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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Rescuing complementarity with little drama

The AMPS paradox challenges black hole complementarity by apparently constructing a way for an observer to bring information from the outside of the black hole into its interior if there is no drama at its horizon, making manifest a violation of monogamy of entanglement. We propose a new resolution to the paradox: this violation cannot be explicitly checked by an infalling observer in the finite proper time they have to live after crossing the horizon. Our resolution depends on a weak relaxation of the no-drama condition (we call it “little-drama”) which is the “complementarity dual” of scrambling of information on the stretched horizon. When translated to the description of the black hole interior, this implies that the fine-grained quantum information of infalling matter is rapidly diffused across the entire interior while classical observables and coarse-grained geometry remain unaffected. Under the assumption that information has diffused throughout the interior, we consider the difficulty of the information-theoretic task that an observer must perform after crossing the event horizon of a Schwarzschild black hole in order to verify a violation of monogamy of entanglement. We find that the time required to complete a necessary subroutine of this task, namely the decoding of Bell pairs from the interior and the late radiation, takes longer than the maximum amount of time that an observer can spend inside the black hole before hitting the singularity. Furthermore, an infalling observer cannot observe monogamy violation before encountering the singularity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2019

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration - FY2018 Final Report

High-value R2R processing is used to support a wide range of products in applications which span many industrial business sectors. The overall R2R process technology can be considered as “mature” as the process methodology and has been in use for decades. This continuous processing technique traditionally involves deposition of material(s) onto moving webs or carriers or other continuous R2R, belt-fed, or conveyor-based processes that enable successive steps to build a final version which serves to support the deposited materials. Current process technologies, which typify “roll to roll”, include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes for energy storage, and barrier materials. Due to innovation in materials and process equipment, high-quality yet very low-cost multi-layer technologies can be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, a means must be available to enable manufacture of these products in a cost-competitive manner that is affordable by the general consumer. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches.Within the DOE EERE AMO, it was recognized that establishment of a program supported at the DOE National Laboratories, along with their immense design of materials and equipment modelling capabilities enabled with use of high-performance computing, could take advantage of available R2R infrastructure to manufacture new technologies. In FY 2016, a R2R Consortium was established and provided with initial “seed” funding to take an approach that was envisioned to be supportable by advanced manufacturing R2R processes. This collaborative approach was designed to foster identification and development of materials and processes related to R2R for clean-energy product development. Using computational and experimental capabilities by acknowledged subject matter experts within the supported National Laboratory system, this collaborative project would leverage the capabilities and expertise at each of four laboratories to further the development of an enabling high-volume cost-competitive platform technology. The collaboration team that is comprised of ORNL, ANL, NREL and LBNL, coordinating with EPB and other selected industry partners, was formed in April 2016 to initially address enhancing battery electrode performance and R2R manufacturing challenges. The research efforts were to predict and measure changes and results in electrode morphology and performance based on process condition changes; to evaluate mixed, active, particle size deposition and drying for novel electrode materials; to model various process condition changes and the resulting morphology and electrode performance; and to develop and validate NDE techniques for in-line measurement of battery electrode material properties. These efforts carried through FY 2017 and completed at the end of FY 2018.The approach was to look at compositions of materials with different particle sizes to make electrode samples using a R2R manufacturing process. The shape, size, and morphology of the materials, the chemistry of the formulation, the nature of slurries, their coating rate, the rate of drying all play a role in determining the final coating architecture, quality, and performance. A commercial cathode material was selected to make a series of cathodes and anodes by single pass, dual pass and slot die methods. Analysis of all the compiled results for this battery electrode development were that the best performing cathodes included: dual-pass electrode with large particles near the foil, mixed small and large particles, and small particles only. Whereas, the best performing anodes were with a mix of small and large graphite particles. An additional core project was added in FY 2017 to conduct studies of fuel cell materials that can be produced using R2R processes. The goal of this project is to explore, understand and optimize material and process parameters to support increased throughput, increased quality, and reduced cost for high volume production of gas-diffusion electrodes (GDEs) for PEMFCs. Project work in FY 2018 were to use a R2R process to fabricate electrodes without ionomer overlayer that can produce the equivalent mass activity as spray-coated electrodes with an ionomer overlayer. Oxygen-limiting current measurements were utilized to optimize oxygen mass transport. Alcohol-rich solvents were investigated, and results were that the alcohol and water ratio can be tuned to control ionomer distribution. Water-rich solvents produce a more dispersed ink which results in better high-current density performance.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Comparison of subchannel and averaged channel thermal-hydraulic descriptions on coupled pin-by-pin neutronic calculations

