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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Design principles from multiscale simulations to predict nanostructure in self-assembling ionic liquids

Molecular dynamics simulations (up to the nanoscale) were performed on the 3-methyl-1-pentylimidazolium ionic liquid cation paired with three anions; chloride, nitrate, and thiocyanate as aqueous mixtures, using the effective fragment potential (EFP) method, a computationally inexpensive way of modeling intermolecular interactions. The simulations provided insight (preferred geometries, radial distribution functions and theoretical proton NMR resonances) into the interactions within the ionic domain and are validated against 1 H NMR spectroscopy and small- and wide-angle X-ray scattering experiments on 1-decyl-3-methylimidazolium. Ionic liquids containing thiocyanate typically resist gelation and form poorly ordered lamellar structures upon mixing with water. Conversely, chloride, a strongly coordinating anion, normally forms strong physical gels and produces well-ordered nanostructures adopting a variety of structural motifs over a very wide range of water compositions. Nitrate is intermediate in character, whereby upon dispersal in water it displays a range of viscosities and self-assembles into nanostructures with considerable variability in the fidelity of ordering and symmetry, as a function of water content in the binary mixtures. The observed changes in the macro and nanoscale characteristics were directly correlated to ionic domain structures and intermolecular interactions as theoretically predicted by the analysis of MD trajectories and calculated RDFs. Specifically, both chloride and nitrate are positioned in the plane of the cation. Anion to cation proximity is dependent on water content. Thiocyanate is more susceptible to water insertion into the second solvent shell. Experimental 1 H NMR chemical shifts monitor the site-specific competition dependence with water content in the binary mixtures. As a result, thiocyanate preferentially sits above and below the aromatic ring plane, a state disallowing interaction with the protons on the imidazolium ring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Elucidating Hydrogen Reaction-Induced Water Desorption from Oxide-Passivated Metal Surfaces for Plasma Applications

Elucidating the mechanisms responsible for sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for understanding pulsed power behavior. Ionization of desorbed impurities in the vacuum regions causes power or current loss; devising methods to limit such desorption during the short time scale of pulsed power is needed to improve corresponding applications. Previous molecular modeling studies have strongly suggested that, under high vacuum conditions, the amount of water impurity desorbing from oxide surfaces on metal electrodes is at a sub-monolayer level at room temperature, which appears insufficient to explain observed pulsed power energy losses at high current densities. In this work, we apply Density Functional Theory (DFT) techniques to show that hydrogen trapped inside iron metal can diffuse into hematite (α-Fe 2 O 3 ) on the metal surface, ultimately reacting with the oxide to form Fe(II) and H 2 O. The latter desorbs at elevated temperature and may explain the anomalous amount of desorbed impurity inferred from pulsed-power experiments. We also apply a suite of characterization techniques to demonstrate that when iron metal is heated to 650 °C, the dominant surface oxide component becomes α-Fe 2 O 3 . The oxide facets exposed are found to be a mixture of (0001), (10-10), and others, in agreement with the DFT models used.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Effects of spatiotemporal plasma power distribution on the modeling of ignition kernel evolution in quiescent and turbulent methane/air mixtures

