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At least 595 records · Page 33

Pressure-induced high-temperature superconductivity retained without pressure in FeSe single crystals

To raise the superconducting-transition temperature (T c ) has been the driving force for the long-sustained effort in superconductivity research. Recent progress in hydrides with T c s up to 287 K under pressure of 267 GPa has heralded a new era of room temperature superconductivity (RTS) with immense technological promise. Indeed, RTS will lift the temperature barrier for the ubiquitous application of superconductivity. Unfortunately, formidable pressure is required to attain such high T c s. The most effective relief to this impasse is to remove the pressure needed while retaining the pressure-induced T c without pressure. Here, we show such a possibility in the pure and doped high-temperature superconductor (HTS) FeSe by retaining, at ambient pressure via pressure quenching (PQ), its T c up to 37 K (quadrupling that of a pristine FeSe at ambient) and other pressure-induced phases. We have also observed that some phases remain stable without pressure at up to 300 K and for at least 7 d. The observations are in qualitative agreement with our ab initio simulations using the solid-state nudged elastic band (SSNEB) method. We strongly believe that the PQ technique developed here can be adapted to the RTS hydrides and other materials of value with minimal effort.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Universal relations for neutron star 𝑓-mode and 𝑔-mode oscillations

Among the various oscillation modes of neutron stars, 𝑓- and 𝑔- modes are the most likely to be ultimately observed in binary neutron star mergers due to their relatively large coupling and shared frequencies with tidal excitations. The 𝑓-mode frequency and damping time are known to correlate in normal neutron stars with their compactness, and previous fits to hadronic stars are extended and shown to be valid for an extremely broad sampling of equations of state using a piecewise polytropic parametrization scheme for hadrons and a constant sound-speed parametrization for quark matter. Separate fits applicable to quark (self-bound) stars are improved. Much more significant correlations exist with tidal deformability, and therefore with moment of inertia and quadrupole moment. It is conclusively demonstrated that these correlations are the same for all types of stars, whether hadronic, hybrid, or pure quark, and its accuracy is quantified. A novel 1-node branch of the 𝑓-mode that occurs in low-mass hybrid stars in a narrow mass range just beyond the critical mass necessary for a phase transition to appear is identified. This 1-node branch shows the largest, but still small, deviations from the universal correlation for any configuration. It is characterized by a nonmonotonic relation between neutron star mass and 𝑓-mode frequency, in contrast to the behavior otherwise observed in normal, quark and hybrid stars. The 𝑔-mode only exists in matter with a nonbarotropic equation of state involving temperature, chemical potential or composition (such as being out of beta equilibrium), or a phase transition in barotropic matter. Here, the 𝑔-mode therefore could serve as a probe for studying phase transitions in hybrid stars. In contrast with the 𝑓-mode, 𝑔-mode frequencies do not correlate well with tidal deformability, but depend strongly on properties of the transition (the density and the magnitude of the discontinuity) at the transition. Imposing causality and maximum mass constraints, a fit involving neutron star and phase transition properties is found and the 𝑔-mode frequency is determined to have an upper bound of about 1.25 kHz. However, if the sound speed 𝑐𝑠 in the inner core at densities above the phase transition density is restricted to 𝑐$^{2}_{𝑠}$ ≤1/3, 𝑔-mode frequencies can only reach about 0.8 kHz, which are significantly lower than 𝑓-mode frequencies (1.3–2.8 kHz). 𝑔-mode gravitational wave damping times are found to be extremely long, >10 4 s (102 s) in the inner core with 𝑐$^{2}_{𝑠}$ ≤1/3 (1), in comparison with 𝑓-mode damping times (0.1–1 s).

Composition of astronomical objects↗

Precise Control of Phase Separation Enables 12% Efficiency in All Small Molecule Solar Cells

Abstract Compared to conjugated polymers, small‐molecule organic semiconductors present negligible batch‐to‐batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small‐molecular organic solar cells (SM‐OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small‐molecular donors H13 and H14 , created by fluorine and chlorine substitution of the original donor molecule H11 , are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open‐circuit voltage with IDIC‐4F as acceptor. Due to kinetic and thermodynamic reasons, H13 ‐based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14 ‐based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14 ‐based SM‐OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM‐OSCs using IDIC‐4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine‐tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design.

