• Journal of the Korean Ceramic Society
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• v.30 no.5
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• pp.365-372
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• 1993

Variation of dielectric constant in PMN-Pyrochlore diphasic mixtures were investigated with grain size of pyrochlore phase. Size of pyrochlore phase was controlled by the numbers of calcining and sedimentation method during powder processing. When grain size of pyrochlore phase is large in the sintered specimen, dielectric constant slowly decreased with increase of amount of pyrochlore phase. On the contary, grain size of pyrochlore phase is small, dielectric constant drastically decreased. It was thought that small sized pyrochlore grains more easily surrounded high dielectric phase (perovskite PMN) than large ones with addition of pyrochlore phase.

• The Korean Journal of Ceramics
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• v.4 no.3
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• pp.260-267
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• 1998

A homogeneous and stoichimetric fine powder of the ferroelectric $Pb_[0.97}La_{0.02}(Zr_{0.64}Sn_{0.25}Ti_{0.11})O_3$ (PLZST) has been prepared by the hydroxide coprecipitation method. Studies on the crystallization behavior of precursor as a function of temperature by X-ray powder diffraction and transmission electron microscopy technique were consistent with the formation of the pyrochlore phase from amorphous, initially at low temperatures around 500~$550^{\circ}C$. Further heat treatment up to $750^{\circ}C$ resulted in development of the perovskite phase with no significant pyrochlore crystallite growth. At intermediate temperatures the precursor yields a fine mixture of pyrochlore and perovskite phases. When the pyrochlore phase was heat teated in air, slight weight increase was observed in the temperature range of 300~$700^{\circ}C$, which is thought to be caused from oxygen absorption. In argon atmosphere, weight increase was not observed. On the other hand, weight loss began to occur near $700^{\circ}C$, with giving off mostly CO2 gas. This implies that the pyrochlore phase seems to be crystallorgraphycally and thermodynamically metastable. An apparent activation energy of 53.9 ㎉/mol was estimated for the pyrochlore-perovskite phase transformation.

• Journal of the Korean Ceramic Society
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• v.34 no.5
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• pp.500-504
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• 1997

Perovskite Pb0.7Ba0.3Zn1/3Nb2/3O3 substituted with 0.3 mole fraction for Pb-site in PbZn1/3Nb2/3O3 relaxor and pyrochlore Pb1.83Ba0.29Zn1.71Nb2/3O6.39 were mixed and dielectric characteristics of this composites were investigated. Percolation limit of perovskite phase, which was determined by microstructural observation in the composite as an isolation of perovskite phase from pyrochlore matrix, was 28.9-47.5 vol%. Ferroelectric phase transition below percolation limit depends on a parameter which affects the propagation of lattice vibration between isolated perovskite phase and pyrochlore matrix. Therefore, it is believed that ferroelectric lattice vibration of isolated perovskite phase could be transfered to pyrochlore matrix when the oxygen octahedra are linked in 3-dimension and highly polarizable Pb2+ ions are contained in both phases.

• Journal of the Korean Ceramic Society
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• v.30 no.1
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• pp.78-84
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• 1993

In PMN-pyrochlore phase mixtures, dielectric constant was measured as a function of the volume fraction of pyrochlore phase and considered with general effective media(GEM) equation. For the application of GEM equation to this system, the critical volume fraction(Vc) where connectivity between the perovskite PMN and pyrochlore phase changed from 0-3 to 3-3, was determined based on the each particle size ratio of two phases with microstructural observation. And then the t value was determined from modified percolation powder-law dependence ( K-Kc (V-Vc)t). In the case of applying such values of t and Vc to the GEM equation, which provided a reasonable fit to the measured dielectric constant within the experimental error range.

• Journal of the Korean Ceramic Society
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• v.32 no.3
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• pp.295-304
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• 1995

Stabilization of the perovskite phase and sequence of reactions occuring during calcination were studied with solid solutions formed between Pb(Zn1/3Nb2/3)O3 and Pb(Fe1/2Nb1/2)O3. In the PZN-PFN composition of equal molar ratio, rhombohedral type pyrochlore phase (Pb2Nb2O7) and PbO-rich distorted cubic type pyrochlore phase (Pb3Nb2O8) were coexisted as intermediate phases at temperatures below 85$0^{\circ}C$, and these phases transformed to a stable cubic type pyrochlore phase, Pb3Nb4O13 solid solution and a perovskite solid solution at temperatures above 85$0^{\circ}C$. The major stable phase as increasing sintering temperatures was a perovskite phase in this binary system and prominent suppression of the pyrochlore phase was achieved by substituting Zn2+ with Fe3+ or by increasing sintering temperature. The composition containing 20mol% PZN possessed the best dielectric properties, and the dissipation factor was lower than 5% in all compositions.

