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A Multiscale Approach to Simulate Non‐Isothermal Multiphase Flow in Deformable Porous Materials

Coupled thermal, hydraulic, and mechanical processes in porous materials play important roles in several energy and environmental technologies. The Darcy-Brinkman-Biot (DBB) framework has proven effective in modeling multiphase fluid flow in deformable porous solids across both pore and Darcy scales, including in systems where fractures coexist with a porous matrix. In this study, we extend the DBB framework, originally designed for isothermal conditions, to address non-isothermal problems by incorporating an energy conservation equation. The resulting solver, hybridBiotThermalInterFoam, enables simulations of coupled multiphase fluid flow, heat transfer, and solid deformation in hybrid-scale systems containing both solid-free regions and ductile porous domains. The new solver is validated through comparisons with analytical solutions and, also, against established heat transfer solvers chtMultiRegionFoam and compressibleInterFoam. Further, a series of 2D and 3D case studies, including two-phase heat transfer in solid-free, static, or deformable porous media, highlights the solver's capacity to simulate complex flow dynamics and heat transport in systems involving high mobility ratios, viscous fingering, and fracture propagation. Our results establish the feasibility of incorporating thermal effects in simulations of a wide variety of energy geotechnics and environmental applications, including enhanced hydrocarbon recovery, soil remediation, and enhanced geothermal energy systems.

04 OIL SHALES AND TAR SANDS↗

Thermal properties and Thermodynamic Equilibrium Modeling of Cementitious Waste Forms

INTRODUCTION Cementitious matrices are used in the US DOE complex and worldwide to solidify aqueous radioactive, hazardous, mixed salt solutions, and sludges to meet low-level radioactive waste (LLW) disposal requirements. Blended formulations are used for most waste form mix designs. Substitution of pozzolans for Class F fly ash has the potential to alter the processing properties and stabilization properties of the resulting waste forms because they add chemical and mineralogical complexity to the final material. The Savannah River Site saltstone waste form was selected as the test case material. CemGEMS software was chosen as the model for predicting hydrated cementitious phases assemblages and phase evolution. Isothermal calorimetry was used as the method for evaluating processing and properties of fresh, uncured waste forms. The test cases consisted of reference case saltstone, and five natural pozzolan substituted saltstone mixes.

Bustamante, Michael E. [Savannah River National La↗

Validation of Numerical Tools for Calculating Reactivity Feedback in Sodium Fast Reactors Using SEFOR Experimental Data

The Southwest Experimental Fast Oxide Reactor (SEFOR) was an experimental sodium-cooled fast breeder reactor operated from 1969 to 1972 with experiments designed to measure Doppler reactivity feedback in a wide temperature range from around 350 °F to temperatures approaching the melting point of mixed oxide fuel of around 5000 °F, providing valuable data for code validations. Co-supported by the Department of Energy (DOE) Fast Reactor Program (FRP) and the DOE Nuclear Energy Advanced Modeling and Simulation (NEAMS) program, the SEFOR benchmark project focused on using the experimental data to validate numerical tools that are used in industry and academia to design and license sodium-cooled fast reactors (SFRs). By the end of FY-25, substantial progress was achieved in the SEFOR benchmark study. A variety of numerical tools commonly used for modeling SFRs were applied to develop models for SEFOR core configurations I-D, I-E, I-I, and I-J. These included Monte Carlo codes such as MCNP, Serpent, and Shift; deterministic codes such as the legacy Argonne Reactor Computation (ARC) suite and the high-fidelity NEAMS code Griffin; and the system analysis code SAS4A/SASSYS-1 (SAS). Using these models, both SEFOR zero-power experiments and power-ascending tests were successfully simulated. Comparisons were performed against experimental measurements of core criticalities, reflector worth, kinetics parameters (Λ/βeff), isothermal reactivity feedback (from 350 °F to 760 °F at zero power), and power-ascending reactivity feedback (as power increased from 0.4 MW to 17 MW). In general, these comparisons demonstrated very good agreement between numerical results and experimental data. In Fiscal Year 26 (FY-26), the SEFOR benchmark project will continue to address the modeling issues identified in FY-25. Effort will focus on the simulation of reactivity insertion transients in SEFOR core II using the ARC/SAS model. Future work will also focus on incorporating BISON into the SEFOR core modeling process to enable the first Multiphysics simulations of the isothermal tests based on the MOOSE framework.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Development of a Cure Model for Unsaturated Polyester Resin Systems Based on Processing Conditions

