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.

Influence of grain boundary sliding on diffusion in yttria doped zirconia

Grain boundary sliding during high temperature deformation can lead to stress concentrations and an enhancement of diffusion in mobile boundaries. Experiments were conducted on a fine grained 3 mol% yttria stabilized tetragonal zirconia, under conditions associated with superplastic flow involving grain boundary sliding. Tracer diffusion studies under creep conditions and without load indicate that there is no enhancement in either the lattice or grain boundary diffusivities. The experimental creep data are consistent with an interface controlled diffusion creep mechanism. (C) 2011 Elsevier Ltd. All rights reserved.

The structure of amorphous platinum disulfide as studied by anomalous x-ray-scattering

Anomalous X-ray scattering (AXS) has been applied to study the structure of amorphous platinum disulfide, Pt1-xS2, prepared by the precipitation process. The local atomic arrangement in amorphous Pt1-xS2 was determined by the least-squares variational method so as to reproduce the experimental differential interference function at the Pt L(III) absorption edge by the AXS method as well as the ordinary interference function by MoK alpha. The structural unit in amorphous Pt1-xS2 is found to be a PtS6 octahedron, similar to that in crystalline PtS2. These octahedra share both their corners and edges, while only edge-sharing linkages occur in crystalline PtS2.

Anomalous X-ray scattering study of local structures in the superionic conducting class (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35)

The anomalous X-ray scattering (AXS) method using Cu and Mo K absorption edges has been employed for obtaining the local structural information of superionic conducting glass having the composition (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35). The possible atomic arrangements in near-neighbor region of this glass were estimated by coupling the results with the least-squares analysis so as to reproduce two differential intensity profiles for Cu and Mo as well as the ordinary scattering profile. The coordination number of oxygen around Mo is found to be 6.1 at the distance of 0.187 nm. This implies that the MoO6 octahedral unit is a more probable structural entity in the glass rather than MoO4 tetrahedra which has been proposed based on infrared spectroscopy. The pre-peak shoulder observed at about 10 nm(-1) may be attributed to density fluctuation originating from the MoO6 octahedral units connected with the corner sharing linkage, in which the correlation length is about 0.8 nm. The value of the coordination number of I- around Cu+ is estimated as 4.3 at 0.261 nm, suggesting an arrangement similar to that in molten CuI.

Anomalous viscous loss in emulsions

We propose a model for concentrated emulsions based on the speculation that a macroscopic shear strain does not produce an affine deformation in the randomly close-packed droplet structure. The model yields an anomalous contribution to the complex dynamic shear modulus that varies as the square root of frequency. We test this prediction using a novel light scattering technique to measure the dynamic shear modulus, and directly observe the predicted behavior over six decades of frequency and a wide range of volume fractions.

Temperature-dependent photoluminescence of GaN grown on beta-Si3N4/Si (111) by plasma-assisted MBE

Photoluminescence (PL) of high quality GaN epitaxial layer grown on beta-Si3N4/Si (1 1 1) substrate using nitridation-annealing-nitridation method by plasma-assisted molecular beam epitaxy (PA-MBE) was investigated in the range of 5-300 K. Crystallinity of GaN epilayers was evaluated by high resolution X-ray diffraction (HRXRD) and surface morphology by Atomic Force Microscopy (AFM) and high resolution scanning electron microscopy (HRSEM). The temperature-dependent photoluminescence spectra showed an anomalous behaviour with an `S-like' shape of free exciton (FX) emission peaks. Distant shallow donor-acceptor pair (DAP) line peak at approximately 3.285 eV was also observed at 5 K, followed by LO replica sidebands separated by 91 meV. The activation energy of the free exciton for GaN epilayers was also evaluated to be similar to 27.8 +/- 0.7 meV from the temperature-dependent PL studies. Low carrier concentrations were observed similar to 4.5 +/- 2 x 10(17) Cm-3 by measurements and it indicates the silicon nitride layer, which not only acts as a growth buffer layer, but also effectively prevents Si diffusion from the substrate to GaN epilayers. The absence of yellow band emission at around 2.2 eV signifies the high quality of film. The tensile stress in GaN film calculated by the thermal stress model agrees very well with that derived from Raman spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Shear-induced enhancement of self-diffusion in interacting colloidal suspensions

We set up the generalized Langevin equations describing coupled single-particle and collective motion in a suspension of interacting colloidal particles in a shear how and use these to show that the measured self-diffusion coefficients in these systems should be strongly dependent on shear rate epsilon. Three regimes are found: (i) an initial const+epsilon(.2), followed by (ii) a large regime of epsilon(.1/2) behavior, crossing over to an asymptotic power-law approach (iii) D-o - const x epsilon(.-1/2) to the Stokes-Einstein value D-o. The shear dependence is isotropic up to very large shear rates and increases with the interparticle interaction strength. Our results provide a straightforward explanation of recent experiments and simulations on sheared colloids.

