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At least 307 records · Page 17

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications. This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2 H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature T g can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in T g and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of T g with increased confinement that is strongly influenced by the pore-liquid interface characteristics. This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. Finally, while the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of fast-running eighth core nodal solution

A fast-running, eighth-core solution technique has been developed for the quick core calculations in ANC, the Westinghouse core analysis code based on the nodal expansion method, and the BEACON{sup TM} Core Monitoring System (BEACON). This technique, referred to as 'Fast Eighth' (Fast8), enables users to obtain satisfactory macroscopic core calculation results such as reactivity, axial offset and assembly power much more quickly than calculations performed in the standard full-core or quarter-core geometry. Fast8 uses three techniques: folding the radial geometry into eighth-core geometry, reducing the axial geometry into a coarse axial mesh geometry, and smearing the spacer grids into nodes on-the-fly after the first calculation in the standard geometry. These geometry adjustments in Fast8 contribute to the reduction of the number of neutronic and material nodes while maintaining the reaction rates in each node. The axial mesh condition dependency in Fast8 is investigated in a xenon transient calculation in single assembly geometry, and the Fast8 maximum axial mesh size is determined based on these results. Fast8 is then applied to the load swing calculation, and the results are compared with the reference, full-core geometry, solution. The critical boron concentration and axial offset of Fast8 show good agreement with the reference solutions, and that Fast8 is a good technique for obtaining macroscopic core calculation results in significantly shorter time. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Bulk nanocrystalline Al alloys with hierarchical reinforcement structures via grain boundary segregation and complexion formation

Grain size engineering, particularly reducing grain size into the nanocrystalline regime, offers a promising pathway to further improve the strength-to-weight ratio of Al alloys. Unfortunately, the fabrication of nanocrystalline metals often requires non-equilibrium processing routes, which typically limit the specimen size and require large energy budgets. In this study, multiple dopant elements in ternary Al alloys are deliberately selected to enable segregation to the grain boundary region and promote the formation of amorphous complexions. Three different fully dense bulk nanocrystalline Al alloys (Al-Mg-Y, Al-Fe-Y, and Al-Ni-Y) with small grain sizes were successfully fabricated using a simple powder metallurgy approach, with full densification connected directly to the onset of amorphous complexion formation. All the compositions demonstrate densities above 99% with grain sizes <60 nm following consolidation via hot pressing at 585 °C. The very fine grain structure results in excellent mechanical properties, as evidenced by nanoindentation hardness values in the range of 2.2-2.8 GPa. Detailed microstructural characterization verifies the segregation of all dopant species to grain boundaries as well as the formation of amorphous complexions, which suggests their influential role in aiding effective consolidation and endowing thermal stability in the alloys. Moreover, nanorods with a core-shell structure are also observed at the grain boundaries, which likely contribute to the stabilization of the grain structure while also strengthening the materials. Lastly, intermetallic particles with sizes of hundreds of nanometers form in all systems. As a whole, the results presented here demonstrate a general alloy design strategy of segregation and boundary evolution pathway that enables the fabrication of multiple nanocrystalline Al alloys with hierarchical microstructures and improved performance.

36 MATERIALS SCIENCE↗

Mass transfer in catalytic depolymerization: External effectiveness factors and serendipitous processivity in stagnant and stirred melts

Several heterogeneous catalysts are being developed to recycle plastics. Most operate in viscous polymer melts, where external mass transfer effects could limit the supply of co-reactants to active sites. External mass transfer can also impede the diffusion of long chain products away from the catalyst after each cut. Product egress limitations could potentially confer unintentional processivity to catalyst operation, i.e. a tendency for the catalyst to repeatedly cut the same chain after an initial encounter. We formulate reaction–diffusion equations to quantify mass transfer effects on the co-reactant transport to the catalyst and the degree of serendipitous processivity. Results are developed for catalysts in stagnant or stirred melts, with simple expressions involving Damkohler, Peclet, and Sherwood numbers, i.e. dimensionless combinations of rate constants, catalyst particle size, polymer diffusivities, and shear rates (where applicable). In conclusion, we estimate the impact of these effects for a spherical core–shell catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evidence of a glassy magnetic transition driven by structural disorder in BiFeO 3 nanoparticles

