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71 records · Page 4

Optimization of WAAM Process to Produce AUSC Components with Increased Service Life

Additive manufacturing has the potential to revolutionize industrial hardware and unlock efficiency gains through the fabrication of geometries and architectures not possible by conventional processing. Wire Arc Additive manufacturing (WAAM) process is a class of directed energy deposition process enabling higher build rate and allowing custom wire feedstock allowing spatial variation of microstructure. The larger spot size and lower speed creates a larger melt pool, reducing residual stress and often time creating directional/columnar microstructure for Ni-superalloy. The use of flexible platform provides freedom in deposition strategy, which can accommodate complex substrates, including feature addition onto existing structures, non-flat layers, and repair methods. However, the certification of the final component needs to match the strength requirement. Hence, the quality of the component produced is stringently monitored to avoid buildup of residual stress, cracks, porosity and to reduce detrimental segregated phases commonly observed during alloy solidification. Simulation plays a huge role in predicting the melt pool dimension and can be used to optimize the process parameter. Similar development is also required to perform physics-based modeling of microstructural development in WAAM that can predict the microstructural features during solidification and can be used to optimize the process more effectively. To move toward this goal, Raytheon Technologies Research Center together with Siemens worked to create a set of computational tools to control the process parameters, enable on-line measurements and acquisition with feedback to the optimized process parameters, and eventually track material evolution through each step of the additive process. Computational fluid dynamics is used for accurate prediction and calibration of the thermal field during WAAM process. and phase field models for microstructure evolution as a function of processing parameters to establish a connection between additive parameters and the final microstructure. Here we report cellular automata (CA) model development to predict the dendritic microstructure evolution with surface and bulk nuclei for single track and multiple layers. The CA model was developed to account for secondary element addition and predict segregation, local melting, and latent heat release as well as prediction of Euler angles from orientation information and validated against experiments. This framework was utilized to tailor spatially-varying composition in a part by appropriately controlling the microstructure evolution during the additive process. Functionally graded Haynes 282 alloy with high Cr content at the surface was tested for oxidation and mechanical properties. An advanced physics-based reaction-diffusion model predicting the simultaneous creation of chromium oxide and alumina is developed and validated to extend life expectancy of the WAAM manufactured high temperature part. A machine-learning data-driven framework establishing the process-structure relationship from a dataset of real microstructure images and corresponding process history data has been developed and implemented in the NX Siemens design system. The digital twin configuration along with the tool path generation enabled prediction of WAAM component buildup time and the techno-economic analysis provided a favorable option for all 4 cases with 15-40% cost reduction.

33 ADVANCED PROPULSION SYSTEMS↗

Probing the Structure and Dynamics of Fluid Mixtures in Porous Materials Through Ultrafast Vibrational Spectro-Microscopy and Many-Body Molecular Dynamics

This research program focused on the characterization of both molecular structure and dynamics of aqueous solutions in various metal-organic frameworks (MOFs) and organic polymers that have recently been proposed for applications in water treatment technologies. This was accomplished by integrating ultrafast vibrational spectroscopy and microscopy, which are sensitive to local environments, molecular orientation, and dynamical couplings, with many-body molecular dynamics (MB-MD) simulations, which enable realistic modeling of aqueous systems and porous materials under different thermodynamic conditions. Our studies allowed for identifying the physical mechanisms and characterizing the underlying molecular interactions between water and host materials that determine the adsorption and transport processes of water in various MOFs and β-cyclodextrin polymers – prototypical examples of porous materials and polymers, that have recently been proposed for technological applications in water purification. By combining bulk- and surface-sensitive, spatially resolved ultrafast vibrational spectroscopy with MB-MD simulations, it was possible to gain broad insight into the structure and mobility of water under heterogeneous confinement at various length scales. In particular, measurements of surface- and bulk-sensitive vibrational spectra at single crystal level, integrated with MB-MD simulations were used to characterize domain-specific, structure–binding affinity relationships. Besides providing specific information about the behavior of aqueous solutions in prototypical MOFs and organic polymers for potential applications in water treatment technologies, our studies also provided fundamental insights into the properties of aqueous solutions in confined heterogeneous environments, which have broad implications in many areas, ranging from heterogeneous catalysis to oil recovery, ion transport processes, and reaction-diffusion processes in crowded systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining Graphite Degradation in Molten Salt Environments: A Chemical, Physical, and Material Analysis

