• Journal of the Korean Physical Society
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• v.73 no.10
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• pp.1535-1540
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• 2018

In this study, we prepared and characterized Nb-doped $Li_7La_3Zr_{2-x}O_{12}$ (LLZNO) powder and pellets with a cubic garnet structure by using a modified sol-gel synthesis and hot pressing. LLZNO powder with a very small grain size and cubic structure without secondary phases could be obtained by using a synthesis method in which Li and La sources in a propanol solvent were mixed together with Zr and Nb sources in 2-methoxy ethanol. A pure cubic phase LLZNO pellet could be fabricated from the prepared LLZNO and an additional 6-wt% of $Li_2CO_3$ powder by hot pressing at $1050^{\circ}C$ and 15.8 MPa. The hot-pressed LLZNO pellet with a relative density of 99% exhibited a very dense surface morphology. The total Li ionic conductivity of the hot-pressed LLZNO was $7.4{\times}10^{-4}S/cm$ at room temperature, which is very high level compared to other reported values. The activation energy for ionic conduction was estimated to be 0.40 eV.

• Journal of the Korean Ceramic Society
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• v.56 no.2
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• pp.111-129
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• 2019

Recently, all-solid-state batteries (ASSBs) have attracted increasing interest owing to their higher energy density and safety. As the core material of ASSBs, the characteristics of the solid electrolyte largely determine the performance of the battery. Thus far, a variety of inorganic solid electrolytes have been studied, including the NASICON-type, LISICON-type, perovskite-type, garnet-type, glassy solid electrolyte, and so on. The garnet Li₇La₃Zr₂O₁₂ (LLZO) solid electrolyte is one of the most promising candidates because of its excellent comprehensively electrochemical performance. Both, experiments and theoretical calculations, show that cubic LLZO has high room-temperature ionic conductivity and good chemical stability while contacting with the lithium anode and most of the cathode materials. In this paper, the crystal structure, Li-ion transport mechanism, preparation method, and element doping of LLZO are introduced in detail based on the research progress in recent years. Then, the development prospects and challenges of LLZO as applied to ASSBs are discussed.

• Journal of the Mineralogical Society of Korea
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• v.2 no.1
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• pp.26-36
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• 1989

Clinopyroxene in the Geodo mine belongs to diopside-hedenbergite series. It is widely distributed throughout the mine area together with garnet and is also closely related with Fe-mineralization. Clinopyroxenes in the Geodo mine including two samples from the sangdong and Ulchin Mines are studied using polarized microscope, EPMA, XRD, and IR spectroscopy for occurrence, chemistry, structure, and crystal chemistry. Especially, variations in unit-cell parameters are examined in relation with the substitution scheme between Fe and Mg cations. Clinopyroxenes in the Geodo mine occur in both endoskarn and exoskarn zone. It is mostly anhedral to subhedral with fine- to medium-grained in texture, but some have bigger crystals of short prismatic or columnar habits. Clinopyroxene occurs as monomineralic or is associated with mostly garnet and sometimes with actinolite, magnetite, epidote, and chlorite. Chemical analysis reveals that the Geodo clinopyroxene is diopsidic in composition (Di: 65-96%). This fact is in good contrast with garnet chemistry showing mostly andraditic (An: 41-82%). Especially, clinopyroxene coexisting with magnetite belongs to nearly end member diopside (Di: 97-99%). Thus, diopside-andradite pair indicates that Geodo skarns were formed under the reduced environment. X-ray diffraction analysis shows unit-cell parameters vary with increase of Fe contents: a = 9.765-9.838$\AA$, b = 8.943-9.020$\AA$, c= 5.240-5.253$\AA$.$\beta$ = 105.70-104.83$^{\circ}$, and V =440.64-448.19$\AA$3. It is noted from the least square regression that a, b and V increase linearly with increase of Fe content, while $\beta$ slightly decreases and c remains nearly unchanged as change in Fe content. These trends are to difference between synthetic and natural clinopyroxenes. This fact is also recognized in IR spectra which show a slight shift of several absorption bands toward lower wavenumber region with increasing Fe content.

