Salt and Water Transport in Reverse Osmosis Membranes: Beyond the Solution-Diffusion Model
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54 ENVIRONMENTAL SCIENCES↗
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Gas Transport in the Insensitive High Explosive PBX 9502
Small-scale laboratory experiments were performed to analyze gas transport mechanics in PBX 9502, an insensitive high explosive (IHE) composition. Two independent investigations are reported here. First, gas permeametry and dynamic pycnometry techniques were used to measure the molecular flow (Knudsen) coefficient and the internally interconnected void fraction of pristine and thermally damaged samples in two uniaxial pressing orientations. The permeability of PBX 9502 was found to be unmeasurably low (of the same order of magnitude as PTFE) with gas transport being diffusion-dominated. Secondly, a pressure vessel experiment was developed to measure quasi-static and dynamic gas generation as the explosive was heated to self-ignition (cookoff). The gas generation results and the permeability/diffusivity findings provide evidence that PBX 9502 remains impermeable until seconds prior to self-ignition. At ignition, internal void-pressure drives macro-scale cracking and the sample becomes uniformly incorporated in the following deconsolidating deflagration. These results are discussed within the context of previous observations of pressure-dependent cookoff behavior of PBX 9502 and provide a more complete description of thermal damage evolution in this explosive composition.
45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
Understanding coarsening of a post-corrosion microstructure in a molten salt by combining phase-field modeling and in situ tomography
Alloys corroding in molten salt have been observed to form bicontinuous, nanoporous microstructures via dealloying, which subsequently undergo coarsening due to facile transport in high-temperature conditions. In this work, we describe a methodology to elucidate the underlying transport mechanisms during coarsening of a bicontinuous microstructure via quantitative comparisons between phase-field simulations and four-dimensional in situ experiments, in this case X-ray nanotomography of the coarsening of a dealloyed 80 wt% Ni-20 wt% Cr microwire in molten KCl-MgCl 2 at 800°C. We conduct phase-field simulations initialized from experimental data to model coarsening via three different transport mechanisms: surface diffusion, solid bulk diffusion, and liquid bulk diffusion. These simulations reproduce key features of the experiment, such as the densification of the outer layer of the dealloyed wire and the reduction in radius over time. We quantitatively compare different microstructural characteristics between the simulations and experiment and extract temporal scaling factors that optimally match the time scales of the simulations to that of the experiment. This allows us to evaluate morphological similarity between the simulations and experiment and relate the experimental coarsening kinetics to fundamental material properties. We find that surface diffusion is most likely to be the dominant coarsening mechanism, and its kinetics imply a surface diffusivity of D S = 8.9 x 10 -20 m 3 /s, which is within the range of reported values for Ni-vacuum interfaces at 800°C. However, the difference between the experiment and the surface diffusion simulation increases substantially at late times, suggesting that other mechanisms, such as the dissolution of residual Cr, may be at play.
36 MATERIALS SCIENCE↗
Hygro-thermo-mechanical modeling of partially saturated air-entrained concrete containing dissolved salt and exposed to freeze-thaw cycles
Highlights: • A model for cyclic freezing of air-entrained concrete containing salt is proposed. • The freeze-thaw hysteresis, also including the effect of dissolved salt, is modeled. • The diffusive and convective flux of salt is coupled to the freeze-thaw processes. • The freeze-thaw response of air-entrained concrete containing salt is reproduced. • Liquid absorption from reservoirs increases with an increased concentration of salt. In cold regions, understanding the freeze-thaw behavior of air-entrained concrete is important for designing durable structures and assessing the remaining service life of existing structures. This study presents a hygro-thermo-mechanical multiphase model that describes the cyclic freeze-thaw behavior of partially saturated air-entrained concrete containing dissolved salt. An equilibrium and a non-equilibrium approach are adopted to model the ice formation, including the freeze-thaw hysteresis, inside the porous network. The model also considers the diffusive and convective transport of the dissolved salt coupled to the freeze-thaw processes. Two examples are presented to verify and highlight the capabilities of the model. The first example shows that the model is capable of reproducing the experimentally observed mechanical response of specimens containing NaC1-solutions of different concentrations. In the second example, a larger absorption of liquid from an external reservoir is obtained with an increasing salt concentration in the reservoir, which is consistent with experimental observations.
