• 제목/요약/키워드: perovskite/pyrochlore phase

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Pb계 Perovskite-Pyrochlore 복합체의 강유전특성 (Ferroelectric Characteristics of Pb-containing Perovskite-Pyrochlore Composites)

  • 조진우;손정호;조상희
    • 한국세라믹학회지
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    • 제34권5호
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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.

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$Pb(Zn_{1/3}Nb_{2/3})O_3-Pb(Fe_{1/2}Nb_{1/2})O_3$계에서의 Perovskite상의 안정성 및 유전특성 (Stabilization of the Perovskite Phase and Dielectric Properties in the System $Pb(Zn_{1/3}Nb_{2/3})O_3-Pb(Fe_{1/2}Nb_{1/2})O_3$)

  • 김정욱;최성철;이응상
    • 한국세라믹학회지
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    • 제32권3호
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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.

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Pyrochlore상의 입자크기에 따른 PMN-Pyrochlore 2상 혼합체의 유전율 변화 (Variation of Dielectric Constnat with Grain Size of Pyrochlore Phase in the PMN-Pyrochlore Diphasic Mixtrues)

  • 허강일;김정주;조상희
    • 한국세라믹학회지
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    • 제30권5호
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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.

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Powder Preparation by Hydroxide Coprecipitation and Phase Development of Pb0.97La0.02(Zr0.64Sn0.25Ti0.11)O3 Ceramics

  • Lee, Joon-Hyung;Chiang, Yet-Ming
    • The Korean Journal of Ceramics
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    • 제4권3호
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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.

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PMN-PT-BT 고용체의 합성반응기구 (Reaction Mechanism in the Formation of PMN-PT-BT Solid Solution)

  • 박현;이응상
    • 한국세라믹학회지
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    • 제31권12호
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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.

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Oxygen Evolution Reaction at Electrodes of Single Phase Ruthenium Oxides with Perovskite and Pyrochlore Structures$^{**}$

  • 최은옥;권영욱;모선일
    • Bulletin of the Korean Chemical Society
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    • 제18권9호
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    • pp.972-976
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    • 1997
  • Single phase ruthenium oxides with perovskite (ATi1-xRuxO3 (A=Ca, Sr)) and pyrochlore structure (Bi2Ru2O7, Pb2Ru2O6.5) have been prepared reproducibly by solid state reaction methods and their electrocatalytic activities for oxygen evolution have been examined by Tafel plots. Tafel slopes vary from a low value of 42 mV/decade up to 222 mV/decade at room temperature. The high exchange current densities and high Tafel slopes compared with those obtained from the RuO2 DSA electrode at the crystalline single phase metal oxide electrodes suggest that they are better electrocatalysts at low overpotentials. A favorable change in the Tafel slope for the oxygen evolution reaction occurs as the ruthenium content increases. Substitution of Ti for Ru in the perovskite solid solutions enhanced their chemical stability by losing marginal electrochemical activity.

RF-마그네트론 스퍼터링법으로 제작한 이층형 PZT의 특성평가 (Evaluating Properties for Bi-layer PZT thin film Fabricated by RF-Magnetron Sputtering System)

