• 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.

• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.600-603
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• 1995

A series of samples in the Sm1-xSrxCoO3-y(x=0.00, 0.25, 0.50, 0.75 and 1.00) system has been prepared at 1200 ℃ under ambient atmosphere. The X-ray diffraction patterns of the samples with x=0.00 and 0.25 are indexed with orthorhombic symmetry like GdFeO3 and x=0.50 appears to be perfectly cubic. In the tetragonal system (x=0.75), the structure is similar to that of SrCoO2.80. The composition of x=1.00, SrCoO2.52, shows the brownmillerite-type structure. The reduced lattice volume is increased with x value in this system. The chemical analysis shows the τ value (the amount of the Co4+ ions in the system) is maximized at the composition of x=0.50. Nonstoichiometric chemical formulas are determined by the x, τ and y values. The electrical conductivity has been measured in the temperature range of 78 to 1000 K. The activation energy is minimum for those of x=0.25 and x=0.50 with metallic behavior. First-order semiconductor-to-metal transition of SmCoO3 is not observed. Instead, a broad, high-order semiconductor-to-metal transition is observed. In general, the effective magnetic moment is increased with increasing τ values at low temperature. At high temperature, the magnetic moment is maximum for that of x=0.00. The 3d-electrons are collective and give ferromagnetism in x=0.50.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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• pp.616-622
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• 1994

The oxidation of carbon monoxide by gaseous oxygen in the presence of a powdered $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution as a catalyst has been investigated in the temperature range from 150$^{\circ}$C to 300$^{\circ}$C under various CO and $O_2$ partial pressures. The site of Sr substitution, nonstoichiometry, structure, and microstructure were studied by means of powder X-ray diffraction and infrared spectroscopy. The electrical conductivity of the solid solution has been measured at 300$^{\circ}$C under various CO and $O_2$ partial pressures. The oxidation rates have been correlated with 1.5-and 1.2-order kinetics with and without a $CO_2$ trap, respectively; first-and 0.7 order with respect to CO and 0.5-order to $O_2$. For the above reaction temperature range, the activation energy is in the range from 0.25 to 0.35 eV/mol. From the infrared spectroscopic, conductivity and kinetic data, CO appears essentially to be adsorbed on the lattice oxygens of the catalyst, while $O_2$ adsorbs as ions on the oxygen vacancies formed by Sr substitution. The oxygen vacancy mechanism of the CO oxidation and the main defect of $Nd_{1-x}Sr_xCoO_{3-y}$ solid solution are supported and suggested from the agreement between IR data, conductivities, and kinetic data.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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• pp.636-640
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• 1994

The nonstoichiometric perovskite solid solutions of the $Nd_{1-x}Sr_xFeO_{3-y}$ system for the compositions of x=0.00, 0.25, 0.50, 0.75, and 1.00 have been prepared at $1150^{\circ}C$ in the air pressure. The compound of x=0.00, NdFe$O_{3.0}$, contains only $Fe^{3+}$ ion in octahedral site and the others involves the mixed valence state between $Fe^{3+}$ and $Fe^{4+}$ ions. The mole ratio of $Fe^{4+}$ ion or the ${\tau}$-value increases steadily with the x-value and then is maximized at the compositionof x= 1.00. The nonstoichiometric chemical formulas of the system are formulated from the x, ${\tau}$ and y values. From the Mossbauer spectroscopy, the isomer shift of $Fe^{3+}$ ion decreases with the increasing x-value, which is induced by the electron transfer between the$Fe^{3+}$ and $Fe^{4+}$ ions. The transfer is made possible by the indirect interaction between $Fe^{3+}$ and$Fe^{4+}$ ions via the oxygen ion. The eg electrons of the$Fe^{3+}$ ions are delocalized over all the Fe ions. Due to the electron transfer, the activation energy of electrical conductivity is decrease with the increasing amount of $Fe^{4+}$ ion.

• 한국분말재료학회지
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• 제23권5호
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• pp.379-383
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• 2016

A thick film of $Li_7La_3Zr_2O_{12}$ (LLZO) solid-state electrolyte is fabricated using the tape casting process and is compared to a bulk specimen in terms of the density, microstructure, and ion conductivity. The final thickness of LLZO film after sintering is $240{\mu}m$ which is stacked up with four sheets of LLZO green films including polymeric binders. The relative density of the LLZO film is 83%, which is almost the same as that of the bulk specimen. The ion conductivity of a LLZO thick film is $2.81{\times}10^{-4}S/cm$, which is also similar to that of the bulk specimen, $2.54{\times}10^{-4}S/cm$. However, the microstructure shows a large difference in the grain size between the thick film and the bulk specimen. Although the grain boundary area is different between the thick film and the bulk specimen, the fact that both the ion conductivities are very similar means that no secondary phase exists at the grain boundary, which is thought to originate from nonstoichiometry or contamination.