Important effects appear in low and high temperature magnetometry of multiferroic BiFeO 3 (BFO) nanoparticles as sizes are reduced from 105 nm to 18 nm. In these particles, a magnetic transition appears close to 200 K probably associated with a spin reorientation which is absent in bigger particles. At higher temperatures and up to the bulk ferroelectric Curie temperature (1000 K), two additional magnetic transitions can be identified. Around T N 600 K, a size-dependent magnetic transition appears, associated with an antiferromagnetic transition. A model based on atomic vibration instability can describe the variation of T N with nanoparticle size. Furthermore, for certain sizes, the properties are dominated by the glassy state arising from the disorder produced by the formation of a core-shell structure. This implies that the magnetic behavior of nanoparticles is strongly affected by their crystal structure close to the transition temperature. Finally, the structural disorder which couples to the magnetic properties add control to the magnetic and ferroelectric properties of BFO nanoparticles.

36 MATERIALS SCIENCE↗

Irradiation performance of a U-7Mo in Al-Si matrix dispersion full-size fuel plate assembly

The Korea Atomic Energy Research Institute (KAERI) is leading the Ki-Jang Research Reactor (KJRR) project with the intent to develop a new reactor for medical isotope production and other nuclear research purposes. The KJRR core is designed to use high density fuel system where uranium alloyed with 7 wt% molybdenum (U-7Mo) particles are dispersed in a matrix of aluminum alloyed with 5 wt% silicon (Al-5Si) and clad in aluminum alloy 6061 (Al-6061) to form fuel plates. KAERI developed a fabrication facility to construct KJRR fuel assemblies and partnered with the Idaho National Laboratory (INL) to irradiate a full-size fuel assembly, with 21 total fuel plates, in the Advanced Test Reactor (ATR). Irradiation testing and subsequent Post Irradiation Exam (PIE) campaigns were performed successfully over a multi-year project. Monte Carlo neutronic calculations, coupling with a depletion code, were performed based on ATR’s as-run power history which showed that the highest power plate (plate 20) reached 83.1 % end-of-life (EOL) local burnup based on initial 235 U content. Additionally, finite element thermal modeling was performed based as-run power history which showed a beginning-of-life (BOL) peak local heat flux of 184 W/cm 2 . No anomalous fuel performance was observed during the irradiation and target test conditions were achieved. PIE showed favorable performance of the fuel assembly regarding all important phenomena. This paper describes the KJRR fuel assembly irradiation conditions and PIE data to support the conclusion that it performed well, without evidence of unexpected or problematic fuel performance, within an irradiation test designed to bound the KJRR design environment.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Surrogate-constructed scalable-circuits adaptive variational quantum eigensolver in the Schwinger model

Inspired by recent advancements in simulating periodic systems on quantum computers, we develop an approach to further advance the simulation of these systems, named (SC) 2 -ADAPT-VQE. Our approach extends the scalable-circuits ADAPT-VQE framework, which builds an ansatz from a pool of coordinate-invariant operators defined for arbitrarily large, though not arbitrarily small, volumes. Our method uses a classically tractable “surrogate constructed” method to remove irrelevant operators from the pool, reducing the minimum size for which the scalable circuits are defined. Bringing together the scalable circuits and the surrogate constructed approaches forms the core of the (SC) 2 methodology. Our approach allows for a wider set of classical computations on small volumes, which can be used for a more robust extrapolation protocol. While developed in the context of lattice models, the surrogate construction portion is applicable to a wide variety of problems where information about the relative importance of operators in the pool is available. As an example, we use it to compute the properties of the Schwinger model—quantum electrodynamics for a single, massive fermion in 1 +1 dimensions—and show that our method can be used to accurately extrapolate to the continuum limit.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Surrogate Constructed Scalable Circuits ADAPT-VQE in the Schwinger model

Inspired by recent advancements of simulating periodic systems on quantum computers, we develop a new approach, (SC)$^2$-ADAPT-VQE, to further advance the simulation of these systems. Our approach extends the scalable circuits ADAPT-VQE framework, which builds an ansatz from a pool of coordinate-invariant operators defined for arbitrarily large, though not arbitrarily small, volumes. Our method uses a classically tractable ``Surrogate Constructed'' method to remove irrelevant operators from the pool, reducing the minimum size for which the scalable circuits are defined. Bringing together the scalable circuits and the surrogate constructed approaches forms the core of the (SC)$^2$ methodology. Our approach allows for a wider set of classical computations, on small volumes, which can be used for a more robust extrapolation protocol. While developed in the context of lattice models, the surrogate construction portion is applicable to a wide variety of problems where information about the relative importance of operators in the pool is available. As an example, we use it to compute properties of the Schwinger model - quantum electrodynamics for a single, massive fermion in $1+1$ dimensions - and show that our method can be used to accurately extrapolate to the continuum limit.

