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At least 955 records · Page 53

3D microstructures for rapid absorption/desorption in mechanically constrained liquid absorbents

An absorber or desorber contains one or more micro-channels that have a 3-D structured heat-exchanging surface and a membrane on the microchannel situated distal to the 3-D structured heat-exchanging surface, where the membrane is permeable to a solvent of a solution employed in the absorber or desorber. The 3-D structured surface promotes mixing of hot and cold solution between the 3-D structured heat-exchanging surface and a vapor-exchanging surface proximal to the membrane. The mixing reduces the differences in concentration and temperature of the bulk solution and the solution at the vapor-exchanging surface to enhance the efficiency and rate of absorption or desorption of the solvent.

36 MATERIALS SCIENCE↗

Wettability of ultra-small pores of carbon electrodes by size-asymmetric ionic fluids

Recently, we studied the phase behavior of ionic fluids under confinement using the classical density functional theory within the framework of the restricted primitive model. Additionally, the theoretical results indicate that narrowing the pore size may lead to a drastic reduction in the electric double layer capacitance, while increasing the surface electrical potential would improve the ionic accessibility of micropores. In this work, we extend the theoretical investigation to systems containing size-asymmetric electrolytes that may exhibit a vapor-liquid like phase transition in the bulk phase. The effects of pore size and surface electric potential on the phase diagram and microscopic structures of the confined electrolytes were studied over a broad range of parameters. We found that decreasing the pore size or increasing the surface potential could destabilize the liquid phase in micropores, and capillary evaporation could occur regardless of the size asymmetry between cations and anions. Compared to that in a symmetric ionic system, the vapor-liquid phase separation is more likely to take place as the size asymmetry becomes more pronounced. The phase transition would alter the “accessibility” of ions to micropores and lead to coexisting micropores with different surface charge densities as identified by Monte Carlo simulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnesium production by molten salt electrolysis with liquid tin cathode and multiple effect distillation

Low-cost clean primary production of magnesium metal is important for its use in many applications, from light-weight structural components to energy technologies. This work describes new experiments and cost and emissions analysis for a magnesium metal production process. The process combines molten salt electrolysis of MgO using MgF₂-CaF₂ electrolyte and a reactive liquid tin cathode, with gravity-driven multiple effect thermal system (G-METS) distillation to separate out the magnesium product, and re-use of the tin. Electrolysis experiments with carbon anodes showed current yield above 90%, while a yttria-stabilized zirconia solid oxide membrane (SOM) anode experiment showed 84% current yield. G-METS distillation is an important component of the envisioned process. It can potentially lower costs and energy use considerably compared with conventional magnesium distillation. Techno-economic analysis including detailed mass and energy balances shows that this electrolyte composition could lower costs by utilizing CaO, which is the primary impurity in MgO, as the Hall-Héroult process uses the sodium impurity in alumina. Analysis options include: raw material types (magnesite rock vs. brine or seawater), drying and calcining using electricity vs. natural gas, and carbon vs. SOM anode type. Using SOM inert anodes results in a cost premium around 10%–15%, mostly due to higher electrical energy usage resulting from membrane resistance, and reduces GHG emissions by approximately 1 kg CO₂/kg Mg product. Capital and operating cost estimates, and cradle to gate greenhouse gas (GHG) emissions analysis under several raw material and process technology scenarios, show comparable costs and emissions to those of aluminum production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-organized patterns at the plasma–liquid anode interface in a helium glow discharge: temporal development and mechanisms

Self-organization at the plasma–liquid anode interface is a commonly observed phenomenon for atmospheric pressure glow plasmas, resulting in patterns with distinctive shapes such as circular ring, star-shaped, and gear-like structures, depending primarily on the discharge current and solution conductivity. Recent studies have shown that the electrode gap distance, solute used for liquid anode solution, and gas composition can also significantly impact pattern formation. Nonetheless, an overarching model or explanation of the key underlying mechanisms consistent with all experimentally observed trends is not yet reported. We propose a key underlying mechanism enabling pattern formation motivated by a detailed parametric study of pattern formation complemented by the temporal development of patterns and consistent with all observed trends. Pattern formation was observed to be on a time scale of 100 μs, similar to the time scales of gas heating and evaporation. It was found that a minimum water evaporation rate of (3.5 ± 0.5) × 10 –6 kg s –1 and reduced electric field in the positive column of 16.6 ± 0.4 Td is required for pattern formation in the investigated cases irrespective of solution conductivity and gas composition for NaCl solutions. Nonetheless, the presence of cations for which the corresponding metal atom has a low ionization energy was identified as a necessary condition for pattern formation. Furthermore, the reported results suggest that the presence of a small amount of metal atoms in the gas phase with low ionization energy enhances the overall ionization rate in the near anode region which triggers pattern formation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Structural Insights into Low and High Recalcitrance Natural Poplar Variants Using Neutron and X-ray Scattering

