Simultaneous bright- and dark-field X-ray microscopy at X-ray free electron lasers.

The structures, strain fields, and defect distributions in solid materials underlie the mechanical and physical properties across numerous applications. Many modern microstructural microscopy tools characterize crystal grains, domains and defects required to map lattice distortions or deformation, but are limited to studies of the (near) surface. Generally speaking, such tools cannot probe the structural dynamics in a way that is representative of bulk behavior. Synchrotron X-ray diffraction based imaging has long mapped the deeply embedded structural elements, and with enhanced resolution, dark field X-ray microscopy (DFXM) can now map those features with the requisite nm-resolution. However, these techniques still suffer from the required integration times due to limitations from the source and optics. This work extends DFXM to X-ray free electron lasers, showing how the [Formula: see text] photons per pulse available at these sources offer structural characterization down to 100 fs resolution (orders of magnitude faster than current synchrotron images). We introduce the XFEL DFXM setup with simultaneous bright field microscopy to probe density changes within the same volume. This work presents a comprehensive guide to the multi-modal ultrafast high-resolution X-ray microscope that we constructed and tested at two XFELs, and shows initial data demonstrating two timing strategies to study associated reversible or irreversible lattice dynamics.

X-ray free electron laser observation of ultrafast lattice behaviour under femtosecond laser-driven shock compression in iron.

Over the past century, understanding the nature of shock compression of condensed matter has been a major topic. About 20 years ago, a femtosecond laser emerged as a new shock-driver. Unlike conventional shock waves, a femtosecond laser-driven shock wave creates unique microstructures in materials. Therefore, the properties of this shock wave may be different from those of conventional shock waves. However, the lattice behaviour under femtosecond laser-driven shock compression has never been elucidated. Here we report the ultrafast lattice behaviour in iron shocked by direct irradiation of a femtosecond laser pulse, diagnosed using X-ray free electron laser diffraction. We found that the initial compression state caused by the femtosecond laser-driven shock wave is the same as that caused by conventional shock waves. We also found, for the first time experimentally, the temporal deviation of peaks of stress and strain waves predicted theoretically. Furthermore, the existence of a plastic wave peak between the stress and strain wave peaks is a new finding that has not been predicted even theoretically. Our findings will open up new avenues for designing novel materials that combine strength and toughness in a trade-off relationship.

First-Principles Calculations with Six Structures of Alkaline Earth Metal Cyanide A(CN)2 (A = Be, Mg, Ca, Sr, and Ba): Structural, Electrical, and Phonon Properties.

This work examines six structures (P4̅3m, P42 nm, R3m, P21/c, R3̅m, and C2/m) of alkaline earth metal cyanide A(CN)2 (A = Be, Mg, Ca, Sr, and Ba) using first-principles calculations. The symmetries of P4̅3m, P42 nm, and R3m reflect a variation of Pn3̅m, previously reported as occurring on Be(CN)2 and Mg(CN)2 in X-ray diffraction studies, while the symmetries of P21/c, R3̅m, and C2/m were selected from the P3̅m1 symmetry found using Mg(OH)2 as the initial structures, with -OH being replaced by -CN. The band structure, density of states, and phonon properties of all A(CN)2 structures were then investigated using density functional theory (DFT), with a generalized gradient approximation (GGA) applied for the exchange and correlation energy values. The simulation results for the phonon spectra indicate that the stable structures are Be(CN)2 (P4̅3m, P42 nm, and C2/m), Mg(CN)2 (P4̅3m, P42 nm, and C2/m), Ca(CN)2 (P21/c), Sr(CN)2 (P21/c and R3̅m), and Ba(CN)2 (R3̅m) at 0 GPa. For the effects of high pressure, Ca(CN)2 and Sr(CN)2 were thus found to be stable as C2/m at pressures above 10 and 3 GPa, respectively, while Ca(CN)2 is as stable as R3̅m above 15 GPa. In the calculated band structures, all of the compounds with the C2/m structure demonstrated good conductivity, while the other structures have a band gap range of 2.83-6.33 eV.

Formation of Novel Bimetal Oxide In2V2O7 through a Shock Compression Method.

