Multi-architecture Monte-Carlo (MC) simulation of soft coarse-grained polymeric materials: SOft coarse grained Monte-Carlo Acceleration (SOMA)
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Schneider, L. (ORCID:0000000239108217)↗
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Review of stability and thermal conductivity enhancements for salt hydrates
Salt hydrates can be used as phase change materials for thermal energy storage. Critical technical challenges for their widespread deployment include poor cycling stability, large supercooling, and low thermal conductivity. Here in this work, numerous enhancement techniques are reviewed. Related to stability, numerous existing methods to characterize the number of thermal cycles are summarized. Following this, 11 techniques to mitigate phase separation (plus 9 studies on macro-, micro-, and nano-encapsulation types) are reviewed. For supercooling, 38 nucleator-salt hydrate combinations to minimize subcooling are reviewed. The empirically observed effect of isomorphism in minimizing subcooling is explored and discussed, with cross-study trends depicted for 38 nucleators across 9 salt hydrates. In addition, several studies reporting combined effects on stability and supercooling are presented. Related to thermal conductivity, 32 combinations of conductivity enhancement material and salt hydrate are reviewed. For those using graphite, the dependence of conductivity enhancement on graphite mass fraction is shown across numerous studies for different graphite types. The performance and stability of calcium chloride hexahydrate, sodium sulfate decahydrate, and sodium acetate were explored and are discussed in-depth. Finally, the status of enhancement to salt hydrates is summarized, and remaining challenges are identified.
25 ENERGY STORAGE↗
Chemical specificity in polyzwitterion-polyelectrolyte coacervates: polycations vs polyanions
Aqueous solutions containing polyzwitterions and polyelectrolytes were studied to probe the effects of chemical specificity on the complexation among different types of chains and resulting liquid–liquid phase separation (coacervation). Two kinds of blends were studied. A polyzwitterion, poly(sulfobetaine methacrylate) (PSBMA), was blended with either (1) a polycation, poly(diallydimethylammonium chloride) (PDADMAC), or (2) a polyanion, sodium poly(styrene sulphonate) (NaPSS). Coacervation was observed in both blends after equilibration, while the freshly prepared blend solutions exhibited distinct behavior dependent on the mixing protocols. Mixing solutions of the polyzwitterions and the polycations led to coacervation almost instantaneously. In contrast, the blends containing the same polyzwitterions and the polyanions exhibited no such coacervation by following the same mixing protocol. However, blends prepared after dissolving a solid mixture containing the same polyzwitterions and the polyanions in water exhibited coacervation. Based on the small-angle X-ray scattering (SAXS), cryo-electron microscopy, and rheology measurements, complexation and coacervation in the polyzwitterion-polyelectrolyte blends is rationalized in terms of the entropy change associated with reorganization of solvent (water), which appears to be larger in the polyzwitterion-polycation case in comparison with the polyzwitterion-polyanion blends. These results highlight the importance of chemical specificity and mixing protocols leading to metastable structures in designing a new class of materials based on macromolecular complexation of polyzwitterions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of blending ratio of loblolly pine wood and bark on the properties of pyrolysis bio-oils
Bark, which is available in abundance, has recently become a topic of interest when considering alternative materials for the production of pyrolysis bio-oil. Previous studies have revealed that the pyrolysis behavior of bark differs remarkably from that of wood in that bark typically generates a phase-separated bio-oil. Here, blends of loblolly pine wood and bark were pyrolyzed to investigate the effect of blending ratio on the yield and properties of derived bio-oils. Trends of lower decomposition rate, decreased organic yield, and increased bio-char yield were observed as bark percentage in the feedstock increased, while the amount of levoglucosan in bio-oil increased. Pyrolysis reactivity, which includes yield and physical properties of the bio-oil, was found to have a linear relationship with the blending ratio of pine bark. Lastly, it was found that blending up to 50% bark in the feedstock still produced a homogeneous bio-oil.