Molten-salt reactors (MSRs) are Generation IV nuclear reactors that use liquid salt as a coolant and/or fuel. In several MSR designs, graphite serves as a moderator and/or reflector. However, due to limited experimental data and operational experience, our understanding of graphite behavior in molten salt environments remains incomplete. This report aims to identify the degradation mechanisms of nuclear graphite in MSRs, detail the mechanisms of each factor, and provide an initial assessment of their impact on the structural integrity of graphite components. This assessment is based on an extensive literature review and insights from subject matter experts. Furthermore, given the limited data, a modeling strategy using existing Grizzly software is proposed for a more thorough analysis where appropriate. Additionally, it presents mitigation strategies where applicable. The report covers physical degradation mechanisms such as infiltration, erosion, and abrasion, as well as chemical degradation mechanisms including fluorination, intercalation, corrosion, and oxidation. Molten salt can infiltrate the porous structure of graphite, leading to several detrimental effects. Entrapment of fissile products within the graphite pores can cause radiation damage and could pose challenges in the handling and disposal of contaminated components. The differential thermal expansion between the infiltrated salt and graphite, along with internal stress from pressurized molten salt and volumetric heating, can compromise the structural integrity of graphite. To mitigate these effects, employing ultra-fine graphite grades and applying sealants and coatings are effective strategies. A computational model based on coupled solid mechanics and heat transfer phenomena could be used to predict the internal stresses using Grizzly software. In pebble-bed MSRs, graphite fuel pebbles can cause abrasion against reactor components due to friction and wear. The severity of wear is influenced by various factors such as temperature, environment, and the presence of lubricants. Tribological studies reveal that higher temperatures and molten salt environments, such as FLiBe, significantly reduce wear rates compared to dry conditions. Additionally, the chemical composition of the salt can further optimize graphite's tribological performance. Long-term wear effects can be modeled by incorporating surface defects into the geometry and predict stresses under thermal and radiation effects using Grizzly software. Chemical degradation of graphite in a molten salt environment can occur through fluorination and intercalation. Fluorination can occur via replacement of hydrogen or oxygen atoms, or at the active sites, but does not cause structural degradation. Intercalation, on the other hand, can lead to exfoliation, where layers of graphite separate and peel away, damaging the graphite. Protective coatings can enhance graphite's resistance to intercalation. Graphite generally exhibits good chemical stability in molten salt environments, though it can corrode under specific conditions, particularly in the presence of impurities or oxidants. Studies have shown that protective coatings, such as plasma-sprayed partially stabilized zirconia (PSZ), can effectively prevent such degradation. Corrosion behavior varies significantly with different graphite grades and coating applications, underscoring the need for detailed studies on uncoated and coated graphite to understand and mitigate corrosion mechanisms in MSRs. Research indicates that the presence of oxidants and impurities can accelerate graphite degradation in molten salts, making it essential to explore acceptable impurity limits. Oxidation is another critical degradation mechanism, leading to weight loss and structural damage due to the formation of CO and CO 2 from the reaction of carbon atoms with oxygen. This process creates new porosity and compromises graphite's integrity. While extensive research on graphite oxidation has been conducted for gas-cooled reactors, studies specific to MSRs are limited. Findings from the coal industry suggest that molten alkali metal salts can significantly accelerate graphite oxidation, a hypothesis worth exploring for fluoride salts in MSRs. Understanding oxidation behavior in MSRs is vital for developing protective measures. The analysis of post-irradiated graphite from the MSRE experiment demonstrated exceptional chemical compatibility with molten fluoride salt, suggesting that the extent of chemical attack on graphite largely depends on the salt's infiltration capability. Therefore, the use of ultra-fine grade graphite could help mitigate chemical degradation effects. Existing oxidation modeling capabilities in Grizzly, which use reaction-diffusion equations to model graphite-air interactions, could be adapted to simulate the chemical degradation effects of graphite in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Developing the Science Basis for Understanding Polymer Encapsulant Degradation Mechanisms: DuraMAT 2.0 Final Project Report