Best-estimate transient analysis of Light Water Reactors (LWRs) requires high accuracy code systems solving neutronics (NK), thermal-hydraulics (TH) and thermal-mechanics to model the core behavior. For long time, nodal diffusion methods for solution of the transport equation using assembly size computational meshes have been applied neglecting the details within the fuel assembly, or using 'pin power reconstruction' techniques to predict those details. Moreover, the multiphysics analysis has been commonly performed coupling those neutronic diffusion methods to thermal-hydraulic system codes using a nodalization of several fuel assemblies per computational node without taking into account the effects that this type of averaging can have on the results obtained. This paper presents the work accomplished with the coupled system COBAYA4/CTF for a preliminary analysis of the effect of the different accuracy levels in the NK and TH domain. COBAYA4 is a neutronic code able to solve the diffusion equation at two resolution levels, nodal and pin by pin (PbP). CTF is a thermo-hydraulic code able to solve the coolant conservation equations also at two levels, channel (fuel assembly averaged solution) and sub-channel (real cooling channel) level. The coupled system COBAYA4/CTF is used through SALOME platform, i.e. SALOME is the software able to map conveniently the NK and TH meshes. This coupling allows combining different resolution levels for NK and TH problems. Therefore, the study of the effect of using different resolutions for the NK and TH nodalizations has been performed applying the system to a fuel assembly with selected boundary conditions. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Rotational Dynamics and Transition Mechanisms of Surface-Adsorbed Proteins

Assembly of biomolecules at solid-water interfaces requires molecules to traverse complex orientation-dependent energy landscapes through processes that are poorly understood, largely due to the dearth of in-situ single molecule measurements and statistical analyses of the rotational dynamics that define directional selection. Emerging capabilities in high-speed atomic force microscopy and machine learning have allowed us to directly determine the orientational energy landscape and observe and quantify the rotational dynamics for protein nanorods on the surface of muscovite mica under a variety of conditions. Comparisons with kinetic Monte Carlo simulations show that the transition rates between adjacent orientation-specific energetic minima can largely be understood through traditional models of in-plane Brownian rotation across a biased energy landscape, with resulting transition rates that are exponential in the energy-barriers between states. However, transitions between more distant angular states are decoupled from barrier height, with jump-size distributions showing a power-law decay that is characteristic of a non-classical Levy-flight random walk, indicating that large jumps are enabled by alternative modes of motion via activated states. The findings provide new insights into the dynamics of biomolecules at solid-liquid interfaces that lead to self-assembly, epitaxial matching and other orientationally anisotropic outcomes and define a general procedure for exploring such dynamics with implications for hybrid biomolecular-inorganic materials design.

