26 Search Results

Synchrotron X-ray diffraction has been used to investigate the structure and equation of state (EOS) of hydrazine (N2H4) up to 54.3 GPa at 298 K. The diffraction patterns could be fit to a monoclinic unit-cell structure and put strong constraints on previously reported phase transitions documented by vibrational spectroscopy over this pressure range. Pressure-volume (P-V) data were fit using a Vinet EOS, yielding parameters: V 0 = 45.2 & Aring;3/molecule (fixed), K 0 = 11.8(7) GPa, and K 0 ' = 6.5(2). Previously measured high-pressure vibrational frequency shifts were used to estimate the vibrational free energy and model P-V-T isothermsmore » from 0 to 1200 K. The results of the P-V-T isotherms are compared to existing shock Hugoniot data on hydrazine and 298 K isotherms for assemblages of possible decomposition products. This comparison suggests dissociation at high density under shock loading. Good correspondence was found between the static lattice EOS as calculated by the model and the previously reported EOS as calculated by density functional theory. These results resolve existing uncertainties about the EOS and crystal symmetry of hydrazine at high pressure and provide valuable baseline information on this important energetic material.« less

At ambient conditions 3R-polytypes of transition metal dichalcogenides (TMDs) demonstrate fascinating properties because of their unique layer stacking. Understanding the structure-property relationship is essential for the realization of their use in spintronic, valleytronic, and optoelectronic applications. Herein, after the high pressure-temperature synthesis of 3R-MoS2 in a large volume cubic press, a concomitant experimental and theoretical high-pressure study of 3R-MoS2 is reported, leading to the discovery of pressure-induced reversible isostructural phase transitions without symmetry breaking. Concurrent with the isostructural transitions, a semiconductor-to-metal transition is observed, owing to strong interlayer interaction and charge redistribution across the van der Waals gap under pressure.more » The pressure-induced enhancement of interlayer interactions together with the robust intrinsic layer stacking in 3R-MoS2 prevent the layers from sliding under pressure and hinder a corresponding volume collapse. This study on continuous pressure-tuning of crystal and electronic structure in 3R-MoS2 will play a vital role in developing the next-generation devices involving coupling of structural, optical, and electrical properties of 3R-polytypes of TMDs and other layered materials.« less

Various metastable ice phases and their complicated transition pathways have been found by pressurization at low temperatures at which slow kinetics and high metastability are easily achieved. By contrast, such diversity is less expected at room or elevated temperatures. Here, using a combination of a dynamic diamond anvil cell and X-ray free electron laser techniques, we demonstrate that supercompressed water transforms into ice VI through multiple freezing–melting pathways at room temperature, hidden within the pressure region of ice VI. These multiple transition pathways occur via a metastable ice (more specifically, ice XXI with body-centred tetragonal structure ($$I\bar{4}2d$$)) discovered in thismore » study and a metastable ice VII that exists within the pressure range of ice VI. We find that supercompressed water structurally evolves from high-density water to very-high-density water, causing multiple transition pathways. These findings provide an insight to find more metastable ice phases and their transition pathways at elevated temperatures.« less

Gold is an unreactive metal and its chemical interactions with hydrogen have only recently been explored. Here, in this study, we report the formation of gold hydride above 40 GPa and 2200 K in X-ray free electron laser heated diamond anvil cells using various hydrocarbons as hydrogen sources. Above 40 GPa, a hexagonal phase emerges close to the gold melting point, corresponding to a hydride with stoichiometry Au₂H_x, with x increasing from 0 to near 1 with pressure from 40 to 80 GPa. This is a high-temperature phase which reverts to face centered cubic gold on cooling to 295 K.more » Accompanying DFT-MD simulations are in excellent agreement with experiment and reveal the structure to consist of an hexagonal close packed gold lattice with atomic hydrogen disordered in the interstices. The hydrogen is superionic and exhibits high diffusivity through the crystalline gold lattice. Our results present the first solid-state binary compound of gold and hydrogen.« less

The structural evolution of molecular hydrogen H₂ under multi-megabar compression and its relation to atomic metallic hydrogen is a key unsolved problem in condensed-matter physics. Although dozens of crystal structures have been proposed by theory, only one, the simple hexagonal-close-packed (hcp) structure of only spherical disordered H₂, has been previously confirmed in experiments. Through advancing nano-focused synchrotron X-ray probes, here we report the observation of the transition from hcp H₂ to a post-hcp structure with a six-fold larger supercell at pressures above 212 GPa, indicating the change of spherical H₂ to various ordered configurations. Theoretical calculations based on our XRDmore » results found a time-averaged structure model in the space group $$P\bar{6}2c$$ with alternating layers of spherically disordered H₂ and new graphene-like layers consisting of H₂ trimers (H₆) formed by the association of three H₂ molecules. Here, this supercell has not been reported by any previous theoretical study for the post-hcp phase, but is close to a number of theoretical models with mixed-layer structures. The evidence of a structural transition beyond hcp establishes the trend of H₂ molecular association towards polymerization at extreme pressures, giving clues about the nature of the molecular-to-atomic transition of metallic hydrogen. Considering the spectroscopic behaviours that show strong vibrational and bending peaks of H₂ up to 400 GPa, it would be prudent to speculate the continuation of hydrogen molecular polymerization up to its metallization.« less