Here, we used small-angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS) to study two Populus trichocarpa variants, GW-11012 and BESC-316, with lignin contents of 17.8 and 23.2%, respectively, to understand why the low lignin variant has increased sugar release during liquid hot water (LHW) pretreatment. SANS showed differences in cell wall polymer arrangement in the variants. In GW-11012, the cellulose microfibrils were similar in size to BESC-316 but were not equally spaced and lignin was aggregated rather than homogenously interspersed with other matrix co-polymers. However, after LHW pretreatments, the SANS profiles of the pretreated variants were almost indistinguishable, indicating that the nanoscale structural features could not adequately explain the increased sugar release observed in GW-11012. WAXS analysis revealed higher cellulose crystallinity and larger crystallite size in native and pretreated GW-11012. However, the most significant difference was that the crystallite orientation was approximately 2-fold higher in GW-11012. This suggests that higher crystallite orientation may be favorable for the action of processive cellulases leading to increased sugar release from GW-11012. Our study shows that there is a complex interplay between cell wall polymers during their deposition resulting in changes in lignin distribution and cellulose structure, highlighting the importance of investigating plant cell wall architecture across multiple length scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-molecule 3D imaging of HIV cellular entry by liquid-phase electron tomography

Enveloped viruses, including human immunodeficiency virus (HIV) and SARS-CoV-2, target cells through membrane fusion process. The detailed understanding of the process is sought after for vaccine development but remains elusive due to current technique limitations for direct three-dimensional (3D) imaging of an individual virus during its viral entry. Recently, we developed a simple specimen preparation method for real-time imaging of metal dynamic liquid-vaper interface at nanometer resolution by transmission electron microscopy (TEM). Here, we extended this method to study biology sample through snapshot 3D structure of a single HIV (pseudo-typed with the envelope glycoprotein of vesicular stomatitis virus, VSV-G) at its intermediate stage of viral entry to HeLa cells in a liquid-phase environment. By individual-particle electron tomography (IPET), we found the viral surface release excess lipids with unbound viral spike proteins forming ~50-nm nanoparticles instead of merging cell membrane. Moreover, the spherical-shape shell formed by matrix proteins underneath the viral envelope does not disassemble into a cone shape right after fusion. Further, the snapshot 3D imaging of a single virus provides us a direct structure-based understanding of the viral entry mechanism, which can be used to examine other viruses to support the development of vaccines combatting the current ongoing pandemic.

Kong, Lingli↗

Zero-field Hall effect emerging from a non-Fermi liquid in a collinear antiferromagnet V 1/3 NbS 2

Magnetically intercalated transition metal dichalcogenides (TMDs) provide a versatile three-dimensional (3D) material platform to explore quantum phenomena and functionalities that emerge from an intricate interplay among magnetism, band structure, and electronic correlations. Here, we report the observation of a nearly magnetization-free anomalous Hall effect (AHE) accompanied by non-Fermi liquid (NFL) behavior and collinear antiferromagnetism (AFM) in V 1/3 NbS 2 . Our single-crystal neutron diffraction measurements identify a commensurate, collinear AFM order formed by intercalated V moments. In the magnetically ordered state, the spontaneous AHE is tenfold greater than expected from empirical scaling with magnetization, and this strongly enhanced AHE arises in the NFL regime that violates the quasiparticle picture. V 1/3 NbS 2 challenges the existing single-particle framework for understanding AHEs based on one-body Berry curvature and highlights the potential of magnetically intercalated TMDs to unveil new electronic functionalities where many-body correlations play a critical role.

36 MATERIALS SCIENCE↗

Noninvasive liquid level sensing with laser generated ultrasonic waves

This article proposes a noninvasive liquid level sensing technique using laser-generated ultrasound waves for nuclear power plant applications. Liquid level sensors play an important role of managing the coolant system safely and stably in the plant structure. Current sensing techniques are mostly intrusive, performing inside the fluidic structure, which is disadvantageous in terms of the regular maintenance of the plant system. Furthermore, typical intrusive sensors do not perform stably under varying environmental conditions such as temperature and radiation. In this study, sensing units are attached to the outer surface of a liquid vessel to capture guided ultrasound waves in a nonintrusive manner. The signal intensity of the guided wave dissipates when the signal interacts with the internal liquid media. The sensing mechanism is mathematically expressed as an index value to correlate the liquid level with the sensor signal. For the acoustic wave generation, laser-generated ultrasound was adopted instead of using typical contact type transducers. Following the simulation validation of the proposed concept, the performance of the developed sensor was confirmed through experimental results under elevated liquid temperature conditions. Finally, the nonlinear multivariable regression exhibited the best-fit to the datasets measured under the variable liquid level and temperature conditions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Multiple experimental studies of pore structure and mineral grain sizes of the Woodford shale in southern Oklahoma, USA

