Papers by Author: Masayuki Takada

Abstract: With the goal of fabricating low-breakdown-voltage varistors, the effect of adding Ba to ZnO varistors on the ZnO grain size was investigated. Grain growth of ZnO could be markedly promoted by adding both Ba and Bi. The maximum grain size was approximately 150 μm and the minimum varistor voltage was approximately 12 V/mm. However, it had relatively poor tolerance characteristics for electrical degradation. It is speculated that when adding both Ba and Bi to a Mn–Co-added ZnO varistor, it is necessary to form the molten phases of Ba and Bi to promote grain growth of ZnO. It is also conjectured that the growth of ZnO grains is not promoted when Ba and Bi do not coexist in the molten phase because Ba forms compounds with Mn independently with the addition of small amounts of Bi.

Abstract: The effects of the addition of Y or both Y and Zr to Bi-Mn-Co-Sb-Si-Cr-Ni-added ZnO varistors on the varistor voltage and the tolerance characteristics of electrical degradation were investigated. The deterioration of the tolerance characteristics of electrical degradation by the addition of Y was probably caused by an increase in the number of willemite (Zn2SiO4)-type particles or a decrease in the number of spinel (Zn2.33Sb0.67O4)-type particles, but this deterioration was reduced by adding Zr. Moreover, the reduction in the average ZnO grain size due to the addition of Y was a major factor in the increased varistor voltage, and the ZnO grain growth was inhibited by the formation of an un-known compound after adding Y. The varistor voltage of a varistor with 2 mol% added Y increased by approximately 50% compared to a varistor with no Y added.

Abstract: The effects of thermal annealing on the electrical degradation of Sb2O3-Bi-Mn-Co-doped ZnO varistors were investigated. For samples with 0.04 mol% Sb2O3 or more, the nonlinearity index  of the voltage-current (V-I) characteristics after electrical degradation increased upon annealing. More-over, the value of  after electrical degradation was proportional to the full width at half maximum (FWHM) of the X-ray diffraction peak for Zn2.33Sb0.67O4-type spinel particles under various annealing conditions. The added Sb2O3 did not dissolve in the ZnO grains but became segregated at grain boundaries. Therefore, it is speculated that the increase in the FWHM of the spinel particles is due to an increase in the numbers of fine spinel particles at grain boundaries and triple points during annealing. Furthermore, it is suggested that the improvement in the electrical degradation upon annealing is due to a decrease in the mobility of oxide ions or Zn2+ ions owing to their being blocked by uniformly distributed fine spinel particles at grain boundaries.

Abstract: ZnO varistors of the excellent tolerance characteristics for electrical degradation were made by adding Bi2O3-MnO2-Co3O4-Cr2O3-SiO2-Sb2O3-NiO in ZnO. The tolerance characteristics for electrical degradation were evaluated by changing amount of ZrO2-additive. The evaluation methods are voltage-current characteristics, X-ray diffraction, scanning electron microscope, and energy dispersion X-ray spectroscopy. Monoclinic and tetragonal ZrO2 and the compounds originated in Zr were observed at both grain boundaries and triple points. Moreover, the compounds originated in both Zr and Sb improved the tolerance characteristics for electrical degradation. On the other hand, especially monoclinic ZrO2 deteriorated the tolerance characteristics for electrical degradation. It is one key factor of the improvements of the tolerance characteristics for electrical degradation that the mobility of oxide ions or interstitial Zn2+ ions was hindered by forming the compounds contained Zr, Sb, Si, and, Bi atoms.

Abstract: The mechanism of the recovery of the nonlinearity voltage-current (V-I) characteristics after electrical degradation was investigated from various viewpoints. The recovery processes of ZnO varistors in various gas atmospheres, and at various pressures, temperatures, and absolute humidity levels were evaluated. The evaluation involved the analysis of V-I characteristics, capacitance-voltage (C-V) characteristics, and X-ray diffraction (XRD). The height of the Schottky barrier and the thickness of the depletion layer were almost constant for sintering times between 3 and 5 h. On the other hand, the rate of recovery exhibited a change with sintering time. The recovery speed of the nonlinearity was also temperature dependent. It is suggested that the recovery process is caused by the transport of oxide ions through the grain boundaries between ZnO grains. It was found that the recovery process is affected by the crystal structure of Bi2O3 particles, which exist at the boundaries between ZnO grains.