Gustafson, Erik [RIACS, Mtn. View] (ORCID:00000001↗

Computational Investigation of Fuel Dispersal Phenomena during Large-Break Loss of Coolant Accident in Light-Water Reactors

In the event of cladding rupture, which could occur in light water reactor fuel assemblies during a loss-of-coolant accident (LOCA), fuel particles, along with fission gases, can be expelled into the reactor core from the fractured fuel rod. This expulsion of fragmented fuel particles, referred as fuel dispersal, is the subject of investigation to evaluate the safety implications of increasing fuel burnup in light water reactors, with a specific focus on fuel fragmentation, relocation, and dispersal. Particle trajectories and the resulting mass distribution of the settled particles within the reactor pressure vessel can pose a long-term cooling challenge for the reactor core. The fuel dispersal phenomenon is significantly influenced by the ejection characteristics of the fuel fragments, as well as the size and shape of the cladding rupture and fuel rod depressurization history during LOCA transients. In this study, the transport of fuel particles within a scaled 5 × 5 lattice of a pressurized water reactor rod bundle geometry is modeled through a two-fluid Eulerian framework that treats the gas and solid phases as interpenetrating continua. The required boundary conditions are evaluated from the fuel performance code BISON in a postulated large-break LOCA scenario. The modeling framework considers solid fuel particles as granular matter, interacting with the gaseous dry steam phase and fission gases through the governing interfacial momentum and energy exchange between the gas and solid phases. The simulation results provide the volume fraction of the solids settled on the bottom surface of the fuel bundle, quantifying the deposition within the bundle geometry.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Verification and validation of the Alternative Nonlinear Two-phase Subchannel (ANTS) code

The Alternative Nonlinear Two-phase Subchannel solver (ANTS) code was written to provide a fast-running, steady-state, pin-resolved modeling and simulation tool for analysis of common boiling water reactor (BWR) geometry and common operating conditions. ANTS has been integrated into the Virtual Environment for Reactor Application (VERA) core simulator software, where it can be used to provide a thermal/hydraulic (T/H) subchannel solution that is then used to provide neutronic feedback as well as perform the fuel depletion and temperature solution. Herein, this paper presents the rigorous analysis performed on the ANTS code, which includes both code and solution verification testing, benchmarking with the existing two-phase subchannel capability in VERA, CTF, and validation testing using popular two-phase experiments such as PWR Sub-channel and Bundle Tests (PSBT), BWR Full-size Fine-mesh Bundle Tests (BFBT), Risø, and FRIGG. This assessment was used to qualify ANTS for its intended applications before its use for core-scale, multiphysics BWR simulations. In general, it was found that agreement with experimental data was good; errors were within the range of experimental data uncertainty. Furthermore, code and solution verification confirmed that the governing equations and the most important closure terms were correctly implemented and behaving as expected.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A semi-analytic study of self-interacting dark-matter haloes with baryons

ABSTRACT We combine the isothermal Jeans model and the model of adiabatic halo contraction into a semi-analytic procedure for computing the density profile of self-interacting dark-matter (SIDM) haloes with the gravitational influence from the inhabitant galaxies. The model agrees well with cosmological SIDM simulations over the entire core-forming stage up to the onset of gravothermal core-collapse. Using this model, we show that the halo response to baryons is more diverse in SIDM than in CDM and depends sensitively on galaxy size, a desirable feature in the context of the structural diversity of bright dwarfs. The fast speed of the method facilitates analyses that would be challenging for numerical simulations – notably, we quantify the SIDM halo response as functions of the baryonic properties, on a fine mesh grid spanned by the baryon-to-total-mass ratio, Mb/Mvir, and galaxy compactness, r1/2/Rvir; we show with high statistical precision that for typical Milky-Way-like systems, the SIDM profiles are similar to their CDM counterparts; and we delineate the regime of core-collapse in the Mb/Mvir − r1/2/Rvir space, for a given cross section and concentration. Finally, we compare the isothermal Jeans model with the more sophisticated gravothermal fluid model, and show that the former yields faster core formation and agrees better with cosmological simulations. We attribute the difference to whether the target CDM halo is used as a boundary condition or as the initial condition for the gravothermal evolution, and thus comment on possible improvements of the fluid model. We have made our model publicly available at https://github.com/JiangFangzhou/SIDM.

