Search

We have developed a new all-optical method to directly measure the pressure-volume-temperature (PVT) equation of state (EOS) of fluids and transparent solids in the diamond anvil high pressure cell by measuring the volume of the sample chamber. Our method combines confocal microscopy and white light interference with a new analysis method which exploits the mutual dependence of sample density and refractive index: Experimentally, the refractive index determines the measured sample chamber thickness (and therefore the measured sample volume/density), yet the sample density is by far the dominant factor in determining the variation in refractive index with pressure. Our analysis method allows us to obtain a set of values for the density and refractive index which are mutually consistent, and agree with the experimental data within error. We have conducted proof-of-concept experiments on a variety of samples (H$_{2}$O, CH$_{4}$, C$_{2}$H$_{6}$, C$_{3}$H$_{8}$, KCl and NaCl) at ambient temperature, and at high temperatures up to just above 500 K. Our proof-of-concept data demonstrate that our method is able to reproduce known fluid and solid EOS within error. Furthermore, we demonstrate that our method allows us to directly and routinely measure the PVT EOS of simple fluids at GPa pressures up to, at least, 514 K (the highest temperature reached in our study). A reasonable estimation of the known sources of error in our volume determinations indicates that the error is currently $\pm$ 2.7% at high temperature, and that it is feasible to reduce it to ca. $\pm$ 1% in future work., Comment: Accepted for publication in Physics of Fluids

Physics-based first-principles pressure-volume-temperature equations of state (EOS) exist for solids and gases but not for liquids due to the long-standing fundamental problems involved in liquid theory. Current EOS models that are applicable to liquids and supercritical fluids at liquid-like density under conditions relevant to planetary interiors and industrial processes are complex empirical models with many physically meaningless adjustable parameters. Here, we develop a generally applicable physics-based (GAP) EOS for liquids including supercritical fluids at liquid-like density. The GAP equation is explicit in the internal energy, and hence links the most fundamental macroscopic static property of fluids, the pressure-volume-temperature EOS, to their key microscopic property: the molecular hopping frequency or liquid relaxation time, from which the internal energy can be obtained. We test our GAP equation against available experimental data in several different ways and find good agreement. Our GAP equation, unavoidably and similarly to solid EOS, contains a semi-empirical term giving the energy of the static sample as a function of volume only (E_ST(V)). Our testing includes studies along isochores, in order to examine the validity of the GAP equation independently of the validity of any function we may choose to utilize for E_ST(V). The only other adjustable parameter in the equation is the Gruneisen parameter for the fluid. We observe that the GAP equation is similar to the Mie-Gruneisen solid EOS in a wide range of the liquid phase diagram. This similarity is ultimately related to the condensed state of these two phases. On the other hand, the differences between the GAP equation and EOS for gases are fundamental. Finally, we identify the key gaps in the experimental data that need to be filled in to proceed further with the liquid EOS.

We have studied in detail the transition from gas-like to rigid liquid-like behaviour in supercritical $N_2$ at 300 K (2.4 $T_C$). Our study combines neutron diffraction and Raman spectroscopy with empirical potential structure refinement and ab-initio molecular dynamics simulations. We observe a narrow transition from gas-like to rigid liquid-like behaviour at ca. 150 MPa, which we associate with the Frenkel line. Our findings allow us to reliably characterize the Frenkel line using both diffraction and spectroscopy methods, backed up by simulation, for the same substance. We clearly lay out what parameters change, and what parameters do not change, when the Frenkel line is crossed., Comment: Accepted for J. Phys. Chem. Lett. on 8th October 2019

We report a combined experimental and theoretical study of the melting curve and the structural behavior of vanadium under extreme pressure and temperature. We performed powder x-ray diffraction experiments up to 120 GPa and 4000 K, determining the phase boundary of the bcc-to-rhombohedral transition and melting temperatures at different pressures. Melting temperatures have also been established from the observation of temperature plateaus during laser heating, and the results from the density-functional theory calculations. Results obtained from our experiments and calculations are fully consistent and lead to an accurate determination of the melting curve of vanadium. These results are discussed in comparison with previous studies. The melting temperatures determined in this study are higher than those previously obtained using the speckle method, but also considerably lower than those obtained from shock-wave experiments and linear muffin-tin orbital calculations. Finally, a high-pressure high-temperature equation of state up to 120 GPa and 2800 K has also been determined., Comment: 20 pages, 5 figures

The effect of pressure on the room temperature solubility of hydrogen in Zircaloy-4 was examined using synchrotron X-ray diffraction on small ground flake samples in a diamond anvil cell at pressures up to 20.9 GPa. Different combinations of hydrogen level/state in the sample and of pressure transmitting medium were examined; in all three cases examined, it could be concluded that pressure resulted in the dissolution of d hydrides and that interstitial hydrogen retards the formation of w Zr. A pressure of around 9 GPa was required to halve the hydride fraction. These results imply that the effect of pressure is thermodynamically analogous to that of increasing temperature, but that the effect is small. The results are consistent with the volume per Zr atom of the a, d and w phases, with the bulk moduli of a and d, and with previous measurements of the hydrogen site molar volumes in the a and d phases. The results are interpreted in terms of their implication for our understanding of the driving forces for hydride precipitation at crack tips, which are in a region of hydrostatic tensile stress on the order of 1.5 GPa., Comment: Updated in response to reviewer comments; results identical but discussion elaborated on some points. Accepted for publication in J. Nuclear Materials, 11 Jul 2019

