| 高锆含量改性聚硼硅氮烷的合成与表征 |
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| 引用本文： | 龙鑫,邵长伟,王军.高锆含量改性聚硼硅氮烷的合成与表征[J].稀有金属材料与工程,2018,47(S2):122-128. |
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| 作者姓名： | 龙鑫 邵长伟 王军 |
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| 作者单位： | 国防科技大学航天科学与工程学院新型陶瓷纤维及其复合材料重点实验室,国防科技大学航天科学与工程学院新型陶瓷纤维及其复合材料重点实验室,国防科技大学航天科学与工程学院新型陶瓷纤维及其复合材料重点实验室 |
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| 基金项目： | 国家自然科学基金资助(项目号51203184)、863项目(项目号2012AA03A210)、湖南省高校科技创新团队支持计划和国防科技大学创新群体资助 |
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| 摘 要： | 本文通过Cp2Zr(CH2CH=CH2)2与液态聚硼硅氮烷(LPBSZ)在过氧化二异丙苯的作用下发生自由基共聚反应,制备了锆含量大于10wt%的含锆聚硼硅氮烷(PZC-PBSZ)。采用红外光谱、核磁共振、光电子能谱等方法研究了PZC-PBSZ的分子结构及合成机理。结果表明在先驱体的合成过程中,Cp2Zr(CH2CH=CH2)2除了自身发生自由基聚合反应外,还会与LPBSZ中的Si-H发生硅氢加成和取代反应,生成Zr-C和Zr-Si。通过TG-MS和29Si MAS NMR分析表明,PZC-PBSZ先驱体中Cp、(CH3)3Si和(CH3)2SiH等官能团的脱除主要发生在400~800℃。当温度升高到800~1200℃后,先驱体基本无机化,主要发生SiHN2C和SiN3C结构向SiN4结构的转变。PZC-PBSZ经1000℃以上高温热解后可以转化为ZrC纳米颗粒分布均匀在SiBNC基体的ZrC/SiBNC纳米复相陶瓷。经1800℃高温处理后,ZrC/SiBNC陶瓷仍保持均匀和晶粒细化的纳米晶结构。
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| 关 键 词： | 陶瓷先驱体 锆 聚硼硅氮烷 纳米复相陶瓷 SiBNC |
| 收稿时间： | 2017/12/4 0:00:00 |
| 修稿时间： | 2017/12/4 0:00:00 |
Synthesis and characterization of high zirconium content modified polyborosilazane |
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| Xin Long,Changwei Shao and Jun Wang.Synthesis and characterization of high zirconium content modified polyborosilazane[J].Rare Metal Materials and Engineering,2018,47(S2):122-128. |
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| Authors: | Xin Long Changwei Shao and Jun Wang |
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| Affiliation: | Science and Technology on Advanced Ceramic Fibers and Composites Laboratory,College of Areospace Science and Engineering,National University of Defense Technology,Science and Technology on Advanced Ceramic Fibers and Composites Laboratory,College of Areospace Science and Engineering,National University of Defense Technology,Science and Technology on Advanced Ceramic Fibers and Composites Laboratory,College of Areospace Science and Engineering,National University of Defense Technology |
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| Abstract: | In this work, Zr-modified polyborosilazanes (PZC-PBSZ) with a high zirconium content over 10wt% were synthesized via radical reaction between Cp2Zr(CH2CH=CH2)2 and liquid polyborosilazane under the existence of dicumyl peroxide. The structure and reaction mechanism of PZC-PBSZ were studied using Fourier transforminfrared spectra, nuclear magnetic resonance and X-ray photoelectron spectroscopy. The results shown that besides the self-polymerization, Cp2Zr(CH2CH=CH2)2 can also reacted with Si-H in LPBSZ via hydrosilylation reaction and substitution reaction to form Zr-C and Zr-Si, respectively. The thermogravimetric-mass spectrometry and 29Si MAS NMR results shown that the escape of goups such as Cp, (CH3)3Si and (CH3)2SiH was ooccured at temperature range from 400 oC to 800 oC. As the temperature went up to 800~1200oC, the polymer PZC-PBSZ converted into inorganic mineral, and the evolution of SiHN2C and SiN3C structure to SiN4 structure was occurred at that temperature. After pyrolyzing at above 1000 oC, PZC-PBSZ can convert into ZrC/SiBNC ceramic nanocomposites, with ZrC nanoparticles finely dispersed in SiBNC matrix. The obtained ZrC/SiBNC ceramic nanocomposites can remain fine and nanocrystalline microstructure after annealing at 1800 oC. |
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| Keywords: | polyborosilazane Zr preceramic polymer UHTCs ceramic nanocomposites |
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