在鈦酸鋇陶瓷的研究領域中，常常探討其引響成長的機制原因，不管是在不同溫度、時間、氧分壓、添加不純物等，都會使其產生晶粒成長或抑制的效果，在最近的研究中，常討論到異常的晶粒成長(AGG or EGG)對於鈦酸鋇晶粒造成的影響，而造成此一影響的因素為添加的不純物，雖然有些不純物會抑制其異常晶粒的成長，但卻也有人發現添加了某些不純物在鈦酸鋇表面時，會使得異常晶粒成長的效應非常明顯，甚至可以用此種方法長出鈦酸鋇單晶，而為了了解添加物在成長中所扮演的關鍵角色，本次的研究將探討在添加不同成分的不純物，在一大氣壓下(PO2=0.21 atm)，且溫度高於共晶溫度(Te=1332 oC)燒結，對於鈦酸鋇試片的微結構產生何種影響，以及異常晶粒成長是否可在此研究中被發現。

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目錄..........................................................................................................Ⅰ
圖目錄 ....................................................................................................Ⅲ
表目錄 ………….......VII
第 1 章 前言..........................................................................................1
第 2 章 文獻回顧..................................................................................3
2.1 鈣鈦礦陶瓷結構與特性...........................................................3
2.2 碳酸鋇結晶結構.......................................................................6
2.3正方體(tetragonal)鈦酸鋇結構................................................10
2.4 BaO-TiO2系統之相平衡圖燒結驅動力.................................12
2.5 Ba6Ti17O40..............................................................................16
2.6燒結驅動力...............................................................................16
2.7雙晶面邊界(TPRE) ..................................................................17
2.8液相形成(the liquid form) ........................................................19
2.9面間夾角(dihedral angle) .........................................................20
2.10主要異常晶粒成長PAGG (primary abnormal grain growth) 和二次異常晶粒成長SAGG (secondary abnormal grain growth)
………………………………………………………………..21
第 3 章 實驗步驟.................................................................................23
3.1 BaTiO3粉未.............................................................................23
3.2 BaTiO3試片的製備.................................................................25
3.3 微結構觀察和分析..................................................................28
3.3.1 x-ray繞射分析.................................................................29
3.3.2 光學顯微鏡(OM)............................................................29
3.3.3 掃瞄式電子顯微鏡(SEM)..............................................30
3.3.4 穿透式電子顯微鏡(TEM)..............................................30
3.3.4.1 試片的準備(Thin foil preparation).........................31
第 4 章 實驗結果..................................................................................33
4.1 X-ray繞射分析..........................................................................33
4.2光學顯微鏡觀察........................................................................35
4.3掃描式電子顯微鏡觀察添加Al2O3的試片...........................41
4.4掃描式電子顯微鏡觀察添加SiO2的試片..............................45
4.5掃描式電子顯微鏡觀察未添加的試片....................................49
4.6掃描式電子顯微鏡觀察夾層試片............................................52
4.7穿透式電子顯微鏡觀察添加Al2O3的試片.............................57
4.8穿透式電子顯微鏡觀察夾層的試片........................................66
第 5 章 實驗結果討論..........................................................................69
5.1 SEM橫切面觀察添加Al2O3的分析......................................69
5.2 SEM橫切面觀察添加SiO2的分析.........................................69
5.3 TEM觀察添加Al2O3的分析..................................................70
5.4夾層試片的分析……………………………………………….71
5.5 OM的種晶試片分析………………………………………….71
第 6 章未來工作....................................................................................72
參考文獻(reference)................................................................................74
附錄 (appendix)......................................................................................79
附錄1 實驗中所研究結構於JCPDS-ICDD卡之相對資料........79
附錄2 型號3010 AEM之量測規格...............................................83
附錄3 正方相鈦酸鋇結構由[001]方向上所得立體投影圖….....84
附錄4 正方相鈦酸鋇結構之標準Kikuchi電子繞射圖...............85
附錄5 藉由電腦模擬所得標準繞射電子圖..................................86