Polymeric encapsulants are essential materials in photovoltaic modules, protecting sensitive electronics from the environment while providing mechanical integrity to the multilayered assembly. However, these polymeric materials are susceptible to degradation processes driven by the ingress of environmental species, ultraviolet radiation, thermal stresses, and mechanical loading. In this study, we employ a combined atomistic simulation and accelerated aging experimental approach to study the molecular-scale mechanisms of encapsulant degradation. Classical molecular dynamics simulations quantify the diffusion of environmental and degradation species through the polymer matrix, producing composition-specific diffusion coefficients. Reactive simulations characterize activation energy barriers and reaction rate constants for key chemical pathways. In parallel, thermal-desorption analyses coupled with mass spectrometry monitor the emergence and concentration profiles of degradation products under controlled stressor conditions. By integrating simulation and experiment, we establish quantitative correlations between polymer composition, species diffusivity, and chemical reactivity. We anticipate that these relations and quantitative values could serve as high-fidelity inputs to reaction-diffusion models, enabling physics-informed lifetime predictions and guiding the design of more durable encapsulant materials for solar energy applications.

36 MATERIALS SCIENCE↗

Instability of steady-state mixed-state symmetry-protected topological order to strong-to-weak spontaneous symmetry breaking

Recent experimental progress in controlling open quantum systems enables the pursuit of mixed-state nonequilibrium quantum phases. We investigate whether open quantum systems hosting mixed-state symmetry-protected topological states as steady states retain this property under symmetric perturbations. Focusing on the decohered cluster state – a mixed-state symmetry-protected topological state protected by a combined strong and weak symmetry – we construct a parent Lindbladian that hosts it as a steady state. This Lindbladian can be mapped onto exactly solvable reaction-diffusion dynamics, even in the presence of certain perturbations, allowing us to solve the parent Lindbladian in detail and reveal previously-unknown steady states. Using both analytical and numerical methods, we find that typical symmetric perturbations cause strong-to-weak spontaneous symmetry breaking at arbitrarily small perturbations, destabilize the steady-state mixed-state symmetry-protected topological order. However, when perturbations introduce only weak symmetry defects, the steady-state mixed-state symmetry-protected topological order remains stable. Additionally, we construct a quantum channel which replicates the essential physics of the Lindbladian and can be efficiently simulated using only Clifford gates, Pauli measurements, and feedback.

Shah, Jeet [University of Maryland, College Park, ↗

Reaction Diffusion Modelling of 3D Pillar Electrodes in Single-Catalyst CO 2 Reduction Cascades

Effective electrochemical CO 2 reduction to liquid fuels requires that the local catalytic environment facilitates the desired reactivity, yet a microscopic understanding of this environment is difficult to achieve from experiment alone. In this work, a 3D reaction-diffusion model was developed to explore the effects of electrode surface area and local geometry on the performance of a heterogeneous catalyst that performs a two-step CO 2 reduction cascade reaction to CO and then CH 3 OH under aqueous conditions. Kinetic parameters for the model were inspired by experimental results using a cobalt phthalocyanine (CoPc) catalyst. Three-dimensional architectures composed of arrays of square pillars with varying dimensions and either smooth or periodically modulated surfaces were tested, revealing the extent to which geometry modulates the performance of the cascade reactions. Although structural variations modulate local concentration gradients, we find that electrochemically active surface area predominantly governs the overall cascade reaction. Moreover, the results suggest that supersaturation of CO, with concentrations up to ten-fold higher than the equilibrium solubility limit, might be critical for more efficient conversion to CH 3 OH. For any given geometry, the spatially averaged ratio of [CO] to [CO 2 ] is dictated by the electrochemically active surface area and determines the yield of CH 3 OH. For a fixed surface area, geometries that spatially confine the electrolyte yield moderate local [CO] to [CO 2 ] ratios within small volumes. In contrast, less confining geometries result in a broader distribution of local ratios spread over larger volumes, with both configurations yielding the same spatially averaged [CO] to [CO 2 ] ratio. These insights provide valuable design principles—highlighting the critical importance of surface area and possibly CO supersaturation—for engineering advanced electrode architectures that leverage intermediate trapping and CO supersaturation to enhance overall performance in tandem CO 2 reduction systems.

