Carmen Sanchez-Valle

Brillouin scattering study on the single-crystal elastic properties of natrolite and analcime zeolites

The Brillouin light-scattering technique was used to investigate the single-crystal elastic properties of two aluminosilicate zeolites, natrolite (NAT) and analcime (ANA), at ambient conditions. An inversion of the acoustic velocity data results in the full set of elastic stiffness moduli (Cij’s) for both materials. From the single-crystal moduli the aggregate adiabatic bulk moduli (Ks), shear moduli (G), and Poisson’s ratios (ν) were found to be Ks=48.5(1.0)GPa, G=31.6(1.0)GPa, and ν=0.232(5) for NAT, and Ks=59.8(1.2)GPa, G=32.1(1.0)GPa, and ν=0.272(5) for ANA (Voigt-Reuss-Hill averages). The bulk and shear moduli of both zeolites are relatively low compared with those of densely packed aluminosilicates, reflecting an open framework structure of (Al,SiO4) tetrahedra which is easily deformed by bending the Si–O–Al angles. As expected for a less dense crystal, NAT is softer and more compressible than ANA. An evaluation of the directional Young’s moduli shows that the compressibility of NAT is nearly unifor...

Dissolution of strontianite at high P-T conditions: An in-situ synchrotron X-ray fluorescence study

Abstract In-situ measurements of the amount of dissolution of carbonate minerals at high pressures (up to 3.6 GPa) and temperatures (up to 523 K) are reported. Using an externally heated diamond anvil cell (DAC) and synchrotron X-ray fluorescence (SXRF), the extent of dissolution of strontianite (SrCO3) has been followed as a function of time by monitoring the fluorescence of Sr cations in the fluid surrounding the crystal. This work demonstrates that Sr2+ concentrations as low as 1000 ppm can be detected and measured in-situ in a DAC, using a forward transmission geometry. The preliminary data presented here indicate that this technique has high potential for determining solution composition in high-pressure and high-temperature geochemical studies.

Brillouin spectrometer interfaced with synchrotron radiation for simultaneous x-ray density and acoustic velocity measurements

We describe a new Brillouin spectrometer that has been installed on a synchrotron x-ray beamline for simultaneous measurements of sound velocities (by Brillouin scattering) and density (by x-ray diffraction). The spectrometer was installed at the 13-BM-D station (GSECARS) of the Advanced Photon Source. This unique facility has been tested in studies of transparent single crystal and polycrystalline materials at high pressure and temperature. The equation of state, acoustic velocities, and, hence, elastic moduli of materials as a function of pressure and temperature can now be determined without resort to a secondary pressure standard, such as the ruby fluorescence scale, or the equation of state of standard materials such as Au, Pt, or MgO, thus offering the potential to determine an absolute pressure scale. This article describes the design of the combined Brillouin-x-ray system and the first experimental results obtained. As a general-user facility, the system was designed to require minimal setup time ...

Elastic behavior and phase stability of pollucite, a potential host for nuclear waste

