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At least 73 records · Page 4

On-the-fly machine learned force fields for the study of warm dense matter: Application to diffusion and viscosity of CH

We develop a framework for on-the-fly machine learned force field (MLFF) molecular dynamics (MD) simulations of warm dense matter (WDM). In particular, we employ an MLFF scheme based on the kernel method and Bayesian linear regression, with the training data generated from the Kohn–Sham density functional theory (DFT) using the Gauss spectral quadrature method, within which we calculate energies, atomic forces, and stresses. We verify the accuracy of the formalism by comparing the predicted properties of warm dense carbon with recent Kohn–Sham DFT results in the literature. In so doing, we demonstrate that ab initio MD simulations of WDM can be accelerated by up to three orders of magnitude, while retaining ab initio accuracy. We apply this framework to calculate the diffusion coefficients and shear viscosity of CH at a density of 1 g/cm3 and temperatures in the range of 75 000–750 000 K. We find that the self- and inter-diffusion coefficients and the viscosity obey a power law with temperature, and that the diffusion coefficient results suggest a weak coupling between C and H in CH. In addition, we find agreement within standard deviation with previous results for C and CH but disagreement for H, demonstrating the need for ab initio calculations as presented here.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mechanisms of Ti 3 Al precipitation in hcp α -Ti

Here, nucleation and growth of Ti3Al α( 2 ) ordered domains in alpha-Ti-Al-X alloys were characterised using a combination of transmission electron microscopy, atom probe tomography and small angle X-ray scattering. Model alloys based on Ti-7Al (wt.%) and containing O, V and Mo were aged at 550 °C for times up to 120d and the resulting precipitate dispersions were observed at intermediate points. Precipitates grew to around 30nm in size, with a volume fraction of 6-10% depending on tertiary solutes. Interstitial O was found to increase the equilibrium volume fraction of α 2 , while V and Mo showed relatively little influence. Addition of any of the solutes in this study, but most prominently Mo, was found to increase nucleation density and decrease precipitate size and possibly coarsening rate. Coarsening can be described by the Lifshitz-Slyozov-Wagner model, suggesting a matrix diffusion-controlled coarsening mechanism (rather than control by interfacial coherency). Solutionising temperature was found to affect nucleation number density with an activation energy of E f = 1.5 +/- 0.4 eV, supporting the hypothesis that vacancy concentration affects α 2 nucleation. The observation that all solutes increase nucleation number density is also consistent with a vacancy-controlled nucleation mechanism.

36 MATERIALS SCIENCE↗

Assessing dual continuum method for multicomponent reactive transport

The subsurface flow and reactive transport code PFLOTRAN can accommodate fracture–matrix interaction for multicomponent reactive transport using a Dual Continuum formulation. In this work we present two examples to assess this approach. Through these examples, we also illustrate how this Dual Continuum model can be parameterised and what kind of grid spacing is needed to accurately capture reactive transport in the secondary continuum. The results of the calculations show that when geochemical reactions in the matrix (or the secondary continuum) are included, a very fine grid spacing close to the fracture–matrix interface is required to properly capture geochemical gradients at the interface. We also show that one can reduce the computational cost by using a variable grid spacing, that limits the total number in the secondary continuum, and yet obtain accurate results. Furthermore, this feature makes the Dual Continuum approach suitable for large-scale reactive transport modelling in fractured crystalline rock.

58 GEOSCIENCES↗

Response to Extreme Temperatures of Mesoporous Silica MCM-41: Porous Structure Transformation Simulation and Modification of Gas Adsorption Properties

