含锆、硅有机陶瓷前驱体的制备及其陶瓷化研究
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摘要
以正丙醇锆、乙酰丙酮,1,2-丙二醇为原料,制备主链为-Zr-O-CH2-CH-,侧链含有不饱和基团的含锆聚合物(ZMP)并作为锆源。将主链为-Si H、-C≡C-的硅炔树脂(PTSA)作为硅源。将二者以质量比2∶5进行复配,制得陶瓷前驱体(PMS)。采用FT-IR和NMR对ZMP结构进行表征,EDS分析了ZMP的元素组成;利用原位红外分别探讨了PMS的固化行为,运用TGA研究了PMS的耐热性能; TGA测试表明,陶瓷前驱体具有良好的耐热及热稳定性能,在氮气和空气气氛下1000℃时的质量保留率分别为90. 24%和88. 53%。通过XRD、SEM、TEM和Raman研究了PMS的陶瓷化演变。陶瓷化演变结果表明,PMS在1600℃下的陶瓷转化率高达57. 4%,且陶瓷产物中含高结晶度的Zr C、Si C晶体。
Zirconium-containing polymer( ZMP) with a main chain of-Zr-O-CH2-CH-and an unsaturated group in the side was prepared by using zirconium n-propoxide,acetylacetone and 1,2-propanediol as raw materials of zirconium source. A silicon alkyne resin( PTSA) with a main chain of-Si H,-C≡C-was used as a silicon source. The two were reconstituted at a mass ratio of 2 ∶ 5 to obtain a ceramic precursor( PMS). The ZMP structure was characterized by FT-IR and NMR. The elemental composition of ZMP was analyzed by EDS. The curing behavior of PMS was investigated by DSC and in-situ infrared,and the heat resistance of PMS was studied by TGA.The TGA test shows that the precursor has good heat and thermal stability,and the mass retention rates at 1000 ℃under nitrogen and air atmosphere are 90. 24% and 88. 53%,respectively. The ceramization evolution of PMS was studied by XRD,SEM,TEM and Raman. The ceramization evolution results show that the ceramic conversion rate of PMS at 1600 ℃ is as high as 57. 4%,and the ceramic products contain high crystallinity Zr C and SiC crystals.
Zirconium-containing polymer( ZMP) with a main chain of-Zr-O-CH2-CH-and an unsaturated group in the side was prepared by using zirconium n-propoxide,acetylacetone and 1,2-propanediol as raw materials of zirconium source. A silicon alkyne resin( PTSA) with a main chain of-Si H,-C≡C-was used as a silicon source. The two were reconstituted at a mass ratio of 2 ∶ 5 to obtain a ceramic precursor( PMS). The ZMP structure was characterized by FT-IR and NMR. The elemental composition of ZMP was analyzed by EDS. The curing behavior of PMS was investigated by DSC and in-situ infrared,and the heat resistance of PMS was studied by TGA.The TGA test shows that the precursor has good heat and thermal stability,and the mass retention rates at 1000 ℃under nitrogen and air atmosphere are 90. 24% and 88. 53%,respectively. The ceramization evolution of PMS was studied by XRD,SEM,TEM and Raman. The ceramization evolution results show that the ceramic conversion rate of PMS at 1600 ℃ is as high as 57. 4%,and the ceramic products contain high crystallinity Zr C and SiC crystals.
引文
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[3] Marschall J,Pejakovic D,Fahrenholtz W G,et al. Temperature jump phenomenon during plasmatron testing of Zr B2-Si C ultrahightemperature ceramics[J]. Journal of Thermophysics&Heat Transfer,2013,26(4):559-572.
[4]Kim S,Szlufarska I,Morgan D. Ab initio study of point defect structures and energetics in Zr C[J]. Journal of Applied Physics,2010,107(5):163-05.
[5]黄传进,王明存. Si C-Zr C陶瓷单组分前驱体树脂的制备与性能[J].固体火箭技术,2015(2):291-294.
[6]Shi J M,Feng J C,Tian X Y,et al. Interfacial microstructure and mechanical property of Zr C-Si C ceramic and Ti6Al4V joint brazed with Ag CuTi alloy[J]. Journal of the European Ceramic Society,2017,37(8):2769-2778.
[7]Cai T,Qiu W F,Liu D,et al. Synthesis of soluble poly-yne polymers containing zirconium and silicon and corresponding conversion to nanosized Zr C/Si C composite ceramics[J]. Dalton Transactions,2013,42(12):4285-4290.
[8]Sacks M D,Wang C A,Yang Z,et al. Carbothermal reduction synthesis of nanocrystalline zirconium carbide and hafnium carbide powders using solution-derived precursors[J]. Journal of Materials Science,2004,39(19):6057-6066.
[9]Peter Snedden,A I C,Keith Scott A,et al. Cross-linked polymerionic liquid composite materials[J]. Macromolecules,2003,36(12):4549-4556.
[10]Juanli Y U,Wang T,Yi L V,et al. Continuous SiBN fiber reinforced nitride ceramic matrix composites fabricated by PIP I-Performance analysis of precursor and fibers[J]. Aerospace Materials&Technology,2015,3(5):19-23.
[11]Yu Z,Yang L,Zhan J,et al. Preparation,cross-linking and ceramization of AHPCS/Cp2Zr Cl2,hybrid precursors for Si C/Zr C/C composites[J]. Journal of the European Ceramic Society,2012,32(6):1291-1298.
[12]郭建辉,张治军.二氧化硅修饰纳米氧化锆陶瓷材料的制备及性能[J].化学研究,2012,23(2):68-72.
[13]Zhao Y,Wang L J,Zhang G J,et al. Effect of holding time and pressure on properties of Zr B2-Si C composite fabricated by the spark plasma sintering reactive synthesis method[J]. International Journal of Refractory Metals&Hard Materials,2009,27(1):177-180.
[14]赵光辉. Zr B2和Si C在高温低氧压下氧化的原位研究[D].浙江:浙江大学,2014.
[15] Lv X,Yu S,Ge M,et al. Synthesis and microstructure of continuous composite ceramic fibres of Zr C/Zr B2-Si C derived from polymeric precursors[J]. Ceramics International,2016,42(7):9299-9303.
[16]刘长青.有机含锆陶瓷前驱体的合成研究[D].西安:西北工业大学,2016.