Orientational energy landscapes, Rotational dynami↗
DOE OSTI2016

An analysis of the structure of an n-dodecane spray flame using TPDF modelling

With a view to understanding ignition and combustion behaviours in diesel engines, this study investigates several aspects of ignition and combustion of an n-dodecane spray in a high pressure, high temperature chamber, known as Spray A, using data resulting from modelling using the transported probability density function (TPDF) method. The model has been validated comprehensively with good to excellent agreement in our previous work against all available experimental data including for mixture-fraction and velocity fields in non-reacting cases, and flame lift-off length and ignition delay in reacting cases. This good agreement encourages further investigation of the numerical model results to help understand the structure of this flame, which serves to complement the experimental information that is available, which is very limited due to the difficult experimental conditions in which this flame exists. For example, quantitative experimental measurements of local mixture-fraction, temperature, velocity gradients, etc. are not yet possible in reacting cases. Analysis of the model results shows that two-stage ignition is found to occur across the ambient temperature conditions considered: the first stage is rapidly initiated on the lean side where temperatures are high and sequentially moves to richer, cooler conditions. The first stage is extremely resilient to turbulence, occurring in a region of very low Damkohler number. The second stage of ignition occurs first in rich mixtures in a region behind the head of the fuel jet where mixture gradients are low, and appears to be influenced strongly by turbulence. Relative to a homogeneous reactor, it is delayed on the lean side but advanced on the rich side, suggesting entrainment and mixing from the early igniting lean regions into richer mixtures is an important moderator of the ignition process. The second-stage ignition front propagates at very high velocities initially, suggesting it is a sequential ignition moving according to gradients of ignition delay and/or residence time. The flame stabilises however on the lean side in a region of much lower velocity, where turbulent velocity fluctuations are sufficiently high such that turbulent transport influences the propagation. It stabilises in a region of low Damkohler number which implies that a competition of chemistry versus micro-mixing might also be involved in stabilisation. The stabilisation mechanism is investigated by an analysis of the transport budgets, showing the flame is stabilised by autoignition but moderated by turbulent diffusion. Further analysis of the flame index supports this stabilisation mechanism, and demonstrates the simultaneous existence of non-premixed and premixed combustion modes in the same flame. Analysis of the flow fields also reveals that local entrainment and dilatation are important flow features near the flame base. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Diesel↗
DOE OSTI2014

FAR-INFRARED EXTINCTION MAPPING OF INFRARED DARK CLOUDS

Progress in understanding star formation requires detailed observational constraints on the initial conditions, i.e., dense clumps and cores in giant molecular clouds that are on the verge of gravitational instability. Such structures have been studied by their extinction of near-infrared and, more recently, mid-infrared (MIR) background light. It has been somewhat more of a surprise to find that there are regions that appear as dark shadows at far-infrared (FIR) wavelengths as long as ∼100 μm! Here we develop analysis methods of FIR images from Spitzer-MIPS and Herschel-PACS that allow quantitative measurements of cloud mass surface density, Σ. The method builds on that developed for MIR extinction mapping by Butler and Tan, in particular involving a search for independently saturated, i.e., very opaque, regions that allow measurement of the foreground intensity. We focus on three massive starless core/clumps in the Infrared Dark Cloud (IRDC) G028.37+00.07, deriving mass surface density maps from 3.5 to 70 μm. A by-product of this analysis is the measurement of the spectral energy distribution of the diffuse foreground emission. The lower opacity at 70 μm allows us to probe to higher Σ values, up to ∼1 g cm{sup –2} in the densest parts of the core/clumps. Comparison of the Σ maps at different wavelengths constrains the shape of the MIR-FIR dust opacity law in IRDCs. We find that it is most consistent with the thick ice mantle models of Ossenkopf and Henning. There is tentative evidence for grain ice mantle growth as one goes from lower to higher Σ regions.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Short-range order and dynamics of atoms in liquid gallium

The features of the microscopic structure, as well as one-particle and collective dynamics of liquid gallium in the temperature range from T = 313 to 1273 K, are studied on the p = 1.0 atm isobar. Detailed analysis of the data on diffraction of neutrons and X-rays, as well as the results of atomic dynamics simulation, lead to some conclusions about the structure. In particular, for preset conditions, gallium is in the equilibrium liquid phase showing no features of any stable local crystalline clusters. The pronounced asymmetry of the principle peak of the static structure factor and the characteristic “shoulder” in its right-hand part appearing at temperatures close to the melting point, which are clearly observed in the diffraction data, are due to the fact that the arrangement of the nearest neighbors of an arbitrary atom in the system is estimated statistically from the range of correlation length values and not by a single value as in the case of simple liquids. Compactly located dimers with a very short bond make a significant contribution to the statistics of nearest neighbors. The temperature dependence of the self-diffusion coefficient calculated from atomic dynamics simulation agrees well with the results obtained from experimental spectra of the incoherent scattering function. Interpolation of the temperature dependence of the self-diffusion coefficient on a logarithmic scale reveals two linear regions with a transition temperature of about 600 K. The spectra of the dynamic structure factor and spectral densities of the local current calculated by simulating the atomic dynamics indicate the existence of acoustic vibrations with longitudinal and transverse polarizations in liquid gallium, which is confirmed by experimental data on inelastic scattering of neutrons and X-rays. It is found that the vibrational density of states is completely reproduced by the generalized Debye model, which makes it possible to decompose the total vibrational motion into individual contributions associated with the formation of acoustic waves with longitudinal and transverse polarizations. Comparison of the heights of the low-frequency component and of the high-frequency peak in the spectral density of vibrational states also indicates a temperature of T ≈ 600 K, at which the diffusion type of one-particle dynamics changes to the vibrational type upon a decrease in temperature. It is demonstrated that the modified Einstein–Stokes relation can be derived using the generalized Debye model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Turbulent transport and mixing in transitional Rayleigh-Taylor unstable flow: A priori assessment of gradient-diffusion and similarity modeling

