Acoustic properties, elasticity, and equation of state of glycerol under pressure.

We employed high-pressure Brillouin scattering to study the pressure dependencies of acoustic modes of glycerol up to 14 GPa at 300 K. We observed longitudinal acoustic velocities and transverse acoustic velocities for the first time from 5 to 14 GPa. The results allow the determination of a complete set of elastic properties and an accurate determination of the pressure-volume (P-V) equation of state (EOS). EOS parameters, K0 = 14.9 ± 1.8 GPa and K'0 = 5.6 ± 0.5, were determined from fits to the data from ambient pressure to 14 GPa. Direct volume measurements of the P-V EOS are consistent with those determined by Brillouin scattering. A deviation from a Cauchy-like relationship for elastic properties was observed, and the pressure dependencies of the photoelastic constants and relaxation times were documented from 5 to 14 GPa. These results have broad implications for glass-forming liquids, viscoelastic theory, and mode coupling theory.

P-V-T equation of state of boron carbide.

We report the P-V-T equation of state measurements of B4C to 50 GPa and approximately 2500 K in laser-heated diamond anvil cells. We obtain an ambient temperature, third-order Birch-Murnaghan fit to the P-V data that yields a bulk modulus K0 of 221(2) GPa and derivative, (dK/dP)0 of 3.3(1). These were used in fits with both a Mie-Grüneisen-Debye model and a temperature-dependent, Birch-Murnaghan equation of state that includes thermal pressure estimated by thermal expansion (α) and a temperature-dependent bulk modulus (dK0/dT). The ambient pressure thermal expansion coefficient (α0 + α1T), Grüneisen γ(V) = γ0(V/V0)q and volume-dependent Debye temperature, were used as input parameters for these fits and found to be sufficient to describe the data in the whole P-T range of this study. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Sound Velocity and Equation of State of Ballistic Gelatin by Brillouin Scattering.

Brillouin scattering spectroscopy with diamond anvil cells was used by measuring the pressure dependence of the sound-relevant polymer material, glass-forming liquid, and H2O (water and ice VII) velocities of the material from ambient pressure to 12 GPa at room temperature. Measurements of 20%, 10%, and 4% gelatin solutions were performed. For comparison purposes, we also measured the pressure dependence of the sound velocity of animal tissue up to 10 GPa. We analyzed the Brillouin data using the Tait and Vinet equations of state. We discussed the possible influence of frequency dispersion on bulk modulus at low pressure. We compared the elastic moduli obtained for gelatin to those of several other polymers.

X-ray diffraction and equation of state of the C-S-H room-temperature superconductor.

X-ray diffraction indicates that the structure of the recently discovered carbonaceous sulfur hydride (C-S-H) room-temperature superconductor is derived from previously established van der Waals compounds found in the H2S-H2 and CH4-H2 systems. Crystals of the superconducting phase were produced by a photochemical synthesis technique, leading to the superconducting critical temperature Tc of 288 K at 267 GPa. X-ray diffraction patterns measured from 124 to 178 GPa, within the pressure range of the superconducting phase, are consistent with an orthorhombic structure derived from the Al2Cu-type determined for (H2S)2H2 and (CH4)2H2 that differs from those predicted and observed for the S-H system at these pressures. The formation and stability of the C-S-H compound can be understood in terms of the close similarity in effective volumes of the H2S and CH4 components, and denser carbon-bearing S-H phases may form at higher pressures. The results are crucial for understanding the very high superconducting Tc found in the C-S-H system at megabar pressures.

Evidence for Superconductivity above 260 K in Lanthanum Superhydride at Megabar Pressures.

Recent predictions and experimental observations of high T_{c} superconductivity in hydrogen-rich materials at very high pressures are driving the search for superconductivity in the vicinity of room temperature. We have developed a novel preparation technique that is optimally suited for megabar pressure syntheses of superhydrides using modulated laser heating while maintaining the integrity of sample-probe contacts for electrical transport measurements to 200 GPa. We detail the synthesis and characterization of lanthanum superhydride samples, including four-probe electrical transport measurements that display significant drops in resistivity on cooling up to 260 K and 180-200 GPa, and resistivity transitions at both lower and higher temperatures in other experiments. Additional current-voltage measurements, critical current estimates, and low-temperature x-ray diffraction are also obtained. We suggest that the transitions represent signatures of superconductivity to near room temperature in phases of lanthanum superhydride, in good agreement with density functional structure search and BCS theory calculations.

New high-pressure tetragonal polymorphs of SrTiO3-molecular orbital and Raman band change under pressure.

