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| 研究生： |
薛志宗 Shiue, Jyh-Tzong |
|---|---|
| 論文名稱： |
氧化鈰添加鍶鋇鈮陶瓷的反應動力學、燒結行為及介電性質研究 The Reaction Kinetics, Sintering Behavior, and Dielectric Properties of Ceria-Doped Strontium Barium Niobate |
| 指導教授： |
方滄澤
Fang, Tsang-Tse |
| 學位類別： |
博士 Doctor |
| 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： | 2004 |
| 畢業學年度： | 92 |
| 語文別： | 中文 |
| 論文頁數： | 151 |
| 中文關鍵詞： | 氧化鈰 、鍶鋇鈮 、反應動力學 、燒結行為 、介電性質 |
| 外文關鍵詞： | dielectric properties, sintering behavior, reaction kinetic, ceria, strontium barium niobate |
| 相關次數： | 點閱：67 下載：1 |
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在所有電光材料中，鍶鋇鈮單晶具有最高的線性電光係數、高的焦電係數以及良好的光折射效應(photorefractive effect)。因此，鍶鋇鈮單晶的成長技術及其性質已廣泛被研究，且已有部分產品應用於工業上。但單晶在實際應用上仍然受形狀、大小、機械強度、價格等因素所限制，所以開發多晶鍶鋇鈮陶瓷乃必然的趨勢。本實驗室已使用反應燒結方法製備高密度的多晶鍶鋇鈮陶瓷。CeO2添加物可改善鍶鋇鈮的光學性質，因此欲以反應燒結方法製得鈰添加的鍶鋇鈮陶瓷，需先了解CeO2添加對於SBN的反應動力學、燒結行為及燒結緻密化控制機構等做探討，另外添加物對於其性質亦有很大的影響，故本研究亦討論CeO2添加對於SBN的介電性質的影響。
在反應動力學方面，以不同比例的SrNb2O6(SN)、BaNb2O6(BN)及CeO2來合成Sr0.5Ba0.5CexNb2O6+δ。首先以不同升溫速率探討不同CeO2添加量的SBN生成量與溫度的關係。以X光繞射定量分析反應生成量並計算其反應動力學。以非等溫的反應動力學方程式來推算不同CeO2添加量的SBN反應活化能（Q）、反應級數（n）及截距（A）。將非等溫動力學所求得的反應活化能（Q）、反應級數（n）及截距（A）代入等溫動力學方程式，發現所預測的在等溫下某一時間下的反應量與實驗結果相符合。
在燒結行為方面，以近乎相同的顆粒大小粉末之不同CeO2添加量的SBN粉末，探討其恆溫燒結行為，利用修正後的統計燒結理論模式來推算燒結活化能。隨著CeO2添加量的增加，其緻密化速率會降低，而活化能會增加。由晶格常數可以觀察到，隨著CeO2添加量的增加，c軸收縮而a軸膨脹。由Nb5+為擴散限制元素來推論，CeO2添加會產生額外氧離子佔據空的O(4)及O(5)位置的電荷補償缺陷。以EELS及XPS證實額外氧離子佔據空的O(4)及O(5)位置是Ce添加所產生的電荷補償缺陷。
在CeO2添加SBN的relaxor行為方面，未添加及已添加Ce3+之SBN的P-E曲線可以指數型random field model來描述。而且 random fields, the excess polarization和volume contribution of the excess polarization與Ce添加呈線性關係。再者Ce添加SBN的random fields center為Ce3+-O2- center。
Strontium barium niobate (SBN) ceramic is a good electro-optic material and has been widely used. Though the properties of the single-crystal SBN have been intensively studied, there are still some restrictions in their applications because of the small size, low mechanical strength, and high cost. Hence, it has been intrigued to develop the strontium barium niobate ceramic. Lee and Fang had used reaction sintering to obtain a high-density, and translucent pure SBN ceramic. Ceria dopant could improve the optical properties of SBN. So if we want to use reaction sintering to obtain ceria doped SBN ceramics, we must understand the effect of ceria dopant on the reaction kinetics, sintering behaviors and the densification mechanism of SBN. On the other hand, the dopant has a great influence on the properties of SBN. So in this study, we also discuss the effect of ceria dopant on the dielectric properties of SBN.
The reaction kinetics were analyzed by X-ray diffraction for quenched samples and the internal standard method was used to quantify the extent of the reaction. A non-isothermal kinetic empirical model was used to evaluate the activation energy, order of reaction, and rate constant of reaction for forming SBN with different ratio of ceria. We used the parameters, i.e., Q, A and n, to obtain the isothermal reaction kinetics equation and use this isothermal equation to predict the real reaction fraction.
The sintering behavior has been investigated. The morphological kinetics of sintering was used to evaluate the activation energy of sintering. The densification rate was decreased with the increase of the ceria dopants, and the activation energy of sintering was increased with the increase of the ceria dopants. From the activation energy of sintering and the lattice parameter, we suggest that the charge-compensating defect was the excessive oxygen ion occupying the empty O(4) and O(5) sites.
We use the P-E curve to study the polarization reversal of ceria-doped SBN. We found that the P-E curve of pure and Ce-doped SBN can be fitted to the power law of random field model. And the random fields, the excess polarization and the volume contribution of the excess polarization were increased with the increase of the ceria dopants. The random field source is the Ce3+-O2- center.
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