79 ASTRONOMY AND ASTROPHYSICS↗

CORE DESIGN AND NEUTRONIC ANALYSIS OF THE EUROPEAN SODIUM FAST REACTOR WITH METALLIC FUEL

The current ESFR (European Sodium Fast Reactor) design was proposed and in-depth evaluated in the frame of the past ESFR-SMART project. As a follow-up project, the ESFR-SIMPLE has been launched with the aim of challenging the current commercial-size ESFR design in terms of safety features and economic performance. Among the new safety measures to be developed and assessed in ESFR-SIMPLE, the current oxide fuel ESFR design will be challenged by a modified version of the core with metallic fuel. This intends to conclude on what types of benefits can be obtained with high-density fuel, under similar safety and design constraints. In this paper, the designing approach for enabling the use of metallic fuel in the current ESFR core is described and a preliminary neutronic evaluation is carried out. The optimal configuration is established through the optimization of key neutronic parameters aiming at the potential reduction of the plutonium inventory. The resulting core configuration serves as a basis for further safety assessment analyses, which will provide insight into the advantages and drawbacks of the two types of fuels.

Jiménez-Carrascosa, Antonio↗

Alternating salt and freshwater floods of coastal soils impact soil structure, hydraulic properties, and oxygen dynamics

Coastal soils are increasingly impacted by hydrologic intensification in the form of rising sea level and flooding from storm surges and precipitation. Alternating saltwater (SW) and freshwater (FW) exposure has the potential to disperse colloids, which can lead to disintegration of soil structure, clogging of pore spaces, and reduction in ecologically and biogeochemically important functions like infiltration or gas exchange. To investigate how hydrologic intensification affects soil structure and oxygen dynamics, we conducted a series of laboratory-based flood simulations. Intact soil cores of the A and B horizons (22 total) from the toe slope of an upland coastal forest along the western shore of Chesapeake Bay. We subjected the cores to 24 h of saturation with either FW or alternating brackish SW and FW, with a 24-h draining event in between flood events. Oxygen diffusion into soil during draining was reduced by up to 30% for soils flooded alternating SW-FW compared to soils flooded only with FW. We attributed the reduced oxygen diffusion to clogging of smaller pores by colloids, with colloid redistribution observed as an increase in specific surface area down the core profile of up to 59%. After three SW-FW floods (six floods total), there were significant changes in pore size distribution, significant redistribution of colloids, and the A horizon became sodic. We concluded that a small number of SW flooding events can induce a measurable change in soil physical properties that directly impacts the biogeochemical dynamics.

Rod, Kenton A. [Pacific Northwest National Laborat↗

Interplay of Surface and Interior Modes in Exciton–Phonon Coupling at the Nanoscale

Exciton-phonon coupling (EXPC) plays a key role in the optoelectronic properties of semiconductor nanocrystals (NCs), but a microscopic picture of EXPC is still lacking, particularly regarding the magnitude and scaling with NC size, the dependence on phonon frequency, and the role of the NC surface. The computational complexity associated with accurately describing excitons and phonons has limited previous theoretical studies of EXPC to small NCs, noninteracting electron-hole models, and/or a small number of phonon modes. We develop an atomistic approach for describing EXPC in NCs of experimentally relevant sizes. We validate our approach by calculating the reorganization energies, a measure of EXPC, for CdSe and CdSe-CdS core-shell NCs, finding good agreement with experimental measurements. We demonstrate that exciton formation distorts the NC lattice primarily along the coordinates of low-frequency acoustic modes. Modes at the NC surface play a significant role in smaller NCs while interior modes dominate for larger systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A new generation of effective core potentials: Selected lanthanides and heavy elements

Here, we construct correlation-consistent effective core potentials (ccECPs) for a selected set of heavy atoms and ƒ-elements that are of significant current interest in materials and chemical applications, including Y, Zr, Nb, Rh, Ta, Re, Pt, Gd, and Tb. As is customary, ccECPs consist of spin orbit averaged relativistic effective potential (AREP) and effective spin-orbit (SO) terms. For the AREP part, our constructions are carried out within a relativistic coupled-cluster framework while also taking into account objective function one-particle characteristics for improved convergence in optimizations. The transferability is adjusted using binding curves of hydride and oxide molecules. We address the difficulties encountered with ƒ-elements, such as the presence of large cores and multiple near-degeneracies of excited levels. For these elements, we construct ccECPs with core valence partitioning that includes 4ƒ-subshell in the valence space. The developed ccECPs achieve an excellent balance between accuracy, size of the valence space, and transferability and are also suitable to be used in plane wave codes with reasonable energy cutoffs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exact matrix product state representation and convergence of a fully correlated electronic wavefunction in the infinite-basis limit

