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At least 235 records · Page 13

Crystallographic Evidence of Size-Dependent Bond Flexibility in Metal–Organic Framework Nanocrystals

Size-dependent electronic, magnetic, and optical behavior suggests that metal–organic frameworks become softer materials as their particle sizes decrease, but direct evidence is lacking. Here, we report variable-temperature powder X-ray diffraction data of Fe(1,2,3-triazolate)2 particles that offer crystallographic insight into size-dependent bond flexibility. Rietveld refinement reveals size-dependent positive thermal expansion upon downsizing the crystalline domains from 178 to 9 nm, with a 6-fold increase from 16 MK –1 to 96 MK –1 . Here, this behavior occurs in tandem with size-dependent elongation of metal–ligand bonds and increasing thermal displacement parameters, consistent with pronounced metal-linker bond lability. We propose that these effects, as well as size-dependent annealing of crystallite sizes, originate from the high charge density and surface stress of smaller particles. Taken together, these results provide structural evidence that size reduction serves as a synthetic route to controlling the dynamic response of materials to external stimuli.

Crystals↗

Study of diamond film growth and properties

The objective was to study diamond film growth and its properties in order to enhance the laser damage threshold of substrate materials. Calculations were performed to evaluate laser induced thermal stress parameter, R(sub T) of diamond. It is found that diamond has several orders of magnitude higher in value for R(sub T) compared to other materials. Thus, the laser induced damage threshold (LIDT) of diamond is much higher. Diamond films were grown using a microwave plasma enhanced chemical vapor deposition (MPECVD) system at various conditions of gas composition, pressure, temperature, and substrate materials. A 0.5 percent CH4 in H2 at 20 torr were ideal conditions for growing of high quality diamond films on substrates maintained at 900 C. The diamond films were polycrystalline which were characterized by scanning electron microscopy (SEM) and Raman scattering spectroscopy. The top surface of the growing film is always rough due to the facets of polycrystalline film while the back surface of the film replicates the substrate surface. An analytical model based on two dimensional periodic heat flow was developed to calculate the effective in-plane (face parallel) diffusivity of a two layer system. The effective diffusivity of diamond/silicon samples was measured using a laser pulse technique. The thermal conductivity of the films was measured to be 13.5 W/cm K, which is better than that of a type Ia natural diamond. Laser induced damage experiments were performed on bare Si substrates, diamond film coated Si, and diamond film windows. Significant improvements in the LIDT were obtained for diamond film coated Si compared to the bare Si.

Albin, Sacharial↗

Effects of selected trajectory parameters on weight trends in the shuttle thermal protection system

An empirical heating model, thermal protection system unit weight correlation, and trajectory analysis were used to develop a computation procedure for studying the sensitivity of thermal protection system weights to variations in pertinent trajectory parameters. The analytical techniques used in developing this computer program are described. Application of the analysis to a Space Shuttle Orbiter configuration was performed to demonstrate gross thermal protection system weight trends with selected entry trajectory parameters.

Curry, D. M.↗

Engineering design of a kW-scale continuous reactor-heat exchanger for high temperature discharge of particle-based thermochemical energy storage

This study investigates the theoretical design parameters and thermal performance of a kW-scale continuous oxidation reactor for high temperature (~1000 °C) thermochemical energy storage (TCES) applications. The concept comprises a counter-current particle-based system that includes a reaction zone with a heat exchanger to extract the heat produced from the oxidation reaction. Both above and below the hot reactive volume are sensible heat recuperation zones to enable the feed and removal of particles and oxidizing gas near ambient temperature during steady state operation. Two operation types for the reaction zone are studied, a fluidized bed reactor (FBR) and a moving bed reactor (MBR). The results of the parametric analysis suggest that the MBR requires a smaller volume per kW of heat produced, achieving power densities in excess of 2500 kW/m3 compared to ~ 900 kW/m 3 in the FBR. Additionally, the MBR achieves between 0.71 and 0.99 oxidation conversions compared to between 0.23 and 0.38 conversions in the FBR with the same volumes and flowrates. However, the FBR has the potential to maintain a uniform reactor temperature which can produce heat transfer fluid (HTF) outlet temperatures as high as the reactor temperature, i.e., ~1000 °C, whereas the MBR produces variable reactor temperatures that can create overheating zones and low HTF outlet temperatures (< 800 °C) depending on the operating conditions selected. Future work should aim at understanding the coupled fluid dynamics, heat and mass transfer, and thermochemical reaction for any given combination of reactor volume and contacting patterns. Here, these studies should be complemented by experimental work on particle-gas TCES reactors.