Abstract The elastic behavior and the phase stability of natural pollucite, (Cs,Na)16Al16Si32O96⋅nH2O, were investigated at hydrostatic pressure by in situ single-crystal X-ray diffraction with a diamond-anvil cell. Pollucite experiences a P-induced phase transition, not previously reported in the literature, at P = 0.66 ± 0.12 GPa from cubic (Ia3̅d) to triclinic symmetry (P1̅). The phase transition is completely reversible and without any appreciable hysteresis effect. No further phase transition has been observed up to 9 GPa. Fitting the pressure-volume data of the low-pressure cubic polymorph with a second-order Birch-Murnaghan Equation-of-State (BM-EoS), we obtain V0 = 2558.3(4) Å3, KT0 = 41(2) GPa, and K′T = 4 (fixed). For the high-pressure triclinic polymorph, a third-order BM-EoS fit gives V0 = 2577.5(40) Å3, KT0 = 25.1(9) GPa, and K′T = 6.5(4). The axial bulk moduli of the high-pressure triclinic polymorph were calculated with a third-order “linearized” BM-EoS. The EoS parameters are a0 = 13.699(12) Å, KT0(a) = 25.5(17) GPa, and K′T(a) = 6.8(6) for the a axis; b0 = 13.728(12) Å, KT0(b) = 23.2(15) GPa, and K′T(b) = 7.7(7) for the b axis; c0 = 13.710(7) Å, KT0(c) = 25.2(10) GPa, and K′T(c) = 6.8(4) for the c axis [KT0(a):KT0(b):KT0(c) = 1.10:1:1.09]. Brillouin light-scattering was used to investigate the single-crystal elastic properties of pollucite at ambient conditions. The aggregate adiabatic bulk modulus (Ks) and shear modulus (G), calculated using the Voigt-Reuss-Hill averaging procedures, are Ks = 52.1(10) GPa and G = 31.5(6) GPa. The elastic response of pollucite and other isotypic materials (e.g., analcime, leucite, and wairakite) is compared. The high thermo-elastic stability of pollucite, reflected by the preservation of crystallinity at least up to 9 GPa (at room T) and 1470 K (at room P) in elastic regime, the large amount of Cs hosted in this material (Cs2O ~ 30 wt%), the immobility of Cs at high-temperature and high-pressure conditions, and the extremely low leaching rate of Cs, make of this open-framework silicate a functional material with potential use for fixation and deposition of Cs radioisotopes in high-level nuclear waste.

Optimization of Sm3+ fluorescence in Sm-doped yttrium aluminum garnet: Application to pressure calibration in diamond-anvil cell at high temperature

Sm3+ concentration in Sm-doped yttrium aluminum garnet (Sm3+:YAG) has been optimized for fluorescence yield and synthesis procedure for the production of strain-free small grain-size powder established. Concentration of 0.5 wt % Sm3+ displays an optimal fluorescence signal, three to five times stronger than the generally proposed concentration (4 wt %). The fluorescence of the samples has been studied as a function of temperature (300–873 K) and pressure (0–15 GPa). A comparison with standard pressure scales shows that the pressure evolution of Sm3+:YAG fluorescence is insensitive to the doping rate, and that temperature has only a limited effect on the pressure scale established at 300 K. The present results indicate that pressure can be determined from the Y1 line of 0.5 wt % Sm-doped YAG, with temperature correction for ϖ at room pressure and constant pressure shift, within the 300–873 K and 10−4−15 GPa pressure-temperature range, through the linear relation: P (GPa)=0.127×[(ϖ0−0.018×ΔT)−ϖ] where ϖ0 co...

Amorphous mAteriAls: properties, structure, And durAbility† Compositional dependent compressibility of dissolved water in silicate glasses

Abstract The sound velocities and elastic properties of a series of hydrous rhyolite, andesite, and basalt glasses have been determined by Brillouin scattering spectroscopy at ambient conditions to elucidate the effect of glass composition on the compressibility of dissolved water. Both the adiabatic bulk (KS) and shear modulus (μ) of the dry glasses decrease with increasing silica content (KS,basalt > KS,andesite > KS,rhyolite and μbasalt > μandesite > μrhyolite). For each composition, the shear modulus systematically decreases with increasing water content. Although the addition of up to 14 mol% water decreases the KS of andesite and basalt glasses by up to 6%, there is no discernable effect of water on the KS of the rhyolite glasses. The partial molar KS of dissolved water (KS) in rhyolite, andesite, and basalt glasses are 37 ± 5, 19 ± 7, and 40 ± 3 GPa, corresponding to partial molar isothermal compressibilities (β̅T) of 0.029 ± 0.005, 0.042 ± 0.004, and 0.026 ± 0.002 GPa−1, respectively. These results indicate that the compressibility of dissolved water strongly depends on the bulk composition of the glass; hence, the partial molar volume of water cannot be independent of the bulk composition at elevated pressure. If the compressibility of dissolved water also depends on composition in the analog melts at high temperature and pressure, these observations will have important consequences for magmatic processes such as magma mixing/unmixing and fractional crystallization.

