• Journal of the Korean Magnetics Society
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• v.24 no.2
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• pp.46-50
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• 2014

The crystallographic properties and cationic distribution of $M_{0.2}Fe_{2.8}O_4$ (M =Mn, Ni, Cu) and $Fe_3O_4$ thin films prepared by sol-gel method have been investigated by X-ray diffraction (XRD) and conversion electron M$\ddot{o}$ssbauer spectroscopy (CEMS). The ionic valence, preferred site, and hyperfine field of Fe ions of the ferrites could be obtained by analyzing the CEMS spectra. The $M_{0.2}Fe_{2.8}O_4$ films were found to maintain cubic spinel structure as in $Fe_3O_4$ with the lattice constant slightly decreased for Ni substitution and increased for Mn and Cu substitution from that of $Fe_3O_4$. Analyses on the CEMS data indicate that $Mn^{2+}$ and $Ni^{2+}$ ions substitute octahedral $Fe^{2+}$ sites mostly, while $Cu^{2+}$ ions substitute both the octahedral and tetrahedral sites. The observed intensity ratio $A_B/A_A$ of the CEMS subspectra of the samples exhibited difference from the theoretical value. It is interpreted as due to the effect of the M substitution for A and B on the Debye temperature of the site. The relative line-broadening of the B-site CEMS subspectra can be explained by the dispersion of magnetic hyperfine fields due to random distribution of M cations in the B sites.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3588-3592
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

• Journal of the Mineralogical Society of Korea
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• v.6 no.1
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• pp.17-26
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• 1993

Mineralogical characteristics of tosudite from the Sungsan and Bubson mines were studied and correlated using X-ray diffraction analysis, chemical analysis and electron microscopy. Tosudite occurs as an alteration product of Cretaceous volcanoclastic rocks in both mines. It is associated with microcrystalline quartz, dickite, illite/smectite or mica/smectite mixed-layer mineral. It forms cryptocrystalline aggregates with flaky habit. XRD analysis suggests that tosudite is an 1:1regularly interstratified dioctahedral smetite/dioctahedral chlorite. Bubsoo tosudite has more(00ℓ ) reflections and more periodice stacking sequence than Syngsan tosudite. Chemical analysis shows that tosudite is a Li-bearing aluminous 1:1 regularly interstrattified mineral composed of K-bedellite and donbassite. Cookeite component may be present in the chlorite layer. Bubsoo tosudite is more Al in tetrahedral site and Ca in interlayer, but less Al in octahedral site than Sugsan tosudite. Tosudite may be formed as the intermediate alteration products, forming after muscovite and before illite/smectite or mica/s$^{\circ}C$mectite, with the range from 100 $^{\circ}C$ to 360 ~ 480 $^{\circ}C$. The hydrothermal solution forming tosudite may be acidic solution with high activities of Si and Al.

• Journal of the Korean Vacuum Society
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• v.20 no.3
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• pp.205-210
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• 2011

Structural and electrochemical properties of spinel oxide $LiMn_2O_4$ thin films prepared by using a sol-gel method on Pt/Ti/$SiO_2$/Si substrates were investigated. When Li/Mn molar ratio of the film was smaller than 0.5, $Mn_2O_3$hase was found to coexist with $LiMn_2O_4$. Half-cell batteries fabricated using the $LiMn_2O_4$ films as the cathode were put into chargedischarge (C-D) cycles and the change in structural properties of the cathode after the cycles was examined by X-ray diffraction and Raman spectroscopy. As the C-D cycle number increases, the discharge capacity of pure $LiMn_2O_4$ battery gradually decreases, being reduced to 72% of the initial capacity at 300 cycles. Such capacity fading is attributable to the decrease in the number of $Li^+$ ions that return to the tetrahedral sites of the spinel structure during the discharge step and the resultant increase in $Mn^{4+}$ density in the film. Also, $Mn_2O_3$ phase gradually appeared in the film as the cycle number increases.