25 ENERGY STORAGE↗

Thermal Equations of State of Magnesite: Implication for the Complex Mid‐Lower Mantle Seismic Scatterers

Abstract Magnesite (MgCO 3 ) entering the lower mantle together with the subducted oceanic crust is an important carbon carrier. The reaction between magnesite and mantle minerals has been documented, but its influence on the density and velocity profiles of lower mantle remains unexplored. To decipher the deep carbon transportation and its associated effect, here we determined the thermal equations of state of magnesite up to 120 GPa and 2600 K using X‐ray diffraction in laser‐heated diamond anvil cells. The obtained thermal elastic parameters of magnesite facilitated a comprehensive understanding on the influence of magnesite‐SiO 2 reaction, variation of carbon and SiO 2 content, and temperature on the origin of lower‐mantle scatterers at 1,000–1,800 km depth. Our modeling revealed that the depth of the lower‐mantleV S scatterers is mainly controlled by the Al 2 O 3 content in SiO 2 , while its magnitude depends on the SiO 2 content. Along normal geotherm, the magnesite‐SiO 2 reaction would occur before the post‐stishovite transition, consuming substantial SiO 2 in the subducted oceanic crust. Depending on the amount of residual SiO 2 , the post‐stishovite transition can produce a 2.5–5.2 (2)%V S reduction, compatible with the observed seismic scatterers in Izu‐Bonin and Mariana subduction zones. Along slab geotherm, this reaction occurs after the post‐stishovite transition, generating a greaterV S reduction of 4.4–6.4 (4)%. We thus propose that the reaction between sinking MgCO 3 and SiO 2 in the slab is one of the potential factors influencing the magnitude of the lower‐Vs scatterers at 1,000–1,900 km depth. Our results provide new insights into the deep‐mantle carbonate transportation influencing regional geophysics.

Geochemistry & Geophysics↗

Raman and X-ray diffraction study of pressure-induced phase transition in synthetic Mg 2 TiO 4

Synthetic Mg 2 TiO 4 qandilite was investigated to 50 and 40.4 GPa at room temperature using Raman spectroscopy and X-ray diffraction, respectively. The Raman measurements showed that cubic Mg 2 TiO 4 spinel transforms to a high pressure tetragonal (I4 1 /amd, No.141) phase at 14.7 GPa. Owing to sluggish kinetics at room temperature, the spinel phase coexists with the tetragonal phase between 14.7 and 24.3 GPa. In the X-ray diffraction experiment, transformation of the cubic Mg 2 TiO 4 to the tetragonal structure was complete by 29.2 GPa, ~5 GPa higher than the transition pressure obtained by Raman measurements, owing to slow kinetics. The obtained isothermal bulk modulus of Mg 2 TiO 4 spinel is K T0 = 148(3) GPa when K T0 ’ = 6.6, or K T0 = 166(1) GPa when K T0 ’ is fixed at 4. The isothermal bulk modulus of the high-pressure tetragonal phase is calculated to be 209(2) GPa and V 0 = 270(2) Å 3 when K T0 ’ is fixed at 4, and the volume reduction on change from cubic to tetragonal phase is about 9%. The calculated thermal Grüneisen parameters (γ th ) of cubic and tetragonal Mg 2 TiO 4 phases are 1.01 and 0.63. Based on the radii ratio of spinel cations, a simple model is proposed to predict post-spinel structures.

36 MATERIALS SCIENCE↗

Neutron diffraction and DFT studies of oxygen defect and transport in higher-order Ruddlesden–Popper phase materials