Abstract The present work improves a phenomenological plasma-assisted combustion model by integrating the spatiotemporal distribution of plasma power density, thereby considering the evolution of plasma streamers in the modeling, and subsequently, better predicting the ignition kernel evolution. The improved phenomenological model is validated against experiments representing the plasma discharge and post-discharge ignition kernel evolution. Specifically, the new model demonstrates a more accurate prediction of ultrafast gas heating and O 2 dissociation during the plasma discharge, compared to the original model. In addition, the new model is found to closely match the experimental pressure wave and heated channel profiles post-discharge without the need for tuning the energy deposition (unlike the original model), highlighting its accuracy of post-discharge ignition kernel dynamics. The improved phenomenological model is then employed to investigate ignition kernel evolution for a stoichiometric methane-air discharge across various discharge gap configurations. Simulations reveal a non-uniform temperature and streamer distribution progressing from the electrode tips toward the center, contrasting uniform cylindrical discharges previously described in the original model. Streamer propagation is observed to be faster for larger gaps when maintained at the same average electric field for different discharge gaps. The tendency of smaller gaps to produce detached toroidal ignition kernels is observed, while larger gaps promote cylindrical and attached ignition kernels. Interactions between successive ignition kernels from consecutive discharges varied significantly, with the smallest gap (1 mm) promoting the quenching of the preceding ignition kernel due to the initial kernel–kernel separation. The intermediate gap (2 mm) promotes detached kernel growth. In contrast, in the largest gap (4 mm), kernels consistently combine and expand attached to electrodes. The impact of homogeneous isotropic turbulence is also explored, showing the persistence of ignition kernels early on but eventually quenching due to enhanced radical and heat losses with pronounced turbulence intensity.

Johnson, Praise Noah↗
DOE OSTI2021

Oxidation of an iso-paraffinic alcohol-to-jet fuel and n-heptane mixture: an experimental and modelling study

Oxidation of ATJ/n-heptane blends was studied over a wide range of test conditions, using single pulse shock tubes. Test conditions were designed to study the effect of pressure (4 and 50 bar), and fuel loading (~100-1400 ppm) on the oxidation of the blends across a wide range of temperatures (800-1300 K). These effects were observed by measuring concentrations of intermediate species formed using in-line Gas Chromatography (GC) and GCxGC TOF-MS. Results showed that increasing the initial fuel load does not have a significant impact on the results. However, increasing the pressure shifts the mixture reactivity to a lower temperature by about 150 K and causes the fuel to be oxidized instead of decomposing pyrolytically as at lower pressures. Additional experiments for pure ATJ and pure n-heptane were performed at conditions matching the ATJ/n-heptane 50 bar experiments to analyze the differences between the pure and mixed fuels. Speciation measurements were compared against predictions from a detailed kinetic model. The ability of the kinetic model to capture the effects of varying experimental test conditions on the evolution of intermediate species is discussed and kinetic analyses have been conducted to identify the important reaction pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

HIGH-FIDELITY SIMULATION OF SOOT FORMATION AND THERMAL RADIATION IN A LABORATORY-SCALE RICH-QUENCH-LEAN BURNER

High-fidelity simulations of a swirl-stabilized turbulent spray flame in a laboratory-scale aero-combustor have been performed to evaluate the predictability of state-of-the-art models in capturing soot formation. The simulations employ a complex chemical mechanism developed for Jet-A with PAH chemistry, coupled with the Hybrid Method of Moments (HMOM) soot model, and a Lagrangian dilute spray model for the fuel injection. Two simulations are performed to compare the results when thermal radiation is neglected or included in the solution with a mean spectral model. Modeling closures for the soot differential diffusion effects in mixture fraction space, as well as turbulence-radiation interaction are also evaluated using the data generated by the simulations. Given the degree of complexity of the simulation, the results showed good agreement with experimental measurements of the spatial distribution of the soot volume fraction ensemble average. A closer agreement with the experiment is observed when thermal radiation is included in the solution. Thermal radiation is observed to reduce the flame temperature and increase the flame intermittency, denoted by the increase in the temperature standard deviation in mixture fraction space. The reduction in temperature also leads to a reduction in PAH production and soot volume fraction. Turbulence is observed to have different effects on radiative emission depending on the mixture fraction. Turbulent scalar fluctuations significantly enhance radiative emission in fuel lean mixtures and can also play a role for fuel rich conditions. The statistical description of the turbulence-radiation interaction, previously proposed in the literature, was observed to correctly reproduce the high-fidelity results. Model coefficients were provided for swirl-stabilized flames. The soot differential diffusion model, previously proposed in the literature, based on the residual between the exact term and its model approximation, was also evaluated. The residual correction term further improved the agreement with exact differential diffusion term evaluated with the high-fidelity simulation data in mixture fraction space. The results suggest that the effective turbulent Lewis number can be equal to unity in simulations of turbulent non-premixed recirculating flames.