36 MATERIALS SCIENCE↗
Influence of salinity gradients on the diffusion of water and ionic species in dual porosity clay samples
Not Available
58 GEOSCIENCES↗
Protecting groups in insertion chemistry: Site-selective positioning of lithium ions in intercalation hosts
The expanding toolbox of functionalization chemistries for selectively installing moieties on specific sites of a substrate underpins almost all modern organic and biochemical syntheses. Likewise, the installation of mobile guest ions in specific interstitial sites and their transport along specific diffusion pathways forms the basis of modern lithium (Li)-ion battery electrodes. Many insertion hosts afford a diverse range of accessible interstitial sites. However, site-selective positioning of cations with atomic precision remains almost entirely unexplored. Here, we show that by deciphering site preferences of co/pre-intercalated cations, we can position Li ions in four distinct sites within a 1D ζ-V 2 O 5 insertion host. The use of topochemistry to effect single-crystal-to-single-crystal transformations enables atomic-resolution mapping of the selective positioning of Li ions through single-crystal X-ray diffraction. Here we image interstitial sites that are occupied at high depths of discharge, thereby obtaining unprecedented structural insight into “fully stuffed” frameworks critical for the realization of high-energy-density intercalation electrodes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Water and salt transport properties of pentiptycene-containing sulfonated polysulfones for desalination membrane applications
A series of pentiptycene-containing disulfonated polysulfone copolymers (PENT-BP) were synthesized via condensation polymerization. Water and salt transport properties (solubility, diffusivity and permeability) were characterized for acid-form membranes (PENT-BP(H)) and compared with triptycene-based sulfonated polysulfones (TRP-BP(H)) and a non-iptycene-containing 4,4'-biphenol-based series (BPS(H)) of polysulfones to investigate the effect of pentiptycene on membrane performance. At comparable water content, the PENT-BP(H) exhibited increased water and salt permeability due to the additional free volume introduced by the pentiptycene units. Enhanced water/salt permeability selectivity of PENT-BP(H) series was also observed due to a significantly higher diffusivity selectivity. At comparable water permeance (P w D ~ 8 X 10 -6 cm 2 /s), the salt rejection of PENT-BP (H) copolymers obtained from dead-end filtration reached 91–93% at 400 psi, higher than that of a corresponding BPS(H) series. This study suggests that incorporation of iptycene moieties into polymer backbone is an effective strategy to enhance desalination membrane performance.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene
We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.
2D nanosheets↗
Bounce-averaged theory in arbitrary multi-well plasmas: solution domains and the graph structure of their connections
Bounce-averaged theories provide a framework for simulating relatively slow processes, such as collisional transport and quasilinear diffusion, by averaging these processes over the fast periodic motions of a particle on a closed orbit. This procedure dramatically increases the characteristic time scale and reduces the dimensionality of the modelled system. The natural coordinates for such calculations are the constants of motion (COM) of the fast particle motion, which by definition do not change during an orbit. However, for sufficiently complicated fields – particularly in the presence of local maxima of the electric potential and magnetic field – the COM are not sufficient to specify the particle trajectory. In such cases, multiple domains in COM space must be used to solve the problem, with boundary conditions enforced between the domains to ensure continuity and particle conservation. Previously, these domains have been imposed by hand, or by recognising local maxima in the fields, limiting the flexibility of bounce-averaged simulations. Here, we present a general set of conditions for identifying consistent domains and the boundary condition connections between the domains, allowing the application of bounce-averaged theories in arbitrarily complicated and dynamically evolving electromagnetic field geometries. We also show how the connections between the domains can be represented by a directed graph, which can help to succinctly represent the trajectory bifurcation structure.
fusion plasma↗
Polyethylene Blends for Improved Oxygen Barrier: Processing-Dependent Microstructure and Gas Permeability
Here this work demonstrates a greater than expected enhancement of oxygen barrier properties in linear low-density polyethylene (LLDPE)-based materials by blending LLDPE with high-density polyethylene (HDPE). The films made by melt pressing the LLDPE/HDPE blends had a greater reduction in oxygen permeability coefficients (PO 2 ) than predicted using common permeability reduction models, i.e., the harmonic average model and zero-permeability nanofiller model. The reduction of PO 2 was attributed to the presence of spherulite crystal structures, as revealed by atomic force microscopy combined with infrared spectroscopy (AFM-IR). The LLDPE matrix exhibited significant spherulite formation even at a relatively low addition of HDPEs, which likely formed tortuous pathways for diffusing oxygen molecules. Transport results from melt-pressed films contrast with the results from films with similar compositions prepared by film blowing, which did not show barrier enhancement beyond expectation. AFM-IR revealed that the blown films lacked spherulite crystals likely due to stretching in the machine direction followed by rapid cooling. These findings demonstrate the role of processing in controlling microstructures and thus the oxygen barrier performance. This work offers the possibility of achieving easily recyclable LLDPE-based packaging materials by simple blending of polyethylenes with different crystalline content.
