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At least 199 records · Page 11

Enhanced dynamics in fusion of neutron-rich oxygen nuclei at above-barrier energies

Above-barrier fusion cross sections for an isotopic chain of oxygen isotopes with A = 16 –19 incident on a C 12 target are presented. Experimental data are compared with both static and dynamical microscopic calculations. Here, these calculations are unable to explain the ≈ 37 % increase in the average above-barrier fusion cross section observed for O 19 as compared to β -stable oxygen isotopes. This result suggests that for neutron-rich nuclei existing time-dependent Hartree-Fock calculations underpredict the role of dynamics at near-barrier energies. High-quality measurement of above-barrier fusion for an isotopic chain of increasingly neutron-rich nuclei offers an effective means to probe this fusion dynamics.

6 ≤ A ≤ 19↗

Hydration‐Induced β‐Sheet Crosslinking of α‐Helical‐Rich Spider Prey‐Wrapping Silk

Abstract Due to its moderate strength (≈700 MPa) and impressive extensibility before breaking (≈60–80%), orb‐weaving spider aciniform (AC) prey‐wrapping silks are actually the toughest of the spider silks but are remarkably understudied. The previous results indicate that native AC silk fibers are an α‐helix rich coiled‐coil/β‐sheet hybrid nanofiber, and that conversion of disordered or helical domains to β‐sheet aggregates is surprisingly minimal and overall β‐sheet content is low (≈15%). In this work, it is demonstrated through scanning electron microscopy that native AC silk fibers undergo matted cross‐linking upon exposure to moisture that increases silk stiffness. The unique molecular mechanism of water‐induced cross‐linking is revealed with solid‐state NMR (SSNMR) methods; water‐induced morphological changes are correlated with an increase in AC silk protein β‐sheet content, and additionally a minor unfolding of coiled‐coil regions is observed. Continued and increased β‐sheet cross‐linking is observed upon application of mechanical shear. The size of these β‐sheet domains to be 4–6 nm using Wide‐Line Separation SSNMR is determined. The observation that merely water treatment can be used to convert a protein‐based material from a flexible/extensible α‐helix‐rich fiber to a rigid crossed‐linked β‐sheet mat is a novel observation that should provide new avenues in bioinspired materials design.

Stengel, Dillan↗

A Fluoride-Rich Solid-Like Electrolyte Stabilizing Lithium Metal Batteries

To address the problems associated with Li metal anodes, a fluoride-rich solid-like electrolyte (SLE) that combines the benefits of solid-state and liquid electrolytes is presented. Its unique triflate-group-enhanced frame channels facilitate the formation of a functional inorganic-rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li + and provide hopping sites for rapid Li + transport, enabling a high room-temperature ionic conductivity of 1.1 mS cm -1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm -2 and support a high critical current up to 2 mA cm -2 . Here, the assembled Li||LiFePO 4 solid-like batteries exhibit exceptional cyclability for over 1 year and a half, even outperforming liquid cells. Additionally, high-voltage cylindrical cells and high-capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all-solid-state batteries.

25 ENERGY STORAGE↗

Minimizing Inter‐Lattice Strain to Stabilize Li‐Rich Cathode by Order–Disorder Control

Li-rich Mn-based layered (LMR) cathodes with anionic redox chemistry show great potential for next-generation sustainable Li-ion battery (LIB) applications due to the low cost and high energy density. However, the asynchronous structural evolutions with cycling in the heterogeneous composite structure of LMR lead to serious lattice strain and thus fast electrochemical decay, which hinders the commercialization of LMR cathodes. Here, in this study, an order–disorder coherent LMR cathode is demonstrated that exhibits a higher average voltage (by 0.25 V), negligible voltage decay (97.6% voltage retention after 100 cycles at 100 mA g −1 ), and enhanced cycling stability (98% capacity retention after 200 cycles at 100 mA g −1 ) compared to its layered oxide counterparts. It is proposed that this order–disorder coherent structure design can promote a more synchronous and homogeneous structure evolution during charge and discharge, thus minimizing lattice strain, which significantly prevents layer collapse and collective degradation at high voltage, improving the electrochemical stability. The study displays the feasibility of optimizing the performance of Li-rich cathode materials through a dedicated order–disorder structure control for sustainable energy storage.

