Early crystallization of amorphous selenium under high pressure studied by synchrotron XRD method.

The amorphous selenium (a-Se) was studied via x-ray diffraction (XRD) under pressures ranging from ambient pressure up to 30 GPa at room temperature to study its high-pressure behavior. Two compressional experiments on a-Se samples, with and without heat treatment, respectively, were conducted. Contrary to the previous reports that a-Se crystallized abruptly at around 12 GPa, in this work we report an early partially crystallized state at 4.9 GPa before completing the crystallization at around 9.5 GPa based onin-situhigh pressure XRD measurements on the a-Se with 70 °C heat treatment. In comparison, crystallization pressure on another a-Se sample without thermal treatment history was observed to be 12.7 GPa, consistent with the previously reported crystallization pressure. Thus, it is proposed in this work that prior heat treatment of a-Se can result in an earlier crystallization under high pressure, which helps to understand the possible mechanism caused by the previous controversial reports on pressure induced crystallization behavior in a-Se.

Superconductivity above 200 K discovered in superhydrides of calcium.

Searching for superconductivity with Tc near room temperature is of great interest both for fundamental science & many potential applications. Here we report the experimental discovery of superconductivity with maximum critical temperature (Tc) above 210 K in calcium superhydrides, the new alkali earth hydrides experimentally showing superconductivity above 200 K in addition to sulfur hydride & rare-earth hydride system. The materials are synthesized at the synergetic conditions of 160~190 GPa and ~2000 K using diamond anvil cell combined with in-situ laser heating technique. The superconductivity was studied through in-situ high pressure electric conductance measurements in an applied magnetic field for the sample quenched from high temperature while maintained at high pressures. The upper critical field Hc(0) was estimated to be ~268 T while the GL coherent length is ~11 Å. The in-situ synchrotron X-ray diffraction measurements suggest that the synthesized calcium hydrides are primarily composed of CaH6 while there may also exist other calcium hydrides with different hydrogen contents.

Single-crystal Brillouin spectroscopy with CO2 laser heating and variable q.

We describe a Brillouin spectroscopy system integrated with CO2 laser-heating and Raman spectroscopic capabilities. Temperature is determined by measurements of the grey-body thermal radiation emitted by the hot sample, with the system response calibrated relative to a standard tungsten ribbon lamp. High-pressure laser-heating Brillouin scattering measurements of acoustic velocities on liquid water and ice compressed in a diamond-anvil cell were performed at temperatures up to 2500 ± 150 K at high pressure. Single-crystal laser-heating Brillouin measurements were made on the (111) plane of San Carlos olivine at ∼13 GPa, 1300 ± 200 K. The pressure as measured by ruby fluorescence is shown to be within ±0.5 GPa of the pressure on the olivine sample during laser heating when KCl and KBr are used as pressure-transmitting media. In addition, the system is designed for continuously variable scattering angles from forward scattering (near 0° scattering angle) up to near back scattering (∼141°). This novel setup allows us to probe a wide range of wave vectors q for investigation of phonon dispersion on, for example, crystals with large unit cells (on the scale of hundreds of nm).

Anisotropic lattice expansion of three-dimensional colloidal crystals and its impact on hypersonic phonon band gaps.

We report anisotropic expansion of self-assembled colloidal polystyrene-poly(dimethylsiloxane) crystals and its impact on the phonon band structure at hypersonic frequencies. The structural expansion was achieved by a multistep infiltration-polymerization process. Such a process expands the interplanar lattice distance 17% after 8 cycles whereas the in-plane distance remains unaffected. The variation of hypersonic phonon band structure induced by the anisotropic lattice expansion was recorded by Brillouin measurements. In the sample before expansion, a phononic band gap between 3.7 and 4.4 GHz is observed; after 17% structural expansion, the gap is shifted to a lower frequency between 3.5 and 4.0 GHz. This study offers a facile approach to control the macroscopic structure of colloidal crystals with great potential in designing tunable phononic devices.

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.