We report experimental evidence for a crossover between a liquid-like state and a gas-like state in fluid methane (CH4). This crossover is observed in all of our experiments, up to 397 K temperature; 2.1 times the critical temperature of methane. The crossover has been characterized with both Raman spectroscopy and X-ray diffraction in a number of separate experiments, and confirmed to be reversible. We associate this crossover with the Frenkel line - a recently hypothesized crossover in dynamic properties of fluids extending to arbitrarily high pressure and temperature, dividing the phase diagram into separate regions where the fluid possesses liquid-like and gas-like properties. On the liquid-like side the Raman-active vibration increases in frequency linearly as pressure is increased, as expected due to the repulsive interaction between adjacent molecules. On the gas-like side this competes with the attractive Van der Waals potential leading the vibration frequency to decrease as pressure is increased., Comment: Uploaded version with higher resolution figures on 23/10/17. Accepted in Physical Review E

We report a high-pressure study of monoclinic monazite-type SrCrO4 up to 26 GPa. Therein we combined x-ray diffraction, Raman and optical-absorption measurements with ab initio calculations, to find a pressure-induced structural phase transition of SrCrO4 near 8-9 GPa. Evidence of a second phase transition was observed at 10-13 GPa. The crystal structures of the high-pressure phases were assigned to the tetragonal scheelite-type and monoclinic AgMnO4-type structures. Both transitions produce drastic changes in the electronic band gap and phonon spectrum of SrCrO4. We determined the pressure evolution of the band gap for the low-pressure and high-pressure phases as well as the frequencies and pressure dependences of the Raman-active modes. In all three phases most Raman modes harden under compression; however the presence of low-frequency modes which gradually soften is also detected. In monazite-type SrCrO4, the band gap blue-shifts under compression, but the transition to the scheelite phase causes an abrupt decrease of the band gap in SrCrO4. Calculations showed good agreement with experiments and were used to better understand the experimental results. From x-ray diffraction studies and calculations we determined the pressure dependence of the unit-cell parameters of the different phases and their ambient-temperature equations of state. The results are compared with the high-pressure behavior of other monazites, in particular PbCrO4. A comparison of the high-pressure behavior of the electronic properties of SrCrO4 (SrWO4) and PbCrO4 (PbWO4) will also be made. Finally, the possible occurrence of a third structural phase transition is discussed., Comment: 41 pages, 9 figures, 7 tables

In a recent publication (D. Bolmatov et al. Sci.Rep. 5, 15850 (2015)) the experimental observation of structural transformations on crossing the Frenkel line in supercritical argon is claimed. Here we show that no experimental evidence of the structural transformation was presented. The reported experimental observations which Bolmatov et al. claim as evidence of a transition across the Frenkel line are instead due to the irregularity of the experimental (P,T) path in their work.

The goal of compressive sensing is efficient reconstruction of data from few measurements, sometimes leading to a categorical decision. If only classification is required, reconstruction can be circumvented and the measurements needed are orders-of-magnitude sparser still. We define enhanced sparsity as the reduction in number of measurements required for classification over reconstruction. In this work, we exploit enhanced sparsity and learn spatial sensor locations that optimally inform a categorical decision. The algorithm solves an l1-minimization to find the fewest entries of the full measurement vector that exactly reconstruct the discriminant vector in feature space. Once the sensor locations have been identified from the training data, subsequent test samples are classified with remarkable efficiency, achieving performance comparable to that obtained by discrimination using the full image. Sensor locations may be learned from full images, or from a random subsample of pixels. For classification between more than two categories, we introduce a coupling parameter whose value tunes the number of sensors selected, trading accuracy for economy. We demonstrate the algorithm on example datasets from image recognition using PCA for feature extraction and LDA for discrimination; however, the method can be broadly applied to non-image data and adapted to work with other methods for feature extraction and discrimination., Comment: 13 pages, 11 figures

Studies of the mechanical properties of single-walled carbon nanotubes are hindered by the availability only of ensembles of tubes with a range of diameters. Tunable Raman excitation spectroscopy picks out identifiable tubes. Under high pressure, the radial breathing mode shows a strong environmental effect shown here to be largely independent of the nature of the environment . For the G-mode, the pressure coefficient varies with diameter consistent with the thick-wall tube model. However, results show an unexpectedly strong environmental effect on the pressure coefficients. Reappraisal of data for graphene and graphite gives the G-mode Grueuneisen parameter gamma = 1.34 and the shear deformation parameter beta = 1.34., Comment: Submitted to Physical Review B