臺灣博碩士論文加值系統

摘 要
為降低BaTiO3(BT)之燒結溫度，本研究用兩相混燒法將低熔點(930℃)之Pb(Fe2/3W1/3)O3(PFW)弛緩體(Relaxor)介電材料添加至BT中，製備可低溫燒結結之xBT-(1-x)PFW介電材料。PFW的添加可降低系統之燒結溫度，其燒結的機制可分為兩個階段，在750℃~850℃範圍胚體之燒結收縮由低熔點之PFW與二次相BaWO4所貢獻，而在1050℃由於非化學計量PFW有液相生成，造成胚體在900℃~1050℃階段有燒結收縮反應。
x=0.2、0.5樣品產生的非化學計量PFW在1050℃附近形成液相，並且在樣品晶粒間形成潤溼，促使各晶粒產生重排來形成液相燒結效果，此一液相生成溫度隨著PFW與BT的擴散程度增加而提升。
xBT-(1-x)PFW各組成樣品之電性表現深受二次相BaWO4與BaFe12O19影響，介電常數隨BaWO4相形成量的增加而降低。增進電性可調整之因素有PFW含量(50wt﹪)、快速的升溫速率(15℃/min)、短暫持溫燒結(30min)與BT與PFW晶粒接觸面積。過量的PFW與緩慢的升溫速率會使系統易生成低介電常數的BaWO4相。短時間的持溫燒結樣品可在低溫(930℃)燒成且BaWO4相形成量較少，但因保有較大量的PFW使得介電損較高，而長時間的燒結會因BaFe12O19相的晶粒成長而使樣品介電損隨之提高。
x=0.5樣品以快速升溫速率(15℃/min)、短暫持溫燒結(30min)並減少PFW與BT晶粒的接觸面積燒成下，在930℃即可燒結並能有效減少BaWO4二次相晶粒的成長，如此可獲得1670的介電常數，為理論計算值的84﹪，其中之差異可視為無法完全避免BaWO4與BaFe12O19二次相之形成與燒結體並非完全無孔隙存在有關。

Abstract
In order to decrease the firing temperature of Barium Titanate (BaTiO3, BT), low-melting(930℃) point Lead Iron Tungstate (Pb(Fe2/3W1/3)O3, PFW) relaxor has used as sintering aid. Lead Iron Tungstate has high dielectric constant and diffuse phase transform characteristics. Binary system in composition of xBT-(1-x)PFW (x =wt﹪) was prepared by mixed-oxides or BT-PFW mixed phases methods.
BaWO4 and BaFe12O19 phases were observed in the samples prepared by mixed-oxides or mix-phases processes when the samples were heat-treated at 500℃ for 2hours. Electrical and physical properties of BT-PFW ceramics were affected by the formation of BaWO4 and BaFe12O19 phases. Dielectric constants of BT-PFWs were in the range of 500s, since the dielectric constant of BaWO4 was as low as 8.
Two shrinkage stages were observed from the xBT-(1-x)PFW samples with x=0.2、0.5. The first shrinkage stage was considered as low-firing temperature PFW and BaWO4 phases reacting at 750℃-850℃. The second shrinkage was due to the formation of non-stoichimetric PFW liquid at 1050℃. BT particles were wetted by PFW liquid. Due to particle rearrangement, the BT-PFW samples shrunk at this temperature.
Dielectric properties of xBT-(1-x)PFW are dependent on grain size and amount of second phases BaWO4 and BaFe12O19 formed. Dielectric constant increased by the conditions of exact PFW(x=0.5) content, rapid heating rate(15℃/min), short dwelling time(30min), it reduced the contact area between BT and PFW grain and decreased the amount of second phases. Samples prepared by those conditions and sintered at 930℃, had dielectric constant of 1670. Influences from second phases and pores were not completely excluded in this research.

目錄
中文摘要 I
英文摘要 III
致謝 IV
目錄 V
圖目錄 VIII
表目錄 XI
附圖目錄 XII
第一章 緒論 1
1-1. 前言 1
1-2. 研究動機及目的 4
1-3. 研究目標 4
第二章 前人相關研究與理論基礎 5
2-1.鈦酸鋇結晶結構及介電特性 5
2-1-1.介電損 7
2-2.鈦酸鋇相關研究 8
2-2-1.降低燒結溫度系統 8
2-2-2.溫度補償效應系統 9
2-2-3.NPO系統 9
2-3.弛緩體相關研究 10
2-3-1.PFW系統 10
2-3-2.降低燒結溫度系統 11
2-3-3居禮溫度位移劑系統 12
2-4.BT與弛緩體相關研究 13
2-5.兩相混燒法(Mixed-Sintering ) 25
2-6.孔洞對介電性質影響 14
2-7.假設第二相均勻散佈在連續相 14
2-8.液相燒結 16
第三章 實驗步驟及方法 19
3-1.PFW粉末製備 19
3-2.兩相混燒製備xBT-(1-x)PFW 19
3-2-1.氧化物合成法 20
3-2-2.BT晶粒大小對二次相與電性之影響 20
3-3.特性分析 20
3-3-1.物性量測 21
3-3-2.電性量測 21
3-3-3.結晶構造分析 21
3-3-4.掃瞄式電子顯微鏡分析 21
3-3-5.熱差分析 21
3-3-6.穿透式電子顯微鏡分析 22
第四章 結果與討論 27
4-1.PFW粉末製備 27
4-2.兩相混燒法與氧化物合成法樣品特性分析 28
4-2-1.兩相混燒法 28
4-2-2.兩相混燒法與氧化物合成法樣品燒結收縮率比較 31
4-2-3.兩相混燒法與氧化物合成法樣品介電常數比較 32
4-2-4.兩相混燒法與氧化物合成法樣品結晶構造分析與微觀組織比較 35
4-3.兩相混燒法樣品燒結行為分析 42
4-3-1.BaWO4與BaFe12O19二次相之形成溫度確定 42
4-3-2. BaWO4與BaFe12O19相的形成及其對xBT-(1-x)PFW燒結的影響 44
4-4.兩相混燒法樣品製備參數對二次相與電性之影響 46
4-4-1.PFW含量對二次相之影響 46
4-4-2.燒結升溫速率對二次相與電性之影響 49
4-4-3.燒結持溫時間對二次相與電性之影響 53
4-4-4.燒結溫度對二次相與電性之影響 57
4-5.BT晶粒粒徑對二次相與電性之影響 61
第五章 結論 66
參考文獻 67
附錄 70

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