• Transactions on Electrical and Electronic Materials
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• v.13 no.1
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• pp.39-42
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• 2012

To study the physical and chemical properties, solid solutions of $(Sr_{1-x}Ba_x)NdFe{^{3+}}_{1-\tau}Fe{^{4+}}_{\tau}O_{4-y}$ system with x=0.0(SBN-0), 0.1(SBN-1), 0.2(SBN-2) and 0.3(SBN-3) were synthesized in air at 1,473 K and annealed in air at 1,073 K for 24 h. X-ray powder diffraction assured that the four samples had tetragonal symmetries (I4/mmm). Their lattice volumes increased gradually with x values. Nonstoichiometric chemical formulas were formulated using the data such as $\tau$(amount of $Fe^{4+}$ ion) and y(oxygen deficiency) values using Mohr salt analysis. It was found out that all the four samples had excessive oxygen (4-y>4.0). All the samples started to lose some of their oxygen at around 613K(TG/DTA thermal analysis). They exhibited semiconductivities in the temperature range of around 283-1173K. All the four specimens had sufficient tensile strength to endure the force of 19.6 N (2 kg of weights) and the conductivity values of the ECIAs which were painted on pieces of glass with the area of $150mm^2$ ($10mm{\times}15mm$) and it was in the order of ECIA-0${\rightarrow}$ECIA-1${\rightarrow}$ECIA-2${\rightarrow}$ECIA-3 at a constant temperature.

• Bulletin of the Korean Chemical Society
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• v.16 no.3
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• pp.261-264
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• 1995

A series of samples of the Nd1-x(Ba0.40Mg0.60)1+xFeO4-y (x=0.00, 0.10, 0.20, and 0.30) system has been synthesized at 1450 ℃ under an atmospheric air pressure. The x-ray powder diffraction analysis of the solid solutions assigns the structure of all the compositions to orthorhombic system. Mohr salt analysis shows that τ and y values increase with x value and nonstoichiometric chemical formulas of the system can be formulated from the x, τ, and y values. Oxygen vacancies are distributed along c-axis in the perovskite layer. The magnetic ordering temperature remains unchanged with x value. Electrical conductivity and activation energy depend only on the mixed valence state of Fe ion. Conduction mechanism can be suggested as the hopping of electron between eg orbitals of Fe3+ and Fe4+ ions through Fe3+-O-Fe4+ bonds. Magnetic susceptibility and electrical conductivity are discussed with the nonstoichiometric chemical formulas.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.295-301
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• 1996

A series of solid solutions of the $CaGa_1-xFexO_3-y$ system with the compositions of x=0.25, 0.50, 0.75, and 1.00 has been prepared at $1150^{\circ}C$ under an atmospheric air pressure. The structure, nonstoichiometric chemical formula, and the distribution of cations for the solid solutions are determined by X-ray diffraction analysis, Mohr salt titration, Mossbauer spectroscopic analysis. Their physical properties are discussed with electrical conductivity and magnetic measurements. The crystal system of all the compositions is a brownmillerite orthorhombic system from the X-ray diffraction analysis and the reduced lattice volume increases linearly with x value except that of the composition of x=0.25. All the solid solutions do not contain $Fe^{4+}$ ion and the mole number of oxygen vacancies or y value is 0.50 from Mohr salt analysis. The oxidation state of Fe ion, the coordination state, the structure change in the Brownmillerite-type structure, and the distribution of $Ga^{3+}$ and $Fe^{3+}$ ions are discussed with Mossbauer spectroscopic analysis. The electrical conductivity increases and activation energy decreases, as x value increases. The traditional semiconducting property of this system is described in terms of band theory. The compositions of x=0.50∼1.00 show a thermal magnetic hysteresis in the magnetic measurement with the cooling conditions, which is discussed in terms of the space group and Dzyaloshinsky-Moriya interaction.

• Bulletin of the Korean Chemical Society
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• v.16 no.10
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• pp.934-938
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• 1995

A series of solid solutions in the Ca2AlxFe2-xO5 (x=0.00, 0.50, 0.66, 1.00 and 1.34) system with brownmillerite structure has been synthesized at 1100 ℃ under an atmospheric air pressure. The solid solutions are analysed by powder x-ray diffraction analysis, Mohr salt titration, thermal analysis, and Mossbauer spectroscopic analysis. The x-ray diffraction analysis assigns the compositions of x=0.00 and 0.50 to the space group Pcmn and those of x=0.66, 1.00, and 1.34 to the Ibm2. Mo&ssbauer spectra have shown the coordination state and disordering of Al3+ and Fe3+ ions. The substituting preference of Al3+ ions for the tetrahedral site decreases with increasing x value. Magnetic susceptibility of the system has been measured in the temperature range of 5 K to 900 K. The solid solutions of the compositions of x=0.00, 0.50 and 0.66 have shown a thermal hysteresis and the thermoremanent magnetization gap decreases with increasing x value in the above systems. However the compositions of x=1.00 and 1.34 do not show the hysteresis. The exchange integral is calculated from Fe3+ ion occupancy ratio. The integral decreases with x value and thus the magnetic transition temperature decreases with the increasing x value.