• 대한화학회지
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• 제39권3호
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• pp.157-162
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• 1995

비화학량론적 산화물$WO_{3-x}$의 비화학량 x값과 전기전도도를 350~700$^{\circ}C$의 온도 범위와 $2{\times}10_{-1}\;to\;1{\times}10_{-5}$ atm의 산소분압 범위에서 측정하였다. 비화학량론적 조성식에서 x의 생성엔탈피 ${\Delta}H^{\circ}_f$가 양의 값을 가지는 것으로 보아 결함생성은 흡열 과정이고, 결함생성의 산소분압 의존성인 1/n값은 -1/5.7~-1/6.1로 변하였다. 전기전도도의 활성화에너지는 각 산소분압에 따라 0.24~0.29 eV이었고, 전기전도도의 산소분압 의존성인 1/n은 -1/4.3~-1/7.6의 값을 나타내었다. 이로부터 n형 반도체로써 산화텅스텐의 결함모델은 낮은 온도에서는 1가로 하전된 산소공위가 우세하지만 온도가 상승함에 따라 2가로 하전된 산소공위가 우세해진다.

• 한국세라믹학회지
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• 제54권4호
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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.

• 대한화학회지
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• 제28권4호
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• pp.231-237
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• 1984

$YO_{1.5+x}$와 $HoO_{1.5+x}$로 표시되는 산화이트륨과 산화홀뮴의 비화학양론적 조성식의 x-값을 700$^{\circ}$C에서 1000$^{\circ}$C까지의 온도영역과 대기압에서 $1{\times}10^{-6}$기압 산소압력까지의 구간에서 중량 분석법에 의하여 측정하였다. 측정된 x-값은 온도가 상승하면 증가하고 산소압력이 증가하면 또한 증가하였다. 비화학양론적 조성의 생성엔탈피 $({\Delta}H_f)$는 산소압력이 감소하면 감소하였고 그 값이 양의 값을 갖는 것으로 과잉산소의 형성 과정이 흡열과정임을 알 수 있다. 산소압력 의존성 1/n-값은 온도가 상승하면 상승하고 양의 값을 갖는 것으로 높은 온도일수록 산소압력 의존성이 커짐을 보여 주었다. 그리고 x-값과 열역학적 자료로 부터 비화학양론적 결합과 전도성메카니즘을 규명하였다.

• 대한화학회지
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• 제33권5호
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• pp.445-451
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• 1989

$Er_{1-x}Sr_xFeO_{3-y}(0.0{\leq}X{\leq}1.0)$계의 고용체들을 $1200^{\circ}C$에서 24시간 동안 가열하여 합성하였다. X-선 회절분석을 통하여 x = $0.0{\sim}0.6$의 조성은 사방정계이고 x = 0.8 및 1.0은 입방정계의 결정구조라는 것을 알았으며 Sr의 양이 증가할수록 격자체적이 증가하였다. 본 철산화물계에서 두 종류의 철이온의 혼합원자가 상태는 모어염 적정법으로 분석하였다. x = 0.0과 0.5조성의 상온에서 측정한 Mossbauer 분광분석은 자기모멘트의 정렬에 의한 미세자기장 분열을 보이고 고용체 내에 팔면체와 사면체 배위된 철이온이 존재하는 것을 지적하고 있다. 전기전도도 측정으로부터 본 시료들의 전기전도가 팔면체 자리의 철이온 간을 건너뛰는 메카니즘이라는 것을 확인하였다.

• 한국재료학회지
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• 제20권2호
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• pp.55-59
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• 2010

$Na^+$ ion conductivity can be improved by the substitution of an Mg atom for an Al atom to form a nonstoichiometric $Na^+$ $\beta$-alumina. We performed a first principles study to investigate the most stable substitution site of an Mg atom and the resulting structural change of the nonstoichiometric $Na^+$ $\beta$-alumina. Al atoms were classified as four different layers in the spinel block that are separated by conduction planes in the nonstoichiometric $Na^+$ $\beta$-alumina. The substitution of an Mg atom for an Al atom at a tetragonal site was more favorable than that at an octahedral site. The substitution in the spinel block was more favorable than that close to the conduction plane. This result was well explained by the volume changes of the polyhedrons, by the standard deviation of the Mg-O distance, and by the comparison with bulk MgO structure. Our result indicates that the most preferable site for the Mg atom was the tetrahedral site at the spinel block in the nonstoichiometric $Na^+$ $\beta$-alumina.