Curing behavior, chain dynamics, and microstructure of high Tg thiol-acrylate networks with systematically varied network heterogeneity
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99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “Mesoscale”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Wave climate and energy resources in the Mariana Islands from a 42-year high-resolution hindcast
We report a high-resolution wave hindcast from 1979 to 2020 was developed for Guam and the Commonwealth of the Northern Mariana Islands, which are influenced by mesoscale and synoptic weather systems from the western Pacific Rim to the Central Pacific. The spectral wave modeling utilized structured global and unstructured regional grids with improved resolution in nearshore waters, where wave resources development is most feasible. The hindcast demonstrates its capability in capturing multi-modal seas through reproduction of bulk and partitioned wave parameters derived from altimetry and buoy measurements. The local wave climate is influenced by the year-round trade winds and tropical cyclones as well as seasonal monsoons, frontal systems, and mid-latitude high- and low-pressure systems. The strong intra-annual variation of the significant wave height and power flux reflects transitions between local and distant weather systems, which account for the diverse wave conditions comprised of short-period wind waves, intermediate-period seas, and long-period swells around the islands. Among the Pacific island regions, spectral partitioning is particularly important for describing the dominant wave components by period and direction with pertinent information conducive to energy resources characterization and coastal zone management in the Mariana Islands.
16 TIDAL AND WAVE POWER↗
Impacts of the morphology of new neighborhoods on microclimate and building energy
In anticipation of emerging global urbanization and consequent increases in energy use and carbon dioxide emissions, better understanding and quantification of climate effects on energy use in cities are needed, requiring coordinated research into large-scale, regional, and microclimate impacts to and from the city structure. The methodology described here addresses this need by (1) demonstrating a process for creating and testing example morphologies for new neighborhoods for their impact on local and regional meteorology within a two-way-coupled four-domain nested mesoscale weather model (6 km horizontal resolution outer domain, 90 m horizontal innermost domain) and (2) allocating resulting building-level meteorological profiles to each building in a neighborhood for parallel computation of building-by-building energy use. Our Chicago Loop test case shows that the morphology of even a small new added development to a neighborhood affects not only its own microclimate, but also the microclimate of the original neighborhood to which the development was added, and that these changes in microclimate affect both neighborhoods’ building energy use. Furthermore, this method represents an important step toward quantifying and analyzing the relationships among climatic conditions, urban morphology, and energy use and using these relationships to inform energy-efficient urban development and planning.
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
Synchrotron infrared nano-spectroscopy and -imaging
Infrared (IR) spectroscopy has evolved into a powerful analytical technique to probe molecular and lattice vibrations, low-energy electronic excitations and correlations, and related collective surface plasmon, phonon, or other polaritonic resonances. In combination with scanning probe microscopy, near-field infrared nano-spectroscopy and -imaging techniques have recently emerged as a frontier in imaging science, enabling the study of complex heterogeneous materials with simultaneous nanoscale spatial resolution and chemical and quantum state spectroscopic specificity. Here, we describe synchrotron infrared nano-spectroscopy (SINS), which takes advantage of the low-noise, broadband, high spectral irradiance, and coherence of synchrotron infrared radiation for near-field infrared measurements across the mid- to far-infrared with nanometer spatial resolution. This powerful combination provides a qualitatively new form of broadband spatio-spectral analysis of nanoscale, mesoscale, and surface phenomena that were previously difficult to study with IR techniques, or even any form of micro-spectroscopy in general. We review the development of SINS, describe its technical implementations, and highlight selected examples representative of the rapidly growing range of applications in physics, chemistry, biology, materials science, geology, and atmospheric and space sciences.
47 OTHER INSTRUMENTATION↗
Turbulent exchanges between near-inertial waves and balanced flows
Wind generated near-inertial waves are ubiquitous in the upper ocean. An improved understanding of near-inertial wave dynamics following their excitation in the ocean and their subsequent interaction with mesoscale geostrophic balanced flows is key to decoding oceanic energy flow pathways. In this regard, multiple oceanic data sets accumulated over the past few decades reveal that the relative strength of near-inertial waves and geostrophic balanced eddy fields is highly variable, both geographically and seasonally. Inspired by these observations, we investigate turbulent interactions and energy exchanges between near-inertial waves and balanced flows using freely evolving numerical simulations of the non-hydrostatic Boussinesq equations. Here, we find accelerated vertical propagation and dissipation of the waves in regimes where balanced and wave fields have comparable strengths. In such regimes we also find that near-inertial waves directly extract energy from balanced flows, with O(10%) being the amount of balanced energy loss. In contrast, we find that near-inertial waves transfer energy to balanced flows in regimes where balance-to-wave energy ratio is small, with the gain in balanced energy being dependent on the relative strength of waves. Furthermore, these regimes are characterized by relatively weaker vertical propagation and dissipation of the near-inertial wave field. One of the key outcomes of this study is the demonstration of the lack of a unique direction for near-inertial wave-balanced flow energy transfers. Depending on the balance-to-wave energy ratio, near-inertial waves can act as an energy sink or energy source for the geostrophic balanced flow.