Xu, Shenyang [Peking University, Shenzhen (China)]↗

Al‐Rich AlGaN Transistors with Regrown p‐AlGaN Gate Layers and Ohmic Contacts

Abstract Epitaxial regrowth processes are presented for achieving Al‐rich aluminum gallium nitride (AlGaN) high electron mobility transistor (HEMTs) with p‐type gates with large, positive threshold voltage for enhancement mode operation and low resistance Ohmic contacts. Utilizing a deep gate recess etch into the channel and an epitaxial regrown p‐AlGaN gate structure, an Al 0.85 Ga 0.15 N barrier/Al 0.50 Ga 0.50 N channel HEMT with a large positive threshold voltage (V TH = +3.5 V) and negligible gate leakage is demonstrated. Epitaxial regrowth of AlGaN avoids the use of gate insulators which can suffer from charge trapping effects observed in typical dielectric layers deposited on AlGaN. Low resistance Ohmic contacts (minimum specific contact resistance = 4 × 10 −6 Ω cm 2 , average = 1.8 × 10 −4 Ω cm 2 ) are demonstrated in an Al 0.85 Ga 0.15 N barrier/Al 0.68 Ga 0.32 N channel HEMT by employing epitaxial regrowth of a heavily doped, n‐type, reverse compositionally graded epitaxial structure. The combination of low‐leakage, large positive threshold p‐gates and low resistance Ohmic contacts by the described regrowth processes provide a pathway to realizing high‐current, enhancement‐mode, Al‐rich AlGaN‐based ultra‐wide bandgap transistors.

36 MATERIALS SCIENCE↗

Sodium Rich Vanadium Oxy‐Fluorophosphate – Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O – as Advanced Cathode for Sodium Ion Batteries

Abstract Conventional sodium‐based layered oxide cathodes are extremely air sensitive and possess poor electrochemical performance along with safety concerns when operating at high voltage. The polyanion phosphate, Na 3 V 2 (PO 4 ) 3 stands out as an excellent candidate due to its high nominal voltage, ambient air stability, and long cycle life. The caveat is that Na 3 V 2 (PO 4 ) 3 can only exhibit reversible capacities in the range of 100 mAh g −1 , 20% below its theoretical capacity. Here, the synthesis and characterizations are reported for the first time of the sodium‐rich vanadium oxyfluorophosphate, Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O, a tailored derivative compound of Na 3 V 2 (PO 4 ) 3 , with extensive electrochemical and structural analyses. Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O delivers an initial reversible capacity of 117 mAh g −1 between 2.5 and 4.5 V under the 1C rate at room temperature, with 85% capacity retention after 900 cycles. The cycling stability is further improved when the material is cycled at 50 °C within 2.8–4.3 V for 100 cycles. When paired with a presodiated hard carbon, Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O cycled with a capacity retention of 85% after 500 cycles. Cosubstitution of the transition metal and fluorine in Na 3.2 Ni 0.2 V 1.8 (PO 4 ) 2 F 2 O as well as the sodium‐rich structure are the major factors behind the improvement of specific capacity and cycling stability, which paves the way for this cathode in sodium‐ion batteries.

25 ENERGY STORAGE↗

Modulating the Surface Ligand Orientation for Stabilized Anionic Redox in Li‐Rich Oxide Cathodes

Abstract Anionic redox chemistry is emerging as a key concept in the development of high‐energy lithium‐ion batteries, as it enables a nearly doubled charge storage capacity, aiding the development of high‐capacity batteries. However, the anionic reactivity is frequently irreversible from charge to discharge, leading to rapid decay of the capacity and voltage of batteries over long‐term cycling. Although the possibility of controlling the anionic redox reactions by tuning the geometric and electronic structures has recently been proposed, the implementation of this strategy is still a critical challenge. Herein, a strategy is proposed to improve the anionic redox reversibility of a model anionic redox active cathode material, Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 , by tuning the surface ligand geometry via the growth of a lattice‐compatible spinel LiCoO 2 coating layer on the particle surface. Detailed local structure and first principles investigations reveal that the shape and orientation of the octahedral layer in the host lattice are modified. Accordingly, a two‐band oxygen redox behavior is triggered in the ligand‐orientation‐regulated Li‐rich cathode, leading to enhanced reversibility, and thus, remarkably improved capacity and voltage retention over cycling. This study highlights the importance of controllable ligand orientation, carving a new path for the development and design of Li‐rich cathodes in the future.

