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摘要: 非氧化物陶瓷作為一種性能優異的高溫結構材料，廣泛應用于冶金、化工等高溫行業。在實際應用過程中氧化和應力耦合的服役環境加速了非氧化物陶瓷高溫性能失效最終降低服役壽命，甚至引發安全事故。因此研究非氧化物陶瓷在復雜服役環境下尤其應力條件下的氧化進程尤為重要，建立此條件下的氧化動力學模型是掌握材料實際服役行為規律的有效手段。本文對比了非氧化物陶瓷分別在無應力和應力條件下的氧化機理和相應動力學模型，通過對不同模型的應用對比分析，從量化角度明確了應力對非氧化物陶瓷氧化過程的影響，在此基礎上初步建立了考慮應力的非氧化物陶瓷氧化動力學模型，為進一步揭示非氧化物陶瓷在復雜條件下的服役行為提供科學模型，為提高材料服役壽命提供有效理論指導。Abstract: Nonoxide ceramics (NOCs) as representative high-temperature structural materials are widely applied in various key fields, such as metallurgy, electric power, and chemical industry, owing to combined excellent characteristics including high strength, lightweight, good thermal shock resistance, and erosion resistance. In practical applications, NOCs are often exposed to high temperatures containing oxygen; thus, they are inevitably confronted with the oxidation issue. In addition, NOCs are mostly used as lining materials for high-temperature containers and transmission components for high-temperature devices, in which they are also subjected to external loads. Simultaneously, internal stress will be generated inside the oxide film during oxidation, owing to the density difference and thermal expansion coefficient difference between the oxidation products and substrate. The coupled effect of oxidation and complex stresses accelerates the degradation of high-temperature performance and ultimately reduces the service life of NOCs, even causing severe industrial accidents. Therefore, studying the oxidation of NOCs under complex conditions is essential. However, limited by the high temperature and long serving time, an experimental approach to the oxidation of NOCs remains a challenge. By comparison, kinetic models based on specific reaction principles and different assumptions have become an effective tool for understanding and analyzing the oxidation of NOCs. This article compares the oxidation mechanism and corresponding kinetic models of NOCs under stressfree and stress conditions. Through comparing and analyzing the application effects of different models, the effect of stress on oxidation of NOCs is determined from a quantitative point, and the oxidation kinetic models of NOCs considering stress are preliminarily established, which can provide a scientific model for further recognition of service behavior of NOCs under complex conditions and provide effective theoretical guidance for improvement of the service life of materials.
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Key words:
- nonoxide ceramics /
- oxidation /
- diffusion /
- stress /
- kinetic model
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圖 1 非氧化物陶瓷氧化過程示意圖。（a）薄塊體材料；（b）球體材料
Figure 1. Schematic diagram of the oxidation process of non-oxide ceramics: (a) bulk material; (b) spherical material
圖 3 氧化膜和基底之間的應力關系示意圖。（a）不受外加載荷作用；（b）受外加載荷作用
Figure 3. Schematic diagram of the stress relationship between the oxide film and the substrate: (a) without applied load; (b) with applied load
圖 4 應力?擴散耦合模型的應用。（a）計算結果和不同溫度下片狀SiC氧化的實驗數據對比圖[33]；（b）應力?擴散耦合模型與未考慮內應力的拋物線模型計算結果和1300 ℃下片狀SiC氧化的實驗數據對比圖[33]
Figure 4. Application of the stress-diffusion coupling model: (a) comparison of calculation curves using the stress–diffusion coupling model and experimental data of bulk SiC oxidized at different temperatures[33]; (b) comparison of calculation curves using the stress–diffusion coupling model and parabolic model without the stress factor and experimental data of bulk SiC oxidized at 1300 ℃[33]
圖 5 氧化膜/基底系統和氧化過程的示意圖
Figure 5. Schematic diagram of the oxide film/substrate system and oxidation process
圖 6 應力?氧化耦合模型的應用。（a）模型計算結果和不同溫度下Si片氧化的實驗數據對比圖[7]；（b）模型中考慮/不考慮應力因素的計算結果和1100 ℃下Si片氧化實驗數據對比圖[7]
Figure 6. Application of the stress-oxidation coupling model: (a) comparison of calculation curves using the stress–oxidation coupling model and the experimental data of bulk Si oxidized at different temperatures[7]; (b) comparison of calculation curves using the stress–oxidation coupling model and parabolic model without the stress factor and the experimental data of bulk Si oxidized at 1100 ℃[7]
圖 7 不同溫度下片狀SiC氧化產生的內應力預測圖
Figure 7. Prediction curves of internal stress produced by oxidation of bulk SiC at different temperatures
圖 8 RPP模型的應用。（a）模型計算結果和不同溫度下片狀SiC氧化實驗數據的對比圖[33]；（b）RPP模型與未考慮內應力的拋物線模型計算結果和1300 ℃下片狀SiC氧化實驗數據的對比圖[33]
Figure 8. Application of RPP model: (a) comparison of calculation and prediction curves using the RPP model and experimental data of bulk SiC oxidized at different temperatures[33]; (b) comparison of calculation curves using the RPP model and parabolic model without the stress factor and experimental data of bulk SiC oxidized at 1300 ℃[33]
圖 9 三點彎曲下的氧化和應力疊加示意圖
Figure 9. Schematic diagram of the oxidation and stress superposition under a three-point bending
圖 10 三點彎曲模型的應用（
$ \widetilde h $ ,$ \tau $ 分別表示量綱為一的氧化膜厚度和量綱為一的時間）。（a）模型計算結果和800 ℃下片狀SiC氧化的實驗數據對比圖[37]；（b）施加不同載荷對試樣頂部和底部氧化影響對比圖Figure 10. Application of the three-point bending model (
$ \widetilde h $ ,$ \tau $ represent the dimensionless oxide film thickness and dimensionless time, respectively): (a) comparison of calculation curves using the three-point bending model and experimental data of bulk SiC oxidized at 800 ℃[37]; (b) comparison of the influence of different applied loads on the oxidation of the top and bottom of the sample259luxu-164<th id="5nh9l"></th> <strike id="5nh9l"></strike> <th id="5nh9l"><noframes id="5nh9l"><th id="5nh9l"></th> <strike id="5nh9l"></strike> <th id="5nh9l"><noframes id="5nh9l"> <th id="5nh9l"></th> <strike id="5nh9l"><noframes id="5nh9l"><span id="5nh9l"></span> <span id="5nh9l"><noframes id="5nh9l"><span id="5nh9l"></span> <strike id="5nh9l"><noframes id="5nh9l"><strike id="5nh9l"></strike> <span id="5nh9l"><noframes id="5nh9l"> <span id="5nh9l"><noframes id="5nh9l"> <span id="5nh9l"></span> <span id="5nh9l"><video id="5nh9l"></video></span> <th id="5nh9l"><noframes id="5nh9l"><th id="5nh9l"></th> -
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