• Journal of Magnetics
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• v.13 no.3
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• pp.110-113
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• 2008

In this study, heavy rare earth garnet $Tb_2Bi_1Ga_1Fe_4O_{12}$ powders were fabricated by a sol-gel and vacuum annealing process. The crystal structure was found to be single-phase garnet with a space group of Ia3d. The lattice constant $a_0$ was determined to be 12.465 ${\AA}$. From the analysis of the vibrating sample magnetometer (VSM) hysteresis loop at room temperature, the saturation magnetization and coercivity of the sample are 7.64 emu/g and 229 Oe, respectively. The N$\acute{e}$el temperature($T_N$) was determined to be 525 K. The M$\ddot{o}$ssbauer spectrum of $Tb_2Bi_1Ga_1Fe_4O_{12}$ at room temperature consists of 2 sets of 6 Lorentzians, which is the pattern of single-phase garnet. From the results of the M$\ddot{o}$ssbauer spectrum at room temperature, the absorption area ratios of Fe ions on 24d and 16a sites are 74.7% and 25.3%(approximately 3:1), respectively. These results show that all of the non-magnetic Ga atoms occupy the 16a site by a vacuum annealing process. Absorption area ratios of Fe ions are dependent not only on a sintering condition but also on the temperature of the sample. It can then be interpreted that the Ga ion distribution is dependent on the temperature of the sample. The M$\ddot{o}$ssbauer measurement was carried out in order to investigate the atomic migration in $Tb_2Bi_1Ga_1Fe_4O_{12}$.

• Journal of the Korean Magnetics Society
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• v.16 no.5
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• pp.245-248
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• 2006

[ $Tb_{3-x}Bi_xFe_5O_{12}$ ] has been studied by x-ray diffraction (XRD), vibrating sample magnetometer, $M\"{o}ssbauer$ spectroscopy. The crystal structures were found to be a cubic garnet structure with space group Ia3d. The lattice constants increase linearly with increasing bismuth concentration. With increase of bismuth substitution, the $N\'{e}el$ temperature increases but the compensation temperature decreases. We have observed the negative magnetization in Bi-TbIG system which has not been reported in garnet systems. $M\"{o}ssbauer$ spectra were measured at various temperatures from 4.2 K to $N\'{e}el$ temperature. The isomer shifts at room temperature are ${\sim}0.26mm/s$ which is consistent with ferric state.

• Korean Journal of Materials Research
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• v.13 no.1
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• pp.48-52
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• 2003

The substituted yttrium iron garnet systems $Y_{ 3-x}$/Gd$_{x}$X$0.2_{0.2}$ $Fe_{4.8}$ $O _{12}$ (x = 0.2, 0.4, 0.6) have been investigated by means of X-ray diffraction, Mossbauer spectroscopy and SQUID. The X-ray diffraction patterns at room temperature confirm the samples to have a single phase of the garnet structure over the whole composition range. The lattice constants of all the samples linearly change with increasing x due to the size of substituted ions in the dodecahedral sites. $Y_{3-x}$ $Gd_{x}$ X$Fe_{4.8}$ $In_{0.2}$ $O_{12}$ system which $Y_{3-x}$ ions are substituted with Gd$^{ 3＋}$ ions, the Mossbauer spectrum consists of three Zeeman sextets at room temperature, one due to the $Fe^{3＋}$ ions on the octahedral(a-) sites and the others due to the $Fe^{3＋}$ ions on the tetrahedral(d-, d'-) sites, respectively. From the hysteresis loop measured by means of SQUID over the whole composition range, the saturation magnetization $M_{s}$ and magnetic moments $\mu_{ B}$ per unit cell have been obtained. The increment of Gd-ion content causes $M_{s}$ and $\mu_{B}$ decrease while the increment of In-ion content does not.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.11a
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• pp.322-323
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• 2006

