• Title/Summary/Keyword: manganese oxide

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Corrosion Failure Analysis of a Biogas Pipe (바이오가스 배관의 부식 파손 원인 분석)

  • Min Ji Song;Woo Cheol Kim;Heesan Kim;Jung-Gu Kim;Soo Yeol Lee
    • Journal of the Korean Society for Heat Treatment
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    • v.36 no.3
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    • pp.153-160
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    • 2023
  • The use of biogas is an industrially necessary means to achieve resource circulation. However, since biogas obtained from waste frequently causes corrosion in pipes, it is important to elucidate corrosion mechanisms of the pipes used for biogas transportation. Recently, corrosion failure occurred in a pipe which supplied for the biogas at the speed of 12.5 m/s. Pinholes and pits were found in a straight line along the seamline of the pipe. By using corrosion-damaged samples, residual thickness, microstructure, and composition of oxide film and inclusion were examined to analyze the cause of the failure. It was revealed that the thickness reduction of biogas pipe was ~0.11 mm per year. A thin sulfuric acid film was formed on the surface of the interior of a pipe due to moisture and hydrogen sulfide contained in a biogas. Near the seamline, microstructure was heterogeneous and manganese sulfide (MnS) was found. Pits were generated by micro-galvanic corrosion between the manganese sulfide and the matrix in the interior of the pipe along the seamline. In addition, microcracks formed along the grain boundaries beneath the pits revealed that hydrogen-induced cracking (HIC) also contributed to accelerating the pitting corrosion.

Mineral Products and Characteristics of Phase Transformation after Hydrothermal Treatment according to the Synthetic Method and Cation Combination during Birnessite Synthesis (버네사이트 합성 시 합성 방법 및 양이온 조건에 따른 생성 광물 및 열수처리 후 상전이 특성)

  • Min, Soyoung;Kim, Yeongkyoo
    • 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+.

Electrochemical Characteristics of Transition Metal Pyrophosphate as Negative Electrode Materials through Solid-state Reaction (고상법으로 합성된 리튬이온 이차전지용 음극물질로서 전이금속 피로인산화물의 전기화학적 특성)

  • Hong, Min Young;An, Sang-Jo;Ryu, Ji Heon
    • Journal of the Korean Electrochemical Society
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    • v.23 no.4
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    • pp.105-112
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    • 2020
  • Transition metal oxide, which undergoes a conversion reaction in the negative electrode material for a lithium-ion batteries, has a high specific capacity, but still has several critical problems. In this study, manganese pyrophosphate (Mn2P2O7), nickel pyrophosphate (Ni2P2O7), and carbon composite materials with pyrophosphates as novel negative electrode materials instead of transition metal oxide, are synthesized through simple solid-state reaction. The initial reversible capacity of Mn2P2O7 and Ni2P2O7 are 333 and 340 mAh g-1, and when the composite materials are composed with carbon, the reversible capacity increases to 433 and 387 mAh g-1, respectively. The initial Coulombic efficiency is also improved by about 10%. The Mn2P2O7 and carbon composite material has the highest initial capacity and efficiency, and has the best cycle performance. Mn2P2O7 containing polyanion, has a lower specific capacity due to the large mass of polyanion compared to MnO (manganese oxide). However, since Mn2P2O7 shows a voltage curve with a slope, the charging (lithiation) voltage increases from 0.51 to 0.57 V (vs. Li/Li+), and the discharge (delithiation) voltage decreases from 1.15 to 1.01 V (vs. Li/Li+). Therefore, the voltage efficiency of the cell is improved because the voltage difference between charging and discharging is greatly reduced from 0.64 to 0.44 V, and the operating voltage of the full cell increases because the negative electrode potential is lowered during the discharging process.