Bin, Haijun↗

Smaller and faster: a review of conventional and nanocalorimetry techniques for determining thermophysical properties of nuclear materials

Thermal analysis of nuclear materials is critical for the advancement of nuclear technology. The heat effects associated with heat capacity, phase transformation, and radiation damage can be measured with conventional calorimeters. However, conventional calorimetric techniques are often restricted in terms of heating rate and sample mass, especially when studying the limited amounts of materials subject to extreme conditions. In this review, we summarize conventional calorimetric studies of critical thermophysical and thermochemical properties of pure actinide metals (U, Np, Am, Pu), fast reactor metallic fuel alloy systems (U–Zr, U–Pu–Zr, Pu–U, Pu–Zr), and actinide oxides that are primary constituents or transmutation products in light water reactor fuel rods (U–O, Np–O, Am–O, Pu–O, Pu–U–O). Adiabatic and drop calorimetry have been the primary techniques used for these studies, however the development of fast scanning calorimetry using micro-electro-mechanical-based systems allows determination of thermodynamic properties from smaller sample masses. We report recent investigations that leverage the fast heating rates of nanocalorimetry by itself or combined with other characterization techniques. Furthermore, we then discuss opportunities for nanocalorimetry to provide solutions to some of the technical challenges inherent in thermal analysis of nuclear materials, namely a reduction in sample activity, emulating heating transients, investigation of phase evolution in irradiated samples, and characterization of radiation damage evolution. Nanocalorimetry has the potential to significantly advance the understanding of thermophysical properties in nuclear materials and thus accelerate the development of nuclear technology.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Numerical and experimental characterization of twin transmission across grain boundaries along the forward and lateral directions

Pervasive deformation twinning and transmission events across grain boundaries (GBs) affect the strength and failure of hexagonal close-packed (HCP) magnesium. A three-dimensional twin can transmit along the twinning shear direction, (forward), and along the direction perpendicular to both the twinning plane normal and the shear direction, (lateral). For the first time, phase-field calculations and electron backscatter diffraction (EBSD)-based statistical analysis are combined to investigate the effect of the twinned grain boundary characteristics on twin transmission (TT) along the forward and lateral directions. This combined analysis reveals that TT propensity decreases with increasing misorientation angle across the GB for both forward and lateral directions. Also, the TT is more favorable along the lateral than along the forward direction. Twin transmission seems harder across GBs with a misorientation axis closer to the twin -direction than the other directions ( and ). Further, the PF calculations reveal that, at the onset of a transmission process, the crystallography tends to be preserved in the case of lateral transmission, whereas, in the forward transmission case, the transmitted twin punches straight through the GBs and its morphology prevails. Additionally, the EBSD analysis finds that pure forward and lateral transmissions do not occur often, yet reveals a preference for lateral propagation consistent with PF simulations. Further, the local twin transmission configurations observed in the actual material do not correspond to pure tilt or twist GBs, which are most commonly considered as model cases.

36 MATERIALS SCIENCE↗

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable salt hydrate-based thermal energy storage materials

Heating and cooling systems in building infrastructure utilize conventional materials that account for a considerable amount of energy usage and waste. Phase change material (PCM) is considered a promising candidate for thermal energy storage that can improve energy efficiency in building systems. In this work, a novel salt hydrate-based PCM composite with high energy storage capacity, relatively higher thermal conductivity, and excellent thermal cycling stability was designed and developed. The thermal cycling stability of the PCM composite was enhanced by using dextran sulfate sodium (DSS) salt as a polyelectrolyte additive, which significantly reduced the phase segregation of salt hydrate. The energy storage capacity and the thermal conductivity of the composite were enhanced by the addition of various graphitic materials along with Borax nucleator. A significant increase in thermal cycling stability was observed for the DSS-modified composite, with over 100 thermal cycles without degradation. The final PCM composite exhibited as much as 290% increase in energy storage capacity relative to the pure salt hydrate, and approximately 20% increase in thermal conductivity. In addition, the PCM composite developed can be produced at larger scale, and can potentially change the future of heating/cooling system in building infrastructure.

