A comparative study of the magnetic and electrical properties of perovskite oxides and the corresponding two-dimensional oxides of K2NiF4

Electrical and magnetic properties of several oxide systems of K2NiF4 structure have been compared to those of the corresponding perovskites. Members of the La1−xSr1+xCoO4 system are all semiconductors with a high activation energy for conduction unlike La1−xSrxCoO3 (x ≥ 0.3) which is metallic; the latter oxides are ferromagnetic. La0.5Sr1.5CoO4 shows a magnetization of 0.5 μB at 0 K (compared to 1.5 μB of La0.5Sr0.5CoO3), but the high-temperature susceptibilities of the two systems are comparable. In SrO · (La0.5Sr0.5MnO3)n, both magnetization and electrical conductivity increase with the increase in n approaching the value of the perovskite La0.5Sr0.5MnO3. LaSrMn0.5Ni0.5(Co0.5)O4 shows no evidence of long-range ferromagnetic ordering unlike the perovskite LaMn0.5Ni0.5(Co0.5)O3; high-temperature susceptibility behavior of these two insulating systems is, however, similar. LaSr1−xBaxNiO4 exhibits high electrical resistivity with the resistivity increasing proportionately with the magnetic susceptibility (note that LaNiO3 is a Pauli-paramagnetic metal). High-temperature susceptibility of LaSrNiO4 and LaNiO3 are comparable. Susceptibility measurements show no evidence for long-range ordering in LaSrFe1−xNixO4 unlike in LaFe1−xNixO3 (x ≤ 0.35) and the electrical resistivity of the former is considerably higher. Electrical resistivity of Sr2RuO4 is more than an order of magnitude higher than that of SrRuO3. Some generalizations of the properties of two- and three-dimensional oxide systems have emerged from these experimental observations.

Multiferroic and magnetoelectric properties of core-shell CoFe2O4@BaTiO3 nanocomposites

Core-shell CoFe2O4@BaTiO3 nanoparticles and nanotubes have been prepared using a combination of solution processing and high temperature calcination. Both the core-shell nanostructures exhibit magnetic and dielectric hysteresis at room temperature and magnetoelectric effect. The dielectric constant of both the nanocomposites decreases upon application of magnetic field. The core-shell nanoparticles exhibit 1.7% change in magnetocapacitance around 134 K at 1 T, while the core-shell nanotubes show a remarkable 4.5% change in magnetocapacitance around 310 K at 2 T.(C) 2010 American Institute of Physics. [doi:10.1063/1.3478231].

Pyroelectric properties of Bi2VO5.5 ceramic

The dielectric, pyroelectric and thermal properties of ferroelectric Bi2VO5.5(Bi4V2O11) ceramic have been studied over a temperature range of 300-780 K. The sign of the pyroelectric coefficient is positive at room temperature. The dielectric constant, pyroelectric coefficient and specific heat exhibit anomalies around the Curie temperature, 725 K. The frequency response of the dielectric constant and tan delta has been studied over a frequency range of 1-100 kHz. It is found that both the dielectric constant and the loss tangent decrease with increasing frequency. The pyroelectric figures of merit from the point of view of different applications have been calculated at 320 K by combining pyroelectric, dielectric and thermal properties.

Chemical toughening of epoxies. II. Mechanical, thermal, and microscopic studies of epoxies toughened with hydroxyl-terminated poly(butadiene-co-acrylonitrile)

Diglycidyl ether–bisphenol-A-based epoxies toughened with various levels (0–12%) of chemically reacted liquid rubber, hydroxyl-terminated poly(butadiene-co-acrylonitrile) (HTBN) were studied for some of the mechanical and thermal properties. Although the ultimate tensile strength showed a continuous decrease with increasing rubber content, the toughness as measured by the area under the stress-vs.-strain curve and flexural strength reach a maximum around an optimum rubber concentration of 3% before decreasing. Tensile modulus was found to increase for concentrations below 6%. The glass transition temperature Tg as measured by DTA showed no variation for the toughened formulations. The TGA showed no variations in the pattern of decomposition. The weight losses for the toughened epoxies at elevated temperatures compare well with that of the neat epoxy. Scanning electron microscopy revealed the presence of a dual phase morphology with the spherical rubber particles precipitating out in the cured resin with diameter varying between 0.33 and 6.3 μm. In contrast, a physically blended rubber–epoxy showed much less effect towards toughening with the precipitated rubber particles of much bigger diameter (0.6–21.3 μm).

Crystal structure and electrical properties of CaNaBi2Nb3O12 ceramics

Monophasic CaNaBi2Nb3O12 powders were synthesized via the conventional solid-state reaction route. Rietveld refinement of the X-ray powder diffraction (XRD) data and selected area electron diffraction (SAED) studies confirmed the phase to be a three-layer Aurivillius oxide associated with an orthorhombic B2cb space group. The dielectric properties of the ceramics have been studied in the 300-800 K temperature range at various frequencies (1 kHz to 1 MHz). A dielectric anomaly was observed at 676 K for all the frequencies corresponding to the ferroelectric to paraelectric phase transition as it was also corroborated by the high temperature X-ray diffraction studies. The incidence of the polarization-electric field (P vs. E) hysteresis loop demonstrated CaNaBi2Nb3O12 to be ferroelectric.

