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At least 145 records · Page 8

Multiscale Reactive Model for 1,3,5-Triamino-2,4,6-trinitrobenzene Inferred by Reactive MD Simulations and Unsupervised Learning

When high-energy-density materials are subjected to thermal or mechanical insults at extreme conditions (shock loading), a coupled response between the thermo-mechanical and chemical behaviors is systematically induced. Herein we develop a reaction model for the fast chemistry of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) at the mesoscopic scale, where the chemical behavior is determined by underlying microscopic reactive simulations. The slow carbon cluster formation is not discussed in the present work. All-atom reactive molecular dynamics (MD) simulations are performed with the ReaxFF potential, and a reduced-order chemical kinetics model for TATB is fitted to isothermal and adiabatic simulations of single crystal chemical decomposition. Unsupervised machine learning techniques based on non-negative matrix factorization are applied to MD trajectories to model the decomposition kinetics of TATB in terms of a four-component model. The associated heats of reaction are fit to the temperature evolution from adiabatic decomposition trajectories. Using a chemical species analysis, we show that non-negative matrix factorization captures the main chemical decomposition steps of TATB and provides an accurate estimation of their evolution with temperature. The final analytical formulation, coupled to a diffusion term, is incorporated into a continuum formalism, and simulation results are compared one-to-one against MD simulations of 1D reaction propagation along different crystallographic directions and with different initial temperatures. A good agreement is found for both the temporal and spatial evolution of the temperature field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiphysics and Multiscale Modeling of Coupled Transport of Chloride Ions in Concrete

Chloride ions (Cl−)-induced corrosion is one of the main degradation mechanisms in reinforced concrete (RC) structures. In most situations, the degradation initiates with the transport of Cl− from the surface of the concrete towards the reinforcing steel. The accumulation of Cl− at the steel-concrete interface could initiate reinforcement corrosion once a threshold Cl− concentration is achieved. An accurate numerical model of the Cl− transport in concrete is required to predict the corrosion initiation in RC structures. However, existing numerical models lack a representation of the heterogenous concrete microstructure resulting from the varying environmental conditions and the indirect effect of time dependent temperature and relative humidity (RH) on the water adsorption and Cl− binding isotherms. In this study, a numerical model is developed to study the coupled transport of Cl− with heat, RH and oxygen (O2) into the concrete. The modeling of the concrete microstructure is performed using the Virtual Cement and Concrete Testing Laboratory (VCCTL) code developed by the U.S. National Institute of Standards and Technology (NIST). The concept of equivalent maturation time is utilized to eliminate the limitation of simulating concrete microstructure using VCCTL in specific environmental conditions such as adiabatic. Thus, a time-dependent concrete microstructure, which depends on the hydration reactions coupled with the temperature and RH of the environment, is achieved to study the Cl− transport. Additionally, Cl− binding isotherms, which are a function of the pH of the concrete pore solution, Cl− concentration, and weight fraction of mono-sulfate aluminate (AFm) and calcium-silicate-hydrate (C-S-H), obtained from an experimental study by the same authors are utilized to account for the Cl− binding of cement hydration products. The temperature dependent RH diffusion was considered to account for the transport of Cl− with moisture transport. The temperature and RH diffusion in the concrete domain, composite theory, and Cl− binding and water adsorption isotherms are used in combination, to estimate the ensuing Cl− diffusion field within the concrete. The coupled transport process of heat, RH, Cl−, and O2 is implemented in the Multiphysics Object-Oriented Simulation Environment (MOOSE) developed by the U.S. Idaho National Laboratory (INL). The model was verified and validated using data from multiple experimental studies with different concrete mixture proportions, curing durations, and environmental conditions. Additionally, a sensitivity analysis was performed to identify that the water-to-cement (w/c) ratio, the exposure duration, the boundary conditions: temperature, RH, surface Cl− concentration, Cl− diffusion coefficient in the capillary water, and the critical RH are the important parameters that govern the Cl− transport in RC structures. In a case study, the capabilities of the developed numerical model are demonstrated by studying the complex 2D diffusion of Cl− in a RC beam located in two different climatic regions: warm and humid weather in Galveston, Texas, and cold and dry weather in North Minnesota, Minnesota, subjected to time varying temperature, RH, and surface Cl− concentrations.

