• Economic and Environmental Geology
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• v.26 no.3
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• pp.279-287
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• 1993

In the zinc-lead (-silver) ores from the Yeonhwa 1 mine, stannite is widespread, though minor in amount It may be divided largely into two species on the basis of its chronological order during mineralization; i.e., stannite I formed in Stage I, and stannite II formed in Stage II. Also, the mineral may be classified into two types according to the difference of its associates; i.e., stannite 1 closely associated with sphalerite, and stannite 2 with galena. In general, the stannite 1 tends to predominate in the stannite I and the stannite 2 in the stannite II. The formation temperature and sulphur fugacity of stannite 1 deduced from stannite-sphalerite geothermometry are from 280 to $350^{\circ}C$ and from $10^{-11}$ to $10^{-8}$ atm.

• Economic and Environmental Geology
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• v.8 no.1
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• pp.1-23
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• 1975

The subject of this study deals with phase relations between stannite ($Cu_2FeSnS_4$) and sphalerite (${\beta}-ZnS$)/wurtzite (${\alpha}-ZnS$). The phase relations were systematically investigated from liquidus temperature to $400^{\circ}C$ under controlled conditions. ${\beta}-stannite$ (tetragonal) is stable up to $706{\pm}5^{\circ}C$, where it inverts to a high-temperature polymorph ${\alpha}-stannite$ (cubic) melting congruently at $867{\pm}5^{\circ}C$. Sphalerite (cubic, ${\beta}-ZnS$) inverts at $1013{\pm}3^{\circ}C$ to wurtzite, which is the hexagonal hightemperature polymorph of ZnS. Between ${\alpha}-stannite$ and sphalerite a complete solid solution series exists above approximately $870^{\circ}C$ up to solidus temperature. The melting temperature of ${\alpha}-stannite$ rises towards sphalerite and reaches a maximum at $1074{\pm}3^{\circ}C$, which is the peritectic with the composition of 91 wt. % sphalerite and 9 wt. % ${\alpha}-stannite$. At this temperature, wurtzite takes only 5wt. % ${\alpha}-stannite$ in solid solution which decreases with increasing temperature. The inverson temperature of ${\alpha}/{\beta}-stannite$ is lowered with increasing amounts of sphalerite in solid solution down to $614{\pm}7^{\circ}C$, which is the eutectoid with the composition of 13 wt. % sphalerite and 87 wt. % ${\alpha}-stannite$. Here, ${\beta}-stannite$ contains only 10wt. % sphalerite in solid solution. With decreasing temperature, the ranges of the solid solution on both sides of the system narrow. The phase relations in the above pure system changed due to the FeS impurities in the sphalerite solid solution. The eutectoid increased from $614{\pm}7^{\circ}C$ up to $695{\pm}5^{\circ}C$ (5 wt. % FeS) and $700{\pm}5^{\circ}C$ (10wt. % FeS), while the peritectic decreased from $1074{\pm}3^{\circ}C$ down to $1036{\pm}3^{\circ}C$ (wt. %FeS) and $987{\pm}3^{\circ}C$ (10wt. %FeS). A most notable change is the appearance of non-binary regions. An important feature is the combination of this study system with the experimental results reported by Sprinfer (1972). If a stannite-kesterite solid solution is used in the place of stannite as a bulk composition, the inversion temperature is lowered to less than $400^{\circ}C$ which belongs to temperatures of the hydrothermal region.

• Economic and Environmental Geology
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• v.13 no.4
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• pp.205-213
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• 1980

