Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

Fe-57 Mössbauer and Mo K-EXAFS Investigations of MoxFe3-xO4, an Interesting Mixed-Valent Oxide System

Ferrites of the formula MoxFe3-xO4, prepared by a soft-chemistry route, show mixed valence states of both iron and molybdenum cations. Mössbauer studies show that Fe2+ and Fe3+ ions are present on both the A and B sites, giving Fe an average oxidation state between 2+ and 3+. Molybdenum is present in the 3+ and the 4+ states on the B sites. The presence of Mo in the 3+ state has been established by determining the Mo3+-O distance (2.2 Å), for the first time, by Mo K-EXAFS. The mixed valence of Fe on both the A and B sites and of Mo on the B sites is responsible for the fast electron transfer between the cations. All the Mössbauer parameters including the line width show a marked change at a composition (x ? 0.3) above which the concentration of Fe2+A increases rapidly.

Non-Darcy mixed convection flow with thermal dispersion on a vertical cylinder in a saturated porous medium

The non-Darcy mixed convection flow on a vertical cylinder embedded in a saturated porous medium has been studied taking into account the effect of thermal dispersion. Both forced flow and buoyancy force dominated cases with constant wall temperature condition have been considered. The governing partial differential equations have been solved numerically using the Keller box method. The results are presented for the buoyancy parameter which cover the entire regime of mixed convection flow ranging from pure forced convection to pure free convection. The effect of thermal dispersion is found to be more pronounced on the heat transfer than on the skin friction and it enhances the heat transfer but reduces the skin friction.

Reduction behaviour of Fe3+/Al2O3 obtained from the mixed oxalate precursor and the formation of the Fe0-Al2O3 metal-ceramic composite

Reduction behaviour of Fe3+/Al2O3 obtained by the decomposition of the oxalate precursor has been investigated by employing X-ray diffraction (XRD), Mössbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. Calcination of Fe3+/Al2O3 at or below 1070 K yields mainly a poorly ordered, fine particulate form of ?-Al2�xFexO3. Calcination at or above 1220 K yields ?-Al2�xFexO3. Reduction of Fe3+/Al2O3 samples calcined at or below 1070 K gives the FeAl2O4 spinel on reduction at 870 K; samples calcined at or above 1220 K give Al2-xFexO3 with a very small proportion of metallic iron. Fe3+/Al2O3 samples calcined at 1220 K or above yield metallic iron and a very small proportion of the spinel on reduction below 1270 K. In the samples reduced at or above 1270 K, the main product is metallic iron in both ferromagnetic and superparamagnetic forms. The oxalate precursor route yields more metallic iron than the sol�gel route.

Simultaneous heat and mass transfer under unsteady mixed convection along a vertical slender cylinder embedded in a porous medium