58 GEOSCIENCES↗
Elucidating the Origins of High Capacity in Iron-Based Conversion Materials: Benefit of Complementary Advanced Characterization toward Mechanistic Understanding
Lithium-ion batteries are recognized as an important electrochemical energy storage technology due to their superior volumetric and gravimetric energy densities. Graphite is widely used as the negative electrode, and its adoption enabled much of the modern portable electronics technology landscape. However, developing markets, such as electric vehicles and grid-scale storage, have increased demands, including higher energy content and a diverse materials supply chain. Alternatives that provide the opportunity to increase capacity and address supply chain concerns are of interest. Understanding the fundamental mechanisms that govern battery function is crucial to driving further improvements in the field. Advanced characterization techniques, such as those enabled by synchrotron light sources and high-resolution electron microscopes, that can uncover these mechanisms have become a necessity for elucidating structural evolution upon electrochemical conversion at the nano- to mesoscales. Performing these experiments with relevant electrochemistry using in situ and operando experiments imparts the ability to identify critical reaction pathways and capture intermediate (dis)charge products not discernible by traditional experiments.
36 MATERIALS SCIENCE↗
Thermodynamic and Kinetic Modulation of Methylammonium Lead Bromide Crystallization Revealed by In Situ Monitoring
Hybrid organic–inorganic perovskite (HOIP) crystals are promising optoelectronic materials, but little is known about either the thermodynamic and kinetic controls on crystal growth or the underlying growth mechanism(s). Herein, we use fluid cell atomic force microscopy (AFM) and solution nuclear magnetic resonance (NMR) spectroscopy to investigate growth of the model HOIP crystal CH 3 NH 3 PbBr 3 (MAPbBr 3 ) and to determine how formic acid (HCOOH) modulates the thermodynamics and kinetics of growth. The results show that growth of MAPbBr 3 in dimethylformamide (DMF) proceeds through the classical pathway by the spreading of atomic crystal steps generated at screw dislocations on the {100} surface. Temperature dependent step velocity measurements demonstrate that with increasing concentration, HCOOH decreases both the solubility of MAPbBr 3 and the kinetic coefficient (b) of step movement. 1 H-NMR measurements indicate that HCOOH increases the lifetime of the methylammonium (MA + ) ions and promotes the association of MAPbBr 3 , thus tuning the solubility of the perovskite. HCOOH also alters the molecular tumbling motion and bulk diffusion of the MA + ions, possibly via H-bonding. Further, our findings establish a direct correlation between the mesoscale crystal growth kinetics and the molecular-scale interactions between organic additives and constituent ions, providing unprecedented insights for developing predictive syntheses of HOIP crystals with defined size, crystal habit and shape, and defect distribution.