Pore structure study is an important part of unconventional shale reservoir characterization, since the pore system provides the primary petroleum storage space and fluid flow pathways. Previous studies have suggested that the pore structure is related to the total organic carbon (TOC) content, mineral compositions, and the maturity of the organic matter (OM). However, few studies have focused on the mineral grains, the primary grains being deposited but before cementation, which are the building blocks of shale. Eight Woodford Shale outcrop samples from southern Oklahoma were chosen to study the effects of mineral grain size on the pore structure characterization, using multiple and complementary experimental approaches, including laser diffraction, mineralogy, TOC, pyrolysis, liquid immersion porosimetry, mercury intrusion porosimetry, gas physisorption, (ultra) small angle X-ray scattering, scanning electron microscopy, and spontaneous imbibition. The results from different experiments of eight samples show that the Woodford Shale has the mean mineral grain diameters at 3–6 μm, a wide range of porosity at 3–40% and pore diameters at 50–1,000 nm, and various pore connectivity. Grain size variation was probably caused by the sea-level fluctuation during its deposition, which affect the porosity, pore size distribution, and pore connectivity. With decreasing mineral grain sizes, the porosity tends to increase while the pore connectivity worsens. The results also indicate that OM and carbonates in this low-maturity Woodford Shale could block the pores and decrease the porosity. Coupling with the grain size analyses, the control of depositional environment on grain sizes and subsequent effects on pore structure is identified. The pore structure characteristics over a wide pore-diameter range provided by multiple experiments could improve the understanding of storage space and fluid flow in the Woodford Shale to further increase its petroleum production.

54 ENVIRONMENTAL SCIENCES↗

Origins of Clustering of Metalate–Extractant Complexes in Liquid–Liquid Extraction

Effective and energy-efficient separation of precious and rare metals is very important for a variety of advanced technologies. Liquid-liquid extraction (LLE) is a relatively less energy intensive separation technique, widely used in separation of lanthanides, actinides, and platinum group metals (PGMs). In LLE, the distribution of an ion between an aqueous phase and an organic phase is determined by enthalpic (coordination interactions) and entropic (fluid reorganization) contributions. The molecular scale details of these contributions are not well understood. Preferential extraction of an ion from the aqueous phase is usually correlated with the resulting fluid organization in the organic phase, as the longer-range organization increases with metal loading. However, it is difficult to determine the extent to which organic phase fluid organization causes, or is caused by, metal loading. In this study, we demonstrate that two systems with the same metal loading may impart very different organic phase organizations and investigate the underlying molecular scale mechanism. Small-angle X-ray scattering shows that the structure of a quaternary ammonium extractant solution in toluene is affected differently by the extraction of two metalates (octahedral PtCl 6 2- and square-planar PtCl 6 2- ), although both are completely transferred into the organic phase. The aggregates formed by the metalate-extractant complexes (approximated as reverse micelles) exhibit a more long-range order (clustering) with PtCl 6 2- compared to that with PtCl 6 2- . Vibrational sum frequency generation spectroscopy and complementary atomistic molecular dynamics simulations on model Langmuir monolayers indicate that the two metalates affect the interfacial hydration structures differently. Furthermore, the interfacial hydration is correlated with water extraction into the organic phase. Overall, these results support a strong relationship between the organic phase organizational structure and the different local hydration present within the aggregates of metalate-extractant complexes, which is independent of metalate concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupled model for liquid lithium plasma facing components

Numerical analysis provides the design choice and operating window of liquid metal Plasma Facing Components (PFC) concepts. Coupled analysis of boundary plasma together with the surrounding boundary structures is required. Here, to achieve this goal, PPPL is developing a comprehensive multi-physics model for modeling of PFCs in fusion devices. The model includes the fluid-kinetic code SOLPS-ITER and the flow and heat transfer code CFX from ANSYS. SOLPS-ITER was augmented with a liquid metal boundary condition algorithm, allowing direct two-way coupling of the plasma analysis with the two-dimensional analytical slab flow model which includes heat convection in the liquid metal PFC. The target heat flux resulting from this coupled analysis is used as a boundary condition for detailed 3D Computational Fluid Dynamics (CFD) Magneto Hydro Dynamics (MHD) and heat transfer analysis. A new formulation of MHD equations is introduced in the numerical procedure ensuring current conservation of the discretized equations. Results of the 3D analysis are used for final validation of the coupled model. A PFC design where a porous wall is used to stabilize the liquid metal surface, while MHD drive is used to push the liquid metal flow inside the PFC, will be investigated in the regimes where vapor shielding is created for enhanced volumetric plasma heat dissipation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Physical properties investigation of tetragonal Ba T 2 P 2 (T = Ru, Pd)