Relationship between Particle Density and Electrochemical Properties of Spherical LiMn2-xMxO4 (M = Al, Mg, B) Spinel Cathode Materials (구형 스피넬계 LiMxMn2-xO4 (M = Al, Mg, B) 양극소재의 입자치밀도와 전지성능간의 상관관계에 대한 연구)

  • Kim, Kyoung-Hee;Jung, Tae-Gyu;Song, Jun-Ho;Kim, Young-Jun
    • Journal of the Korean Electrochemical Society
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    • v.15 no.2
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    • pp.67-73
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    • 2012
  • Spherical lithium manganese oxide spinel, $LiMn_{2-x}M_xO_4$ (M = Al, Mg, B) prepared by wet-milling, spray-drying, and sintering process has been investigated as a cathode material for lithium ion batteries. As-prepared powders exhibit various surface morphologies and internal density in terms of boron (B) doping level. It is found that the dopant B drives the growth of the primary particle and minimizes the surface area of the powder. As a result, the dopant enhances the internal density of the particles. Electrochemical tests demonstrated that the capacity of the synthesized material at 5 C could be maintained up to 90% of that at 0.2 C. The cycle performance of the material showed that the initial capacity was retained up to 80% even after 500 cycles under the high temperature of $60^{\circ}C$.

Investigation of Spherical LiMn2O4 Cathode Materials by Spray-drying with Different Electrochemical Behaviors at High Rate (분무건조법으로 제조한 구형 스피넬계 LiMn2O4 양극소재의 합성 조건에 따른 고출력 거동에 대한 연구)

  • Song, Jun Ho;Cho, Woosuk;Kim, Young Jun
    • Journal of the Korean Electrochemical Society
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    • v.19 no.2
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    • pp.50-56
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    • 2016
  • Spherical lithium manganese oxide spinel, $Li_{1.10}Mn_{1.86}Al_{0.02}Mg_{0.02}O_4$ was prepared by wet-milling, spray-drying, and sintering process. In the spray-drying process, solid content in slurry was varied from 20 to 30 wt%. In the sintering process, the precursors have been sintered under air or $O_2$ atmosphere. While the as-prepared samples exhibit excellent electrochemical properties at room temperature, the discharge voltage profiles at 5.0C are very different one from another. The origin for the difference especially at initial state of discharge is oxygen defect. The sample prepared in air has larger capacity related to the plateau at 3.3 V (vs. $Li/Li^+$) which is caused by the oxygen defects than the one prepared in $O_2$. The difference of discharge voltage profiles especially at the final state of discharge comes from different diffusion rate of $Li^+$ ions. The sample prepared from 30 wt% solid content of slurry shows twice higher diffusion rate than the samples prepared from 20 wt% solid content, which is attributed to better compactness between primary particles for the sample prepared from 30wt % solid content than the one prepared by 20 wt%.

Study on the Annealing Effect and Magnetic Properties of a Zn0.7Mn0.3O Film (열처리 효과에 따른 Zn0.7Mn0.3O박막의 자기 특성 연구)

  • Kim, Y.M.;Kim, Y.;Yoon, M.;Park, C.S.;Lee, Y.S.;Jeon, M.S.;Park, I.W.;Park, Y.J.;Lyou, Jong H.;Kim, S.S.
    • Journal of the Korean Magnetics Society
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    • v.13 no.4
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    • pp.155-159
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    • 2003
  • We report on the annealing effect and ferromagnetic characteristics of Zn$_{0.7}$Mn$_{0.3}$O film prepared by sol-gel method on the silicon (100) substrate using field emission-scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), X-ray diffractometry (XRD) and superconducting quantum interference device (SQUID) magnetometry. Magnetic measurements show thatZn$_{0.7}$Mn$_{0.3}$O films exhibit ferromagnetism at 5 K revealing the coercive field of ∼110 Oe for as grown sample and 360, 1035 Oe for samples annealed at 700, 800 $^{\circ}C$, respectively. Our experimental evidence suggests that ferromagnetic precipitates of a manganese oxide may be responsible for the observed ferromagnetic behaviors of the film.he film.