COMSOL↗

BETO 2021 Peer Review - Biochemical Process Modeling and Simulation (BPMS)

The Biochemical Process Modeling and Simulation project aims to reduce the cost and time of research by applying theory, modeling, and simulation to the most relevant bottlenecks in the biochemical process. We use molecular modeling, quantum mechanics, metabolic modeling, fluid dynamics, and reaction-diffusion methods in close collaboration with pretreatment, hydrolysis, upgrading, and TEA. The project's outcomes are increased yields and efficiency of the biochemical process, added value to products, and reduced price of fuels by specifically targeting catalytic efficiency, reactor design, enzyme efficiency, and microbial design.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Biochemical Process Modeling and Simulation (BPMS)

The Biochemical Process Modeling and Simulation project aims to reduce the cost and time of research by applying theory, modeling, and simulation to the most relevant bottlenecks in the biochemical process. We use molecular modeling, quantum mechanics, metabolic modeling, fluid dynamics, and reaction-diffusion methods in close collaboration with pretreatment, hydrolysis, upgrading, and TEA. The project's outcomes are increased yields and efficiency of the biochemical process, added value to products, and reduced price of fuels by specifically targeting catalytic efficiency, reactor design, enzyme efficiency, and microbial design. We work closely with experimental projects to identify problems and iterate with experiments to find and refine solutions. By working with experimentalists, we decide on problems that can be solved with simulation that could otherwise not be solved or would take too long with experiment alone to reach BETO's targets. Over the years, we have produced solutions that have resulted in determining the most likely fatty-acid derivative for passive transport out of bacteria that upgrade biomass, and we have also designed enzyme mutations for enhanced lignin upgrading. Metabolic models have been developed to tune the activity of 2,3 butanediol production for the 2030 target. A computational method to deliver understanding of how complex omics data can be interpreted in the metabolic pathways of organisms used in the Agile Biofoundry. We have found methods to overcome specific barriers and continue to develop those methods. Our reactor studies have guided the design of both the microbes and reactors for aerobic and micro-aerobic production at all scales and have been instrumental in improving the accuracy of techno-economic analysis models. This project is essential in the process of selecting the final processes for 2030 SAF production targets. More specifically, recently, we have: 1) Predicted the strength of the basic structural interactions in commodity plastics to provide guidance for plastics upcycling strategies. 2) Developed computational tool to improve the characterization of lignin-derived compounds 3) Developed new methodologies to enable Machine Learning-based Directed Evolution for protein engineering. 4) Developed Machine Learning methods to predict protein promiscuity and mutations to further improve microbial and enzymatic driven processes and demonstrated the utility of ML approaches to engineering proteins from sparse experimental datasets. 5) Developed new methods to enable high-fidelity simulation of aerobic fermentation at industrial scale and resolving mismatch of time scales through subcycling/operator splitting 7) Identified the difficulty in preventing local high-oxygen conditions in industrial bubble columns, which leads to less-desirable acetoin production, suggesting future research directions in alternative reactor configurations (e.g loop reactors, shallow-channel reactors).

BIOMASS FUELS↗

Morphogenic Growth 3D Printing

Inspired by nature's morphogenesis, a new 3D printing process –growth printing (GP)– takes advantage of a self‐propagating curing front to produce 3D polymeric parts following a growth‐like development plan. The propagation of the curing front is driven by the exothermic polymerization of dicyclopentadiene (DCPD), which transforms the liquid resin into a stiff polymer as it propagates at 1 mm s −1 . GP is triggered when a heated initiator contacts the uncured liquid resin in an open container. The initiator nucleates the frontal polymerization reaction and the isotropic radial propagation of the growth front. Simultaneously, the initiator is moved up across the free surface of the resin, pulling the cured object out of the uncured resin. The motion trajectory of the initiator with respect to the free resin surface controls the growth morphology of the 3D part. An inverse design algorithm is developed to produce 3D parts by modeling the reaction‐diffusion‐driven solidification process. This process has substantial energy savings and high printing speeds.