Data from a 1152×760×1280 direct numerical simulation of a Rayleigh-Taylor mixing layer modeled after a small-Atwood-number water-channel experiment is used to investigate the validity of gradient diffusion and similarity closures a priori. The budgets of the mean flow, turbulent kinetic energy, turbulent kinetic energy dissipation rate, heavy-fluid mass fraction variance, and heavy-fluid mass fraction variance dissipation rate transport equations across the mixing layer were previously analyzed at different evolution times to identify the most important transport and mixing mechanisms. Here a methodology is introduced to systematically estimate model coefficients as a function of time in the closures of the dynamically significant terms in the transport equations by minimizing the L2 norm of the difference between the model and correlations constructed using the simulation data. It is shown that gradient-diffusion and similarity closures used for the turbulent kinetic energy K, turbulent kinetic energy dissipation rate ε, heavy-fluid mass fraction variance S, and heavy-fluid mass fraction variance dissipation rate χ equations capture the shape of the exact, unclosed profiles well over the nonlinear and turbulent evolution regimes. Using order-of-magnitude estimates for the terms in the exact transport equations and their closure models, it is shown that several of the standard closures for the turbulent production and dissipation (destruction) must be modified to include Reynolds-number scalings appropriate for Rayleigh-Taylor flow at small to intermediate Reynolds numbers. The late-time, large Reynolds number coefficients are determined to be different from those used in shear flow applications and largely adopted in two-equation Reynolds-averaged Navier-Stokes (RANS) models of Rayleigh-Taylor turbulent mixing. In addition, it is shown that the predictions of the Boussinesq model for the Reynolds stress agree better with the data when additional buoyancy-related terms are included. It is shown that an unsteady RANS paradigm is needed to predict the transitional flow dynamics from early evolution times, analogous to the small Reynolds number modifications in RANS models of wall-bounded flows in which the production-to-dissipation ratio is far from equilibrium. Although the present study is specific to one particular flow and one set of initial conditions, the methodology could be applied to calibrations of other Rayleigh-Taylor flows with different initial conditions (which may give different results during the early-time, transitional flow stages, and perhaps asymptotic stage). Finally, the implications of these findings for developing high-fidelity eddy viscosity-based turbulent transport and mixing models of Rayleigh-Taylor turbulence are discussed.

42 ENGINEERING↗
DOE OSTI2016

Characterization and Modeling of Grain Boundary Chemistry Evolution in Ferritic Steels under Irradiation

