• Title/Summary/Keyword: Mn valence

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Preparation and Characterization of LiMn₂O₄ Powder by Combustion of Poly(ethylene glycol)-Metal Nitrate Precursor

  • 박휴범;홍영식;이지은;권호진;김시중
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.612-618
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    • 1997
  • $LiMn_2O_4$ powders were prepared by burning and subsequent calcination of PEG-metal nitrate precursor. After the burning stage of the precursor, some minor phases such as $Mn_2O_3$ (or $Mn_3O_4$), MnO, and carbonate were formed and single phases of $LiMn_2O_4$ were obtained by further calcinations above 400 ℃. From thermal analysis of the precursor, a violent thermal decomposition, which was indicated by a drastic weight loss accompanied by a sharp and strong exothermic peak, was observed and probably caused by an oxidation-reduction reaction between oxidizer and fuel. The formation of the minor phases could be explained in terms of the burning behavior of the precursor by employing valence concepts of propellant chemistry. The calcined powders were composed of submicron-sized but highly agglomerated particles and showed very broad particle size distribution.

Effects of $Mn_2O_3, Y_2O_3$ Additives and Valence State of Mn ion in $Sr(Zr, Ti)O_3$ Microwave Dielectrics ($Sr(Zr, Ti)O_3$ 마이크로파 유전체에 첨가된 $Mn_2O_3, Y_2O_3$ 의 영향과 Mn의 산화상태)

  • 정하균;박도순;박윤창
    • Journal of the Korean Ceramic Society
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    • v.34 no.6
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    • pp.583-590
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    • 1997
  • The effects of Mn2O3 and Y2O3 additives on the microstructure and dielectric properties of Sr(Zr, Ti)O3 have been investigated. Powders with Sr(Zr1-xTix)O3(0$\leq$x$\leq$0.1) composition were prepared by the conventional solid state processing from commercial TiO2 and precipitation-processed ZrO2. The powders containing sintering additives of Mn2O3 and Y2O3 were compacted and then sintered at 1,55$0^{\circ}C$ for 4 h to get>97% relative density. Mn2O3 suppressed the grain growth and Y2O3 enhanced the density of sintered body. The oxidation state of Mn ions were determined by a chemical wet method and EPR spectroscopy. Mn ions were present as Mn2+ and Mn4+ in SrZrO3, while as Mn3+ and Mn4+ in Ti-substituted Sr(Zr, Ti)O3. With the substitution of Ti, the lattice parameters of SrZrO3 decreased and its dielectric constant increased with remarkable decrease in Q value. The dielectric constant of Sr(Zr, Ti)O3 was in the range of 30 to 40, Q values 1,200~5,400 at 6 GHz and temperature coefficient of resonant frequency -67~100 ppm/K.

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Ferromagnetism of Chalcopyrite AlGaAs2:Mn Quaternary Alloys (4원 합금 AlGaAs2:Mn의 강자성)

  • Kang, Byung-Sub
    • Korean Journal of Materials Research
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    • v.30 no.12
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    • pp.666-671
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    • 2020
  • The electronic structure and magnetic properties of chalcopyrite (CH) AlGaAs2 with dopant Mn at 3.125 and 6.25 % concentrations are investigated using first-principles calculations. The CH AlGaAs2 alloy is a p-type semiconductor with a small band-gap. The AlGaAs2:Mn shows that the ferromagnetic (FM) state is the most energetically favorable one. The Mn-doped AlGaAs2 exhibits FM and strong half-metallic ground states.The spin polarized Al(Ga,Mn)As2 state (Al-rich system) is more stable than the (Al,Mn)GaAs2 state (Ga-rich system), which has a magnetic moment of 3.82mB/Mn. The interaction between Mn-3d and As-4p states at the Fermi level dominates the other states.The states at the Fermi level are mainlyAs-4p electrons, which mediate strong interaction between the Mn-3d and As-4p states. It is noticeable that the FM ordering of dopant Mn with high magnetic moment originates from the As(4p)-Mn(3d)-As(4p) hybridization, which is attributed to the partially unfilled As-4pbands. The high FM moment of Mn is due to the double-exchange mechanism mediated by valence-band holes.