Unsteady laminar mixed convection flow (combined free and forced convection flow) along a vertical slender cylinder embedded in a porous medium under the combined buoyancy effect of thermal and species diffusion has been studied. The effect of the permeability of the medium as well as the magnetic field has been included in the analysis. The partial differential equations with three independent variables governing the flow have been solved numerically using a implicit finite difference scheme in combination with the quasilinearization technique. Computations have been carried out for accelerating, decelerating and oscillatory free stream velocity distributions. The effects of the permeability of the medium, buoyancy forces, transverse curvature and magnetic field on skin friction, heat transfer and mass transfer have been studied. It is found that the effect of free stream velocity distribution is more pronounced on the skin friction than on the heat and mass transfer. The permeability and magnetic parameters increase the skin friction, but reduce the heat and mass transfer. The skin friction, heat transfer and mass transfer are enhanced due to the buoyancy forces and curvature parameter. The heat transfer is strongly dependent on the viscous dissipation parameter and the Prandtl number, and the mass transfer on the Schmidt number. Untersucht wurde die instationäre laminare Mischkonvektion längs eines vertikalen, in einem porösen Medium eingebetteten Zylinders unter kombinierten Auftriebseffekten von thermischer und spezieller Diffusion. Der Einfluß der Permeabilität des Mediums sowie des magnetischen Feldes wurden in die Betrachtung einbezogen. Die partiellen Differentialgleichungen mit drei unabhängigen Variablen, welche die Strömung beschreiben, wurde numerisch anhand des Schemas der endlichen Differenzen in Verbindung mit der Technik der Quasilinearisation gelöst. Berechnungen für die beschleunigte, verzögerte und oszillierende Geschwindigkeitsverteilung der freien Strömung sind durchgeführt worden. Untersucht wurden ebenfalls die Effekte der Permeabilität des Mediums, der Auftriebskräfte, der transversalen Krümmung, des magnetischen Feldes auf die Oberflächenreibung sowie die Wärmeund Stoffübertragung. Es wurde festgestellt, daß die Geschwindigkeit mehr Einfluß auf die Oberflächenreibung als auf die Wärmeund Stoffübertragung hat. Die Oberflächenreibung sowie die Wärme- und Stoffübertragung werden durch die Auftriebskräfte und die Krümmungsparameter verbessert. Die Wärmeübertragung ist stark abhängig von den Parametern der viskosen Dissipation und der Prandtl-Zahl; die Stoffübertragung von der Schmidt-Zahl.

Synthesis of Layered Perovskite Oxides, ACa2-xLaxNb3-xTix010 (A = K, Rb, Cs), and Characterization of New Solid Acids, HCa2-xLaxNb3-xTixOlo (0 < x d 2), Exhibiting Variable Bronsted Acidity?

Layered perovskite oxides of the formula ACa~,La,Nb3-,Ti,010 (A = K, Rb, Cs and 0 < x d 2) have been prepared. The members adopt the structures of the parent ACazNb3010. Interlayer alkali cations in the niobium-titanium oxide series can be ion-exchanged with Li+, Na+, NH4+, or H+ to give new derivatives. Intercalation of the protonated derivatives with organic bases reveals that the Bronsted acidity of the solid solution series, HC~ ~ , L ~ ,N~ ~ , T ~ ,dOep~eOnd, s on the titanium content. While the x = 1 member (HCaLaNbzTiOlo) is nearly as acidic as the parent HCazNb3010, the x = 2 member (HLazNbTizOlo) is a weak acid hardly intercalating organic bases with pKa - 11.3. The variation of acidity is probably due to an ordering of Nb/Ti atoms in the triple octahedral perovskite slabs, [Ca~,La,Nb~,Ti,0~0], such that protons are attached to NbO6 octahedra in the x = 1 member and to Ti06 octahedra in the x = 2 member.

Thermodynamic Study of Mixed Anionic Solid Solutions Using Gradient Solid Electrolytes System K2CO3 - K2SO4

The thermodynamic properties of K2CO3 -KSO, solid solutions with hexagonal structure have been measured using a solid-state cell, incorporating a composite solid electrolyte with step-changes in composition. The cell with the configuration Pt, CO2' + O2' || K2CO3 | K2(CO3)x(SO4)1-x || CO2'' + O2'' + Pt X =1 X=X was investigated in the temperature range of 925 to 1165 K. The composite gradient solid electrolyte consisted of pure K2CO3 at one extremity and the solid solution under study at the other. The Nernstian response of the cell to changes in partial pressures of CO2 and O2 at the electrodes and temperature was demonstrated. The activity of K2CO3 in the solid solution was measured by three techniques. All three methods gave identical results, indicating unit transport number for K+ ions and negligible diffusion potential due to concentration gradients of carbonate and sulfate ions. The activity of K2CO3 exhibits positive deviation from Raoult's law. The excess Gibbs energy of mixing of the solid solution can be represented using a subregular solution model DELTAG(E) = X(1 - X)[5030X + 4715(1 - X)] J mol-1 By combining this information with the phase diagram, mixing properties of the liquid phase were obtained.