Liu, Yanchen↗

An Inorganic-Rich Solid Electrolyte Interphase for Advanced Lithium-Metal Batteries in Carbonate Electrolytes

In carbonate electrolytes, the organic-inorganic solid electrolyte interphase (SEI) formed on the lithium (Li) metal anode surface is strongly bonded to Li and experiences the same volume change as Li, thus it undergoes continuous cracking/reformation during plating/stripping cycles. Here we report, an inorganic-rich SEI is designed on a Li metal surface to reduce its bonding energy with Li metal by dissolving 4 M concentrated LiNO 3 in dimethyl sulfoxide (DMSO) as an additive for a fluoroethylene carbonate (FEC) based electrolyte. Due to the aggregate structure of NO 3 - ions and its participation in the primary Li + solvation sheath, abundant Li 2 O, Li 3 N, and LiN x O y grains are formed in the resulting SEI, in addition to the uniform LiF distribution from the reduction of PF 6 - ions. The inorganic-rich SEI’s weak bonding (high interface energy) to Li can effectively promote Li diffusion along the SEI/Li interface and prevent Li dendrite penetration into the SEI. As a result, our designed carbonate electrolyte enables a Li anode to achieve a high Li plating/stripping CE of 99.55% (1 mA cm -2 , 1.0 mAh cm -2 ) and the electrolyte also enables a Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) full cell (2.5 mAh cm -2 ) to retain 75%of its initial capacity after 200 cycles with an outstanding CE of 99.83%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Response of Pseudomonas putida to Complex, Aromatic-Rich Fractions from Biomass

There is strong interest in the valorization of lignin to produce valuable products; however, its structural complexity has been a conversion bottleneck. Chemical pretreatment liberates lignin-derived soluble fractions that may be upgraded by bioconversion. Here, cholinium ionic liquid pretreatment of sorghum produced soluble, aromatic-rich fractions that were converted by Pseudomonas putida (P. putida), a promising host for aromatic bioconversion. Growth studies and mutational analysis demonstrated that P. putida growth on these fractions was dependent on aromatic monomers but unknown factors also contributed. Proteomic and metabolomic analyses indicated that these unknown factors were amino acids and residual ionic liquid; the oligomeric aromatic fraction derived from lignin was not converted. A cholinium catabolic pathway was identified, and the deletion of the pathway stopped the ability of P. putida to grow on cholinium ionic liquid. This work demonstrates that aromatic-rich fractions obtained through pretreatment contain multiple substrates; conversion strategies should account for this complexity.

09 BIOMASS FUELS↗

Alloying of Mn with Bi‐Rich Surfaces of Bi 2 Te 3 by Topotactic Reaction

Interfacing topological insulators (TI) with magnetic materials enables accessing quantum effects for advanced devices. The synthesis of such heterostructures faces challenges due to interlaying mixing and the often-complex multicomponent materials required to combine the desired properties. An alternative synthesis to direct growth is the modification of 2D materials by topotactic reactions to introduce new functionalities into pre-formed single or few-component 2D sheets. Here, the self-formation of bismuthene (a bilayer of Bi; Bi 2 ) is utilized by thermal decomposition of Bi 2 Te 3 as a platform to create novel 2D overlayers on the TI- substrate. Specifically, the Bi 2 layer is modified by reacting it with vapor deposited Mn in an attempt to induce magnetic properties. Scanning tunneling microscopy indicates that the Mn modified surface remains in a planar 2D layer, indicating the formation of an ordered Mn-rich surface layer. Density functional theory (DFT) is used to develop models of both the Bi-rich Bi 2 Te 3 surface as well as their subsequent Mn-modified structure. The DFT models indicate the possibility of magnetic ordering of the high spin Mn 2+ ions. The successful synthesis of planar MnBi alloys on a van der Waals material illustrates topotactic reactions as an alternative for creating novel layered heterostructures.