• Journal of the Mineralogical Society of Korea
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• v.3 no.1
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• pp.1-6
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• 1990

Clacic amphiboles along the tremolite (Tr)-tschermakite(Ts) joint were synthesized using a piston-cylinder appratus. At 750-85$0^{\circ}C$and 12-2 kb, amphibole+corundum coexist with zoisite($\pm$talc, chlorite, and Mg-staurolite), but with anorthite($\pm$cholorite, spinel, pyroxenes, and sapphirine) at lower P. At 90$0^{\circ}C$, amphibole+corundum+clinopyroxene($\pm$anorthite, forsterite, sapphirine, and garnet) are stable over the P range 12-18 kb. These amphibole-bearing assemblages are replaced at high P by clcinopyroxene+talc+chlorite+zoisite at 650-75$0^{\circ}C$, and at higher temperatures by garnet+clinopyroxene($\pm$zoisite, orthopyroxene, and Mg-staurolite). Synthetic amphiboles with Ts>~45 mol% contain as much as 0.15 excess cations per formula unit(pfu) based on 23 oxygens(anhydrous formula), whereas less tschermakitic ones are deficient in cation occupancy by up to 0.18 pfu. This trend is attributed to the 야/trioctahedral substitution in Ca-amphiboles. Compositions of synthetic amphiboles display systematic changes with P and T governed by coexisting mineral assemblages. The Ts content (=[8-Si-Na]/2) increases with increasing T( Ts/ T=~0.1 nik% K-1) in the range 750-85$0^{\circ}C$, but remains nearly constant at 850-90$0^{\circ}C$. Pressure dramatically affects the Ts content of Ca-amphiboles:it increases with P at 8-12 kb( Ts/ T=2-3 mol% K-1), but significantly decreases at 12-21 kb( Ts/ P=-2.5 mol% Kb-1). Hence, the most tschermakitic amphiboles, containing 60$\pm$5 mol % Ts, or 1.2$\pm$0.1 tetrahedral Al, occur at 12 kb and 850-90$0^{\circ}C$. Compositions of Ca-amphiboles defined by a simple reaction, 3 Tr+2 zoisite+7 corundum+H2O=5 Ts, are reversed and used to estimate thermodynamic parameters of tschermakite assuming ideal mixing of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$of Tr-Ts solid solutions. Predicted standard molal entropy and enthalpy of tschermakite are : S$^{\circ}$=566.9$\pm$13.7 J mol-1K, -1and H$^{\circ}$=-12518.36$\pm$15.17 kJ mol.-1

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.327-337
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• 2007

Mineral compositions were determined using quantitative X-ray diffraction analysis on the three kinds of Youngdong illite consisting of white, yellow and refined yellow samples. Mean particle size and their size distribution patterns were measured by laser particle size analyzer. The characteristics of phosphate adsorption on illite were studied through batch adsorption experiments. The white illite has less illite content, but is finer than that of yellow. The refined yellow illite has more illite content and finer particle size compared with those of raw yellow illite. The adsorption rate of phosphate generally increases when the mass of illite increases, whereas adsorption quantity decreases with ascending pH. The phosphate adsorption usually increases with ascending illite content or descending particle size. Although the white illite has lower illite content than the yellow, the former has higher phosphate adsorption quantity than the latter. This can be ascribed to the fine particle size, high interlayer charge, and low substitution in tetrahedral site of white illite. The adsorption isotherms of white illite are well fitted with the Langmuir equation, however those of yellow one are better with Freundlich equation.

• Journal of the Mineralogical Society of Korea
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• v.20 no.4
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• pp.367-376
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• 2007

Aenigmatite, $Na_4(Fe^{2+},Ti,Fe^{3+}){_{12}}(Fe^{3+},Si){_{12}}O_{40}$, is a common constituent of sodium-rich alkaline igneous rocks and is classified a an open-branched single-chain silicate. $M\ddot{o}ssbauer$ spectroscopy of three natural aenigmatite specimens were done and the detailed crystal chemistry was obtained. Fitting of $M\ddot{o}ssbauer$ spectra led to the resolution of nine peaks. They consist of three doublets of $Fe^{2+}/oct$ and one merged peak at low velocity matching to two small peaks at high velocity which were assigned to $Fe^{3+}/tet\;and\;Fe^{2+}/oct$, respectively. Using the peak area for $Fe^{2+}\;and\;Fe^{3+}$ peaks, analytical data were recalculated. Precise assignment of $Fe^{2+}\;and\;Fe^{3+}$ ions in tetrahderal and octahedral sites revealed detailed crystal chemistry of aenigmatite. The existence of significant amounts of $Fe^{3+}/tet$ indicates that $Fe^{3+}$ has preference over $Al^{3+}$ for the tetrahedral sites. Crystal chemistry of aenigmatite (AEN1) yields the formula of $(Na_{3.97}Ca_{0.03})(Ca_{0.11}Mn_{0.59}Fe^{2+}{_{8.07}}Ti_{2.07}Mg_{0.70}Fe^{3+}{_{0.43}}Al_{0.04})(Fe^{3+}{_{0.56}}Al_{0.18}Si_{11.26})O_{40}$.

