A MHz X-ray diffraction set-up for dynamic compression experiments in the diamond anvil cell.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s-1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s-1 was observed during the fast compression of Au, while a strain rate of ∼1100 s-1 was achieved during the rapid compression of N2 at 23 TPa s-1.

Laser heating system at the Extreme Conditions Beamline, P02.2, PETRA III.

A laser heating system for samples confined in diamond anvil cells paired with in situ X-ray diffraction measurements at the Extreme Conditions Beamline of PETRA III is presented. The system features two independent laser configurations (on-axis and off-axis of the X-ray path) allowing for a broad range of experiments using different designs of diamond anvil cells. The power of the continuous laser source can be modulated for use in various pulsed laser heating or flash heating applications. An example of such an application is illustrated here on the melting curve of iron at megabar pressures. The optical path of the spectroradiometry measurements is simulated with ray-tracing methods in order to assess the level of present aberrations in the system and the results are compared with other systems, that are using simpler lens optics. Based on the ray-tracing the choice of the first achromatic lens and other aspects for accurate temperature measurements are evaluated.

Automated pipeline processing X-ray diffraction data from dynamic compression experiments on the Extreme Conditions Beamline of PETRA III.

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 multiphase 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.

Oxidation of iron by giant impact and its implication on the formation of reduced atmosphere in the early Earth.

Giant impact-driven redox processes in the atmosphere and magma ocean played crucial roles in the evolution of Earth. However, because of the absence of rock records from that time, understanding these processes has proven challenging. Here, we present experimental results that simulate the giant impact-driven reactions between iron and volatiles (H2O and CO2) using x-ray free electron laser (XFEL) as fast heat pump and structural probe. Under XFEL pump, iron is oxidized to wüstite (FeO), while volatiles are reduced to H2 and CO. Furthermore, iron oxidation proceeds into formation of hydrides (γ-FeHx) and siderite (FeCO3), implying redox boundary near 300-km depth. Through quantitative analysis on reaction products, we estimate the volatile and FeO budgets in bulk silicate Earth, supporting the Theia hypothesis. Our findings shed light on the fast and short-lived process that led to reduced atmosphere, required for the emergence of prebiotic organic molecules in the early Earth.

Dynamic compression of Ce and Pr with millisecond time-resolved X-ray diffraction.

Both cerium (Ce) and praseodymium (Pr) undergo a volume collapse transition under compression that originate from similar electronic mechanisms. Yet the outcome could not be more different. In the case of Ce with one affected 4f electron the volume collapse leaves the crystal symmetry intact, whereas for Pr with two 4f electrons the crystal symmetry changes from a distorted face centered cubic structure to a lower symmetry orthorhombic structure. In this paper, we present a study of the effect of strain/compression rate spanning nearly 4 orders of magnitude on the volume collapse phase transitions in Ce and Pr. These dynamic compression experiments in a diamond anvil cell also reveal kinetic differences between the phase transformations observed in these two materials. The transition cannot be overdriven in pressure in Ce, which indicates a fast kinetic process, whereas fast compression rates in Pr lead to a shift of the phase boundary to higher pressures, pointing to slower kinetics possibly due to the realization of a new crystal structure.

Compression-rate dependence of pressure-induced phase transitions in Bi.

It is qualitatively well known that kinetics related to nucleation and growth can shift apparent phase boundaries from their equilibrium value. In this work, we have measured this effect in Bi using time-resolved X-ray diffraction with unprecedented 0.25 ms time resolution, accurately determining phase transition pressures at compression rates spanning five orders of magnitude (10-2-103 GPa/s) using the dynamic diamond anvil cell. An over-pressurization of the Bi-III/Bi-V phase boundary is observed at fast compression rates for different sample types and stress states, and the largest over-pressurization that is observed is ΔP = 2.5 GPa. The work presented here paves the way for future studies of transition kinetics at previously inaccessible compression rates.

X-ray Free Electron Laser-Induced Synthesis of ε-Iron Nitride at High Pressures.

The ultrafast synthesis of ε-Fe3N1+x in a diamond-anvil cell (DAC) from Fe and N2 under pressure was observed using serial exposures of an X-ray free electron laser (XFEL). When the sample at 5 GPa was irradiated by a pulse train separated by 443 ns, the estimated sample temperature at the delay time was above 1400 K, confirmed by in situ transformation of α- to γ-iron. Ultimately, the Fe and N2 reacted uniformly throughout the beam path to form Fe3N1.33, as deduced from its established equation of state (EOS). We thus demonstrate that the activation energy provided by intense X-ray exposures in an XFEL can be coupled with the source time structure to enable exploration of the time-dependence of reactions under high-pressure conditions.

Intense Reactivity in Sulfur-Hydrogen Mixtures at High Pressure under X-ray Irradiation.

Superconductivity near room temperature in the sulfur-hydrogen system arises from a sequence of reactions at high pressures, with X-ray diffraction experiments playing a central role in understanding these chemical-structural transformations and the corresponding S:H stoichiometry. Here we document X-ray irradiation acting as both a probe and as a driver of chemical reaction in this dense hydride system. We observe a reaction between molecular hydrogen (H2) and elemental sulfur (S8) under high pressure, induced directly by X-ray illumination, at photon energies of 12 keV using a free electron laser. The rapid synthesis of hydrogen sulfide (H2S) at 0.3 GPa was confirmed by optical observations, spectroscopic measurements, and microstructural changes detected by X-ray diffraction. These results document X-ray induced chemical synthesis of superconductor-forming dense hydrides, revealing an alternative production strategy and confirming the disruptive nature of X-ray exposure in studies on high-pressure hydrogen chalcogenides, from water to high-temperature superconductors.

Distortions in the cubic primitive high-pressure phases of calcium.

The superconductivity in highly compressed calcium involves the occurrence of closely related low-symmetry structural patterns with an exceptionally low coordination number. Earlier theoretical and experimental results are controversial and some findings are inconsistent with our later observations in the pressure range up to 60 GPa. This situation motivated the present concerted computational and experimental re-investigation of the structural arrangement of calcium slightly above the high-pressure limit of the bcc arrangement at low-temperatures. We report here reproducible experimental evidence for a monoclinic distortion (mC4, space group C2/c) of the calcium polymorph previously assigned to the tetragonal ß-Sn structure type. In accordance, the enthalpies calculated by electronic band structure calculations show the mC4 phase to be more stable than the undistorted ß-Sn type by about 100 meV in the entire phase space. The other low-temperature phase of calcium adopts space group Cmcm (oC4) rather than the earlier assigned Cmmm symmetry. These structural alterations substantially effect the density of states at the Fermi level and, thus, the electronic properties.