• Economic and Environmental Geology
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• v.52 no.6
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• pp.509-517
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• 2019

The birnessite (7Å manganate, δ-MnO₂) which is a manganese oxide and comprises manganese nodules, is a major manganese mineral on the earth surface and a precursor in the synthesis of todorokite. In this study birnessite was synthesized by three different methods: Feng et al. (2004) and Luo et al. (1998) based on redox reaction and Ma et al. (1999) based on reduction reaction. 12 birnessite samples were synthesized by different combinations of Na⁺ and K⁺ cations based on the base (OH^-) and permanganate (MnO₄^-) reagents in the synthesis. The mineral compositions of synthesized birnessite were identified by XRD, and the two cation ratio in the mineral was measured by ICP. The products obtained after hydrothermal treatment of Mg-buserite, by the precursor of birnessite, was examined by XRD, and then phase transition to todorokite and their characteristics were compared. Our results show that the byproducts and the characteristics of phase transition by each synthetic method have different trends. Hausmannite (γ-Mn₃O₄) and feitknechtite (β-MnOOH) were formed by both methods in the redox reaction mechanism. By Feng et al. (2004)'s method, manganite (γ-MnOOH) phase only appeared when cation was predominantly Na⁺. Two birnessite samples synthesized by redox reaction mechanism showed phase transition to todorokite (10Å manganate, OMS-1) when both NaOH and KMnO₄ were used together. However, single-phase birnessite was formed by Ma et al. (1999)'s method, and phase transition was confirmed only for the sample when the cation was only composed of Na⁺.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.21 no.7
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• pp.638-644
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• 2008

The effects of $Nb_2O_5$ and $MnO_2$ on the positive temperature coefficient of resistivity (PTCR) behavior of lead-free $Ba_{0.99}(Bi_{1/2}Na_{1/2})_{0.01}TiO_3$ (BaBiNT) ceramics were investigated in order to fabricate a PTC thermistor available at high temperature of > $120^{\circ}C$. In particular, 0.05 mol% $Nb_2O_5$ added BaBiNT ceramic, which has significantly increased Curie temperature (Tc) of $160^{\circ}C$, showed good PTCR behavior; low resistivity at room temperature $(\rho_r)$ of $80.1{\Omega}{\cdot}cm$, a high $\rho_{max}/\rho_{min}$ ratio of $5.65{\times}10^3$ and a large resistivity temperature factor (a) of 18.5%/$^{\circ}C$. Furthermore, the improved $\rho_{max}/\rho_{min}$ of $6.48{\times}10^4$ and a of 25.4%/$^{\circ}C$ along with higher $T_c$ of $167^{\circ}C$ despite slightly increased $\rho_r$ of $569{\Omega}{\cdot}cm$, could be obtained for the BaBiNT + 0.05 mol% $Nb_2O_5$ + 0.02 wt% $MnO_2$ ceramic cooled down at a rate of $200^{\circ}C/h$.

• Resources Recycling
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• v.12 no.1
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• pp.33-40
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• 2003

Mn was extracted by using a nitric acid from the reduced ferromanganese dust and the basic experiments were taken to refine the manganese nitrate solution by means of precipitation of Ca, Mg oxalate. The dust was generated in AOD process producing a medium-low carbon ferromanganese and collected in the bag filter. Manganese oxide content in the dust was about 90% and its phase was confirmed as $Mn_3$$O_4$. $Mn_3$$O_4$ in the dust was reduced to MnO by roasting with activated charcoal. The main impurities in the extracted solution prepared by leaching the reduced dust with nitric acid were Na, K, Fe, Si, Ca, Mg etc. Among them, Fe was removed by controlling pH of the solution more than 4 and precipitating $Fe(OH)_3$, simultaneously silicious material solved in the solution was removed by co-precipitation with the ferric hydroxide. Addition of 150 g reduced dust into 4N HNO3 solution 1$\ell$ was appropriate to control the pH of the solution to pH 4. To differ greatly the solubilities of manganese oxalate and calcium or magnesium oxalate in a solution containing a high concentration of Mn, pH of 4 or less and addition of ($NH_4$)$_2$$C_2$$O_4$ in equivalent with Ca and Mg are recommended. At this time, the higher temperature was the shorter the precipitation reaction time was needed.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_{2}$(0 ${\times}$ 0.14) oxides have been synthesized by hydrothermal treatment of $(Co_{x}Mn_{1-x})_{3}O_{4}$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}-NaMnO_{2}$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_{2}$, comparing to orthorhombic $LiMnO_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_2$ (0 x 0.14) oxides have been synthesized by hydrothermal treatment of ($Co_{x}Mn_{1-x}$)$_3O_4$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}$-$NaMnO_2$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_2$, comparing to orthorhombic $LiMnO_2$.

