恒温环境中ZrB2氧化行为模拟

doi:10.15541/jim20180395

摘要/Abstract

摘要：

二硼化锆(ZrB₂)是一种应用于高超声速飞行器的新型防热材料, 近年来受到广泛关注。本研究根据ZrB₂在不同温度下的氧化产物二氧化锆(ZrO₂)与三氧化二硼(B₂O₃)的微观结构和形貌, 改进了原有的ZrB₂氧化唯象模型, 研究了ZrB₂的氧化行为, 提出了中等温度区间液态B₂O₃的生成、蒸发、填充的动态平衡关系, 并考虑了孔隙出口处的B₂O₃蒸气浓度。研究结果表明: 改进后的模型能够预测低流速准静态条件下ZrB₂的氧化行为, 与加热炉中的样品恒温氧化测试结果吻合良好; 孔隙对氧化过程有较大影响, 在相同的温度、氧分压下, 孔隙率越大, 被氧化程度越高; 在基材表面存在B₂O₃液态膜的情况下, 扩散过程对氧化速率的控制被极大地降低, 材料表现出最强的抗氧化性能。

关键词: 二硼化锆, 氧化行为, 孔隙率, 模拟, 液态膜

Abstract:

Zirconium diboride (ZrB₂), a thermal protection material for hypersonic vehicle, has received widespread attention in recent years. Here we advance an oxidation model based on oxidation products (ZrO₂and B₂O₃) and their morphology at different temperatures to simulate the oxidation behavior of ZrB₂. This study further establishes the dynamic equilibrium among formation, evaporation and supplement of B₂O₃ whose concentration at ambient was assumed to be nonzero. Research results indicate that the advanced model can predict the oxidation behavior of ZrB₂ under quasi-static low flow conditions and the simulation results are consistent with the data obtained from sample suspended in wire heater furnace at constant temperature. The porosity has a great influence on the oxidation process, and at the same temperature and oxygen partial pressure, the larger the porosity, the higher the oxidation degree. The oxidation rate controlled by diffusion in the presence of liquid B₂O₃film laying outer surface of substrate reduces greatly and the material exhibits the strongest oxidation resistance.

Key words: zirconium diboride, oxidation behavior, pore fraction, simulation, film

中图分类号:

周述光, 国义军, 刘骁. 恒温环境中ZrB₂氧化行为模拟[J]. 无机材料学报, 2019, 34(6): 660-666.

Shu-Guang ZHOU, Yi-Jun GUO, Xiao LIU. Simulation of ZrB₂ Oxidation Behavior at Constant Temperature Ambient[J]. Journal of Inorganic Materials, 2019, 34(6): 660-666.

图/表 4

图1 ZrB2氧化产物及其微观结构的示意图

Fig. 1 Schematic sketch of the oxidation products of ZrB2 and morphology assumed in the model L: scale thickness; Rs: recession of substrate; hext: outside layer thickness of B2O3; hint: inside layer thickness of B2O3; a: interface between ambient and oxide; zb: interface between liquid and inside solid; s: interface between oxides and substrate; i: interface between inside liquid and solid

图2 孔隙率对ZrB2氧化前后质量损失的影响

Fig. 2 Effect of pore fraction on weight change of ZrB2

图3 不同温度下ZrB2氧化前后质量变化模拟结果与测试结果的比较

Fig. 3 Comparison of mass change obtained from simulation results and sample measurement results of ZrB2 at different temperatures

表1 不同温度下氧化物B2O3与ZrO2的厚度比

Table 1 Ratio of thickness of B2O3 to that of ZrO2 at different temperatures

T/K	1098	1163	1263	1365	1478	1573	1673
Ratio	1.05	1.04	1.03	0.99	0.96	0.87	0.70

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恒温环境中ZrB₂氧化行为模拟

Simulation of ZrB₂ Oxidation Behavior at Constant Temperature Ambient

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