分析.......................................................................................... 43
3-3-8 穿透式電子顯微鏡.................................................................................. 43
3-3-9 補償式熱掃描卡量計.............................................................................. 45
3-3-10 燒結體密度量測.................................................................................... 45
3-3-11 燒結體顯微結構觀察............................................................................ 45
3-4 性質分析............................................................................................................... 45
3-4-1 粉末樣品準備與介電常數量測.............................................................. 45
3-4-2 陶瓷體樣品準備與介電常數量測.......................................................... 46
第四章 結果與討論........................................................................................................... 47
4-1 起始粉末之 DTA/TGA 分析............................................................................ 47
4-2 Ba/Ti 比之定量分析........................................................................................... 47
4-3 非計量比鈦酸鋇粉末之材料分析..................................................................... 47
4-3-1 結晶相分析.............................................................................................. 47
4-3-2 粒徑大小分析及計算.............................................................................. 52
4-3-3 相轉換溫度分析...................................................................................... 64
4-3-4 拉曼光譜分析.......................................................................................... 64
4-3-5 晶格常數計算.......................................................................................... 68
4-3-6 綜合討論.................................................................................................. 74
4-4 非計量比鈦酸鋇陶瓷體之微結構..................................................................... 77
4-5 鋇鈦比對鈦酸鋇介電常數之影響..................................................................... 77
4-5-1 鈦酸鋇陶瓷體之介電常數...................................................................... 77
4-5-2 鈦酸鋇粉末之介電常數.......................................................................... 82
第五章 結論....................................................................................................................... 85
第六章 未來研究方向與建議........................................................................................... 87
參考文獻............................................................................................................................. 88
附錄A................................................................................................................................ 91
附錄B ................................................................................................................................ 93
                                    

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