臺灣博碩士論文加值系統

本研究是以化學沈澱法製備氧化鋁膠體，利用陳化處理及超音波處理
兩種方式，再以不同的煆燒條件進行熱處理，分別獲得不同晶徑之θ-Al2O3
（不含α-Al2O3相）及含有θ與α-Al2O3兩相共存的兩類煆燒粉末。
為了瞭解獲得α-氧化鋁的關鍵過程θ→α-Al2O3相轉換，藉由這些煆
燒粉末之熱差分析（DTA），觀察晶徑對θ→α-Al2O3相轉換過程的影響。
結合煆燒粉末之晶徑及粉末凝聚體粒徑（BET粒徑）與DTA放熱曲線的變化
，獲得下列結論：

1. 經由DTA的熱行為分析之結果得知：不含或含極少量α-Al2O3之θ-Al2O3
粉末，其晶徑越大，相轉換的孕核及成長發生溫度越低，而成長的放熱峰
高度也下降，而趨於平緩不明顯。但放熱峰的高峰出現溫度及結束溫度仍
不變。當θ-Al2O3晶徑大於臨界粒徑後，只可看見一個放熱峰，孕核成長
是同時進行的。

2. 煆燒粉末含有α相（晶徑小於60 nm），則相轉換之α-相孕核與成長開始
溫度均隨α-相存在比例的升高而下降。但放熱高峰溫度則維持不變。

3. 既使起始煆燒粉末θ-Al2O3晶徑不同，相轉換後的α-Al2O3晶徑均約在60
~70nm，此晶徑可能為其在此製備條件下的穩定粒徑。

摘要I
致謝II
目 錄III
表目錄V
圖目錄VI
第 一 章 緒 論1
1-1前言1
1-2 研究目的2
第 二 章 理論基礎與前人研究3
2-1 氧化鋁簡介3
2-2氧化鋁結晶相3
2-2-1 氧化鋁膠體之結晶相3
2-2-2 氧化鋁的過渡結晶相4
2-3 氧化鋁相轉換9
2-3-1 孕核與成長（Nucleation & growth）9
2-3-2 θ→α-Al2O3相轉換10
2-3-3 θ→α-Al2O3相轉換與DTA曲線14
2-4 前人研究19
第 三 章 實驗方法21
3-1 實驗流程圖21
3-2 膠體製備21
3-3 煆燒粉末分析製備23
3-4 最終α-Al2O3之獲得23
3-5 性質檢測23
3-5-1 煆燒粉末結晶相之鑑定23
3-5-2 θ及α-Al2O3之晶徑量測23
3-5-3 粉末比表面積分析24
3-5-4 粉末熱差分析25
3-6 α-Al2O3相轉換定量分析25
3-7 影像及顯微結構分析25
第 四 章 結果與討論27
4-1 起始膠粉之結晶相27
4-2 θ-Al2O3粉末27
4-2-1 煆燒粉末之結晶相27
4-2-2 粉末晶徑與比表面積粒徑32
4-3 熱差分析（DTA）39
4-3-1 θ-Al2O3晶徑之影響39
4-3-2 含有α-Al2O3相之影響48
4-4 穿透式電子顯微分析（TEM）51
第 五 章 結 論58
參考文獻59
附 錄63

1. W. H. Gitzen, Alumina as a Ceramic Material, The American Ceramic Society, 1970.
2. E. Dorre and H. Hubner, Alumina: Processing, Properties, and Applications, Springer-Verlag , 1984.
3. F. Wakai, "Superplastic Ceramics-Today & Tomorrow,"