36 MATERIALS SCIENCE↗
Advanced Materials for Energy-Water Systems: The Central Role of Water/Solid Interfaces in Adsorption, Reactivity, and Transport
The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water-and often the water molecules themselves-to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and finally, provide an outlook for prioritizing strategic research directions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thermal Energy Transport in Oxide Nuclear Fuel
To efficiently capture the energy of the nuclear bond, advanced nuclear reactor concepts seek solid fuels that must withstand unprecedented temperature and radiation extremes. In these advanced fuels, thermal energy transport under irradiation is directly related to reactor performance as well as reactor safety. The science of thermal transport in nuclear fuel is a grand challenge as a result of both computational and experimental complexities. Here we provide a comprehensive review of thermal transport research on two actinide oxides: one currently in use in commercial nuclear reactors, uranium dioxide (UO 2 ), and one advanced fuel candidate material, thorium dioxide (ThO 2 ). In both materials, heat is carried by lattice waves or phonons. Crystalline defects caused by fission events effectively scatter phonons and lead to a degradation in fuel performance over time. Bolstered by new computational and experimental tools, researchers are now developing the foundational work necessary to accurately model and ultimately control thermal transport in advanced nuclear fuels. We begin by reviewing research aimed at understanding thermal transport in perfect single crystals. The absence of defects enables studies that focus on the fundamental aspects of phonon transport. Next, we review research that targets defect generation and evolution. Here the focus is on ion irradiation studies used as surrogates for damage caused by fission products. We end this review with a discussion of modeling and experimental efforts directed at predicting and validating mesoscale thermal transport in the presence of irradiation defects. While efforts in these research areas have been robust, challenging work remains in developing holistic tools to capture and predict thermal energy transport across widely varying environmental conditions.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Theoretical and Experimental Advances in High-Pressure Behaviors of Nanoparticles
Using compressive mechanical forces, such as pressure, to induce crystallographic phase transitions and mesostructural changes while modulating material properties in nanoparticles (NPs) is a unique way to discover new phase behaviors, create novel nanostructures, and study emerging properties that are difficult to achieve under conventional conditions. In recent decades, NPs of a plethora of chemical compositions, sizes, shapes, surface ligands, and self-assembled mesostructures have been studied under pressure by in-situ scattering and/or spectroscopy techniques. As a result, the fundamental knowledge of pressure–structure–property relationships has been significantly improved, leading to a better understanding of the design guidelines for nanomaterial synthesis. In the present review, we discuss experimental progress in NP high-pressure research conducted primarily over roughly the past four years on semiconductor NPs, metal and metal oxide NPs, and perovskite NPs. We focus on the pressure-induced behaviors of NPs at both the atomic- and mesoscales, inorganic NP property changes upon compression, and the structural and property transitions of perovskite NPs under pressure. We further discuss in depth progress on molecular modeling, including simulations of ligand behavior, phase-change chalcogenides, layered transition metal dichalcogenides, boron nitride, and inorganic and hybrid organic–inorganic perovskites NPs. These models now provide both mechanistic explanations of experimental observations and predictive guidelines for future experimental design. Here, we conclude with a summary and our insights on future directions for exploration of nanomaterial phase transition, coupling, growth, and nanoelectronic and photonic properties.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modeling Single-Crystal Battery Materials: From Fundamental Understanding to Performance Evaluation
The performance of rechargeable batteries is fundamentally influenced by the physicochemical properties and microstructural features of their key material components. Recent experimental advancements have highlighted the potential of single-crystal (SC) morphologies to address inherent limitations of polycrystalline (PC) electrodes and solid-state electrolytes, offering tunable charge transport kinetics and improved cell cycling performance. Here, this review examines how state-of-the-art computational modeling, from atomistic and mesoscale to continuum-level approaches, including machine learning methodologies, has been utilized to investigate the critical factors governing the electrochemical behavior of SC battery materials. We explore how predictive modeling can elucidate the processing–structure–property–performance relationships of SC cathodes, anodes, and solid-state electrolytes, with a focus on unique SC characteristics such as crystallographic anisotropy, size effects, and facet-dependent properties. Additionally, we identify limitations in commonly used modeling techniques and discuss strategies to address these challenges. By integrating high-fidelity simulations with experimental insights, this review aims to outline a clear path for the rational design and optimization of SC battery components, paving the way for accelerated advancements in energy storage technologies.
Materials science↗
Uranium recovery from seawater using amidoxime-based braided polymers synthesized from acrylic fibers
Global demand for nuclear energy is expected to rise in the coming decades. To meet these growing needs, new uranium resources must be explored. One of the potential alternatives to traditional uranium mining is oceanic uranium. The capture and recovery of uranium from the ocean has been under investigation for some time, with many recent studies focused on amidoxime based adsorbents. These adsorbents while able to achieve high uranium recovery capacities are, nevertheless, expensive to produce and adsorb a significant amount of hard to remove vanadium. The purpose of this study is to evaluate the adsorption performance of amidoxime based polymer braids synthesized from acrylic fibers which are designed to significantly cut polymer synthesis and conditioning costs. Adsorption experiments were performed in a recirculating raceway flume system at environmental conditions, approximately 10.8 oC, with 40-micron prefiltered seawater over 28 days for small and large sized LCW polymer braids. For both braid sizes, the adsorption of vanadium was far lower on the LCW materials than on Oak Ridge National Laboratory’s amidoxime based AF1 and AI8 small braids, with the LCW small braids outperforming both materials with respect to uranium adsorption under similar conditions. Adsorption modeling was used to simulate the performance at higher temperatures based on 20oC experiments previously performed with similar materials. Simulation results indicated that the small LCW braids would have a less significant advantage with respect to uranium adsorption over both AF1 and AI8 at 20oC and adsorb slightly less uranium than AF1 at 31oC. Vanadium adsorption by LCW small braids was less than one third of vanadium adsorption by either AF1 or AI8 for all temperatures. This behavior indicates that the LCW materials are able to achieve comparable uranium adsorption to other amidoxime adsorbents previously developed, while being cheaper to produce and adsorbing significantly less vanadium.
