本論文研究包含兩大主題：(1)氮化硼(Boron Nitride, BN)高導熱複合材料製程開發及 (2)矽長晶抗侵蝕氮化硼塗料開發。在BN高導熱複合材料開發方面，係以環氧樹脂為基材，使用市售及本實驗室自製不同條件之BN進行混摻，並經過不同研磨過篩、熱壓製程製成高導熱複合材料，針對試片緻密程度與熱傳導值進行探討；在矽長晶塗料開發方面，係針對矽長晶工業之問題，研發設計不同配方之BN塗料，經過不同溫度、氣氛進行熱處理後，測試塗層與基材之附著度、塗層機械強度以進行探討。在BN高導熱複合材料方面，主要目的為經由製程改良以減少試片內部孔洞使試片更加緻密，同時探討BN於試片內部之方向性。實驗室原製程所製之複合材試片，其密度無法接近理論密度，代表內部孔洞較多使結構不緻密。經製程改良後，使試片緻密化且達理論密度。本論文研究發現不同結構之BN適用於不同製程，使其因其方向性的差異以提升熱傳導值。本實驗室球磨後加熱酸洗之BN為碎裂之平鋪片狀，市售粉體A結構則為片狀聚集體，與本實驗室無球磨BN結構相似。經實驗室原製程與改良製程製備試片，以SEM觀察其橫截面發現原製程之碎裂片狀BN在試片內部方向呈現隨機分布，改良製程則呈現水平分布，得知因碎裂片狀BN之方向性導致改良製程與實驗室原製程比較，其平均熱傳導值下降16%。片狀聚集體之BN不論經原製程與改良製程製備試片，其試片內部BN方向皆呈現隨機分布，但改良製程使試片更加緻密導致其熱傳導值較實驗室原製程提高45%。由DSC分析高分子基材可得知其處於可塑熔融膠態與初始交聯反應之溫度，此分析結果可作為設計多程序熱壓之參考。將熱壓程序由原實驗室製程之單程序改為多程序，研究發現多程序熱壓與抽真空皆有去除試片內部孔洞之效果，經過多程序熱壓之試片，與實驗室原單程序熱壓相比，其視孔隙率下降7-13%且視密度些微上升，若在多程序熱壓的同時將腔體抽真空，試片之孔隙率下降達17%。在矽長晶抗侵蝕BN塗料方面，本論文研究之塗料最佳配方於800℃、1000℃、1450℃熱處理後其塗層機械強度、與基材附著度皆優異。於氬氣氣氛經1600℃高溫熱處理後，市售塗料A表面粗糙且有些許裂痕；市售塗料B之塗層呈現點狀不連續狀態，表面產生之裂痕較為明顯且深至基材；本實驗室研發塗料之塗層光滑緻密同時可抵抗石英轉變為方石英所產生之體積效應，避免表面產生許多裂痕而容易崩落，其塗料效果優於市售。

This study is constructed of two main subjects, the first subject is boron nitride high thermal conductivity composite materials, and the second subject is boron nitride anti-corrosion coatings. In the first subject, the boron nitride powder and epoxy were made into composites by different sieving and hot pressing processes. The investigation of the first subject was focused on density, porosity and thermal conductivity of specimens. The second subject is recipe design and process development of boron nitride anti-corrosion coatings to solve the problems of silicon crystal growth industry. The investigation of the second subject was focused on the adhesion between coating layer and substrate and mechanical strength of coatings after different temperature heat treatment. The abstract is divided into two subjects as following.The first subject: The major purpose was to remove the pores inside specimens by improved process and observe the orientation of BN inside specimens at the same time. The results showed that the apparent density of specimens cannot reach the theoretical density by the raw process. It indicated that there were lots of pores inside the specimens. After conducting improved process, the specimens were denser and their density reach the theoretical density.It was found that the different morphology of BN was suitable to different process. Due to orientation of BN, it enhanced the thermal conductivity. The morphology of acid washing after ball milling BN made by our laboratory(LAMSA) was sheet-like and the commercial BN which was similar to LAMSA no ball milling BN was the agglomeration of sheets. The LAMSA acid washing after ball milling BN and commercial BN were made into composites by the raw and the improved process. The cross section of specimens were observed by SEM. The results showed that the orientation of sheet-like BN inside specimen was random distribution by raw process and horizontal distribution by improved process. The thermal conductivity of specimens made by improved process were 16% lower than that by raw process. The orientation of sheet-like agglomeration BN was all random distribution by raw process and improved process. The thermal conductivity of specimens made by improved process were 45% higher than that by raw process because the specimens made by improved process were denser. The temperature of initial cross-linking and plastic state of polymer substrate was analyzed by DSC; took them as reference for multi-step hot pressing design. The results showed that the apparent porosity of specimens made by multi-step hot pressing process decreased in the range form 7% to 13%.If we conduct the multi-step hot pressing process and make chamber vacuum at the same time, the apparent porosity of specimens decreased 17%.The second subject: The optimal recipe of BN coatings presented excellent adhesion and mechanical strength after 800, 1000 and 1450℃ heat treatment. After 1600℃ heat treatment at Ar, the coating surface of commercial coatings A was rough and a little cracked. The coating surface of commercial coatings B was discontinuous state. There were many obvious cracks which were deep to quartz plate on the coating surface. The coating surface of LAMSA coatings was smooth and dense; it could resist the volumetric effect of the cristobalite so there were few cracks which made coating layer easy to be crumbled. The performance of LAMSA coatings was better than commercial coatings.