4. T. G. Langdon, "Review Paper Superplastic-like Flow in Ceramics: Recent Developments and Potential Application," Ceram. Inter., 19, 279-286 (1993).
5. 陳智成, "氧化鋁-氧化鋯陶瓷複合材料之製備與性質研究," 成功大學礦冶及材料科學研究所博士論文 (1994).
6. 許文誠, "鋁及鋁－鋯水合物之超音波處理及其生成氧化鋁、鋁鋯微粉之特性研究", 成功大學資源工程研究所碩 士論文(1997）.
7. T. G. Pearson, The Chemical Background of the Aluminium Industry, Monograph of the Royal Institute of Chemistry, London (1955).
8. K. Wefers and M. Bell, "Oxide and Hydroxide of Alumina," Aloca Research Lab., Technical Paper No.19 (1972).
9. B. C. Lippens and J. H. de Boer, "Study of Phase Transformations during Calcination of Aluminum Hydroxides by Selected Area Electron Diffraction," Acta Cryst., 17, 1312-21 (1964).
10. Pyzalski and M. Wojcik, "The Dehydroxylation of Aluminium Hydroxides and the Kinetics of α-Al2O3 formation," J. Therm. Anal., 36, 2147-51 (1990).
11. W. H. Gitzen, ed., Alumina as a Ceramic Material, Am. Ceram. Soc., Columbus, Ohio (1970).
12. S. J. Wilson and J. D. Mcconnel, "A Kinetic Study of The System γ-AlOOH," J. Solid State Chem., 34, 315-22 (1989).
13. I. M. Low and R. Mcpherson, "Crystallization of Gel-Derived Alumina and Alumina-Zirconia Ceramics," J. Mat. Sci., 24, 892-98 (1989).
14.
15. J. A. Kohn, G. Katz, and J. D. Broder, "β-Ga2O3 and Its Alumina Isomorph, θ-Al2O3," Am. Miner., 42, 398-408 (1957).
16. H. Saalfeld, "The Dehydration of Gibbsite and of the Intermediate Products of Its Dehydration," N. Jb. Miner. Abh., 95, 1-87 (1960).
17. L. D. Hart, Editor, "Alumina Chemical: Science and Technology Handbook," Am. Ceram. Soc., Inc. (1990).
18. J. L. McArdle, "Seeding with Ferric-Oxide for Enhanced Transformation and Microstructure Development in Boehmite-Derived Alumina," Ph.D. Thesis, The Pennsylvania State University (1989).
19. R. S. Zhou and R. L. Snyder, "Structures and Transformation Mechanisms of theη,γ and θTransition Aluminas," Acta Cryst., B47, 617-30 (1991).
20. F. W. Dynys and J. W. Halloran, "Alpha Alumina Formation in Alum-Derived Gamma Alumina," J. Am. Ceram. Soc., 65 [9] 442-48 (1982).
21. F. W. Dynys and J. W. Halloran, "Alpha Alumina Formation in Al2O3 Gels," pp. 142-51 in Ultrastructure Processing of Ceramics, and Composites. Edited by L. L. Hench and D. R. Ulrich. Wiley, New York, 1984.
22. T. C. Chou and T. G. Nieh, "Nucleation and Concurrent Anomalous Grain Growth of α-A12O3 during γ→α Phase Transformation." J. Am. Ceram. Soc., 74 [9] 2270-79 (1991).
23. T. C. Chou and T. G. Nieh, "Interface-Controlled Phase Transformation and Abnormal Grain Growth of α-A12O3 in the γ -alumina films," Thin Solid Films, 221 89-97 (1992).
24. W. D. Kingery, H. K. Bowen, and D. R. Uhlmann, Introduction To Ceramics. 2nd Ed., Wiley & Sons, Inc., New York, 448-68
25. 陳怡堯, "θ-Al2O3相轉換為α-Al2O3之臨界粒徑", 成功大學資源工程研究所碩士論文(1998）.
26. L. Pach, R. Roy and S. Komarneni, "Nucleation of alpha alumina in boehmite gel," J. Mater. Res., 5〔2〕278-85 (1990).
27. K. Kaniya, J. Yotani, R. Senba, J. Maesuoka, and H. Nasu, "Sol - Gel Preparation of Alumina Gels Forming α-Al2O3 around 500℃," J. Ceram. Soc. Jpn, Intl. Ed., 104 664-66 (1997).
28. E. Kato, K. Daimon, and M. Nanbu, "Decomposition of Two Sulfates and Characterization of the Resultant Aluminas," J. Am. Ceram. Soc., 64 [8] 436-43 (1981).
29. R. A. Shelleman, G. L. Messing, and M. Kumagai, "Alpha Alumina Transformation in Seeded Boehmite Gels," J. Non-Cryst. Solid., 92 277-85 (1986).
30. M. Kumagai and G. L. Messing, "Controlled Transformation and Sintering of a Boehmite Sol-Gel by α-Alumina Seeding," J. Am. Ceram. Soc., 68 [9] 500-05 (1985).
31. P. A. Badker and J. E. Bailey, "The Mechanism of Simultaneous Sintering and Phase Transformation in Alumina," J. Mat. Sci., 11 1794 (1976)
32. P. A. Zielinski, R. Schulz, S. Kaliaguine, and A. Van Neste, "Structural Transformation of Alumina by High Energy Ball Milling," J. Mater. Res., 8 [11], 2985-92 (1993).
33. R. K. Iler, "Fibrillar Colloidal Boehmite: Progressive Conversion to Gamma, Theta, and Alpha Aluminas," J. Am. Ceram. Soc., 44 [12] 618-24 (1961).
34. G. Carturan, R. D. Maggio, M. Montagna, O. Pilla, and P. Scardi, "Kinetics of Phase Separation and Thermal Behavior of Gel-Derived Al2O3 Doped by Cr2O3: An X-ray Diffraction and Fluorescence Spectroscopy Study," J. Mater. Sci., 25 2705-10 (1990).
35. J. L. Henry and H. I. Kelly, "Preparation and Properties of Ultrafine High-Purity Alumina," J. Am. Ceram. Soc., 48 [4] 217-18 (1965).
36. K. Hayashi, S. Toyoda, H. Takebe, and K. Morinaga, "Phase Transformation of Alumina Derived from Ammonium Aluminum Carbonate Hydroxide (AACH)," J. Ceram. Soc. Japan. Int. Ed., 99 535-40 (1991).
37. A. Putnis, Introduction to Mineral Sciences, Cambridge University Press, (location) (1992).
38. M. W. Chase, Jr., C. A. Davies, J. R. Downey, Jr. Fruip, R. R. McDonald, and A. N. Syverud, "JANAF Thermodynamical Tables," 3rd Ed., Am. Chem. Soc..