Single-crystal elastic properties of (Cs,Na)AlSi2O6⋅H2O pollucite: A zeolite with potential use for long-term storage of Cs radioisotopes

The single-crystal and aggregate elastic properties of the zeolite pollucite (Cs,Na)AlSi2O6⋅H2O, a potential host for Cs radionucleides in geological repositories, have been determined by Brillouin scattering spectroscopy at ambient conditions. The three nonzero individual elastic constants of cubic pollucite are: C11=105.0(1.3) GPa, C44=27.0(3) GPa, and C12=25.7(6) GPa. The Voigt–Reuss–Hill average of the aggregate bulk, shear modulus, Youngs modulus and Poisson’s ratio are KS=52.2(1.0) GPa, G=31.5(7) GPa, E=78.6(1.0) GPa, and ν=0.248(4), respectively. The bulk modulus of pollucite is 12.7% lower than that of the all-Na isotypic mineral analcime NaAlSi2O6⋅H2O whereas the shear moduli G are identical within mutual uncertainties. The higher compressibility of pollucite results from the weaker Cs–O bonds compared to Na–O bonds, suggesting strong control of the nature and configuration of the extraframework content on the behavior of the structure. The elastic properties of pollucite reported here will help...

Negative Poisson's ratios in siliceous zeolite MFI-silicalite

Brillouin scattering measurements of the single-crystal elastic properties of the as-made zeolite silicalite mid R:(C(3)H(7))(4)NFmid R:(4)[Si(96)O(192)]-MFI provides the first experimental evidence for on-axis negative Poissons ratios (auxeticity) in a synthetic zeolite structure. MFI laterally contracts when compressed and laterally expands when stretched along x(1) and x(2) directions in the (001) plane (nu(12)=-0.061, nu(21)=-0.051). The aggregate Poissons ratio of MFI, although positive, has an anomalously low value nu=0.175(3) compared to other silicate materials. These results suggest that the template-free MFI-silicalite [Si(96)O(192)] might have potential applications as tunable sieve where molecular discriminating characteristics are adjusted by application of stress along specific axes.

Stagnant lid convection in bottom‐heated thin 3‐D spherical shells: Influence of curvature and implications for dwarf planets and icy moons

Because the viscosity of ice is strongly temperature dependent, convection in the ice layers of icy moons and dwarf planets likely operates in the stagnant lid regime, in which a rigid lid forms at the top of the fluid and reduces the heat transfer. A detailed modeling of the thermal history and radial structure of icy moons and dwarf planets thus requires an accurate description of stagnant lid convection. We performed numerical experiments of stagnant lid convection in 3-D spherical geometries for various ice shell curvatures f (measured as the ratio between the inner and outer radii), effective Rayleigh number Ram, and viscosity contrast Δ�� . From our results, we derived scaling laws for the average temperature of the well-mixed interior, �� m, and the heat flux transported through the shell. The nondimensional temperature difference across the bottom thermal boundary layer is well described by (1 − �� m )= 1.23 �� f 1.5 ,

Equation of state, refractive index and polarizability of compressed water to 7 GPa and 673 K

The equation of state (EoS), refractive index n, and polarizability α of water have been determined up to 673 K and 7 GPa from acoustic velocity measurements conducted in a resistively heated diamond anvil cell using Brillouin scattering spectroscopy. Measured acoustic velocities compare favorably with previous experimental studies but they are lower than velocities calculated from the extrapolation of the IAPWS95 equation of state above 3 GPa at 673 K and deviations increase up to 6% at 7 GPa. Densities calculated from the velocity data were used to propose an empirical EoS suitable in the 0.6-7 GPa and 293-673 K range with a total estimated uncertainty of 0.5% or less. The density model and thermodynamic properties derived from the experimental EoS have been compared to several EoS proposed in the literature. The IAPWS95 EoS provides good agreement, although underestimates density by up to 1.2% at 7 GPa and 673 K and the thermodynamic properties deviate greatly (10%-20%) outside the estimated uncertainties above 4 GPa. The refractive index n of liquid water increases linearly with density and do not depend intrinsically on temperature. The polarizability decreases with pressure by less than 4% within the investigated P-T range, suggesting strong intermolecular interactions in H(2)O that are consistent with the prevalence of the hydrogen bond network in the fluid. The results will allow the refinement of interaction potentials that consider polarization effects for a better understanding of solvent-solvent and ion-solvent interactions in aqueous fluids at high pressure and temperature conditions.