• Economic and Environmental Geology
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• v.8 no.3
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• pp.117-124
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• 1975

Wet chemical analysis (for $MnO_2$, MnO, and $H_2O$(+)) and electron microprobe analysis (for $Fe_2O_3$ and PbO) give $MnO_2$ 74.91, MnO 11.33, $Fe_2O_3$ (total Fe) 4.19, PbO 0.03, $H_2O$ (+) 9.46, sum 99.92%. 'Available oxygen determined by oxalate titration method is allotted to $MnO_2$ from total Mn, and the remaining Mn is calculated as MnO. Traces of Ba, Ca, Mg, K, Cu, Zn, and Al were found. Li and Na were not found. The existence of (OH) is verified from the infrared absorption spectra. The analysis corresponds to the formula $Mn^{4+}{_{4.85}}(Mn^{2+}{_{0.90}}Fe^{3+}{_{0.30}})_{1.20}O_{8.09}(OH)_{5.91}$, on the basis of O=14, 'or ideally $Mn^{4+}{_{5-x}}(Mn^{2+},Fe^{3+})_{1+x}O_{8}(OH)_{6}$ ($x{\approx}0.2$). X-ray single crystal study could not be made because of the distortion of single crystals. But the x-ray powder pattern is satisfactorily indexed by an orthorhombic cell with a 9.324, b 14.05, c $7.956{\AA}$., Z=4. The indexed powder diffraction lines are 9.34(s) (100), 7.09(s) (020), 4.62(m) (200, 121), 4.17(m) (130), 3.547(s) (112), 3.212(vw) (041), 3.101(s) (300), 2.597(w) (013), 2.469(m) (331), 2.214(vw)(420), 2.098(vw) (260), 2.014 (vw) (402), 1.863(w) (500), 1.664(w) (314), 1.554(vw) (600), 1.525(m) (601), 1.405(m) (0.10.0). DTA curve shows the endothermic peaks at $250-370^{\circ}C$ and $955^{\circ}C$. The former is due to the dehydration: and oxidation forming$(Mn,\;Fe)_2O_3$(cubic, a $9.417{\AA}$), and the latter is interpreted as the formation of a hausmannite-type oxide (tetragonal, a 5.76, c $9.51{\AA}$) from $(Mn,\;Fe)_2O_3$. Infrared absorption spectral curve shows Mn-O stretching vibrations at $515cm^{-1}$ and $545cm^{-1}$, O-H bending vibration at $1025cm^{-1}$ and O-H stretching vibration at $3225cm^{-1}$. Opaque. Reflectance 13-15%. Bireflectance distinct in air and strong in oil. Reflection pleochroism changes from whitish to light grey. Between crossed nicols, color changes from yellowish brown with bluish tint to grey in air and yellowish brown to grey through bluish brown in oil. No internal reflections. Etching reactions: HCl(conc.) and $H_2SO_4+H_2O_2$-grey tarnish; $SnCl_2$(sat.)-dark color; $HNO_3$(conc.)-grey color; $H_2O_2$-tarnish with effervescence. It is black in color. Luster dull. Cleavage one direction perfect. Streak brownish black to dark brown. H. (Mohs) 2-3, very fragile. Specific gravity 3.59(obs.), 3.57(calc.). It occurs as radiating groups of flakes, flower-like aggregates, colloform bands, dendritic or arborescent masses composed of fine grains in the cementation zone of the supergene manganese oxide deposits of the Janggun mine, Bonghwa-gun, southeastern Korea. Associated minerals are calcite, nsutite, todorokite, and some undetermined manganese dioxide minerals. The name is for the mine, the first locality. The mineral and name were approved before publication by the Commission on New Minerals and Mineral Names, I.M.A.

• 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.