• Title/Summary/Keyword: pyrochlore phase

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

  • ;;;Yudintsev, S. V²
    • Economic and Environmental Geology
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    • v.35 no.2
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    • pp.97-102
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    • 2002
  • Ce-pyrochlore (CaCe $Ti_2 $O_7)was synthesized to study its properties and phase relations in CaO-Ce $O_2$-Ti $O_2$ system because Ce-pyrochlore was known as a promising material for the immobilization of radioactive actinide. The samples were prepared from the high purity starling materials under the pressure of 200~400 kg/$\textrm{cm}^2$ at room temperature, and annealed at 1000~ 150$0^{\circ}C$. The Synthesized samples were analysed and indentified with XRD and SEM/EDS methods. The optimal formation condition of Ce-pyrochlore was at 130$0^{\circ}C$ under $O_2$ atmosphere and the chemical composition of it wasCa$Ca_{1-x}Ti_{2-y}O_{7-x-2y}$(x=0.03-0.05, y=0.02~0.04) At temperature between 130$0^{\circ}C$ 140$0^{\circ}C$, Ce-pyrochlore underwent rapidly the incongruent decomposition to perovskite. Ce-perovskite, a partial solid solution between perovskite and loparite (C $e_{0.66}$Ti $O_3$), was observed as a major phase above 140$0^{\circ}C$.>.

Synthesis of Pyrochlore in the System of Ca-Ce-Hf-Ti-O (Ca-Ce-Hf-Ti-O System에서의 파이로클로어 합성)

  • ;;;S. V. Yudintsev
    • Economic and Environmental Geology
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    • v.37 no.4
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    • pp.375-381
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    • 2004
  • Pyrochlore was known as one of the most promising materials for the immobilization of radioactive actinide. This study includes the synthesis, phase relation and characteristics of pyrochlores (CaCeH$f_xTi_{2-x}O_7$=0.2, 0.6, 1.0, 1.4, 1.8, 2.0) in the system of Ca-Ce-Hf-Ti-O. The samples were prepared from high purity of starting materials under the pressure of 400kg/cm$^2$ at room temperature, and were sintered at 1200∼1$600^{\circ}C$ The synthesized samples were analyzed and identified with XRD. The optimal formation conditions of pyrochlores were at 1300∼150$0^{\circ}C$ under $O_2$ atmosphere with batch compositions. During synthesis, pyrochlore, perovskite and $A_{2}BO_{5}$ oxide were formed. The characteristics of this system is that parameter of pyrochlore was increased with the content of hafnium. This phenomenon was due to the difference of ionic size between hafnium and titanium in six coordinated site.

Phase Evolution and Thermal Conductivities of (La1-xGdx)2Zr2O7 Oxides for Thermal Barrier Coatings (열차폐코팅용 (La1-xGdx)2Zr2O7 산화물의 상형성과 열전도도)

  • Kwon, Chang-Sup;Lee, Sung-Min;Oh, Yoon-Suk;Kim, Hyung-Tae;Jang, Byung-Koog;Kim, Seong Won
    • Journal of Powder Materials
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    • v.19 no.6
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    • pp.429-434
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    • 2012
  • With increase in operating temperature of gas turbine for higher efficiency, it is necessary to find new materials of TBC for replacement of YSZ. Among candidate materials for future TBCs, zirconate-based oxides with pyrochlore and fluorite are prevailing ones. In this study, phase structure and thermal conductivities of $(La_{1-x}Gd_x)_2Zr_2O_7$ oxide system are investigated. $(La_{1-x}Gd_x)_2Zr_2O_7$ system are comprised by selecting $La^{3+}/Gd^{3+}$ as A-site ions and $Zr^{4+}$ as B-site ion in $A_2B_2O_7$ pyrochlore structures. With powder mixture from each oxide, $(La_{1-x}Gd_x)_2Zr_2O_7$ oxides are fabricated via solid-state reaction at $1600^{\circ}C$. Either pyrochlore or fluorite or mixture of both appears after heat treatment. For the developed phases along $(La_{1-x}Gd_x)_2Zr_2O_7$ compositions, thermal conductivities are examined, with which the potential of $(La_{1-x}Gd_x)_2Zr_2O_7$ compositions for TBC application is also discussed.