• Journal of the Mineralogical Society of Korea
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• v.3 no.1
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• pp.34-43
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• 1990

Crystal-chemical study of hexagonal 7$\AA$ phyllomanganate minerals reveals that they have hexagonal layer structures with variable c dimensions which depend on the nature of interlayer cations and content of water molecules between edge-sharing [MnO6] octahedral layers. Approximately one out of nine octahedral sites is statistically vacant, leading to the general unit cell formula R2xMn4+1-xO2.nH2O, where R=Ca, Mn2+, Mg, K, Na;x=0.09-0.14 ; n-0.37-0.84. Z=1. The minerals of this formula fall under the name of rancieite group. It includes Ca-diminant (rancieite), Mn2+-dominant (takanelite), Na-dominant (birnessite), and Mg-dominant members. Minerals of the rancieite group occur predominantly in two different hydration states, i.e., n shows the values around 0.35 and 0.75. It is suggested that minerals of higher hydration state be called as species(i.e., rancieite, etc.) and those of lower hydration state be called as dehydrated varieties(i.e., dehydrated rancieite,etc.).

• Korean Chemical Engineering Research
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• v.46 no.1
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• pp.94-98
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• 2008

In order to improve the specific capacitance of amorphous hydrous manganese oxide ($MnO_2$) for supercapacitors, it is made into composites with vapour-grown carbon nanofibers (VGCF) having the VGCF ratio as 40 wt% in the composites. The electrochemical properties of these composites are investigated in 1.0 M $Na_2SO_4$ by cyclic voltammetry (CV), impedance measurements and chronopotentiometric charger/discharger. The composite with 40 wt% VGCF shows the superior electrochemical performance, whose specific capacitance (based on the mass of $MnO_2$, $0.8mg/cm^2$) is 380 F/g at 20 mV/s and 230 F/g at 500 mV/s. Also, the cycle-life testing of this electrode carried out for 3,000 charge/discharge cycles at $2.0mA/cm^2$ shows 97% capacitance retention.

• Journal of the Korean Ceramic Society
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• v.29 no.11
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• pp.900-904
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• 1992

High temperature electrical conductivity was measured for perovskite La0.98Sr0.02MnO3 at 200~130$0^{\circ}C$ as a function of Po2 and 1/T. Perovskite La1-xSrxMnO3 system is the typical oxygen electrode in solid oxide fuel cell (SOFC). Acetate precursors were used for the preparation of mixed water solution and the calcined powders were reacted with Na2CO3 flux in order to obtain highly reactive powders of perovskite La0.98Sr0.02MnO3. The relative density was greatly increased above 90% because of the homogeneous sintering. From the conductivity ($\sigma$)-temperature and conductivity-Po2 at constant temperature, the defect structure of La0.98Sr0.02MnO3 was discussed. From the slope of 1n($\sigma$) vs 1/T, the activation energy of 0.069 and 0.108eV were evaluated for above 40$0^{\circ}C$, respectively. From the relationship between $\sigma$ and Po2, it was found that the decomposition of La0.98Sr0.02MnO3 was occurred at 10-15.5 atm(97$0^{\circ}C$) and 10-11 atm(125$0^{\circ}C$). It is supposed that the improvement of p-type conductivity may be leaded by the increase of Mn4+ concentration through the substitution of divalent/monovalent cations for La site in LaMnO3.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.27 no.1
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• pp.14-17
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• 2014

In this study, lead-free Piezoelectric $(Na_{0.47}K_{0.47}Sr_{0.03}Ca_{0.03})(Nb_{0.94}Ti_{0.06})O_3$-0.1 $MnO_2$ ceramics were fabricated using mixed oxide method and the effects of various sintering temperature on the structural and electrical properties were investigated. For the $(Na_{0.47}K_{0.47}Sr_{0.03}Ca_{0.03})(Nb_{0.94}Ti_{0.06})O_3$-0.1 $MnO_2$ (NKN-SCT-$MnO_2$) ceramics sintered at temperatures of $1,025{\sim}1,100^{\circ}C$. The results indicated that all specimens were perovskite single phase formation without any second phase. It has been shown that relative density is increased to increasing sintering temperature. When the sintered temperature at $1,075^{\circ}C$, highest sintered density and maximum value of $4.45g/cm^3$. Average grain size is increased to increasing sintering temperature. The electromechanical coupling factor, dielectric constant, dielectric loss, d33 and curie temperature at the sintering temperature $1,075^{\circ}C$ of NKN-SCT-$MnO_2$ specimens were 0.22, 511, 0.033, 103 and $380^{\circ}C$, respectively.

• Korean Chemical Engineering Research
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• v.51 no.3
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• pp.308-312
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• 2013

Active carbons with high specific surface area and micro pore structure were prepared from the coconut shell char using the chemical activation method of NaOH. The preparation process has been optimized through the analysis of experimental variables such as activating chemical agents to char ratio and the flow rate of gas during carbonization. The active carbons with the surface area (2,481 $m^2/g$) and mean pore size (2.32 nm) were obtained by chemical activation with NaOH. The electrochemical performances of hybrid capacitor were investigated using $LiMn_2O_4$, $LiCoO_2$ as the positive electrode and prepared active carbon as the negative electrode. The electrochemical behaviors of hybrid capacitor using organic electrolytes ($LiPF_6$, $TEABF_4$) were characterized by constant current charge/discharge, cyclic voltammetry, cycle and leakage tests. The hybrid capacitor using $LiMn_2O_4$/AC electrodes had better capacitance than other hybrid systems and was able to deliver a specific energy as high as 131 Wh/kg at a specific power of 1,448 W/kg.