A series of higher-order Ruddlesden–Popper phase materials – La 3 PrNi 3 O 10-δ , La 2 Pr 2 Ni 3 O 10-δ and LaPr 3 Ni 3 O 10-δ – were synthesised and investigated by neutron powder diffraction to understand the oxygen defect structure and propose possible pathways for oxygen transport in these materials. Further complimentary DFT calculations of the materials were performed to support the experimental analysis. All of the phases were hypostoichiometric and it was observed that the majority of the oxygen vacancies were confined to the perovskite layers, with a preference for equatorial oxygen sites. A particular preference for vacancies in O(1) and O(5) sites at high temperatures was observed from neutron diffraction measurements which were further complimented by DFT calculations wherein the vacancy formation energy was found to be lowest at the O(1) site. Also, a preference for a curved oxygen transport pathway around the NiO 6 octahedra was observed which agrees with the published literature for Ruddlesden–Popper phase materials. Lattice parameters for all three compositions showed a linear increase with increasing temperature, but the increase was greatest in the c parameter while the b parameter showed only a slight increase when compared to the a parameter. The thermal expansion coefficient was calculated for all compositions and was found to be in the range 13.0–13.4 × 10 -6 °C -1 , which is compatible with the commonly used electrolyte materials for solid oxide fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling of tungsten filament in gas discharge in H - ion source

Sources of negative ions such as H - are essential elements of proton accelerators and tokamaks. They have limited lifetime. The replacement of an ion source is a costly process causing delays in the operation of the entire machine. The hot tungsten filament is the key element that limits the lifetime of the H - ion source at the Los Alamos Neutron Science Center (LANSCE) facility. An accurate model, which describes the filament physics and provides a reliable estimate on its lifetime, may significantly improve the operation of the facility. In this report we describe such a model, including a comprehensive list of relevant physical processes from first principles. The model can be used to describe different regimes of operation using diagnostics data as input parameters. It has been benchmarked against the data collected during the production cycle at LANSCE and shows good agreement with experimental data.

47 OTHER INSTRUMENTATION↗

Investigation of tearing mode stability near ideal stability boundaries via asymptotic matching techniques

A number of improvements to the TJ toroidal tearing mode code [Fitzpatrick, Phys. Plasmas 31, 102507 (2024)] are documented. The TJ code is also successfully benchmarked against the STRIDE toroidal tearing mode code [Glasser and Koleman, Phys. Plasmas 25, 082502 (2018)]. Finally, the new capabilities of the TJ code are used to investigate the stability of tearing modes in tokamak plasmas as an ideal stability boundary, associated with either an external-kink or an internal-kink mode, is approached. All elements of the tearing stability matrix are found to tend to infinity as an ideal stability boundary is approached. Furthermore, as the stability boundary is approached, the eigenfunctions of the various tearing modes in the plasma, which are decoupled by sheared plasma rotation, are all found to morph into that of the marginally stable ideal mode. However, the growth-rates and real frequencies of the various “ideal-tearing-modes” are different from one another. Moreover, the growth-rate of the ideal-tearing-mode that reconnects magnetic flux at the rational surface that lies closest to the edge of the plasma is the one that tends to a very large value as the stability boundary is approached. A relatively simple test for ideal stability that is capable of detecting stability boundaries for external-kink and internal-kink modes, even in the presence of a very close-fitting ideal wall, is described and verified.

FOS: Physical sciences↗

Crystal structure and thermal expansion of Ta 2 ⁢O 5 from neutron diffraction

Tantalum pentoxide (Ta 2 ⁢O 5 ) is a component of technologies ranging from photographic lenses to medical implants. Despite more than six decades of interest, however, there is no consensus on the crystal structure of Ta 2 ⁢O 5 . Here, we report the results of neutron diffraction experiments on Ta 2⁢ O 5 powders at temperatures up to 1000⁢°⁢C. Because neutron diffraction is sensitive to the positions of O atoms in the presence of heavy elements, our results provide strong evidence that the orthorhombic L SR structure can account for experimental observations better than any other proposal in the literature. Here, we also determine the anisotropic crystallographic thermal expansion parameters of Ta 2 ⁢O 5 , which are important for modeling the performance of Ta 2⁢ O 5 -bearing technologies.

36 MATERIALS SCIENCE↗

Ab initio anharmonic thermodynamic properties of cubic Ca Si O 3 perovskite

We present an ab initio study of the thermodynamic properties of cubic CaSiO 3 perovskite (CaPv) over the pressure and temperature range of the Earth's lower mantle. We compute the anharmonic phonon dispersions throughout the Brillouin zone by utilizing the phonon quasiparticle approach, which characterizes the intrinsic temperature dependence of phonon frequencies and, in principle, captures full anharmonicity. Such temperature-dependent phonon dispersions are used to calculate ab initio free energy in the thermodynamic limit (N → ∞) within the framework of the phonon gas model. Accurate free energy calculations enable us to investigate cubic CaPv's thermodynamic properties, e.g., thermal expansivity, Grüneisen parameter, bulk modulus, heat capacity and thermal equation of state, where anharmonic effects are demonstrated. Furthermore, the present methodology provides an important theoretical approach for exploring phase boundaries, thermodynamic, and thermoelastic properties of strongly anharmonic materials at high pressures and temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Coexistence of low and high spin states in La 18 Co 28 Pb 3