09 BIOMASS FUELS↗
Plasticity in irradiated FeCrAl nanopillars investigated using discrete dislocation dynamics
Here, in this paper, we investigate plasticity in irradiated FeCrAl nanopillars using discrete dislocation dynamics simulations (DDD), with comparisons to transmission electron microscopic (TEM) in situ tensile tests of ion- and neutron-irradiated commercial C35M FeCrAl alloy. The effects of irradiation-induced defects, such as a/2<111> and a<100> type loops and composition fluctuations representative of phase separation in irradiated FeCrAl alloys, are investigated separately as well as superposed together in simulations. We explore the effects of defects on the stress-strain behavior, specifically yield strength and hardening response, of FeCrAl nanopillars. Our simulations confirm the widely accepted fact that irradiated alloys exhibit a stress-strain response with higher yield strength as compared to unirradiated alloys. However, our DDD calculations reveal an atypical superposition of the hardening contributions due to composition inhomogeneity and irradiation loops wherein composition inhomogeneity annihilates the hardening due to irradiation loops at small scales. As a result, we observe that the yield strength in irradiated alloys, after taking into consideration the effects of both composition inhomogeneity and irradiation loops, is smaller than the yield strength of the alloys with only irradiation loops and is approximately same for the alloy with composition inhomogeneity alone. This is referred to as “destructive interference” between the hardening contributions due to composition fluctuations and irradiation loops in the paper. We also identify this destructive interference in the superposition in our parallel TEM in situ tensile tests on unirradiated, ion-irradiated, and neutron-irradiated C35M FeCrAl alloy. This destructive interference in the hardening contributions contrasts with the dispersed barrier hardening (DBH) models widely utilized by the experimental community to model the hardening contributions due to different irradiation induced defects. The effects of the loading orientations on the yield strength and hardening are investigated and the mechanisms for the hardening in irradiated FeCrAl alloys are also reported.
36 MATERIALS SCIENCE↗
Solvothermal hot injection synthesis of core-shell AgNi nanoparticles
Silver-nickel core-shell nanoparticles (NP) were prepared by solvothermal hot injection synthesis by simultaneous thermolysis/reduction of AgNO 3 and Ni(acac) 2 precursors in the hot mixture of octadecene and oleylamine. Oleylamine decreases decomposition temperature of AgNO 3 to that of Ni(acac) 2 thus ensuring favorable reaction conditions. The prepared AgNi NPs with different Ag/Ni ratios were completely characterized. Dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) were used for particle size characterization of as-prepared AgNi colloids. There is no dependence of the particle size (13–21 nm by SAXS) on the Ag/Ni stoichiometric ratio, but the ultraviolet–visible spectroscopy (UV–vis) reveals that the intensity of the surface plasmon (SPR) decreases with increasing Ni content. Transmission electron microscopy (TEM) verified the results of DLS and SAXS and showed spherical nanoparticle shape. Distribution of individual elements in the nanoparticles was mapped by high resolution scanning transmission electron microscopy and energy dispersive X-ray spectroscopy (STEM-EDS) and revealed their core-shell structure where an Ag nucleus is covered by a thin amorphous Ni layer. Upon heating to 400 °C, Ni crystallization is substantiated by appearance of diffractions in the high-temperature X-ray powder diffractograms (HT-XRD) and of a magnetic moment. Ultimate phase separation was proven by scanning electron microscopy and energy dispersive X-ray analysis (SEM-EDS) in samples heated to 1000 °C. The reaction course and nanoparticle formation studied by DLS, UV–vis, and Ag and Ni elemental analyses reveal an initial Ag seed formation with subsequent Ni overlayer deposition after 180 s.
