臺灣博碩士論文加值系統

本研究是以鈣鈦礦結構之NaNbO3材料為主探討對象，並以雙異價數LaCrO3及BiCrO3離子來取代NaNbO3基材，製備成(1-x)NaNbO3-xACrO3 (A=La、Bi)之價數補償型鈣鈦礦陶瓷體。本研究主要由三個部份所構成：（1）以反應燒結法製備NaNbO3介電陶瓷，（2）以固態反應法合成Na1-xLaxNb1-xCrxO3及其介電性質研究，（3）以固態反應法合成(1-x)NaNbO3-xBiCrO3雙相陶瓷及其介電性質研究。
本研究成功的以反應燒結法合成NaNbO3之緻密鈣鈦礦陶瓷。塊體在混合NaNbO3劑量比的原料直接壓胚且無煆燒步驟進行燒結，得單一NaNbO3鈣鈦礦相陶瓷在溫度1100-1200 ℃間。在1200 ℃燒結6小時後約22.9 %的高線收縮率及1.6 %的低開孔率，且約有95.4 %的理論密度。NaNbO3陶瓷不同燒結條件的電性質，在1170 ℃燒結可得最高介電常數約27，在高溫度下燒結漸漸變成高電阻的絕緣體。NaNbO3陶瓷分別在3和6小時的持溫，得到微米尺度的晶粒成長活化能約在87~90 kJ/mol (或5.4~5.7×1021 eV/mol)。當在1200 ℃燒結3小時下，可得之斜方形外觀(rhomb-shaped)晶粒具有清析可辨的邊線和平面，此結果接近於理想晶粒成長模型。
以固態反應法合成(1-x)NaNbO3-xACrO3 (A=La、Bi)之價數補償型鈣鈦礦電子陶瓷。Na1-xLaxNb1-xCrxO3 (0.01≦x≦0.4)的鈣鈦礦固溶體，當x�d0.05時由原來的斜方晶結構(orthorhombic)往立方晶結構(cubic)轉變，以離子半徑較大的La+3(1.32 Å)取代離子半徑較小的Na+1 (1.18 Å)，因離子半徑效應之故，造成晶格常數上升。根據Arrhenius方程式所得之NLNC弛緩體陶瓷相對於組成x=0.2, 0.3和0.4時在介電弛緩過程所需的活化能分別為0.22, 0.21和0.19 eV，而偶極弛緩時間約10-11秒。根據阻抗分析量測，NLNC之介電陶瓷是由半導體的晶粒與高電阻晶界所組成的晶界層電容。據XRD分析此(1-x)NaNbO3-xBiCrO3之結構陶瓷在1250 ℃持溫3小時，顯示具有立方鈣鈦礦與焦綠石相混合結構，焦綠石含量則隨著x的增加而呈線性增加。1-x)NaNbO3-xBiCrO3之介電特性(在x＝0.3具有似模糊相轉換(diffuse-like phase transition)的陶瓷，當量測頻率由0.5 kHz上升到100 kHz，發生最高介電常數(�掭ax)之溫度值隨著頻率變化約固定在63 ℃，從Cole-Cole阻抗分析結果顯示為晶界型電容。介電特性在x＝0.4具有明顯遲緩體(relaxor-like)的現象，介電常數最高值(�掭ax)在頻率0.5, 1, 5, 10,和100 kHz時的溫度位置分別為55, 59, 67, 80和84 ℃，具有環保無鉛遲緩體的陶瓷潛在應用。

The present investigation focused on the NaNbO3, which has an perovskite structure. The perovskite ceramic NaNbO3 powders doped with double valence compensated LaCrO3 and BiCrO3 ions were synthesized. The experimentation consists three parts as： NaNbO3 oxides prepared using reaction-sintering method, Na1-xLaxNb1-xCrxO3 and (1-x)NaNbO3-xBiCrO3 characterized by solid state reaction.
The NaNbO3 perovskite dense ceramic has been successful synthesized by reaction-sintering method. The raw materials for stoichiometric NaNbO3 were weighted and pressed into disks. Without any calcining involved, the pellets were sintered directly and pure perovskite NaNbO3 was obtained between 1100 ℃ and 1200 ℃. The maximum linear shrinkage and minimum porosity of the NaNbO3 was 22.9 % and 1.6 % at 1200 ℃, respectively, and thus had high density about 95.4 % of the theoretical value. The dielectric properties of NaNbO3 ceramics sintered at 1170 ℃has a maximum about 27. In this study, the NaNbO3 ceramics became more insulating at higher sintering temperature. The activation energy of grain growth for 3 and 6 h were between 87~90 kJ/mol (or 5.4~5.7×1021 eV/mol) , respectively. The realistic rhomb-shaped grains in pellets were found with well-defined edges and face, which are similar to the ideal grain growth models at the temperature of 1200 ℃ for 3 h.
The valence compensated perovskite ceramics (1-x)NaNbO3-xACrO3 (A=La、Bi) was synthesized by solid-state reaction. The solid solution perovskite Na1-xLaxNb1-xCrxO3 (0.01 ≦ x≦ 0.4) system has the orthorhombic phase, and slowly transform to the cubic phase when x�d 0.05. These results can be arise to come from the substitution of La3+ (1.32 Å) ions for Na+(1.18 Å), which increased lattice constants. According to the Arrhenius relationship, NLNC relaxor ceramic with activation energy for relaxation process for x= 0.2, 0.3, and 0.4 were 0.22, 0.21, and 0.19 eV, respectively. The values of relaxation time constants were of the order 10-11 s. The impedance of the NLNC dielectric ceramics showed grain boundary capacitors effect with semiconducting grain and high resistivities in the grain boundary layers.
The crystal structures of the samples (1-x)NaNbO3-xBiCrO3 sintered at 1250 ℃ for 3 h were characterized as cubic perovskite-pyrochlore mixed phase from XRD patterns. The relative amounts of pyrochlore increased linearly with x content. The dielectric relaxation behavior for sample x= 0.3 involves a diffuse-like phase transition. The peak of �掭ax is fixed approximately at 63 ℃ as the frequency increased from 0.5 to 100 kHz. The complex impedance was used to verify the presence of grain boundary capacitors. The sample with x= 0.4 exhibited the relaxor-like phenomenon. The temperatures corresponding the �掭ax at frequencies 0.5, 1, 5, 10 and 100 kHz are 55, 59, 67, 80 and 84 ℃, respectively.