composite theory↗

Discovery of two bright high-redshift gravitationally lensed quasars revealed by Gaia

We present the discovery and preliminary characterisation of two high-redshift gravitationally lensed quasar systems in Gaia Data Release 2 (DR2). Candidates with multiple close-separation Gaia detections and quasar-like colours in WISE, Pan-STARRS, and DES are selected for follow-up spectroscopy with the New Technology Telescope. We confirm DES J215028.71-465251.3 as a $z$ = 4.130 ± 0.006 asymmetric, doubly imaged lensed quasar system and model the lensing mass distribution as a singular isothermal sphere. The system has an Einstein radius of 1.202 ± 0.005 arcsec and a predicted time delay of ~122.0 d between the quasar images, assuming a lensing galaxy redshift of $z$ = 0.5, making this a priority system for future optical monitoring. We confirm PS J042913.17+142840.9 as a $z$ = 3.866 ± 0.003 four-image quasar system in a cusp configuration, lensed by two foreground galaxies. The system is well modelled using a singular isothermal ellipsoid for the primary lens and a singular isothermal sphere for the secondary lens with Einstein radii 0.704 ± 0.006 and 0.241 ± 0.030 arcsec, respectively. A maximum predicted time delay of 9.6 d is calculated, assuming lensing galaxy redshifts of $z$ = 1.0. Furthermore, PS J042913.17+142840.9 exhibits a large flux ratio anomaly, up to a factor of 2.66 ± 0.37 in i band, that varies across optical and near-infrared wavelengths. We discuss LSST and its implications for future high-redshift lens searches and outline an extension to the search using supervised machine learning techniques.

Astronomy & Astrophysics↗

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. Finally, the porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.

36 MATERIALS SCIENCE↗

Influence of fine-scale B2 precipitation on dynamic compression and wear properties in hypo-eutectic Al0.5CoCrFeNi high-entropy alloy

The near equiatomic high-entropy alloys based on Al, Co, Cr, Fe, Ni have provided a novel microstructural template for alloy design. The face-centered cubic (FCC) matrix strengthened by body-centered cubic (BCC) based ordered B2 precipitates can be used to develop a new generation of precipitation strengthened alloys. The present study focuses on an Al0.5CoCrFeNi hypo-eutectic alloy consisting of an as-solidified FCC+B2 microstructure. Guided by solution thermodynamic modeling, this alloy has been isothermally aged for solid-state precipitation of a high fraction of fine-scale intragranular B2 particles. The dynamic compressive strength, hardness, and sliding wear response of the alloy as a function of B2 phase fraction is examined. The flow stress at 0.02% true strain increased from ~ 670 MPa to ~1350 (102%) MPa, the ultimate compressive strength increased from ~1160 MPa to 1500 MPa (20%), and the wear resistance increased more than 5 times with progressively increasing phase fraction of B2 precipitates.

Gwalani, Bharat↗

Multistage Condensation Pathway Minimizes Hysteresis in Water Harvesting with Large-Pore Metal–Organic Frameworks

