纳米SiC陶瓷的氧化特性的研究
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摘要
采用差示扫描量热DSC研究了在不同的升温条件下的聚碳硅烷PCS热解产物纳米Si C粉末在空气环境中的氧化反应动力学,并结合X射线衍射和拉曼光谱技术探讨其氧化特性。结果表明:升温速度对PCS热解产物纳米Si C粉末的氧化过程有较大的影响,随着升温速度的增加,1100℃左右的放热氧化峰向高温方向偏移。动力学研究表明微米Si C氧化活化能为115.90 k J/mol,PCS热解产物纳米Si C粉末氧化活化能为485.73 k J/mol,表明PCS热解产物纳米Si C粉末具有较好的抗氧化性能。
DSC thermal analysis technique combined with X-ray diffraction and Raman spectroscopy were used to study the oxidation characteristics and oxidation reaction kinetic of polycarbosilane(PCS)pyrolysis products(nano Si C powders)and commercial Si C powders in the air environment.The results showed that the heating rate of oxidation process had a greater impact on the oxidation reaction of Si C nano powders,with the increase of heating rate,exothermic oxidation peak around 1100 ℃ shifted to a higher temperature.Kinetic studies revealed that the oxidation reaction activation energy of commercial SiC powders was about 115.90 k J/mol and the oxidation reaction activation energy of PCS pyrolysis products is 485.73 k J/mol,which indicated PCS pyrolysis products had a good antioxidant property.
DSC thermal analysis technique combined with X-ray diffraction and Raman spectroscopy were used to study the oxidation characteristics and oxidation reaction kinetic of polycarbosilane(PCS)pyrolysis products(nano Si C powders)and commercial Si C powders in the air environment.The results showed that the heating rate of oxidation process had a greater impact on the oxidation reaction of Si C nano powders,with the increase of heating rate,exothermic oxidation peak around 1100 ℃ shifted to a higher temperature.Kinetic studies revealed that the oxidation reaction activation energy of commercial SiC powders was about 115.90 k J/mol and the oxidation reaction activation energy of PCS pyrolysis products is 485.73 k J/mol,which indicated PCS pyrolysis products had a good antioxidant property.
引文
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[2]肖汉宁,高朋召.高性能结构陶瓷及其应用[M].北京:化学工业出版社2006.4.
[3]冯祖德,何立志,王艳艳.聚碳硅烷SiC纤维的高温氧化行为研究进展[J]理化检测-物理分册2005(41):59-62.
[4]谢征芳,王军,肖加余,等.Al/SiC/PCS先驱体裂解-反应机理研究[J],硅酸盐学报,2002,8:476-481.
[5]FUKUSHIMA Manabu,ZHOU You,YOSHIZAWA Yuichi,et al.Preparation of Mesoporous Silicon Carbide from Nano-Sized SiC Particle and Polycarbosilance[J],Journal of the Ceramic of Japan 2006(1):571-574.
[6]赵玉梅,斯永敏,潘洁.聚碳硅烷的短程有序结构[J]有机硅材料2008,22(3):119-121.
[7]陈文怡,丁治.聚碳硅烷的热裂解动力学行为研究[J]硅酸盐学报2012,40(9):1278-1283.
[8]胡荣祖等著.热分析动力学[M].北京:科技出版社,2001.3.
[9]Taki T,Inui M,Okamura K,Sato M.Source Conversion process of poly-carbosilane to SiC by solid-state highresolution NMR[J].Journal of Materials Science Letters,1989,(8):918-920.
[10]程祥珍,肖加余,谢征芳,等.聚碳硅烷纤维的不熔化与Sic纤维制备研究[J],材料工程,2004(1):29-37.
[11]周长城,张长瑞,胡海峰,等.准陶瓷Cf/SiC复合材料的制备[J]国防科技大学学报,2008(2):41-43.
[12]Masaki Narisawa,Hiroyuki Kado,Ryota Mori,et al.Microstructure of silicon carbide nano powder polycarbosil-ane solvent mixed slurries and observed shear rate dependence in slurry viscosity[J].Materials Science and Engineering148(2008)187-191.
[13]K.Suzuki,K.Kumagawa,T.Kkamiyama,et al.Characterization of the medium-range structure of Si-Al-C-O,SiZr-C-O and Si-Al-C Tyranno fibers by small angle X-ray scattering[J].Journel of Materials Science(2002):949-953.