氮化鋁粉體的表面改質技術開發

Development of Surface Treatment Technology for Aluminum Nitride Powder

許倍華

氮化鋁 ； 矽氧烷耦合劑 ； 磷酸 ； Aluminum nitride ； silane coupling agent ； phosphoric acid

成功大學化學工程學系學位論文

2011年

碩士

鍾賢龍

繁體中文

氮化鋁(AlN)在陶瓷材料中擁有高熱傳導的優異性能，本實驗室使用燃燒合成法合成氮化鋁，再經過球磨法研磨氮化鋁至小粒徑。然而氮化鋁在濕氣存在時易反應成氫氧化鋁而使得整體熱傳導值下降，當粉體粒徑變小時，這個問題更加嚴重。欲藉由表面處理，來解決此問題。本論文選用四種具有不同官能基的矽氧烷耦合劑改質氮化鋁粉。經抗濕測試證明添加矽氧烷耦合劑可使氮化鋁具有抵抗濕氣的能力。並且因為氮化鋁的表面性能改變而未來可以應用在高分子/氮化鋁複合材料上。本論文亦尋找出合適的矽氧烷耦合劑添加量使其有較佳的抗濕能力。另外，亦使用磷酸改質氮化鋁粉，其亦可使氮化鋁粉具有良好的抗濕性。添加磷酸的量需控制得宜，否則可能會使得處理後的氮化鋁粉氧含量太高。最後並比較研發表面改質的氮化鋁粉與市售氮化鋁粉之抗濕效果，發現研發的氮化鋁粉具有在高溫抵抗濕氣的優異性能。

Aluminum nitride (AlN) is a kind of ceramic material with high thermal conductivity. Aluminum nitride is synthesized by self-propagating high temperature synthesis method in the author’s laboratory. It is milled to small size by ball milling. However, its thermal conductivity decreases when it reacts with moisture to form aluminum hydroxide. This problem becomes even more serious when the size of the powder decreases. In this thesis, four kinds of silane coupling agents with different functional groups were used to treat the aluminum nitride powder. Aluminum nitride powder treated with the silane coupling agents could prevent itself from hydrolysis. By moisture resistance test, aluminum nitride powder with surface treatment was proved to have ability to resist moisture attack. In addition, it can be used in fabrication of polymer/aluminum nitride composite materials because the surface treatment agent is also a coupling agent. Besides, aluminum nitride powder can also possess water-resistant capability by treating with phosphoric acid. The appropriate amount of phosphoric acid was also investigated in this study so that the oxygen content of aluminum nitride powder after the treatment will not be too high. We also compare the moisture resistant capability of the aluminum nitride powder treated in the present study with the commercial products and they have better moisture resistant capability than the most commercial products.