摘要……………………………………………………………………….I
Abstract……………………………………………………………………...III
目錄……………………………………………………………………………V
表目錄………………………………………………………………………VIII
圖目錄………………………………………………………………………IX
第一章 諸論.......................................................................................................1
1-1. 前言…………………………………………………….......…………..1
1-2. A+1B+5O3鈣鈦礦材料………………………………………………….2
1-3. 研究動機……………………………………………………………….3
1-4. 研究目的……………………………………………………………….4
第二章 基礎理論………………………………………….…………………..8
2-1 介電理論……………….……………………………………………….8
2-1-1. 介電特性…………………………………………………………..8
2-1-2. 極化機構………………………………………………………..…8
2-1-3. 介電損失……………………………………………………....…10
2-2 複合型鈣鈦礦之結構與特性………………………………………..11
2-2-1. 結構置換作用…………………………………..…………..……11
2-2-2. 異價取代與缺陷化學式…………………………………..…......12
2-2-3. 拉曼光譜鑑定…………………………..………………………..13
2-2-4. 弛緩性質……………………....…………………………………15
2-2-5. 擴散性相變………………………………………………………16
2-3 能障型電容…………...…………………………….………………...17
2-4 阻抗分析原理…………………………………………………………19
2-5 反應燒結法…….………….…………………………………………..23
2-5-1 反應燒機構………………………..…...………………………..23
2-6 固態反應法….………...…………………..………………………...24
2-6-1 固態反應機構…………………..……………………………….24
2-6-2 固態反應法之優缺點…..……..………………………………...25
2-7 固態燒結過程及理論…………..…………………………………...26
2-7-1 燒結的基本原理及機構…………..…………………………….26
2-7-2 幾何形狀的考量…………………..…………………………….26
2-7-3 粉末顆粒大小分布對燒結行為及顯微結構的影響……..…….27
2-8 晶粒成長…………..………………………………………………...28
2-8-1 晶粒成長的發生及驅動力……………..……………………….28
2-8-2 晶粒成長的類型…………………..…………………………….28
2-8-3 在緻密固體中正常晶粒成長之模式…………………..……….29

第三章 實驗方法……………………………………………….……………45
3-1 實驗藥品……………………………………………………….………45
3-2 反應燒結法……………………………………………………….……45
3-3 固態反應法……………………………………………………………46
3-4 晶粒大小………………………………………..……………………46
3-5. 收縮率、孔隙率、密度量測………………….………..……………..46
3-6. 結構與成份分析……………………………………….…….………..47
3-6-1. X光繞射分析……..………………………………………………47
3-6-2. 掃瞄式電子顯微鏡分析……………..……………………..………49
3-6-3. ..X-光光電子能譜儀(XPS)分析……...…..…………………………50
3-6-4. 拉曼光譜(Raman)分析…..……..………..…………………………50
3-7. 性質量測………………………..……………………………………..50
3-7-1. 介電性質量測……………………………………………………..50
3-7-2. 阻抗分析量測……………………………………………………..51
3-7-3. 電阻率量測………………………………………………………..51
第四章 結果與討論………………………….………………………………55
4-1. 以反應燒結法製備NaNbO3介電陶瓷….…………………………..55
4-1-1. NaNbO3燒結體之微結構分析…………..……………………55
4-1-2. 燒結密度和電性分析…………………..…………………...57
4-1-3. 晶粒成長活化能與成長機構分析…….………..………....58
4-1-4. 結語……………………………………………………………59
4-2. 固態反應法合成Na1-xLaxNb1-xCrxO3及其介電性質研究……….…...70
4-2-1. Na1-xLaxNb1-xCrxO3之晶體結構………………………...………….70
4-2-2. SEM表面微結構分析………………..……….…………………….72
4-2-3. 介電性質分析……………………………………………………….73
4-2-4. 阻抗分析量測……………………………………………………….78
4-2-5. 結語………………………………………………………………….79
4-3. (1-x)NaNbO3-xBiCrO3雙相陶瓷及其介電性質研究…….......………94
4-3-1. 在x=0.5時(NaBi)(NbCr)O6焦綠石相之結構及介電性質分..94
4-3-1-1 (NaBi)(NbCr)O6之結晶與微結構.....................94
4-3-1-2 介電性質…………………………………………………..96
4-3-1-3 電導行為..............................................................................96
4-3-1-4 結語………………………………………………………..97
4-3-2 固態反應法製備(1-x)NaNbO3-xBiCrO3雙相陶瓷…..…….105
4-3-2-1 結晶與微結構行為………………………………...…..…105
4-3-2-2 介電性質分析…………...………………………………..107
4-3-2-3 拉曼光譜分析.....................................................................109
4-3-2-4結語…………………………………………...……………111
4-4. 綜合討論…………………………………………………….……...123
第五章 結論………………………………………………………………..125
第六章 研究展望與建議…………………………………………………..127
參考文獻.…………………………………………………………………...128
附錄A 以 GSAS-Rietveld 法擬合 XRD 粉末繞數圖譜之結果………136

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