• Nuclear Engineering and Technology
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• v.28 no.2
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• pp.118-128
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• 1996

The lattice parameters of stoichiometric $UO_2$ and $U_{1-y}Er_{y}O_2$ in the range of y=0.01 to y =0.33 were determined with use of X-ray diffraction data. Oxygen potentials have been measured by means of a thermogravimetric method in the range of 1200~$1500^{\circ}C$ and $10^{-14}$ $\leq$ $Po_2$ $\leq$ $10^{-3}$ for pure $UO_2$ and $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions with y=0.02, y=0.06 and y=0.20, respectively. Their oxygen partial pressures were maintained by controlling $CO_2$/CO mixture atmosphere, and the $Po_2$ values corresponding to x of $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions were measured with an electrolyte oxygen sensor. The lattice parameter decreases linearly with an increase in the erbium content. The change of the lattice parameter can be expressed in a linear equation of y as a($\AA$) =5.4695-0.220y for 0 $\leq$y$\leq$0.33. The experimental coefficient of y -0.220 in $U_{1-y}Er_{y}O_2$ was an intermediate value between the calculated values -0.273 and -0.156 in the case of $U^{5+}$ and $U^{6+}$, respectively. The (equation omitted) has been found to undergo abrupt increase in the range of -360 to -270 kJ/mole for y=0.06 and -320 to -220 H/mole for y=0.20, respectively, in the temperature range of 1200-$1500^{\circ}C$. (equation omitted) increases with erbium content, but the effect of the dopant for x =0.01 is less significant than that for stoichiometry. The oxygen potentials for $UO_2$ and $U_{0.98}Er_{0.02}O_{2+x}$ can be approximately represented by the $U^{5+}$/$U^{4+}$ model but those for y$\geq$ 0.06 in $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions cannot be interpreted by the mean uranium valence model.

• Economic and Environmental Geology
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• v.19 no.3
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• pp.199-218
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• 1986

Arsenopyrite in arsenic and polymetallic ores from calcic Fe-W skarn deposit of the Ulsan mine, Republic of Korea, has been investigated by means of electron microprobe analysis and X-ray diffractometry. As a result, it is revealed that the Ulsan arsenopyrite may be classified into the following three species with different generation on the basis of its mode of occurrence, chronological order during polymetallic mineralization and chemical composition; arsenopyrites I, II and III. 1) Arsenopyrite I-(Ni, Co)-bearing species belonging to the oldest generation, which has crystallized together with (Ni, Co)-arsenides and -sulpharsenides in the early stage of polymetallic mineralization. In rare cases, it contains a negligible amount of antimony. It occurs usually as discrete grains with irregular outline, showing rarely subhedral form, and is diffused in skarn zone. The maximum contents of nickel and cobalt are 10.04 Ni and 2.45 Co (in weight percent). Occasionally, it shows compositional zoning with narrow rim of lower (Ni+Co) content. 2) Arsenopyrite II-arsenian species, in which (Ni+Co) content is almost negligible, may occur widely in arsenic ores, and its crystallization has followed that of arsenopyrite I. It usually shows subhedral to euhedral form and is closely associated with $l{\ddot{o}}llingite$, bismuth, bismuthinite, chalcopyrite, sphalerite, bismuthian tennantite, etc. It is worthy of note that arsenopyrite II occasionally contains particles consisting of both bismuth and bismuthinite. 3) Arsenopyrite III-(Ni, Co)-free, S-excess and As-deficient species is close to the stoichiometric composition, FeAsS. It occurs in late hydrothermal veins, which cut clearly the Fe-W ore pipe and the surrounding skarn zone. It shows euhedral to subhedral form, being extremely coarse-grained, and is closely associated with pyrite, "primary" monoclinic pyrrhotite, galena, sphalerite, etc. Among three species of the Ulsan arsenopyrite, arsenopyrite I does not serve as a geothermometer, because (Ni+Co) content always exceeds 1 weight percent. In spite of the absence of Fe-S minerals as sulphur-buffer assemblage, the presence of $Bi(l)-Bi_2S_3$ sulphur-buffer enables arsenopyrite II to apply successfully to the estimation of either temperature and sulphur fugacity, the results are, $T=460{\sim}470^{\circ}C$, and log $f(S_2)=-7.4{\sim}7.0$. With reference to arsenopyrite III, only arsenopyrite coexisting with pyrite and "primary" monoclinic pyrrhotite may serve to restrict the range of both temperature and sulphur fugacity, $T=320{\sim}440^{\circ}C$, log $f(S_2)=-9.0{\sim}7.0$. These temperature data are consistent with those obtained by fluid inclusion geothermometry on late grandite garnet somewhat earlier than arsenopyrite II. At the beginning of this paper, the geological environments of the ore formation at Ulsan are considered from regional and local geologic settings, and physicochemical conditions are suspected, in particular the formation pressure (lithostatic pressure) is assumed to be 0.5kb (50MPa). The present study on arsenopyrite geothermometry, however, does not bring about any contradictions against the above premises. Thus, the following genetical view on the Ulsan ore deposit previously advocated by two of the present authors (Choi and Imai) becomes more evident; the ore deposit was formed at shallow depth and relatively high-temperature with steep geothermal gradient-xenothermal conditions.

• Applied Microscopy
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• v.38 no.4
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• pp.279-284
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• 2008

The phase change materials have been extensively used as an optical rewritable data storage media utilizing their phase change properties. Recently, the phase change materials have been spotlighted for the application of non-volatile memory device, such as the phase change random access memory. In this work, we have investigated the crystallization behavior and microstructure analysis of In-Sb-Te (IST) thin films deposited by RF magnetron sputtering. Transmission electron microscopy measurement was carried out after the annealing at $300^{\circ}C$, $350^{\circ}C$, $400^{\circ}C$ and $450^{\circ}C$ for 5 min. It was observed that InSb phases change into $In_3SbTe_2$ phases and InTe phases as the temperature increases. It was found that the thickness of thin films was decreased and the grain size was increased by the bright field transmission electron microscopy (BF TEM) images and the selected area electron diffraction (SAED) patterns. In a high resolution transmission electron microscopy (HRTEM) study, it shows that $350^{\circ}C$-annealed InSb phases have {111} facet because the surface energy of a {111} close-packed plane is the lowest in FCC crystals. When the film was heated up to $400^{\circ}C$, $In_3SbTe_2$ grains have coherent micro-twins with {111} mirror plane, and they are healed annealing at $450^{\circ}C$. From the HRTEM, InTe phase separation was occurred in this stage. It can be found that $In_3SbTe_2$ forms in the crystallization process as composition of the film near stoichiometric composition, while InTe phase separation may take place as the composition deviates from $In_3SbTe_2$.