Soriano, Bruno [Sandia National Laboratories (SNL)↗
DOE OSTI2017

NiAl Oxidation Reaction Processes Studied In Situ Using MEMS-Based Closed-Cell Gas Reaction Transmission Electron Microscopy

The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Al 2 O 3 . After oxidation at 750 °C, nucleation of voids at the Ni/Al 2 O 3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO 2 due to the outward self-diffusion of Ni 2+ ions, followed by the formation of a mixture of metastable and stable α-Al 2 O 3 at the oxide/metal interface that is attributed to a PO 2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. Furthermore, the results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl 2 –KCl Mixtures

The development of technologies for nuclear reactors based on molten salts has seen a big resurgence. The success of thermodynamic models for these hinges in part on our ability to predict at the atomistic level the behavior of pure salts and their mixtures under a range of conditions. In this letter, we present high-energy X-ray scattering experiments and molecular dynamics simulations that describe the molten structure of mixtures of MgCl 2 and KCl. As one would expect, KCl is a prototypical salt in which structure is governed by simple charge alternation. In contrast, MgCl 2 and its mixtures with KCl display more complex correlations including intermediate-range order and the formation of Cl – -decorated Mg 2+ chains. A thorough computational analysis suggests that intermediate-range order beyond charge alternation may be traced to correlations between these chains. Here, an analysis of the coordination structure for Mg 2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.

36 MATERIALS SCIENCE↗
NASA NTRS1998

Fiber Supported Droplet Combustion-2 (FSDC-2)

Experimental results for the burning characteristics of fiber supported, liquid droplets in ambient Shuttle cabin air (21% oxygen, 1 bar pressure) were obtained from the Glove Box Facility aboard the STS-94/MSL-1 mission using the Fiber Supported Droplet Combustion - 2 (FSDC-2) apparatus. The combustion of individual droplets of methanol/water mixtures, ethanol, ethanol/water azeotrope, n-heptane, n-decane, and n-heptane/n-hexadecane mixtures were studied in quiescent air. The effects of low velocity, laminar gas phase forced convection on the combustion of individual droplets of n-heptane and n-decane were investigated and interactions of two droplet-arrays of n-heptane and n-decane droplets were also studied with and without gas phase convective flow. Initial diameters ranging from about 2mm to over 6mm were burned on 80-100 micron silicon fibers. In addition to phenomenological observations, quantitative data were obtained in the form of backlit images of the burning droplets, overall flame images, and radiometric combustion emission measurements as a function of the burning time in each experiment. In all, 124 of the 129 attempted experiments (or about twice the number of experiments originally planned for the STS-94/MSL-1 mission) were conducted successfully. The experimental results contribute new observations on the combustion properties of pure alkanes, binary alkane mixtures, and simple alcohols for droplet sizes not studied previously, including measurements on individual droplets and two-droplet arrays, inclusive of the effects of forced gas phase convection. New phenomena characterized experimentally for the first time include radiative extinction of droplet burning for alkanes and the "twin effect" which occurs as a result of interactions during the combustion of two-droplet arrays. Numerical modeling of isolated droplet combustion phenomenon has been conducted for methanol/water mixtures, n-heptane, and n-heptane/n-hexadecane mixtures, and results compare quantitatively with those found experimentally for methanol/water mixtures. Initial computational results qualitatively predict experimental results obtained for isolated n-heptane and n-heptane/n-hexadecane droplet combustion, although the effects of sooting are not yet included in the modeling work. Numerical modeling of ethanol and ethanol/water droplet burning is under development. Considerable data remain to be fully analyzed and will provide a large database for comparisons with further numerical and analytical modeling and development of future free droplet experiments aboard space platforms.