• Journal of the Korean Ceramic Society
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• v.26 no.2
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• pp.249-257
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• 1989

Dielectric properties and the stability of the perovskite phase in the Pb(Mg1/3Nb2/3)O3 system have been investigated as a function of amount of BaTiO3 and firing temperature. In the specimens fired at 120$0^{\circ}C$, the pyrochlore phase was eliminated by the addition of 10-15m/o BaTiO3 and also the dielectric constant increased. However, the dielectric constant decreased with further addition of BaTiO3 even though no pyrochlore phase was found to be present. The reducing tendency of the pyrochlore phase decreased with lowering the firing temperature in the system of Pb(Mg1/3Nb2/3)O3 with BaTiO3. Dielectric properties in PMN ceramics were affected by the character of the BaTiO3 rather than the pyrochlore phase.

• Journal of the Korean Ceramic Society
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• v.28 no.2
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• pp.160-166
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• 1991

Microstructure and phase changes during the sintering of ZnO varistors were studied in ZnO-Bi2O3-CoO-Sb2O3 and ZnO-Bi2O3-CoO-Sb2O3-Cr2O3 systems using acanning electron microscopy (SEM) with an energy dispersive X-ray analysis (EDAX), X-ray diffraction (XRD) and differential thermal analysis (DTA). The spinel phase and the Bi2O3 phase were formed by the decomposition of the pyrochlore phase during heating. The spinel particles (2-4$\mu\textrm{m}$), which were formed both along ther grain boundaries and within the ZnO grain, were always found near the pyrochlore phase. Intergranular phases (Bi2O3 and pyrochlore) were precipitated from the liquid phase during cooling. The Bi2O3 phases were located at the triple (or multiple) point of the ZnO grains. Cr2O3 played a role in decreasing the formation temperature of the spinel phase and Bi2O3 phase during sintering, and inhibited the grain growth.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1989.06a
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• pp.105-106
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• 1989

The effects of pyrochlore phase and micostructure on the dielectric properties. such as dielectric constant, dissipation factor, diffusensess coefficient and dielectric hysteresis characteristics, of Lead magnesium niobate(PMN) ceramics have been studied as a function of the amount of excess MgO. The pyrochlore phase in PMN was completely eliminated with the addition of 5 m/o excess MgO. Also, the dielectric constant and remanent polarization increased with increase in grain size, density and then decreased with grain growth inhibitation for further addition of excess MgO. The diffuseness coefficient showed a tendency nearly reverse to that for the dielectric constant and remanent polarization change.

• Journal of the Korean Ceramic Society
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• v.31 no.9
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• pp.1030-1036
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• 1994

The ceramics in the system 0.5[Pb(Ni1/3Nb2/3)O3]-0.5[0.65PbTiO3-0.35PbZrO3] were prepared by conventional solid state reaction method, double calcined method (columbite precursor method) and flux method using NaCl-KCl. Amount of pyrochlore phase for the calcined powders, sintering charateristrics, dielectric and piezoelectric properties were then investigated. Sintering temperature was 1000~120$0^{\circ}C$ and in case of flux method, the amount of flux to oxide was 1 : 1 mole ratio. The dielectric and piezoelectric properties of ceramics prepared by double calcined method and flux method were found to be better than those by conventional method. It was also possible to lower sintering temperature and reduce the amount of pyrochlore phase either by double calcined method or flux method. But with increasing sintering temperature, the difference in characteristrics due to diffrent fabrication method gradually.

• Journal of the Korean Ceramic Society
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• v.31 no.12
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• pp.1443-1448
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• 1994

Pb(Mg1/3Nb2/3)O3-PbTiO3-BaTiO3 solid solution was formed by mixed-oxide method. The phase during formation was analysed by XRD and formation mechanism was investigated. While heat-treating Pb(Mg1/3Nb2/3)O3 composition, the first, Pb2Nb2O7 and Pb3Nb2O8 pyrochlore phases are formed, and finally Pb(Mg1/3Nb2/3)O3 perovskite phase with containing Pb3Nb4O13 pyrochlore phase is obtained at 80$0^{\circ}C$. When Pb(Mg1/3Nb2/3)O3 composition is modified with PbTiO3 which have strong ionic bonding and high tolerance factor, the amount of pyrochlore phase is decreased by increasing of stability in perovskite structure.