摘要
针对陶瓷前驱体转化率低、热稳定性差的缺点,以正丙醇锆为锆源,苯硼酸为硼源,乙酰丙酮为配位剂,通过配位鳌合反应、取代反应成功制备了主链为B-O-Zr结构的线型含硼、锆聚合物PBZ。将其与硅炔树脂(PTSA)共混制备具有优异耐高温性能和高陶瓷化产率的复相陶瓷前驱体PBZS,该前驱体通过硅氢加成反应以及脱氢偶联反应形成高度交联的三维立体网络固化物。采用FT-IR对PBZ结构进行表征,XRF分析了PBZ的元素组成;利用固化前后的红外分析探讨了PBZS的固化行为,运用TGA研究了PBZS的耐热性能;TGA测试表明,固化产物具备优异的热稳定性能,1000℃以下,氮气中的质量残留率为94.12%。通过XRD、XRF、TEM和Raman研究了PBZS的陶瓷化演变,结果表明,前驱体PBZS经过1600℃热解后转化为ZrB_(2)/ZrC/SiC复相陶瓷,陶瓷产率为66.2%,晶粒尺寸在100 nm左右且分布均匀。
In this research,zirconium n-propoxide was used as the source of zirconium,benzoic acid was used as the source of boron,and acetylacetone was used as the complexing agent.The linear polymer PBZ with B-O-Zr structure was successfully prepared by coordination reaction and substitution reaction.A multiphase ceramic precursor PBZS with excellent heat resistance and high ceramic yield was prepared by blending it with a silicone resin(PTSA).The precursor formed a highly crosslinked three-dimensional network solidified by a hydrosilylation reaction and a dehydrogenation coupling reaction.The PBZ structure was characterized by FT-IR.The elemental composition of PBZ was analyzed by XRF.The curing behavior of PBZS was investigated by FT-IR analysis before and after curing.The heat resistance of PBZS was studied by TGA.The TGA test showed that the cured product had excellent thermal stability,and the mass residual ratio in nitrogen at 1000℃was 94.12%.Ceramic precursors had good heat and thermal stability.The ceramization evolution of PBZS was studied by XRD,XRF,TEM and Raman.The ceramization evolution results revealed that the precursor PBZS was transformed into ZrB_(2)/ZrC/SiC multi-phase ceramic after pyrolysis at 1600℃.The ceramic yield was 66.2%,and the grain size was between 100~200 nm and evenly distributed.
作者
杨明泽
周权
宋宁
倪礼忠
YANG Ming-ze;ZHOU Quan;SONG Ning;NI Li-zhong(Key Laboratory of Special Functional Polymer Materials and Related Technology,Ministry of Education,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China)
出处
《广西大学学报（自然科学版）》
CAS
北大核心
2021年第2期482-490,共9页
Journal of Guangxi University（Natural Science Edition）
基金
国家自然科学基金资助项目(51573044)。
关键词
含硼
锆前驱体
共混
陶瓷化
复相陶瓷
ceramic precursor containing zirconium and boron
blending
ceramization
multiphase ceramics