Melting temperatures of materials at high-pressure are one of the key physical properties that can be measured. However, large discrepancies in high-pressure melt lines exist between different experimental and theoretical approaches. In this paper, we present a novel approach for melting determination at high pressure where time-resolved synchrotron X-ray phase contrast imaging is used to observe the solid to liquid phase transition in laser heated samples in the diamond anvil cell along with simultaneous X-ray diffraction. Optical radiometric temperature measurements are correlated with the observed phase boundaries determined from X-ray phase contrast images and structural information from X-ray diffraction patternsmore » to determine the melting temperature. We benchmarked this new technique with experiments on the high-pressure melting of platinum (Pt). Our new Pt melting results are compared with several recent studies on the high pressure melt line of Pt which utilized different techniques to determine melting. The technique can readily be applied to other materials and offers great potential for the determination of accurate and precise melting temperatures.« less

Pressure-induced polymorphism has recently been demonstrated in several high entropy alloys. This offers a new window into the much-debated issue of phase selection and stability in these systems. Here, we examine the effect of cryogenic temperatures on the pressure-induced transition from face centered cubic to hexagonal close-packed structures of the prototype CoCrFeMnNi (Cantor) alloy. We observe a reduction in the critical pressure for the onset of the polymorphic transition as the temperature decreases, confirming the progressive stabilization of the hexagonal phase with decreasing temperature previously predicted by ab initio calculations accounting for magnetic interactions. We argue that in situ high-pressuremore » experiments at cryogenic temperatures, which suppress time-dependent transformation triggered at higher temperatures, present a unique opportunity to significantly improve our understanding of these complex alloys.« less

Presented and discussed here is the implementation of a software solution that provides prompt X-ray diffraction data analysis during fast dynamic compression experiments conducted within the dynamic diamond anvil cell technique. It includes efficient data collection, streaming of data and metadata to a high-performance cluster (HPC), fast azimuthal data integration on the cluster, and tools for controlling the data processing steps and visualizing the data using the DIOPTAS software package. This data processing pipeline is invaluable for a great number of studies. The potential of the pipeline is illustrated with two examples of data collected on ammonia–water mixtures and multiphasemore » mineral assemblies under high pressure. The pipeline is designed to be generic in nature and could be readily adapted to provide rapid feedback for many other X-ray diffraction techniques, e.g. large-volume press studies, in situ stress/strain studies, phase transformation studies, chemical reactions studied with high-resolution diffraction etc.« less

Metal carbides are known to contain small carbon units similar to those found in the molecules of methane, acetylene, and allene. However, for numerous binary systems ab initio calculations predict the formation of unusual metal carbides with exotic polycarbon units, [C₆] rings, and graphitic carbon sheets at high pressure (HP). Here we report the synthesis and structural characterization of a HP-CaC₂ polymorph and a Ca₃C7 compound featuring deprotonated polyacene-like and para-poly(indenoindene)-like nanoribbons, respectively. We also demonstrate that carbides with infinite chains of fused [C6] rings can exist even at conditions of deep planetary interiors (~140 GPa and ~3300 K). Hydrolysismore » of high-pressure carbides may provide a possible abiotic route to polycyclic aromatic hydrocarbons in Universe.« less

The yttrium-hydrogen system has gained attention because of near-ambient temperature superconductivity reports in yttrium hydrides at high pressures. We conducted a study using synchrotron single-crystal x-ray diffraction (SCXRD) at 87 to 171 GPa, resulting in the discovery of known (two YH3 phases) and five previously unknown yttrium hydrides. These were synthesized in diamond anvil cells by laser heating yttrium with hydrogen-rich precursors—ammonia borane or paraffin oil. The arrangements of yttrium atoms in the crystal structures of new phases were determined on the basis of SCXRD, and the hydrogen content estimations based on empirical relations and ab initio calculations revealed themore » following compounds: Y₃H₁₁, Y₂H₉, Y₄H₂₃, Y₁₃H₇₅, and Y₄H₂₅. The study also uncovered a carbide (YC₂) and two yttrium allotropes. Complex phase diversity, variable hydrogen content in yttrium hydrides, and their metallic nature, as revealed by ab initio calculations, underline the challenges in identifying superconducting phases and understanding electronic transitions in high-pressure synthesized materials.« less