42 ENGINEERING↗

Thermal Charging Rate of Composite Wax-Expanded Graphite Phase Change Materials

Phase change materials (PCMs) are valuable for their ability to store heat nearly isothermally around their phase transition temperature. PCMs are at the core of latent heat thermal energy storage (LHTES) systems, which provide the ability to buffer high thermal loads or decouple the time when heating or cooling is needed from when it is produced. Thermal charging and discharging of LHTES systems often employ a constant temperature source, and the rate at which heat can be exchanged is dependent on the thermophysical properties of the PCM. For graphite composite PCMs, the high thermal conductivity of the graphite enables an increased heat transfer rate through the material, but its presence displaces PCM which reduces the effective volumetric latent heat of the composite relative to the pure PCM. This results in a tradeoff between thermal power and volumetric energy storage capacity. The thermal charging rate is the average thermal energy stored in the material for some elapsed time. In this study, composite PCMs of compressed expanded natural graphite (CENG) and n-Octadecane are studied. Samples with varying CENG mass fractions were synthesized and the thermal charging rate was measured under a constant temperature boundary condition. For evaluation of the expanded graphite-PCM composite, one boundary of the material was exposed to a 50°C constant temperature plate, above the 27.5°C melting temperature of the PCM. The melting front progression [mm-s-1] and the thermal charging rate [W-cm-2] of the PCM were determined, and the results were compared with analytical predictions for the 1-D semi-infinite phase change. For CENG addition up to 5.75% mass fraction, a 450% thermal conductivity increase was observed with a 5% decrease in volumetric energy density as compared to pure octadecane. The average thermal charging rate was increased by over 430% for the melt to penetrate a depth of 22 mm. The experimental results matched analytical predictions, indicating that higher CENG fractions can be evaluated using analytical approaches.

Hirschey, Jason↗

Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins

Abstract Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high‐performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high‐ceiling‐temperature biodegradable poly(δ‐valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m −3 , and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non‐selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.

Li, Xin‐Lei↗

Dual Recycling of Depolymerization Catalyst and Biodegradable Polyester that Markedly Outperforms Polyolefins

Chemically recyclable, circular polymers continue to attract increasing attention, but rendering both catalysts for depolymerization and high-performance polymers recyclable is a more sustainable yet challenging goal. Here we introduce a dual catalyst/polymer recycling system in that recyclable inorganic phosphomolybdic acid catalyzes selective depolymerization of high-ceiling-temperature biodegradable poly(δ-valerolactone) in bulk phase, which, upon reaching suitable molecular weight, exhibits outstanding mechanical performance with a high tensile strength of ≈66.6 MPa, fracture strain of ≈904 %, and toughness of ≈308 MJ m –3 , and thus markedly outperforms commodity polyolefins, recovering its monomer in pure state and quantitative yield at only 100 °C. In sharp contrast, the uncatalyzed depolymerization not only requires a high temperature of >310 °C but is also low yielding and non-selective. Importantly, the recovered monomer can be repolymerized as is to reproduce the same polymer, thereby closing the circular loop, and the recycled catalyst can be reused repeatedly for depolymerization runs without loss of its catalytic activity and efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Impurities on the Redox Properties of Goethite

Iron oxide minerals regulate the flux of electrons in the environment and are important hosts for trace and minor, yet critical, elements. Here, we present the first evidence of a direct link between the local coordination environments of Ni and Zn and the redox properties of their host phase goethite (α-FeOOH), the most abundant Fe(III) (oxyhydr)oxide at Earth’s surface. Here, we used aqueous redox measurements to show that the redox potential E H 0 , and hence the mineral’s stability, follows the order: pure goethite ≥ Zn-goethite > Ni-goethite. Parallel X-ray absorption and scattering measurements demonstrate, using quantum-informed analysis, that the local coordination environment of the smaller impurity, Ni, causes more bulk strain energy than Zn, which nearly accounts for the difference in E H 0 between Ni- and Zn-goethite. Our theory-informed, experimental study reveals how two common impurities affect the stability of goethite with implications for the biogeochemical reactivity of Fe(III) (oxyhydr)oxide in mediating elemental and electron fluxes in the environment.

