• Journal of the Korean Ceramic Society
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• v.54 no.4
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• pp.323-330
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• 2017

To understand the defect chemistry of multiferroic $BiFeO_3-based$ systems, we synthesized nonstoichiometric $Bi_{1+x}FeO_{3{\pm}{\delta}}$ ceramics by conventional solid-state reaction method and studied their structural, dielectric and high-temperature charge transport properties. Incorporation of an excess amount of $Bi_2O_3$ lowered the Bi deficiency in $BiFeO_3$. Polarization versus electric field (P-E) hysteresis loop and dielectric properties were found to be improved by the $Bi_2O_3$ addition. To better understand the defect effects on the multiferroic properties, the high temperature equilibrium electrical conductivity was measured under various oxygen partial pressures ($pO_2{^{\prime}}s$). The charge transport behavior was also examined through thermopower measurement. It was found that the oxygen vacancies contribute to high ionic conduction, showing $pO_2$ independency, and the electronic carrier is electron (n-type) in air and Ar gas atmospheres.

• Korean Journal of Materials Research
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• v.5 no.7
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• pp.808-815
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• 1995

The magnetic states of nonstoichiometric substituted ferrite Fe$_{}1.429$(Al$_{4-x}$ Ga$_{x}$)$_{0.286}$ Si$_{0.143}$ /O$_4$ system have been investigated using Mossbauer spectroscopy and SQUID. The Mossbauer spectra at room temperature show well-defined two Zeeman patterns for x=0.2, superpositions of two Zeeman patterns and a doublet for x=0.4. The doublet peak seems to be originated from the superparamagnetic clusters. The system shows significant departures from the Neel's collinear model and seems to be the diluted ferrites. The Mossbauer spectra below R.T show various and complicated patterns, which can be explained by freezing of the superparamagnetic clusters. On cooling, magnetic states of the system may be various and multicritical, Resulting from SQUID measurements, there was an unexpected dip in magnetization curves below 50K. It was interpreted as an effect of spin canting including spin freezing or collective spin behavior.

• Korean Journal of Materials Research
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• v.21 no.8
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• pp.439-443
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• 2011

The crystal structure and magnetic properties of a new solid solution type ferrite $(Fe_2O_3)_5-(Al_2O_3)_{3.4}-(Ga_2O_3)_{0.6}-SiO$ were investigated using X-ray diffraction and M$\"{o}$ssbauer spectroscopy. The results of the X-ray diffraction pattern indicated that the crystal structure of the sample appears to be a cubic spinel type structure. The lattice constant (a = 8.317 ${\AA}$) decreases slightly with the substitution of $Ga_2O_3$ even though the ionic radii of the Ga ions are larger than that of the Al ions. The results can be attributed to a higher degree of covalency in the Ga-O bonds than in the Al-O and Fe-O bonds, which can also be explained using the observed M$\"{o}$ssbauer parameters, which are the magnetic hyperfine field, isomer shift, and quadrupole splitting. The drastic change in the magnetic structure according to the Ga ion substitution in the $ (Fe_2O_3)_5(Al_2O_3)_{4-x}(Ga_2O_3)_xSiO$ system and the low temperature variation have been studied through a M$\"{o}$ssbauer spectroscopy. The M$\"{o}$ssbauer spectrum at room temperature shows the superpositions of two Zeeman patterns and a strong doublet. It shows significant departures from the prototypical ferrite and is comparable with the diluted ferrite. The doublet of spectrum at room temperature appears to originate from superparamagnetic clusters and also the asymmetry of the doublet appears to be caused by the preferred orientation of the crystallites. The M$\"{o}$ssbauer spectra below room temperature show various complicated patterns, which can be explained by the freezing of the superparamagnetic clusters. On cooling, the magnetic states of the sample were various and multi critical.

• Journal of the Korean Magnetics Society
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• v.17 no.6
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• pp.232-237
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• 2007

We have synthesized the low temperature sintered of Ni-Zn-Cu ferrite with nonstoichiometric composition a little deficient in $Fe_2O_3$ from $(Ni_{0.2}Cu_{0.2}Zn_{0.6})_{1+x}(Fe_2O_3)_{1-x}$. For low loss and acceleration of grain growth $TiO_2$ and $Li_2CO_3$ was added from 0.25 mol% to 1.0 mol%. The mixture of the law materials was calcinated and milled. The compacts of toroidal type were sintered at different temperature $(875^{\circ}C,\;900^{\circ}C,\;925^{\circ}C\;950^{\circ}C)$ for 2 hours in air followed by an air cooling. Then, effects of composition and sintering temperatures on the physical properties such as density, resistivity, magnetic induction, coercive force, initial permeability, and quality factor of the Ni-Zn-Cu ferrite were investigated. The density of the Ni-Zn-Cu ferrite was $4.85\sim5.32g/cm^3$, resistivity revealed $10^8\sim10^{12}\Omega-cm$. The magnetic properties obtained from the aforementioned Ni-Zn-Cu ferrite specimens were 1,300 gauss for the maximum induction, 4.5 oersted for the coercive force, 275 for the initial permeability, and 83 for the quality factor. The physical properties indicated that the specimens could be utilized as the core of high frequency range (involved microwave range) communication and deflection yoke of T.V.