1. [1]J. C. Nipko and C.-K. Loong, “Phonon excitations and related thermal properties of aluminum nitride”, The American Physical Society, Vol. 57 number 17, p550-554, (1998)
   連結：
2. [3] Y. Baik and R.A.L. Drew, “Aluminum Nitride: Processing and Applications”, Key Engineering Materials, Vols. 122-124, p553-570, (1996)
   連結：
3. [4] A. A. Gallo, C. S. Bischof, K. E. Howard, S.D. Dunmead and S. A. Anderson, “Moisture Resistant Aluminum Nitride Filler for HighConductivity Microelectronic Molding Compounds”, Electronic components and Technology Conference, p335-342, (1996)
   連結：
4. [5]謝承佑, “高導熱氮化鋁陶瓷粉體在複合材料與電子基板應用之先導研究”, 國立成功大學博士論文, (2006)
   連結：
5. [6]林靜欣, “不同形態之鋁粉之燃燒合成氮化鋁粉體之製程開發”, 國立成功大學碩士論文, (2010)
   連結：
6. [7]謝承佑, “氮化鋁粉體水解性質探討與抗濕技術開發”, 國立成功大學碩士論文, (2002)
   連結：
7. [8] K.L. Mittal, “Silanes and Other Coupling Agents”, Vol. 5, (2009)
   連結：
8. [9]E. P. Plueddemann, “Silane Coupline Agents”, 2ed Edition, New York, p154, (1991)
   連結：
9. [10] D. Hotza, O. Sahling and P. Greil, “Hydrophobing of aluminium nitride powders”, Journal of Materials Science, Vol. 30, p127-132, (1995)
   連結：
10. [11]K. Krnel and T. Kosmač, “Aqueous Processing of AlN Powder”, Materials Science Forum Vol. 554, p189-196, (2007)
    連結：
11. [13] A. V. Virkar, T. B. Jackson and R. A. Cutler, “ Thermodynamic and Kinetic Effects of Oxygen Removal on the Thermal Conductivity of Aluminum Nitride”, Journal of the American Ceramic Society, Vol. 72, No. 11, p2031-2042, (1989)
    連結：
12. [14] K. C. Yung, B. L Zhu, J. Wu, T. M. Yue and C. S. Xie, “Effect of AlN Content on the Performance of Brominated Epoxy Resin for Printed Circuit Board Substrate”. Journal of Polymer Science: Part B: Polymer Physics, Vol. 45, p1662-1674, (2007)
    連結：
13. [15] A. Kuntman and H. Kuntman, “A study on dielectric properties of a new polyimide film suitable for interlayer dielectric material in microelectronics applications”, Microelectronics Journal, Vol.31, p629-634, (2000)
    連結：
14. [16] S. H. Xie, B. K. Zhu, J. B. Li, X. Z. Wei and Z. K. Xu, “Preparation and properties of polyimide/aluminum nitride composites”, Polymer Testing, Vol.23, p797-801, (2004)
    連結：
15. [17] Y. Xu, D.D.L. Chung and C. Mroz, “Thermally conducting aluminum nitride polymer-matrix composites”, Composites: Part A, Vol. 32, p1749-1757, (2001)
    連結：
16. [18] Z. Guo, T. Pereira, O. Choi, Y. Wang and H. T. Hahn, “Surface functionalized alumina nanoparticle filled polymeric nanocomposites with enhanced mechanical properties”, Journal of Materials Chemistry, Vol.16, p2800-2808, (2006)
    連結：
17. [19]D. J. Kim, P. H. Kang and Y. C. Nho, “Characterization of Mechanical Properties of γAl2O3 Dispersed Epoxy Resin Cured by γ-ray Radiation” Journal of Applied Polymer Science, Vol. 91, 1898-1903, (2004)
    連結：
18. [20] K. Krnel and T. Kosmac, “Reactivity of Aluminum Nitride Powder in Dilute Inorganic Acids”, Journal of the American Ceramic Society, Vol. 83, No. 6, p1375-1378, (2000)
    連結：
19. [21] M. Egashira, Y. Shimizu and S. Takatsuki, “Chemical surface treatments of aluminium nitride powder suppressing its reactivity with water”, Journal of Materials Science Letters, Vol. 10, p994-996, (1991)
    連結：