Metal-organic frameworks (MOFs) have emerged as promising materials for atmospheric water harvesting (AWH). Large-pore MOFs provide high water capacity, but their significant hysteresis between sorption and desorption makes them unsuitable for AWH. Co2Cl2(BTDD) is a noteworthy exception. This MOF has large, 2.2 nm diameter one-dimensional pores, and combines both record-high water capacity and minimal hysteresis, making it an excellent material for water capture in arid areas. Sorption reversibility in Co2Cl2(BTDD) has been attributed to continuous water uptake. However, the sharp adsorption/desorption in the isotherms supports a discontinuous first-order transition. Here we use molecular simulations to compute the water adsorption and desorption pathways and isotherms in a Co2Cl2(BTDD) model, to elucidate how does this MOF achieve reversibility despite its large pore size. The simulations reveal a multi-stage mechanism of discontinuous water uptake facilitated by spatial segregation of rows of hydrophilic metal sites bridged by ~1 nm hydrophobic ligands. The multi-stage mechanism breaks the barrier of capillary condensation into smaller, easier to surmount ones, resulting in a facile process despite the sharp density discontinuity between confined liquid and vapor. Our results explain why exchanging Co2+ for Ni2+ or Clfor F- in the MOF have minimal impact on the condensation and desorption pressures. On the other hand, we predict that a decrease in hydrophilicity of the MOF vertices would strongly increase the hysteresis. We expect that the relationships between spatial distribution of hydrophilic sites and hysteresis unraveled in this study assist the design of water harvesting materials with maximal capacity and reversibility.

Zaragoza, Alberto↗

Elucidating the Influence of Metal Surface Composition on Organic Adsorbate Binding Using Active Particle Dynamics

The adsorption strengths of organic compounds on metal surfaces are sensitive to the metal composition, and they play a central role in many catalytic reactions, helping to control the coverage of the reactant and altering the overall reaction rate. While adsorption energies are straightforward to measure and calculate in vacuum and gas-phase environments, adsorption energetics can be dramatically altered by the presence of solvent in liquid-phase reactions. However, the effects of metal composition on binding strengths in a liquid environment are less well understood, primarily due to the difficulty of accurate in situ measurements of organic binding on metal surfaces in the liquid phase. Here, we utilize the motion of active particles in water to probe the adsorption energies of an organic adsorbate (furfural) on a range of metal surfaces (pure Pd, pure Pt, and four PdAu alloy compositions) to elucidate the effect of metal composition. Janus particles with catalytic caps of particular metal compositions all exhibited active motion resulting from consumption of H 2 O 2 ; adsorbate binding was inferred through the decrease in the velocity of active motion and was modeled by a Langmuir adsorption isotherm. The measured adsorption affinities were used to extract the adsorption enthalpy of furfural on the different metals. The Pd surface was found to bind furfural more strongly than the Pt surface by some 10 kJ/mol. Furthermore, the adsorption of furfural on the alloys was found to increase monotonically in magnitude with Pd content. As a result, the data reported herein aid the development of accurate understanding of organic adsorption in the presence of solvent and the role of the metal surface in tuning adsorption strengths to optimize catalytic processes in the liquid phase.

36 MATERIALS SCIENCE↗

Nanotubes Growth by Self-Assembly of DNA Strands at Room Temperature

Artificial biomolecular nanotubes are a promising approach to building materials mimicking the capacity of the cellular cytoskeleton to grow and self-organize dynamically. Nucleic acid nanotechnology has demonstrated a variety of self-assembling nanotubes with programmable, robust features and morphological similarities to actual cytoskeleton components. However, their production typically requires thermal annealing, which not only poses a general constraint on their potential applications but is also incompatible with physiological conditions. Here, we demonstrate that DNA nanotubes can self-assemble from a simple mixture of five short DNA strands at constant room temperature, growing for extended periods of time in bulk conditions as well as under confinement. Assembly is achieved using a monovalent salt buffer, which ensures a faithful nanoscale arrangement and avoids nanotube aggregation. We observe the formation of individual nanotubes up to 20 days with a diameter of 22 ± 4 nm and length of several tens of micrometers. We finally encapsulate the strands in microsized compartments, such as water-in-oil microdroplets and giant unilamellar vesicles serving as simple cell models. Notably, nanotubes not only isothermally self-assemble directly inside the microcompartments but also self-organize into dynamic higher-order structures resembling rings and dynamic networks. Our study provides an advantageous method for in situ assembly of programmable biomolecular scaffolds and materials using synthetic DNA strands without requirements of thermal treatment.

