• 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.

• 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.

• 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.

• Proceedings of the Materials Research Society of Korea Conference
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• 1993.05a
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• pp.122-122
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• 1993

Perovskite형 PMN 은 약 -12$^{\circ}C$에서 Curie 최대치를 (Tm)를 가지며 1KHz에서 매우 5598;은 유전상수(~18000)를 갖기 때문에 유전체로의 응용이 큰데, PMN의제조시 쉽게 생성되는 Pyrochlore상은 일반적으로 매우 낮은 유전률(⊆210)을 가져 계의 전체 유전률을 크게 저하시키는 것으로 알려져 있으며 이런 이유로 이제까지의 연구의 초점의 주로 제조공정중 Pyrochlore 상의 첨가량 및 입자크기에 따른 PMN-Pyrechlore 2상혼합체에서 Prochlore 상의부피분률을 변화시킬 때 유전물의 변화률 GEM(General Effective Media)식을 이용하여 논의하고자한다. Pyrochlore상의 입자크기가 클 경우 2상혼합체 PMN 의 유전률은 Pyrocholre 상의 양이 증가함에 따라 서서히 감소하였으나 입자크기가 작은 겨우 급겨한 갑소를 보였다. 결국 2상의 입자크기 차이는 2상혼합체인 PMN의유전류과 밀접하 ㄴ관계가 있으며. 또한 유전률이 급격히 떨어지는 임계부피분률이 달라짐을 확인할 수 있었다. 또한 Pyrochlore상의첨가량이 증가함에 따라 2상혼합체인 PMN의 유전률의 변화는 GEM식 적용에 있어서는 임계부피률과 t값을 정확히 정하는 것이 중요한데 임계부피분률의 설정은 Perovskite PMN 과 Pyrochlore상의 입자 크기비를 이용하여 Kusy 이론을 기초로 결정하였으며, t 값은 퍼콜레이션 Power-law식에 적용시켜 정하였다였다

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.245-245
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• 2007

본 연구는 $Bi_2O_3$, ZnO 및 $Nb_2O_5$로 이루어진 두 가지의 $Bi_2(Zn_{1/3}Nb_{2/3})_2O_7$와 $(Bi_{1.5}Zn_{0.5})(Zn_{0.5}Nb_{1.5})O_7$ pyrochlore를 제조한 후, ZBS 및 BZBS 유리를 각각 첨가하여 저온 소결 및 마이크로파 유전 특성을 고찰하였다. 두 가지의 pyrochlore에 대하여 하소 온도에 따른 상 합성 유무를 고찰한 결과 $900^{\circ}C$에서 단일 상을 갖는 pyrochlore를 제조할 수 있었다. 두 가지의 pyrochlore에 ZnO-rich ZBS 유리와 $Bi_2O_3$-rich BZBS 유리를 3, 5 wt%로 첨가한 후 $800{\sim}950^{\circ}C$에서 소결한 결과 ZBS 및 BZBS 유리를 5wt%를 첨가하였을 때 $900^{\circ}C$에서 소결이 가능하였다. 또한 마이크로파 유전 특성을 고찰한 결과, $(Bi_{1.5}Zn_{0.5})(Zn_{0.5}Nb_{1.5})O_7$의 pyrochlore는 고주파에서 유전 특성 측정이 되지 않았다. $Bi_2(Zn_{1/3}Nb_{2/3})_2O_7$의 pyrochlore의 경우 5 wt% ZBS 및 BZBS 유리를 첨가하여 $900^{\circ}C$에서 소결한 시편의 마이크로파 유전 특성은 ${\varepsilon}_r$= 62.8~68.3, $Q{\times}f$ value= 3,500~2,700 GHz을 나타내었다.

• Economic and Environmental Geology
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• v.37 no.6 s.169
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• pp.603-612
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• 2004

Pyrochlore is known as one of the most promising materials for the immobilization of radionuclide in high level waste. This study included the synthesis, phase relation and characteristics of $pyrochlore(CaCeZr_xTi_{2-x}O_{7,\;x=0.2\~2.0)$ in the system of Ca-Ce-Zr-Ti-O. Using the CPS(Cold pressing and sintering) method, the mixtures of $CaCO3_,\;CeO_2,\;ZrO_2\;and\;TiO_2$ oxides were pressed, and sintered at $1100\~1600^{\circ}C$ for 20 hours. The optimal synthetic conditions at various compositions were differed from 1300 to $1600^{\circ}C$ Even in the optimal temperatures, pyrochlore or fluorite coexisted with minor amount of perovskite, $CeO_2\;or\;Ce_{0.75}Zr_{0.25}O_2$. It was confirmed that pyrochlore and fluorite structures were stable at $x\leq0.6\;and\;x\geq1.0$, respectively. Especially, the compositions of pyrochlore or fluorite showed non-stoichiometric compositions in that contents of Ca and Ti were more deficient and those of Zr and Ce were more excess than batch compositions with the increase of x value. These characteristics stemmed from the behavior of elements occupied at eight- and six-coordinated site, and then caused the coexistence of perovskite, $CeO_2\;or\;Ce_{0.75}Zr_{0.25}O_2$ along with pyrochlore or fluorite.

• 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.

• 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.