Order-disorder structural tailoring and its effects on the chemical stability of (Gd, Nd)2(Zr, Ce)2O7 pyrochlore ceramic for nuclear waste forms

  • Wang, Yan;Wang, Jin;Zhang, Xue;Li, Nan;Wang, Junxia;Liang, Xiaofeng
    • Nuclear Engineering and Technology
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    • v.54 no.7
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    • pp.2427-2434
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    • 2022
  • Series of unequal quantity Nd/Ce co-doped ceramic nuclear waste forms, (Gd, Nd)2(Zr, Ce)2O7, were prepared to tailor its ordered pyrochlore or disordered fluorite structure. The phase transition, microtopography, and elemental composition of the ceramic samples were systematically investigated, especially the effect of order-disorder structure on the chemical stability. It was confirmed that unequal quantity of Nd/Ce could synchronously replace the Gd/Zr-sites of Gd2Zr2O7. And the phase transition of order-disorder structure could be successfully tailored by regulating the average cationic radius ratio of (Gd, Nd)2(Zr, Ce)2O7 series. The elements of Gd, Nd, Zr, and Ce are uniformly distributed in the ordered or disordered structures. The MCC-1 leaching results showed that (Gd, Nd)2(Zr, Ce)2O7 pyrochlore ceramic nuclear waste forms had excellent chemical stability, whose elements' normalized leaching rates were as low as 10-4-10-7 g·m-2·d-1 after 7 days. In particular, the chemical stability of disordered structure was superior to that of ordered structure. It was proposed that the force constant and the closest packing were changed with the structure transformation resulting the chemical stability difference.

Preparation and Characterization of Ta-substituted Li7La3Zr2-xO12 Garnet Solid Electrolyte by Sol-Gel Processing

  • Yoon, Sang A;Oh, Nu Ri;Yoo, Ae Ri;Lee, Hee Gyun;Lee, Hee Chul
    • Journal of the Korean Ceramic Society
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    • v.54 no.4
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    • pp.278-284
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    • 2017
  • In this work, Ta-substituted $Li_7La_3Zr_{2-x}O_{12}$ (LLZTO) powder and pellets with garnet cubic structure were fabricated and characterized by modified and optimized sol-gel synthesis. Ta-substituted LLZO powder with the smallest grain size and pure cubic structure with little pyrochlore phase was obtained by synthesis method in which Li and La sources in propanol solvent were mixed together with Zr and Ta sources in 2-methoxy ethanol. The LLZTO pellets made with the prepared powder showed cubic garnet structure for all conditions when the amount of Li addition was varied from 6.2 to 7.4 mol. All the X-ray peaks of the pyrochlore phase disappeared when the Li addition was increased above 7.0 mol. When the final sintering temperature was varied, the LLZTO pellet had a pyrochlore-mixed cubic phase above $1000^{\circ}C$. However, the surface morphology became much denser when the final sintering temperature was increased. The sol-gel-driven LLZTO pellet with a sintering temperature of $1100^{\circ}C$ showed a lithium ionic conductivity of 0.21 mS/cm when Au was adopted as electrode material for the blocking capacitor. The results of this study suggest that modified sol-gel synthesis is the optimum method to obtain cubic phase of LLZTO powder for highly dense and conductive solid electrolyte ceramics.

Sintering and the Electrical Properties of Co-doped $ZnO-Bi_2O_3-Sb_2O_3$ Varistor System (Co를 첨가한 $ZnO-Bi_2O_3-Sb_2O_3$ 바리스터의 소결 및 전기적 특성)

  • 김철홍;김진호
    • Journal of the Korean Ceramic Society
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    • v.37 no.2
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    • pp.186-193
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    • 2000
  • Effects of 1.0 mol% CoO addition on sintering and the electrical properties of ZnO-Bi2O3-Sb2O3(ZBS) varistor system with 3.0 mol% co-addition of Sb2O3 and Bi2O3 at various Sb/Bi ratio (0.5, 1.0, and 2.0) were investigated. Cobalt had little influence on the liquid-phase formation and the pyrochlore decomposition temepratures of ZBS, while densification was mainly dependent on Sb/Bi ratio: when Sb/Bi=0.5, excess Bi2O3 irrelevant to the formation of pyrochore(Zn2Sb3Bi3O14) forms eutectic liquid at ~75$0^{\circ}C$ which promotes densification and grain growth; with Sb/Bi=2.0, the second phase Zn7Sb2O12 formed by excess Sb2O3 irrelevant to the formation of the pyrochlore retards densification up to ~100$0^{\circ}C$. These phases caused the coarsening and uneven distribution of the second phase particles on the grain boundaries of ZnO above the pyrochlore decomposition temperature(~105$0^{\circ}C$), which led to broad size dist-ribution of ZnO; the specimen with Sb/Bi=1.0 showed homogeneous microstructure compared with the others, which enabled improved varistor characteristics. Doping of Co increased the nonlinearity and the potential barrier height of ZBS, which is thought to stem from improved sintering behavior such as homogenized microstructure due to size reduction and even distribution of the second phase and suppressed volatility of Bi2O3, as well as the improvement in the potential barrier structure via increased donor and interface electron trap densities.