Ferritic/martensitic (FM) steels such as HT-9, T-91 and NF12 with chromium concentrations in the range of 9-12 at.% Cr and high Cr ferritic steels (oxide dispersion strengthened steels with 12-18% Cr) are receiving increasing attention for advanced nuclear applications, e.g. cladding and duct materials for sodium fast reactors, pressure vessels in Generation IV reactors and first wall structures in fusion reactors, thanks to their advantages over austenitic alloys. Predicting the behavior of these alloys under radiation is an essential step towards the use of these alloys. Several radiation-induced phenomena need to be taken into account, including phase separation, solute clustering, and radiation-induced segregation or depletion (RIS) to point defect sinks. RIS at grain boundaries has raised significant interest because of its role in irradiation assisted stress corrosion cracking (IASCC) and corrosion of structural materials. Numerous observations of RIS have been reported on austenitic stainless steels where it is generally found that Cr depletes at grain boundaries, consistently with Cr atoms being oversized in the fcc Fe matrix. While FM and ferritic steels are also subject to RIS at grain boundaries, unlike austenitic steels, the behavior of Cr is less clear with significant scatter and no clear dependency on irradiation condition or alloy type. In addition to the lack of conclusive experimental evidence regarding RIS in F-M alloys, there have been relatively few efforts at modeling RIS behavior in these alloys. The need for predictability of materials behavior and mitigation routes for IASCC requires elucidating the origin of the variable Cr behavior. A systematic detailed high-resolution structural and chemical characterization approach was applied to ion-implanted and neutron-irradiated model Fe-Cr alloys containing from 3 to 18 at.% Cr. Atom probe tomography analyses of the microstructures revealed slight Cr clustering and segregation to dislocations and grain boundaries in the ion-irradiated alloys. More significant segregation was observed in the neutron irradiated alloys. For the more concentrated alloys, irradiation did not affect existing Cr segregation to grain boundaries and segregation to dislocation loops was not observed perhaps due to a change in the dislocation loop structure with increasing Cr concentration. Precipitation of α’ was observed in the neutron irradiated alloys containing over 9 at.% Cr. However ion irradiation appears to suppress the precipitation process. Initial low dose ion irradiation experiments strongly suggest a cascade recoil effect. The systematic analysis of grain boundary orientation on Cr segregation was significantly challenged by carbon contamination during ion irradiation or by existing carbon and therefore carbide formation at grain boundaries (sensitization). The combination of the proposed systematic experimental approach with atomistic modeling of diffusion processes directly addresses the programmatic need for developing and benchmarking predictive models for material degradation taking into account atomistic kinetics parameters

36 MATERIALS SCIENCE↗
DOE OSTI2012

Report on the Initial Fundamental Sodium-CO 2 Interaction Experiment

The U.S. Department of Energy (U.S. DOE) Advanced Reactor Concepts (ARC) Program is developing the Sodium-Cooled Fast Reactor (SFR) as a reactor that could dramatically improve performance in sustainability, safety, economics, security, and proliferation resistance. The near-term Program goal is to reduce technical barriers to improve the prospects of advanced technology reactor systems. In the long-term, integrated advanced reactor system designs will be developed that implement the chosen missions and complete the testing and demonstration necessary for licensing. The supercritical carbon dioxide (S-CO 2 ) Brayton cycle, coupled with an SFR, has been identified as a new and innovative energy conversion technology that could contribute to meeting these objectives especially in terms of improving economics. One appealing feature of this energy conversion system is the smaller footprint that the hardware requires relative to the traditional superheated steam cycle, which is in part due to the use of Printed Circuit Heat Exchanger TM (PCHE TM ) compact diffusion-bonded heat exchangers as the heat source heat exchanger (sodium-to-CO 2 ) as well as the recuperator and cooler modules. Although PCHEs have a high degree of structural integrity, the potential for leaks to develop between the sodium and CO 2 coolant channels in the secondary heat exchanger cannot be ruled out, leading to discharge of high pressure CO2 into the secondary coolant circuit. Due to the robustness of the PCHE design, catastrophic failure leading to CO2 jet blowdown into the intermediate sodium loop is not deemed likely. Rather, small cracks (or micro-leaks) may develop in which CO 2 will bleed into the secondary system at a relatively low rate and chemically react with the sodium. The 2012 Sodium Fast Reactor Research Plan produced by Sandia National Laboratory (Denman et al., 2012) identified the interaction between sodium and CO 2 as being among the highest priority areas of research for SFR accident initiators. In fact, the report rated both the experimental database and modeling capabilities of Na-CO 2 interactions at the lowest current state of knowledge compared with the other listed high-priority accident initiator items. In recognition of the anticipated failure mode for a PCHE sodium-to-CO 2 heat exchanger, an Argonne experiment program, called SNAKE, was initiated in FY 2010 to investigate the reaction characteristics between sodium and CO 2 under micro-leak conditions.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2014

