Local structures around Y and Ce cations in 10 mol% Y2O3 doped ceria ceramics by EXAFS spectroscopy

Local structures around host Ce and dopant Y cations in 10 mol% Y2O3 doped ceria solid solutions have been investigated by room and high temperature EXAFS spectroscopy. The results show that the local structures around the Cc cation in doped ceria samples are similar to that in the fluorite CeO2 structure though the coordination numbers of Ce-O tend to be smaller than 8. The local structures around Y cation, however, are significantly different from those around Ce cation, and show more resemblance to that around Y cation in the C-type Y2O3 Structure. A more accurate description of the local structures around Y cation in doped ceria was given by analyzing Y-K edge EXAFS spectra based on the C-type Y2O3 structure. (c) 2006 Elsevier B.V. All rights reserved.

Characterization of titanium phosphate as electrolytes in fuel cells

Titanium phosphate is currently a promising material for proton exchange membrane fuel cells applications (PEMFC) allowing for operation at high temperature conditions. In this work, titanium phosphate was synthesized from tetra iso-propoxide (TTIP) and orthophosphoric acid (H3PO4) in different ratios by a sol gel method. High BET surface areas of 271 m(2).g(-1) were obtained for equimolar Ti:P samples whilst reduced surface areas were observed by varying the molar ratio either way. Highest proton conductivity of 5.4 x 10(-2) S.cm(-1) was measured at 20 degrees C and 93% relative humidity (RH). However, no correlation was observed between surface area and proton conductivity. High proton conductivity was directly attributed to hydrogen bonding in P-OH groups and the water molecules retained in the sample structure. The proton conductivity increased with relative humidity, indicating that the Grotthuss mechanism governed proton transport. Further, sample Ti/P with 1:9 molar ratio showed proton conductivity in the order of 10(-1) S.cm(-1) (5% RH) and similar to 1.6x10(-2) S.cm(-1) (anhydrous condition) at 200 degrees C. These proton conductivities were mainly attributed to excess acid locked into the functionalized TiP structure, thus forming ionisable protons.

A unified friction description and its application to the simulation of frictional instability using the finite element method

This article first summarizes some available experimental results on the frictional behaviour of contact interfaces, and briefly recalls typical frictional experiments and relationships, which are applicable for rock mechanics, and then a unified description is obtained to describe the entire frictional behaviour. It is formulated based on the experimental results and applied with a stick and slip decomposition algorithm to describe the stick-slip instability phenomena, which can describe the effects observed in rock experiments without using the so-called state variable, thus avoiding related numerical difficulties. This has been implemented to our finite element code, which uses the node-to-point contact element strategy proposed by the authors to handle the frictional contact between multiple finite-deformation bodies with stick and finite frictional slip, and applied here to simulate the frictional behaviour of rocks to show its usefulness and efficiency.

Anisotropic viscous models of large-deformation Mohr-Coulomb failure

We have developed a way to represent Mohr-Coulomb failure within a mantle-convection fluid dynamics code. We use a viscous model of deformation with an orthotropic viscoplasticity (a different viscosity is used for pure shear to that used for simple shear) to define a prefered plane for slip to occur given the local stress field. The simple-shear viscosity and the deformation can then be iterated to ensure that the yield criterion is always satisfied. We again assume the Boussinesq approximation, neglecting any effect of dilatancy on the stress field. An additional criterion is required to ensure that deformation occurs along the plane aligned with maximum shear strain-rate rather than the perpendicular plane, which is formally equivalent in any symmetric formulation. We also allow for strain-weakening of the material. The material can remember both the accumulated failure history and the direction of failure. We have included this capacity in a Lagrangian-integration-point finite element code and show a number of examples of extension and compression of a crustal block with a Mohr-Coulomb failure criterion. The formulation itself is general and applies to 2- and 3-dimensional problems.

Finite deformation model of simple shear of fault with microrotations: apparent strain localisation and en-echelon fracture pattern

Strain localisation is a widespread phenomenon often observed in shear and compressive loading of geomaterials, for example, the fault gouge. It is believed that the main mechanisms of strain localisation are strain softening and mismatch between dilatancy and pressure sensitivity. Observations show that gouge deformation is accompanied by considerable rotations of grains. In our previous work as a model for gouge material, we proposed a continuum description for an assembly of particles of equal radius in which the particle rotation is treated as an independent degree of freedom. We showed that there exist critical values of the model parameters for which the displacement gradient exhibits a pronounced localisation at the mid-surface layers of the fault, even in the absence of inelasticity. Here, we generalise the model to the case of finite deformations characteristic for the gouge deformation. We derive objective constitutive relationships relating the Jaumann rates of stress and moment stress to the relative strain and curvature rates, respectively. The model suggests that the pattern of localisation remains the same as in the linear case. However, the presence of the Jaumann terms leads to the emergence of non-zero normal stresses acting along and perpendicular to the shear layer (with zero hydrostatic pressure), and localised along the mid-line of the gouge; these stress components are absent in the linear model of simple shear. These additional normal stresses, albeit small, cause a change in the direction in which the maximal normal stresses act and in which en-echelon fracturing is formed.

