本研究探討Bi2O3-doped ZnO的活化燒結機制與其在束縛燒結下的緻密行為。透過摻雜1wt%的Bi2O3，可將ZnO的自由燒結緻密溫度從1200oC降到850oC，並將束縛燒結緻密溫度從1400 oC以上降到950 oC，使 ZnO可以在束縛燒結下達到緻密。摻雜的Bi2O3在晶界形成一富含Bi的晶界玻璃膜(Intergranular glassy film, IGF)結構，此晶界玻璃膜具有較低的晶界能，因此提高了熱力學上的燒結驅動力。透過分子動力學模擬，驗證此晶界玻璃膜可降低晶界能中的應變能部分，因此擁有較低的整體晶界能。另外，在動力學上，晶界玻璃膜可降低晶界移動的活化能，提高晶界遷移行為，因而大幅提升ZnO系統的緻密行為。
　　在束縛燒結下，摻雜Bi2O3造成Al2O3束縛層對ZnO產生的平面張應力下降。因此， 1 wt% Bi2O3-doped ZnO (BZ1)在束縛燒結下，擁有與自由燒結時相同的緻密機制以及等向性的微結構。而若由Z軸向施加壓應力提升束縛燒結下BZ1的緻密度，在750-950oC使束縛燒結下的BZ1具有與自由燒結相同的緻密速率所需之單軸向應力為200-1100 kPa，此結果與利用構成方程式(constitutive equations)的理論計算相符，亦驗證了微結構的等向性。

Effects of Bi2O3 on activated and constrained sintering of ZnO have been investigated. The densification temperature of ZnO is greatly reduced from 1200 oC for pure ZnO to 850 oC with the presence of 1 wt% Bi2O3 under free sintering. For the samples with 1 wt% Bi2O3, the constrained densification is slowed down, but a high sintered density of >95% at 950oC, which is close to those sintered freely, is still obtained. The above results are caused by the formation of Bi2O3-rich film at the grain boundaries, which reduces the grain boundary energy. The above results are also confirmed by the molecular dynamic simulation, at which the ratio of grain boundary energy of ZnO between with and without Bi2O3 is 0.62, consistent with that obtained experimentally, 0.69. Bi2O3-rich intergranular glassy film (IGF) lowers the tensile stress caused by constraining layers, resulting in an isotropic microstructure and unchanged densification mechanism under constrained sintering. With the presence of IGF, the polycrystalline Bi2O3-doped ZnO system can be densified under constrained sintering.

一、前言--------------------------------1
二、實驗方法----------------------------6
2.1試片製備-----------------------------6
2.2緻密度與收縮性質量測------------------7
2.3顯微結構觀察與統計分析----------------8
2.4兩面角分析---------------------------8
2.5模擬方法-----------------------------9
三、結果與討論---------------------------10
3.1活化燒結-----------------------------10
3.1.1添加Bi2O3對ZnO緻密行為的影響--------10
3.1.2顯微結構觀察-----------------------11
3.1.3燒結驅動力-------------------------11
3.1.4分子動力學模擬---------------------13
3.1.5晶粒成長動力學---------------------14
3.2束縛燒結-----------------------------15
3.2.1緻密行為---------------------------15
3.2.2平面張應力-------------------------16
3.2.3緻密機制分析-----------------------18
3.2.4晶粒方向分析-----------------------19
3.2.5外加應力---------------------------20
3.2.6燒結行為分析------------------------21
四、結論--------------------------------25
五、參考文獻-----------------------------26

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