Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Large-scale convective dynamos in a stratified rotating plane layer

We study the effect of stratification on large-scale dynamo action in convecting fluids in the presence of background rotation. The fluid is confined between two horizontal planes and both boundaries are impermeable, stress-free and perfectly conducting. An asymptotic analysis is performed in the limit of rapid rotation (τ???1 where τ is the Taylor number). We analyse asymptotic magnetic dynamo solutions in rapidly rotating systems generalising the results of Soward [A convection-driven dynamo I. The weak field case. Philos. Trans. R. Soc. Lond. A 1974, 275, 611–651] to include the effects of compressibility. We find that in general the presence of stratification delays the efficiency of large-scale dynamo action in this regime, leading to a reduction of the onset of dynamo action and in the nonlinear regime a diminution of the large-scale magnetic energy for flows with the same kinetic energy.     

Structural and vibrational behaviour of fluorapatite with pressure. Part I: in situ single-crystal X-ray diffraction investigation

Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β _a =3.32(8)?10^?3 and β _c =2.40(5)?10^?3 GPa^?1, giving a ratio β _a :β _c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K ₀=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?ų at room pressure to 44.78?ų at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.     

土在高压力段的压缩性参数外推方法探讨

根据土高压固结试验的压缩曲线几何特征,提出了基于一定较高压力水平的固结试验结果外推更大压力段的压缩性参数和压缩曲线的方法。实际验证结果表明,该方法简便易行,且精确度较高。     

Structure modelling and cation partitioning of spinel solid solutions at high <Emphasis Type="Italic">T</Emphasis>,<Emphasis Type="Italic">P</Emphasis> conditions

This paper presents evaluation of cation distributions from diffraction data collected at high T, P, and is an extension of the spinel structure modelling procedure by Lavina et al. (2002). Optimised cation-to-oxygen distances are modified for thermal expansion and compressibility at T and P of interest following Hazen and Prewitt (1977) and Hazen and Yang (1999). The procedure is applied to literature data concerning hercynite, spinel s.s., Zn aluminate, Zn ferrite, magnetite and the (Fe₃O₄)_{1– x} (MgAl₂O₄) _x join. Calculated cation distribution is strongly affected by standard deviations in cell parameters and oxygen coordinates. The underestimated values often reported in the literature for powder profile refinements may strongly affect the cation distribution; however, if standard deviations are increased to physically realistic values, consistent results are obtained. For P up to 10 GPa, reasonable evaluations of cation distribution are obtained for spinel s.s., Zn aluminate and magnetite, whereas for Zn ferrite they are limited to 1.8 GPa. For P beyond 10 GPa, compressibility cannot be assumed to be linear; the relationship between cell parameter and pressure is well-defined, but the inaccuracy of oxygen coordinate prevents simple modelling of bond distances with pressure.     

High-pressure behaviour along the jadeite NaAlSi2O6–aegirine NaFeSi2O6 solid solution up to 10 GPa

The volume variation as a function of pressure along the jadeite–aegirine solid solution was determined at room temperature up to pressures between 6.5 and 9.7 GPa by single-crystal X-ray diffraction. The unit-cell volumes collected at room pressure for the different compositions indicate a slight deviation from linearity along the join. The pressure–volume data have been fitted using a third-order Birch-Murnaghan equation of state (BM3-EoS). The bulk modulus, K _T0, varies from 134.0(7) GPa for pure jadeite to 116.1(5) GPa for pure aegirine. Its evolution with composition along the join is not linear and can be described by the following second order polynomial:

The effect of stratification and compressibility on anelastic convection in a rotating plane layer

We study the effect of stratification and compressibility on the threshold of convection and the heat transfer by developed convection in the nonlinear regime in the presence of strong background rotation. We consider fluids both with constant thermal conductivity and constant thermal diffusivity. The fluid is confined between two horizontal planes with both boundaries being impermeable and stress-free. An asymptotic analysis is performed in the limits of weak compressibility of the medium and rapid rotation (τ^?1/12???|θ|???1, where τ is the Taylor number and θ is the dimensionless temperature jump across the fluid layer). We find that the properties of compressible convection differ significantly in the two cases considered. Analytically, the correction to the characteristic Rayleigh number resulting from small compressibility of the medium is positive in the case of constant thermal conductivity of the fluid and negative for constant thermal diffusivity. These results are compared with numerical solutions for arbitrary stratification. Furthermore, by generalizing the nonlinear theory of Julien and Knobloch [Fully nonlinear three-dimensional convection in a rapidly rotating layer. Phys. Fluids 1999, 11, 1469–1483] to include the effects of compressibility, we study the Nusselt number in both cases. In the weakly nonlinear regime we report an increase of efficiency of the heat transfer with the compressibility for fluids with constant thermal diffusivity, whereas if the conductivity is constant, the heat transfer by a compressible medium is more efficient than in the Boussinesq case only if the specific heat ratio γ is larger than two.     

Multiscale finite-volume formulation for multiphase flow in porous media: black oil formulation of compressible,three-phase flow with gravity

Most practical reservoir simulation studies are performed using the so-called black oil model, in which the phase behavior is represented using solubilities and formation volume factors. We extend the multiscale finite-volume (MSFV) method to deal with nonlinear immiscible three-phase compressible flow in the presence of gravity and capillary forces (i.e., black oil model). Consistent with the MSFV framework, flow and transport are treated separately and differently using a sequential implicit algorithm. A multiscale operator splitting strategy is used to solve the overall mass balance (i.e., the pressure equation). The black-oil pressure equation, which is nonlinear and parabolic, is decomposed into three parts. The first is a homo geneous elliptic equation, for which the original MSFV method is used to compute the dual basis functions and the coarse-scale transmissibilities. The second equation accounts for gravity and capillary effects; the third equation accounts for mass accumulation and sources/ sinks (wells). With the basis functions of the elliptic part, the coarse-scale operator can be assembled. The gravity/capillary pressure part is made up of an elliptic part and a correction term, which is computed using solutions of gravity-driven local problems. A particular solution represents accumulation and wells. The reconstructed fine-scale pressure is used to compute the fine-scale phase fluxes, which are then used to solve the nonlinear saturation equations. For this purpose, a Schwarz iterative scheme is used on the primal coarse grid. The framework is demonstrated using challenging black-oil examples of nonlinear compressible multiphase flow in strongly heterogeneous formations.     

Assessment of crushed shales for use as compacted landfill liners

The possibility of using crushed shales as landfill liners is investigated in this study. Two types of shales were studied by performing the following laboratory tests: hydraulic conductivity, compaction, swelling, consolidation, X-ray diffraction (XRD), scanning electron microscope (SEM) and chemical analysis. For both compacted shales, the hydraulic conductivity was in order of 10^− 7 cm/s or less which satisfies the specifications for landfill liners. The results of XRD and SEM support the low values of the hydraulic conductivity. Because of the dominant presence of low-activity kaolinite, there was no significant change in the hydraulic conductivity when the compacted shales are exposed to calcium chloride solution. The compressibility of the compacted clay was low and no serious post-construction settlement is expected. The shear strength of the compacted shales was within the usual expected range for earthen liners and, therefore, should pose no challenges with respect to shear strength. The crushed shales also satisfy the other criteria related to Atterberg limits and grain size.