1.L. vel, G. Demazeau and J. Etourneau, " Cubic boron nitride: synthesis, physicochemical properties and applications," Materials Science and Engineering, B10, 149-164 (1991)
2.宋健民，超硬材料，全華科技圖書股份有限公司，(2000)
3.G. A. Slack, R. A. Tanzilli, R. O. Pohl, and J. W. Vandersande, "The intrinsic thermal conductivity of AIN," Journal of Physics and Chemistry of Solids, 48, 641-647, (1987)
4.E. K. Sichel, R. E. Miller, M. S. Abrahams, and C. J. Buiocchi, "Heat capacity and thermal conductivity of hexagonal pyrolytic boron nitride, " Physical Review, B13(10), 4609, (1976)
5.J. Gu, Q. Zhang, J. Dang and C. Xie, "Thermal conductivity epoxy resin composites filled with boron nitride," Polymers Advanced Technologies, 23, 1025-1028, (2012)
6.S. Rudolph, "Boron nitride release coatings",7th Australian Asian Pacific Conference, Aluminum Cast House Technology,163-170, (2001)
7.Y. Kimura, T. Wakabayashi, K. Okada, T. Wada, and H. Nishikawa " Boron nitride as a lubricant additive," Wear, 232(2), 199-206, (1999)
8.徐煜翔，"燃燒合成氮化硼之製程開發"，國立成功大學博士論文, (2015)
9.C. Zhi, Y. Bando, C. Tan and D. Golberg. "Effective precursor for high yield synthesis of pure BN nanotubes," Solid State Commun, 135(1-2), 67-70, (2005)
10.A. Lipp, K. A. Schwetz and K. Hunold, "Hexagonal boron nitride: Fabrication, properties and applications," Journal of the European Ceramic Society, 5(1), 3-9, (1989)
11.R. T. Paine and C. K. Narula, "Synthetic routes to boron nitride," Chemical Reviews, 90(1), 73-91, (1990)
12.S. J. Yoon and A. Jha, "Vapour-phase reduction and the synthesis of boron-based ceramic phases," Journal of Materials Science, 30(3), 607-614, (1995)
13. F. L. Deepak, C.P. Vinod, K. Mukhopadhyay, A. Govindaraj and C. N. R. Rao, "Boron nitride nanotubes and nanowires," Chemical Physics Letters, 353(5-6), 345-352, (2002)
14.Y. Wang, Y. Yamamoto, H. Kiyono and S. Shimada, "Effect of Ambient Gas and Temperature on Crystallization of Boron Nitride Spheres Prepared by Vapor Phase Pyrolysis of Ammonia Borane," Journal of the American Ceramic Society, 92(4), 787-792, (2009)
15.G. Lian, X. Zhang, S. Zhang, D. Liu, D. Cui and Q.Wang, "Controlled fabrication of ultrathin-shell BN hollow spheres with excellent performance in hydrogen storage and wastewater treatment," Engerg Environmental Science, 5(5), 7072-7080, (2012)
16.P. Judeinstein and C. Sanchez, " Hybrid organic-inorganic materials: a land of multidisciplinarity," Journal of Materials Chemistry, 6, 511-525, (1996)
17.H. Lee and K. Neville, Handbook of Epoxy Resins, McGraw Hill, New York, (1967)
18.L. C. Chan, H. N. Nae and J. K. Gillham," Time-temperature–transformation (TTT) diagrams of high Tg epoxy systems: Competition between cure and thermal degradation," Journal of Applied Polymer Science, 29(11), 3307-3327, (1984)
19.劉獻文，"高折射率及高穿透度之二氧化鈦－環氧樹脂奈米複合材料之合成與物性研究"，國立台灣大學工學院高分子科學與工程研究所碩士論文，(2008)
20.黃俊豪，"含硫與芳香環之高折射率環氧樹脂的合成與硬化後物性研究"，國立交通大學應用化學所碩士論文，(2004)
21.R. E. Cuthrell, " Macrostructure and environment-influenced surface layer in epoxy polymers," Journal of Applied Polymer Science, 11(6), 949-952, (1967)
22.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"，國立成功大學化學工程所博士論文，(2006)
23.ASTM C830-00, "Standard Test Methods for Apparent Porosity, Liquid Absorption, Apparent Specific Gravity, and Bulk Density of
Refractory Shapes by Vacuum Pressure."
