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    热处理工艺对ZnO压敏陶瓷本征点缺陷及电气性能的影响

    Effect of Annealing Process on Intrinsic Point Defects and Electrical Properties of ZnO Varistor Ceramics

    • 摘要: 基于正交试验方法研究了热处理的升温速率、保温温度、保温时间和降温速率4个参数对ZnO压敏陶瓷物相组成、微观结构、本征点缺陷和势垒结构的影响,综合分析陶瓷的电气性能以获得ZnO压敏陶瓷的最佳热处理工艺。结果表明:1 ℃·min−1升降温速率、600 ℃保温温度以及2 h保温时间条件下的热处理使得富铋相发生由γ-Bi2O3α-Bi2O3的转变,平均晶粒尺寸略微增大,晶粒尺寸分布更加集中,元素分布更加均匀,陶瓷的微观结构更加均匀,相对密度更大,晶粒的缺陷平衡状态Zni••和VO含量维持在较低的水平,势垒高度较高;热处理工艺参数按照对ZnO压敏陶瓷电气性能影响程度由大到小顺序依次为保温温度、降温速率、保温时间、升温速率。最优热处理工艺为升温速率6 ℃·min−1、热处理温度600 ℃、保温时间2 h、降温速率1 ℃·min−1。在该条件下对ZnO陶瓷热处理后,势垒高度由热处理前的0.58 eV提高为0.70 eV,电压梯度由355.0 V·mm−1提高为370.1 V·mm−1,泄漏电流密度从1.38 µA·cm−2减小为0.41 µA·cm−2,非线性系数保持在72。

       

      Abstract: Based on the orthogonal test method, the effects of four parameters of heat treatment, namely the heating rate, holding temperature, holding time and cooling rate, on the phase composition, microstructure, intrinsic point defects and barrier structure of ZnO varistor ceramics were studied. The electrical properties of ceramics were comprehensively analyzed to obtain the optimal heat treatment process for ZnO varistor ceramics. The results show that the heat treatment under the conditions of cooling and heating rates of 1 ℃·min−1, a holding temperature of 600 ℃, and a holding time of 2 h caused the bismuth-rich phase to transform from γ-Bi2O3 to α-Bi2O3, the average grain size slightly increased, the grain size distribution became more concentrated, the element distribution became more uniform, the microstructure of the ceramic became more uniform, and the relative density was greater; the defect equilibrium state of the grains, with the contents of Zni•• and VO remaining at a relatively low level and the barrier height being relatively high. The heat treatment process parameters, in order of their influence on the electrical properties of ZnO varistor ceramics from largest to smallest, were holding temperature, cooling rate, holding time, and heating rate. The optimal heat treatment process was as follows: heating rate of 6 ℃·min−1, heat treatment temperature of 600 ℃, holding time of 2 h, and cooling rate of 1 ℃·min−1. After heat treatment of ZnO ceramics under this condition, the barrier height increased from 0.58 eV before heat treatment to 0.70 eV, the voltage gradient increased from 355.0 V·mm−1 to 370.1 V·mm−1, the leakage current density decreased from 1.38 µA·cm−2 to 0.41 µA·cm−2, and the nonlinear coefficient remained at 72.

       

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