Effects of $MnO_2$ on the Dielectric and Piezoelectric Properties of Pb($Zr_{0.52}$ $Ti_{0.48}$)$O_3$ Ceramics (Pb($Zr_{0.52}$ $Ti_{0.48}$)$O_3$세라믹스의 유전 및 압전성에 미치는 $MnO_2$ 의 영향)

  • 김종선;윤기현;최병현;박종옥;이종민
    • Journal of the Korean Ceramic Society
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    • v.27 no.2
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    • pp.187-194
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    • 1990
  • Effects of MnO2 addition ranged from 0.0wt% to 5.0wt% on the microstructure and dielectric and piezoelectric properties of the Pb(Zr0.52 Ti0.48)O3 Ceramics have been investigated. The solubility limit of MnO2 in Pb(Zr0.52 Ti0.48)O3 is about 0.5wt%, and MnO2 as a valence state of Mn3+ is substituted for (Zr, Ti) lattice site in PZT solid-solution. The addition of MnO2 up to 0.5wt% in Pb(Zr0.52 Ti0.48)O3 brings increase of density, but decreased of grain size and tetragonality. Dielectric constant slightly decreases, but both coupling factor(Kp) and mechanical quality factor(Qm) increase with the addition of MnO2. However, excess amount of MnO2 addition more than 0.75wt% results in rapid decrease of resistance. Dielectric constant and tan $\delta$ increase due to the second phase and inhomogeneous Mn distribution.

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XPS Study of Mn 2pp and 3s Satellite Structures of Heusler Alloys: NiMnSb, ppdMnSb, pptMnSb

  • Yang, See-Hun;Oh, Se-Jung;ppark, Je-Geun
    • Proceedings of the Korean Vacuum Society Conference
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    • 1994.02a
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    • pp.50-50
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    • 1994
  • Half-metallic Heusler alloys (NiMnSb, ppdMnSb, pptMnSb) have attracted much attention due to their unique electronic and magnetic structures. Sppin-ppolarized band structure calculation ppredicts metallic behavior for the majority sppin states and semiconductor behavior for the minority sppin states. We have studied the electronic structures of these half-metallic Heusler alloys by core-level pphotoemission sppectroscoppy of Mn 2pp and 3s XppS sppectra. We found large intensities of Mn 2pp satellites and 3s exchange spplitting comppared with other metal Mn-alloys. These satellite structure can be understood by applying Anderson imppurity model. This fact supports the calculated sppin pprojected ppartial density of states which suggests that the valence electrons be highly sppin ppolarized near Fermi level and that the electrons involved with charge-transfer be mainly minority sppin ones which have semiconducting band structure. The trend of charge transfer energies Δ from ligands (Sb 5pp) to Mn 3d, obtained from our model fitting, is consistent with that calculated from sppin pprojected ppartial density of state. Also the trend of d-d electron correlation energies U calculated from Mn Auger line L3 VV by Mg $K\alpha$ source is comppatible with that resulted from our model fitting. We fitted the Mn 3s curve in the same way as for insulating Mn comppounds by using the same pparameters calculated from Mn 2pp curve fitting exceppt for the Coulomb interaction energy Q between core hole and d-electrons. The 3s sppectra were analyzed by combing the charge transfer model and a simpple model taking into account the configuration mixing effect due to the intra-shell correlation. We found that the exchange interaction between 3s hole and 3d electrons is mainly respponsible for the satellite of Mn 3s sppectra. This is consistent with the neutron scattering data, which suggests local 3d magnetic moment. We find that the XppS analysis results of Mn 2pp and 3s satellite structures of half-metallic Heusler alloys are very similar to those of insulating transition metal comppounds.

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Magnetic Susceptibility of the Single Crystal MnF2(1.5% EuF3) (단결정 MnF2(1.5% EuF3)의 자기 감수율)

  • Lee, Jun-Young;Nahm, Kyun;Kim, Chul-Koo
    • Journal of the Korean Magnetics Society
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    • v.16 no.5
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    • pp.261-263
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    • 2006
  • In order to investigate the magnetic properties of Eu ions in the single crystal $MnF_2$, the temperature dependent magnetic susceptibilities of the antiferromagnetic $MnF_2$ and the single crystal $MnF_2$(1.5% $EuF_3$) with the rutile structures were measured in the temperature range from 4K to 300K. The detailed analysis of the measured susceptibilities showed that the magnetic susceptibility by the doping of the small amount $EuF_3$ in the antiferromagnetic single crystal $MnF_2$ follows the antiferromagnetic Curie-Weiss law with the negative paramagnetic Curie temperature similarly as in $MnF_2$. It was also found that Eu ion has +3 valence. This solves the long standing discrepancy on this problem.