Unsaturated polyester resin (UPR) systems are extensively used in composite materials for applications in the transportation, marine, and infrastructure sectors. There are continually evolving formulations of UPRs that need to be evaluated and optimized for processing. Differential Scanning Calorimetry (DSC) provides valuable insight into the non-isothermal and isothermal behavior of UPRs within a prescribed temperature range. In the present work, non-isothermal DSC tests were carried out between temperatures of 0.0 °C and 250 °C, through different heating and cooling ramp rates. The isothermal DSC tests were carried out between 0.0 and 170 °C. The instantaneous rate of cure of the tested temperatures were measured. The application of an autocatalytic model in a calculator was used to simulate curing behaviors under different processing conditions. As the temperature increased from 10 °C up to 170 °C, the rate of cure reduced, and the heat of reaction increased. The simulated cure behavior from the DSC data showed that the degree of cure (α) maximum value of 71.25% was achieved at the highest heating temperature of 85 °C. For the low heating temperature, i.e., 5 °C, the maximum degree of cure (α) did not exceed 12% because there was not enough heat to activate the catalyst to crosslink further.

Polymer Science↗

Use of a Lignin-Based Admixture for Tailoring the Rheological Properties of Mortars for 3D Printing: Preprint

Efforts toward decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a more reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of polycarboxylate ether admixtures with a smaller carbon footprint. The present study examines the use of lignin-based water-reducing admixture in cement pastes and mortar mixtures for 3D printing. The experimental program explores the use of different dosages of lignin-based admixture to produce 3D-printed samples with appropriate extrudability and buildability. The rheological characterization was performed to determine the flow curve of various mixtures. Finally, the heat of hydration of cement pastes was monitored via isothermal calorimetry to assess the impact of lignin-based admixtures on the hydration process of cement. The results of this study indicate that the use of biomass by-products, such as lignin-based admixtures have great potential to effectively control the fresh-state properties of cement-based materials.

bio-based admixtures↗

Modeling ethanol/water adsorption in all-silica zeolites using the real adsorbed solution theory

A comprehensive set of single-component and binary isotherms were collected for ethanol/water adsorption into the siliceous forms of 185 known zeolites using grand-canonical Monte Carlo simulations. Using these data, a systematic analysis of ideal/real adsorbed-solution theory (IAST/RAST) was conducted and activity coefficients were derived for ethanol/water mixtures adsorbed in different zeolites based on RAST. It was found that activity coefficients of ethanol are close to unity while activity coefficients of water are larger in most zeolites, indicating a positive excess free energy of the mixture. This observation can be attributed to water/ethanol interactions being less favorable than water/water interactions in the single-component adsorption of water at comparable loadings. The deviation from ideal behavior can be highly structure-dependent but no clear correlation with pore diameters was identified. Furthermore, our analysis also demonstrates the following: (1) accurate unary isotherms in the low-loading regime are critical for obtaining physically sensible activity coefficients; (2) the global regression scheme to solve for activity model parameters performs better than fitting activity models to activity coefficients calculated locally at each binary state point; and (3) including the dependence on adsorption potential offers only a minor benefit for describing binary adsorption at the lowest fugacities. Finally, the Margules activity model was found incapable of capturing the non-ideal adsorption behavior over the entire range of fugacities and compositions in all zeolites, but for conditions typical of solution-phase adsorption, RAST predictions using zeolite-specific or even bulk Margules parameters provide an improved description compared to IAST.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical-Free Lithium Separation from High-Salinity Brines Using Model-Informed and Machine Learning-Optimized Multi-Column Zwitterionic Chromatography