The structural, thermal, electrical transport, and magnetic properties of ternary compounds BaT 2 P 2 (T = Ru, Pd) are reported together with electronic structure calculations. Our results show that BaRu 2 P 2 crystallises in the layered tetragonal ThCr 2 Si 2 -type structure (space group I4/mmm) whereas BaPd 2 P 2 adopts the primitive tetragonal CeMg 2 Si 2 -type structure (space group P4/mmm). The combined experimental results and electronic structure calculations suggest metallic and diamagnetic ground states for both materials. Electrical transport measurements further indicate non-Fermi liquid behaviour at low temperatures. Notably, BaRu 2 P 2 exhibits an anomalous feature in the magnetic susceptibility at T ~ 260 K, similar to that observed in BaRu 2 As 2 . A comparison between the bare density of states obtained from electronic structure calculations and the experimentally estimated values suggests the presence of strong correlation effects in the material. Furthermore, the heat capacity of BaPd 2 P 2 , calculated using the full phonon dispersion relation, is in good agreement with the experimental data, particularly at low temperatures, highlighting the significant contribution of optical phonon branches to C P in this temperature range.

flat bands↗

Hierarchical Defect Engineering for LiCoO 2 through Low-Solubility Trace Element Doping

Real-world industry-relevant battery composite electrodes are hierarchically structured. Their structural and chemical complexity is featured by ubiquitous multi-scale porosity and cracks, solid-solid and solid-liquid interfaces, compositional and redox heterogeneity, as well as lattice disordering and deformation. In particular for the active cathode particles, which are the fundamental building blocks for the energy reservoir, it is a consensus that these structural and chemical defects could have a profound impact on the battery performance. An in-depth understanding of the underlying mechanisms could critically inform the cathode material engineering, which would have a tremendous potential but remains a daunting challenge at present. In this work, we tackle this question by studying LiCoO 2 (LCO) with trace doping of Ti, which exhibits a low solubility in the LCO layered lattice. Additionally, we observed the spontaneous and heterogeneous segregation of the dopant (Ti) across a wide range of length scales. In addition to the modification of the particle surface and the buried grain boundaries within the particle, we reveal that the Ti doping has induced a significant amount of lattice distortions, which, in turn, promotes the robustness of the LCO lattice at high state of charge (above 4.5V). Our result formulates a multi-scale defect engineering strategy that could be applicable to the synthesis of a broad range of energy materials for applications in batteries and beyond.

36 MATERIALS SCIENCE↗

Functionalization of Cathode–Electrolyte Interface with Ionic Liquids for High-Performance Quasi-Solid-State Lithium–Sulfur Batteries: A Low-Sulfur Loading Study

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li6PS5F0.5Cl0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries.

25 ENERGY STORAGE↗

Li 2 GeS 3 : Lithium Ionic Conductor with an Unprecedented Structural Type

Lithium-ion batteries (LIBs) are widely used in electric vehicles, mobile electronic devices, and large-scale stationary energy storage systems. However, their liquid electrolytes present significant safety concerns due to their inherent flammability. To address this, the focus has shifted toward all-solid-state batteries (ASSBs) utilizing inorganic solid electrolytes that promise enhanced safety. In this work, we report the discovery of a new crystal structural type of Li-ion conductor, Li 2 GeS 3 , with a unique structure, synthesized by a solid-state reaction from Li 2 S and GeS 2 . It was first reported in 2000 with an orthorhombic unit cell, but its detailed crystal structure remains veiled. Here, we have unveiled its structure for the first time, employing an ab initio structure determination technique from powder X-ray and time-of-flight neutron diffraction data. The compound has an unprecedented crystal structural type with a hexagonal $P6_1$ symmetry and a unit cell of α = 6.79364(4) Å and c = 17.90724(14) Å. Its structure is comprised of a distorted hexagonal close-packed arrangement of sulfur anions with three asymmetric metal atoms: Li1, Li2, and Ge are in tetrahedral cavities surrounded by sulfur atoms. The ionic conductivity of Li 2 GeS 3 was measured to be 1.63 × 10 –8 S cm –1 at 303 K and 2.45 × 10 –7 S cm –1 at 383 K. Bond valence energy landscape calculations revealed three-dimensional lithium diffusion pathways within the structure. This novel crystal structure in Li 2 GeS 3 holds the potential for developing high-performance ionic conductors through suitable chemical substitution and offers valuable insights into designing new ionic conductors for ASSBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Processing Effects on the Self-Assembly of Brush Block Polymer Photonic Crystals