The vibrational and structural properties of SrTiO3 were investigated using Raman spectroscopy, synchrotron x-ray powder diffraction up to 55 GPa at 300 K, and ab initio quantum chemical molecular orbital (MO) calculations. These measurements and calculations revealed the structure transformation from cubic to tetragonal phase at about 9 GPa. Above 9 GPa, sharper new peaks were associated with a tetragonal structure. At about 30 GPa some bands disappeared and several new bands emerged. Structure transformation from I4/mcm to a new structure of P4/mbm was found at above 30 GPa by Rietveld profile fitting analysis. The diffraction pattern gave no indication of a Cmcm orthorhombic phase. Ab initio MO calculation proved the change of the molecular orbital coupling with a structure transformation. The Mulliken charge of Ti is increased with increasing pressure in the cubic phase, but the Sr charge continuously decreased. The d-p-π hybridization of the Ti-O bond and localizing the electron density are decreased with increasing pressure. The Ti-O bond becomes shorted in the P4/mbm phase and the change in the Ti charge accelerated more. All present investigations by x-ray diffraction, Raman spectra study and MO calculation show consistent results.

Synthesis and Stability of Lanthanum Superhydrides.

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1 Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.

Pressure Dependence of the Boson Peak of Glassy Glycerol.

The pressure dependence of the boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency νBP is proportional to (1+P/P0)1/3, where P and P0 are the pressure and a constant, respectively, consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, as predicted by the medium range order of a BP excitation using molecular dynamics simulations, and the pressure dependence of a characteristic medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers persisting to at least 11 GPa. Pressure dependence of the intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distances gradually decrease up to the glass transition pressure of ∼5 GPa and become nearly constant in the glassy state, indicating the disappearance of free volume in the dense glass.

High-pressure measurements of hydrogen phase IV using synchrotron infrared spectroscopy.

Phase IV of dense solid hydrogen has been identified by its infrared spectrum using high-pressure synchrotron radiation techniques. The spectrum exhibits a sharp vibron band at higher frequency and lower intensity than that for phase III, indicating the stability of molecular H(2) with decreased intermolecular interactions and charge transfer between molecules. A low-frequency vibron having a strong negative pressure shift indicative of strongly interacting molecules is also observed. The character of the spectrum is consistent with an anisotropic, mixed layer structure related to those recently predicted theoretically. Phase IV was found to be stable from 220 GPa (300 K) to at least 340 GPa (near 200 K), with the I-III-IV triple point located. Infrared transmission observed to the lowest photon energies measured places constraints on the electronic properties of the phase.

Density dependence of dynamical heterogeneity in fluid methanol.

Brillouin and Raman scattering experiments on methanol through its glass transition under pressure are reported. The Brillouin scattering data were analyzed using viscoelastic theory and a fit to the Vinet equation of state. The variation in the linewidth of the longitudinal acoustic mode with pressure shows a broad maximum centered around 3 GPa. The pressure evolution of the relaxation time in the GHz range is obtained, and the Raman data are analyzed in terms of the Boson peak and its associated relaxation time in the THz range. The pressure evolution of these two relaxation processes extends previous determinations of relaxations at lower frequency based on dielectric measurements in supercooled methanol. The relaxation processes in glass-forming methanol have now been investigated over a wide frequency range and their evolution followed over a large variation of density.

Probing the different spatial scales of Kel F-800 polymeric glass under pressure.

One of the fundamental open questions in condensed matter science is the origin of the unique universal characteristics of glasses. Among them, the Boson peak (BP) and the first sharp diffraction peak (FSDP) are directly related with the disordered nature of these solids. The lack of widely accepted understanding of the origin of these features makes the characterization of glass forming systems on the microscopic level challenging. Moreover a strong and open debate exists on the possible correlation between BP and FSDP and its origin. Here we present the first detailed concomitant Raman and x-ray diffraction study of these two features under hydrostatic pressure. Surprisingly, we find that the previously proposed correlations between the positions of BP and FSDP do not hold under pressure. Based on the anticorrelation of the characteristic dimensions, we conclude that, BP and FSDP probe different spatial scales corresponding to dynamical and structural dimensions, respectively.

Acoustic properties of Kel F-800 copolymer up to 85 GPa.

Acoustic properties of the fluorinated copolymer Kel F-800 were determined with Brillouin spectroscopy up to pressures of 85 GPa at 300 K. This research addresses outstanding issues in high-pressure polymer behavior, as to date the acoustic properties and equation of state of any polymer have not been determined above 20 GPa. We observed both longitudinal and transverse modes in all pressure domains, allowing us to calculate the C(11) and C(12) moduli, bulk, shear, and Young's moduli, and the density of Kel F-800 as a function of pressure. We found the behavior of the polymer with respect to all parameters to change drastically with pressure. As a result, we find that the data are best understood when split into two pressure regimes. At low pressures (less than ∼5 GPa), analysis of the room temperature isotherm with a semi-empirical equation of state yielded a zero-pressure bulk modulus K(o) and its derivative K(0) (') of 12.8 ± 0.8 GPa and 9.6 ± 0.7, respectively. The same analysis for the higher pressure data yielded values for K(o) and K(0) (') of 34.9 ± 1.7 GPa and 5.1 ± 0.1, respectively. We discuss this significant difference in behavior with reference to the concept of effective free volume collapse.