From point defects to plate tectonic faults

Understanding and explaining emergent constitutive laws in the multi-scale evolution from point defects, dislocations and two-dimensional defects to plate tectonic scales is an arduous challenge in condensed matter physics. The Earth appears to be the only planet known to have developed stable plate tectonics as a means to get rid of its heat. The emergence of plate tectonics out of mantle convection appears to rely intrinsically on the capacity to form extremely weak faults in the top 100 km of the planet. These faults have a memory of at least several hundred millions of years, yet they appear to rely on the effects of water on line defects. This important phenomenon was first discovered in laboratory and dubbed ``hydrolytic weakening''. At the large scale it explains cycles of co-located resurgence of plate generation and consumption (the Wilson cycle), but the exact physics underlying the process itself and the enormous spanning of scales still remains unclear. We present an attempt to use the multi-scale non-equilibrium thermodynamic energy evolution inside the deforming lithosphere to move phenomenological laws to laws derived from basic scaling quantities, develop self-consistent weakening laws at lithospheric scale and give a fully coupled deformation-weakening constitutive framework. At meso- to plate scale we encounter in a stepwise manner three basic domains governed by the diffusion/reaction time scales of grain growth, thermal diffusion and finally water mobility through point defects in the crystalline lattice. The latter process governs the planetary scale and controls the stability of its heat transfer mode.

Stirring in 3-d spherical models of convection in the Earth's mantle

On a global scale basalts from mid-ocean ridges are strikingly more homogeneous than basalts from intraplate volcanism. The observed geochemical heterogeneity argues strongly for the existence of distinct reservoirs in the Earth's mantle. It is an unresolved problem of Geodynamics as to how these findings can be reconciled with large-scale convection. We review observational constraints, and investigate stirring properties of numerical models of mantle convection. Conditions in the early Earth may have supported layered convection with rapid stirring in the upper layers. Material that has been altered near the surface is transported downwards by small-scale convection. Thereby a layer of homogeneous depleted material develops above pristine mantle. As the mantle cools over Earth history, the effects leading to layering become reduced and models show the large-scale convection favoured for the Earth today. Laterally averaged, the upper mantle below the lithosphere is least affected by material that has experienced near-surface differentiation. The geochemical signature obtained during the previous episode of small-scale convection may be preserved there for the longest time. Additionally, stirring is less effective in the high viscosity layer of the central lower mantle [1, 2], supporting the survival of medium-scale heterogeneities there. These models are the first, using 3-d spherical geometry and mostly Earth-like parameters, to address the suggested change of convective style. Although the models are still far from reproducing our planet, we find that proposal might be helpful towards reconciling geochemical and geophysical constraints.

A molecular dynamics model of the atomic structure of dysprosium alumino-phosphate glass

Molecular dynamics (MD) has been used to identify the relative distribution of dysprosium in the phosphate glass DyAl0.30P3.05O9.62. The MD model has been compared directly with experimental data obtained from neutron diffraction to enable a detailed comparison beyond the total structure factor level. The MD simulation gives Dy ... Dy correlations at 3.80(5) and 6.40(5) angstrom with relative coordination numbers of 0.8(1) and 7.3(5), thus providing evidence of minority rare-earth clustering within these glasses. The nearest neighbour Dy-O peak occurs at 2.30 angstrom with each Dy atom having on average 5.8 nearest neighbour oxygen atoms. The MD simulation is consistent with the phosphate network model based on interlinked PO4 tetrahedra where the addition of network modifiers Dy3+ depolymerizes the phosphate network through the breakage of P-(O)-P bonds whilst leaving the tetrahedral units intact. The role of aluminium within the network has been taken into explicit account, and A1 is found to be predominantly (78 tetrahedrally coordinated. In fact all four A1 bonds are found to be to P (via an oxygen atom) with negligible amounts of Al-O-Dy bonds present. This provides an important insight into the role of Al additives in improving the mechanical properties of these glasses.

Structure and thermal properties of yttrium alumino-phosphate glasses

The structure and thermal properties of yttrium alumino-phosphate glasses, of nominal composition (Y2O3)(0.31-z)(Al2O3)(z)(P2O5)(0.69) with 0 less than or similar to z less than or similar to 0.31, were studied by using a combination of neutron diffraction, Al-27 and P-31 magic angle spinning nuclear magnetic resonance, differential scanning calorimetry and thermal gravimetric analysis methods. The Vickers hardness of the glasses was also measured. The data are compared to those obtained for pseudo-binary Al2O3-P2O5 glasses and the structure of all these materials is rationalized in terms of a generic model for vitreous phosphate materials in which Y3+ and Al3+ act as modifying cations that bind only to the terminal (non-bridging) oxygen atoms of PO4 tetrahedra. The results are used to help elucidate the phenomenon of rare-earth clustering in phosphate glasses which can be reduced by substituting Al3+ ions for rare-earth R3+ ions at fixed modifier content.

