Effects of Zr and Ti doping on the dielectric response of CeO2: A comparative first-principles study

Zr doping in ceria (CeO2) results in enhanced static dielectric response compared to pure ceria. On the other hand, Ti doping in ceria keeps its dielectric constant unchanged. We use first-principles density functional theory calculations based on pseudopotentials and a plane wave basis to determine electronic properties and dielectric response of Zr/Ti-doped and oxygen-vacancy-introduced ceria. Softening of phonon modes is responsible for the enhancement in dielectric response of Zr-doped ceria compared to that of pure ceria. The ceria-zirconia mixed oxides should have potential use as high-k materials in the semiconductor industry. (c) 2010 Elsevier Ltd. All rights reserved.

Reactivity with hydrogen of pure iron oxide and of iron oxides doped with oxides of Mn, Co, Ni and Cu

Using dynamic TG in H2, X-ray powder diffraction and Mössbauer Spectroscopy the reactivities fot hydrogen reduction of Fe2O3 prepared at different temperatures, Fe2O3 doped with oxides of Mn, Co, Ni and Cu prepared at 300DaggerC from nitrate precursors and intermediate spinels derived from above samples during reduction have been explored. The reactivity is higher for finely divided Fe2O3 prepared at 250DaggerC. The reduction is retarded by Mn, marginally affected by Co and accelerated by Ni and Cu, especially at higher (5 at.%) dopant concentration. These reactivities confirmed also by isothermal experiments, are ascribed to the nature of disorder in the metastable intermediate spinels and to hydrogen rsquospill overrsquo effects.

Surface recombination at semiconductor electrodes: a single level study

The recombination and the faradaic fluxes are shown to be sensitive to the location of a single level recombination center, when it is located near the band edges. As the surface level is shifted deeper into the band gap from either of the band edges, the back emission terms are dominated by electron capture and hole capture terms, and the occupancy of the surface level is no longer determined by its location in the band gap. However, when one of the back emission terms determines the surface state occupancy, it is shown that there exists a simple relation between the value of the surface level and the recombination and the faradaic fluxes respectively. Expressions to this effect are derived and verified in the case of the recombination flux, which characterized by the potential at which it attains its maximum value. For the faradaic flux the results are qualitative.

The contribution of polarons, bipolarons and intersite tunneling to low temperature conductivity in doped polypyrrole

The conductivity of highly doped polypyrrole is less than that of intermediately doped samples, by two orders of magnitude, at 4.2 K. This may be due to more number of bipolarons in highly doped samples. Bipolarons require four times more activation energy than single polarons to hop by thermally induced virtual transitions to intermediate dissociated polaron states than by the nondissociated process. The conduction process in these polyconjugated systems involve ionization from deep trapped states, having a View the MathML source dependence, hopping from localised states, having View the MathML source dependence, and intersite tunnel percolation, having T−1 dependence. The interplay of these factors leads to a better fit by View the MathML source. The mechanism for this exponential behaviour need not be same as that of Motts variable range hopping. Conduction by percolation is possible, if an infinite cluster of chains can be connected by impurity centers created by dopant ions. The tendency for the saturation of conductivity at very low temperatures is due to the possibility of intersite tunnel percolation is disordered polaronic systems.

Metal-insulator transitions in Cr-doped V2O3 by x-ray and ultraviolet photoelectron spectroscopy

X-ray and ultraviolet photoelectron spectroscopy have been employed to investigate the high temperature metal-insulator transitions in V2O3 and (V0.99Cr0.01)2O3. The high temperature transitions are associated with more gradual changes in the 3d bands compared to the low-temperature transitions

Rapid synthesis of room temperature ferromagnetic Ag-doped LaMnO3 perovskite phases by the solution combustion method

We report the rapid solution combustion synthesis and characterization of Ag-substituted LaMnO3 phases at relatively low temperature using oxalyl dihydrazide, as fuel. Structural parameters were refined by the Rietveld method using powder X-ray diffraction data. While the parent LaMnO3 crystallizes in the orthorhombic structure, the Ag-substituted compounds crystallize in the rhombohedral symmetry. On increasing Ag-content, unit cell volume and Mn-O-Mn bond angle decreases. The Fourier transform infra red spectrum shows two absorption bands corresponding to Mn-O stretching vibration (v(s) mode) and Mn-O-Mn deformation vibration (v(b) mode) around 600 cm(-1) and 400 cm(-1) for the compositions x = 0.0, 0.05 and 0.10, respectively. Electrical resistivity measurements reveal that composition-controlled metal to insulator transition, with the maximum metal to insulator being 280 K for the composition La0.75Ag0.25MnO3. Increase in magnetic moment was observed with increase in Ag-content. The maximum magnetic moment of 35 emu/g was observed for the composition La0.80Ag0.20MnO3. (C) 2010 Elsevier Ltd. All rights reserved.

Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modified neodymium doped TiO2 hybrid nanoparticles. For the first time, surface modification of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modifier under mild hydrothermal conditions. The modified nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modified neodymium doped TiO2 nanoparticles was more compared to pure TiO2, which can be attributed to the doping and modification with n-butylamine.