2D materials↗

Acylation as a successful derivatization strategy for the analysis of pinacolyl alcohol in a glycerol-rich matrix by GC-MS: application during an OPCW Proficiency Test

A derivatization protocol based on the acylation of pinacolyl alcohol (PA), an important marker for the nerve agent soman, is presented. The procedure provides a convenient means of detecting, by gas chromatography-mass spectrometry (GC-MS), PA when present at a low concentration in a complex glycerol/alcohol-rich matrix. While there are only two reports describing the specific analysis of PA in matrices at low concentrations, the protocol described herein represents the first of its kind in the analysis of PA in a highly reactive matrix. Two alternative paths for the protocol’s execution are presented. The first involves the direct derivatization of the PA with either acetyl or benzoyl chloride; both reactions yield ester products with significantly different retention times than those of the interferences of the reactive glycerol-rich matrix and in areas of the GC-chromatogram featuring lower levels of matrix interferences. A second procedure involved an initial diethyl ether/aqueous extraction of the matrix; while the extraction was found to substantially remove many of the hydrophilic matrix components and improve the overall derivatization, it also led to some loss of PA available for the derivatization. Both protocols were applied to the successful derivatization and analysis of PA by GC-MS when present at a 5 μg.mL -1 concentration in a glycerol-rich matrix sample administered during the 48th Proficiency Test administered by the Organisation for the Prohibition of Chemical Weapons (OPCW).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light Dark Matter Detection with Hydrogen-Rich Targets and Low-$T_c$ TES Detectors

Direct detection of nuclear scatterings of sub-GeV dark matter (DM) particles favors low-Z nuclei. Hydrogen nucleus, which has a single proton, provides the best kinematic match. The characteristic nuclear recoil energy is boosted by a factor of a few tens from those for larger nuclei used in traditional Weakly Interacting Massive Particles searches. Furthermore, hydrogen is optimal for detecting spin-dependent nuclear scatterings of sub-GeV DM, where large parameter space still remains unconstrained yet. In this paper, we first introduce several hydrogen-rich targets, which emit two classes of signals under kinetic excitations. One class of the signals is infrared photons, which are from fundamental vibrational and rotational modes of molecules and at several characteristic wavelengths. Another is acoustic phonons and optical phonons that decay into acoustic phonons. Then we discuss the technical status and future researches of low-T c transition-edge sensor (TES) detectors, which measure the infrared photons and acoustic phonons with desirable sensitivities. Utilization of hydrogen-rich targets and ultra-sensitive low-T c TES detectors for light DM detection requires both theoretical modeling and experimental prototyping.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Temperature-Dependence of Corrosion of Ni-Based Superalloys in Hot CO 2 -Rich Gases Containing SO 2 Impurities

Future power plants will require Ni-based superalloys resistant to high-temperature corrosion in CO 2 -rich environments containing impurities. In this work, several commercially available Ni-based alloys (617, 230, 625, 263, 740H) were exposed at 600°C, 650°C, 750°C and 1 atm to 95% CO 2 , 4% H 2 O, 1% O 2 without/with 0.1% SO 2 to simulate compositions expected in a direct-fired supercritical CO 2 power cycle. The results indicate no effect of SO 2 at 750°C, a small negative effect at 650°C, and a large negative effect at 600°C. Alloys exposed at the higher temperatures (650–750°C) formed thin Cr-rich oxide scales, whereas the lowest temperature (600°C) resulted in thicker scales consisting of non-protective oxides and sulfates. Thermodynamic analysis indicates this increased corrosion is associated with a transition in the stable compounds in contact with the gas. Understanding the factors that affect this transition will aid in the selection or design of alloys for future CO 2 -based power systems.