Chemistry↗

Fluid-like shock compression of dilute polymer nanocomposites

The shock Hugoniot of heterogenous mixtures of discrete particles has been experimentally investigated for porous agglomerates and fluids, while the study of full-density solids has been primarily limited to compressed powders and high-dimensional composites. By dispersing ceria nanoparticles in a polyethylene matrix, we are able to examine the hydrodynamic behavior of a nonporous, heterogenous solid in thermal equilibrium during weak shock compression. Phase-driven discontinuities in the Hugoniot particle velocity–shock velocity (u−D) relationship of pure polyethylene are replicated in the nanocomposites but are shifted to lower velocity and to higher pressure with higher particle concentration. The results are explained using an isothermal, two-velocity fluid model under the hydrodynamic approximation. The model, which assumes a theoretical equation-of-state for ceria and either a low-order or high-order fit to the measured polyethylene Hugoniot, reasonably predicts the Hugoniot for two different polyethylene/ceria nanocomposites. Using the model, the mixture Hugoniot is shown to be insensitive to the Hugoniot of the stiffer constituent when the moduli are sufficiently disparate, while dependence on particle density and volume fraction is preserved through fluid-like motion.

Moore, Nathan W. [Sandia National Laboratories (SN↗

Impact of collisionality on turbulence in the edge of tokamak plasma using 3D global simulations

Collisionality is one of the key parameters in determining turbulent transport in the plasma edge, regulating phenomena such as 'shoulder formation', separation of scale lengths in the scrape-off layer (SOL), turbulence damping and zonal flow dynamics. Understanding its role is therefore of primary importance for future reactors like ITER. Getting reliable predictions and a better characterization of plasma flow properties when varying collisionality remains, however, a critical challenge for the simulations. This paper focuses on the impact of varying collisionality in a non-isothermal three-dimensional fluid model of the plasma edge. A high field side limited configuration encompassing open and closed magnetic field lines with parameters typical of a medium-sized tokamak is considered. The present model can consistently account for the variations of collisionality and its impact on both the parallel resistivity η ∥ and the ion and electron parallel thermal conductivities χ ∥e,i . Details on mean flow and turbulence properties are given. Changing collisionality leads to significant changes in the flow properties both on the mean and fluctuating quantities. In particular, lowering collisionality decreases the size of coherent structures, the fluctuation levels of turbulence, and steepens the density and temperature equilibrium profiles around the separatrix leading to a global reduction of the turbulent transport. The SOL width is observed to increase with collisionality, eventually resulting in the disappearance of the scale lengths separation between near and far SOL, consistently with previous experimental observations. At low collisionality, where the presence of narrow feature is well-established, a contribution of heat conduction increases up to compete with heat convection.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Gas and dust dynamics in γ Cephei-type disks

Context. Giant planets are observed orbiting the primary stars of close binary systems. Such planets may have formed in compact circumprimary disks, which once surrounded these stars, under conditions much different than those encountered around single stars. Aims. In order to quantify the effects of the strong gravitational perturbations exerted on circumprimary disk material, the three-dimensional (3D) dynamics of gas and dust in orbit around the primary star of a compact and eccentric binary system was modeled by applying the stellar and orbital parameters of γ Cephei, a well-known system that can be representative of a class of close binaries. Methods. Circumprimary gas was approximated as an Eulerian viscous and compressible fluid and modeled by means of 3D hydrodynamical simulations, assuming locally isothermal conditions in the medium around the primary star. Dust grains were modeled as Lagrangean particles, subjected to gravity and aerodynamic drag forces. Models that include a giant planet were also considered. Results. Models indicate that spiral density waves excited around pericenter passage propagate toward the inner boundary of the disk, through at least a few pressure scale-heights from the mid-plane, inducing radial and vertical mixing in the gas. However, perturbations imparted to gas, both in terms of eccentricity and precession, are far weaker than previously estimated by two-dimensional (2D) simulations. Models predict small eccentricities, ≲0.03, and slow retrograde precession. The addition of a giant planet does not change the low eccentricity state of the disk. The parameters applied to the disk would lead to the formation of a massive planet, many times the mass of Jupiter, in agreement with some observations. Micron to mm-size dust grains are well coupled to the gas, resulting in similar dynamics and statistically similar distributions of orbital elements. The planet only affects the dust distributions locally. In agreement with outcomes of recent 2D models, the lifetime of an isolated circumprimary disk would be brief, ~10 5 years, because of its compact nature, requiring a long-term external supply of mass to allow for the in situ formation of a giant planet.