Colantonio, Renato↗
DOE OSTI2016

Hierarchical mixture of experts and diagnostic modeling approach to reduce hydrologic model structural uncertainty

In most water resources applications, a single model structure might be inadequate to capture the dynamic multi-scale interactions among different hydrological processes. Calibrating single models for dynamic catchments, where multiple dominant processes exist, can result in displacement of errors from structure to parameters, which in turn leads to over-correction and biased predictions. An alternative to a single model structure is to develop local expert structures that are effective in representing the dominant components of the hydrologic process and adaptively integrate them based on an indicator variable. In this study, the Hierarchical Mixture of Experts (HME) framework is applied to integrate expert model structures representing the different components of the hydrologic process. Various signature diagnostic analyses are used to assess the presence of multiple dominant processes and the adequacy of a single model, as well as to identify the structures of the expert models. The approaches are applied for two distinct catchments, the Guadalupe River (Texas) and the French Broad River (North Carolina) from the Model Parameter Estimation Experiment (MOPEX), using different structures of the HBV model. Furthermore, the results show that the HME approach has a better performance over the single model for the Guadalupe catchment, where multiple dominant processes are witnessed through diagnostic measures. Whereas, the diagnostics and aggregated performance measures prove that French Broad has a homogeneous catchment response, making the single model adequate to capture the response.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1998

Effects of Radiative Emission and Absorption on the Propagation and Extinction of Premixed Gas Flames

Premixed gas flames in mixtures of CH4, O2, N2, and CO2 were studied numerically using detailed chemical and radiative emission-absorption models to establish the conditions for which radiatively induced extinction limits may exist independent of the system dimensions. It was found that reabsorption of emitted radiation led to substantially higher burning velocities and wider extinction limits than calculations using optically thin radiation models, particularly when CO2, a strong absorber, is present in the unburned gas, Two heat loss mechanisms that lead to flammability limits even with reabsorption were identified. One is that for dry hydrocarbon-air mixtures, because of the differences in the absorption spectra of H2O and CO2, most of the radiation from product H2O that is emitted in the upstream direction cannot be absorbed by the reactants. The second is that the emission spectrum Of CO2 is broader at flame temperatures than ambient temperature: thus, some radiation emitted near the flame front cannot be absorbed by the reactants even when they are seeded with CO2 Via both mechanisms, some net upstream heat loss due to radiation will always occur, leading to extinction of sufficiently weak mixtures. Downstream loss has practically no influence. Comparison with experiment demonstrates the importance of reabsorption in CO2 diluted mixtures. It is concluded that fundamental flammability limits can exist due to radiative heat loss, but these limits are strongly dependent on the emission-absorption spectra of the reactant and product -gases and their temperature dependence and cannot be predicted using gray-gas or optically thin model parameters. Applications to practical flames at high pressure, in large combustion chambers, and with exhaust-gas or flue-gas recirculation are discussed.

Ju, Yiguang↗
NASA NTRS1993

Fourier transform infrared studies of the interaction of HCl with model polar stratospheric cloud films

Heterogeneous reactions involving hydrochloric acid adsorbed on the surfaces of polar stratospheric clouds (PSCs) are postulated to contribute to polar ozone loss. Using FTIR spectroscopy to probe the condensed phase, we have examined the interaction of HCl with ice and nitric acid trihydrate (NAT) films representative of types II and I PSCs, respectively. For HCl pressures in the range of 10 exp -7 to 10 exp -5 Torr, our FTIR studies show that a small amount of crystalline HCl-6H2O formed on or in ice at 155 K. However, for higher HCl pressures, we observed that the entire film of ice rapidly converted into an amorphous 4:1 H2O:HCl mixture. From HCl-uptake experiments with P(HCl) = 8 x 10 exp -7 Torr, we estimate roughly that the diffusion coefficient of HCl in ice is around 2 x 10 exp -12 sq cm/s at 158 K. For higher temperatures more closely approximating those found in the stratosphere, we were unable to detect bulk HCl uptake by ice. Indirect evidence suggests that HCl adsorption onto the surface of model PSC films inhibited the evaporation of both ice and NAT by 3-5 K.