3D printing↗

Virtual Volumetric Additive Manufacturing (VirtualVAM)

Abstract Tomographic volumetric additive manufacturing (VAM) produces arbitrary 3D geometries by exposure of a rotating volume of photopolymer resin to tomographically‐patterned illumination. This enables high speed, layer‐less printing of parts from a wide range of photopolymers not amenable to layer‐by‐layer processes. Since the entire geometry is produced at once over the course of a few seconds to minutes, molecular diffusion length scales become significant to the printing process. Understanding these molecular reaction and diffusion processes is imperative for advancing VAM to a usable technology. These processes are experimentally very difficult to monitor and measure. Herein, VirtualVAM ‐ a simulation framework for modeling the tomographic VAM process, is developed and experimentally validated. VirtualVAM simulates reaction, diffusion, and heat generation processes over the course of a print with single‐voxel resolution. From a few experimentally‐determined input parameters and a set of images for projection, VirtualVAM is able to generate a large spatio‐temporal data set for any given tomographic VAM print. Using VirtualVAM, a number of experimentally‐unattainable aspects of the VAM process are investigated such as single‐voxel conversion profiles, effect of molecular oxygen, and stopping time determination. VirtualVAM also enables the optimization of exposure patterns to further improve contrast between in‐part and out‐of‐part delivered dose.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reaction–Diffusion Coupling Facilitates the Sequential Precipitation of Metal Ions from Battery Feedstock Solutions

Here, the development of new technologies for chemical separations is urgently needed to meet the surging demand for critical materials that has strained resources and caused environmental challenges. Inspired by the classic Liesegang experiment, we demonstrated the separation of critical metal ions based on the coupling of ion diffusion and precipitation kinetics. For this purpose, a model feedstock solution simulating dissolved battery electrodes was placed on top of a hydrogel loaded with a precipitating agent, namely sodium hydroxide. As the lithium, manganese, cobalt, and nickel ions diffused into the gel, a gradient of precipitates formed along the length of the reactor. Elemental analysis of the spatially distributed precipitates showed the enrichment of nickel near the gel-solution interface, followed by the formation of an almost pure (>96%) manganese product further along the reactor. Optimization experiments revealed that a sodium hydroxide concentration of 10 mM and a gel/solution volume ratio of 2:1 favored efficient separations. The robustness of the method was demonstrated in four out of five feedstock compositions of typically used battery cathodes. Our proof-of-concept experiments present a paradigm for critical materials separations that does not require specialty chemicals, binding agents, membranes, or toxic solvents.

25 ENERGY STORAGE↗

Reversible Reactions, Mesh Size, and Segmental Dynamics Control Penetrant Diffusion in Ethylene Vitrimers

The diffusion of two aromatic dyes with nearly identical sizes was measured in ethylene vitrimers with precise linker lengths and borate ester cross-links using fluorescence recovery after photobleaching (FRAP). One dye possessed a reactive hydroxyl group, while the second was inert. The reaction of the hydroxyl group with the network is slow relative to the hopping times of the dye, resulting in a large slowdown by a factor of 50 for a reactive probe molecule. A kinetic model was fit to the fluorescence intensity data to determine rate constants for the reversible reaction of the dye from the network, which confirms the role of slow reaction kinetics. A second network cross-linker was also investigated with a substituted boronic ester showing ∼10,000 times faster exchange kinetics. In this system, the two dyes show the same diffusion coefficient, as the reaction is no longer the rate-limiting step. The role of dense meshes on small and large dyes is also discussed in the context of the existing theories. Finally, these results highlight the potential of dynamic networks to control penetrant transport through synergistic effects of the mesh size, dynamic bond kinetics, and penetrant–network interactions.

confinement↗

The scaling of kinetic and transport behaviors in the solution-phase chemistry of a plasma–liquid interface

