• 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 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.

• Journal of the Mineralogical Society of Korea
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• v.15 no.1
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• pp.78-84
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• 2002

New pyrochlore-type phases($A_2$$B_2$$O_{7}$) were synthesized in the systems: CaO-C$eO_2$-T$iO_2$, CaO-$UO_2$(T$hO_2$)-Z$rO_2$, CaO-$UO_2$(T$hO_2$)-$Gd_2$$O_3$-T$iO_2$-Z$rO_2$, 및 CaO-T$hO_2$-S$nO_2$. The starting materials were pressed with the pressure of 200~400 MPa and sintered at 1500~ 155$0^{\circ}C$ for 4~8 hours in air and at 1300~ 135$0^{\circ}C$ for 5 ~50 hours under oxygen atmosphere. The products were characterized using XRD, SEM/EDS and TEM. In the bulk compositions of CaCe$Ti_2$$O_{7}$, CaTh$Zr_2$$O_{7}$,($Ca_{0.5}$ Gd$Th_{0.5}$)(ZrTi)$O_{7}$) ($Ca_{0.5}$Gd$Th_{0.5}$)(ZrTi)$O_{7}$, ($Ca_{0.5}$G$dU_{0.5}$)(ZrTi)$O_{7}$ and CaTh$Sn_2$$O_{7}$ , pyrochlore was the major phase, together with other oxide phase $of_2$$O_{7}$ fluorite structure. In the samples with target compositions CaU$Zr_2$$O_2$및 $Ca_{0.5}$ G$dU_{0.5}$)$Zr_2$T$iO_{7}$ pyrochlore was not identified, but a fluorite-structured phase was detected. The formation factor as the stable phase depended on crystal chemical characteristics of the actinide and lanthanide elements of the system concerned.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.407-413
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• 2003

The geology of the Apdong Nb-Ta deposit, is hosted by alkali metasomatites, consist of Upper Proterozoic sedimentary rocks, alkali syenites(Hoamsan intrusive) of Phyonggang Complex(late Paleozoic to early Mesozoic), Jurassic granite and Quaternary basalt. Alkali syenites are distinguished as alkali amphibole-pyroxene syenite, alkali amphibole-biotite syenite, biotite-nepheline syenite, biotite syenite, and quartz-alkali amphibole-pyroxene syenite. Alkali metasomatites are the products of intense post-magnatic metasomatism, and form the Nb-Ta ore bodies as the belt, irregular vein and lenticular types in the southern part of Hoamsan intrusive. The ore mineralization is characterized by the occurrence of pyrochlore, zircon, and small amounts of columbite, fergusonite. magnetite, fluorite, molybdenite, ilmenite, titanite, apatite, and monazite. Pyrochlore is one of the niobium/tantalum oxides and contains substantial amounts of rare earths and radioactive elements. The compositional varieties of pyrochlore can be defined: (1) enriched in tantalum, uranium and cerium, (2) substantially tantalum- and fluorine-poor, and (3) enriched in thorium or barium. The geochemical characteristics, ore textures and mineral occurrences indicate that alkali metasomatism of the mineralizing fluid was the dominant ore-forming process.

• 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.

• Journal of Powder Materials
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• v.22 no.6
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• pp.420-425
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• 2015

Rare-earth zirconates, such as lanthanum zirconates and gadolinium zirconates, have been intensively investigated due to their excellent properties of low thermal conductivity as well as chemical stability at high temperature, which can make these materials ones of the most promising candidates for next-generation thermal barrier coating applications. In this study, three compositions, lanthanum/gadolinium zirconates with reduced rare-earth contents from stoichiometric $RE_2Zr_2O_7$ compositions, are fabricated via solid state reaction as well as sintering at $1600^{\circ}C$ for 4 hrs. The phase formation, microstructure, and thermo-physical properties of three oxide ceramics are examined. In particular, each oxide ceramics exhibits composite structures between pyrochlore and fluorite phases. The potential of lanthanum/gadolinium zirconate ceramics for TBC applications is also discussed.

• Journal of Powder Materials
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• v.22 no.6
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• pp.413-419
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• 2015

Lanthanum zirconate, $La_2Zr_2O_7$, is one of the most promising candidates for next-generation thermal barrier coating (TBC) applications in high efficient gas turbines due to its low thermal conductivity and chemical stability at high temperature. In this study, bulk specimens and thermal barrier coatings are fabricated via a variety of sintering processes as well as suspension plasma spray in lanthanum zirconates with reduced rare-earth contents. The phase formation, microstructure, and thermo-physical properties of these oxide ceramics and coatings are examined. In particular, lanthanum zirconates with reduced rare-earth contents in a $La_2Zr_2O_7-4YSZ$ composite system exhibit a single phase of fluorite or pyrochlore after fabricated by suspension plasma spray or spark plasma sintering. The potential of lanthanum zirconate ceramics for TBC applications is also discussed.