Koehler, Birgit G.↗
DOE OSTI2014

How does a thermal binary crystal break under shear?

When exposed to strong shearing, the particles in a crystal will rearrange and ultimately, the crystal will break by forming large nonaffine defects. Even for the initial stage of this process, only little effort has been devoted to the understanding of the breaking process on the scale of the individual particle size for thermalized mixed crystals. Here, we explore the shear-induced breaking for an equimolar two-dimensional binary model crystal with a high interaction asymmetry between the two different species such that the initial crystal has an intersecting square sublattice of the two constituents. Using Brownian dynamics computer simulations, we show that the combination of shear and thermal fluctuations leads to a characteristic hierarchical breaking scenario where initially, the more strongly coupled particles are thermally distorted, paving the way for the weakly coupled particles to escape from their cage. This in turn leads to mobile defects which may finally merge, proliferating a cascade of defects, which triggers the final breakage of the crystal. This scenario is in marked contrast to the breakage of one-component crystals close to melting. Moreover, we explore the orientational dependence of the initial shear direction relative to the crystal orientation and compare this to the usual melting scenario without shear. Our results are verifiable in real-space experiments of superparamagnetic colloidal mixtures at a pending air-water interface in an external magnetic field where the shear can be induced by an external laser field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

On the Bayesian calibration of computer model mixtures through experimental data, and the design of predictive models

For many real systems, several computer models may exist with different physics and predictive abilities. To achieve more accurate simulations/predictions, it is desirable for these models to be properly combined and calibrated. Here, we propose the Bayesian calibration of computer model mixture method which relies on the idea of representing the real system output as a mixture of the available computer model outputs with unknown input dependent weight functions. The method builds a fully Bayesian predictive model as an emulator for the real system output by combining, weighting, and calibrating the available models in the Bayesian framework. Moreover, it fits a mixture of calibrated computer models that can be used by the domain scientist as a mean to combine the available computer models, in a flexible and principled manner, and perform reliable simulations. It can address realistic cases where one model may be more accurate than the others at different input values because the mixture weights, indicating the contribution of each model, are functions of the input. Inference on the calibration parameters can consider multiple computer models associated with different physics. The method does not require knowledge of the fidelity order of the models. We provide a technique able to mitigate the computational overhead due to the consideration of multiple computer models that is suitable to the mixture model framework. We implement the proposed method in a real-world application involving the Weather Research and Forecasting large-scale climate model.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2015

Toxicological responses of environmental mixtures: Environmental metal mixtures display synergistic induction of metal-responsive and oxidative stress genes in placental cells

Exposure to elevated levels of the toxic metals inorganic arsenic (iAs) and cadmium (Cd) represents a major global health problem. These metals often occur as mixtures in the environment, creating the potential for interactive or synergistic biological effects different from those observed in single exposure conditions. In the present study, environmental mixtures collected from two waste sites in China and comparable mixtures prepared in the laboratory were tested for toxicogenomic response in placental JEG-3 cells. These cells serve as a model for evaluating cellular responses to exposures during pregnancy. One of the mixtures was predominated by iAs and one by Cd. Six gene biomarkers were measured in order to evaluate the effects from the metal mixtures using dose and time-course experiments including: heme oxygenase 1 (HO-1) and metallothionein isoforms (MT1A, MT1F and MT1G) previously shown to be preferentially induced by exposure to either iAs or Cd, and metal transporter genes aquaporin-9 (AQP9) and ATPase, Cu{sup 2+} transporting, beta polypeptide (ATP7B). There was a significant increase in the mRNA expression levels of ATP7B, HO-1, MT1A, MT1F, and MT1G in mixture-treated cells compared to the iAs or Cd only-treated cells. Notably, the genomic responses were observed at concentrations significantly lower than levels found at the environmental collection sites. These data demonstrate that metal mixtures increase the expression of gene biomarkers in placental JEG-3 cells in a synergistic manner. Taken together, the data suggest that toxic metals that co-occur may induce detrimental health effects that are currently underestimated when analyzed as single metals. - Highlights: • Toxicogenomic responses of environmental metal mixtures assessed • Induction of ATP7B, HO-1, MT1A, MT1F and MT1G by metal mixtures observed in placental cells • Higher gene induction in response to metal mixtures versus single metal treatments.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Experimental methods for laboratory measurements of helium spectral line broadening in white dwarf photospheres

