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At least 577 records · Page 32

Evolution of the Ureilite Parent Body

Ureilites are ultramafic achondrites composed primarily of olivine and pyroxene with intergranular fine-grained metal, sulfides, and silicates. Ureilites contain significant amounts of carbon (up to about 6.5 wt%) as graphite, lonsdaleite, and/or diamond. It has been shown that carbon-silicate redox (i.e. "smelting") reactions are responsible for the negative FeO-MnO (or positive Fe/Mn-Fe/Mg with constant Mn/Mg) trend seen in the mineral and bulk compositions of ureilites and for the positive correlation between modal percent pigeonite and mg#. Carbon redox reactions are strongly exothermic and pressure dependent; so ureilites with the largest mg# are the most reduced, experienced the highest temperatures, and formed at the lowest pressures, i.e. near the surface of the ureilite parent body. Ureilites with the largest mg# have the smallest the delta(sup 18)O and the largest Delta(sup 17)O. To explain this, Singletary and Grove proposed that heterogeneous accretion took place on the ureilite parent body, which lead to a radial distribution of the oxygen isotopes. To further investigate possible relationships, we performed carbon isotope and electron probe measurements on a suite of 27 ureilites in order to see the type of correlation that exists between mg#, oxygen isotopes, and carbon.

Hudson, P.↗

Indications for Lifshitz transitions in the nodal-line semimetal ZrSiTe induced by interlayer interaction

The layered material ZrSiTe is currently extensively investigated as a nodal-line semimetal with Dirac-like band crossings protected by nonsymmorphic symmetry close to the Fermi energy. A recent infrared spectroscopy study on ZrSiTe under external pressure found anomalies in the optical response, providing hints for pressure-induced phase transitions at ≈4.1 and ≈ 6.5GPa. By pressure-dependent Raman spectroscopy and x-ray diffraction measurements combined with electronic band structure calculations we find indications for two pressure-induced Lifshitz transitions with major changes in the Fermi surface topology in the absence of lattice symmetry changes. These electronic phase transitions can be attributed to the enhanced interlayer interaction induced by external pressure. Overall, our findings demonstrate the crucial role of the interlayer distance for the electronic properties of layered van der Waals topological materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Anomalous temperature-dependent magnetization in the nearly collinear antiferromagnet Y 2 Co 3

Y 2 Co 3 is a newly discovered antiferromagnetic (AFM) compound with distorted kagome layers. Here, previous investigations via bulk magnetization measurements suggested a complex non-collinear magnetic behavior, with magnetic moments primarily anti-aligned along the b axis and some canting towards the ac plane. In this study, we report the magnetic structure of Y 2 Co 3 to be an A-type AFM structure with ferromagnetic (FM) interactions within the distorted kagome plane and an inter-plane antiferromagnetic interaction, as determined by single crystal neutron diffraction. The magnetic moments align along the b axis, with minimal canting towards the c axis, at odds with the previous interpretation of bulk magnetization measurements. The magnetic moments on the two distinct Co sites are (0, -0.68, 0) μB and (0, 1.25, 0.07) μ B . We attribute the previously reported ”non-collinear” behavior to the considerable temperature dependence of itinerant AFM exchange interactions, induced by thermal contraction along the b axis. Additionally, our examination of lattice constants through pressure studies reveals compensating effects on FM and AFM interactions, resulting in negligible pressure dependence of T N .

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Magnetic and Superconducting Materials at High Pressures