Structure of glassy GeO2

The full set of partial structure factors for glassy germania, or GeO2, were accurately measured by using the method of isotopic substitution in neutron diffraction in order to elucidate the nature of the pair correlations for this archetypal strong glass former. The results show that the basic tetrahedral Ge(O-1/2)(4) building blocks share corners with a mean inter-tetrahedral Ge-O-Ge bond angle of 132(2)degrees. The topological and chemical ordering in the resultant network displays two characteristic length scales at distances greater than the nearest neighbour. One of these describes the intermediate range order, and manifests itself by the appearance of a first sharp diffraction peak in the measured diffraction patterns at a scattering vector k(FSDP) approximate to 1.53 angstrom(-1), while the other describes so-called extended range order, and is associated with the principal peak at k(PP) = 2.66( 1) angstrom(-1). We find that there is an interplay between the relative importance of the ordering on these length scales for tetrahedral network forming glasses that is dominated by the extended range ordering with increasing glass fragility. The measured partial structure factors for glassy GeO2 are used to reproduce the total structure factor measured by using high energy x-ray diffraction and the experimental results are also compared to those obtained by using classical and first principles molecular dynamics simulations.

Study of thermal spin crossover in [Fe(II)(isoxazole)6](BF4)2 with Mössbauer spectroscopy

57Fe Mössbauer spectroscopy of the mononuclear [Fe(II)(isoxazole)6](BF4) 2compound has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S = 0) and high-spin (S = 2) states. A temperature-dependent spin transition curve has been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures in the 240-60K range during the cooling and heating cycle. The compound exhibits a temperature-dependent two-step spin transition phenomenon with Tsco (step 1) = 92 and Tsco (step2) = 191K. The compound has three high-spin Fe(II) sites at the highest temperature of study; among them, two have slightly different coordination environments. These two Fe(II) sites are found to undergo a spin transition, while the third Fe(II) site retains the high-spin state over the whole temperature range. Possible reasons for the formation of the two steps in the spin transition curve are discussed. The observations made from the present study are in complete agreement with those envisaged from earlier magnetic and structural studies made on [Fe(II)(isoxazole)6](BF4)2, but highlights the nature of the spin crossover mechanism.

The structure of the rare-earth phosphate glass(Sm2O3)0.205(P2O5)0.795 studied by anomalous dispersion neutron diffraction

The role of the Sm3+ ions in the structure of vitreous Sm2O3•4P2O5 has been investigated using the neutron diffraction anomalous dispersion technique, which employs the wavelength dependence of the real and imaginary parts of the neutron scattering length close to an absorption resonance. The data described here represent the first successful complete neutron anomalous dispersion study on an amorphous material. This experimental methodology permits one to determine exclusively the closest Sm• •• Sm separation. Knowledge of the R•••R (R = rare-earth) pairwise correlation is key to understanding the optical and magnetic properties of rare-earth phosphate glasses. The anomalous difference correlation function, ΔT''(r), shows a dominant feature pertaining to a Sm•••Sm separation, centred at 4.8 Å. The substantial width and marked asymmetry of this peak indicates that the minimum approach of Sm3+ ions could be as close as 4 Å. Information on other pairwise correlations is also revealed via analysis of T (r) and ΔT (r) correlation functions: Sm3+ ions display an average co-ordination number, n Sm(O), of 7, with a mean Sm–O bond length of 2.375(5) Å whilst the PO4 tetrahedra have a mean P–O bond length of 1.538(2) Å. Second- and third-neighbour correlations are also identified. These results corroborate previous findings. Such consistency lends support to the application of the anomalous dispersion technique to determine separations.

Structure of dysprosium and holmium phosphate glasses by the method of isomorphic substitution in neutron diffraction

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction and, by taking the role of Al into explicit account, a self-consistent model of the glass structure was developed. The glass network is found to be made from corner sharing PO4 tetrahedra in which there are, on average, 2.32(9) terminal oxygen atoms, OT, at 1.50(1) Å and 1.68(9) bridging oxygen atoms, OB, at 1.60(1) Å. The network modifying R3+ ions bind to an average of 6.7(1) OT and are distributed such that 7.9(7) R–R nearest neighbours reside at 5.62(6) Å. The Al3+ ion also has a network modifying role in which it helps to strengthen the glass through the formation of OT–Al–OT linkages. The connectivity of the R-centred coordination polyhedra in (M2O3)x(P2O5)1−x glasses, where M3+ denotes a network modifying cation (R3+ or Al3+), is quantified in terms of a parameter fs. Methods for reducing the clustering of rare-earth ions in these materials are then discussed, based on a reduction of fs via the replacement of R3+ by Al3+ at fixed total modifier content or via a change of x to increase the number of OT available per network modifying M3+ cation.

Pair breaking and bound states in disordered superconductors

We study the effects of inhomogeneous pairing interactions and impurities in short-coherence-length superconductors. Within the Born approximation, the effects of pairing disorder and magnetic impurities are identical. The T-matrices for pairing disorder sites with and without an impurity give rise to bound states within the BCS (Bardeen-Cooper-Schrieffer) gap, consistent with scanning tunnelling microscopy results on Bi2Sr2CaCu2O8+δ with Zn or Ni impurities.