• Bulletin of the Korean Chemical Society
• /
• v.15 no.7
• /
• pp.541-545
• /
• 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
• /
• v.16 no.7
• /
• pp.600-603
• /
• 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
• /
• v.17 no.9
• /
• pp.794-798
• /
• 1996

Solid solutions of the nonstoichiometric Dy1-xSrxCoO3-y system with the compositions of x=0.00, 0.25, 0.50, 0.75, and 1.00 have been synthesized by the solid state reaction at 1000 ℃ under atmospheric air pressure. The crystallographic structures of the solid solutions are analyzed by the powder X-ray diffraction patterns at room temperature. The analyses assign the compositions of x=0.00 and 0.25 to the orthorhombic system with space group of Pbnm/D2h16, the compositions of x=0.50 and 0.75 to the tetragonal system like a typical SrCoO2.86, and the composition of x=l.00 or SrCoO2.50 to the brownmillerite type system with space group of I**a. The reduced lattice volumes increase with x value due to the larger radius of Sr2+ ion than that of Dy3+ ion. The mole ratio of Co4+ ion to total Co ion with mixed valence state between Co3+ and Co4+ ions at B sites or τ value has been determined by an iodometric titration. All the samples except for the DyCoO3 compound show the mixed valnce state and thus the composition of x=0.50 has the maximum τ value in the system. The oxygen vacancies increasing with x value are randomly distributed over the crystal lattice except for the composition of x=l.00 which have the ordering of the oxygen vacancies. The nonstoichiometric chemical formulas of the Dy1-xSrxCo3+1-τCo4+τO3-(x-τ)/2 system are formulated from the x, τ, and y values. The electrical conductivity in the temperature range of 100 to 900 K increases with τ value linearly because of positive holes of the Co4+ ions in π* band as a conducting carrier. The activation energy of the x=0.50 as Ea=0.17 eV is minimum among other compouds. Broad and high order transition due to the overlap between σ* and π* bands broadened by the thermal activation is observed near 1000 K and shows a low temperature-semiconducting behavior. Magnetic properties following the Currie-Weiss law show the low to high spin transition in the cobaltate perovskite. Especially, the composition of x=0.75 presents weak ferromagnetic behavior due to the Co3+-O2--Co4+ indirect superexchange interaction.