The work concentrates on few important tasks in enabling techniques for search of superconducting compressed hydrogen compounds and pure hydrogen, investigation of mechanisms of high-Tc superconductivity, and exploring new superconducting materials. Along that route we performed several challenging tasks, including discovery of new forms of polyhydrides of alkali metal Na at very high pressures. These experiments help us to establish the experimental environment that will provide important information on the high-pressure properties of hydrogen-rich compounds. Our recent progress in RIXS measurements opens a whole field of strongly correlated 3d materials. We have developed a systematic approach to measure major electronic parameters, like Hubbard energy U, and charge transfer energy Δ, as function of pressure. This technique will enable also RIXS studies of magnetic excitations in iridates and other 5d materials at the L edge, which attract a lot of interest recently. We have developed new magnetic sensing technique based on optically detected magnetic resonance from NV centers in diamond. The technique can be applied to study superconductivity in high-TC materials, to search for magnetic transitions in strongly correlated and itinerant magnetic materials under pressure. Summary of Project Activities; development of high-pressure experimentation platform for exploration of new potential superconductors, metal polyhydrides (including newly discovered alkali metal polyhydrides), and already known superconductors at the limit of static high-pressure techniques; investigation of special classes of superconducting compounds (high-Tc superconductors, new superconducting materials), that may provide new fundamental knowledge and may prove important for application as high-temperature/high-critical parameter superconductors; investigation of the pressure dependence of superconductivity and magnetic/phase transformations in 3d transition metal compounds, including transitions from magnetic to nonmagnetic phases in a broad pressure-temperature range; using X-ray methods including the newly developed RIXS high-pressure technique to explore pressure-tuned electronic excitations in strongly correlated 3d-materials; and advancing transport and magnetic techniques for measurements on small samples at very high pressures in a wide temperature range, with the application of focused ion beam technology and photolithography tailored to the design of microcircuits down to a nanoscale size, thus expanding the horizon in the search for novel physical phenomena at ultrahigh pressures. Apply new optical magnetic sensing techniques with NV- centers in diamond to detect superconductivity and magnetic transitions with unprecedented spatial resolution.

36 MATERIALS SCIENCE↗

Pyroxene thermobarometry in LL-group chondrites and implications for parent body metamorphism

Geothermometry based on the compositions of clinopyroxenes in type 6 and 7 LL chondrites gives coherent results, but the estimated temperatures from coexisting orthopyroxenes are consistently lower than for clinopyroxenes. Orthopyroxene thermometry is suspect because of compositional effects of polymorphic inversions and/or unknown kinetic factors. Lack of clinopyroxene equilibration precludes accurate estimation of peak metamorphic temperatures for type 4 and 5 chondrites. There is no apparent correlation between Al content (a pressure-dependent variable) and equilibration temperature in chondritic pyroxenes. This finding, which is at variance with a previously published conclusion that temperature and pressure are correlated in metamorphosed chondrites, may have important implications for asteroid thermal models.

Mcsween, Harry Y., Jr.↗

Plastic flow modeling in glassy polymers

Glassy amorphous and semi-crystalline polymers exhibit strong rate, temperature, and pressure dependent polymeric yield. As a rule of thumb, in uniaxial compression experiments the yield stress increases with the loading rate and applied pressure, and decreases as the temperature increases. Moreover, by varying the loading state itself complex yield behavior can be observed. One example that illustrates this complexity is that most polymers in their glassy regimes (i.e., when the temperature is below their characteristic glass transition temperature) exhibit very pronounced yield in their uniaxial stress stress-strain response but very nebulous yield in their uniaxial strain response. In uniaxial compression, a prototypical glassy-polymer stress-strain curve has a stress plateau, often followed by softening, and upon further straining, a hardening response. Uniaxial compression experiments of this type are typically done from rates of 10{sup -5} s{sup -1} up to about 1 s{sup -1}. At still higher rates, say at several thousands per second as determined from Split Hopkinson Pressure Bar experiments, the yield can again be measured and is consistent with the above rule of thumb. One might expect that that these two sets of experiments should allow for a successful extrapolation to yet higher rates. A standard means to probe high rates (on the order of 105-107 S-I) is to use a uniaxial strain plate impact experiment. It is well known that in plate impact experiments on metals that the yield stress is manifested in a well-defined Hugoniot Elastic Limit (HEL). In contrast however, when plate impact experiments are done on glassy polymers, the HEL is arguably not observed, let alone observed at the stress estimated by extrapolating from the lower strain rate experiments. One might argue that polymer yield is still active but somehow masked by the experiment. After reviewing relevant experiments, we attempt to address this issue. We begin by first presenting our recently developed glassy polymer model. While polymers are well known for their non-equilibrium deviatoric behavior we have found the need for incorporating both equilibrium and non-equilibrium volumetric behavior into our theory. Experimental evidence supporting the notion of non-equilibrium volumetric behavior will be summarized. Our polymer yield model accurately captures the stress plateau, softening and hardening and its yield stress predictions agree well with measured values for several glassy polymers including PMMA, PC, and an epoxy resin. We then apply our theory to plate impact experiments in an attempt to address the questions associated with high rate polymer yield in uniaxial strain configurations.