Here In this paper we present the exact representation of a fully correlated electronic wavefunction as the single-particle basis approaches completeness. It consists of a half-infinite chain of matrices of exponentially increasing size. The complete basis limit is illustrated numerically using the density-matrix renormalization-group method by computing the core-valence entanglement in the C 2 ground state in increasing subsets of cc-pVTZ and pVQZ bases until convergence is reached.

36 MATERIALS SCIENCE↗

Polarimetric Radar Characteristics of Simulated and Observed Intense Convective Cores for a Midlatitude Continental and Tropical Maritime Environment

This study contrasts midlatitude continental and tropical maritime deep convective cores using polarimetric radar observables and retrievals from selected deep convection episodes during the MC3E and TWPICE field campaigns. The continental convective cores produce stronger radar reflectivities throughout the profiles, while maritime convective cores produce more positive differential reflectivity Z dr and larger specific differential phase K dp above the melting level. Hydrometeor identification retrievals revealed the presence of large fractions of rimed ice particles (snow aggregates) in the continental (maritime) convective cores, consistent with the Z dr and K dp observations. The regional cloud-resolving model simulations with bulk and size-resolved bin microphysics are conducted for the selected cases, and the simulation outputs are converted into polarimetric radar signals and retrievals identical to the observational composites. Both the bulk and the bin microphysics reproduce realistic land and ocean (L-O) contrasts in reflectivity, polarimetric variables of rain drops, and hydrometeor profiles, but there are still large uncertainties in describing Z dr and K dp of ice crystals associated with the ice particle shapes/orientation assumptions. Sensitivity experiments are conducted by swapping background aerosols between the continental and maritime environments, revealing that background aerosols play a role in shaping the distinct L-O contrasts in radar reflectivity associated with raindrop sizes, in addition to the dominant role of background thermodynamics.

54 ENVIRONMENTAL SCIENCES↗

A graphics processing unit accelerated sparse direct solver and preconditioner with block low rank compression

We present the GPU implementation efforts and challenges of the sparse solver package STRUMPACK. The code is made publicly available on github with a permissive BSD license. STRUMPACK implements an approximate multifrontal solver, a sparse LU factorization which makes use of compression methods to accelerate time to solution and reduce memory usage. Multiple compression schemes based on rank-structured and hierarchical matrix approximations are supported, including hierarchically semi-separable, hierarchically off-diagonal butterfly, and block low rank. Here, in this paper, we present the GPU implementation of the block low rank (BLR) compression method within a multifrontal solver. Our GPU implementation relies on highly optimized vendor libraries such as cuBLAS and cuSOLVER for NVIDIA GPUs, rocBLAS and rocSOLVER for AMD GPUs and the Intel oneAPI Math Kernel Library (oneMKL) for Intel GPUs. Additionally, we rely on external open source libraries such as SLATE (Software for Linear Algebra Targeting Exascale), MAGMA (Matrix Algebra on GPU and Multi-core Architectures), and KBLAS (KAUST BLAS). SLATE is used as a GPU-capable ScaLAPACK replacement. From MAGMA we use variable sized batched dense linear algebra operations such as GEMM, TRSM and LU with partial pivoting. KBLAS provides efficient (batched) low rank matrix compression for NVIDIA GPUs using an adaptive randomized sampling scheme. The resulting sparse solver and preconditioner runs on NVIDIA, AMD and Intel GPUs. Interfaces are available from PETSc, Trilinos and MFEM, or the solver can be used directly in user code. We report results for a range of benchmark applications, using the Perlmutter system from NERSC, Frontier from ORNL, and Aurora from ALCF. For a high frequency wave equation on a regular mesh, using 32 Perlmutter compute nodes, the factorization phase of the exact GPU solver is about 6.5× faster compared to the CPU-only solver. The BLR-enabled GPU solver is about 13.8× faster than the CPU exact solver. For a collection of SuiteSparse matrices, the STRUMPACK exact factorization on a single GPU is on average 1.9× faster than NVIDIA’s cuDSS solver.

97 MATHEMATICS AND COMPUTING↗