Zeng Guang, Xu Ping, Zeng Chen, Huang Qizhong, Su Zhean
National Key Laboratory of Science and Technology on High-Strength Structural Materials, Central South University, Changsha 410083, China.
Materials (Basel). 2023 Jun 16;16(12):4426. doi: 10.3390/ma16124426.
HfCN nanoparticles were synthesized using the urea-glass route, employing hafnium chloride, urea, and methanol as raw materials. The synthesis process, polymer-to-ceramic conversion, microstructure, and phase evolution of HfCN/C nanoparticles were thoroughly investigated across a wide range of molar ratios between the nitrogen source and the hafnium source. Upon annealing at 1600 °C, all precursors demonstrated remarkable translatability to HfCN ceramics. Under high nitrogen source ratios, the precursor exhibited complete transformation into HfCN nanoparticles at 1200 °C, with no observed presence of oxidation phases. In comparison to HfO, the carbothermal reaction of HfN with C significantly reduced the preparation temperature required for HfC. By increasing the urea content in the precursor, the carbon content of the pyrolyzed products increased, leading to a substantial decrease in the electrical conductivity of HfCN/C nanoparticle powders. Notably, as the urea content in the precursor increased, a significant decrease in average electrical conductivity values was observed for the R4-1600, R8-1600, R12-1600, and R16-1600 nanoparticles measured at a pressure of 18 MPa, yielding values of 225.5, 59.1, 44.8, and 46.0 S·cm, respectively.
采用尿素-玻璃路线,以氯化铪、尿素和甲醇为原料合成了HfCN纳米颗粒。在氮源与铪源的广泛摩尔比范围内,对HfCN/C纳米颗粒的合成过程、聚合物到陶瓷的转变、微观结构和相演变进行了深入研究。在1600℃退火时,所有前驱体都表现出向HfCN陶瓷的显著可转化性。在高氮源比例下,前驱体在1200℃时完全转变为HfCN纳米颗粒,未观察到氧化相的存在。与HfO相比,HfN与C的碳热反应显著降低了制备HfC所需的温度。通过增加前驱体中尿素的含量,热解产物的碳含量增加,导致HfCN/C纳米颗粒粉末的电导率大幅下降。值得注意的是,当前驱体中尿素含量增加时,在18MPa压力下测量的R4-1600、R8-1600、R12-1600和R16-1600纳米颗粒的平均电导率值显著下降,分别为225.5、59.1、44.8和46.0 S·cm。