36 MATERIALS SCIENCE↗

Prediction of the Al-rich part of the Al-Cu phase diagram using cluster expansion and statistical mechanics

In this work, the thermodynamic properties of α-Al and other phases (GP zones, θ'', θ' and θ) in the Al-rich part of the Al-Cu system have been obtained by means of the cluster expansion formalism in combination with statistical mechanics. This information was used to build the Al-rich part of the Al-Cu phase-diagram taking into account vibrational entropic contributions for θ', as those of the other phases were negligible. The simulation predictions of the phase boundaries between α-Al and either θ'', θ' or θ phases as a function of temperature are in good agreement with experimental data and extend the phase boundaries to a wider temperature range. The DFT calculations reveal the presence of a number of metastable Guinier-Preston-zone type configurations that may coexist with α-Al and θ'' at low temperatures. They also demonstrate that θ' is the stable phase below 550K but it is replaced by θ above this temperature due to the vibrational entropic contribution to the Gibbs energy of θ'. This work shows how the combination of cluster expansion and statistical mechanics can be used to expand our knowledge of the phase diagram of metallic alloys and to provide Gibbs free energies of different phases that can be used as input in mesoscale simulations of precipitation.

36 MATERIALS SCIENCE↗

Equation of state of neutron-rich matter in d -dimensions

Nuclear systems under constraints, with high degrees of symmetries and/or collectivities may be considered as moving effectively in spaces with reduced spatial dimensions. We first derive analytical expressions for the nucleon specific energy E 0 (ρ), pressure P 0 (ρ), incompressibility coefficient K 0 (ρ) and skewness coefficient J 0 (ρ) of symmetric nucleonic matter (SNM), the quadratic symmetry energy E sym (ρ), its slope parameter L(ρ) and curvature coefficient K sym (ρ) as well as the fourth-order symmetry energy E sym,4 (ρ) of neutron-rich matter in general d spatial dimensions (abbreviated as "dD") in terms of the isoscalar and isovector parts of the isospin-dependent single-nucleon potential according to the generalized Hugenholtz-Van Hove (HVH) theorem. The equation of state (EOS) of nuclear matter in dD can be linked to that in the conventional 3-dimensional (3D) space by the ε-expansion which is a perturbative approach successfully used previously in treating second-order phase transitions and related critical phenomena and more recently in studying the EOS of cold atoms. The ε-expansion of nuclear EOS in dD based on a reference dimension d f = d – ε is shown to be effective with –1 ≲ ε ≲ 1 starting from 1 ≲ d f ≲ 3 in comparison with the exact expressions derived using the HVH theorem. Moreover, the EOS of SNM (with/without considering its potential part) is found to be reduced (enhanced) in lower (higher) dimensions, indicating in particular that the many-nucleon system tends to be deeper bounded but saturate at higher densities in spaces with lower dimensions. Here, the links between the EOSs in 3D and dD spaces from the ε-expansion provide new perspectives to the EOS of neutron-rich matter.

79 ASTRONOMY AND ASTROPHYSICS↗

Probing signals of self-interacting dark matter core collapse in H I -rich galaxies

Here, we analyze rotation curves of five Hi-rich galaxies recently discovered with MeerKAT. These galaxies exhibit sharply rising rotation curves, while their baryonic components are not dynamically dominant, suggesting that their dark matter halos have high inner densities. When fitting the standard Navarro–Frenk–White (NFW) halo model, four galaxies require extremely high halo concentrations, exceeding the cosmological median by 5σ. In contrast, self-interacting dark matter (SIDM) halos in the core-collapse phase naturally account for the high densities in these galaxies. For halos with masses around 10 11 M ⊙ , those in cosmic filaments exhibit concentrations consistent with the cosmological average, while halos in cosmic nodes show relatively higher concentrations that align with the SIDM fits but remain insufficient for the NFW fits. Our analysis indicates that these Hi-rich galaxies may have formed in cosmic nodes of dark matter with significant self-interactions.

dark matter↗

Dissolution and reprecipitation of amorphous silica in silica Rich shales induces Non-Monotonic evolution of porosity in acidic reactive environments