Investigation on the Magnetic Anomaly and the Role of Orbital Moment on the Magnetic Properties of LaMn0.5Co0.5O3

Two distinct ferromagnetic phases are present in LaMn0.5Co0.5O3 for which the spin-only magnetic moment calculated from the high temperature dc susceptibility is found to be unusually high. Such a high moment can only be accounted for by assigning the valence state of the cations to Mn2+-Co4+. This is unrealistic as the earlier report based on X-ray absorption spectroscopy (XAS) has suggested the valence state to be mainly Mn4+-Co2+ with traces of Co3+. Also from our studies using XAS, it is found that the valence state is mainly Mn4+-Co2+. In addition, no notable difference is observed in the minor Co3+ present in both phases. Our results based on X-ray magnetic circular dichroism studies (XMCD) reveal the presence of ``distinct'' high orbital moment associated with Co2+ for both phases. Thus it is found that the distinctness of the orbital moment also plays a vital role in determining the magnetic moment and T-c of both phases of LaMn0.5Co0.5O3. By considering the orbital moment obtained from XMCD, the anomaly in the paramagnetic susceptibility is resolved and thus we are able to assign the valence state to Mn4+-Co2+ configuration. The difference in the magnitude of orbital moment in both phases is believed to be due to the crystal field effects.

Relation between integral and partial properties of ternary solutions along different composition trajectories

The relations between partial and integral properties of ternary solutions along composition trajectories suggested by Kohler, Colinet and Jacob, and along an arbitrary path are derived. The chemical potentials of the components are related to the slope of integral free energy by expressions involving the binary compositions generated by the intersections of the composition trajectory with the sides of the ternary triangle. Only along the Kohler composition trajectory it is possible to derive the integral free energy from the variation of the chemical potential of a single component with composition or vice versa. Along all other paths the differential of the integral free energy is related to two chemical potentials. The Gibbs-Duhem integration proposed by Darken for the ternary system uses the Kohler isogram. The relative merits of different limits for integration are discussed.

Structure and electrical properties of sputtered lithium cobaltite thin films

LixCoOy films with x < 1 and y > 2 have been prepared by radio-frequency (rf) sputtering from high temperature (HT) LiCoO2 targets. Their structures have been examined with high resolution electron microscopy. Conductivities have been studied between 77 and 400 K. The electrochemical behaviour of film electrodes have been investigated with Li/LiClO4-PC/LixCoOy cells. The annealed films consist of nanocrystalline domains with amorphous boundaries. Electrical conductivities appear to arise from variable-range hopping (VRH) of holes. The films form good electrodes with operating potentials between 2.7 and 3.8 V. The observations have been discussed on the basis of a tentative and heuristic molecular orbital based energy band diagram. (C) 2002 Published by Elsevier Science Ltd.

A Single-Crystal Study Of The Defect Chemistry And Transport-Properties Of Silver Selenide, Ag2+Delta-Se

Electronic and ionic conductivities of silver selenide crystal (Ag$_2+\delta$ Se) have been measured over a range of stoichiometry through the $\alpha - \beta$ transition by using solid state electrochemical techniques. In the high temperature $\beta$-phase Ag$_2$Se shows metallic behaviour of electronic conductivity for high values of $\delta$; with decrease in $\delta$, the conductivity of the material exhibits a transition. The magnitude of change in electronic conductivity at the $\alpha - \beta$ transition is also determined by stoichiometry. Ionic conductivity of the $\beta$-phase does not vary significantly with stochiometry. Ionic conductivity of the $\beta$-does not vary significantly with stoichiometry. A model to explain the observed transport properties has been suggested.

EPR, thermo and photoluminescence properties of ZnO nanopowders

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at similar to 343 degrees C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various gamma-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application. (C) 2011 Elsevier B.V. All rights reserved.

Thermodynamic properties of oxygen in RE-O (RE = Gd, Tb, Dy, Er) solid solutions

The oxygen potentials of four rare-earth metal – oxygen (RE–O: RE=Gd, Dy, Tb, Er) solid solutions have been measured by equilibration with yttrium – oxygen (Y–O) and titanium – oxygen (Ti–O) solid solutions. Rare-earth metal, yttrium and titanium samples were immersed in calcium-saturated CaCl2 melt at temperatures between 1093 and 1233 K. Homogeneous oxygen potential was established in the metallic samples through the fused salt, which contains some dissolved CaO. The metallic samples were analyzed for oxygen after quenching. The oxygen potentials of RE–O solid solutions were determined using either Y–O or Ti–O solid solution as the reference. This method enabled reliable measurement of extremely low oxygen potentials at high temperature (circa pO2=10−48 atm at 1173 K). It was found that the oxygen affinity of the metals decreases in the order: Y>Er>Dy>Tb>Gd>Ti. Values for the standard Gibbs energy of solution of oxygen in RE metals obtained in this study, permit assessment of the extent of deoxidation that can be achieved with various purification techniques. It may be possible to achieve an oxygen level of 10 mass ppm using an electrochemical deoxidation method.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.