36 MATERIALS SCIENCE↗

Steady detonation propagation in thin channels with strong confinement

We examine asymptotically the dynamics of two-dimensional, steady detonation wave propagation and failure for a strongly confined high explosive (HE), in which the width of the explosive is small relative to the reaction zone length. An energy balance equation is derived, which shows how the longitudinal acceleration of subsonic flow behind the detonation shock is influenced both by chemical reaction and by the effects of HE boundary streamline deflection, specifically via the induced rate of change of mass flux through the detonation wave. The latter serves to either counteract or reinforce the acceleration of longitudinal flow, depending on the sign of the gradient of the boundary streamline deflection at the detonation shock. The analysis is valid for general equations of state and chemical reaction rates in the HE. The asymptotically derived form of the energy equation represents an eigenvalue problem for the determination of the steady detonation propagation speed, solved via a shooting method. We explore specific results for ideal and stiffened equations of state, along with a pressure-dependent reaction rate for which changes in the pressure exponent and reaction order are also studied. We consider the influences of both straight and curved HE boundary streamline shapes. The asymptotic analysis reveals significant physical insights into how detonation propagation and failure are affected by strong confinement.

42 ENGINEERING↗

Distinct superconducting states in the pressure-induced metallic structures of the nominal semimetal Bi[subscript 4]Te[subscript 3]

The end members, Bi and Bi{sub 2}Te{sub 3}, of the infinitely adaptive (Bi{sub 2})m(Bi{sub 2}Te{sub 3}){sub n} series of compounds have not only been revealed to be topological insulators under the appropriate conditions, but have also been shown to be superconductors under pressure, suggesting the potential for bulk superconductor-topological-insulator interfaces and associated quantum computing applications. Herein, we report the pressure-dependent evolution of the structure and electrical transport of the nominal semimetal Bi4Te{sub 3}, a member of the (Bi{sub 2})m(Bi{sub 2}Te{sub 3}){sub n} series. Under pressure, Bi4Te{sub 3} undergoes several structural phase transformations, ultimately yielding a metallic body-centered-cubic structure exhibiting superconductivity with a maximum T{sub c} = 8.4 K at 16.2 GPa. The occurrence of structure-dependent superconductivity in Bi{sub 4}Te{sub 3} is remarkably similar to the end members of the (Bi{sub 2})m(Bi{sub 2}Te{sub 3}){sub n} series, intimating a convergence to high-pressure universal behavior that may expose the subtle variations that lead to the topological insulating and superconducting states in these systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pressure-Induced Polymorphic, Optical, and Electronic Transitions of Formamidinium Lead Iodide Perovskite

Formamidinium lead iodide (FAPbI 3 ) perovskite as a superior solar cell material was investigated in two polymorphs at high pressures using in situ synchrotron X-ray diffraction, FTIR spectroscopy, photoluminescence (PL) spectroscopy, electrical conductivity (EC) measurements, and ab initio calculations. We identified two new structures (i.e., Imm2 and Immm) for α-FAPbI 3 but only a structural distortion (in C2/c) for δ-FAPbI 3 upon compression. A pressure-enhanced hydrogen bond plays a prominent role in structural modifications, as corroborated by FTIR spectroscopy. PL measurements and calculations consistently show the structure and pressure dependences of the band gap energies. Lastly, EC measurements reveal drastically different transport properties of α- and δ-FAPbI 3 at low pressures but a common trend to metallic states at high pressures. All of these observations suggest strongly contrasting structural stabilities and pressure-tuned optoelectric properties of the two FAPbI 3 polymorphs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oceanic lithosphere and asthenosphere: The thermal and mechanical structure

