• Journal of the Korean Ceramic Society
• /
• v.37 no.5
• /
• pp.491-496
• /
• 2000

Single phae Pb(Mg1/3Nb2/3)O3-based solid solutions, the Mg2+ of which are replaced by 20mol% of Ni2+, Zn2+, Cd2+, and the Pb2+ of which are replaced by 0∼20 mol% of La3+, were synthesized and their ordering structures of B-site cations were investigated by XRD and TEM. The B'-site cations (Mg2+, Ni2+, Zn2+, Cd2+) are disordered while these B'-site cations and the B"-site cations (Nb5+) are nonstoichiometrically 1:1 ordered within the ordered nano-domains dispersed in the Nb5+-rich disordered matrix. The charge imbalance between the B'-rich ordered nano-domains and the B"-rich disordered matrix are compensated by the doping of electron donor such as La3+, which enhances the degree of nonstoichiometric 1:1 ordering. For a given La3+ content, the degree of nonstoichiometric 1:1 ordering increases as the average ionic size difference between the B'-and B"-site cations increases, Ni2+

• Journal of the Korean Ceramic Society
• /
• v.49 no.1
• /
• pp.56-65
• /
• 2012

Functional materials are often exposed to high temperatures and inherent temperature gradients. These temperature gradients act as thermodynamic driving forces for the diffusion of mobile components. The detailed consequences of thermodiffusion depend on the boundary conditions of the non-isothermal sample: Once the boundaries of the sample are inert and closed for exchange of the mobile components, thermodiffusion leads to their pile-up in the stationary state (the so called Soret effect). Once the system is open for an exchange of the mobile component, chemical diffusion adds to the Soret effect, and stationary non-zero component fluxes are additionally observed in the stationary state. In this review, the essential aspects of thermodiffusion and Soret effect in inorganic functional materials are briefly summarized and our current practical knowledge is reviewed. Major examples include nonstoichiometric binary compounds (oxides and other chalcogenides) and ternary solid solutions. The potential influence of the Soret effect on the long term stability of high temperature thermoelectrics is briefly discussed. Typical Soret coefficients for nonstoichiometric compounds are found to be of the order of (d${\delta}$/dT) ${\approx}$ 1%/K.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.1
• /
• pp.29-35
• /
• 1986

An empirical formula for semiconductive metal oxides is proposed relating nonstoichiometric value x to a temperature or an oxygen partial pressure such that experimental data can be represented more accurately by the formula than by the well-known Arrhenius-type equation. The proposed empirical formula is log x = A + $B{\cdot}1000/T\;+\;C{\cdot}$exp$(-D{\cdot}1000/T)$ for a temperature dependence and $log\;{\times}\;=a\;+b{\cdot}log\;Po_2\;+\;c{\cdot}$exp$(-d{\cdot}log\;Po_2)$ for an oxygen partial pressure dependence. The A, B, C, D and a, b, c, d are parameters which are evaluated by means of a best-fitting method to experimental data. Subsequently, this empirical formula has been applied to the n-type metal oxides of $Zn_{1+x}O,\; Cd_{1+x}O,\;and\;PrO_{1.8003-x}$, and the p-type metal oxides of $CoO_{1+x},\; FeO_{1+x},\;and\;Cu_2O_{1+x}$. It gives a very good agreement with the experimental data through the best-fitted parameters within 6% of relative error. It is also possible to explain approximately qualitative characters of the parameters A, B, C, D and a, b, c, d from theoretical bases.

• Bulletin of the Korean Chemical Society
• /
• v.15 no.8
• /
• pp.636-640
• /
• 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.

• Applied Chemistry for Engineering
• /
• v.19 no.3
• /
• pp.326-331
• /
• 2008

The purpose of this work is to develope sodium-containing nonstoichiometric apatitic coatings on solid substrate. The apatitic coatings prepared at different concentrations of sodium salt indicated that the presence of sodium ions exerted significant effects on the physicochemical properties of the apatitic coating including surface morphology, chemical state, and Ca/P ratio. The variation of these properties was sustained up to 0.01 mM of sodium ion concentration. The ratio of calcium to phosphorus was varied from 2.18 to 2.03 which indicated the apatitic coating prepared in this study was calcium-rich nonstoichiometric apatite. The structure of all the samples appeared to be low crystalline. In the presence of sodium ion within the apaptitic coating, the adhesion of human osteoblast-like SaOS-2 cells was significantly promoted. On the other hand, the proliferation of the cells on the apatitic coatings was decreased with the increase of sodium ions. This reverse response of SaOS-2 cells indicates that the interaction between SaOS-2 and apatitic surface triggered considerable changes in intracellular mechanisms including cellular signal transductions.

• 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.

• Proceedings of the Korean Powder Metallurgy Institute Conference
• /
• 2004.04a
• /
• pp.53-54
• /
• 2004

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.24 no.12
• /
• pp.955-961
• /
• 2011

We investigated the physical properties of stoichiometric and non-stoichiometric oxide doped complex perovskite, $Ba(Zn_{1/3}Ta_{2/3})O_3$ ceramics and their impacts on the microwave dielectric performances using various characterization techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and network analyzer. According to the measurement of lattice constant changes, anomalous lattice volume contraction of $ZrO_2$ doped $Ba(Zn_{1/3}Ta_{2/3})O_3$ sample only showed the dielectric quality factor enhancements, which was due to the lattice volume contraction as well as the 1:2 B-site cation ordering. In addition, NiO doping was useful to the stabilization of temperature coefficient of resonance frequency.

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

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