Bimetal oxides with a chemical formula of A2B2O7 have received much attention from plenty of research groups owing to their outstanding properties, such as electronic, optical, and magnetic properties. Among the abundant element combinations of cations A and B, some theoretically predicted compounds have not successfully been synthesized in experiments, such as In2Zr2O7, In2V2O7, etc. In this study, a novel tetragonal pyrochlore-like In2V2O7 nanopowder has been reported for the first time. In2O3 and VO2 powders mixed through ball milling were reacted to form In2V2O7 by shockwave loading. The recovered sample is investigated to be nanocrystalline In2V2O7 powder through various techniques, such as X-ray diffraction, scanning electron microscopy, X-ray energy spectrum analysis, and transmission electron microscopy. The formed In2V2O7 is indexed as a tetragonal cell with a = b = 0.7417 nm and c = 2.1035 nm. Moreover, the formation mechanism of In2V2O7 through a shock synthesis process is carefully analyzed based on basic laws of shockwave. The experimental results also confirm that a high shock temperature and high shock pressure are the two key factors to synthesize the In2V2O7 nanopowder. Our investigation demonstrates the high potential application of a shock-induced reaction on the synthesis of novel materials, including the preparation of new bimetal oxides.

Ultrafast olivine-ringwoodite transformation during shock compression.

Meteorites from interplanetary space often include high-pressure polymorphs of their constituent minerals, which provide records of past hypervelocity collisions. These collisions were expected to occur between kilometre-sized asteroids, generating transient high-pressure states lasting for several seconds to facilitate mineral transformations across the relevant phase boundaries. However, their mechanisms in such a short timescale were never experimentally evaluated and remained speculative. Here, we show a nanosecond transformation mechanism yielding ringwoodite, which is the most typical high-pressure mineral in meteorites. An olivine crystal was shock-compressed by a focused high-power laser pulse, and the transformation was time-resolved by femtosecond diffractometry using an X-ray free electron laser. Our results show the formation of ringwoodite through a faster, diffusionless process, suggesting that ringwoodite can form from collisions between much smaller bodies, such as metre to submetre-sized asteroids, at common relative velocities. Even nominally unshocked meteorites could therefore contain signatures of high-pressure states from past collisions.

Experimental Investigation of the Formation of Formaldehyde by Hadean and Noachian Impacts.

Formaldehyde (FA) is an important precursor in the abiotic synthesis of major biomolecules including amino acids, sugars, and nucleobases. Thus, spontaneous formation of prebiotic FA must have been crucial for the chemical origin of life. The frequent impacts of meteorites and asteroids on Hadean Earth have been considered one of the abiotic synthetic processes of organic compounds. However, the impact-induced formation of FA from CO2 as the major atmospheric constituent has not been confirmed yet. This study investigated the formation of FA in impact-induced reactions among meteoritic minerals, bicarbonate, gaseous nitrogen, and water to simulate the abiotic process experimentally. Products were analyzed with ultra-high-performance liquid chromatography/tandem mass spectrometry and powder X-ray diffraction techniques. The results show the formation of FA and oxidation of metallic iron to siderite in the impact shock experiments. This indicates that this important prebiotic molecule was also synthesized by impacts of iron-bearing meteorites/asteroids on the Hadean oceans. The impact events might have generated spatially and temporally FA-enriched localized environments. Moreover, the impact-induced synthesis of FA may have also occurred on Noachian Mars given the presence of liquid water and a CO2-N2-rich atmosphere on the planet.

Shock Response of Full Density Nanopolycrystalline Diamond.

Hugoniot of full-dense nanopolycrystalline diamond (NPD) was investigated up to 1600 GPa. The Hugoniot elastic limit of NPD is 208 (±14) GPa, which is more than twice as high as that of single-crystal diamond. The Hugoniot of NPD is stiffer than that of single-crystal diamond up to 500 GPa, while no significant difference is observed at higher pressures where the elastic precursor is overdriven by a following plastic wave. These findings confirm that the grain boundary strengthening effect recognized in static compression experiments is also effective against high strain-rate dynamic compressions.