36 MATERIALS SCIENCE↗
Identifying higher oxygenate synthesis sites in Cu catalysts promoted and stabilized by atomic layer deposited Fe 2 O 3
The conversion of syngas to higher oxygenates is an important step in the pathway towards the long-term sustainable production of fuels and chemicals. Mixed Cu/Fe catalysts combine metals with different CO activation characteristics, a property that makes them promising candidates for higher oxygenate production. However, Cu/Fe catalysts suffer from instability due to sintering and phase separation, and the active sites for higher oxygenate formation on these materials are not well understood. In this work, we use atomic layer deposition (ALD) to modify silica-supported Cu nanoparticles with monolayer precise amounts of Fe 2 O 3 and study the effects on catalyst structure, reactivity, and stability. We demonstrate that the Fe 2 O 3 ALD process is inherently selective towards deposition on the SiO 2 surface versus the Cu nanoparticles. As a result, a sufficiently thick Fe 2 O 3 layer surrounding the Cu nanoparticles acts as a barrier against Cu migration, preventing catalyst deactivation through sintering without covering the Cu. In syngas conversion reactions, we find that higher oxygenate selectivity increases with Fe 2 O 3 loading at low and intermediate ALD cycle numbers. Furthermore, using in situ X-ray absorption spectroscopy, we demonstrate that the Fe near the Cu nanoparticles is reduced to a metallic state under reaction conditions. From these measurements, we identify these metallic Cu/Fe interfaces as the active sites for higher oxygenate formation, which are most abundant at intermediate Fe 2 O 3 ALD cycle numbers. As the Fe 2 O 3 loading increases, higher oxygenate selectivity falls, resulting from encapsulation of the Cu nanoparticles by thick Fe 2 O 3 layers. Overall, the results demonstrate how thickness-controlled ALD Fe 2 O 3 can be used as both a promoter and stabilizer of Cu-based higher oxygenate synthesis catalysts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A novel coupling of noise reduction algorithms for particle flow simulations
Proper orthogonal decomposition (POD) and its extension based on time-windows have been shown to greatly improve the effectiveness of recovering smooth ensemble solutions from noisy particle data. However, to successfully de-noise any molecular system, a large number of measurements still need to be provided. In order to achieve a better efficiency in processing time-dependent fields, we have combined POD with a well-established signal processing technique, wavelet-based thresholding. In this novel hybrid procedure, the wavelet filtering is applied within the POD domain and referred to as WAVinPOD. The algorithm exhibits promising results when applied to both synthetically generated signals and particle data. In this work, the simulations compare the performance of our new approach with standard POD or wavelet analysis in extracting smooth profiles from noisy velocity and density fields. Numerical examples include molecular dynamics and dissipative particle dynamics simulations of unsteady force- and shear-driven liquid flows, as well as phase separation phenomenon. Simulation results confirm that WAVinPOD preserves the dimensionality reduction obtained using POD, while improving its filtering properties through the sparse representation of data in wavelet basis. This paper shows that WAVinPOD outperforms the other estimators for both synthetically generated signals and particle-based measurements, achieving a higher signal-to-noise ratio from a smaller number of samples. The new filtering methodology offers significant computational savings, particularly for multi-scale applications seeking to couple continuum informations with atomistic models. It is the first time that a rigorous analysis has compared de-noising techniques for particle-based fluid simulations.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Phase transitions and magnetic domain coexistence in Nd0.5Sr0.5MnO3 thin films
We present a study of the physical properties of perovskite oxide Nd 0.5 Sr 0.5 MnO 3 (NSMO) thin films grown on (110)-oriented SrTiO 3 substrates. In bulk form, NSMO displays coupled magnetic and electronic transitions from paramagnetic/insulator to ferromagnetic (FM)/metal and then to antiferromagnetic (AFM)/charge-ordered insulator with decreasing temperature. In thin films, the AFM ordering only occurs when the films exist in an anisotropic strain state such as those obtained on (110)-oriented cubic substrates. In this work, resonant X-ray reflectivity, soft X-ray photoemission electron microscopy (X-PEEM), and magnetometry measurements showed that the NSMO film displays both vertical and lateral magnetic phase separation. Specifically, the film consists of three layers with different density and magnetic properties. The FM and AFM properties of the main NSMO layer were probed as a function of temperature using soft X-ray magnetic spectroscopy, and the coexistence of lateral FM and AFM domains was demonstrated at 110 K using X-PEEM.