The electronic structure and magnetic properties of a newly predicted stable ternary compound La 18 ⁢Co 28 ⁢Pb 3 are studied using electronic structure analysis. The ground state of this compound is ferromagnetic, with three positions of nonequivalent magnetic Co atoms. A strong dependence of magnetic properties on volume shows that this system is situated near the point of magnetic instability. The coexistence of high- and low-spin ferromagnetic states as a function of volume near equilibrium was discovered. A corresponding spin tunneling splitting was estimated. The stability of the theoretically predicted magnetic ground state was tested by varying the Hubbard parameter. The thermal spin fluctuations were added to estimate the paramagnetic moment and a Curie temperature. Finally, the necessity of experimental verification of the obtained results is emphasized.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Verification and Validation of the STAT7 Code

This document presents the verification and validation of the STAT7 Version 1.0 code which has been developed to perform the steady-state thermal hydraulic safety calculation of the MIT Research Reactor required upon conversion of the reactor from high enrichment uranium fuel to low enrichment uranium fuel. The key capabilites of the code including the statistical processing, water property generation, and thermal hydraulic solution are verified independently. While the first two capabilites are checked using statistical tests and NIST data tables, each component of the thermal hydraulic solution is verified using simple geometry test problems. The comparison between results obtained by the code and hand calculations on these problems shows that each of these components work correctly. Additionally, a comprehensive comparison between STAT7 Version 1.0 and PLTEMP/ANL Version 4.2 calculations for a five-channel test problem is performed for the validation. The good agreement between the obtained results for all thermal hydraulic parameters belonging to the fuel core region is achieved. An issue in bypass flowrate calculation was detected when both fin-friction and bypass flow claculations are involved. This problem can be corrected in a later version of the code, however, does not affect the application of STAT7 code as it has been used to date where the flow distribution in the core region and bypass channel is specified as an input parameter.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Verification and Validation of the STAT7 Code

This document presents the verification and validation of the STAT7 Version 1.0 code which has been developed to perform the steady-state thermal hydraulic safety calculation of the MIT Research Reactor required upon conversion of the reactor from highly enriched uranium fuel to low- enriched uranium fuel. The key capabilities of the code including the statistical processing, water property generation, and thermal hydraulic solution are verified independently. While the first two capabilities are checked using statistical tests and NIST data tables, each component of the thermal hydraulic solution is verified using simple geometry test problems. The comparison between results obtained by the code and hand calculations on these problems shows that each of these components work correctly. Additionally, a comprehensive comparison between STAT7 Version 1.0 and PLTEMP/ANL Version 4.2 calculations for a five-channel test problem is performed for the validation. The good agreement between the obtained results for all thermal hydraulic parameters belonging to the fuel core region is achieved. An issue in bypass flowrate calculation was detected when both fin-friction and bypass flow calculations are involved. This problem can be corrected in a later version of the code. However, it does not affect the application of STAT7 as it has been used to date where the flow distribution in the core region and bypass channel is specified as an input parameter.