The reactions at a plasma–liquid interface often involve species such as the solvated electron or the hydroxyl radical, which initiate the reduction or oxidation of solution-phase reactants (so-called scavengers) or are consumed by their own second-order recombination. Here, the mathematical scaling of the reaction–diffusion equations at the interface is used to obtain a characteristic time that can be used to determine the transition from highly efficient scavenger reduction or oxidation to lower efficiencies due to transport limitations. The characteristic time (tc) is validated using numerical solutions of the reaction–diffusion equations. When the scavenger kinetics are faster than second-order recombination, this characteristic transition time scales proportionally with the scavenger diffusivity (Ds) and the square of the scavenger bulk concentration (SB) and inversely proportional to the electron flux (J) squared; that is, t c = D s S B 2 F 2 /J 2 , where F is Faraday’s constant. However, when the scavenger kinetics are comparable or slower than second-order recombination, this scaling does not hold. Extending this analysis to three-dimensional systems shows that the profile of the electron flux on the surface affects the spatial location where reactions are most effective. Finally, the assessment of the implications of these behaviors for the reactor design highlights how effectively controlling the electron flux and solution transport may be necessary to improve the efficiency of scavenger reactions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Resonant amplification of enzymatic chemical oscillations by oscillating flow

Using theory and simulation, we analyzed the resonant amplification of chemical oscillations that occur due to externally imposed oscillatory fluid flows. The chemical reactions are promoted by two enzyme-coated patches located sequentially on the inner surface of a pipe that transports the enclosed chemical solution. In the case of diffusion-limited systems, the period of oscillations in chemical reaction networks is determined by the rate of the chemical transport, which is diffusive in nature and, therefore, can be effectively accelerated by the imposed fluid flows. In this work, we first identify the natural frequencies of the chemical oscillations in the unperturbed reaction–diffusion system and, then, use the frequencies as a forcing input to drive the system to resonance. We demonstrate that flow-induced resonance can be used to amplify the amplitude of the chemical oscillations and to synchronize their frequency to the external forcing. In particular, we show that even 10% perturbations in the flow velocities can double the amplitude of the resulting chemical oscillations. Particularly, effective control can be achieved for the two-step chemical reactions where during the first half-period, the fluid flow accelerates the chemical flux toward the second catalytic patch, while during the second half-period, the flow amplifies the flux to the first patch. The results can provide design rules for regulating the dynamics of coupled reaction–diffusion processes and can facilitate the development of chemical reaction networks that act as chemical clocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding copper diffusion in CuInSe 2 with first-principles based atomistic and continuum models

We investigate the diffusion of copper in CuInSe 2 using thermodynamic and kinetic models based on density functional theory calculations, attempting to reconcile large differences in reported experimental diffusivities. We find that observations of rapid chemical diffusion can be explained by large thermodynamic factors, which we calculate using a compositionally constrained model of intrinsic point defect formation. We further characterize how copper diffusion coefficients depend on material synthesis conditions and exhibit their variation across the CuInSe 2 secondary phase diagram. In doing so, we identify stable off-stoichiometries that are dominated by either vacancy- or interstitial-mediated diffusion mechanisms. These results are employed in the development of a continuum reaction–diffusion model, which we use to simulate experimental depth profiles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A model of spatio-temporal regulation within biomaterials using DNA reaction–diffusion waveguides

In multi-cellular organisms, cells and tissues coordinate biochemical signal propagation across length scales spanning micrometres to metres. Designing synthetic materials with similar capacities for coordinated signal propagation could allow these systems to adaptively regulate themselves across space and over time. Here, we combine ideas from cell signalling and electronic circuitry to propose a biochemical waveguide that transmits information in the form of a concentration of a DNA species on a directed path. The waveguide could be seamlessly integrated into a soft material because there is virtually no difference between the chemical or physical properties of the waveguide and the material it is embedded within. We propose the design of DNA strand displacement reactions to construct the system and, using reaction–diffusion models, identify kinetic and diffusive parameters that enable super-diffusive transport of DNA species via autocatalysis. Finally, to support experimental waveguide implementation, we propose a sink reaction and spatially inhomogeneous DNA concentrations that could mitigate the spurious amplification of an autocatalyst within the waveguide, allowing for controlled waveguide triggering. Chemical waveguides could facilitate the design of synthetic biomaterials with distributed sensing machinery integrated throughout their structure and enable coordinated self-regulating programmes triggered by changing environmental conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