Stannite is mainly found in hypothermal ore deposits, whereas mawsonite and stannoidite occur characteristically with bornite and chalcopyrite in subvolcanic (xenothermal) ore deposits. Mawsonite always shows the replacement on the rims of stannoidite grains or along the grain boundaries of stannoidite, bornite and chalcopyrite. In the Tada mine, Japan, the following mineral assemblages of the Cu-Fe-Sn-S minerals were observed. 1) bornite-stannoidite; 2) stannoidite-chalcopyrite; 3) stannite-chalcopyrite; 4) bornite-mawsonite-stannoidite; 5) bornite-stannoidite-chalcopyrite; 6) mawsonite-stannoidite-chalcopyrite; 7) stannoidite-stannite-chalcopyrite; 8) bornite-mawsonite-stannoidite-chalcopyrite The heating and D.T.A. experimental results indicate that natural stannoidite containing 3 weight percent of zinc decomposes to bornite, stannite and chalcopyrite at above $500^{\circ}C$, whereas zinc-free synthetic stannoidite is stable up to $800^{\circ}C$. The stability temperature of zincian stannoidite depends on the zinc content. Mawsonite is stable at temperatures below $390^{\circ}C$ and decomposed to stannoidite, bornite and chalcopyrite above it. According to the sulfur fugacity determination by the electrum tarnish method the univariant assemblage of mawsonite, bornite, stannoidite and chalcopyrite requires a higher sulfur fugacity than that of bornite, stannoidite and chalcopyrite assemblage.

• Economic and Environmental Geology
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• v.10 no.3
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• pp.99-105
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• 1977

Mineralogical study of original and crushed zinc ores as well as mill products was made in order to find out the cause of low-grade concentrate and the scheme of raising its grade. Low-grade concentrate is due to 1) the abundance of other independent sulfides (arsenopyrite, pyrrhotite, chalcopyrite, stannite) and silicate (quartz) in the zinc concentrate, 2) the presence of composite grains of sphalerite and other sulfides or silicate, 3) the presence of a lot of very fine-grained particle of stannite and chalcopyrite within the sphalerite grains, and 4) the high content of iron in sphalerite. It is proposed that further crushing and other appropriate processing should be made in order to increase the grade of zinc concentrate.

• Proceedings of the Korean Magnestics Society Conference
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• 2010.06a
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• pp.53-54
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• 2010

• Economic and Environmental Geology
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• v.19 no.spc
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• pp.121-130
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• 1986

In the Janggun mine, stannite occurs as anhedral grains, up to 500 micrometer in long dimension, closely associated with sphalerite, chalcopyrite, arsenopyrite, pyrrhotite, galena and rhodochrosite in the periphery of the South ore body. In reflected light, stannite is grayish yellow green in color and exhibits moderate bireflectance and strong anisotropism without any intenal reflections. Reflection; Rmax. =29.0, Rmin. =27.8 percent at a wavelength of 560nm, and VHN; 219~244kg/mm at a 50g load. The chemical composition on the average from 35 spot analyses by electron microprobe is, Cu 28.0, Fe 12.7, Zn 2.9, Mn 0.2, Sn 25.8, S 30.3, sum 99.9 (all in weight percent); the corresponding chemical formula as calculated on the basis of total atoms=8 is, Cu 1.88 Fe 0.97 Zn 0.19 Mn 0.02 Sn 0.93 S 4.01, which fulfills approximately the ideal formula of $Cu_2FeSnS_4$. The strongest reflections on the X-ray diffraction patterns are; $3.10{\AA}$ (10) (112), $2.72{\AA}$ (5) (020, 004), $1.922{\AA}$ (5) (024), $1.642{\AA}$ (3) (132), $1.244{\AA}$ (3) (143, 136, 235), $1.111{\AA}$(3) (244), $0.958{\AA}$ (1) (048, 422), the patterns are identical with those of literature. From the textural evidence of the microscopic observation, the mineral is considered to have been formed at the middle stage of hydrothermal lead-zinc-silver mineralization.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.134-137
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• 2009

Commercially available elemental powders of Cu, Zn, Sn and Se were employed for crystallizing a stannite-type $Cu_2ZnSnSe_4$ compound by means of solid state reaction. $Cu_2ZnSnSe_4$ reaction chemistry was also modeled based on differential-thermal analysis and X-ray powder diffraction results. It was observed that Se tends to react preferably with Cu to form CuSe and $CuSe_2$ phases at low reaction temperature. The formation of $Cu_5Zn_8$ intermetallic phase was found to be the intermediate reaction path for the binary ZnSe formation. A solid state reaction at $320^{\circ}C$ reacted elemental powderst obinary selenides of CuSe, ZnSe and SnSe completely. The crystallization of $Cu_2ZnSnSe_4$ was was detected to begin at $300^{\circ}C$ and its weight fraction increased with an increase of reaction temperature, which most probably formed from the reaction between $Cu_2SnSe_3$ and ZnSe.