Anomalous Behavior of Linear Hydrocarbon Chains in Water-DMSO Binary Mixture at Low DMSO Concentration

We find that at a mole fraction 0.05 of DMSO (x(DMSO) = 0.05) in aqueous solution, a linear hydrocarbon chain of intermediate length (n = 30-40) adopts the most stable collapsed conformation. In pure water, the same chain exhibits an intermittent oscillation between the collapsed and the extended coiled conformations. Even when the mole fraction of DMSO in the bulk is 0.05, the concentration of the same in the first hydration layer around the hydrocarbon of chain length 30 (n = 30) is as large as 17%. Formation of such hydrophobic environment around the hydrocarbon chain may be viewed as the reason for the collapsed conformation gaining additional stability. We find a second anomalous behavior to emerge near x(DMSO) = 0.15, due to a chain-like aggregation of the methyl groups of DMSO in water that lowers the relative concentration of the DMSO molecules in the hydration layer. We further find that as the concentration of DMSO is gradually increased, it progressively attains the extended coiled structure as the stable conformation. Although Flory-Huggins theory (for binary mixture solvent) fails to predict the anomaly at x(DMSO) = 0.05, it seems to capture the essence of the anomaly at 0.15.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

Local environmental structures of Mo in the superionic conducting glass (AgI)(0.6)(Ag2MoO4)(0.4) by anomalous X-ray scattering

The anomalous X-ray scattering (AXS) method using Mo K absorption edges has been employed for obtaining the local structural information of superionic conducting glass having the composition (AgI)(0.6)(Ag2MoO4)(0.4). The possible atomic arrangements in the near-neighbor region of this glass were estimated by coupling the results with the least-squares variational analysis so as to reproduce the differential intensity profile for Mo as well as the ordinary scattering profile. The coordination number of oxygen around Mo is found to be about 4 at the distance of 0.180 mn. This implies that the most probable structural entity in the glass is the MoO4 tetrahedral unit which has been proposed based on infrared spectroscopy. The value of the coordination number of I- around Ag+ is estimated as 4.4 at 0.287 nm, suggesting an arrangement similar to that of crystalline or molten AgI.

Polar and nonpolar solvation dynamics, ion diffusion, and vibrational relaxation: Role of biphasic solvent response in chemical dynamics

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Diffusion and Growth of the mu Phase (Ni6Nb7) in the Ni-Nb System

Incremental diffusion couple experiments are conducted to determine the average interdiffusion coefficient and the intrinsic diffusion coefficients of the species in the Ni6Nb7 (mu phase) in the Ni-Nb system. Further, the tracer diffusion coefficients are calculated from the knowledge of thermodynamic parameters. The diffusion rate of Ni is found to be higher than that of Nb, which indicates higher defect concentration in the Ni sublattice.

Growth mechanism of phases by interdiffusion and atomic mechanism of diffusion in the molybdenum-silicon system

Tracer diffusion coefficients are calculated in different phases in the Mo-Si system from diffusion couple experiments using the data available on thermodynamic parameters. Following, possible atomic diffusion mechanism of the species is discussed based on the crystal structure. Unusual diffusion behaviour is found in the Mo(5)Si(3) and Mo(3)Si phases, which indicate the nature of defects present on different sublattices. Further the growth mechanism of the phases is discussed and morphological evolution during interdiffusion is explained. (C) 2011 Elsevier Ltd. All rights reserved.

Hydrolytic degradation and diffusion studies on a polyphosphate ester

A polyphosphate ester was synthesized by interfacial polycondensation of bisphenol-A and phenylphosphorodichloridate. Accelerated hydrolytic degradation studies were conducted under alkaline conditions. The effect of concentration of alkali and temperature were monitored. The rate of degradation reached a maximum value at 6 molar sodium hydroxide solution and then reduced. The activation energy for hydrolytic degradation was found to be 45 kcal/mol. Diffusion of alkali into the polymer pellet was studied at various concentrations of alkali and at various temperatures. The rate of diffusion also attained a maximum at 6M NaOH and the activation energy for diffusion process was found to be 12 kcal/mol. (C) 2002 John Wiley Sons, Inc.