  • 임실묵
    • 한국산학기술학회논문지
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    • 제21권8호
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    • pp.222-227
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    • 2020
  • 페로부스카이트(Perovskite) 구조의 Pb(Zr,Ti)O3(PZT)는 우수한 강유전 특성으로 인해 유전체, 압전체, 초전체 재료로 널리 사용된다. Pb1.3(Zr0.52Ti0.48)O3조성의 스퍼터링 타겟을 제조하여 RF 마그네트론 스퍼터링 공정으로 PZT박막을 형성하였다. PZT박막은 동일 스퍼터링 출력으로 연속 제조한 단층형 PZT와 2단계화한 스퍼터링 출력으로 제조한 2층형 PZT박막으로 구분하여 제조하였다. 2층형의 PZT는 저출력의 스퍼터링 조건으로 제작한 하부층과, 단층형 PZT와 동일한 조건으로 제작한 상부층으로 이루어진다. 제조한 박막에 대한 엑스선 회절분석결과, 단층형 PZT에서는 페로부스카이트상(Perovskite Phase)과 미소한 파이로클로르상(Pyrochlore Phase)이 혼합된 상태로 존재하나, 2층형 PZT에서는 페로부스카이트상만이 검출되었다. 전자현미경과 원자힘 현미경으로 표면상태를 관찰한 결과, 2층형 PZT박막의 상부는 단층형에 비해 치밀하고 평활한 표면상태를 나타냈으며, 단층형에 비해 낮은 표면거칠기값(RMS)을 보였다. 또한 이층형 PZT는 단층형에 비해 우수한 대칭성의 분극곡선형태를 보였고, 단층형에 비해 매우 저감된 1×10-5 A/㎠ 이하수준의 누설전류 특성을 나타냈다. 이층형 PZT에서 보이는 이러한 현상은 치밀하게 형성한 하부 PZT층이 순차적으로 형성되는 상부PZT내의 미소 파이로클로르상 형성을 억제하여, 순수한 페로부스카이트상으로의 성장을 유도한 것으로 판단된다.

Pyrochlore상의 부피분율에 따른 PMN-Pyrochlore 2상 혼합체의 유전율변화;General Effective Media식의 적용 (Variation of Dielectric Constant with the Volume Fraction of Pyrochlore Phae in the PMN-Polychlore Diphasic System ; Application of General Effective Media Equation)

  • 허강일;김정주;김남경;김진호;조상희
    • 한국세라믹학회지
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    • 제30권1호
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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.

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Pb(Mg1/3Nb2/3)O3계의 유전성에 미치는 BaTiO3첨가량 및 열처리 온도의 영향 (PMN-BaTiO3계 세라믹스의 합성 및 유전성) (Influence of BaTiO3 Content and Firing Temperature on the Dielectric Properties of Pb(Mg1/3Nb2/3)O3 Ceramics)

  • 윤기현;강동헌
    • 한국세라믹학회지
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    • 제26권2호
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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.

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고준위 핵페기물의 고정화를 위한 메트릭스 개발 : Ce파이로클로어 합성 연구 (Development of Matrix for the Immobilization of High Level Radioactive Waste : Study on the Synthesis of Ce-pyrochlore)

  • 채수천;장영남;배인국
    • 자원환경지질
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    • 제35권2호
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    • pp.97-102
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    • 2002
  • Ce-파이로클로어(Ce-pyrochlore; CaCe $Ti_2 $O_7)는 장주기 방사성 폐기물인 악티나이드 원소들을 고정화시킬 수 있는 새로운 물질이므로 Ce-파이로클로어를 합성하여 강평형 관계 및 특성을 연구하였다. 혼합된 시료는 상온에서 200-400kg/$\textrm{cm}^2$의 압력으로 성형한 후, 1000-150$0^{\circ}C$ 범위에서 소결온도 및 분위기를 변화시키면서 소성하였다. 합성된 시료는 XRD, SEM/EDS를 사용하여 상분석과 정량분석을 실시하였다. 실험결과, Ce-파이로클로어이 최적 합성조건은 산소분위기 하에서, 130$0^{\circ}C$로 소결하였을 때였으며, 이때의 화학조성은 $Ca_{1-x}Ti_{2-y}O_{7-x-2y}$ (x=0.03-0.05, y=0.02~0.04) 으로써 비화학양론적인 특성을 보였다. Ce-파이로클로어는 1300~140$0^{\circ}C$에서 빠른 비조화 분해현상을 나타내었으며, 140$0^{\circ}C$ 이상에서는 페로브스카이트(perovskite)와 로파라이트(loparite; $Ce_{0.66}TiO_{3}$)사이의 부분 고용체인 Ce(III)페로브스카이트가 주요상으로써 관찰되었다.