A coupled thermal and mechanical solid state model of the oceanic lithosphere and asthenosphere is presented. The model includes vertical conduction of heat with a temperature dependent thermal conductivity, horizontal and vertical advection of heat, viscous dissipation or shear heating, and linear or nonlinear deformation mechanisms with temperature and pressure dependent constitutive relations between shear stress and strain rate. A constant horizontal velocity u sub 0 and temperature t sub 0 at the surface and zero horizontal velocity and constant temperature t sub infinity at great depth are required. In addition to numerical values of the thermal and mechanical properties of the medium, only the values of u sub 0, t sub 0 and t sub infinity are specified. The model determines the depth and age dependent temperature horizontal and vertical velocity, and viscosity structures of the lithosphere and asthenosphere. In particular, ocean floor topography, oceanic heat flow, and lithosphere thickness are deduced as functions of the age of the ocean floor.

Schubert, G.↗

Bulk moduli and high pressure crystal structure of U 3 Si 2

Bulk moduli are vital parameters to assess the mechanical performance of materials including nuclear fuels. Yet, little experimental data exist for U 3 S i2 , a potential accident-tolerant nuclear fuel, whose bulk modulus has only been measured by resonant ultrasonic spectroscopy (RUS). In addition, the knowledge for high-pressure structural behavior and phase equilibrium of U 3 Si 2 is largely lacking. Here we reviewed pressure dependence of the crystal structure of U 3 Si 2 using high-energy synchrotron X-ray diffraction coupled with Rietveld analysis. The pressurization was achieved using a diamond anvil cell (DAC) which provides quasi-hydrostatic pressures up to 37.6 GPa. Crystal structural variation and equations of state of U 3 Si 2 were obtained, and its bulk modulus, a- and c-axial moduli were derived to be 107.11 +/- 5.65 GPa, 82.87 +/- 4.78 GPa and 194.52 +/- 12.03 GPa, respectively. The determined elastic parameters are compared with those obtained by RUS and nanoindentation. (C) 2019 Elsevier B.V. All rights reserved.

36 MATERIALS SCIENCE↗

Pressure effects in the itinerant antiferromagnetic metal TiAu

Here, we report the pressure dependence of the Néel temperature T N up to P ≈ 27 GPa for the recently discovered itinerant antiferromagnet (IAFM) TiAu. The T N (P) phase boundary exhibits unconventional behavior in which the Néel temperature is enhanced from T N ≈ 33 K at ambient pressure to a maximum of T N ≈ 35 K occurring at P ≈ 5.5 GPa. Upon a further increase in pressure, T N is monotonically suppressed to ~22 K at P ≈ 27 GPa. We also find a crossover in the temperature dependence of the electrical resistivity ρ in the antiferromagnetic (AFM) phase that is coincident with the peak in T N (P), such that the temperature dependence of ρ = ρ 0 + A n T n changes from n≈3 during the enhancement of T N to n ≈ 2 during the suppression of T N . Based on an extrapolation of the T N (P) data to a possible pressure-induced quantum critical point, we estimate the critical pressure to be P c ≈ 45 GPa.

36 MATERIALS SCIENCE↗

Interactions between Polyelectrolyte Gel Surfaces

We see surfaces formed by charged polymeric species are highly abundant in both synthetic and biological systems, for which maintaining an optimum contact distance and a pressure balance is paramount. Here we investigate interactions between surfaces of two same-charged and highly swollen polyelectrolyte gels, using extensive molecular dynamic simulations and minimal analytical methods. The external-pressure responses of the gels and the polymer-free ionic solvent layer separating two surfaces are considered. Simulations confirmed that the surfaces are held apart by osmotic pressure resulting from excess charges diffusing out of the network. At a threshold pressure, the counterion-induced osmotic pressure in the gel interiors becomes nearly equal to that in solvent gap, and the gels begin to deform. At the threshold pressure, the distance between surfaces is equivalent to the electrostatic screening length imposed by excess charges. Both the solvent layer and pressure dependence are well described by an analytical model based on the Poisson–Boltzmann solution for low and moderate electrostatic strengths. Scaling descriptions for the threshold pressure and critical distance compare well with the simulations. The threshold pressure decreases with increasing polymerization degree of network chains, similar to sparsely grafted polyelectrolyte brushes. As the electrostatic coupling strength is increased, the deviations from the analytical model also increase due to condensed counterions. Our results are of great importance for systems where charged gels or gel-like structures interact in various solvents, including systems encapsulated by gels and microgels in confinement.