36 MATERIALS SCIENCE↗
Breakage mechanics for granular materials in surface-reactive environments
It is known that the crushing behaviour of granular materials is sensitive to the state of the fluids occupying the pore space. Here, in this work, a thermomechanical theory is developed to link such macroscopic observations with the physico-chemical processes operating at the microcracks of individual grains. The theory relies on the hypothesis that subcritical fracture propagation at intra-particle scale is the controlling mechanism for the rate-dependent, water-sensitive compression of granular specimens. First, the fracture of uniaxially compressed particles in surface-reactive environments is studied in light of irreversible thermodynamics. Such analysis recovers the Gibbs adsorption isotherm as a central component linking the reduction of the fracture toughness of a solid to the increase of vapour concentration. The same methodology is then extended to assemblies immersed in wet air, for which solid-fluid interfaces have been treated as a separate phase. It is shown that this choice brings the solid surface energy into the dissipation equations of the granular matrix, thus providing a pathway to (i) integrate the Gibbs isotherm with the continuum description of particle assemblies and (ii) reproduce the reduction of their yield strength in presence of high relative humidity. The rate-effects involved in the propagation of cracks and the evolution of breakage have been recovered by considering non-homogenous dissipation potentials associated with the creation of surface area at both scales. It is shown that the proposed model captures satisfactorily the compression response of different types of granular materials subjected to varying relative humidity. This result was achieved simply by using parameters based on the actual adsorption characteristics of the constituting minerals. The theory therefore provides a physically sound and thermodynamically consistent framework to study the behaviour of granular solids in surface-reactive environments.
36 MATERIALS SCIENCE↗
Nanoscopic structure of borosilicate glass with additives for nuclear waste vitrification
In this report we investigated the nanoscopic structure of borosilicate glasses as a host for high-level radioactive liquid waste (HLLW) in the presence of the additives Na 2 O and CaO/ZnO with and without Li 2 O. These additives have been used to lower the glass melting point, suppress the macroscopic phase separation, and increase the chemical durability of glasses. Small-angle neutron scattering was used to elucidate the effect of the additives on the nanoscopic structure along with macro- and atomic-scale observations obtained using neutron imaging and X-ray diffraction, respectively. The borosilicate glass made without Na 2 O formed a microphase-separated structure of SiO 2 - and B 2 O 3 -rich domains approximately 100 nm in size, and the material was homogeneous at length scales up to millimeters. With the addition of increasing amounts of Na 2 O, the domain spacing decreased. Introducing CaO/ZnO additives induced inhomogeneities in the glass, such as void structures several nanometers in size, although the inhomogeneity was suppressed by the coaddition of Li 2 O. These results provide insights into the performance of host glasses for HLLW vitrification. Incorporating HLLW into glasses is likely to cause changes in the nanoscopic structure of host glasses similar to those revealed here.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Identification of NpO 2+x in the binary Np-O system
In contrast to UO 2 and PuO 2 , there is no consensus on the existence of mixed valence NpO 2+x , resulting in a gap between NpO 2 and Np 2 O 5 (the highest binary oxide of Np) in the Np-O phase diagram. We now show NpO 2+x via Np L III Extended X-ray Absorption Fine Structure (EXAFS) spectra of three samples of NpO 2 that, analogous to U and Pu, exhibit multisite Np-O distributions with varying numbers of oxygen atoms at 1.87–1.91 Å. Furthermore this is supported by the diffraction pattern of the sample with the largest amount of this oxo-type species that can be refined with both the simple fluorite structure and a trigonal one related to α-U 4 O 9 . The implied Np(V)-bridging oxo moieties as well as possible indications of OH - found by detailed EXAFS analysis suggest that NpO 2+x more closely resembles PuO 2+x than UO 2+x . An additional common characteristic suggested by the EXAFS and X-Ray Diffraction (XRD) is the phase separation into NpO 2 and what would be previously unreported Np 4 O 9(-δ) , indicative of O clustering.