Evidence of denser MgSiO3 glass above 133 gigapascal (GPa) and implications for remnants of ultradense silicate melt from a deep magma ocean.

Ultralow velocity zones are the largest seismic anomalies in the mantle, with 10-30% seismic velocity reduction observed in thin layers less than 20-40 km thick, just above the Earth's core-mantle boundary (CMB). The presence of silicate melts, possibly a remnant of a deep magma ocean in the early Earth, have been proposed to explain ultralow velocity zones. It is, however, still an open question as to whether such silicate melts are gravitationally stable at the pressure conditions above the CMB. Fe enrichment is usually invoked to explain why melts would remain at the CMB, but this has not been substantiated experimentally. Here we report in situ high-pressure acoustic velocity measurements that suggest a new transformation to a denser structure of MgSiO(3) glass at pressures close to those of the CMB. The result suggests that MgSiO(3) melt is likely to become denser than crystalline MgSiO(3) above the CMB. The presence of negatively buoyant and gravitationally stable silicate melts at the bottom of the mantle, would provide a mechanism for observed ultralow seismic velocities above the CMB without enrichment of Fe in the melt. An ultradense melt phase and its geochemical inventory would be isolated from overlying convective flow over geologic time.

Spectroscopic evidence for ultrahigh-pressure polymorphism in SiO2 glass.

Acoustic wave velocities of SiO2 glass were measured up to pressures of 207 GPa using newly developed Brillouin scattering spectroscopic techniques to address the nature of pressure-induced structural changes. The acoustic wave velocity data suggests three distinct pressure regimes, two of which correspond to changes in the Si-O coordination number with pressure, and one of which indicates the stability of sixfold-coordinated Si over a broad pressure interval from approximately 40-140 GPa. An anomalous increase in the effect of pressure on velocity at 140 GPa most likely corresponds to the onset of structural densification associated with an increase in coordination number from sixfold to a higher coordination state.

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 Poisson's 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 Poisson's 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.

The post-stishovite phase transition in hydrous alumina-bearing SiO2 in the lower mantle of the earth.

Silica is the most abundant oxide component in the Earth mantle by weight, and stishovite, the rutile-structured (P4(2)/mnm) high-pressure phase with silica in six coordination by oxygen, is one of the main constituents of the basaltic layer of subducting slabs. It may also be present as a free phase in the lower mantle and at the core-mantle boundary. Pure stishovite undergoes a displacive phase transition to the CaCl(2) structure (Pnnm) at approximately 55 GPa. Theory suggests that this transition is associated with softening of the shear modulus that could provide a significant seismic signature, but none has ever been observed in the Earth. However, stishovite in natural rocks is expected to contain up to 5 wt % Al(2)O(3) and possibly water. Here we report the acoustic velocities, densities, and Raman frequencies of aluminum- and hydrogen-bearing stishovite with a composition close to that expected in the Earth mantle at pressures up to 43.8(3) GPa [where (3) indicates an uncertainty of 0.3 GPa]. The post-stishovite phase transition occurs at 24.3(5) GPa (at 298 K), far lower than for pure silica at 50-60 GPa. Our results suggest that the rutile-CaCl(2) transition in natural stishovite (with 5 wt % Al(2)O(3)) should occur at approximately 30 GPa or approximately 1,000-km depth at mantle temperatures. The major changes in elastic properties across this transition could make it visible in seismic profiles and may be responsible for seismic reflectors observed at 1,000- to 1,400-km depth.

Spectroscopic evidence of polymorphism in vitreous B2O3.

Brillouin and Raman spectroscopy were performed on B2O3 glass compressed to 57 GPa at 273 K. Upon compression the sound velocities increase smoothly and the boroxol ring Raman mode vanishes by 11 GPa. Upon decompression the sound velocities follow a different path and at 3 GPa a discontinuity of 3 km/s in V(p) and 2 km/s in V(s) returns the velocities to the values seen on compression. After the transition, the boroxol ring Raman mode reappears. A second pressure cycle produces the same behavior, suggesting the 3 GPa transition occurs between vitreous polymorphs with different boron coordination.