Critical resistivity in impurity doped binary liquid mixtures

The electrical resistance of the critical binary liquid system C6H12+(CH3CO)2O is measured both in the pure form and when the system is doped with small amounts (≈ 100 ppm) of H2O impurities. Near Tc, the resistance varies as dR/dT = A1+A2 (T-Tc)-b with b ≈ 0.35. Neither the critical exponent b nor the amplitude ratio A1/A2 are affected by the impurities. A sign reversal of dR/dT is noticed at high temperatures T much greater-than Tc.

Thermal expansion of doped lanthanum gallates

Thermal expansion of several compositions of Sr and Mg-doped LaGaO3 including an A-site deficient composition (La0.9Sr0.1)(0.98)(Ga0.8Mg0.2)O-2.821 were measured in the temperature range from 298 to 1273 K. The effect of doping on thermal expansion was studied by varying the composition at one site of the perovskite structure (either A or B), while keeping the composition at the other site invariant. Thermal expansion varied nonlinearly with temperature and exhibited an inflexion between 550 and 620 K, probably related to the change in crystal structure from orthorhombic to rhombohedral. The dependence of average thermal expansion coefficient (alpha (av)) on the dopant concentration on either A or B site of the perovskite structure was found to be linear, when the composition at the other site was kept constant. Mg doping on the B-site had a greater effect on the average thermal expansion coefficient than Sr doping on the A-site. Cation deficiency at the A-site decreases thermal expansion when compositions at both sites are held constant.

Dielectric and Impedance Studies on 0.5Li(2)O-0.5K(2)O-2B(2)O(3) Glasses

Transparent glasses in the system 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) were fabricated via the conventional melt quenching technique. Amorphous and glassy nature of the samples was confirmed by X-ray diffraction and differential scanning calorimetry (DSC) respectively. Complex dielectric and impedance studies were conducted on the samples at different temperatures in the 100 Hz-10 MHz frequency range. ac conductivity was calculated from the dielectric data and the conductivity relaxation was found to obey the Jonscher's law. The Nyquist's plots (Z `'(omega) vs. Z'(omega)) showed single suppressed semicircles at all the temperatures under study indicating the non ideal Debye type relaxation process to be active. Activation energies for conduction and relaxation process were calculated using the Arrhenius relation. The UV-visible optical transmission spectra was shown a wide transmission window and calculated optical band gap was found to be 5.67 eV.

On numerical implementation of an isotropic elastic-viscoplastic constitutive model for bulk metallic glasses

An efficient algorithm within the finite deformation framework is developed for finite element implementation of a recently proposed isotropic, Mohr-Coulomb type material model, which captures the elastic-viscoplastic, pressure sensitive and plastically dilatant response of bulk metallic glasses. The constitutive equations are first reformulated and implemented using an implicit numerical integration procedure based on the backward Euler method. The resulting system of nonlinear algebraic equations is solved by the Newton-Raphson procedure. This is achieved by developing the principal space return mapping technique for the present model which involves simultaneous shearing and dilatation on multiple potential slip systems. The complete stress update algorithm is presented and the expressions for viscoplastic consistent tangent moduli are derived. The stress update scheme and the viscoplastic consistent tangent are implemented in the commercial finite element code ABAQUS/Standard. The accuracy and performance of the numerical implementation are verified by considering several benchmark examples, which includes a simulation of multiple shear bands in a 3D prismatic bar under uniaxial compression.

Magnetic properties of pure, Sr- and Ca-Doped La2NiO4+δ ceramics: Onset of high-Tc superconductivity

We present the results for the temperature and field dependence of the magnetic for ceramic materials of the composition La2−xMxNiO4, with M=Sr or Ca and 0≤x≤0.4. The onset of a strong diamagnetism has been observed at temperatures between 8 and 70 K, depending on sample composition, annealing conditions. and thermal cycling procedures. The results are similar to those obtained earlier for monocrystalline samples and are likewise interpreted as due to the onset of superconductivity in a minority phase. A comparison with the results for superconducting La1.8Sr0.2Cu0.9Ni0.1O4 ceramics is also made; this illustrates some unique features of the nickelate systems, such as the high values of the critical fields Hc1 and Hc2. The differences between monocrystalline and ceramic systems are also discussed.

An Investigation Of Alkali Aluminosilicate Glasses By Si-29 And Al-27 Magic-Angle-Spinning Nmr-Spectroscopy

Alkali aluminosilicate glasses prepared by the gel and the melt routes have been investigated by Si-29 and Al-27 MAS NMR spectroscopy. It is found that Al has a tetrahedral coordination in the gel glasses modified with equivalent proportions of alkalis unlike in a pure aluminosilicate glass where Al has both four and six coordinations. Silicon is present as Q4 units in all the 5M2O 5Al2O3 9OSiO2 ( M = Li, Na and K) gel glasses studied whereas it is present in Q2 or Q3 species in the lithium aluminosilicate glasses of compositions 40Li2O x Al2O3 (1-x)SiO2 (1 less-than-or-equal-to x less-than-or-equal-to 15) and xLi2O 10Al2O3 (1-x)SiO2 (20 less-than-or-equal-to x less-than-or-equal-to 40). The combination of Q2 and Q3 is also found in certain sodium aluminosilicate glasses, but they change to Q2 and Q1 as the concentration of SiO2 decreases.