Dielectric-Spectroscopic and ac Conductivity Investigations on Manganese Doped Layered Na1.9Li0.1Ti3O7 Ceramics (망간이 혼입된 층상구조 Na1.9Li0.1Ti3O7 세라믹스의 유전율 ‒ 분광법과 교류 전도도 측정 연구)

  • Pal, Dharmendra;Pandey, J.L.;Shripal
    • Journal of the Korean Chemical Society
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    • v.53 no.1
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    • pp.42-50
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    • 2009
  • The dielectric-spectroscopic and ac conductivity studies firstly carried out on layered manganese doped Sodium Lithium Trititanates ($Na_{1.9}Li_{0.1}Ti_3O_7$). The dependence of loss tangent (Tan$\delta$), relative permittivity ($\varepsilon_r$) and ac conductivity ($\sigma_{ac}$) in temperature range 373-723K and frequency range 100Hz-1MHz studied on doped derivatives. Various conduction mechanisms are involved during temperature range of study like electronic hopping conduction in lowest temperature region, for MSLT-1 and MSLT-2. The hindered interlayer ionic conduction exists with electronic hopping conduction for MSLT-3. The associated interlayer ionic conduction exists in mid temperature region for all doped derivatives. In highest temperature region modified interlayer ionic conduction along with the polaronic conduction, exist for MSLT-1, MSLT-2, and only modified interlayer ionic conduction for MSLT-3. The loss tangent (Tan$\delta$) in manganese-doped derivatives of layered $Na_{1.9}Li_{0.1}Ti_3O_7$ ceramic may be due to contribution of electric conduction, dipole orientation, and space charge polarization. The corresponding increase in the values of relative permittivity may be due to increase in number of dipoles in the interlayer space while the corresponding decrease in the values of relative permittivity may be due to the increase in the leakage current due to the higher doping.

Production of High purity $Mn_3O_4$Powder by Precipitation of Calcium fluoride in the Manganese Leaching Solution (망간침출액에서 불화칼슘화에 의한 高純度 망간酸化物의 製造)

  • 한기천;이계승;최재석;신강호;조동성
    • Resources Recycling
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    • v.11 no.1
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    • pp.3-8
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    • 2002
  • In order to make the high purity Mn$_3$O$_4$powder for the raw material of soft ferrite, Mn is extracted from the dust and the extracted solution is refined. The dust is generated in producing a medium-low carbon ferromanganese and contains 90% Mn$_3$O$_4$. Mn$_3$O$_4$in the dust was reduced into MnO by roasting with charcoal. Injection of the 180g/L of the reduced dust into 4N HCI solution increased pH of the leaching solution higher than 5 and then a ferric hydroxide was precipitated. Because the ferric hydroxide co-precipitates with Si ion etc, Fe and Si ion was removed from the solution and the about 10% Mn solution was obtained. The solution was diluted with water to Mn-15000 ppm and $NH_4$F was injected into the diluted solution at $70^{\circ}C$ to the F-3000 ppm. As a result, Ca ion is precipitated as $CaF_2$and the residual concentration of Ca was 14 ppm. Injection of the equivalent (NH$1.5M_4$)$_2$$CO_3$solution as 2 L/min at $25^{\circ}C$ into the above solution precipitated a fine and high purity $MnCO_3$powder. The deposition was filtrated and roasted at $1000^{\circ}C$ for 2 hours. As a result, $MnCO_3$powder is converted into $Mn_3$$O_4$powder and it had $8.2\mu$m of median size. The final production is above 99% $Mn_3$$O_4$powder and it satisfied the requirement of high purity $Mn_3$$O_4$powder for a raw material of soft ferrite.