79 ASTRONOMY AND ASTROPHYSICS↗

Machine Learning in Environmental Chemistry: Application to Surface Complexation Modeling

Environmental chemistry – or biogeochemistry – is the scientific discipline typically invoked when examining and quantifying groundwater or surface water contamination, and nutrient cycling in the environment. Over the last three decades, there have been significant advances in mechanistic model development to describe and predict these complex biogeochemical processes. In particular, surface complexation models (SCMs) have been developed to describe the rock/soil surface reactions of metals and radionuclides, and their partitioning between various mobile species in the aqueous phase or immobile species sorbed on solid surfaces. Often represented by a simplified linear isotherm constant – Kd – in reactive transport models, these reactions play a critical role in many environmental science applications; particularly in contamination risk assessments and nuclear waste disposal performance assessments. In the past several decades, efforts by various institutions across the world have focused on developing SCMs based on datasets from laboratory measurements, including the identification of key parameters such as equilibrium constants.

54 ENVIRONMENTAL SCIENCES↗

Generalized Brunauer–Emmett–Teller Isotherm for Mixed-Gas Multilayer Adsorption Equilibria

Here, this work presents a rigorous thermodynamic framework to calculate mixed-gas multilayer adsorption equilibria from single-component isotherms and vapor–liquid equilibria. Named the generalized Brunauer–Emmett–Teller (gBET) isotherm, the newly formulated isotherm considers adsorbent surface heterogeneity, competitive adsorption on the monolayer, condensation–evaporation on the subsequent layers, and adsorbed phase nonideality for the monolayer and the subsequent layers. The monolayer adsorbed phase nonideality is tracked by using an area-based adsorption nonrandom two-liquid activity coefficient model. The adsorbed phase composition and corresponding nonideality in the subsequent layers are calculated at the dew point condition of the mixed gas with either an equation of state or an activity coefficient model for the vapor–liquid equilibria. The proposed model is validated with six single and three binary multilayer adsorption equilibrium systems, and the model results are compared against those from the classical BET isotherm for single-component adsorption and ideal adsorbed solution theory for mixed-gas adsorption equilibria.

09 BIOMASS FUELS↗

Permeation of CO 2 and N 2 through glassy poly(dimethyl phenylene) oxide under steady- and presteady-state conditions

Glassy polymers are often used for gas separations because of their high selectivity. Although the dual-mode permeation model correctly fits their sorption and permeation isotherms, its physical interpretation is disputed, and it does not describe permeation far from steady state, a condition expected when separations involve intermittent renewable energy sources. To develop a more comprehensive permeation model, we combine experiment, molecular dynamics, and multiscale reaction–diffusion modeling to characterize the time-dependent permeation of N 2 and CO 2 through a glassy poly(dimethyl phenylene oxide) membrane, a model system. Simulations of experimental time-dependent permeation data for both gases in the presteady-state and steady-state regimes show that both single- and dual-mode reaction–diffusion models reproduce the experimental observations, and that sorbed gas concentrations lag the external pressure rise. The results point to environment-sensitive diffusion coefficients as a vital characteristic of transport in glassy polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Freundlich isotherm equation best represents phosphate sorption across soil orders and land use types in tropical soils of Puerto Rico