• Tunnel and Underground Space
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• v.30 no.6
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• pp.573-590
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• 2020

This study presents the current status of DECOVALEX-2023 project Task G and our research results so far. Task G, named 'Safety ImplicAtions of Fluid Flow, Shear, Thermal and Reaction Processes within Crystalline Rock Fracture NETworks (SAFENET)' aims at developing a numerical method to simulate the fracture creation and propagation, and the coupled thermohydro-mechanical processes in fracture in crystalline rocks. The first research step of Task G is a benchmark simulation, which is designed for research teams to make their modelling codes more robust and verify whether the models can represent an analytical solution for displacements of a single rock fracture. We reproduced the mechanical behavior of rock and embedded single fracture using a three-dimensional grain-based distinct element model for the simulations. In this method, the structure of the rock was represented by an assembly of rigid tetrahedral grains moving independently of each other, and the mechanical interactions at the grains and their contacts were calculated using 3DEC. The simulation results revealed that the stresses induced along the embedded fracture in the model were relatively low compared to those calculated by stress analysis due to stress redistribution and constrained fracture displacements. The fracture normal and shear displacements of the numerical model showed good agreement with the analytical solutions. The numerical model will be enhanced by continuing collaboration and interaction with other research teams of DECOVALEX-2023 Task G and validated using various experiments in a further study.

• Tunnel and Underground Space
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• v.30 no.6
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• pp.509-518
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• 2020

This study constructed a new simulation platform, including mesh generation process, numerical simulation, and post-processing for results analysis based on exploration data to perform real-scale numerical analysis considering the actual geological structure efficiently. To build the simulation platform, we applied for open-source programs. The source code is open to be available for code modification according to the researcher's needs and compatibility with various numerical simulation programs. First, a three-dimensional model(3D) is acquired based on the exploration data obtained using a drone. Then, the domain's mesh density was adjusted to an interpretable level using Blender, the free and open-source 3D creation suite. The next step is to create a 3D numerical model by creating a tetrahedral volume mesh inside the domain using Gmsh, a finite element mesh generation program. To use the mesh information obtained through Gmsh in a numerical simulation program, a converting process to conform to the program's mesh creation protocol is required. We applied a Python code for the procedure. After we completed the stability analysis, we have created various visualization of the study using ParaView, another open-source visualization and data analysis program. We successfully performed a preliminary stability analysis on the full-scale Dokdo model based on drone-acquired data to confirm the usefulness of the proposed platform. The proposed simulation platform in this study can be of various analysis processes in future research.

• New Physics: Sae Mulli
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• v.68 no.12
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• pp.1302-1307
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• 2018

The crystallographic, electrical and magnetic behaviors of magnetite powder in the vicinity of its Verwey transition were investigated in this study. Magnetite was prepared by synthesizing a nanoparticle precursor and then annealing it at $800^{\circ}C$ for 1 h under a dynamic vacuum. Crystallographic and morphology analyses were done by using scanning electron microscope (SEM) and X-ray diffraction (XRD). The electrical and the magnetic properties were examined by using $M{\ddot{o}}ssbauer$ spectroscopy, vibrating sample magnetometer (VSM) and resistivity measurement. Both the magnetic moment and the resistivity showed discontinuous changes at the Verwey transition temperature ($T_V$). The temperature dependence of magnetic anisotropy constant showed a monotonic decrease with increasing temperature, with slight dip near $T_V$. $M{\ddot{o}}ssbauer$ spectra showed the superposition of two sextets, one from the tetrahedral (A) and the other from the octahedral (B) sites. The results revealed that identical charge states existed in the B site at temperatures both above and below $T_V$. A coordination crossover resulted in a transition from an inverse to a normal spinel at or close to $T_V$.