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摘要: 采用热压烧结制备Ta-W合金和Ta-W-TiB2合金，研究两种合金在700、800和900℃的高温氧化行为，通过X射线衍射分析、扫描电子显微镜观察和能谱分析对合金的氧化层组分和组织形貌进行分析。结果表明：两种合金经热压烧结后的相对密度均达到97%以上，可以实现致密化。在氧化温度范围内所有合金的氧化动力学曲线都遵循直线规律，氧化温度升高氧化速率逐渐增大。Ta-W合金的氧化产物为Ta2O5固溶体，Ta-W-TiB2合金的氧化产物为Ta2O5固溶体和TiO2氧化物。在700~800℃下，稳定的TiO2提高了Ta-W-TiB2合金的抗氧化能力，但在900℃时，TiO2的破坏大大减弱了氧化层对基体的保护能力。Abstract: Ta-W and Ta-W-TiB2 alloys were prepared by hot pressing sintering. The oxidation behavior of Ta-W and Ta-W-TiB2 alloys at the temperature of 700, 800, and 900℃ were studied. The composition and morphology structure of the oxide layer were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy spectrum analysis (EDS). The results show that, the relative density of Ta-W and Ta-W-TiB2 alloys prepared by hot pressing sintering is beyond 97%. In the oxidation temperature range, the oxidation kinetics curves of all alloys follow the linear rate law, and the oxidation rate increases with the increase of oxidation temperature. The oxidation products of Ta-W alloys are the Ta2O5 solid solution, and the oxidation products of Ta-W-TiB2 alloys are the Ta2O5 solid solution and TiO2. The stable TiO2 improves the antioxidant capacity of the alloy at 700~800℃. However, the destrvuction of TiO2 at 900℃ greatly weakens the protection ability of oxide layer to protect the substrate.
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Key words:
- tantalum tungsten alloy /
- TiB2 /
- high temperature oxidation /
- oxidation kinetics
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图 1 Ta及Ta合金在700 ℃的氧化动力学曲线
Figure 1. Oxidation kinetics curves of Ta and Ta alloys at 700 ℃
图 2 Ta及Ta合金在800 ℃的氧化动力学曲线
Figure 2. Oxidation kinetics curves of Ta and Ta alloys at 800 ℃
图 3 Ta及Ta合金在900 ℃的氧化动力学曲线
Figure 3. Oxidation kinetics curves of Ta and Ta alloys at 900 ℃
图 4 氧化速率常数与热力学温度关系曲线
Figure 4. Relationship between oxidation rate constant and thermodynamic temperature
图 5 Ta及Ta合金800 ℃氧化产物X射线衍射图谱
Figure 5. XRD pattern of oxidation products of Ta and Ta alloys at 800 ℃
图 6 700 ℃氧化0.5 h后Ta合金氧化层表面显微形貌：（a）Ta‒10W合金；（b）Ta‒10W‒TiB2合金
Figure 6. Surface morphology of oxide layer of Ta alloys oxidized at 700 ℃ for 0.5 h: (a) Ta‒10W; (b) Ta‒10W‒TiB2
图 7 700 ℃氧化4 h后Ta合金氧化层截面显微形貌：（a）Ta‒10W合金；（b）Ta‒10W‒TiB2合金
Figure 7. Cross section morphology of oxide layer of Ta alloys oxidized at 700 ℃ for 4 h: (a) Ta‒10W; (b) Ta‒10W‒TiB2
图 8 Ta‒10W‒TiB2合金氧化层截面能谱分析（面扫描）
Figure 8. Energy spectrum analysis (map scanning) of oxide layer cross section of Ta‒10W‒TiB2 alloy
表 1 合金化学成分和烧结密度
Table 1. Chemical composition and sintering density of alloys
合金 成分（质量分数）/% 密度 TiB2 W Ta 烧结密度/(g·cm‒3) 相对密度/% Ta‒10W 0 10 90 16.69 98.64 Ta‒20W 0 20 80 16.75 97.10 Ta‒10W‒TiB2 1 10 89 16.47 98.61 
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表 2 Ta及Ta合金氧化速率常数和氧化激活能
Table 2. Oxidation rate constant and oxidation activation energy of Ta and Ta alloys
温度，T/℃ 氧化速率常数，k/(mg·cm‒2·h‒1) 氧化激活能，Ea/(kJ·mol‒1) Ta Ta‒10W Ta‒20W Ta‒10W‒TiB2 Ta Ta‒10W Ta‒20W Ta‒10W‒TiB2 700 8.75 4.04 4.35 1.99 105.9 116.1 122.1 134.0 800 29.59 30.83 37.09 9.29 900 42.02 30.83 57.05 38.15
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