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研究生:賴佳芸
研究生(外文):Jia-yun Lai
論文名稱:氧化釔粉末粒徑對YAG生成活化能之影響
論文名稱(外文):The size effect of Y2O3 on the YAG formation activation energy
指導教授:顏富士顏富士引用關係
指導教授(外文):Fu-su Yen
學位類別:碩士
校院名稱:國立成功大學
系所名稱:資源工程學系碩博士班
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:67
中文關鍵詞:釔鋁石榴石活化能
外文關鍵詞:activation energyYAG
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以往使用微米級Al2O3+Y2O3原料粉末,以固態反應法製備YAG (Y3Al5O12)粉末的過程中,一般歸咎於粉末的合成受限於成分的擴散距離,使煅燒溫度需至1600℃始可得單相YAG,而藉由降低起始反應物之粒徑,使反應物表面積增加,可提高反應物彼此接觸點,促使反應發生,降低活化能,因此原料粉末的尺寸必為合成材料的一項重要因素。然以不同粒徑之原料粉末合成YAG的系統研究尚未被提出,本研究以改變原料粉末之粒徑,觀察其對YAG生成過程的影響。實驗擬使用三種不同粒徑:100 nm (S),400 nm (M),700 nm (L)之氧化釔(Y2O3),分別與固定粒徑(150 nm)之氧化鋁(α-Al2O3)混合為起始粉末,並分別以從室溫升溫與直接置入高溫之快速升溫兩種方式進行煅燒,之後觀察比較YAG合成過程的差異,並計算三系統之YAG生成活化能。實驗結果得知,隨氧化釔粒徑變小,YAM、YAP及YAG之合成溫度亦隨之降低;由定量分析結果並配合YAG生成活化能計算結果可發現,YAG 之生成於不同溫度範圍有不同來源:< 1150℃主要為氧化釔與氧化鋁直接成YAG,生成活化能約100 kJ/mol,為介面控制(Interface control)生成機制;1150-1200℃為YAM及YAP轉換而來,活化能約400 kJ/mol,為擴散控制(Diffusion control)生成機制;> 1200℃則為YAP的轉換或剩餘大粒子之氧化釔反應而來,此部分之活化能於本實驗中不易觀察故無法得知。另外本實驗亦發現使用奈米級起始粉末合成YAG,YAM、YAP、YAG三相均可於快速置入高溫熱處理後瞬間合成,其中生成速率與消失速率均以YAM為最快。
Due to micron-scaled Al2O3+Y2O3 starting powders for synthesizing YAG (Y3Al5O12) powder using via solid state reaction, the temperature for pure YAG formation usually performed above 1600℃. Lowering the particle sizes of reactants could raise contact points, so as to promote the reaction to occur. Therefore, the size of starting powders must be one of crucial factors for material synthesis. However, a systematic research on YAG formation by using different size of starting powders has not be done so far. In this study, the difference in the process of YAG formation caused by reactant particle sizes was observed. The starting powders were mixed respectively from α-Al2O3 (150 nm) and Y2O3 with three different sizes ( 100 nm (S), 400 nm (M), and 700 nm (L)) , then calcined by two ways:(1) treating with a heating rate of 10℃/min from R.T to specific temperatures and (2) placing in high temperatures rapidly. After heat treatment, the comparison of YAG formation processes occurred in three systems was made and YAG formation activation energies (Ea) for three systems were calculated by the isothermal kinetics.
The results are showed as following. The smaller the size of Y2O3 was, the lower temperatures of YAM, YAP and YAG phases formed. Three mechanisms should be existed in three different temperature ranges in the process of YAG formation. (1) Below 1150℃, YAG was formed from reaction between Al2O3 and Y2O3 directly, and the Ea of YAG formation was about 100 kJ/mol caused by interface-control mechanism; (2) between 1150-1200℃, YAG was formed from YAM or YAP reacted with Al2O3, and the Ea of YAG formation was about 400 kJ/mol attributed to diffusion-control mechanism; (3) above 1200℃, YAG was transformed from YAP or the residual Y2O3 reacted with Al2O3, and the mechanism was difficult to be observed in this study. The YAG, YAM, and YAP could be synthesized instantaneously as the samples were subjected to high temperatures rapidly, while nano-scaled powders were used as starting materials. Among these phase, YAM showed the fastest formation rate and disappearing rate.
摘要 Ⅰ
Abstract Ⅱ
圖目錄 Ⅶ
表目錄 Ⅸ