Direct Lithium Extraction (DLE) technologies often struggle to produce high-purity lithium salts from high-salinity brines, as current approaches require chemical-based elution, regeneration, and precipitation steps, resulting in significant environmental footprints. A novel salt fractionation approach using carboxybetaine resin, known as zwitterionic chromatography (ZIC), has demonstrated that lithium ions can be separated from divalent cations under high-salinity conditions using only water as eluent, with no regeneration required. To enable continuous and scalable deployment of this approach, we developed a chemical-free Multi-column Zwitterionic Chromatography (MZC) process and its theoretical and process models. To predict and optimize this nontraditional separation system, we introduced a novel anti-Langmuir isotherm, and the isotherm parameters were estimated through a machine learning-driven optimization based on artificial neural network ensembles with numerical feasibility assessment. Using machine learning-driven optimization, the MZC process achieved 98.0% lithium recovery, 99.5 % Li/(Li + Mg + Ca) purity, a 31.3% productivity increase, and a 33% reduction in water use compared to batch operation. The proposed MZC process enables lithium separation at $0.6-1.2 kg-1 Li, with costs dominated by resin manufacturing, while offering lower separation costs and carbon footprint compared with conventional carbonation. Overall, these findings position the MZC process as an effective polishing step within scalable and sustainable lithium production pipelines.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 Sorption in Moisture Swing Anion Exchange Resins for Direct Air Capture: Experimental Isotherm Determination and Modeling

Moisture swing (MS) sorption is a promising direct air capture (DAC) technology to achieve negative CO 2 emissions and counter global warming. Here, in this study, MS CO 2 sorption in a model MS sorbent, IRA900, was investigated. IRA900 is a macroporous commercial strong-base anion exchange resin (AER) with quaternary ammonium functional groups. A rigorous CO 2 desorption process was developed to desorb all CO 2 from the sample and obtain CO 2 sorption isotherms as a function of relative humidity, CO 2 partial pressure, and temperature. CO 2 sorption increased with decreasing relative humidity, decreasing temperature, and increasing CO 2 partial pressure. Remarkably, the total CO 2 uptake from the sorption isotherms matched the ion exchange capacity (IEC) of the material, suggesting a stoichiometry of one CO 2 molecule reacting per active site. An isotherm model for CO 2 sorption starting with empty sorption sites (i.e., with the AER in the OH – form) described the experimental data well, supporting the hypothesis that the bicarbonate-loaded AER fully unloaded to the OH – state following rigorous CO 2 desorption. CO 2 sorption kinetics were studied, and carbon diffusion coefficients were estimated as a function of %RH and CO 2 partial pressure. Overall, this study provides a roadmap for the systematic evaluation of MS CO 2 DAC materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The Role of Water Volume Fraction on Water Adsorption in Anion Exchange Membranes

Water absorption plays a key role in the performance of polymeric anion exchange membranes. It influences important properties such as ionic conductivity and mechanical strength and alters their performance as solid electrolytes in hydrogen electrochemical devices for energy conversion. However, computational approaches that address the relationship between the polymer design and the absorption process are scarce. In this work, we introduce a simple thermodynamic model to predict the water absorption isotherms of polyelectrolyte membranes in contact with a water vapor reservoir that incorporates the specific chemical design of the polymers. The model accurately predicts the water content and macrostructural properties of polynorbornene membranes as a function of the water activity and successfully captures the effect of various polymer design parameters. The energy of pairwise attractive interactions predicted by our model provides a means to interpret the absorption process at the molecular level. The model also reveals the most significant favorable and unfavorable contributions to the free energy and indicates that their balance is solely governed by the water volume fraction, regardless of the polymer design. This universal behavior leads to important implications in the search for better ion exchange membranes.

