Effect of Zr doping material on the structure and performance of tungsten electrode
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摘要: 采用中频感应加热烧结方法制备了W-1.5%La2O3-0.1%Y2O3-0.1%ZrO2和W-1.5%La2O3-0.1%Y2O3-0.08%ZrH2电子发射材料，烧结样品的致密度约为95.5%。热电子发射测试结果表明，添加氢化锆的热电子发射材料样品的零场发射电流密度大于添加氧化锆的样品，分析认为是添加的氢化锆在烧结时，发生分解，生成活性的Zr可以捕获钨晶界中的杂质氧，净化晶界，从而提高了电子发射；维氏显微硬度表明添加氢化锆样品的硬度高于添加氧化锆的样品，分析表明是氢化锆的添加有效改善了钨晶粒之间的结合性，提升了钨电子发射材料的硬度。利用SEM，EDS，XRD、金相显微镜等表面分析设备对样品进行了表征，样品结构显示添加氢化锆与添加氧化锆相比，不仅钨晶粒尺寸由13.63 μm降至11.63 μm,而且稀土相尺寸由1.87 μm降至1.66 μm，这种组织结构的变化有利于电子发射。
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关键词:
- 稀土钨热电子发射材料 /
- 晶粒尺寸 /
- 第二相尺寸 /
- 热电子发射 /
- 氢化锆
Abstract: The W-1.5%La2O3-0.1%Y2O3-0.1%ZrO2 and W-1.5%La2O3-0.1%Y2O3-0.08%ZrH2 electron emission materials were prepared by the intermediate frequency induction heating sintering method. The density of the sintered sample is about 95.5%. The thermionic emission test results show that the zero field emission current density of the thermionic emission material sample added with zirconium hydride is greater than that of the sample added with zirconia. The analysis illustrates that the added zirconium hydride decomposes during sintering, and the active Zr can capture tungsten. The impurity oxygen in the grain boundary purifies the grain boundary, thereby improving electron emission; Vickers microhardness measurement shows that the hardness of the sample with zirconium hydride added is higher than that of the sample with zirconium oxide. Analysis shows that the addition of zirconium hydride effectively improves the bonding between the tungsten crystal grains and enhances the hardness of the tungsten electron-emitting material. The samples were characterized by SEM, EDS, XRD, metallographic microscope and other surface analysis equipment. The structure shows that the addition of zirconium hydride, compared with the addition of zirconia, not only decreases the size of tungsten grains from 13.63 μm to 11.63 μm, but also decreases the size of the rare earth phase from 1.87 μm to 1.66 μm. This change in organizational structure is conducive to electron emission. -
图 9 不同成分样品的伏安特性曲线
Figure 9. Volt-ampere characteristic curves of samples with different compositions
表 1 氧化物质量分数
Table 1. Oxide mass fraction
number w(La2O3)/% w(Y2O3)/% w(ZrO2)/% 1# 1.5 0.1 0.1 2# 1.5 0.1 0.1（0.08%ZrH2） 
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表 2 不同烧结样品的密度和硬度
Table 2. Density and hardness of different sintered samples
number constituent actual density/(g·cm−3) compactness/% Vicbers hardness/HV 1# W-La2O3-Y2O3-ZrO2 18.37 96.03 384.8（±3） 2# W-La2O3-Y2O3-ZrH2 18.33 95.82 395.8（±5）
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表 3 XRD的半定量分析
Table 3. Semi-quantitative analysis of XRD
number constituent w (La2Zr2O7)/% 1# W-La2O3-Y2O3-ZrO2 0.01256 2# W-La2O3-Y2O3-ZrH2 0.01577
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