In this paper, molecular dynamics (MD) and Monte Carlo (MC) simulations were applied together for the first time to reveal the porous structure transformation mechanisms of mesoporous silica MCM-41 subjected to temperatures up to 2885 K. Silica was experimentally characterized to inform the models and enable prediction of changes in gas adsorption/separation properties. MD simulations suggest that the pore closure process is activated by a collective diffusion of matrix atoms into the porous region, accompanied by bond reformation at the surface. Degradation is kinetically limited, such that complete pore closure is postponed at high heating rates. We experimentally observe decreased gas adsorption with increasing temperature in mesoporous silica heated at fixed rates, due to pore closure and structural degradation consistent with simulation predictions. Applying the Kissinger equation, we find a strong correlation between the simulated pore collapse temperatures and the experimental values which implies an activation energy of 416 ± 17 kJ/mol for pore closure. MC simulations give the adsorption and selectivity for thermally treated MCM-41, for N 2 , Ar, Kr, and Xe at room temperature within the 1–10 000 kPa pressure range. Relative to pristine MCM-41, we observe that increased surface roughness due to decreasing pore size amplifies the difference of the absolute adsorption amount differently for different adsorbate molecules. In particular, we find that adsorption of strongly interacting molecules can be enhanced in the low-pressure region while adsorption of weakly interacting molecules is inhibited. Finally, this then results in higher selectivity in binary mixture adsorption in mesoporous silica.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Sensors for Biomolecules Using Nanoporous Sol-Gel Materials

An important consideration for space missions to Mars is the ability to detect biosignatures. Solid-state sensing elements for optical detection of biological entities are possible using sol-gel based biologically active materials. We have used these materials as optical sensing elements in a variety of bioassays, including immunoassays and enzyme assays. By immobilizing an appropriate biomolecule in the sol-gel sensing element, we have successfully detected analytes such as amino acids and hormones. In the case of the amino acid glutamate, the enzyme glutamate dehydrogenase was the immobilized molecule, whereas in the case of the hormone cortisol, an anti-cortisol antibody was immobilized in the sensing element. In this previous work with immobilized enzymes and antibodies, excellent sensitivity and specificity were demonstrated in a variety of formats including bulk materials, thin films and fibers. We believe that the sol-gel approach is an attractive platform for bioastronautics sensing applications because of the ability to detect a wide range of entities such as amino acids, fatty acids, hopanes, porphyrins, etc. The sol-gel approach produces an optically transparent 3D silica matrix that forms around the biomolecule of interest, thus stabilizing its structure and functionality while allowing for optical detection. This encapsulation process protects the biomolecule and leads to a more "rugged" sensor. The nanoporous structure of the sol-gel matrix allows diffusion of small target molecules but keeps larger, biomolecules immobilized in the pores. We are currently developing these biologically active sol-gel materials into small portable devices for on-orbit cortisol detection

Fang, Jonathan↗

Diffusion of copolymers composed of monomers with drastically different friction factors in copolymer/homopolymer blends

Copolymers are commonly used as interface modifiers that allow for the compatibilization of polymer components in a blend. For copolymers to function as a compatibilizer, they must diffuse through the matrix of the blend to the interface between the two blend components. The diffusivity of a copolymer in a blend matrix therefore becomes important in determining good candidates for use as compatibilizers. In this paper, coarse-grained Monte Carlo simulations using the bond fluctuation model modified with an overlap penalty have been developed to study the diffusive behavior of PS/PMMA random copolymers in a PMMA homopolymer blend. The simulations vary the connectivity between different monomers, the thermodynamic interactions between the monomers which manifest within a chain, and between copolymer and homopolymer matrix and define the monomer friction coefficient of each component independently, allowing for the determination of the combined effect of these parameters on copolymer chain diffusion. Finally, the results of this work indicate that PS-r-PMMA copolymer diffusion is not linearly dependent on the copolymer composition on a logarithmic scale, but its diffusion is a balance of the kinetics governed by the dominant motion of the faster styrene monomers and thermodynamics, which are governed by the concentration of styrene monomer within a given monomer’s local volume.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Durability and Dissolution Kinetics of Iodoapatite in Aqueous Solutions