Zaldivar, Gervasio [New York University, Brooklyn,↗

Thermal management challenges in lithium-ion batteries: understanding heat generation mechanisms

This paper investigates heat generation in commercial 18 650 lithium-ion battery cells and the thermal management challenges from their high energy density and electrochemical processes. Thermal effects can degrade performance, accelerate aging, and increase thermal runaway risk. Using isothermal calorimetry and EIS, the study emphasizes optimizing thermal behavior to improve battery efficiency, safety, and durability.

25 ENERGY STORAGE↗

Dehydroxylation kinetics of kaolinite and montmorillonite examined using isoconversional methods

The use of calcined clays as supplementary cementitious materials (SCMs) in concrete is a promising strategy towards decarbonizing the cement and concrete industry. This is especially relevant considering the ever-increasing demand for concrete. Comprehensive understanding of the kinetics of calcination is essential towards maximizing the potential reactivity of clay minerals while ensuring energy efficiency. In this study, the kinetics of the dehydroxylation of kaolinite and montmorillonite are investigated under non-isothermal conditions at constant heating rate. Activation energies ( E a ) are determined via Friedman differential and advanced Vyazovkin incremental methods over the isoconversional range; these are devoid of computational approximations, thus allowing kinetic analysis without assuming a specific reaction model. Kinetic equations—in the differential form as well as a combination of differential and integral forms are compared against the experimentally determined reaction models to identify the most probable dehydroxylation mechanism for kaolinite and montmorillonite. A reaction order mechanism is established for dehydroxylation of kaolinite, while montmorillonite is noted to undergo dehydroxylation via a single-step reversible diffusion-controlled process. Kinetic triplet—comprising activation energy, reaction model and pre-exponential factor—is used to predict isothermal calcination conditions, which is further verified using analytical techniques. Heat release rates of clay-portlandite blends from isothermal calorimetry are used within a thermodynamic framework to quantify reactivity of the calcined clays. Here, the study demonstrates a general approach based on isoconversional methods to predict calcination conditions for different clays that can be used in efficient and optimized production of blended cements or SCMs.

36 MATERIALS SCIENCE↗

Effect of Sample Mass, Confinement, and Preheating Time on the Thermal Response of LLM‐105: Experiments and Kinetic Analysis

Various small-scale experiments were performed to provide data for developing a model to predict the thermal response of LLM-105 over a wide range of conditions. The thermal decomposition of LLM-105 was studied as a function of sample mass, confinement of volatile products, and preheating time in both isothermal and ramped heating experiments. The thermal decomposition of LLM-105 is a two-step process, as shown by the two exothermic peaks in the heat flow profiles, which were fitted to two nth-order autocatalytic reaction models with a similar activation energy of ∼289 kJ/mol. The magnitude and shape of these peaks varied with sample mass and confinement. Increasing sample mass enhanced the second exotherm with respect to the first one, while increasing the level of confinement promoted a transition from a sublimation-dominated regime towards thermal decomposition. The effect of LLM-105 particle size on the rate of weight loss was evident for open-pan experiments, where bigger particles sublimed at lower temperatures than smaller particles. Thermal response and solid residue composition of LLM-105 samples were analyzed following preheating for different durations. Longer preheating times caused a shift of the second exotherm to lower temperatures and a decrease in the reaction enthalpy, confirming that LLM-105 decay is a consecutive reaction mechanism, probably autocatalytic. In conclusion, the kinetic model derived from ramped experiments was validated against the measured LLM-105 fraction remaining and the enthalpy remaining of the solid residue as a function of preheating times and showed good agreement.

