• Title/Summary/Keyword: cation preference

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Thermodynamic Properties of $NiFe_2O_4-NiFe_2O_4$ Spinel Solid Solution

  • 박봉훈;김동수
    • Bulletin of the Korean Chemical Society
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    • v.20 no.8
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    • pp.939-942
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    • 1999
  • The tie lines delineating ion-exchange equilibria between NiFe2O4-NiCr2O4 spinel solid solution and Fe2O3-Cr2O3 corundum solid solution were determined at 900, 1000, and 1200 ℃ by electron microprobe and energy dispersive X-ray analysis of oxide phases, using the flux growth technique. Activities of the spinel components were calculated from the tie lines, assuming Temkin's ideal mixing in the corundum solid solution. The spinel phase could be expressed by a regular solution with negative deviations from ideality. The Gibbs free energies of mixing for spinel solid solution were discussed in terms of the cation distribution model, based on site preference energies and assuming random mixing on both tetrahedral and octahedral sites.

Mossbauer Study for the Cation Distribution of Co-ferrite (CoxFe1-xO4) Thin Films (Co-ferrite 박막에서 양이온 거동에 관한 Mössbauer 분광 연구)

  • Park, Jae-Yun;Park, Young-Ran;Kim, Hee-Kyung;Kim, Kwang-Joo
    • Journal of the Korean Magnetics Society
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    • v.16 no.1
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    • pp.1-5
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    • 2006
  • The crystallographic properties and cation distribution of oxyspinels ferrite $Co_xFe_{1-x}O_4$ thin films have been explored by X-ray diffraction, vibrating sample magnetometer (VSM), and conversion electron $M\"{o}ssbauer$ spectroscopy (CEMS). Thin films are prepared by sol-gel method. Normal spinel structure is transformed to inverse spinel structure with increasing Co concentration CEMS results indicate that most of $Fe^{3+}$ ions are substituted to $Co^{3+}$ions. Accordingly $Co^{2+}$ ions on octahedral site migrate to tetrahedral site. Magnetic moment is decreased with increasing Co concentration, which means high spin $Fe^{3+}$ ions are replaced by low spin $Co^{3+}$.

Crystallographic Effects of Larger Indium Ion Substitution in NiFe2-xInxO4 (x = 0, 0.2, 0.5, and 1.0) System

  • Yoon, Sung-Hyun;Yoon, Chang-Sun;Kim, Byung-Ho
    • Journal of Magnetics
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    • v.10 no.1
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    • pp.23-27
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    • 2005
  • The crystallographic and magnetic properties of a series of substitutions in nickel ferrite where the Fe3+ is replaced with In3+ have been investigated using X-ray diffraction (XRD) and Mössbauer spectroscopy. Information on the exact crystalline structure, lattice parameters, bond lengths and bond angles were obtained by refining their XRD profiles by a Rietveld method. All the crystal structures were found to be cubic with the space group Fd/3m. The lattice constants increased with In3+ concentration. The expansion of the tetrahedron was outstanding, indicative of the tetrahedral (A) site preference of larger indium ion. The Mossbauer spectra showed two sets of sextuplet originating from ferric ions occupying the tetrahedral sites and the octahedral (B) sites under the Neel temperature TN. Regardless of the composition x, the electric quadrupole splitting was zero within the experimental error. At x = 0.2, the magnetic hyperfine fields increased slightly, which meant that the nonmagnetic indium ions occupied preferentially the A-site. At the same time, the intensity of the B-site sub-spectra decreased markedly at the elevated temperature, indicating that the occupation of the A site by indium induced a considerable perturbation on the B site.

Sorption and Ion Exchange Characteristics of Chabazite: Competition of Cs with Other Cations (차바자이트의 흡착 및 이온 교환 특성: Cs 및 다른 양이온과의 경쟁)

  • Baek, Woohyeon;Ha, Suhyeon;Hong, Sumin;Kim, Seonah;Kim, Yeongkyoo
    • Journal of the Mineralogical Society of Korea
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    • v.29 no.2
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    • pp.59-71
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    • 2016
  • To investigate the sorption characteristics of Cs, which is one of the major isotopes of nuclear waste, on natural zeolite chabazite, XRD, EPMA, EC, pH, and ICP analysis were performed to obtain the informations on chemical composition, cation exchange capacity, sorption kinetics and isotherm of chabazite as well as competitive adsorption with other cations ($Li^+$, $Na^+$, $K^+$, $Rb^+$, $Sr^{2+}$). The chabazite used in this experiment has chemical composition of $Ca_{1.15}Na_{0.99}K_{1.20}Mg_{0.01}Ba_{0.16}Al_{4.79}Si_{7.21}O_{24}$ and its Si/Al ratio and cation exchange capacity (CEC) were 1.50 and 238.1 meq/100 g, respectively. Using the adsorption data at different times and concentrations, pseudo-second order and Freundlich isotherm equation were the most adequate ones for kinetic and isotherm models, indicating that there are multi sorption layers with more than two layers, and the sorption capacity was estimated by the derived constant from those equations. We also observed that equivalent molar fractions of Cs exchanged in chabazite were different depending on the ionic species from competitive ion exchange experiment. The selectivity sequence of Cs in chabazite with other cations in solution was in the order of $Na^+$, $Li^+$, $Sr^{2+}$, $K^+$ and $Rb^+$ which seems to be related to the hydrated diameters of those caions. When the exchange equilibrium relationship of Cs with other cations were plotted by Kielland plot, $Sr^{2+}$ showed the highest selectivity followed by $Na^+$, $Li^+$, $K^+$, $Rb^+$ and Cs showed positive values with all cations. Equilibrium constants from Kielland plot, which can explain thermodynamics and reaction kinetics for ionic exchange condition, suggest that chabazite has a higher preference for Cs in pores when it exists with $Sr^{2+}$ in solution, which is supposed to be due to the different hydration diameters of cations. Our rsults show that the high selectivity of Cs on chabazite can be used for the selective exchange of Cs in the water contaminated by radioactive nuclei.

Mössbauer Study of Crystallographic and Magnetic Properties in Vanadium Ferrite(VxFe3-xO4) Thin Films (바나듐 페라이트 박막의 결정구조 및 자기적 성질에 관한 뫼스바우어 분광학적 연구)

  • Park, Jae-Yun;Kim, Kwang-Joo
    • Journal of the Korean Magnetics Society
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    • v.18 no.1
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    • pp.19-23
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    • 2008
  • The mixed ferrite $V_xFe_{3-x}O_4$(x=0.0, 0.15, 0.5, 1.0) thin films were prepared by sol-gel method. Their crystallographic and magnetic hyperfine properties have been studied using X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and conversion electron $M\"{o}ssbauer$ spectroscopy(CEMS). The crystal structure is found to be cubic spinel throughout the series($x{\leq}1.0$), and the lattice parameter $a_0$ increases linearly with increasing V content. XRD, XSP and CEMS indicate that $V^{3+}$ substitution for $Fe^{3+}$ in B-site is superior to $V^{2+}$ substitution for $Fe^{2+}$ in B-site. It is noticeable that both quadrupole shift and hyperfine field decreases with increasing V composition, suggesting the change of local symmetry and accompanying line-broadening. The line-broadening on CEMS spectra can be explained by the distribution of magnetic hyperfine fields.