Impact-induced amino acid formation on Hadean Earth and Noachian Mars.

Abiotic synthesis of biomolecules is an essential step for the chemical origin of life. Many attempts have succeeded in synthesizing biomolecules, including amino acids and nucleobases (e.g., via spark discharge, impact shock, and hydrothermal heating), from reduced compounds that may have been limited in their availabilities on Hadean Earth and Noachian Mars. On the other hand, formation of amino-acids and nucleobases from CO2 and N2 (i.e., the most abundant C and N sources on Earth during the Hadean) has been limited via spark discharge. Here, we demonstrate the synthesis of amino acids by laboratory impact-induced reactions among simple inorganic mixtures: Fe, Ni, Mg2SiO4, H2O, CO2, and N2, by coupling the reduction of CO2, N2, and H2O with the oxidation of metallic Fe and Ni. These chemical processes simulated the possible reactions at impacts of Fe-bearing meteorites/asteroids on oceans with a CO2 and N2 atmosphere. The results indicate that hypervelocity impact was a source of amino acids on the Earth during the Hadean and potentially on Mars during the Noachian. Amino acids formed during such events could more readily polymerize in the next step of the chemical evolution, as impact events locally form amino acids at the impact sites.

Discovery of moganite in a lunar meteorite as a trace of H2O ice in the Moon's regolith.

Moganite, a monoclinic SiO2 phase, has been discovered in a lunar meteorite. Silica micrograins occur as nanocrystalline aggregates of mostly moganite and occasionally coesite and stishovite in the KREEP (high potassium, rare-earth element, and phosphorus)-like gabbroic-basaltic breccia NWA 2727, although these grains are seemingly absent in other lunar meteorites. We interpret the origin of these grains as follows: alkaline water delivery to the Moon via carbonaceous chondrite collisions, fluid capture during impact-induced brecciation, moganite precipitation from the captured H2O at pH 9.5 to 10.5 and 363 to 399 K on the sunlit surface, and meteorite launch from the Moon caused by an impact at 8 to 22 GPa and >673 K. On the subsurface, this captured H2O may still remain as ice at estimated bulk content of >0.6 weight %. This indicates the possibility of the presence of abundant available water resources underneath local sites of the host bodies within the Procellarum KREEP and South Pole Aitken terranes.

Racemization of Valine by Impact-Induced Heating.

Homochirality plays an important role in all living organisms but its origin remains unclear. It also remains unclear whether such chiral molecules survived terrestrial heavy impact events. Impacts of extraterrestrial objects on early oceans were frequent and could have affected the chirality of oceanic amino acids when such amino acids accumulated during impacts. This study investigated the effects of shock-induced heating on enantiomeric change of valine with minerals such as olivine ([Mg0.9, Fe0.1]2SiO4), hematite (Fe2O3), and calcite (CaCO3). With a shock wave generated by an impact at ~0.8 km/s, both D- and L-enriched valine were significantly decomposed and partially racemized under all experimental conditions. Different minerals had different shock impedances; therefore, they provided different P-T conditions for identical impacts. Furthermore, the high pH of calcite promoted the racemization of valine. The results indicate that in natural hypervelocity impacts, amino acids in shocked oceanic water would have decomposed completely, since impact velocity and the duration of shock compression and heating are typically greater in hypervelocity impact events than those in experiments. Even with the shock wave by the impact of small and decelerated projectiles in which amino acids survive, the shock heating may generate sufficient heat for significant racemization in shocked oceanic water. However, the duration of shock induced heating by small projectiles is limited and the population of such decelerated projectiles would be limited. Therefore, even though impacts of asteroids and meteorites were frequent on the prebiotic Earth, impact events would not have significantly changed the ee of proteinogenic amino acids accumulated in the entire ocean.

How the Toughest Inorganic Fullerene Cages Absorb Shockwave Pressures in a Protective Nanocomposite: Experimental Evidence from Two In Situ Investigations.