36 MATERIALS SCIENCE↗

A Theoretical Study of Methanol Oxidation on RuO 2 (110): Bridging the Pressure Gap

Partial oxidation catalysis is often fraught with selectivity problems, largely because there is a tendency of oxidation products to be more reactive than the starting material. One industrial process that has successfully overcome this problem is partial oxidation of methanol to formaldehyde. This process has become a global success, with an annual production of 30 million tons. Although ruthenium catalysts have not shown activity as high as the current molybdena or silver-based industrial standards, the study of ruthenium systems has the potential to elucidate which catalyst properties facilitate the desired partial oxidation reaction as opposed to deep combustion due to a pressure-dependent selectivity “switch” that has been observed in ruthenium-based catalysts. In this work, we find that we are able to successfully rationalize this “pressure gap” using near-ab initio steady-state microkinetic modeling on RuO 2 (110). We obtain molecular desorption prefactors from experiment and determine all other energetics using density functional theory. We show that, under ambient pressure conditions, formaldehyde production is favored on RuO 2 (110), whereas under ultrahigh vacuum pressure conditions, full combustion to CO 2 takes place. We glean from our model several insights regarding how coverage effects, oxygen activity, and rate-determining steps influence selectivity and activity. As a result, we believe the understanding gained in this work might advise and inspire the greater partial oxidation community and be applied to other catalytic processes which have not yet found industrial success.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure-induced phase transition in barium hydride studied with neutron scattering

Barium hydride can undergo a structural phase transition from an orthorhombic phase to a hexagonal phase induced by high temperature or high pressure. This transition causes an immediate increase in the hydrogen diffusion rates by over an order of magnitude, and therefore, understanding the origin and details of such transition is of great interest not only for fundamental reasons but also for improving materials for future applications. In this work, the pressure evolution of the crystal structure was characterized using neutron powder diffraction up to a maximum pressure of 11.3 GPa. The pressure dependence of the unit cell volumes, lattice parameters, atomic sites, and compressibilities were determined for both phases. A structural phase transition occurred over a wide pressure range of P = 1.3 GPa–4.9 GPa. The transition to the higher density hexagonal phase reduced the volume per formula unit of BaD 2 by 13.6%, hence increasing the volumetric storage density. In addition, we investigated the hydrogen diffusion process using high pressure quasi-elastic neutron scattering up to 7.1 GPa. Our results show that the hydrogen mobility increases with pressure in the hexagonal phase. This work sheds light on the structural and dynamical aspects of barium hydride caused by the application of high pressure. Finally, the results may aid in the development of advanced metal hydride systems with increased hydrogen dynamics.

36 MATERIALS SCIENCE↗

The interplay between magnetism, structure, and strong electron-phonon coupling in binary FeAs under pressure

Unlike the ferropnictide superconductors, which crystallize in a tetragonal crystal structure, binary FeAs forms in an orthorhombic crystal structure, where the local atomic environment resembles a highly distorted variant of the FeAs{sub 4} tetrahedral building block of the ferropnictide superconductors. However, like the parent compounds of the ferropnictide superconductors, FeAs undergoes magnetic ordering at low temperatures, with no evidence favoring a superconducting ground state at ambient pressure. We employ pressure-dependent electrical transport and x-ray diffraction measurements using diamond anvil cells to characterize the magnetic state and the structure as a function of pressure. While the structure persists up to 25 GPa, compressing continuously with pressure, magnetotransport measurements suggests that the magnetic state is destroyed near 11 GPa. The magnetic transition temperature is found to be remarkably robust under pressure, and transport measurements suggest that a dynamical structural instability coupled to the Fermi surface via a strong electron-phonon interaction may play an important role in enabling magnetism in FeAs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