Understanding the long-term release of radionuclides from nuclear waste to the environment is critical for public acceptance and sustainability of nuclear energy. Iodoapatite, a synthetic material similar to mineral vanadinite proposed for radioactive iodine-129 immobilization, is employed in this study as a model system for iodine waste forms and ceramic waste forms in general to understand its long-term chemical durability. Semidynamic leaching experiments were performed in cap-sealed Teflon vessels to evaluate the chemical durability at temperatures from 20 to 90 degrees C and pH values from 4 to 9 using deionized water and pH buffer solutions. The leachates were analyzed using inductively coupled plasma-mass spectrometry. The leached surfaces were examined by X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. Effects of test variables including surface-to-volume ratio, leachant replacement interval, and environmental variables including temperature and pH on the dissolution rate were systematically investigated. The activation energy of the dissolution was 16.9 ± 1.5 kJ/mol for the matrix elements and 34.4 ± 3.9 kJ/mol for the diffusive iodine release. The order of the pH effect on the dissolution rate as a power law exponent was 0.87 ± 0.08. The effect of the surface-to-volume ratio and replacement interval was approximated by a single exponential function rise to maximum. Fully parametrized models were then combined to predict iodine release rate under various conditions. The result suggests that the long-term iodine release is controlled by iodide diffusion when the matrix dissolution rate is very low in near neutral pH solutions and by matrix dissolution when the dissolution rate is high at low pH. The present study demonstrates a mechanistic approach to parametrize models that can be used to evaluate the performance of nuclear waste forms under various disposal environments.

36 MATERIALS SCIENCE↗

Oxidation of Silicon Particles Suspended in Mullite Matrix With Dual-Mode Vacancy Diffusion of Oxygen

Mullite bond coats filled with silicon particles have recently been proposed for the next generation of environmental barrier coatings (EBCs). The sacrificial oxidation of the silicon particles eliminates some of the environmental durability issues associated with traditional EBC designs. To investigate this novel design approach, a mathematical formulation and resulting numerical method have been developed for simulating the oxidation of silicon particles embedded in a mullite matrix. The focus is on the oxidation of the silicon in a dry oxygen environment where the oxidant is presumably oxygen. Oxygen transport from the exterior environment through the mullite is assumed to occur via two lattice defect diffusion mechanisms. As a result, the rate of oxygen transport is dictated by the self-diffusivity of the lattice defects. The numerical method is implemented using the COMSOL Multiphysics® program (COMSOL, Inc.). The method is applied to simulate the oxidation of silicon particles in a mullite pellet in recent oxidation experiments. Numerical results compare favorably with the oxidation behavior observed in the oxidation experiments. The numerical method is also used to investigate the effects of various features of the mullite-silicon particle system on the oxidation behavior.

silicon oxidation↗

Dynamics of moisture diffusion through a partially liquid filled porous matrix.

Models for unsteady water transport in fuel cell configurations of Bacon-Pratt and Whitney type are derived. Tests with a specially constructed isothermal cell producing no water and order of magnitude analysis show that diffusion through the liquid alone cannot account for the observed behavior. An analytical solution which includes diffusion in both the liquid and the gas spaces of the matrix is in better agreement with the data than models which consider diffusion in either the liquid or in the gas phase alone.

Murty, B. G. K.↗

Effects of Moisture on Diffusion in Unmodified Wood Cell Walls: A Phenomenological Polymer Science Approach

Despite the importance of cell wall diffusion to nearly all aspects of wood utilization, diffusion mechanisms and the detailed effects of moisture remain poorly understood. In this perspective, we introduce and employ approaches established in polymer science to develop a phenomenological framework for understanding the effects of moisture on diffusion in unmodified wood cell walls. The premise for applying this polymer-science-based approach to wood is that wood polymers (cellulose, hemicelluloses, and lignin) behave like typical solid polymers. Therefore, the movement of chemicals through wood cell walls is a diffusion process through a solid polymer, which is in contrast to previous assertions that transport of some chemicals occurs via aqueous pathways in the cell wall layers. Diffusion in polymers depends on the interrelations between free volume in the polymer matrix, molecular motions of the polymer, diffusant dimensions, and solubility of the diffusant in the polymer matrix. Because diffusion strongly depends on whether a polymer is in a rigid glassy state or soft rubbery state, it is important to understand glass transitions in the amorphous wood polymers. Through a review and analysis of available literature, we conclude that in wood both lignin and the amorphous polysaccharides very likely have glass transitions. After developing and presenting this polymer-science-based perspective of diffusion through unmodified wood cell walls, suggested directions for future research are discussed. A key consideration is that a large difference between diffusion through wood polymers and typical polymers is the high swelling pressures that can develop in unmodified wood cell walls. This pressure likely arises from the hierarchical structure of wood and should be taken into consideration in the development of predictive models for diffusion in unmodified wood cell walls.