A FOURIER-TRANSFORMED BREMSSTRAHLUNG FLASH MODEL FOR THE PRODUCTION OF X-RAY TIME LAGS IN ACCRETING BLACK HOLE SOURCES

Accreting black hole sources show a wide variety of rapid time variability, including the manifestation of time lags during X-ray transients, in which a delay (phase shift) is observed between the Fourier components of the hard and soft spectra. Despite a large body of observational evidence for time lags, no fundamental physical explanation for the origin of this phenomenon has been presented. We develop a new theoretical model for the production of X-ray time lags based on an exact analytical solution for the Fourier transform describing the diffusion and Comptonization of seed photons propagating through a spherical corona. The resulting Green's function can be convolved with any source distribution to compute the associated Fourier transform and time lags, hence allowing us to explore a wide variety of injection scenarios. We show that thermal Comptonization is able to self-consistently explain both the X-ray time lags and the steady-state (quiescent) X-ray spectrum observed in the low-hard state of Cyg X-1. The reprocessing of bremsstrahlung seed photons produces X-ray time lags that diminish with increasing Fourier frequency, in agreement with the observations for a wide range of sources.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

GLOBAL MODELING OF NEBULAE WITH PARTICLE GROWTH, DRIFT, AND EVAPORATION FRONTS. I. METHODOLOGY AND TYPICAL RESULTS

We model particle growth in a turbulent, viscously evolving protoplanetary nebula, incorporating sticking, bouncing, fragmentation, and mass transfer at high speeds. We treat small particles using a moments method and large particles using a traditional histogram binning, including a probability distribution function of collisional velocities. The fragmentation strength of the particles depends on their composition (icy aggregates are stronger than silicate aggregates). The particle opacity, which controls the nebula thermal structure, evolves as particles grow and mass redistributes. While growing, particles drift radially due to nebula headwind drag. Particles of different compositions evaporate at “evaporation fronts” (EFs) where the midplane temperature exceeds their respective evaporation temperatures. We track the vapor and solid phases of each component, accounting for advection and radial and vertical diffusion. We present characteristic results in evolutions lasting 2 × 10{sup 5} years. In general, (1) mass is transferred from the outer to the inner nebula in significant amounts, creating radial concentrations of solids at EFs; (2) particle sizes are limited by a combination of fragmentation, bouncing, and drift; (3) “lucky” large particles never represent a significant amount of mass; and (4) restricted radial zones just outside each EF become compositionally enriched in the associated volatiles. We point out implications for millimeter to submillimeter SEDs and the inference of nebula mass, radial banding, the role of opacity on new mechanisms for generating turbulence, the enrichment of meteorites in heavy oxygen isotopes, variable and nonsolar redox conditions, the primary accretion of silicate and icy planetesimals, and the makeup of Jupiter’s core.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2026

In situ catalyst activation and regeneration enable energy-efficient high-current CO 2 reduction to ethanol-rich C 2+ mixtures