(Ba3MTiMO9)-Ti-III-O-V (M-III = Fe, Ga, Y, Lu, M-V = Nb, Ta, Sb) perovskite oxides Synthesis, structure and dielectric properties

We describe the synthesis structures and dielectric properties of new perovskite oxides of the formula (Ba3MTiMO9)-Ti-III-O-V for M-III = Fe Ga Y Lu and M-V = Nb Ta Sb While M-V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M-III/Ti/M-V metal-oxygen octahedra are corner connected the M-V = Sb oxides show a distinct preference for the 6H structure where Sb-V/Ti-IV metal-oxygen octahedra share a common face forming (Sb Ti)O-9 dimers that are corner-connected to the (MO6)-O-III octahedra The preference of antimony oxides (Sb-V 4d(10)) for the 6H structure which arises from a special Sb-V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb-V/Ta-V d(0) atoms which prefer similar to 180 degrees Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M-V-O oxides in general The dielectric properties reveal a significant difference among Mill members All the oxides with the 3C structure excepting those with Mill = Fe show a normal low loss dielectric behaviour with epsilon = 20-60 in the temperature range 50-400 degrees C the M-III = Fe members with this structure (M-V = Nb Ta) display a relaxor-like ferroelectric behaviour with large E values at frequencies <= 1 MHz (50-500 degrees C) (C) 2010 Elsevier Masson SAS All rights reserved

Ab initio molecular orbital calculations on ion pair-water complexes of metal halides and oxides

Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H2O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those computed for the complexes of the individual ions. The bifurcated structures are found to be saddle points with an imaginary frequency corresponding to the rocking mode of water molecules. The solvent-shared ion pair complexes have high interaction energies. Trends in the internal force constant and harmonic frequency values are discussed in terms of ion-molecular and ion-pair molecular interactions.

Stress-strain response of plastic waste mixed soil

Recycling plastic waste from water bottles has become one of the major challenges worldwide. The present study provides an approach for the use plastic waste as reinforcement material in soil. The experimental results in the form of stress-strain-pore water pressure response are presented. Based on experimental test results, it is observed that the strength of soil is improved and compressibility reduced significantly with addition of a small percentage of plastic waste to the soil. The use of the improvement in strength and compressibility response due to inclusion of plastic waste can be advantageously used in bearing capacity improvement and settlement reduction in the design of shallow foundations. (C) 2010 Elsevier Ltd. All rights reserved.

A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Diffusion path during internal displacement reactions in multi-component oxides: Reaction between Fe and (Co,Mg)TiO3 solid solution at 1273 K

The reaction between Fe foil and a disc of ilmenite solid solution (Co-0.48 Ni-0.52) TiO3 was studied at 1273 K. At the metal/oxide interface, the displacement reaction, Fe + (Co,Mg)TiO3 = Co + (Fe,Mg)TiO3 occurs, resulting in an ilmenite solid solution containing three divalent cations. Ferrous ions diffuse into the oxide solid solution and cause the precipitation of Co-Fe alloy as discrete particles inside the oxide matrix. The morphology of the product layer was characterized by SEM. Only two phases, alloy and ilmenite, were detected in the reaction zone. This suggests that the local flux condition imposed by ilmenite stoichiometry (Co + Fe + Mg):Ti = 1:1] was satisfied during the reactive diffusion: (J(Co) + J(Fe) + J(Mg)) = J(Ti). The composition of the alloy and the oxide was determined using EPMA as a function of distance in the direction of diffusion. Although Mg does not participate in the displacement reaction, its composition in the ilmenite phase was found to be position dependent inside the reaction zone. The up-hill diffusion of inert Mg is caused by the development of chemical potential gradients as a result of displacement reaction. The evolution of composition gradients inside the reaction zone and the diffusion path in a ternary composition diagram of the system CoTiO3-FeTiO3-MgTiO3 are discussed. (C) 2010 Elsevier B.V. All rights reserved.