White Dwarf (WD) stars are the most common stellar remnant in the universe. WDs usually have a hydrogen or helium atmosphere, and helium WD (called DB) spectra can be used to solve outstanding problems in stellar and galactic evolution. DB origins, which are still a mystery, must be known to solve these problems. DB masses are crucial for discriminating between different proposed DB evolutionary hypotheses. Current DB mass determination methods deliver conflicting results. The spectroscopic mass determination method relies on line broadening models that have not been validated at DB atmosphere conditions. We performed helium benchmark experiments using the White Dwarf Photosphere Experiment (WDPE) platform at Sandia National Laboratories' Z-machine that aims to study He line broadening at DB conditions. Using hydrogen/helium mixture plasmas allows investigating the importance of He Stark and van der Waals broadening simultaneously. Accurate experimental data reduction methods are essential to test these line-broadening theories. In this paper, we present data calibration methods for these benchmark He line shape experiments. We give a detailed account of data processing, spectral power calibrations, and instrument broadening measurements. Uncertainties for each data calibration step are also derived. We demonstrate that our experiments meet all benchmark experiment accuracy requirements: WDPE wavelength uncertainties are <1 Å, spectral powers can be determined to within 15%, densities are accurate at the 20% level, and instrumental broadening can be measured with 20% accuracy. Fulfilling these stringent requirements enables WDPE experimental data to provide physically meaningful conclusions about line broadening at DB conditions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

FORTÉ Machine Learning

Of the non-corrupted data collected by the Orbiting Experiment (forté) satellite’s Photo-Diode Detector during the year 2001, I estimate that 7.9% of 914 894 signals are noise. My result differs dramatically from Guillen’s estimate of 96%. To arrive at this estimate, I used Gaussian mixture model (GMM) clustering–unsupervised machine learning–to aggregate the wave forms into groups based on the absolute value of the lowest 25 positive frequency discrete Fourier transform coefficients. Then, I marked several of the groups as noise by inspecting a random sampling of wave forms from each group. Marking groups as either noise or non-noise is a supervised binary classification operation. After removing the signals in noise groups from further consideration, I clustered the remaining signals into families. Again, I used a GMM, but for the familial clustering I used a Non-Negative Matrix Factorization feature vector transform. The result was 9 distinct families of lightning signals, as well as a second stage of noise filtering. To efficiently represent the entirety of the signal space, I broke each family into deciles based on their distance from the family mean. In this case, distance means the log-likelihood based on the GMM. Signals in lower deciles are more similar in shape and amplitude to their family average. I took the top 200 samples from each decile of each group, resulting in 18 000 signals. These signal approximately represent the entirety of the forté observations. To represent outliers, I also kept a zoo of the 1000 signals furthest from any family’s average. All told, the resulting data set represents the forté data with a reduction of about 51:1. To allow synthesis of an arbitrarily large number of test signals, I also captured each family’s average signal and the time-sample covariance matrix over the signals in each family. Using these two pieces of information, I can synthesize new waveforms by using a Gaussian random realization from the family average and covariance matrix. I wrote a program to test the synthesis quality. The program shows me two signals on the screen, one synthesized and one randomly drawn from the data. I attempted to identify the synthesized signal. Although the synthesis is imperfect, in an A/B comparison I only correctly chose the synthesized signal 36% of the time.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Charge regulation effects on colloidal mixture nanoparticles