Electrochemical conversion of dissolved CO 2 in bicarbonate electrolytes, i.e., bicarbonate electrolysis, offers distinct advantages over gas diffusion electrode systems by enabling direct utilization of the CO 2 capture electrolyte while bypassing the energy-intensive CO 2 release step. However, bicarbonate electrolysis faces challenges such as CO 2 mass-transfer limitation, local pH-driven CO 2 depletion, and high cathodic potentials. The higher potential often causes catalyst surface reorganization, leading to a gradual loss of active sites and variations in selectivity during CO 2 reduction. Here, we report a directed, in situ activation and regeneration method that allows precatalysts to equilibrate under dynamic (pulsed) electrolysis conditions. We demonstrate in situ activation of a scalable Cu 2 O/Cu mesh that, under short-width (t = 4 s) pulsed electrolysis, provides stable mixed oxidation states of Cu, favoring the formation of an ethanol-rich crude mixture. The pulsed electrolysis waveform, consisting of six distinct segments, is tuned to form Cu + oxides, which are then reduced to generate local alkaline conditions favoring C–C coupling. This synergistic effect results in FEs of 73% for C2+ products and 39% for ethanol at an applied current density of −150 mA cm −2 and a cathodic potential of −1.45 V (vs. RHE). The overall half-cell energy efficiency is ∼30% for C 2+ products. The in situ Raman experiments confirm the role of pCO 2 R in dynamically regenerating Cu+-containing surface species during pulsed operation, thereby steering selectivity towards C 2+ products. A comprehensive multiscale, multiphysics model is developed to investigate the dynamic behavior of copper surface species (Cu, Cu + , and Cu 2+ ) and local microenvironmental conditions during the pCO 2 R. The results reveal that the coexistence of different copper oxidation states, especially the Cu+ intermediate, is critical in steering selectivity towards multicarbon (C 2+ ) products. The dynamic modulation of surface redox states via tailored pulsing strategies favors C–C coupling pathways by inducing localized alkaline conditions and stabilizing reactive intermediates. This work establishes a predictive modeling platform that links pulse waveform design with mechanistic insights into catalyst state evolution and product selectivity. Overall, this study provides valuable insights into the synergistic effect of in situ activation of pre-catalysts and pulsed electrolysis for higher selectivity towards C 2+ products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

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↗
DOE OSTI2017

Anomalous Distributions of Primary Cosmic Rays as Evidence for Time-dependent Particle Acceleration in Supernova Remnants

Recent precise measurements of cosmic-ray (CR) spectra show that the energy distribution of protons is softer than those of heavier nuclei, and there are spectral hardenings for all nuclear compositions above ∼200 GV. Models proposed for these anomalies generally assume steady-state solutions of the particle acceleration process. We show that if the diffusion coefficient has a weak dependence on the particle rigidity near shock fronts of supernova remnants (SNRs), time-dependent solutions of the linear diffusive shock acceleration at two stages of SNR evolution can naturally account for these anomalies. The high-energy component of CRs is dominated by acceleration in the free expansion and adiabatic phases with enriched heavy elements and a high shock speed. The low-energy component may be attributed to acceleration by slow shocks propagating in dense molecular clouds with low metallicity in the radiative phase. Instead of a single power-law distribution, the spectra of time-dependent solutions soften gradually with the increase of energy, which may be responsible for the “knee” of CRs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2018

Comparative modelling of the coupled thermal–hydraulic-mechanical (THM) processes in a heated bentonite pellet column with hydration

For the deep geological disposal of high-level radioactive waste in argillaceous rocks, the heat production of the waste is an important driver for thermal–hydraulic-mechanical (THM)-coupled processes. These THM processes influence the properties and conditions of the near field that in many repository designs contains bentonite as a clay buffer. One task in the DECOVALEX-2015 (DEvelopment of COupled models and their VALidation against Experiments) project was the modelling of a heated bentonite column (Villar et al. in Long-term THM tests reports: THM cells for the HE-E test: update of results until February 2014. Deliverable-no: D2.2-7.3. CIEMAT Technical Report IEMAT/DMA/2G210/03/2014, 2014) in preparation for the in situ heater experiment HE-E at the underground rock laboratory Mont Terri. DECOVALEX is an international cooperative project that focuses on the development and validation of mathematical models for simulating such coupled processes associated with disposal in deep geological repositories. Eight modelling teams developed their own THM-coupled models for the bentonite column experiment, using six different simulation codes. Each of the teams individually calibrated the THM parameters for the bentonite material. The eight resulting parameter sets agree well and allow a satisfactory reproduction of the TH measurements by all models. The modelling results for the evolution of temperature and relative humidity over time at three sensors in the bentonite column are in good agreement between the teams and with the measured data. Also, changes of the temperature due to modifications of the insulation and the adjustment of the heating power during the course of the experiment are well reproduced. The models were thus able to reproduce the main physical processes of the experiment, both for vapour-dominated diffusion during the heating phase and combined liquid and vapour transport during a subsequent heating and hydration phase. Lastly, based on the parameter sets, the teams predict a penetration of the water infiltration front in the 48-cm column filled with bentonite pellets to a depth between 25 and 35 cm over the 15,000 h (i.e. over 20 months) of the hydration phase of the experiment.