Abstract: The effects of the thermally annealing of Bi-Mn-Co-Sb2O3-added ZnO varistors on their electrical degradation were investigated. For the samples with 0.01mol% Sb2O3added and without Sb2O3, no marked difference in the non linearity index of the voltage-current (V-I) characteristics was observed upon electrical degradation for the annealed and nonannealed samples. Upon increasing the amount of Sb2O3 added, the values of  increased after electrical degradation for the annealed samples. Moreover, the value of  after electrical degradation was proportional to the full width at half maximum (FWHM) of the X-ray diffraction peak for Zn2.33Sb0.67O4-type spinel particles under various annealing conditions. The added Sb2O3 did not dissolve in the ZnO grains but became segregated at grain boundaries. Therefore, it is speculated that the increase in the FWHM for the spinel particles is due to the increase in the numbers of fine spinel particles at grain boundaries and triple points.

Abstract: The effects of SnO2 addition on the electrical degradation characteristics of Bi2O3-MnO2-Co3O4 -added ZnO varistors were investigated by field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and voltage-current (V-I) characteristics. The ZnO grain size was made uniform by the addition of SnO2 or Sb2O3. The nonlinearity index α of the V-I characteristic for Bi-Mn-Co-SnO2-added samples was approximately 50 and the varistor voltage was 120~140V/mm. The value of α after the electrical degradation showed a local maximum at approximately 0.1mol% added SnO2 and then showed a local minimum at approximately 0.5mol%, similar to the relative integral intensity of the XRD diffraction peak for the (004) plane for a small amount of SnO2 added. It is suggested that the diffusion of oxygen ions through the grain boundary is affected by the change in crystal orientation of ZnO grains at the grain boundary induced by the addition of a small amount of SnO2.

Abstract: The relationship between the crystal structure of Bi2O3 and the recovery of the electrical degradation of ZnO varistors was investigated. The evaluation methods used were analysis of the voltage-current (V-I) characteristics, scanning electron microscopy (SEM), energy-dispersion X-ray spectroscopy (EDX), and X-ray diffraction (XRD) measurements. The electrical degradation was estimated by the nonlinearity of the V-I characteristics. A marked recovery of the nonlinearity of the V-I characteristics was observed for a sample having the crystal structure of δ-type Bi2O3. It is speculated that the electrical degradation is markedly recovered for optimum conditions of both the amount and the crystal structure of the added Bi2O3, because, for samples sintered for a long time, the recovery speed is shorter than that for samples sintered for a shorter time. During long-time sintering, the amount of Bi2O3 decreased because of evaporation. No change of the crystal structure of Bi2O3 was observed upon repeated the electrical degradation and the recovery. It is suggested that another mechanism apart from the diffusion of oxygen ions through the grain boundaries of ZnO particles contributes to the electrical degradation and recovery of the nonlinearity of V-I characteristics.

Abstract: The effects of the electrical degradation characteristics and microstructure of Sb2O3-doped ZnO varistors were investigated by optical microscopy, X-ray diffraction (XRD) analysis, and voltage-current (V-I) characteristics analysis. The nonlinearity index α of the V-I characteristics of the Bi-Mn-Co-Sb2O3-doped ZnO varistors decreased with increasing Sb2O3 content after electrical degradation. The twin crystal of ZnO was formed by doping with Sb2O3. The number of twin crystals, of which two c-axes are perpendicular to the twin plane, increased and the number of twin crystals, of which c-axes are parallel to the twin plane, decreased with increasing amount of Sb2O3 doped. It is suggested that electrical degradation is affected by the combination of the orientation of ZnO grains containing twin planes and a double Schottky barrier may not be formed in the twin plane.

Abstract: The effects of Mn and Co addition on the electrical degradation of ZnO varistors were investigated on the basis of voltage-current (V-I) characteristics, X-ray diffraction (XRD), capacitance-voltage (C-V) characteristics, and isothermal capacitance transient spectroscopy (ICTS). The optimum Co content for preventing electrical degradation was determined to be approximately 0.5mol% in Bi-Mn(0.5mol%)-Co(0~1.0mol%)-added ZnO varistors. Correlations between the improvement of electrical degradation and the structural changes of additives were investigated by XRD. It is suggested that the crystal structure of a-Bi2O3 at the grain boundary changes to a different structure, such as d-Bi2O3 or Bi7.65Zn0.35O11.38 with a fluorite-type structure, at the optimum Co content. It is speculated that the structural change of Bi2O3 at the grain boundary contributes to the improvement of electrical degradation characteristics. Three trap levels were detected in all Bi-Mn-Co-added samples by ICTS. These trap levels showed a local maximum at the optimum Co content.