• Journal of the Korean institute of surface engineering
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• v.44 no.5
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• pp.185-189
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• 2011

$Cu_2ZnSnSe_4$ thin films for solar absorber application were prepared by pulsed laser deposition of a synthesized $Cu_2ZnSnSe_4$ compound target. The film's composition revealed that the deposited films possess an identical composition with the target material. Further film compositional control toward a stoichiometric composition was performed by optimizing substrate temperature, deposition time and target rotational speed. At the optimum condition, X-ray diffraction patterns of films showed that the films demonstrated polycrystalline stannite single phase with a high degree of (112) preferred orientation. The absorption coefficient of $Cu_2ZnSnSe_4$ thin films were above 104 cm.1 with a band gap of 1.45 eV. At an optimum condition, films were identified as a p type semiconductor characteristic with a resistivity as low as $10^{-1}{\Omega}cm$ and a carrier concentration in the order of $10^{17}cm^{-3}$.

• Proceedings of the Korean Vacuum Society Conference
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• 2014.02a
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• pp.398.1-398.1
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• 2014

The $Cu_2ZnSnSe_4$ (CZTSe) thin films solar cell is one of the next generation candidates for photovoltaic materials as the absorber of thin film solar cells because it has optimal bandgap (Eg=1.0eV) and high absorption coefficient of $10^4cm^{-1}$ in the visible length region. More importantly, CZTSe consists of abundant and non-toxic elements, so researches on CZTSe thin film solar cells have been increasing significantly in recent years. CZTSe thin film has very similar structure and properties with the CIGS thin film by substituting In with Zn and Ga with Sn. In this study, As-deposited CZTSe thin films have been deposited onto soda lime glass (SLG) substrates at different deposition condition using Pulsed Laser Deposition (PLD) technique without post-annealing process. The effects of deposition conditions (deposition time, deposition temperature) onto the structural, compositional and optical properties of CZTSe thin films have been investigated, without experiencing selenization process. The XRD pattern shows that quaternary CZTSe films with a stannite single phase. The existence of (112), (204), (312), (008), (316) peaks indicates all films grew and crystallized as a stannite-type structure, which is in a good agreement with the diffraction pattern of CZTSe single crystal. All the films were observed to be polycrystalline in nature with a high (112) predominant orientation at $2{\theta}{\sim}26.8^{\circ}$. The carrier concentration, mobility, resistivity and optical band gap of CZTSe thin films depending on the deposition conditions. Average energy band gap of the CZTSe thin films is about 1.3 eV.

• Economic and Environmental Geology
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• v.19 no.1
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• pp.57-66
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• 1986

The ore deposit of the Ohtani mine is one of representatives of plutonic tungsten-tin veins related genetically to acidic magmatism of Late Cretaceous in the Inner zone of Southwest Japan. Based on macrostructures of vein filling, three major mineralization stages are distinguished by major tectonic breaks. The constituents of ore minerals are scheelite, cassiterite, chalcopyrite, pyrrhotite, sphalerite, with small amounts of cubanite, stannite, galena, native bismuth, bismuthinite, arsenopyrite and pyrite. The relationship between the polymorphic variations of pyrrhotite and the kinds of the associated characteristic of ore mineral, in relation with hypogene mineralization, has been demonstrated. Pyrrhotite of stage I is predominantly of the hexagonal phase (Hpo>Mpo). Pyrrhotite of stage II is mainly of the monoclinic phase ($Hpo{\ll}Mpo$). Pyrrhotite of stage III is a single monoclinic phase ($Hpo{\ll}Mpo$). The compositions of the hexagonal pyrrhotite decrease in Fe content ranging from 47.44 atom % Fe in stage I to 46.88 atom % Fe in stage III.