58 GEOSCIENCES↗
DOE OSTI2012

Optical Thin Films for Gas Sensing in Advanced Coal Fired Power Plants

Even for existing coal based plants, the opportunity for sensors and controls to improve efficiency is great. A wide range of gas species are of interest for relevant applications. Functional sensor layers for embedded sensing must be compatible with extreme conditions (temperature, pressure, corrosive). Au incorporated metal oxides have been looked at by a number of other authors previously for gas sensing, but have often focused on temperatures below 500{degree}C. Au nanoparticle incorporated metal oxide thin films have shown enhanced gas sensing response. In prior work, we have demonstrated that material systems such as Au nanoparticle incorporated TiO{sub 2} films exhibit a potentially useful optical response to changing gas atmospheres at temperatures up to ~800-850{degree}C. Current work is focused on sputter-deposited Au/TiO{sub 2} films. Au and Ti are multi-layered sputter deposited, followed by a 950{degree}C oxidation step. Increasing Au layer thickness yields larger particles. Interband electronic transitions significantly modify the optical constants of Au as compared to the damped free electron theory. A high temperature oxidation (20%O{sub 2}/N{sub 2}) treatment was performed at 700{degree}C followed by a reduction (4%H{sub 2}/N{sub 2}) treatment to illustrate the shift in both absorption and scattering with exposure to reducing gases. Shift of localized surface plasmon resonance (LSPR) absorption peak in changing gas atmospheres is well documented, but shift in the peak associated with diffuse scattering is a new observation. Increasing Au layer-thickness results in an increase in LSPR absorption and a shift to longer wavelengths. Diffuse scattering associated with the LSPR resonance of Au shows a similar trend with increasing Au thickness. To model the temperature dependence of LSPR, the modification to the plasmon frequency, the damping frequency, and the dielectric constant of the oxide matrix must be accounted for. Thermal expansion of Au causes a decrease in free-carrier concentration and plasmon frequency with increasing temperature. Increased scattering of electrons with increasing temperatures results in an increased damping frequency for free carriers. The thermo-optic coefficient of TiO{sub 2} is assumed to be constant or decreasing with increasing temperature. A Custom Designed System Can Be Used to Monitor Optical Transmission and Reflection of Films at Elevated Temperatures and Upon Exposure to Changing Ambient Gas Atmospheres. The calculated extinction peak broadens and reduces peak height with increasing temperature. Extinction spectra measured using the elevated temperature system deviate from measurements performed with an integrating sphere. Modifications to measured transmittance and reflectance spectra are observed with increasing temperatures. Optical constants of Au nanoparticles were measured for elevated temperature. The thermo-optic coefficient of TiO{sub 2} strongly affects the shift in LSPR absorption peak. Peak broadening is dictated by the increased damping frequency of Au. In all cases of the theoretical modeling, we are assuming a particle of Au embedded in a TiO{sub 2} matrix without any interparticle interaction. Localized surface plasmon resonance in noble metal nanoparticles is associated with the free electrons. Surface charges create an internal field that acts as a restoring force on displaced charge carriers resulting in an oscillation with an associated resonance. An estimate of the sensitivity as a function of wavelength for sensing done using a single wavelength transmission measurement can be derived by focusing on the partial derivative of Q{sub abs} with respect to the material parameter that we assume is changing during the experiment. We focus on the free carrier density. However, other material parameters may also change in some cases. Peak sensitivity for transmission or absorption based sensing occurs on either side of the LSPR absorption peak maximum. Theoretically predicted wavelength dependence is consistent with the literature. The wavelength of LSPR absorption peak sensitivity shifts with increasing temperature due to broadening and peak shifting. The maximum sensitivity decreases with increasing temperature. The sensitivity should also depend on the mechanism responsible for the solid-gas interaction.

36 MATERIALS SCIENCE↗