42 ENGINEERING↗

Chromaticity compensation of a ghost collider

The GHOST collider final focus system is a pure quadrupole-drift beamline targeting ¿* = 2 mm at four serial interaction points, with peak ¿-functions reaching ~65 km in the final triplet. Beam tracking simulations reveal that a nominal bunch develops a pronounced C-shape in longitu- dinal phase space at IP1, with ¿¿ growing from 0.15 mm to ~2.3 mm — a factor of ~15× increase that directly re- duces luminosity. The mechanism is identified as chromat- ically amplified betatron path length: off-momentum par- ticles acquire enlarged betatron amplitudes in the high-¿ final triplet, generating excess path length via the geometric ¿¿ = - 1/2 ¿ (¿'2 + ¿'2) ¿¿ integral. Within the monoenergetic Balandin framework, ¿2¿2 with ¿ = - 1/2 ¿ ¿ ¿¿ dominates ¿2¿2 by over four million times; the full beam ¿¿ is a fur- ther factor of ~27 larger, driven by ¿¿ -induced chromatic amplitude growth. Phase-advance scans confirm that ¿¿ is insensitive to the apochromatic (¿ ˜ 0) condition. When combined with the geometric hourglass effect, this distor- tion poses a challenge to maximizing luminosity within the current lattice design.

Gamage, B. [Thomas Jefferson National Accelerator ↗

Layer-by-Layer Organic Solar Cells Enabled by 1,3,4-Selenadiazole-Containing Crystalline Small Molecule with Double-Fibril Network Morphology

A double-fibril network of the photoactive layer morphology is recognized as an ideal structure facilitating exciton diffusion and charge carrier transport for high-performance organic solar cells (OSCs). However, in the layer-by-layer processed OSCs (LbL-OSCs), polymer donors and small molecule acceptors (SMAs) are separately deposited, and it is challenging to realize a fibril network of pure SMAs with the absence of tight interchain entanglement as polymers. Here, in this work, crystalline small molecule donors (SMDs), named TDZ-3TR and SeDZ-3TR, were designed and introduced into the L8-BO acceptor solution, forcing the phase separation and molecular fibrilization. SeDZ-3TR showed higher crystallinity and lower miscibility with L8-BO acceptor than TDZ-3TR, enabling more driving force to favor the phase separation and better molecular fibrilization of L8-BO. On the other hand, two donor polymers of PM6 and D18 with different fibril widths and lengths were put together to optimize the fibril network of the donor layer. The simultaneously optimization of the acceptor and donor layers resulted in a more ideal double-fibril network of the photoactive layer and an impressive power conversion efficiency (PCE) of 19.38 % in LbL-OSCs.

36 MATERIALS SCIENCE↗

Topological carbon materials: A new perspective

Carbon has numerous one-dimensional (1D), two-dimensional (2D), and three-dimensional (3D) allotropic structures. The study of carbon materials has long been a major focus of material sciences and condensed matter physics. Recently, a number of topological semi-metallic carbon allotropes with vastly different topological phases have been predicted from first-principles, showing exceptionally clean and robust topological properties near the Fermi surfaces. Here, we provide a brief summary of the development of carbon allotropes from 1D to 3D. Then, we discuss topological properties of pure carbon materials, despite their exceedingly small spin–orbit coupling. Instead, the nearest-neighbor p z orbit interaction has been identified as the origin for the non-trivial topological properties, which vary due to different p z connectivity: zigzag, armchair, or pentagonal, as well as the interactions among further neighboring atoms. Next, we consider possible expansions of the topological properties of carbon materials to other light-element materials such as boron. Finally, we discuss future prospects in light of experimental feasibility and the recent surge in pursue of exotic carbon physics due to twisted graphene, which may also be viewed as a subset of the topological physics involving sp 2 /p z carbon.