Biomass production in the lowland wet tropical forest is greater than in any other biome, and it is typically limited by soil phosphorus (P) availability. However, the mechanisms involved in the P cycle remain poorly represented in Earth System Models (ESMs). Soil P sorption processes are key in the P cycle and for understanding the extent of P limitation for plant productivity. Currently, a few ESMs include isotherm equations to model these processes. Although the Langmuir equation is widely cited, other isotherm equations may better describe sorption in tropical soils. Here, we use a diverse range of soil samples from Puerto Rico to test the validity of the Langmuir, Freundlich, and Temkin equation. We found that across four soil orders (Inceptisols, Mollisols, Oxisols, Ultisols), and forested and cultivated land use types, the Freundlich equation best represented soil P sorption. Furthermore, the Langmuir and the Temkin equations poorly represent soil P adsorption, especially at low P concentrations. Specifically, the Langmuir equation underestimated soil P adsorption by 40% and the Temkin equation overestimated adsorption by 76%. We also found, as expected, that soil clay content and pH were the most important parameters explaining the variability of the Freundlich (K f ) constant. Greater clay content and lower pH, common in highly weathered Ultisols and Oxisols which are abundant in the tropics, led to greater K f values. Overall, our results suggest that a diversity of soils can prompt underestimation of P sorption when using the Langmuir isotherm, which leads to an overestimation of available P that can have repercussions on ESM predictions of the P cycle and tropical forest productivity.

Earth system models↗

Intrinsic kinetics of water-inhibited ultra-lean methane oxidation over PtPd-Mg/ θ -Al 2 O 3 catalyst

Here, this study develops intrinsic methane oxidation kinetics for ultra-lean methane conditions in the presence of water over a highly active and stable PtPd–Mg/θ-Al 2 O 3 catalyst. Comprehensive laboratory experiments were conducted over a wide range of methane concentrations (150–1200 ppm CH 4 ), water contents (1–5% H 2 O), and industrially relevant space velocities (80,000 ≤ GHSV ≤ 160,000 h -1 ). These systematic experiments informed a two-dimensional, axisymmetric, multiscale reactor model that was used to develop and validate methane oxidation kinetics under practically relevant conditions, including non-isothermal operation and high conversion regimes. Combined experimental and modeling results revealed significant intraparticle diffusion resistance and transport-induced reaction exotherm at elevated temperatures, which limited catalyst utilization despite high intrinsic activity. These transport effects were explicitly incorporated into the reactor model, enabling accurate estimation of intrinsic kinetic parameters without reliance on conventional effectiveness-factor corrections. The resulting kinetic model successfully captured both kinetically controlled and mass-transfer-limited regimes and reliably predicted CH 4 conversion across broad ranges of temperature, methane concentration, and water content

Heat and mass transfer limitations↗

Determination of the enthalpy of adsorption of hydrogen in activated carbon at room temperature

The development of high-performance materials for hydrogen storage by adsorption requires detailed understanding of the adsorbate-adsorbent interactions, e.g., the enthalpy of adsorption ΔH, which measures the interaction strength. The determination of ΔH for a weakly adsorbing gas such as hydrogen in a carbonaceous porous material is difficult experimentally, normally requiring measuring two cryogenic adsorption isotherms. Here we demonstrate a calculation of ΔH based on ca. room temperature adsorption isotherms at 273 K and 296 K using the Clausius-Clapeyron equation. This requires an estimation of the volume of the adsorbed film (~40%, ~12% of the total pore volume at 77 K, 296 K, respectively) obtained from fits of the excess adsorption isotherms to an Ono-Kondo model with the auxiliary use of a fixed point corresponding to the saturation film density (estimated as 100 ± 20 g/L) which appears to be remarkably sample and temperature independent, i.e., a property of the adsorbate. The calculated room temperature enthalpy of adsorption ΔH = 8.3 ± 0.4 kJ/mol is in excellent agreement with the low-coverage cryogenic determination of ΔH. The methodology hereby proposed facilitates reliable calculations of the enthalpy of adsorption at room temperatures for weakly-adsorbing gases.

08 HYDROGEN↗