Here,the self-assembly of poly(dimethylsiloxane)-b-poly(trimethylene carbonate) (PDMS-b-PTMC) bottlebrush block polymers was investigated under different processing conditions. Small-angle X-ray scattering (SAXS) and UV/Visible spectroscopy provided insight into the self-assembly and structure in response to heating and applied pressure. In the absence of applied pressure (i.e., before annealing), the PDMS-b-PTMC bottlebrush block polymers are white solids and adopt small, randomly oriented lamellar grains. Heating the materials to 140 °C in the absence of applied pressure appears to “lock in” the isotropic, short-range-ordered state, preventing the formation of the long-range-ordered lamellar structure responsible for photonic properties. Applying modest anisotropic pressure (3 psi) between parallel plates at ambient temperature orients the short-range lamellar grains; however, applied pressure alone does not produce long-range order. Only when the bottlebrush block polymers were heated (>100 °C) under modest pressure (3 psi) were long-range-ordered photonic crystals formed. Analysis of the SAXS data motivated analogies to liquid crystals and revealed the potential self-assembly pathway. These results provide insight into the structure and self-assembly of bottlebrush block polymers with low glass transition temperature side chains in response to different processing conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Competitive Adsorption of Lubricant Base Oil and Ionic Liquid Additives at Air/Liquid and Solid/Liquid Interfaces

Oil-soluble ionic liquids (ILs) have been proved as effective additives in lubricant oils through tribological experiments and post-test analytical analyses. Here, surface structures of lubricant base oil, oil-soluble ILs, and their mixtures at the air/liquid and solid/liquid interfaces have been studied using sum frequency generation (SFG) vibrational spectroscopy. At the air/base oil and air/IL interfaces, the alkyl chains of the studied compounds were shown to be conformationally disordered and their terminal methyl groups point outward at the liquid surface. The base oil dominates the air/(base oil + IL) interface due to its higher surface excess propensity and larger bulk concentration. At the solid (silica) surface, ILs adopt a structure with their charged headgroups in contact with the silica surface, while their alkyl chains are more conformationally ordered or packed compared to the air/IL interface. At the interface between silica and (base oil + IL) mixtures, ILs also preferentially adsorb to the silica surface with their layer structures somewhat different from those of ILs alone. These results showed that ILs can adsorb onto the solid surface even before tribological contacts are made. The insights obtained from this SFG study provide a better understanding of the role of ionic liquids in lubrication.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heavy Versus Light Lanthanide Selectivity for Graphene Oxide Films is Concentration Dependent

Rare earths are important materials in various technologies such as catalysis and optoelectronics. Graphene oxide (GO) is a promising material for separation applications, including the isolation of lanthanides from complex mixtures. Previous works using fatty acid monolayers have demonstrated preferential heavy versus light lanthanide adsorption, which has been attributed to differences in lanthanide ion size. In this work, we used interfacial X-ray fluorescence measurements to reveal that GO thin films at the air/water interface have no lanthanide selectivity for dilute subphases. However, at high subphase concentrations, ~8 times more Lu is adsorbed than La. By comparing the GO results with an ideal monolayer with a carboxylic acid headgroup, arachidic acid (AA), we demonstrate that the number of Lu ions adsorbed to GO is significantly higher than the number expected to compensate for the surface charge. Vibrational sum frequency generation (SFG) spectroscopy results on both GO thin films and AA monolayers reveal a red-shifted SFG signal in the OH region, which we attribute to partial dehydration of the adsorbed ions and carboxylic acid headgroups. Liquid surface X-ray reflectivity data show that the GO thin film structure does not significantly change between the very dilute and concentrated subphases. We speculate that the functional groups of both GO and AA facilitate cation dehydration, which is essential for ion adsorption. Heavy lanthanide Lu has stronger ion–ion correlations that can overcome the electrostatic repulsion between cations at higher concentrations compared to light lanthanide La, meaning GO and AA can exhibit apparent overcharge with Lu. Lastly, the layered structure of the GO films and reactive chemical nature of GO itself can accommodate ion adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