Structural and Electrical Properties of (La,Nd,Sr)MnO3 Ceramics for NTC Thermistor Devices

  • Shin, Kyeong-Ha;Park, Byeong-Jun;Lim, Jeong-Eun;Lee, Sam-Haeng;Lee, Myung-Gyu;Park, Joo-Seok;Lee, Sung-Gap
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.35 no.3
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    • pp.292-296
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    • 2022
  • (La0.5Nd0.2Sr0.3)MnO3 specimens were prepared by a solid-state reaction. In all specimens, X-ray diffraction patterns of an orthorhombic structure were shown. The fracture surfaces of (La0.5Nd0.2Sr0.3)MnO3 specimens showed a transgranular fracture pattern be possibly due to La ions (0.122 nm) as a perovskite A-site dopant substituting for Nd ions (0.115 nm) having a small ionic radius. The full-width at half maximum (FWHM) of the Mn 2p XPS spectra showed a value greater than that [8] of the single valence state, which is believed to be due to the overlapping of Mn2+, Mn3+, and Mn4+ ions. The dependence of Mn 2p spectra on the Mn3+/Mn4+ ratio according to sintering time was not observed. Electrical resistivity resulted in the minimum value of 100.7 Ω-cm for the specimen sintered for 9 hours. All specimens show a typical negative temperature coefficient of resistance (NTCR) characteristics. In the 9-hour sintered specimen, TCR, activation energy, and B25/65-value were -1.24%/℃, 0.19 eV, and 2,445 K, respectively.

Small Polaron Hopping Conduction of n=3 Ruddlesden-Popper Compound La2.1Sr1.9Mn3O10 System (II) (n=3인 Ruddlesden-Popper형 La2.1Sr1.9Mn3O10 세라믹스의 Small polaron Hopping 전도 (II))

  • Jung, Woo-Hwan;Lee, Joon-Hyung;Sohn, Jeong-Ho
    • Journal of the Korean Ceramic Society
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    • v.39 no.9
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    • pp.878-883
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    • 2002
  • Electrical resistivity and thermoelectric power measurements on Mn-based $La_{2.1}Sr_{1.9}Mn_3O_{10}$ with layered perovskite structure as functions of temperature are presented. The experimental results demonstrate that the electronic transport in $La_{2.1}Sr_{1.9}Mn_3O_{10}$ is well described by the Emin-Holstein adiabatic small polaron model. The thermoelectric power data in the small polaron regime above Curie temperature is nearly equal to that predicted by nominal $Mn^{4+}$ valence arguments. This indicates that transport involves small polaron hopping.

Determination of Mn Oxidation State in Mn-(hydr)oxides using X-ray Photoelectron Spectroscopy(XPS) (X-선 광전자 분광법을 이용한 망간산화물의 망간 산화상태 해석)

  • Song, Kyung-Sun;Bae, Jong-Seong;Lee, Gie-Hyeon
    • Economic and Environmental Geology
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    • v.42 no.5
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    • pp.479-486
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    • 2009
  • In natural environments, manganese (Mn) exists in the valence of +2, +3, and +4 and plays a pivotal role as a strong oxidant or reductant in the geochemical cycles of elements. Especially, Mn forms varying (oxyhydr)oxides. The oxidation state of structural Mn is characteristic to each oxide and is one of the most important factors controlling its geochemical behaviors such as solubility, sorption capacity, and redox potential. Therefore, it is important to elucidate processes governing Mn oxidation state in predicting the fate and transport of many redox sensitive elements in the environment. X-ray photoelectron spectroscopy (XPS) is a very useful method to determine the oxidation state of various elements in solid phases. In this study, the oxidation states of structural Mn in MnO, $Mn_2O_3$, $MnO_2$ were assessed based on the binding energy spectra of $Mn2p_{3/2}$ and Mn3s using XPS and were compared with those reported elsewhere. $Mn2p_{3/2}$ binding energies were determined as 640.9, 641.5, 641.8 eV for MnO, $Mn_2O_3$, $MnO_2$, respectively, which indicates that the binding energy increased with increasing Mn oxidation state. It was also noted that Ar etching may cause changes in electronic structure configuration on surface of the original sample.