圖目錄
圖 2.1.1 立方體鈦酸鋇結構(a) A-type和(b) B-type單胞….................4
圖2.1.2 A-type單胞藉由添加不同原子於DO9和B2兩種晶體中，而 形成立方體鈣鈦礦結(E21)......................................................5
圖2.1.3 B-type單胞藉由添加不同原子於L12晶體中，而形成立方體鈣鈦礦結(E21)..............................................................................6
圖2.2.1 鈦酸鋇結構中八面體之TiO6原子間相對位移的形…............7
圖2.2.2 晶格參數大小隨溫度改變而改變.............................................8
圖2.2.3 介電常數隨溫度變化而變化....................................................8
圖2.2.4 鈦酸鋇晶格常數與相轉換順序................................................9
圖2.3正方體結構 : (a)晶體單胞(b)在100面上、(c)在110和(d)在111面上原子排列情.........................................................................11
圖2.4 BaO和TiO2系統相圖(a) Rase et al. 1955[11], (b) O'Bryan et al. 1974[2], (c) Negas et al. 1974[12], (d) Ritter et al. 1986 and[13][15], (e) Kirby-Wechsler, 1991[14].............................................................12
圖2.7晶核於雙晶邊界(TPRE)上成長情形..........................................19
圖2.9.1 固相-固相-液相平衡的平面夾角............................................20
圖2.9.2 二次相在不同的平面角度分佈情形......................................21
圖2.10示意圖(a) singular, (b) vicinal or stepped, (c) rough表面........22
圖3.3 實驗的製作流程圖.....................................................................26
圖3.4夾層試片壓製的方法..................................................................27
圖3.5夾層試片的製作及分析流程圖..................................................27
圖3.6 SEM 種晶(111)的微結構分布....................................................28
圖4.1.1 初始粉體和在空氣下燒結X-ray繞射圖...............................34
圖4.1.2 添加0.1 mol% Al2O3 1350oC 8小時的鈦酸鋇試片X-ray繞射圖.............................................................................................34
圖4.2.1 添加0.1 mol% Al2O3 1350oC燒結8小時後的鈦酸鋇試片橫切面..........................................................................................35
圖4.2.2 添加1 mol% SiO2 1350oC燒結8小時後的鈦酸鋇試片橫切面..............................................................................................36
圖4.2.3夾層試片經1000oC燒結20h後再以1400oC燒結的橫切面.37
圖4.2.4 (a) upper, (b) middle 和 (c) lower較高倍率的微結構分佈…39
圖4.2.5在TiO2過量的鈦酸鋇試片表面添加5 wt% seed grain 1000oC燒結20h後再以1400oC燒結的橫切面................................40
圖4.3.1 (a)SEI (b)BEI coating 0.1 mol% Al2O3 1350oC for 8 h............42
圖4.3.2 (a)、(b) SEM-SEI玻璃相在試片的上表面晶界均勻分佈情形(c)SEM-BEI玻璃相沿晶界分佈1350oC for 2 h.....................44
圖4.3.3 (a) SEM-SEI (b)SEM-BEI在試片中間區域的觀察；(c) SEM-SEI (d)SEM-BEI在試片底部區域的觀察1350oC for 8 h................................................................................................45
圖4.4.1 (a)SEI (b)BEI coating 1 mol% SiO2 1350oC for 8 h.................47
圖4.4.2 (a)、(b)SEM-SEI試片的上表面分佈情形..............................48
圖4.4.3 (a) SEM-SEI (b)SEM-BEI在試片中間區域的觀察；(c) SEM-SEI (d)SEM-BEI在試片底部區域的觀察....................48
圖4.5.1 (a)SEM-SEI (b)SEM-BEI at 1350oC for 8 h..............................50
圖4.5.2 (a)、(b) SEM-SEI試片的上表面分佈情形..............................51
圖4.6.1 (a)SEM-SEI (b)SEM-BEI at 1000oC for 20 h 1400oC for 1 h....52
圖4.6.2 (a) SEM-SEI、(b)SEM-BEI試片的上層分佈情形..................53
圖4.6.3 (a) SEM-SEI、(b)SEM-SEI、(c)SEM-BEI試片的中層分佈情形..............................................................................................55
圖4.6.4 (a) SEM-SEI、(b)SEM-BEI試片的下層分佈情形..................56
圖4.7.1 低倍率下BT-B6T17界面的觀察.............................................57
圖4.7.2 高倍率下BT-B6T17界面的觀察.............................................58
圖4.7.3 BT-amorphous-BT界面的觀察..................................................59
圖4.7.4 B6T17-amorphous-B6T17 界面的觀察........................................59
圖4.7.5 BT-unknown phase-BT界面的觀察...........................................60
圖4.7.6 unknown phase在高倍率下的觀察...........................................61
圖4.7.7 TEM-EDS定性分析量測在不同鈦酸鋇晶粒的點...................61
圖4.7.8 TEM-EDS在a點的定性分析...................................................62
圖4.7.9 TEM-EDS在b點的定性分析...................................................62
圖4.7.10 TEM-EDS在c點的定性分析.................................................63
圖4.7.11 TEM-EDS在d點的定性分析.................................................63
圖4.7.12 鈦酸鋇晶粒和母相顆粒間的分佈觀察..................................64
圖4.7.13 鈦酸鋇晶粒分佈情形..............................................................64
圖4.8.1. SAGG的晶界處分布情形........................................................66
圖4.8.2. 小顆粒鈦酸鋇分布情形..........................................................67
圖4.8.3. SAGG的晶界處分布情形........................................................67
圖4.8.4. SAG界面處的faceting現象..................................................68
圖4.8.5. SAG和amorphous界面.........................................................68
表目錄
表2-1 鈦酸鋇正方體結構之原子位置和原子半徑..............................10
表2-2 BaO和TiO2相平衡圖中，不同鋇鈦莫耳數比之相對組成結構..................................................................................................12
表3-1 BaTiO3粉未的特性............……………………………………..23
表3-2 0.9894鈦酸鋇粉未的特性....……………………………………24
表3-3 1.0007鈦酸鋇粉未的特性....……………………………………24

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