36 MATERIALS SCIENCE↗
Lower Hybrid Waves at the Magnetosheath Separatrix Region
Lower hybrid waves are investigated at the magnetosheath separatrix region in asymmetric guide field reconnection by using the Magnetospheric Multiscale (MMS) mission. Three of the four MMS spacecraft observe clear wave activities around the lower hybrid frequency across the magnetosheath separatrix, where a density gradient is present. The observed waves are consistent with generation by the lower hybrid drift instability. The characteristic properties of these waves include the following: (1) the waves propagate toward the x-line in the spacecraft frame due to the large out-of-plane magnetic field, which is in the same direction of the diamagnetic drift of the x-line; (2) the wave potential is about 20% of the electron temperature. Furthermore, these drift waves effectively produce cross-field particle diffusion, enabling the transport of magnetosheath electrons into the exhaust region. At last, we suggest that the lower hybrid waves at the magnetosheath separatrix region represent some unique features of asymmetric guide field reconnection, which is different from that widely observed at the magnetospheric side of magnetopause reconnection.
58 GEOSCIENCES↗
Three-dimensional hierarchically porous MoS 2 foam as high-rate and stable lithium-ion battery anode
Architected materials that actively respond to external stimuli hold tantalizing prospects for applications in energy storage, wearable electronics, and bioengineering. Molybdenum disulfide, an excellent two-dimensional building block, is a promising candidate for lithium-ion battery anode. However, the stacked and brittle two-dimensional layered structure limits its rate capability and electrochemical stability. Here we report the dewetting-induced manufacturing of two-dimensional molybdenum disulfide nanosheets into a three-dimensional foam with a structural hierarchy across seven orders of magnitude. Our molybdenum disulfide foam provides an interpenetrating network for efficient charge transport, rapid ion diffusion, and mechanically resilient and chemically stable support for electrochemical reactions. These features induce a pseudocapacitive energy storage mechanism involving molybdenum redox reactions, confirmed by in-situ X-ray absorption near edge structure. The extraordinary electrochemical performance of molybdenum disulfide foam outperforms most reported molybdenum disulfide-based Lithium-ion battery anodes and state-of-the-art materials. This work opens promising inroads for various applications where special properties arise from hierarchical architecture.
25 ENERGY STORAGE↗
Highly skewed current–phase relation in superconductor–topological insulator–superconductor Josephson junctions
Three-dimensional topological insulators (TIs) in proximity with superconductors are expected to exhibit exotic phenomena, such as topological superconductivity (TSC) and Majorana-bound states (MBS), which may have applications in topological quantum computation. In superconductor–TI–superconductor Josephson junctions, the supercurrent versus the phase difference between the superconductors, referred to as the current–phase relation (CPR), reveals important information including the nature of the superconducting transport. Here, we study the induced superconductivity in gate-tunable Josephson junctions (JJs) made from topological insulator BiSbTeSe 2 with superconducting Nb electrodes. We observe highly skewed (non-sinusoidal) CPR in these junctions. The critical current, or the magnitude of the CPR, increases with decreasing temperature down to the lowest accessible temperature ( T ~ 20 mK), revealing the existence of low-energy modes in our junctions. The gate dependence shows that close to the Dirac point the CPR becomes less skewed, indicating the transport is more diffusive, most likely due to the presence of electron/hole puddles and charge inhomogeneity. Our experiments provide strong evidence that superconductivity is induced in the highly ballistic topological surface states (TSS) in our gate-tunable TI-based JJs. Furthermore, the measured CPR is in good agreement with the prediction of a model which calculates the phase-dependent eigenstate energies in our system, considering the finite width of the electrodes, as well as the TSS wave functions extending over the entire circumference of the TI.
36 MATERIALS SCIENCE↗
A two-dimensional numerical study of the magneto-Rayleigh–Taylor instability with FLASH: Application to the staged Z-pinch concept
Magnetically driven implosions involving a liner collapsing onto a target are inherently vulnerable to the magneto-Rayleigh–Taylor instability (MRTI). Among the various approaches proposed to achieve fusion conditions within the target, the staged Z-pinch (SZP) concept employs a high-Z liner, the advantages of which remain an active area of investigation. Consequently, ongoing design optimization efforts are essential, while critical physical processes such as magnetic field (B-field) diffusion and radiation transport increase the complexity of required simulations. In this study, we utilize the new capabilities of the FLASH code to simulate in 2D, for the first time using this code, staged Z-pinch configurations (designated SZP1 and SZP1*), focusing on their stability. First, a comparison of simulation results with theoretical predictions of MRTI growth provide new insights into the often-overlooked influences of high mesh resolution and initial perturbation seeding on instability dynamics. These findings then lead to a discussion on potential improvements for future SZP experiments. These include the use of an axial B-field stabilization and the optimization of radiation transport processes during the implosion. The results presented herein establish the framework for simulating multi-dimensional Z pinches using the FLASH code and pave the way for the development of innovative experimental configurations leveraging its advanced simulation capabilities.