The nano-sized Ce-doped YAG(Yttrium Aluminum Garnet, $Y_3Al_5O_{12}$) phosphor powders were prepared by combustion method from a mixed aqueous solution of metal nitrates, using citric acid as a fuel. The luminescence formation process and structure of phosphor powders were investigated by means of XRD, SEM and PL. The XRD patterns show that YAG phase can form at all of the $Ce^{3+}$ concentration. However, when $Ce^{3+}$ concentration is over 2.0mol%, XRD patterns show $CeO_2$ peak between (321) peak and (400) peak. The pure crystalline YAG:Ce with uniform size of 30nm was obtained at 0.6mol% of the $Ce^{3+}$ concentration. The crystalline YAG:Ce powders showed broad emission peaks in the range 475~630nm and had maximum intensity at 526nm.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.06a
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• pp.489-490
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• 2006

The Ce-doped YAG(Yttrium Aluminum Garnet, $Y_3Al_5O_{12}$) phosphor powders were synthesized by Sol-gel method. The luminescence, formation process and structure of phosphor powders were investigated by means of XRD, SEM and PL. The XRD patterns show that YAG phase can form through sintering at $1000^{\circ}C$ for 2h. This temperature is much lower than that required to synthesize YAG phase via the conventional solid state reaction method. There were no intermediate phases such as YAP(Yttrium Aluminum Perovskite, $YAlO_3$) and YAM(Yttrium Aluminum Monoclinic, $Y_4Al_2O_9$) observed in the sintering process. The powders absorbed excitation energy in the range 410~510nm. Also, the crystalline YAG:Ce showed broad emission peaks in the range 480~600nm and had maximum intensity at 528nm.

• Nuclear Engineering and Technology
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• v.54 no.7
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• pp.2579-2585
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• 2022

Ceramics of quaternary garnets (Gd,Y)₃Al₂Ga₃O₁₂ doped with Ce, Tb have been fabricated and evaluated as prospective materials for indirect energy converters of α-and β-voltaic. Samples were characterized at excitation with an X-ray source and an intense 150 keV electron beam and showed good temperature stability of their emission and tolerance to irradiation. The role of X-rays accompanied the α-particle emitting in the increase of the conversion efficiency is clarified. The garnet-type structure of the matrix in the developed materials allows the production of quality crystalline mass with a light yield exceeding that of the commonly used YAG: Ce scintillator by a factor of two times.

• Economic and Environmental Geology
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• v.38 no.2 s.171
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• pp.187-196
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• 2005

Structural sites which cations can occupy in garnet structure are centers of the tetrahedron, octahedron, and distorted cube sharing edges with the tetrahedron and octahedron. Among them, the size of cation occuping at tetrahedral site (the center of tetrahedron) is closely related with the size of a unit cell of garnet. Accordingly, garnet containing iron with relative large ionic radii in tetrahedral site can be considered as a promising matrix for the immobilization of the elements with large ionic radii, such as actinides in radioactive wastes. We synthesized several garnets with the batch composition of $Ca_{1.5}GdCe_{0.5}ZrFeFe_3O_{12}$, and studied their properties and phase relations under various conditions. Mixed samples were fabricated in a pellet form under a pressure of $200{\~}400{\cal}kg/{\cal}cm^2$ and were sintered in the temperature range of $1100\~1400^{\circ}C$ in air and under oxygen atmospheres. Phase identification and chemical analysis of synthesized samples were conducted by XRD and SEM/EDS. In results, garnet was obtained as the main phase at $1300^{\circ}C$, an optimum condition in this system, even though some minor phases like perovskite and unknown phase were included. The compositions of garnet and perovskite synthesized from the batch composition of $Ca_{1.5}GdCe_{0.5}ZrFeFe_3O_{12}$ were ranged $[Ca_{l.2-1.8}Gd_{0.9-1.4}Ce_{0.3-0.5}]^{VIII}[Zr_{0.8-1.3}Fe_{0.7-1.2}]^{VI}[Fe_{2.9-3.1}]^{IV}O_{12}$ and $Ca_{0.1-0.5}Gd_{0.0-0.8}Ce_{0.1-0.5}\;Zr_{0.0-0.2}Fe_{0.9-1.1}O_3$, respectively. Ca content was exceeded and Ce content was depleted in the 8-coordinated site, comparing to the initial batch composition. This phenomena was closely related to the content of Zr and Fe in the 6-coordinated site.