36 MATERIALS SCIENCE↗

Long-term relaxation of orientational disorder and structural modifications in molecular nitrogen at high pressure

Up to 17 GPa, the crystalline phases of N 2 are characterized by pronounced orientational disorder, whereas the higher-pressure phases of molecular N 2 are ordered. This raises the question about long-term relaxation of orientational disorder within the low- to intermediate-pressure regime. Here, in this study, this question is addressed by comparing synthetic with natural, chemically pure, solid N 2 that resides as inclusions in diamonds at 300 K for about 10 8 years at pressures up to 11 GPa. It is shown that disorder prevails at 8.7 GPa, 300 K, where both synthetic and natural N 2 assume the same structure. However, at 10.8 GPa, natural solid N 2 exhibits monoclinic distortion and partial orientational ordering of the molecules, both of which are not observed in synthetic material. This difference is interpreted as the result of long-term structural relaxation. The ordering mechanism is examined and placed into the context of the δ- to ε-N 2 transition. We present explanations for the absence of complete ordering of δ-N 2 .

Tschauner, Oliver↗

Electrochemical materials including solid and liquid phases

Electrochemical devices, and associated materials and methods, are generally described. In some embodiments, an electrochemical device comprises an electroactive material. The electroactive material may comprise an alloy having a solid phase and a liquid phase that co-exist with each other. As a result, such a composite electrode may have, in some cases, the mechanical softness to permit both high energy densities and an improved current density as compared to, for example, a substantially pure metal electrode.

Chiang, Yet-Ming↗

Synthesis and thermophysical property determination of NaCl-PuCl3 salts

Currently, a knowledge gap exists in the available data and understanding of thermophysical properties relating to fresh fuel salts, especially those containing plutonium. These data are necessary for designing, constructing, and licensing future commercial molten-salt reactors. Thermophysical properties, such as melting temperature, salt stability, density, and heat capacity were ascertained using NaCl-PuCl3 (36 mol% PuCl3) and a more sodium rich composition containing 25 mol% PuCl3. The NaCl-PuCl3 salt mixture was synthesized for this study and contained 63.4 mol% NaCl, 36.3 mol% PuCl3 and was 99.7% pure. Upon heating, the NaCl–PuCl3 eutectic was stable at temperatures up to 800 °C. The onset of melting occurred at 451 ± 3 °C, and the enthalpy of fusion was determined to be 23.0 ± 1.4 kJ/mol. Heat capacity measurements in the liquid phase ranged from 107.7 to 91.3 J/mol.K, with an average value of 104.6 ± 11.4 J/mol.K between 500 and 650 °C. Three independent trials of the molten NaCl-PuCl3 salt found the density to be ?(T) = 3.8589 – 9.5342·10-4 T(°C). In addition, ab initio molecular dynamic simulations to calculate density and heat capacity values are included.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes

The performance of lithium ion electrodes is hindered by unfavorable chemical heterogeneities that pre-exist or develop during operation. Time-resolved spatial descriptions are needed to understand the link between such heterogeneities and a cell's performance. Here, operando high-resolution X-ray diffraction-computed tomography is used to spatially and temporally quantify crystallographic heterogeneities within and between particles throughout both fresh and degraded Li x Mn 2 O 4 electrodes. This imaging technique facilitates identification of stoichiometric differences between particles and stoichiometric gradients and phase heterogeneities within particles. Through radial quantification of phase fractions, the response of distinct particles to lithiation is found to vary; most particles contain localized regions that transition to rock salt LiMnO 2 within the first cycle. Other particles contain monoclinic Li 2 MnO 3 near the surface and almost pure spinel LixMn2O4 near the core. Following 150 cycles, concentrations of LiMnO 2 and Li 2 MnO 3 significantly increase and widely vary between particles.

25 ENERGY STORAGE↗