97 MATHEMATICS AND COMPUTING↗

Validation of SAS4A/SASSYS-1 for Steady-State Single-Phase Natural Circulation

The development of numerical software for engineering applications requires the validation of the code against experimental benchmark datasets. To support the validation of SAS4A/SASSYS-1 in simulating the single-phase natural circulation within nuclear reactor systems, high-precision steady-state experiments are performed to capture single-phase natural circulation phenomena on an existing scaled facility with comprehensive instrumentation. Forced convection tests are designed precisely capturing the facility’s critical thermal-hydraulic parameters required for one-dimensional modeling, and a comprehensive single-phase natural circulation dataset is obtained with well-documented experimental uncertainty and facility description. Analysis and discussion based on the finalized dataset confirm the dataset’s ability in capturing dominant phenomena and address important physical interpretation of parameters. The dataset reported in this project provides a valuable benchmark resource for the validation of system analysis codes under single-phase natural circulation inside nuclear reactors. Validation of SAS4A/SASSYS-1 is then performed against the obtained benchmark dataset to confirm the capability of its physics model in simulating the steady-state single-phase natural circulation. The experimental facility is modeled in the candidate code. Solution verification is performed using Richardson-extrapolation-based estimators to quantify and restrict numerical errors from discretization. Numerical uncertainty originating from finite maximum pseudo-transient time is also quantified and restricted. Input uncertainty provided by the benchmark dataset is forward propagated through the candidate code, directly quantifying the simulation output in a Monte Carlo approach. The composition of the output uncertainty is further determined by the estimators of Sobol’ indices through a variance-based sensitivity analysis. With uncertainty quantified for each individual condition, detailed comparison between the simulation results and experimental data is performed covering the whole dataset, which shows consistent agreement for all important quantities. The validation activity reported in this project demonstrates that SAS4A/SASSYS-1 can predict the primary parameters with satisfactorily accuracy under steady-state single-phase natural circulation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Development of an MC&A toolbox for liquid-fueled molten salt reactors with online reprocessing (Final Report)

A critical barrier to the deployment of MSRs is the absence of a well-defined nuclear material control and accounting (MC&A) approach, a vital prerequisite to meet NRC licensing requirements as well as facilitating future international exports. Liquid-fueled MSR variants (especially those incorporating online refueling or reprocessing) present a unique set of challenges to traditional nuclear material control and accountancy. Unlike solid-fueled light-water reactors, traditional item-counting methods cannot be applied as an accountancy strategy. Rather, MC&A approaches to MSR variants (including both uranium and thorium fueled designs) are more analogous to bulk material handling facilities (e.g., enrichment and reprocessing); yet further complicating matters is the fact that fuel medium is also highly radioactive. Meanwhile, the space of MSRs covers a broad range of design parameters, including thermal and fast spectra designs; operation in actinide breeder or burner modes, choice of actinide fuel used (e.g., 235 U, 232 Th / 233 U, denatured 233 U, etc.), pool or loop-type configuration, and even different salt chemistry. Each of these design choices introduce significant challenges to MC&A approaches within MSR facilities. We propose to bridge this gap for liquid-fueled MSRs by developing a modular, component-based test framework for evaluating viable process monitoring and MC&A techniques specifically suited to liquid-fueled MSR system variants employing online refueling or reprocessing. This test platform will consist of a toolbox of independent process modules representing discrete physical units (such as the reactor core, off-gas processing, decay tanks, and actinide separation units), each with its own self-contained physics responsive to the input mass flow, along with appropriate measurement models that can be coupled to key flow points. These dynamic physical signatures thus afford the ability to test the viability and efficacy of potential accountancy techniques under the full range of reactor operating conditions. As process modules are connected via mass flows, the result is a reconfigurable, generic MSR mass flow model capable of serving as an MC&A test platform for a broad spectrum of possible MSR configurations. The resulting MSR MC&A toolbox will enable robust assessment of accountancy strategies for this unique facility type, including analysis of physical feedbacks arising both from depletion of the fuel over time as well as from potential off-normal events, including those introduced by equipment failures (e.g., a pump failure) as well as by malicious action (i.e., attempts to divert material). The proposed toolbox both addresses a critical needs area for the MPACT analysis toolkit while leveraging existing MPACT-sponsored tools, especially with respect to simulation of measurement and accountancy techniques for advanced fuel cycle facilities. Beyond enabling new analysis capabilities for MSR systems, the design of this toolbox will be to such to maximize compatibility with existing MPACT tools, such to enhance existing facility MC&A analysis capabilities.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Experimental Validation of Thermal Hydraulic Behavior in Sodium Fast Reactors (SFR) with the Thermal Hydraulic Experimental Test Article (THETA)

Thermal stratification and transition to natural circulation pose two of the largest sources of uncertainty in systems-level modeling of liquid metal-cooled fast reactors. As these phenomena typically develop during transient event sequences, licensing-basis events analyzed using systemslevel models may have considerable uncertainties associated with thermal-hydraulic parameters of the system to account for these phenomena. As a result, the validation basis for these phenomena for systems-level codes is insufficient to fully support the wide range of liquid metal fast reactors being developed in the US. Currently, the most viable path for licensing a design is to take significant conservatisms and maintain sufficiently large safety margins to account for this uncertainty.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