36 MATERIALS SCIENCE↗
Effects of Composition and Oxidation States on the Structures of Chromium-Containing Sodium Silicate Glasses: Molecular Dynamics Simulations using Machine Learning Interatomic Potentials
Chromium represents a significant challenge for the vitrification of high-level nuclear waste into silicate and borosilicate glasses due to its low solubility and variable oxidation states, which can limit the waste loading due to promotion of crystallization or phase separation during processing. In this study, we modeled chromium containing silicate glasses using molecular dynamics simulations with three machine learning interatomic potentials (MLIPs), MACE, CHGNet, and PFP were employed, to gain insights on glass composition and oxidation states on the structures of these glasses. One of the goals is to evaluate their ability of these MLIPs to accurately represent the general structure of silicate glasses and chromium local environments as a function of chromium oxidation states. Density Functional Theory (DFT) based calculations and experimental data such as neutron structure factors were used to validate the structural models. It was found that the foundation models of all three MLIPs are able to reproduce general structural features of the sodium silicate glass structure consistent with experimental and DFT data, but only CHGNet and PFP can accurately capture the oxidation states and local environment of chromium: tetrahedral for Cr6+ and octahedral for Cr3+. Furthermore, we studied the effect of varying Cr3+/ Cr6+ (Cr3+/Crtotal) ratio and total chromium content using PFP. Our results show that Cr6+ enhances network polymerization by reducing non-bridging oxygens through Na? charge compensation required due to the formation of chromate (CrO42-) species, while Cr³? acts as a network modifier that disrupts connectivity. System size effects on the structural characteristics and chromium environments were also tested using the PFP potential. This work highlights the importance of careful validation on the precision, transferability, and potential of MLIPs for modeling glasses containing transition metal elements that can exist in multiple oxidation states. It is also encouraging to see the foundational models are all three MLFFs are able to reproduce the basic sodium silicate glass structures, while suggesting additional training or refining is needed to improve the description of more complex systems containing transition metals.
Puga, Christina L.↗
Criteria for extending the operation periods of thermoelectric converters based on IV-VI compounds
The recent energy demands affected by the dilution of conventional energy resources and the growing awareness of environmental considerations, had positioned the research of renewable energy conversion methods in general and of thermoelectric direct conversion of thermal into electrical energies in particular, in the forefront of the currently active applicative sciences. IV-VI thermoelectric compounds (e.g. GeTe, PbTe and SnTe) and their alloys comprise some of the most efficient thermoelectric compositions ever reported. Yet a proper utilization of such materials in practical thermoelectric devices, still requires an overcoming the so-called technological “valley of death”, including among others, transport properties' degradation, due to sublimation of volatile Te rich species, while being subjected to elevated temperatures for long periods of time. In an attempt to establish practical operation criteria for extending the operation periods of such thermoelectric converters, it is currently shown based on thermal gravimetric and metallurgical considerations that such harmful sublimation can be practically bridged over by limiting the maximal operating temperatures to the 410–430 °C range for GeTe rich alloys and to 510–530 °C for PbTe and SnTe rich alloys, depending of the thermoelectric leg's diameter. - Graphical abstract: Evaporation rate in the GeTe and PbTe system showing the measured evaporation rates and the maximal operating temperatures for different compositions. In addition, the microstructure after evaporation is shown for PbTe, TAGS-85, and doped Pb{sub 0.13}Ge{sub 087}Te. Display Omitted - Highlights: • Evaporation rates of GeTe and PbTe based thermoelectric compounds were determined. • A criterion for their maximum operating temperature was established. • The materials showed phase separations and off-stoichiometry compositions.
36 MATERIALS SCIENCE↗
Effect of quenching rate on the microstructure and mechanical behavior of Ce75Al21Ga4 glassy alloy
Highlights: • Structural and microstructural changes with respect to quenching rate have been reported. • Ribbons synthesized at slow cooling rate shows higher hardness and yield strength. • Study is focused on the correlation between quenching rate and mechanical behavior. • Metallic glass synthesized at faster quenching rate contains the highest shear band density. - Abstract: The present study deals with the structural and microstructural changes with respect to the quenching rate and their correlation with mechanical behavior of melt-spun Ce{sub 75}Al{sub 21}Ga{sub 4} glassy alloys. The ribbons of the alloy have been synthesized at different quenching rates obtained through different wheel speeds (44, 36, 29, 22 and 15 m/s). The glass forming indicators and mechanical properties have been investigated at different quenching rates. The higher quenching rate obtained through high wheel speed (44, 36 and 29 m/s) has led to phase separation giving rise to nano-amorphous domains in a glassy matrix while the lower quenching rate obtained through lower wheel speed (22 and 15 m/s) produces nano-crystalline grains with size ranges from 25 ± 1 to 120 ± 1 nm. It has been found that the size of the nano-amorphous domains decreases with decrease in wheel speed. The mechanical behavior has been studied using micro-indentation technique. The indentation test indicates that with the same chemical composition, the ribbons synthesized at slow quenching rate exhibits higher hardness and yield strength than those synthesized at faster quenching rate. The ribbons synthesized at 44 m/s contains the large free volume and has the highest shear band density.