Chemistry - Chemical explosives↗

Role of Metal–Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation

Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Brønsted acidity, and high availability of active sites poise them as potent catalysts for oxidation reactions. Here, metal–organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, K a ) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, the) on POM encapsulation thermodynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid Piston with Spray Cooling Near-Isothermal Compressor

The goal of this project was to prototype and characterize the performance of a liquid-piston spray-cooled gas compressor. The working principle of the compressor enables optimized high-efficiency operation over a very wide range of operating conditions, unlike conventional compressors that are optimized for a narrow range of operating conditions. The compressor technology is suitable for many applications, such as gas pipeline transport, gas storage, and commercial and residential heat pumps. Both physical testing and computational fluid dynamics (CFD) modeling of the processes using the Oak Ridge National Laboratory high-performance computing center were completed. The experimental and CFD studies focused on a near-isothermal liquid-piston compressor (LPC) that uses propylene glycol to compress CO 2 . The first prototype demonstrated isothermal operation during several sequentially executed cycles of CO 2 compression and raised the temperature of the compressed CO 2 by only 2 K, compared with approximately 6 K when the gas was compressed non-isothermally. Isothermal operation was demonstrated at CO 2 flow rates of up to 2 L/min. The second prototype was designed with two compression chambers to allow continuous flow of high-pressure CO 2 . However, the design of the valve train to direct flow between the compression chambers was not sufficient to allow demonstration of CO 2 compression. Numerical simulations of the LPC in which the compression chamber was filled with propylene glycol injected from the bottom inlet were performed using large eddy simulation (LES) with the wall-adapting local eddy-viscosity subgrid-scale model coupled with the multiphase volume of fluid (VOF) model to simulate the transient interface between gas and liquid and to capture the heat and mass transfers within the compression chamber. In this effort, the effects of boundary conditions applied to the LES-VOF calculations (i.e., no wall, an adiabatic wall, and a wall with a heat flux subscribed) on the overall pressure and temperature of the CO 2 gas as well as the transient evolution of flow and heat transfer within the compression chamber were investigated and are discussed in this report. The LES calculation with no wall showed no dynamical flow patterns, and the volume-averaged temperature of CO 2 increased from 305 to 392.7 K, whereas LES calculations with a constant wall temperature or a wall heat flux had similar increases of CO 2 temperatures. The results of the LES simulation using a wall heat flux showed different stages in the compression process and revealed dynamical formation and interaction of CO 2 gas layers and circulation flow patterns within the chamber that contributed to the overall heat transfer between the solid wall, gas, and liquid surface in the compressor. Though an industrial partnership for commercializing the compressor was not secured, the technology was attractive for an industrial partner to use in two research proposals in response to US Department of Energy funding opportunity announcements.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

A quantitative comparison between velocity dependent SIDM cross-sections constrained by the gravothermal and isothermal models

One necessary step for probing the nature of self-interacting dark matter (SIDM) particles with astrophysical observations is to pin down any possible velocity dependence in the SIDM cross-section. Major challenges for achieving this goal include eliminating, or mitigating, the impact of the baryonic components and tidal effects within the dark matter halos of interest – the effects of these processes can be highly degenerate with those of dark matter self-interactions at small scales. In this work, we select 9 isolated galaxies and brightest cluster galaxies (BCGs) with baryonic components small enough such that the baryonic gravitational potentials do not significantly influence the halo gravothermal evolution processes. We then constrain the parameters of Rutherford and Møller scattering cross-section models with the measured rotation curves and stellar kinematics through the gravothermal fluid formalism and isothermal method. Cross-sections constrained by the two methods are consistent at $1\sigma$ confidence level, but the isothermal method prefers cross-sections greater than the gravothermal approach constraints by a factor of ~ 3.

79 ASTRONOMY AND ASTROPHYSICS↗

Pyrolysis of high-density polyethylene: Degradation behaviors, kinetics, and product characteristics