Advances in sustainable subsurface energy technologies are crucial for meeting our energy and resource needs for a climate-resilient future. Novel strategies to harness subsurface shale reservoirs for recovering valuable metals and for enabling CO 2 storage are influenced by the morphological and mineralogical heterogeneities of these materials. In this context, delineating the interactions of highly acidic solutions such as wet supercritical CO 2 on shales with varying mineralogy is crucial to inform the stability of caprock seal for CO 2 storage and enhancements in permeability for fluid transport, reactivity, and storage. The feedback chemical effects associated with the interactions of acidic solutions on the morphologies and mineralogies of shales have not been extensively investigated. These insights are crucial for assessing temporal changes in the reactivity and the fate of the fluids in subsurface environments. In this study, we investigate the effect of 1M HCl solution on the chemistry and morphology of three different shale samples with varying carbonate, clay and silica contents. An increase in the amorphous content, from 37% to 41.3%, of silica-rich and carbonate/clay lean shale is noted due to reactions with an acidic solution which is attributed to the dissolution of Si-bearing phases such as clays, accompanied by SiO 2 precipitation. In shales bearing high content of clays and carbonates, significant increase in the pore volumes and surface areas are noted. Non-monotonic changes in the micron-scale porosity of silica rich–carbonate/clay lean (e.g., Mowry shale) are noted using in-situ X-ray microtomography experiments. Due to the initial mobilization of silica and dissolution of carbonate/clay phases, the total porosity slightly increases from 6.7% to 10.7% followed by a decrease to similar to 4% caused by SiO 2 reprecipitation. In conclusion, these findings suggest that even though silica is less reactive in acidic environments, the changes in the amorphous and crystalline content due to dissolution and reprecipitation alter the porosity and fluid flow paths.

04 OIL SHALES AND TAR SANDS↗

Phase equilibria in iron-rich Sm–Fe–Ti and Sm–(Fe,Co)–Ti alloys at 1100–1200 °C

Iron-rich corners of ternary Sm–Fe–Ti phase diagram at 1100 °C and quasi-ternary Sm–Fe 0.8 Co 0.2 –Ti phase diagrams at 1100 and 1200 °C are constructed based on experimental investigation of equilibrated alloys with electron probe microanalysis, X-ray diffraction and thermomagnetic analysis. In addition, the upper boundaries of the temperature ranges of Sm(Fe,[Co,]Ti) 12 and Sm 3 (Fe,[Co,]Ti) 29 phases are determined with differential thermal analysis to update earlier rough estimates. The existence of a high-temperature phase of the Th 2 Ni 17 type, originally reported by Ivanova et al. [J. Alloys Compd. 224 (1995) 29], is confirmed. In the Sm–Fe 0.8 Co 0.2 –Ti system, the composition and equilibria of this hexagonal phase are established for 1200 °C; it is Sm-depleted (≈9.8 at.% Sm) compared to the 2:17 stoichiometry and it coexists with the rhombohedral 2:17 phase. The magnetic anisotropy of the cobalt-substituted Th 2 Ni 17 -type phase is planar, with the easy magnetization direction parallel to [100]. Equilibrium between a Sm-rich liquid phase and the 1:12 phase, which is important for the development of new high-performance permanent magnets, is absent up to 1000 °C, but does exist at 1100 °C (for the 1:12 phase with at least 8.7–8.9 at.% Ti) and at 1200 °C (for the 1:12 phase with as little as 7.4 at.% Ti). The development of magnets may be complicated, however, by an observed tendency of the high-temperature liquid to solidify into ferromagnetic phases including the Th 2 Ni 17 -type phase. The Curie temperatures of the α-(Fe,Ti), Sm(Fe,Ti) 12 , Sm 3 (Fe,Ti) 29 and rhombohedral Sm 2 (Fe,Ti) 17 phases are not only increased by the partial Co substitution for Fe, but their dependence on the Ti concentration is changed by this Co substitution from positive (or, for the 1:12 phase, zero) to negative values.

36 MATERIALS SCIENCE↗