• Journal of the Korean Chemical Society
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• v.32 no.1
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• pp.9-14
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• 1988

Perovskite type compounds of the $La_{1-x}Ca_xFeO_{3-y}$ system were prepared from stoichiometric mixtures of La_2O_3,\;CaCO_3$, and Fe(NO-3)_3{\cdot}9H_2O$ by heating at 1100$^{\circ}C$ for 24 hours. The crystallographic structures of the solid solutions of all compositions were orthorhombic systems. X-ray diffraction and Mohr salt analysis revealed that at higher y value the phase transition due to vacancy ordering occured and that the lattice volume decreased when the x value was increased. The value of nonstoichiometric ratio y were found to be in the range of $0.0{\sim}0.5$. Electrical conductivities of this systems are measured in temperature range of -100 to 100$^{\circ}C$. Ionic contribution to total conductivity was found from activation energy in the phase containing the open pathway due to vacancy ordering.

• Bulletin of the Korean Chemical Society
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• v.15 no.7
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• pp.541-545
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• 1994

A series of samples of the ${Ca_xEu_{1-x}FeO_{3-y}$ (x=0.00, 0.25, 0.50, 0.75, and 1.00) system has been prepared at $1,250^{\circ}C$ under an atmospheric air pressure. X-ray diffraction analysis of the solid solution assigns the structure of the compositions of x=0.00, 0.25, 0.50, and 0.75 to the orthoferrite-type orthorhombic system, and that of x=1.00 to the brownmillerite-type orthorhombic one. The mole ratios of $Fe^{4+}$ ion in the solid solutions or ${\tau}$ values were determined by the Mohr's salt analysis and nonstoichiometric chemical formulas of the system were formulated from x, ${\tau}$, and y values. From the result of the Mossbauer spectroscopy, the coordination and magnetic property of the iron ion are discussed. The electrical conductivities are measured as a function of temperature. The activation energy is minimum at the composition of x=0.25. The conduction mechanism can be explained by the hopping of electrons between the mixed valences of $Fe^{3+}\;and\;Fe^{4+}$ ions.

• Journal of Environmental Science International
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• v.7 no.2
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• pp.203-208
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• 1998

A simple on-line measurement system consisting of a conventional peristaltic pump, a HPLC-type heater, and a flow-through spectrophotometer is introduced for the determination of chemical oxygen demand(CODI. The system was configured such that the reaction mixture in the highly concentrated surffuric acrid medium flowing through the PTFE reaction tubing was heated at 150℃ and the absorbance of dichromate was continuously moutored at 445 m. The same addation principle as in the standard procedure was employed akcept the use of CoSO4 as a new effective catalyst. To test the system, potassium hydrogen phthalate was selected as a COD standard material. With suitably optimized reaction condition, the applicable concentration range depends on the concentration of potassium dichromate in the oxidizing reagent. With 2.0×10-3 M and 5.0×10-4M dichromate, the linear dynamic range was observed up to 400 ppm and 100 ppm, respectively. The standards in the Unear ranges were shown to be completely oxidized, which was confirmed with sodium oxalate or Mohr's salt. In all cases, the typical reproduclbility for betweenruns was 2% or less. The proposed measurement system provides the valuable in- formation for the further development of automated analysis system based on the present standard procedure.

• 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.35 no.6
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• pp.617-624
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• 1991

Nonstoichiometric solid solutions of $Y_{1-x}A_xFeO_{3-y}$ (A = Ca, Sr) systems with perovskite structure were prepared for x = 0.00, 0.25, 0.50, 0.75 and 1.00 at 1200$^{\circ}C$ under atmospheric pressure, respectively. Crystallographic structures of the solid solutions of all compositions have been determined by the analysis of X-ray diffraction patterns. Reduced lattice volume of the $Y_{1-x}Ca_xFeO_{3-y}$ system was decreased with increasing x value and that of the $Y_{1-x}Sr_xFeO_{3-y}$ system was increased with increasing the x value. The mole ratios of $ Fe^{4+}$ to $ Fe^{3+}$, ${\tau}$, values in the solid solutions have been determined by Mohr salt's method of analysis and then the mixed valency was identified by Mossbauer spectroscopic analysis at 298 K. The y values were calculated from the x and ${\tau}$, and then nonstoichiometric chemical formulas were fixed. The conduction mechanism could be explained by hopping model of the conduction electrons between the mixed valence states.

• 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.