Pyrolysis is a promising technology for converting plastic waste into valuable raw materials while offering a potential solution to the global plastic pollution crisis. In this study, the thermal pyrolysis of high-density polyethylene (HDPE) is investigated in a drop tube reactor under nearly isothermal conditions. The impact of reaction temperature and gas/volatile residence time on carbon conversion and product distribution is examined across a range of 500–900°C and 3.6–32.2s, respectively. Non-condensable gas products detected by online mass spectrometry are H 2 , CH 4 , C 2 H 4 , C 2 H 6 , C 3 H 6 , and C 3 H 8 . At elevated temperatures and prolonged residence time, H 2 yield reaches as high as 8.6 wt% of the initial HDPE mass due to intensified cracking reactions of C 2 –C 3 hydrocarbons and long-chain aliphatic compounds. Consequently, pyrolysis tars consist mainly of polycyclic aromatic hydrocarbons (PAHs) with 5–7 rings, accompanied by visible coke deposition within the reactor. HDPE decomposition to volatiles is an endothermic process and it is complete at a temperature between 492°C and 525°C, depending on the heating rate employed, from non-isothermal thermogravimetric analysis and differential scanning calorimetry (TGA-DSC) measurements. The thermal degradation of HDPE pellets follows the two-dimensional nucleation growth model for conversion levels up to 0.8 with an apparent activation energy of 259–270 kJ/mol and a pre-exponential factor of 4.83 × 10 17 –1.37 × 10 19 min -1 , determined from various isoconversional methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, along with Criado's master plots. Further, these findings provide valuable insights into optimizing process parameters and refining reactor design for pyrolysis, which can be integrated with gasification and reforming processes to enhance hydrogen production on a larger scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Imaging of dynamic processes in materials with a laser-wakefield accelerator

Betatron x rays generated from laser-wakefield accelerators are a promising source for imaging dynamic processes in materials. Here, we present proof-of-concept imaging of microstructural evolution in a hypermonotectic Al-Bi alloy, which consists of liquid Bi particles in a solid Al matrix. The images capture the elongation and fragmentation of Bi particles upon isothermal annealing. Because of the femtosecond time scale of the betatron source, the images are not subject to motion blur, whereas the accessibility of the source allows for studies of long-term processes such as annealing. The high-resolution data reveal that the evolution of Bi particles is mediated by an interplay of grain-boundary wetting and morphological instability, in stark contrast to an earlier proposal for (inverse) coarsening.

Alloys↗

Discerning the effect of various irradiation modes on the corrosion of Zircaloy-4

Using proton irradiation, this study investigates the individual influence of several factors on the corrosion kinetics of Zircaloy-4 in a hydrogenated water environment simulating a Pressurized Water Reactor (PWR). Using both simultaneous irradiation-corrosion and autoclave corrosion, we separately examine: (i) the effect of pre-irradiation on modifying the structure of the material, (ii) the impact of irradiation on creating defects in the growing oxide layer during corrosion, and (iii) the influence of irradiation on increasing the corrosion potential through radiolysis during corrosion. To replicate neutron-irradiated microstructure, two proton pre-irradiation schedules were employed: Schedule 1 (isothermal irradiation at 350 °C to 5 dpa) to simulate high-temperature PWR conditions, and Schedule 2 (two-step process: irradiation to 2.5 dpa at -10 °C followed by 2.5 dpa at 350 °C) to simulate lower temperature PWR and Boiling Water Reactor (BWR) conditions. Long-term autoclave corrosion testing over 360 days at 320 °C revealed no significant difference between unirradiated samples and those pre-irradiated according to either schedule, with all samples exhibiting sub-cubic kinetics within the pre-transition regime. Irradiated samples underwent Simultaneous Irradiation Corrosion (SIC) tests, corroding in 320 °C water while being irradiated with protons. Corrosion was found to accelerate in all SIC-tested samples relative to autoclave conditions, with the greatest increase observed in non-pre-irradiated samples. Pre-irradiation with either schedule resulted in a slower corrosion rate compared to non-pre-irradiated regions under SIC conditions. The degree of radiolysis observed in the SIC tests surpassed typical PWR conditions, approaching levels found in BWRs. Radiolysis products were identified as the primary contributors to accelerated corrosion, corroborated by radiolysis bar tests. Furthermore, these findings underscore the intricate interactions between irradiation, corrosion, and water chemistry in determining Zircaloy-4 corrosion kinetics within nuclear reactor environments.

Pressurized Water Reactor↗