第一章 緒論
1.1 前言 1
1.2 研究動機 2
1.3 研究目的 3
第二章 理論基礎與前人研究
2.1 釔鋁石榴石 4
� � 2.1.1釔鋁石榴石的基本性質 4
2.1.2 釔鋁石榴石的過渡相 4
2.2 釔鋁石榴石製備方法 8
2.2.1 固態反應法(Solid-state reaction) 8
2.2.2 濕化學法(Wet chemical method) 8
2.2.3 比較 9
2.3 反應活化能 11
2.3.1 相轉換動力學 11
� � 2.3.2 相轉換反應速率式 11
� � 2.3.3 反應物粒徑與反應速率 11
2.4 YAG的生成活化能研究 12
2.4.1 影響活化能的因素 12
� � 2.4.2 不同製備方法之活化能比較 15
第三章 研究方法與步驟
3.1熱處理相生成與Y2O3粒徑關係 16
3.1.1實驗原料 16
3.1.2實驗設計 16
3.1.3實驗流程 16
3.2利用快速升溫求YAG生成活化能 20
3.2.1 活化能求法 20
3.2.3 樣品製作 21
3.2.3 熱處理 21
3.3 特性分析 21
3.3.1 比表面積測定(Specific Surface Area) 21
3.3.2 顯微結構分析與觀察( Microstructure Analysis) 22
3.3.3 熱差分析( Differential Thermal Analysis) 22
� 3.3.4 粉末結晶相分析( Phase Identification) 22
3.3.5 結晶相生成量定量分析 22
第四章 結果與討論
4.1熱分析 25
4.2由室溫升溫至特定溫度的熱反應 25
4.3 快速升溫 34
� 4.3.1生成相 34
� 4.3.2 YAG生成活化能比較 34
第五章 結論 45
參考文獻 46
Appendices 51

圖目錄
Fig. 2.1 Phase diagram for Y2O3-Al2O3 system 5
Fig. 2.2 YAG structure and it’s typical material properties 6
Fig. 2.3 Garnet crystals 7
Fig. 3.1 SEM images of (a) α-Al2O3;(b) S-Y2O3;(c) M-Y2O3;(d) L-Y2O3
. ... 17
Fig. 3.2 Particle size distribution of (a) Y2O3;(b) α-Al2O3 particles in powder systems . 18
Fig. 3.3 The flow chart of (a) Y2O3;(b) α-Al2O3 slurry preparation in this study .19
Fig. 3.4 The flow chart of sample preparation in this study ... 23
Fig. 3.5 Calibration lines for yttrium aluminum compounds established by internal standard methods. ……24
Fig. 4.1 Differential thermal analysis profiles of three different starting powders with a heating rate of 10℃/min in air ..29
Fig. 4.2 Differential thermal analysis profiles of starting powders (a) S (b) M (c)L-system with the heating rate of 10℃/min in air and the corresponding quenched samples showing the phase presence at the specific temperature. ……30
Fig. 4.3 The formation change of the (a) YAM (b)YAP and (c) YAG clacined at different temperatures. ……32
Fig. 4.4 Schematic of the starting powder of different systems. ...….33
Fig. 4.5 YAM and YAP formation of (a) S (b) M and (c) L-system calcined at different temperatures for various durations. 36
Fig. 4.6 YAG formation of (a) S (b) M and (c) L-system calcined at different temperatures for various durations.. 37
Fig. 4.7 Plot of ln〔-ln (1-y)〕vs. lnt for isothermal crystallization of YAG. (a) S (b) M and (c) L-system calcined at different temperature for various durations... 39
Fig. 4.8 Activation energies of YAG formation obtained from the Arrhenius plot.. 40
Fig. 4.9 Plot of ln〔-ln (1-y)〕vs. lnt for isothermal crystallization of YAG. (a) M (b) L-system calcined at different temperatures for various durations...........42
Fig. 4.10 Activation energies of YAG formation obtained from the Arrhenius plot.. 43
Fig. 4.11 Particle size distribution of Y2O3 particles in powder systems. 44















表目錄
Table 2.1 Comparison of solid-state and wet-chemical synthesis of YAG 10
Table 2.2 Existing temperature ranges of yttrium aluminum compounds during YAG formation reported in previous solid state reaction studies. 14
Table 2.3 The activation energies of YAG formations derived from isothermal methods 15
Table 3.1 Specific surface area of starting materials and corresponding particle
sizes are tabulated. 17
Table 4.1 The evolution of phase showed in calcined samples with 10℃/min heating rate during elevated temperature... 31
Table 4.2 The evolution of phase showed in calcined samples with rapid heating rate during elevated temperature... 38
Table 4.3 Kinetic data calculated of lower YAG formation for three systems. 41
Table 4.4 Kinetic data calculated of higher YAG formation for three systems. 44
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