59 BASIC BIOLOGICAL SCIENCES↗

Matrix Resin Characterization in Cured Graphite Composites Using Diffuse Reflectance-Ftir

The chemical characterization of cured graphite fiber reinforced polymer matrix composites is complicated by the fact that the resins are insoluble and the composites are apaque. Standard analyses which depend either on the ability to dissolve the sample or to detect transmitted radiation are impossible. As a result, data reported on environmentally exposed composites primarily concern macroscopic information such as weight loss or changes in selected mechanical properties. Diffuse reflectance in combination with fourier transform infrared spectroscopy was developed to gain a basic chemical understanding of composite and adhesive behavior. Several composite and adhesive materials were characterized before and after environmental exposure. In each case significant changes in resin molecular structure were observed and correlated with changes in mechanical properties, providing new insights into material performance.

Young, P. R.↗

Creep and microstructural processes in a low-alloy 2.25%Cr1.6%W steel (ASTM Grade 23)

A low-alloy 2.25%Cr1%Mo steel (ASTM Grade 22) has been greatly improved by the substitution of almost all of the 1%Mo by 1.6%W. The improved material has been standardized as P/T23 steel (Fe–2.25Cr–1.6W–0.25V–0.05Nb–0.07C). The present investigation was conducted on T23 steel in an effort to obtain a more complete description and understanding of the role of the microstructural evolution and deformation processes in high-temperature creep. Constant load tensile creep tests were carried out in an argon atmosphere in the temperature range 500–650 °C at stresses ranging from 50 to 400 MPa. It was found that the diffusion in the matrix lattice is the creep-rate controlling process. The results of an extensive transmission electron microscopy (TEM) analysis programme to investigate microstructure evolution as a function of temperature are described and compared with the thermodynamic calculations using the software package Thermo-Calc. The significant creep-strength drop of T23 steel after long-term creep exposures can be explained by the decrease in dislocation hardening, precipitation hardening and solid solution hardening due to the instability of the microstructure at high temperature. - Highlights: • The constant load creep tests of T23 steel were carried out at 500–650 °C. • The stress exponents of the creep rate correspond to power law (dislocation) creep. • Diffusion in the matrix lattice is the creep-rate controlling process. • The microstructure instability is the main creep degradation process in T23 steel.

36 MATERIALS SCIENCE↗

Structure, Dynamics, and Hydrogen Transport in Amorphous Polymers: An Analysis of the Interplay between Free Volume Element Distribution and Local Segmental Dynamics from Molecular Dynamics Simulations

Polymers are attractive membrane materials owing to their mechanical robustness and relatively inexpensive fabrication. An important indicator of membrane performance are free volume elements (FVE): microporous void spaces created by the inefficient packing of bulky groups along the polymer chain. FVEs tend to degrade over time, as polymer chains reorganize irreversibly. While it is widely accepted that polymer flexibility has an impact on membrane transport properties, the molecular nature of this impact is still not well understood. By the establishment of a correlation between local chain dynamics and the distribution of free volume elements (FVEs), penetrant transport can be regulated more efficiently in amorphous polymer membranes. In this work, we implement all-atom molecular dynamics (MD) simulations to explore the relationship between chain dynamics and free volume in three polymers with different levels of backbone flexibility: polymethylpentene (PMP), polystyrene (PS), and HAB-6FDA thermally rearranged polymer (TRP). We construct these polymers at different temperatures and examine how temperature impacts the FVE distribution and segmental mobility. Our analysis shows that chain segments near FVEs have higher mobility compared with the atoms in the bulk; the extent of this difference increases with chain flexibility. Increasing the chain flexibility by increasing the temperature results in a broader FVE distribution. Rigid polymers such as TRP show the most robust FVE distribution and are not significantly affected by the temperature change. To capture penetrant diffusion through the polymer matrix, hydrogen is inserted and the diffusion is measured at different temperatures; hydrogen mobility is influenced by the FVE structure and overall mobility of polymer chains. Lastly, at low temperatures, hydrogen mobility is influenced by void distribution, while at high temperatures, polymer dynamics dictate hydrogen transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxygen Diffusion and Reaction Kinetics in Continuous Fiber Ceramic Matrix Composites