Brillouin scattering of H2O ice to megabar pressures.

The sound velocity in polycrystalline ice was measured as a function of pressure at room temperature to 100 GPa, through the phase field of ice VII and crossing the ice X transition, by Brillouin scattering in order to examine the elasticity, compression mechanism, and structural transitions in this pressure range. In particular, we focused on previously proposed phase transitions below 60 GPa. Throughout this pressure range, we find no evidence for anomalous changes in compressibility, and the sound velocities and elastic moduli do not exhibit measurable discontinuous shifts with pressure. Subtle changes in the pressure dependence of the bulk modulus at intermediate pressures can be attributed to high shear stresses at these compressions. The C(11) and C(12) moduli are consistent with previously reported results to 40 GPa and increase monotonically at higher pressures.

Origin of morphotropic phase boundaries in ferroelectrics.

A piezoelectric material is one that generates a voltage in response to a mechanical strain (and vice versa). The most useful piezoelectric materials display a transition region in their composition phase diagrams, known as a morphotropic phase boundary, where the crystal structure changes abruptly and the electromechanical properties are maximal. As a result, modern piezoelectric materials for technological applications are usually complex, engineered, solid solutions, which complicates their manufacture as well as introducing complexity in the study of the microscopic origins of their properties. Here we show that even a pure compound, in this case lead titanate, can display a morphotropic phase boundary under pressure. The results are consistent with first-principles theoretical predictions, but show a richer phase diagram than anticipated; moreover, the predicted electromechanical coupling at the transition is larger than any known. Our results show that the high electromechanical coupling in solid solutions with lead titanate is due to tuning of the high-pressure morphotropic phase boundary in pure lead titanate to ambient pressure. We also find that complex microstructures or compositions are not necessary to obtain strong piezoelectricity. This opens the door to the possible discovery of high-performance, pure-compound electromechanical materials, which could greatly decrease costs and expand the utility of piezoelectric materials.

Pressure-induced metallization of silane.

There is a great interest in electronic transitions in hydrogen-rich materials under extreme conditions. It has been recently suggested that the group IVa hydrides such as methane (CH(4)), silane (SiH(4)), and germane (GeH(4)) become metallic at far lower pressures than pure hydrogen at equivalent densities because the hydrogen is chemically compressed in group IVa hydride compounds. Here we report measurements of Raman and infrared spectra of silane under pressure. We find that SiH(4) undergoes three phase transitions before becoming opaque at 27-30 GPa. The vibrational spectra indicate the material transforms to a polymeric (framework) structure in this higher pressure range. Room-temperature infrared reflectivity data reveal that the material exhibits Drude-like metallic behavior above 60 GPa, indicating the onset of pressure-induced metallization.

Brillouin-scattering determination of the acoustic properties and their pressure dependence for three polymeric elastomers.

The acoustic properties of three polymer elastomers, a cross-linked poly(dimethylsiloxane) (Sylgard 184), a cross-linked terpolymer poly(ethylene-vinyl acetate-vinyl alcohol), and a segmented thermoplastic poly(ester urethane) copolymer (Estane 5703), have been measured from ambient pressure to approximately 12 GPa by using Brillouin scattering in high-pressure diamond anvil cells. The Brillouin-scattering technique is a powerful tool for aiding in the determination of equations of state for a variety of materials, but to date has not been applied to polymers at pressures exceeding a few kilobars. For the three elastomers, both transverse and longitudinal acoustic modes were observed, though the transverse modes were observed only at elevated pressures (>0.7 GPa) in all cases. From the Brillouin frequency shifts, longitudinal and transverse sound speeds were calculated, as were the C(11) and C(12) elastic constants, bulk, shear, and Young's moduli, and Poisson's ratios, and their respective pressure dependencies. P-V isotherms were then constructed, and fit to several empirical/semiempirical equations of state to extract the isothermal bulk modulus and its pressure derivative for each material. Finally, the lack of shear waves observed for any polymer at ambient pressure, and the pressure dependency of their appearance is discussed with regard to instrumental and material considerations.

High-pressure Brillouin scattering of amorphous BeH2.

High-pressure micro-Brillouin scattering is employed to investigate the pressure dependence of the sound velocity, refractive index, equation of state, and mechanical properties of amorphous BeH2. The refractive index n has been determined by using two scattering geometries (70 degrees and 180 degrees). The equation of state is deduced from the pressure dependences of the sound velocity. The bulk modulus is 14.2 (+/-3.0) GPa and its pressure derivative is 5.3 (+/-0.5). The polarizability is calculated from the refractive index and the density of the material. It increases with pressure while Poisson's ratio decreases with pressure.