Wiechert, Alexander I.↗
High-Pressure Equation of State of 1,3,5-triamino-2,4,6-trinitrobenzene: Insights into the Monoclinic Phase Transition, Hydrogen Bonding, and Anharmonicity
The high-pressure equation of state (EOS) of energetic materials (EMs) is important for continuum and mesoscale models of detonation performance and initiation safety. Additionally, obtaining a high-fidelity EOS of the insensitive EM 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) has proven to be difficult because of challenges in experimental characterization at high pressures (HPs). In this work, powder X-ray diffraction patterns were fitted using the recently discovered monoclinic I2/a phase above 4 GPa, which shows that TATB is less compressible than when indexed with the triclinic $P\bar{1}$ phase. First-principles calculations were performed with Perdew–Burke–Ernzerhof (PBE) and PBE0 functionals including thermal effects using the $P\bar{1}$ phase. PBE0 improves the description of hydrogen bonding and thus predicts accurate planar a and b lattice parameters under ambient conditions. However, discrepancies in the predicted lattice parameters above 4–10 GPa compared with experimental measurements indexed with $P\bar{1}$ are further evidence of a structural modification at high pressure. Layer sliding defects are formed during molecular dynamics simulations, which induces an anharmonic effect on the thermal expansion of the c lattice parameter. In short, the results provide several insights into determining high-fidelity EOS parameters for TATB and other molecular crystals.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Amphiphile Organization in Organic Solutions: An Alternative Explanation for Small-Angle X-ray Scattering Features in Malonamide/Alkane Mixtures
In this work, the role of different intermolecular interactions in the aggregation of amphiphiles in an organic solvent is studied for systems of relevance to liquid-liquid extraction (LLE), a chemical process used to selectively recover metals from complex mixtures. Of specific interest is the role, or lack thereof, of hydrogen bonding, which is often assumed to be a main driver of the organic phase structural organization that has been linked to separation efficacy. Toward that end, a series of malonamide extractants in n-dodecane have been studied in the absence of any extracted aqueous solutes, including water. The series of extractants includes N,N'-dimethyl-N,N'-dibutyltetradecylmalonamide (DMDBTDMA), two of its homologs, and N,N'-dimethyl-N,N'-dioctylhexylethoxymalonamide (DMDOHEMA). This simplified model LLE system enables systematic investigation of the role of dipole-dipole and alkyl tail steric interactions in amphiphile aggregation. Small-angle X-ray scattering (SAXS) profiles computed from molecular dynamics trajectories are in good agreement with experimental SAXS data. Molecular dynamics simulations show that malonamide aggregation results from dipole-driven self-association and lacks characteristic aggregate sizes. Mid-q correlation peaks in the SAXS profiles emerge at high concentration for each malonamide. In those densely packed solutions, the correlation peaks are observed to result from alkyl tail-induced spacing between electron-rich polar head groups, with peak positions determined by the different alkyl tail lengths present in the malonamide molecule. This explanation of the SAXS correlation peaks contrasts with the prevailing literature, which attributes mesoscale features observed in small-angle scattering to the formation of microemulsions. Instead, this work finds that these features are present in the absence of water or any reverse micellar organization of the malonamides. As such, molecular-scale malonamide self-association and packing, rather than microemulsion-based colloidal-scale descriptions, is a more appropriate framework for these LLE systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure of Sulfuric Acid Solutions Using Pair Distribution Function Analysis
Solvation and mesoscale ordering of sulfuric acid and other strong acid solutions leads to suppressed freezing points and strong rheological changes with varying concentration. While the solid-state structures are well-understood, studies focused on the evolving solvation structure in the solution phase have probed a limited concentration range (~1–6 M). This study applies a total scattering approach in both the wide-angle X-ray scattering (WAXS) and pair distribution function (PDF) regimes to elucidate the evolving solvation structure over its full range of acid concentration (0–18 M). The emergence of a prepeak in the WAXS regime at intermediate concentrations indicates a transition from noninteracting sulfate molecules in the dilute limit to sterically limited sulfates at concentrations near its deep eutectic point. Fits to the PDF data quantify this trend, showing a transition from octahedrally hydrated sulfates up to 6–7 M concentrations, followed by gradual dehydration, and eventually reaching a solution structure similar to that of water-in-salt electrolyte systems at high acid concentrations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modeling Nanoconfinement Effects Using Active Learning