Adaptive mesh refinement↗
Electrochemical Amyloid β Immunosensor Based on Ti 3 C 2 T x MXene Nanosheets
Alzheimer’s disease (AD) is the most common neurodegenerative disease and a major health-care problem. More than 55 million people in the world, including 6.7 million Americans, are living with AD. As AD is characterized by production and deposition of β-amyloid peptide (Aβ) in the brain, Aβ is considered as a potential biomarker for diagnosing and monitoring the progression of AD. Nanomaterials-based electrochemical immunosensor is one of the most promising methods for early diagnosis and therapeutic of AD, due to its highly selective, sensitive, and label-free advantages. The graphene-like two-dimensional (2D) MXene nanosheets have shown large surface area, good conductivity, biocompatibility, high ion transport, and low diffusion barrier, attracting attention in recent years to use it as the nanomaterial substrate for biosensor fabrication. In this paper, we presented a Ti 3 C 2 T x MXene nanosheets-based electrochemical immunosensor to detect trace Aβ for early diagnosis of AD.
59 BASIC BIOLOGICAL SCIENCES↗
Trapping and imaging dynamic battery nanointerfaces via electrified cryo-EM
The electrified interface between a liquid and a solid underpins diverse phenomena, from ion-transfer during battery operation to action potentials enabling biological communication. However, conventional tools are blind to the nanoscale dynamics of this metastable interface. Here, we leverage electrified cryo–electron microscopy (eCryo-EM), a technique that rapidly freezes and kinetically traps these dynamic, nonequilibrium states during battery operation for nanoscale characterization. Collective snapshots of the electrified interface at controlled time intervals quantifies early-stage growth kinetics of the solid electrolyte interphase (SEI), a passivation film that governs electron and ion transport. Unexpectedly, the diffusivity of charged species of the two SEI films with differing chemistry and performance are estimated to be within 10% of the other, indicated by the slope of their diffusion-limited SEI growth regimes. Instead, the slope of the reaction-limited SEI growth regimes differs by a factor of 3, suggesting that lowered reactivity of the high-performance electrolyte is largely responsible for its high coulombic efficiency.
Science & Technology - Other Topics↗
From material properties to multiscale modeling to improve lithium-ion energy storage safety
Energy storage using lithium-ion cells dominates consumer electronics and is rapidly becoming predominant in electric vehicles and grid-scale energy storage, but the high energy densities attained lead to the potential for release of this stored chemical energy. This article introduces some of the paths by which this energy might be unintentionally released, relating cell material properties to the physical processes associated with this potential release. The selected paths focus on the anode–electrolyte and cathode–electrolyte interactions that are of typical concern for current and near-future systems. Relevant material processes include bulk phase transformations, bulk diffusion, surface reactions, transport limitations across insulating passivation layers, and the potential for more complex material structures to enhance safety. We also discuss the development, parameterization, and application of predictive models for this energy release and give examples of the application of these models to gain further insight into the development of safer energy storage systems.
25 ENERGY STORAGE↗
Toward Higher-order Accuracy in Self-gravitating Hydrodynamics
High-order algorithms have emerged in numerical astrophysics as a promising avenue to reduce truncation error (proportional to a power of the linear resolution Δ x ) with only a moderate increase to computational expense. Significant effort has been placed in the development of finite-volume algorithms for (magneto)hydrodynamics; however, state-of-the-art astrophysical simulations tightly couple a plenitude of physics, additionally including gravity, photon transport, cosmic-ray transport, chemistry, and/or diffusion, to name a few. Algorithms frequently operator-split this additional physics (often a first-order error in time) and/or adopt a model wherein their evaluation is limited to second-order accuracy in space. In this work, we present a fourth-order-accurate finite-volume scheme for self-gravitating hydrodynamics on a uniform Cartesian grid. The method supplies source terms for the gravitational acceleration ( ρ g ) and gravitational energy release ( ρ v · g ) associated with fourth-order-accurate solutions to the Poisson equation. Our scheme (1) guarantees the conservation of total linear momentum while (2) decreasing (in proportion to Δ x 4 ) the effects of spurious heating and/or cooling associated with truncation error in the gravity. We demonstrate expected convergence rates for the algorithm by measuring errors in test problems evolving self-gravity modified linear waves and 3D polytropic equilibria. We test robustness of the algorithm by integrating an induced “inside-out” adiabatic collapse. We also discuss a method to smoothly downgrade the solution to second-order spatial accuracy to avoid spurious overshoots near steep density and/or pressure gradients.
79 ASTRONOMY AND ASTROPHYSICS↗