Nanocomposites fabricated using the toughest caged inorganic fullerene WS2 (IF-WS2) nanoparticles could offer ultimate protection via absorbing shockwaves; however, if the IF-WS2 nanomaterials really work, how they behave and what they experience within the nanocomposites at the right moment of impact have never been investigated effectively, due to the limitations of existing investigation techniques that are unable to elucidate the true characteristics of high-speed impacts in composites. We first fabricated Al matrix model nanocomposites and then unlocked the exact roles of IF-WS2 in it at the exact moment of impact, at a time resolution that has never been attempted before, using two in situ techniques. We find that the presence of IF-WS2 reduced the impact velocity by over 100 m/s and in pressure by at least 2 GPa against those Al and hexagonal WS2 platelet composites at an impact speed of 1000 m/s. The IF-WS2 composites achieved an intriguing inelastic impact and outperformed other reference composites, all originating from the "balloon effect" by absorbing the shockwave pressures. This study not only provides fundamental understanding for the dynamic performance of composites but also benefits the development of protective nanocomposite engineering.

Dynamic fracture of tantalum under extreme tensile stress.

The understanding of fracture phenomena of a material at extremely high strain rates is a key issue for a wide variety of scientific research ranging from applied science and technological developments to fundamental science such as laser-matter interaction and geology. Despite its interest, its study relies on a fine multiscale description, in between the atomic scale and macroscopic processes, so far only achievable by large-scale atomic simulations. Direct ultrafast real-time monitoring of dynamic fracture (spallation) at the atomic lattice scale with picosecond time resolution was beyond the reach of experimental techniques. We show that the coupling between a high-power optical laser pump pulse and a femtosecond x-ray probe pulse generated by an x-ray free electron laser allows detection of the lattice dynamics in a tantalum foil at an ultrahigh strain rate of [Formula: see text] ~2 × 108 to 3.5 × 108 s-1. A maximal density drop of 8 to 10%, associated with the onset of spallation at a spall strength of ~17 GPa, was directly measured using x-ray diffraction. The experimental results of density evolution agree well with large-scale atomistic simulations of shock wave propagation and fracture of the sample. Our experimental technique opens a new pathway to the investigation of ultrahigh strain-rate phenomena in materials at the atomic scale, including high-speed crack dynamics and stress-induced solid-solid phase transitions.

Shock compression response of forsterite above 250 GPa.

Forsterite (Mg2SiO4) is one of the major planetary materials, and its behavior under extreme conditions is important to understand the interior structure of large planets, such as super-Earths, and large-scale planetary impact events. Previous shock compression measurements of forsterite indicate that it may melt below 200 GPa, but these measurements did not go beyond 200 GPa. We report the shock response of forsterite above ~250 GPa, obtained using the laser shock wave technique. We simultaneously measured the Hugoniot and temperature of shocked forsterite and interpreted the results to suggest the following: (i) incongruent crystallization of MgO at 271 to 285 GPa, (ii) phase transition of MgO at 285 to 344 GPa, and (iii) remelting above ~470 to 500 GPa. These exothermic and endothermic reactions are seen to occur under extreme conditions of pressure and temperature. They indicate complex structural and chemical changes in the system MgO-SiO2 at extreme pressures and temperatures and will affect the way we understand the interior processes of large rocky planets as well as material transformation by impacts in the formation of planetary systems.

Experimental constraints on light elements in the Earth's outer core.

Earth's outer core is liquid and dominantly composed of iron and nickel (~5-10 wt%). Its density, however, is ~8% lower than that of liquid iron, and requires the presence of a significant amount of light element(s). A good way to specify the light element(s) is a direct comparison of density and sound velocity measurements between seismological data and those of possible candidate compositions at the core conditions. We report the sound velocity measurements of a model core composition in the Fe-Ni-Si system at the outer core conditions by shock-wave experiments. Combining with the previous studies, we found that the best estimate for the outer core's light elements is ~6 wt% Si, ~2 wt% S, and possible ~1-2.5 wt% O. This composition satisfies the requirements imposed by seismology, geochemistry, and some models of the early core formation. This finding may help us to further constrain the thermal structure of the Earth and the models of Earth's core formation.

Survivability and reactivity of glycine and alanine in early oceans: effects of meteorite impacts.