Relationship between Physicochemical Properties, Heavy Metal Contents and Magnetic Susceptibility of Soils (토양의 물리화학적 특성, 중금속 함량, 대자율 간의 상호관계 연구)

  • Chon, Chul-Min;Park, Jeong-Sik;Kim, Jae-Gon;Lee, Youn-Soo
    • Journal of the Mineralogical Society of Korea
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    • v.23 no.4
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    • pp.281-295
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    • 2010
  • This paper deals with magnetic susceptibility, mineralogy, soil properties (pH, EC, CEC, loss on ignition), iron and manganese oxides, the content and partitioning of heavy metals (As, Cd, Cr, Cu, Ni, Pb, Zn), and their mutual relationship in the soil samples of an unpolluted, abandoned mine area, and industrial complex area. The various minerals derived from weathered bedrock were identified by X-ray diffraction in the unpolluted soil samples, except for the magnetic minerals. XRD analysis also revealed the existence of hematite and magnetite related to mine tailings and waste rocks in the abandoned mine area samples. The industrial complex area samples had carbonate minerals, such as calcite and dolomite, that might be due to anthropogenic deposition. The sum of the reducible, oxidizable, and residual fractions was over 80% for the abandoned mine area samples and over 50% for the industrial complex area samples using the sequential extraction method. The industrial complex area samples had a relatively high carbonate fraction that was associated with carbonate minerals. The content of aqua regia-extractable Fe, Mn, As, and Zn had a high positive correlation with the content of the dithionite-citrate-bicarbonate (DCB)-extractable method related to Fe/Mn oxide phases. The 54% and 58% of aqua regia-extractable Fe and As content, respectively, acted together with the concentrations of the DCB-extractable phases. Magnetic susceptibility values of total samples ranged from 0.005 to $2.131{\times}10^{-6}m^3kg^{-1}$. The samples including iron oxide minerals, such as hematite and magnetite, had a high magnetic susceptibility. The magnetic susceptibility showed a significant correlation with the heavy metals, Cd (r=0.544, p<0.05), Cr (r=0.714, p<0.01), Ni (r=0.645, p<0.05), Pb (r=0.703, p<0.01), and Zn (r=0.496, p<0.01), as well as Fe (r=0.608, p<0.01) and Mn (r=0.615, p<0.01). The aqua regia-extractable Fe and Mn content had a significant positive correlation with Cd, Cr, Cu, Ni, and Zn. However, the DCB-extractable Fe and Mn content had a significant positive correlation with As and Ni, indicating that the heavy metals were associated with Fe and Mn oxide minerals.

Electrochemical Characteristics of LiMn2O4 Cathodes Synthesized from Various Precursors of Manganese Oxide and Manganese Hydroxide (다양한 형태 및 구조의 망간산화물 및 망간수산화물 전구체로부터 합성한 LiMn2O4양극의 전기화학적 특성 연구)

  • Lee, Jong-Moon;Kim, Joo-Seong;Hong, Soon-Kie;Lee, Jeong-Jin;Ahn, Han-Cheol;Cho, Won-Il;Mho, Sun-Il
    • Journal of the Korean Electrochemical Society
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    • v.15 no.3
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    • pp.172-180
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    • 2012
  • The $LiMn_2O_4$ cathodes for lithium ion battery were synthesized from various precursors of manganese oxides and manganese hydroxides. As the first step, nanosized precursors such as ${\alpha}-MnO_2$ (nano-sticks), ${\beta}-MnO_2$ (nano-rods), $Mn_3O_4$ (nano-octahedra), amorphous $MnO_2$(nano-spheres), and $Mn(OH)_2$ (nano-plates) were prepared by a hydrothermal or a precipitation method. Spinel $LiMn_2O_4$ with various sizes and shapes were finally synthesized by a solid-state reaction method from the manganese precursors and LiOH. Nano-sized (500 nm) octahedron $LiMn_2O_4$ showed high capacities of 107 mAh $g^{-1}$ and 99 mAh $g^{-1}$ at 1 C- and 50 C-rate, respectively. Three dimensional octahedral crystallites exhibit superior electrochemical characteristics to the other one-dimensional and two-dimensional shaped $LiMn_2O_4$ nanoparticles. After 500 consecutive charge discharge battery cycles at 10 C-rate with the nano-octahedron $LiMn_2O_4$ cathode, the capacity retention of 95% was observed, which is far better than any other morphologies studied in this work.