Previous stressed oxidation tests of C/SiC composites at elevated temperatures (350 C to 1500 C) and sustained stresses (69 MPa and 172 MPa) have led to the development of a finite difference cracked matrix model. The times to failure in the samples suggest oxidation occurred in two kinetic regimes defined by the rate controlling mechanisms (i.e. diffusion controlled and reaction controlled kinetics). Microstructural analysis revealed preferential oxidation along as-fabricated, matrix microcracks and also suggested two regimes of oxidation kinetics dependent on the oxidation temperature. Based on experimental results, observation, and theory, a finite difference model was developed. The model simulates the diffusion of oxygen into a matrix crack bridged by carbon fibers. The model facilitates the study of the relative importance of temperature, the reaction rate constant, and the diffusion coefficient on the overall oxidation kinetics.

Halbig, Michael C.↗

A study of the diffusional behavior of a two-phase metal matrix composite exposed to a high temperature environment

The progress of diffusion-controlled filament-matrix interaction in a metal matrix composite where the filaments and matrix comprise a two-phase binary alloy system was studied by mathematically modeling compositional changes resulting from prolonged elevated temperature exposure. The analysis treats a finite, diffusion-controlled, two-phase moving-interface problem by means of a variable-grid finite-difference technique. The Ni-W system was selected as an example system. Modeling was carried out for the 1000 to 1200 C temperature range for unidirectional composites containing from 6 to 40 volume percent tungsten filaments in a Ni matrix. The results are displayed to show both the change in filament diameter and matrix composition as a function of exposure time. Compositional profiles produced between first and second nearest neighbor filaments were calculated by superposition of finite-difference solutions of the diffusion equations.

Tenney, D. R.↗

Solute Redistribution During Aging in a Laser-Based Powder Bed Fusion-Produced Fe-18Ni-9Co-5Mo-Ti Maraging Steel

Solute distribution during the laser-based powder bed fusion of metals process is highly complex because of solidification. This study builds on a previous investigation of how solute heterogeneities across different scales influence phase distribution and aging physical phenomena in a Fe-18Ni-9Co-5Mo-Ti maraging steel (Santana et al. in Addit Manuf 104494, 2024). Previous work using energy-dispersive X-ray spectroscopy revealed heterogeneous Ni and Mo enrichment at intercellular regions. Using X-ray diffraction, 8 ± 3% retained austenite was quantified in as-built samples. Additionally, electron backscatter diffraction analysis exposed the location of retained austenite along cell boundaries. In this work, scanning transmission electron microscopy results revealed the presence of non-enriched retained austenite in the as-built condition. With increased aging temperature, Ni and Mo enrichment in austenite increased, especially at the austenite/martensite boundary. Solute diffusion was simulated in DICTRA Thermo-Calc® software to assess solute redistribution between the matrix and second phases and to comprehend whether elemental diffusion processes are interconnected. Three different scenarios were considered: (1) solute diffusion in the matrix; (2) diffusion with enriched austenite in the intercellular region; (3) diffusion with non-enriched austenite in the intercellular region. Results showed that Ni partitioning controls austenite growth and that boundary regions exhibit higher element enrichment than the core.

42 ENGINEERING↗

Multi-scale modeling of wastage layer formation in metallic fuel cladding

Fuel-cladding chemical interaction (FCCI) is a major concern for U-Zr metallic fuels' performance, primarily due to the formation of a brittle layer (wastage) in the cladding. This brittle layer, resulting from intermetallic compounds between cladding constituents Fe, Cr, and lanthanide fission products, significantly impacts the cladding's mechanical integrity. Recent efforts focus on developing a mechanistic modeling framework to understand lanthanide production, transport to the fuel-cladding interface, and phase transformation to intermetallic phases. A multi-scale computational approach has been used to calculate lanthanide transport rates, with atomistic calculations determining Nd diffusivities through the solid fuel matrix and along pore surfaces. These diffusivities inform a mesoscale model to determine an effective diffusion coefficient, accounting for porosity and infiltration with bond sodium. This effective diffusivity is used in engineering-scale simulations via the BISON fuel performance code, which has been validated against EBR-II and FFTF reactor experiments.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