36 MATERIALS SCIENCE↗
Evaluation of solid solution formation between ThO2 and δ-Bi2O3 by molecular precursor route
Highlights: • Molecular precursor route for the solid solution evaluation of ThO{sub 2}-BiO{sub 1.5}. • Up to 60 mol % of Bi{sup 3+} could be dissolved in fluorite structured ThO{sub 2}. • Oxygen vacancies manifested as defect bands after Bi{sup 3+} incorporation. • Narrowing of direct band gap with increasing Bi{sup 3+} concentration. - Abstract: The high chelating ability of nitrilotriacetic acid has been advantageously utilized to prepare molecular precursors containing thorium and bismuth. This aided to determine the extent of solid solution formation between thoria and δ-Bi{sub 2}O{sub 3} in fluorite structure by calcining the precursors in air. Up to 60 atomic % of Bi{sup 3+} could be substituted for Th{sup 4+} in fluorite structure beyond which phase separation occurred. Slight increase in cubic lattice constant was observed with increasing bismuth content along with indication of increased tensile strain of lattice. Porous morphology and presence of bismuth in calcined samples were confirmed from SEM and EDX measurements. Defect bands emerged in the Raman spectra near 590 cm{sup −1} in addition to a fluorite band near 460 cm{sup −1} for the bismuth substituted samples. Intermediate energy states were formed by the substitution of Bi{sup 3+} for Th{sup 4+} arising possibly from oxygen vacancies and it resulted in narrowing of direct band gap.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Solid additive engineering enables high-efficiency and eco-friendly all-polymer solar cells
Currently, morphology optimization of all-polymer solar cells (all-PSCs) strongly depends on the use of solvent additives, which are usually highly toxic and harmful to the environment and human health. Here, we report a green and volatile solid additive, 2-methoxynaphthalene (2-MN). It was found that the incorporation of 2-MN into a PM6:PY-DT blend can effectively manipulate the aggregations of PM6 and PY-DT during film depositing and thermal annealing processes and results in highly ordered molecular packing and favorable phase-separated morphology. Consequently, a record-high efficiency of 17.32% is achieved for the PM6:PY-DT device. Moreover, 2-MN-processed all-PSCs were fabricated by using non-halogenated solvent. High efficiencies of 17.03% and 16.67% are obtained for all-PSCs fabricated under nitrogen atmosphere and ambient conditions, respectively. Finally, our work shows that the utilization of 2-MN as a green and solid additive is a simple and feasible strategy to optimize the morphology and sheds new light on eco-friendly fabrication and application of all-PSCs.
14 SOLAR ENERGY↗
Aqueous ion partitioning in Nafion: Applicability of Manning's counter-ion condensation theory
Nafion is a well-studied polymer of significant interest as a fuel cell membrane due to rapid transport of protons, which is often ascribed, at least in part, to its phase-separated morphology. The literature detailing ion sorption and transport in Nafion diverges considerably from that of water purification membranes, with contrasting analyses and models. To help bridge these gaps and facilitate comparisons of membranes with various structures, this study presents measurements of ion activity coefficients and sorption in Nafion 117 equilibrated with aqueous solutions of NaCl, MgCl 2 , and Na 2 SO 4 , which are relevant to water purification. The experimental data are compared to a theoretical framework based on Manning's counter-ion condensation theory and Donnan theory. Good agreement between the model and data is observed for NaCl and MgCl 2 , using no adjustable parameters. However, the model significantly underpredicts Na 2 SO 4 solubility, which is attributed to ion pairing effects. Furthermore, the results highlight the general applicability of counter-ion condensation theory to highly charged polymers, including those exhibiting nanoscale ordering, while revealing fundamental limitations related to ion pairing.
36 MATERIALS SCIENCE↗