24.ISO 2409-1992, "Paints and varnishes,Cross-cut test."
25.ASTM D3359, "Standard Test Methods for Rating Adhesion by Tape Test."
26.GBT9286-1998，色漆和清漆漆膜的划痕實驗
27.鄭仲玹，"燃燒合成氮化硼製程開發"，國立成功大學化學工程所碩士論文, (2016)
28.黃滄閔，"新穎雙官能環氧樹脂之合成與特性探討"，國立成功大學化學工程研究所碩士論文, (2001)
29.林育澍，"含芳香環之高折射環氧樹脂之特性研究"，國立交通大學應用化學所碩士論文, (2004)
30.J. P. Hong, S. W. Yoon, T. Hwang, J. S. Oh, S. C. Hong, Y. Lee and J. D. Nam, " High thermal conductivity epoxy composites with bimodal distribution of aluminum nitride and boron nitride fillers," Thermochimica Acta, 537(10), 70-75, (2012)
31.Y. Xu and D. D. L. Chung, " Increasing the thermal conductivity of boron nitride and aluminum nitride particle epoxy-matrix composites by particle surface treatments," Composite Interfaces, 7(4), 243-256, (2000)
32.黃俊豪，"含硫與芳香環之高折射率環氧樹脂的合成與硬化後物性研究"，國立交通大學應用化學所碩士論文, (2004)
33.C. Xiong and W. Tu, "Synthesis of Water-Dispersible Boron Nitride
Nanoparticles," European Journal of Inorganic Chemistry, 2014(19), 3010-3015, (2014)
34.D. R. Lide, CRC Handbook of Chemistry and Physics 88th Edition, CRC Press, (2007)
35.D. R. Lide, CRC Handbook of Chemistry and Physics 81st Edition, CRC Press, (2000)
36.S. Aramaki and R. Roy, "Revised Phase Diagram for the System Al2O3-SiO2," Journal of the American Ceramic Society, 45(5),229-242, (1962)
37.FToxid-Oxide Phase Diagrams-C. R. C. T.: http://www.crct.polymtl.ca/fact/documentation/FToxid/FToxid_Figs.htm
38.T. J. Rockett and W. R. Foster, "Phase Relations in the System Boron Oxide–Silica," Journal of the American Ceramic Society, 48(2), 75-80, (1965)
39.P. J. M. Gielisse and W. R. Foster, "The System Al2O3–B2O3," Nature, 195, 69-70, (1962)
40.J. Cao, C. Li, X. Song, J. Feng and X. Lin, "Microstructure Evolution of Alumina/Alumina Joint Bonded by Boron Oxide–Alumina Nonmetal Powder Interlayer," International Journal of Applied Ceramic Technology, 12(3), 652-657, (2015)
41.A. C. Akhavan, "Overview of Silica Polymorphs,"：
http://www.quartzpage.de/gen_mod.html
42.A.F. Holleman and E. Wyberg, "Lehrbuch der anorganischen Chemie," Walter Gruyter Verlag, Berlin, New York, (1985) (ISBN:3-11-007511-3)
43.Hans-Rudolph Wenk, A. Bulakh, "Minerals - Their Constitution and Origin," Cambridge University Press, Cambridge, (2003) (ISBN:0-521-52958-1)
44.R. Rykart, " Quarz-Monographie - Die Eigenheiten von Bergkristall, Rauchquarz, Amethyst, Chalcedon, Achat, Opal und anderen Varietäten,"
Ott Verlag Thun, 2nd. Edition, (1995) (ISBN:3-7225-6204-X)
45.H. B. Liu, S. X. Jiang and S. H. Jia, "Preparation and Mechanisms of SiO2/BN Composite Ceramics," Mining and Metallurgical Engineering, 28(6), 105-108, (2008)