• Journal of the Korean Ceramic Society
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• v.53 no.6
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• pp.652-658
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• 2016

Gadolinium zirconate, $Gd_2Zr_2O_7$, is one of the most versatile oxides among the new thermal-barrier-coating (TBC) materials for replacing conventional yttira-stabilized zirconia (YSZ). $Gd_2Zr_2O_7$ exhibits excellent properties, such as low thermal conductivity, high thermal expansion coefficient comparable with that of YSZ, and chemical stability at high temperature. In this study, bulk and coating specimens with $Gd_{2-x}Zr_{2+x}O_{7+0.5x}$ (x = 0.0, 0.5, 1.0) compositions were fabricated in order to examine the characteristics of this gadolinium zirconate system with different Gd content for TBC applications. Especially, coatings with $Gd_{2-x}Zr_{2+x}O_{7+0.5x}$ (x = 0.0, 0.5, 1.0) compositions were produced by suspension plasma spray (SPS) with suspension of raw powder mixtures prepared by planetary milling followed by ball milling. Phase formation, microstructure, and thermal diffusivity were characterized for both sintered and coated specimens. Single phase materials with pyrochlore or fluorite were fabricated by normal sintering as well as SPS coating. In particular, coated specimens showed vertically-separated columnar microstructures with thickness of $400{\sim}600{\mu}m$.

• Economic and Environmental Geology
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• v.46 no.2
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• pp.179-198
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• 2013

The Boziguoer A-type granitoids in Baicheng County, Xinjiang, belong to the northern margin of the Tarim platform as well as the neighboring EW-oriented alkaline intrusive rocks. The rocks comprise an aegirine or arfvedsonite quartz alkali feldspar syenite, an aegirine or arfvedsonite alkali feldspar granite, and a biotite alkali feldspar syenite. The major rock-forming minerals are albite, K-feldspar, quartz, arfvedsonite, aegirine, and siderophyllite. The accessory minerals are mainly zircon, pyrochlore, thorite, fluorite, monazite, bastnaesite, xenotime, and astrophyllite. The chemical composition of the alkaline granitoids show that $SiO_2$ varies from 64.55% to 72.29% with a mean value of 67.32%, $Na_2O+K_2O$ is high (9.85~11.87%) with a mean of 11.14%, $K_2O$ is 2.39%~5.47% (mean = 4.73%), the $K_2O/Na_2O$ ratios are 0.31~0.96, $Al_2O_3$ ranges from 12.58% to 15.44%, and total $FeO^T$ is between 2.35% and 5.65%. CaO, MgO, MnO, and $TiO_2$ are low. The REE content is high and the total ${\sum}REE$ is $(263{\sim}1219){\times}10^{-6}$ (mean = $776{\times}10^{-6}$), showing LREE enrichment HREE depletion with strong negative Eu anomalies. In addition, the chondrite-normalized REE patterns of the alkaline granitoids belong to the "seagull" pattern of the right-type. The Zr content is $(113{\sim}1246){\times}10^{-6}$ (mean = $594{\times}10^{-6}$), Zr+Nb+Ce+Y is between $(478{\sim}2203){\times}10^{-6}$ with a mean of $1362{\times}10^{-6}$. Furthermore, the alkaline granitoids have high HFSE (Ga, Nb, Ta, Zr, and Hf) content and low LILE (Ba, K, and Sr) content. The Nb/Ta ratio varies from 7.23 to 32.59 (mean = 16.59) and the Zr/Hf ratio is 16.69~58.04 (mean = 36.80). The zircons are depleted in LREE and enriched in HREE. The chondrite-normalized REE patterns of the zircons are of the "seagull" pattern of the left-inclined type with strong negative Eu anomaly and without a Ce anomaly. The Boziguoer A-type granitoids share similar features with A1-type granites. The average temperature of the granitic magma was estimated at $832{\sim}839^{\circ}C$. The Boziguoer A-type granitoids show crust-mantle mixing and may have formed in an anorogenic intraplate tectonic setting under high-temperature, anhydrous, and low oxygen fugacity conditions.