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Optical Properties of Lead Zirconate Thin Films by Sol-gel Method (SoI-gel법으로 제작된 lead zirconate 박막의 광학적 특성)

  • Jeon, Kie-Beom;Bae, Se-Hwan
    • Journal of Korean Ophthalmic Optics Society
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    • v.3 no.1
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    • pp.21-25
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    • 1998
  • We investigated the optical properties of lead zirconate($PbZrO_3$, PZ) thin films. The PZ films for the measurement of optical properties were prepared on ITO glass by sol-gel method. By post annealing, with annealing temperature $T=700^{\circ}C$, the pyrochlore phase of as-deposited specimen was transformed into the perovskite phase. The surface of films were plat, transmittance were from 60 to 80% at 480~2000nm, and refractive index were from 2.1 to 1.9 at 480~1000nm.

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Electrical Properties of Pb($Zn_{x}Nb_{1-x}$)$O_3$ Ceramic by Composition (조성비에 따른 Pb($Zn_{x}Nb_{1-x}$)$O_3$세라믹의 전기적 특성)

  • 이수호;사공건
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1993.11a
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    • pp.14-16
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    • 1993
  • In this Paper. Pb($Zn_{x}Nb_{1-x}$)$O_3$ ceramics were fabricated by the mixed oxide method. The sintering temperature and time were 1,000($^{\circ}C$). 1(hr). respectively. According to the contents of $ZnO_2$, the depression of pyrochlore phase and its effects were studied. As the results of the XRD patterns and SEM. the pyrochlore and second phase were increased with increasing the $ZnO_2$. As the $ZnO_2$ content was increased. density was decreased.

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Sintering and Electric Prooperties of Pb(Zn, Nb)$O_3$-Pb(Ni, Nb))$O_3$-$PbTiO_3$-$PbZrO_3$ System (Pb(Zn, Nb)$O_3$-Pb(Ni, Nb))$O_3$-$PbTiO_3$-$PbZrO_3$계 세라믹스의 소결 및 전기적 특성)

  • 박재성;이기태;남효덕
    • Journal of the Korean Ceramic Society
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    • v.27 no.7
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    • pp.934-942
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    • 1990
  • The quarternary system ceramics 0.5[yPb(Zn1/3Nb2/3)O3-(1-y)Pb(Ni1/3Nb2/3)O3]-0.5[xPbTiO3-(1-x)PbZrO3](PZN-PNN-PT-PZ) was fabricated by the columbite precursor method to obtain a stabilized perovskite structure and by conventional method to evaluate the efficiency of the former methd. Dielectric and piezoelectric properties were investigated and the stability of the perovskite phase was studied as a function of PZN and PT contents and firing temperature. In the samples prepared by the columbite precursor method, the pyrochlore phase, which is detrimental to both the dielectric and piezoelectric properties, was not observed in the absence of PZN, and electric properties were improved even when fabricated at low temperature. By adding PZN, some pyrochlore phase appeared and the morphotropic phase boundary of the samples shifted to more Zr-rich composition. The temperature dependence of piezoelectric constant decreased with the addition of PZN, due to the rising of the Curie point.

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Synthesis of $Pb(Mg_{1/3}Nb_{2/3})O_3$ powder by Solvent Evaporation and its Dielectric Property (용매 증발법에 의한 $Pb(Mg_{1/3}Nb_{2/3})O_3$ 분말 합성 및 유전 성질)

  • Lee, Jong-Pil;Lee, Jong-Kook;Kang, Sang-Gu;Kim, Hwan
    • Journal of the Korean Ceramic Society
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    • v.33 no.1
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    • pp.17-24
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    • 1996
  • Pb(Mg1/3Nb2/3)O3 powder with high purity chemical homogeniety and reactivity was prepared by solvent eva-poration of common solution. The common solution was fabricated using a Pb(NO3)2 Mg(NO)3 and NB solution which was prepared by dissolving NbC in H2O2 acquous solution. In precusor powder prepared by solvent evaporation method the synthetic temperature of Pb(Mg1/3 Nb2/3)O3 phase was lowered. And the formation of homogeneous Pb(Mg1/3Nb2/3)O3 phase was enhanced but the formation of pyrochlore phase was reduced. The dielectric constant of PMN ceramics from the synthesized powder was found to increase with both sintering temperature and excess MgO and subsequent analysis of the microstructures confirmed that this was due to an increase in grain size. The grain size dependence is explained as a consequence of low-permittivity grain boundaries.

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