Changes in pH within a system containing dissociable sites affect the protonation and deprotonation of these groups, thereby influencing their physical properties. In response, the system modifies their surface charge, affecting electrostatic interactions, aggregation, stability, and structural behavior. Although the pH can be tuned in experiments, it is difficult to model this phenomenon using simulations or theoretical approaches. Here, we perform hybrid Monte Carlo-molecular dynamics simulations to model charge regulation effects in an equimolar colloidal charged system. We compare charge regulation effects with those of a system in which the charges of colloidal nanoparticles are not dissociable. The comparison between the two cases modifies the phase diagram, and it changes the volume fraction where a percolation network of nanoparticles is found. Charge regulation is found to destroy network formation, as the charge in the nanoparticles is modified because of the cooperativity dependency of the degree of charge dissociation sites among the nanoparticles favoring cluster formation. Furthermore, our work suggests that the ionic and/or electronic conductivity in functionalized nanoparticles can be modified by changing pH values. It also guides the experimental design of oppositely charged nanoparticles as inks for 3D printing processes.

Classical statistical mechanics↗
DOE OSTI2024

Investigation of Frozen Chemistry for Molten Salt Reactors (MSRs)

Understanding accident progression and the potential/conditions for fission product release from fuel is necessary to evaluate safety for any nuclear reactor system. Molten Salt Reactors (MSRs) under development need such analysis to support safety evaluations. Fission product chemistry specific to MSR concepts is a critical area that introduces distinct considerations relative to the current state-of-knowledge in reactor safety, primarily developed for water-moderated nuclear reactor systems. In Light Water Reactor (LWR) systems, it is necessary to capture the chemical interaction of fission products with the reactor evironment, containment and confinement systems. The overall effects at this point are relatively well understood for the purposes of performing safety evaluations. A key insight from LWR studies is that fission product chemical behavior can be reasonably captured by modeling approaches where the chemistry is "frozen". These modeling approaches assume that radionuclide reaction and speciation can be represented by chemical classes, each with characteristic transport behavior that is invariant under a broad range of thermochemical conditions. However, radionuclides can exhibit a range of behavior in the liquid salt-melt phase of the coolant used in MSRs. Radionuclides, salt, and the metal containment surfaces (i.e. pipes) can co-exist in dynamic equilibrium that could evolve with small system mass changes. A detailed investigation to the degree the equilibrium state can dynamically evolve with changes in the conditions of the molten salt mixture has not been previously conducted. It is currently not well understood where frozen chemistry assumptions are valid. Expanding the state-of-knowledge in this regard is relevant to better assessing the range of chemical effects that should be incorporated as part of MSR safety assessments. This investigation used the Oak Ridge Isotope GENeration (ORIGEN) module of the Standardized Computer-Analysis for Licensing Evaluation (SCALE) code to generate simulated radionuclide inventories for the MSR Experiment (MSRE) and then modeled reactor chemical speciation using the Molten Salt Thermodynamic Database – Thermochemical (MSTDB-TC) coupled with Thermochimica. The effect of composition variation during decay of fission product inventory in a molten salt over a period of 500 days prolonged post- at multiple temperatures was studied. Mass fractions for fluorine and berilium were varied in order to probe the effects of free fluorine control. Finally, speciation of fluoride reactors were showed by comparing MSRE readionuclide inventories with a FLiBe based molten salt breeder reactor (MSBR). The results showed that fission product mass change has little effect on phase mass changes and vapor pressures for fluoride species, but differ with varying carrier and fuel salt compositions. However, iodine species were found to have a vapor pressure not only dependent on temperature, but also the free fluorine potential, releasing iodine when the free fluorine potential is equal to the iodine inventory. This observation, however, arose under free fluorine potentials that are very unlikely to be realized in typical molten salt mixtures. Despite this observation, temperature was found to be the dominant parameter that drove phase change and fission product species vapor pressure. The results indicate that the current frozen chemistry approach is adequate for MSR analysis.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