Predicting the spatial configuration of gas in nanopores of is relevant in applications such as fluid flow forecasting and hydrocarbon reserves estimation. For example, shale reservoirs have suffered from computationally intractable multiscale problems, since fluid properties such as viscosity, density, and adsorption must be calculated by using expensive molecular dynamics (MD) simulations within each nanopore, whereas flow through these connected nanopores must be simulated at the micrometer scale. We utilize machine learning techniques to quickly and accurately model nanoscale confinement effects as an important step toward bridging the nano and micro scales. Our workflow is based on building and training physics-based deep-neural-networks models by learning from a database of MD calculations. The model accounts for the adsorption phenomenon by predicting the statistical distribution of gas inside nanopores. Because large databases of MD calculations are expensive to create, we investigate active learning (AL) as a data set construction strategy. In this workflow, new data are selected based on the model uncertainty via the query-by-committee approach. We show that our workflow obtains accurate models that generalize to real scanning electron microscopy geometries with 1/10th of the number of MD calculations required vs random data set generation. Our method enables the possibility of modeling nanoconfinement effects at the mesoscale, where complex connected sets of nanopores affect flow.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure of Water Adsorbed on Nanocrystalline Calcium Silicate Hydrate Determined from Neutron Scattering and Molecular Dynamics Simulations
Calcium silicate hydrate (C-S-H) is a disordered, nanocrystalline material that acts as a primary binding phase in Portland cement. Thin films of water are present on the surfaces and in nanopores of C-S-H, impacting many of its chemical and mechanical properties, such as ion transport, creep, or thermal behavior. Despite decades of research, a full understanding of the structural details of adsorbed, confined, and bulk water in C-S-H remains elusive. In this work, we applied a multitechnique study involving molecular dynamics (MD) simulations validated by neutron diffraction with isotopic substitution (NDIS) and X-ray scattering methods to investigate the structure of water in C-S-H and C-A-S-H (an Al-bearing, low-CO 2 C-S-H substitute). Direct comparison of NDIS data with the MD results reveals that the structure of confined and interfacial water differs significantly from the bulk water and exhibits a larger degree of mesoscale ordering for more hydrated C-S-H structures. As a result, this observation suggests an important role of water as a stabilizer of the atomistic-level structure of C-S-H.
36 MATERIALS SCIENCE↗
Tunability and Long-Range Enhancement of Resonance Energy Transfer Facilitated by Plasmonic Nanorods
Resonance energy transfer (RET) between molecules or quantum dots is an important process in many energy-related applications. Different environmental structures have been studied and demonstrated to be able to enhance the RET rates between a nearby donor–acceptor pair. In particular, cylindrical silver nanorods and nanowires have shown an extraordinary ability to transfer energy along their longitudinal axes over large distances. However, the detailed mechanism of such transfer and the effects on the molecular RET process are as yet elusive. In this study, we use the recently developed computational tool based on the plasmon-coupled RET method to systematically study the effects of nanorods with different dimensions on the RET rates. We find that highly frequency-dependent coupling factor (CF) spectra, whose amplitudes determine RET rates, can be obtained due to the localized surface plasmon polariton modes of the rods with nanoscale dimensions. Simple phenomenological models can be derived for the wavelengths of CF peaks in relation to the length and width of the nanorods, providing easy tunability for enhancing the RET rate in specific wavelength ranges. When coupled to longer rods with mesoscale lengths, exponential decay of the CF over long donor–acceptor distances with a small decay constant is observed, leading to the possibility of long-range RET processes. Furthermore, drumhead resonance modes emerge on the flat ends of the rod when the rod’s diameter reaches 300 nm, resulting in extra enhancement to RET rate compared to certain thinner rods. Furthermore, these findings shed new light on the mechanism of plasmonic enhancement with silver nanorods and establish design principles for how to optimally utilize these structures to manipulate RET processes for various applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