• Korean Journal of Materials Research
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• v.30 no.2
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• pp.61-67
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• 2020

BiFeO₃ with perovskite structure is a well-known material that has both ferroelectric and antiferromagnetic properties called multiferroics. However, leaky electrical properties and difficulty of controlling stoichiometry due to Bi volatility and difficulty of obtaining high relative density due to high dependency on the ceramic process are issues for BiFeO₃ applications. In this work we investigated the sintering behavior of samples with different stoichiometries and sintering conditions. To understand the optimum sintering conditions, nonstoichiometric Bi_1±xFeO_3±δ ceramics and Ti-doped Bi_1.03Fe_1-4x/3Ti_xO₃ ceramics were synthesized by a conventional solid-state route. Dense single phase BiFeO₃ ceramics were successfully fabricated using a two-step sintering and quenching process. The effects of Bi volatility on microstructure were determined by Bi-excess and Ti doping. Bi-excess increased grain size, and Ti doping increased sintering temperature and decreased grain size. It should be noted that Ti-doping suppressed Bi volatility and stabilized the BiFeO₃ phase.

• Bulletin of the Korean Chemical Society
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• v.17 no.4
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• pp.321-324
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• 1996

Sr1+xSm1-xFeO4-y solid solutions with a composition range 0.00 ≤x≤1.00 have been prepared at 1200 ℃ in air under normal atmospheric pressure. All the solutions exhibit the K2NiF4-type structure of tetragonal system. Mohr salt analysis shows that the mole ratio of Fe4+ ion to Fe3+ ion or the τ value increases with the x value. Nonstoichiometric chemical formulas have been formulated from the x, τ, and y values. Electrical conductivity was measured in the temperature range of 173-373 K under atmospheric air pressure. The conductivities of each sample are varied within the semiconductivity range. The conductivity at constant temperature increases steadily with x value and activation energies are varied from 0.14 to 0.32 eV. The conduction mechanism of the ferrite system may be proposed as a hopping model of conduction electrons between the mixed valence states. The Mossbauer spectrum for the composition of x=0.00 shows a six line pattern by which the existence of Fe3+(I.S.=0.32 mm/sec) can only be identified. The spectra for the compositions of x=0.50 and 1.00 presents broad single line patterns showing a mixed valence state.

• Journal of the Korean Chemical Society
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• v.32 no.1
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• pp.3-8
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• 1988

Nonstoichiometric solid solutions of the $Sr_{1+x}Dy_{1-x}FeO_{4-y}$ system (x = 0. 00, 0. 25, 0. 50, 0. 75 and 1. 00) with layered $K-2NiF_4$ type structure were prepared at 1200$^{\circ}$C under atmospheric pressure. X-ray powder diffraction spectra show that the crystallographic phases of the samples are tetragonal within the x range. Nonstoichiometric chemical formulas have been determined by Mohr salt analysis and it shows that the amount of $Fe^{4+}$ ion or ${\tau}$ value increases with increasing x. Electrical conductivities of the samples which were measured in the temperature range of $-100{\sim}200^{\circ}$C under atmospheric air pressure are varied within the semiconductivity range of $l0^{-8}{\sim}10^{-2}(ohm^{-1}{\cdot}cm^{-1}$) and the activation energies are also varied from 0.02 to 0.08 eV. Mixed valency state of $Fe^{3+}$ and $Fe^{4+}$ in the sample of $Sr_{1.00}Dy_{1.00}FeO_{4.04}$ was identified again by Mossbauer spectrum at 200K.

• Journal of the Korean Chemical Society
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• v.35 no.2
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• pp.99-104
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• 1991

Nonstoichiometric solid solutions of Sr$_{1+x}Er _{1-x} FeO _{4-y}$ system (x = 0.00, 0.25, 0.50, 0.75 and 1.00) with layered $K_2NiF_4$ type structure were prepared at 1350$^{\circ}$C under atmospheric pressure. By the analysis of X-ray diffraction, the crystallographic structures of the solid solution of all compositions were found to be pseudo-tetragonal system. Nonstoichiometric chemical formulas have been determined by Mohr salt analysis. It shows that the amount of Fe$^{4+}$ increases with increasing x up to 0.50 and then decreases, and the value of oxygen nonstoichiometry increases with increasing x value. Mixed valency states of Fe$^{3+}$ and Fe$^{4+}$ in the sample were identified again by Mossbauer spectroscopic analysis at 298 K. Electrical conductivity varied within the semiconductivity range of 10-2 ∼ 10-7(${\Omega}$-1cm-1), activation energy for electrical conduction decreased with the increment of the mole ratio of Fe$^{4+}$ or ${\tau}$ value. The conduction mechanism could be explained by the hopping model of the conduction electrons between the valency states of Fe$^{3+}$ and Fe$^{4+}$.

• Applied Chemistry for Engineering
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• v.8 no.6
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• pp.954-959
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• 1997

The solid solutions of the $Sr_{1-X}M_XFeO_{3-y}$ (x=0.1, 0.2, 0.3, 0.4, 0.5, M=Ca) system having perovskite structures were prepared in air by heat treatment at 1473 K for 18hr. X-ray diffraction assigns cubic system for all the samples and shows that the lattice volume of each system decreases with increasing x value until x=0.3, but increases abruptly from x=0.4. The mole fractions of $Fe^{4+}$ ion($\tau$ value), the amounts of oxygen vacancy (y value) and finally nonstoichiometric chemical formulas for each composition were determined from Mohr salt analysis. TG/DTA thermal analysis (temperature range: 300~1173K) exhibits that 3-y values of the samples having x=0.1 and 0.2, decrease with temperature and increase almost reversibly with decreasing temperature. The samples of $x{\geq}0.3$, however, didn't show the reversible weight change and the 3-y values of them were nearly 2.5 in cooling process. Conductivities of each sample were varied within the semiconductivity range at relatively low temperature. And the conductivity at constant temperature decreases steadily with x value. The conduction mechanism of this ferrite system may be proposed as a hopping model of conducting electrons between the mixed valence states. At high temperature semiconductivity of each sample changed into metallic property.