Prebiotic oceans might have contained abundant amino acids, and were subjected to meteorite impacts, especially during the late heavy bombardment. It is so far unknown how meteorite impacts affected amino acids in the early oceans. Impact experiments were performed under the conditions where glycine was synthesized from carbon, ammonia, and water, using aqueous solutions containing (13)C-labeled glycine and alanine. Selected amino acids and amines in samples were analyzed with liquid chromatography-mass spectrometry (LC/MS). In particular, the (13)C-labeled reaction products were analyzed to distinguish between run products and contaminants. The results revealed that both amino acids survived partially in the early ocean through meteorite impacts, that part of glycine changed into alanine, and that large amounts of methylamine and ethylamine were formed. Fast decarboxylation was confirmed to occur during such impact processes. Furthermore, the formation of n-butylamine, detected only in the samples recovered from the solutions with additional nitrogen and carbon sources of ammonia and benzene, suggests that chemical reactions to form new biomolecules can proceed through marine impacts. Methylamine and ethylamine from glycine and alanine increased considerably in the presence of hematite rather than olivine under similar impact conditions. These results also suggest that amino acids present in early oceans can contribute further to impact-induced reactions, implying that impact energy plays a potential role in the prebiotic formation of various biomolecules, although the reactions are complicated and depend upon the chemical environments as well.

Shock-absorbing and failure mechanisms of WS2 and MoS2 nanoparticles with fullerene-like structures under shock wave pressure.

The excellent shock-absorbing performance of WS2 and MoS2 nanoparticles with inorganic fullerene-like structures (IFs) under very high shock wave pressures of 25 GPa is described. The combined techniques of X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, thermal analysis, and transmission electron microscopy have been used to evaluate the diverse, intriguing features of shock recovered IFs, of interest for their tribological applications, thereby allowing improved understanding of their antishock behavior and structure-property relationships. Two possible failure mechanisms are proposed and discussed. The supershock-absorbing ability of the IF-WS2 enables them to survive pressures up to 25 GPa accompanied with concurrent temperatures of up to 1000 degrees C without any significant structural degradation or phase change making them probably the strongest cage molecules now known.

Interplanetary dust from the explosive dispersal of hydrated asteroids by impacts.

The Earth accretes about 30,000 tons of dust particles per year, with sizes in the range of 20-400 microm (refs 1, 2). Those particles collected at the Earth's surface--termed micrometeorites--are similar in chemistry and mineralogy to hydrated, porous meteorites, but such meteorites comprise only 2.8% of recovered falls. This large difference in relative abundances has been attributed to 'filtering' by the Earth's atmosphere, that is, the porous meteorites are considered to be so friable that they do not survive the impact with the atmosphere. Here we report shock-recovery experiments on two porous meteorites, one of which is hydrated and the other is anhydrous. The application of shock to the hydrated meteorite reduces it to minute particles and explosive expansion results upon release of the pressure, through a much broader range of pressures than for the anhydrous meteorite. Our results indicate that hydrated asteroids will produce dust particles during collisions at a much higher rate than anhydrous asteroids, which explains the different relative abundances of the hydrated material in micrometeorites and meteorites: the abundances are established before contact with the Earth's atmosphere.

Shock-wave resistance of WS2 nanotubes.

The shock-wave resistance of WS(2) nanotubes has been studied and compared to that of carbon nanotubes. Detailed structural features of post-shock samples were investigated using HRTEM, XRD, and Raman spectroscopy. WS(2) nanotubes are capable of withstanding shear stress caused by shock waves of up to 21 GPa, although some nanotube tips and nanoparticles containing multiple structural defects in the bending regions are destroyed. Small WS(2) species, consisting of only a few layers, are extruded from the nanotubes. Well-crystallized tube bodies were found to exhibit significant stability under shock, indicating high tensile strength. XRD and Raman analyses have confirmed this structural stability. Under similar shock conditions, WS(2) tubes are more stable than carbon nanotubes, the latter being transformed into a diamond phase. WS(2) nanotubes containing small concentrations of defects possess significantly higher mechanical strength, and, as a consequence, hollow WS(2) nanoparticles are expected to act as excellent lubricants under much higher loading than was previously thought.