20. [22] M. Egashira ,Y. Shimizu,Y. Takao, R. Yamaguchi and Y. Ishikawa, “Effect of Carboxylic Acid Adsorption on the Hydrolysis and Sintered Properties of Aluminum Nitride Powder ”, Journal of the American Ceramic Society, Vol. 71, No.7, p1793-1798, (1994)
    連結：
21. [24] Y. Q. Li, T. Qiu and J. Xu, “ Effect of thermal oxidation treatment in air on the hydrolysis of AlN powder”, Materials Research Bulletin, Vol. 32, No.9, p1173-1179, (1997)
    連結：
22. [25]劉世量, “提升氮化鋁/環氧樹脂複合材料熱傳導性質之研究”, 國立成功大學碩士論文, (2003)
    連結：
23. [26]林宏穎, “氮化鋁量產製程技術開發”, 國立成功大學碩士論文, (2010)
    連結：
24. [27] C. G. Pantano and T. N. Wittberg, “XPS Analysis of Silane Coupling Agents and Silane-treated E-glass Fibers”, Surface and Interface Analysis, Vol. 15, p498-501, (1990)
    連結：
25. [29] H. M. Liao, R. N. S. Sodhi and T. W. Coyle , “Surface composition of AlN powders studied by x‐ray photoelectron spectroscopy and bremsstrahlung‐excited Auger electron spectroscopy”, Journal of Vacuum Science and Technology A: Vacuum, Surfaces, and Films, Vol. 11, No.5, p2681-2686, (1993)
    連結：
26. [30] J.C. Sanchez-Lopez, M.D. Alcala, C. Real and A. Fernandez, “The use of X-ray photoelectron spectroscopy to characterize fine AlN powders submitted to mechanical attrition”, NanoStructured Materials, Vol. 11, No. 2, pp. 249-257, (1999)
    連結：
27. [32]郭忠倫, “氧化鋁粒徑尺寸與晶型對表面反應性的影響”, 國立成功大學碩士論文, (2008)
    連結：
28. [33] I. Ganesh, S. M. Olhero, A. B. Araújo, M. R. Correia, G. Sundararajan and J. M. F. Ferreira, “Chemisorption of Phosphoric Acid and Surface Characterization of As Passivated AlN Powder Against Hydrolysis”, Langmuir, Vol. 24, p5359-5365, (2008)
    連結：
29. [34] R.G. Horn, “Surface Forces and Their Action in Ceramic Materials ” , Journal of the American Ceramic Society ,Vol. 73, No. 5, p 1117-1135, (1990)
    連結：
30. [35] E. S. Lee, S. M. Lee, W. R. Cannon and D. J. Shanefield, “Improved dispersion of aluminum nitride particles in epoxy resin by adsorption of two-layer surfactants”, Colloids and Surfaces A: Physicochem. Eng. Aspects, Vol. 316, p95-103, (2008)
    連結：
31. [36]Q. Zhang, X. Luo, W. Li, H. Zhuang and D. Yan, “Tape casting of AlN/glass composites for LTCC substrate ”, Journal of Material Science, Vol. 38, p1781-1785, (2003)
    連結：
32. [37]歐佩雯, “低溫燒結氮化鋁/玻璃複合材料之製程與性能研究”, 國立成功大學碩士論文, (2007)
    連結：
33. [2]汪建民, “陶瓷技術手冊Ceramic technology handbook”, 中華民國產業科技發展協進會, p781-783, (1994)
34. [12]S. Fukumoto, T. Hookabe and H. Tsubakino, “Hydrolysis behavior of aluminum nitride in various solutions”, Journal of Materials Science, Vol.35, p2743-2748, (2000)
35. [23] Y. Q. Li, T. Qiu, J. Xu and X. C. He, “Surface modification of aluminium nitride powder”, Journal of Materials Science Letters, Vol. 15, p1758-1761, (1996)
36. [28] B. Baur, G. Steinhoff, J. Hernando, O. Purrucker, M. Tanaka, B. Nickel, M. Stutzmann and M. Eickhoff, “ Chemical functionalization of GaN and AlN surfaces”, Applied Physics Letters, Vol. 87, 263901, (2005)
37. [31] I. Bertoti, “Characterization of nitride coatings by XPS”, Surface and Coatings Technology”, Surface and Coatings Technology, p 194-203, (2002)

1. 林宏儒(2012)。氮化鋁粉體表面改質及高導熱複合材料製程開發。成功大學化學工程學系學位論文。2012。1-64。
2. 陳建廷(2013)。氮化鋁表面改質及應用於複合材料之研究。成功大學化學工程學系學位論文。2013。1-114。