• Transactions on Electrical and Electronic Materials
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• 제13권1호
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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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• 제16권3호
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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.

• 대한화학회지
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• 제40권5호
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• pp.295-301
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• 1996

$CaGa_1-xFexO_3-y$계의 x=0.25, 0.50, 0.75 및 1.00에 해당하는 고용체를 $1150^{\circ}C$, 대기압하에서 제조하였다. X-선 회절분석, Mohr염 정정, Mossbauer 분광분석을 수행하여 합성된 고용체들의 구조, 비화학량론적 화학식 및 양이온들의 분포를 결정한 후 전기전도도와 자기측정을 수행하여 물성에 관한 논의를 하였다. X-선 회절분석으로부터 얻은 모든 조성의 결정계는 브라운밀러릿 사방정계이다. 환산 격자부피는 단위세포의 차원이 다른 X=0.25의 조성을 제외하고 x값이 증가함에 따라 직선성을 가지고 증가한다. Mohr염분석 결과 고용체들은 $Fe^{4+}$ 이온을 포함하지 않고 산소공위의 몰수인 y값은 0.50으로 고정된 값을 가진다. Mossbauer 분광분석으로부터 Fe 이온의 산화상태, 배위상태, 브라운밀러릿 구조 및 $Ga^{3+}$와 $Fe^{3+}$ 이온의 분포를 논의하였다. 전기전도도와 활성화에너지는 x값이 증가함에 따라 각각 증가와 감소하고 이들로부터 전자 전기전도 메커니즘을 제안한다. x=0.50~1.00의 조성을 냉각하면서 자기측정을 수행할 때 열적 자기 히스테리시스가 나타나며 이러한 현상을 공간군과 Dzyaloshinsky-Moriya 상호작용을 기초로 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제16권10호
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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.

• 대한화학회지
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• 제32권1호
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• pp.9-14
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• 1988

$La_{1-x}Ca_xFeO_{3-y}$ 계의 perovskite 형의 화합물은 La_2O_3,\;CaCO_3$, 및 Fe(NO-3)_3{\cdot}9H_2O$의 정량적 혼합물은 1100$^{\circ}C$에서 24시간 동안 가열하여 제조하였다. 이 고용체의 결정구조는 모든 조성에서 사방정계였다. X-선 회절분석과 Mohr 염 분석을 통하여 y값이 증가하면 공위배열에 의한 상전이가 일어나며 격자체적은 x값이 증가함에 따라 감소한다는 것을 확인하였다. 비화학양론적 조성 y는 0.0에서 0.5사이의 값을 나타내었다. Mossbauer 분광분석을 298K에서 수행하여 x = 0.75 조성이 높은 닐온도를 갖는다는 것을 확인하였다. 시료의 전기전도도는 $-100{\sim}100^{\circ}C$ 온도범위에서 측정하였다. 활성화 에너지로부터 공위 배열에 기인한 열린 통로를 갖고 있는 시료들은 이온성 전기전도에 의한 기여가 어느 정도 존재하는 것으로 밝혀졌다.

• Bulletin of the Korean Chemical Society
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• 제15권7호
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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.

• 한국환경과학회지
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• 제7권2호
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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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• 제17권4호
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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.

• 대한화학회지
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• 제35권6호
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• pp.617-624
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• 1991

페롭스카이트 구조를 갖는 $Y_{1-x}A_xFeO_{3-y}$ (A = Ca, Sr)계에서 x = 0.00, 0.25, 0.50, 0.75 및 1.00인 비화학양론적 화합물 고용체를 1200$^{\circ}C$ 대기압에서 제조하였다. X-선 회절분석을 통하여 모든 조성의 고용체들에 대한 결정구조를 조사하였다. $Y_{1-x}Ca_xFeO_{3-y}$계의 경우는 x값이 증가함에 따라 환산 격자 부피가 감소하였고, $Y_{1-x}Sr_xFeO_{3-y}$계의 경우는 x의 증가에 따라 환산 부피가 증가하였다. 그 고용체들의$ Fe^{3+}$에 대한 $ Fe^{4+}$의 몰비 ${\tau}$값은 Mohr 분석법으로 구하였고 그 혼합 원자가 상태는 298K에서 Mossbauer 분광분석으로 확인하였다. x값과 ${\tau}$값으로부터 y값을 계산하여 비화학양론적 화학식을 확정하였다. 전도성 메카니즘은 혼합원자가 상태간의 전도성 전자 건너뜀 모델로 설명하였다.

• 대한화학회지
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• 제32권1호
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• pp.3-8
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• 1988

$K_2NiF_4$ 형 층상구조를 갖는 새로운 $Sr_{1+x}Dy_{1-x}FeO_{4-y}$ 계에서 x = 0. 00, 0. 25, 0. 50, 0. 75 및 1. 00 인 비화학양론적 화합물 고용체를 1200$^{\circ}$C 대기압하에서 제조하였다. X-선 회절분석에 의하여 결정구조학적 상들은 모든 시료의 경우 정방정계임을 알 수 있었다. Mohr 염 분석으로 비화학양론적 화학식을 결정하였고 x가 증가함에 따라 $Fe^{4+}$의 몰수(${\tau}$값)가 증가하였다. $-100{\sim}200^{\circ}$C의 온도범위에서 측정한 각 시료의 전기전도도는 $l0^{-8}{\sim}10^{-2}(ohm^{-1}{\cdot}cm^{-1}$)범위의 반도성을 보이며 활성화 에너지는 0.02∼0.08(eV)의 범위에서 변하였다. $Sr_{1.00}Dy_{1.00}FeO_{4.04}$에 대한 $Fe^{3+}$와 $Fe^{4+}$의 혼합원자가 상태를 200K에서 측정한 Mossbauer spectrum으로 재확인하였다.