本實驗第一部分利用脈衝雷射於水中打擊NiO-Al2O3成份系粉末，並且利用X光繞射、光學/電子顯微鏡與振動/吸收光譜觀察粉末變化，以資比較鎳鋁尖晶石NiAl2O4微米級粉末以及端成份NiO/-Al2O3混合微米級粉末，於水中的碎化或剝熔蝕凝聚效應。結果發現NiAl2O4能分解成奈米氧化鎳及含Ni佈植之γ-Al2O3，並重新由水合原子團凝聚為非晶態，或成核為具有奈米粒徑的表面改質鎳鋁尖晶石顆粒，容易相互聚簇成粗糙球團狀，而且因為脈衝雷射動態快速加熱/冷卻以及奈米效應，使其中鎳鋁尖晶石奈米顆粒累積壓縮內應力高達6 GPa，伴隨Raman/FTIR及吸收光譜變化，使最小能隙值降低至5.3 eV; 而雷射剝蝕不全的鎳鋁尖晶石微米級顆粒，除了表面水合改質，內部也因差排、次晶界、累積非均向內應力，以至於具有光學異向性。至於NiO/ -Al2O3混合微米級粉末於水中受脈衝剝熔蝕，則未能反應成具有尖晶石結構的NiAl2O4化合物，僅能各自形
成奈米級具有岩鹽結構的NiO以及具有類似尖晶石結構的殘留γ-Al2O3，而且NiO奈米顆粒比較容易聚簇成粗糙球團狀。
第二部分為利用NiO/NiAl2O4(1:9莫耳比)的次微米/微米粒徑混合粉末，乾壓後於1300℃~1450℃溫度範圍進行大氣等溫熱處理，藉由電子顯微鏡觀察與BET/BJH N2氣吸脫附遲滯曲線記錄比表面積及孔隙變化動力學，根據不同溫度比表面積折半時間，求得活化能為329±5kJ/mol，其機制是由含量較少、熔點較低、粒徑較小的NiO顆粒主導進行早期粗化聚合所控制，適用於比表面積折損速率等於零的溫度(1147℃)以上。此結論除了說明NiO奈米凝聚顆粒於本論文第一部份比較容易聚簇成粗糙球團狀的現象，也支持NiO/NiAl2O4複合陶瓷燒結製程中關於晶界或晶粒內次微米異相顆粒藉由布朗轉動以調整方位的文獻報導，可以提供一般三維制約情況下次微米顆粒布朗轉動的動力學參考。就工業應用而言，藉適當含量與粒徑NiO粉末之添加，可望調控NiO/NiAl2O4燒結體適當的孔隙度及比表面積，作為催化應用的參考。

The first part of this thesis is about pulsed laser ablation of micron size NiAl2O4 spinel powder or NiO-Al2O3 powder mixture in water regarding size/phase changes of the powders. The combined X-ray diffraction and transmission electron microscopic observations indicate that upon laser pulses, the stoichiometric nickel aluminate spinel powder were nanosized and decomposed as atom clusters for further nucleation as Al-doped NiO, Ni-doped -Al2O3 and β-Ni(OH)2 whereas the NiO and Al2O3 powder mixture can also become nanosized β-Ni(OH)2, Al-doped NiO, and Ni-doped -Al2O3 for further composition modification as nonstoichiometric nickel aluminate spinel. The colloidal solution containing the nanosized and hydrated phases in the NiO-Al2O3 system have a bimodal minimum band gap around 5 eV and 3 eV according to UV-visible absorption spectrum for potential photocatalytic applications.
In the second part, an onset sintering-coarsening-coalescence (SCC) event of submicron NiO and micron NiAl2O4 powders (1:9 molar ratio) by isothermal firing in the 1300-1450oC range in air was characterized by N2 adsorption-desorption hysteresis isotherm and scanning electron microscopy. The apparent activation energy of such a rapid SCC process for the composite powders was estimated as 329±5 kJ/mol based on 50% change of specific surface area with accompanied formation of cylindrical pores. This SCC process was controlled by the relatively small-sized and less refractory NiO particles shedding light on their Brownian rotation kinetics at the NiAl2O4 grain boundaries. The minimum temperature of the SCC process, as of concern to optocatalytic applications of NiO/NiAl2O4 composite nanoparticles, is 1147oC based on the extrapolation of steady specific surface area reduction rates to null.

論文審定書 i
致謝 ii
摘要 iv
Abstract vi
目錄 viii
表目錄 x
圖目錄 xi
附錄目錄 xv
第一部份 1
壹、前言 1
貳、實驗流程 3
一、粉體製備(NiAl2O4) 3
二、雷射剝蝕PLA 3
參、實驗步驟及方法 4
一、粉體製備 4
二、雷射剝蝕 4
三、X-ray繞射 4
四、UV-Visible吸收光譜 5
五、偏光顯微鏡 5
六、穿透式電子顯微鏡 5
七、拉曼光譜(Raman) 5
八、霍式轉換紅外光光譜(FT-IR) 6
肆、實驗結果 7
一、XRD分析 7
二、拉曼光譜微探分析 8
三、霍式轉換紅外光譜分析(FT-IR) 8
四、UV-Vis吸收光譜分析 8
五、偏光顯微鏡 9
六、穿透式電子顯微鏡觀察 9
伍、討論 12
陸、結論 16
柒、參考文獻 17
第二部分 50
壹、前言 50
貳、實驗流程 53
一、N1S9粉體製備 53
二、N1S9大氣中的早期燒結 53
参、實驗步驟及方法 54
一、N1S9粉體製備 54
二、N1S9大氣中的早期燒結 54
2-1研磨、過篩 54
2-2壓錠 54
2-3熱處理 54
三、BET 測量 54
四、X-ray 繞射 55
五、掃描式電子顯微鏡 55
六、粒徑分析儀(Dynamics Laser Scattering): 55
肆、實驗結果 56
一、BET比表面積 56
二、BJH氮氣吸脫附曲線 56
三、X光繞射分析 56
四、掃描式電子顯微鏡 57
五、EDS X-ray mapping 57
六、粒徑分析 57
伍、討論 58
陸、結論 61
柒、參考文獻 62

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