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Precision of Property Measurements with Reference Molten Salts

Thermochemical and thermophysical properties of reference molten salt systems are being measured to establish the precisions achievable with current state-of-the-art methods including repeatability within a laboratory and reproducibility between laboratories using the same and different methods. Several laboratories across the United States are analyzing salt samples from single source batches of two salts to provide independent measurements of property values and the precisions of different measurement techniques in an interlaboratory study referred to as the Interlaboratory Salt Study (ISS). The compositions of the two salts produced for the study were reported to be eutectic LiF-NaF-KF (46.5-11.5-42 mol %) and NaCl-KCl (50-50 mol %). These salts are referred to herein as ISS FLiNaK and ISS NaCl-KCl. Thermochemical properties being measured at Argonne include thermal transitions and heat capacity by differential scanning calorimetry. Thermophysical properties being measured at Argonne include liquid density and surface tension by using a buoyancy densitometer and thermal diffusivity by using a laser flash analyzer. Thermal conductivity is calculated from measured thermal diffusivity, density and heat capacity values. The results of property measurements made at Argonne using these inter-laboratory salt study salts are presented here.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Flash Heating of a Hollow Rod to Determine Thermal Properties

In a nuclear reactor, prolonged exposure to high neutron flux levels can change material properties of reactor components. Due to the danger posed to personnel by highly radioactive components such as spent fuel, noncontact methods must be used to determine these properties. The objective of the current research is to test the viability of using a flash-heating method to determine the thermal diffusivity of a silicon carbide (SiC) tube, which could be used as cladding for a nuclear fuel rod. The flash-heating experiment was conducted at Oak Ridge National Laboratory and temperature results were analyzed as a two-Dimensional cross section which assumed axial symmetry. The model was fitted iteratively to the temperature measurements using nonlinear regression which required values for thermal diffusivity, Biot number and a term to determine the magnitude of the heat absorbed by the flash. The method could be expanded in the future to estimate the thermal diffusivity of spent nuclear fuel rods in an effort to increase the certainty of new reactor designs using precise thermal properties throughout the core life. A statistical analysis of the results of this work is provided as part of the analysis.

McMasters, Robert L [Virginia Military Institute, ↗

A phase field study of the thermal migration of gas bubbles in UO 2 nuclear fuel under temperature gradient

Phase field models are developed to study the gas bubble migration in uranium dioxide nuclear fuel in which a large temperature gradient exists during the operation. In this work, thermal diffusion mechanism for nanosized gas bubbles and vapor transport process for micron-sized gas bubbles are considered, respectively. In both cases, gas bubbles migrate to the high-temperature area. Due to the velocity difference between leading and trailing edges of the gas bubbles, nanosized gas bubbles are elongated along the temperature gradient direction when thermal diffusion is dominated. Micron-sized gas bubbles are either compressed along temperature gradient direction to form lenticular shape bubbles or elongated along temperature gradient direction, depending on the location of the gas bubbles within the fuel pellet. Initial gas bubble radius has no significant effect on the gas bubble migration velocity for both thermal diffusion and vapor transport mechanisms. We notice that the shape change of the gas bubble due to vapor transport mechanism has no significant effect on the migration velocity. Furthermore, the center cavity formation is also captured by our model which is due to the migration and accumulation of lenticular gas bubbles at the center of the fuel pellet. The modeling results compare well with experimental observations and theoretical analysis in the literature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Time Domain Thermoreflectance (TDTR) Studies of Microstructural Characterization of as-Fabricated and/or Irradiated TPBAR Components

Paddock et al. demonstrated for the first-time the measurement of thermal diffusivity from thin metal films using picosecond transient thermoreflectance in 1986. This project attempted to use a similar experimental setup based on a femtosecond time domain thermoreflectance (TDTR) to measure the damage to the crystal lattice of LiAlO 2 from irradiation in the reactor and production of tritium and helium. The TDTR is based on a pump-probe laser configuration where the pump laser is used to heat the sample and the probe laser is used to follow the thermal evolution created by the pump laser. The goal for this project is to measure the differences in thermal diffusivity between LiAlO 2 and the irradiated Li AIO 2 sample in a reactor. Unfortunately, COVID-19 restricted laboratory research time and the availability of researchers capable to conduct TDTR work. In addition, the ultrafast laser (Astrella 35fs laser) required to conduct the work was inoperable making this particulate work impossible to conduct in FY20 and FY21. The purpose of the thermal diffusion measurements with a TDTR setup is to probe the damage and disorder to the crystal lattice of pristine and irradiated samples. Since TDTR was not available for this work, a different approach using Raman and luminescence spectroscopy was used to characterize the crystal lattice damage in LiAlO 2 from irradiation.

07 ISOTOPE AND RADIATION SOURCES↗

Mechanical and Thermophysical Properties of 3D-Printed SiC-FY20

In the Transformational Challenge Reactor (TCR), the fuel blocks consist of an additively-manufactured silicon carbide (SiC) matrix and uranium nitride tristructural isotropic (UN TRISO) fuel particles, which are stacked to form fuel columns. The SiC matrix is manufactured using binderjet 3D printing followed by loading the TRISO fuel particles and the chemical vapor infiltration (CVI) process. Because the fuel matrix is a primary component of the TCR core and its response to mechanical and thermal loads during operation is one of the most influential factors on the integrity of TCR core, testing and evaluation have focused on producing mechanical and thermophysical properties data for the binderjet/CVI SiC. Mechanical and thermophysical properties were measured from various types of specimens printed for two or three orientations, which included equibiaxial flexural failure strength, elastic constants, thermal diffusivity and conductivity, density, and the coefficient of thermal expansion. Flexural failure strength datasets showed similar Weibull distributions regardless of sample variants including different orientations. The mean failure strengths of the 3D-printed SiC variants were in the range of 286–306 MPa, which are 22–27% lower than that of the CVD SiC. Thermophysical test results showed that specific heat and thermal expansion are not sensitive to the build directions of SiC samples, while thermal diffusivity is highly dependent on the build direction and can be correlated to the anisotropic character of the 3D-printed SiC. This report also includes discussions on the uniaxial tensile properties of the as-printed SiC before CVI and on ongoing efforts for irradiation effects studies.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Radiation-Enhanced Anion Transport in Hematite

The influence of radiation-induced (1 MeV energy H+ to ~0.1 dpa at 450°C), non-equilibrium point defect populations on mass transport is studied with an integrated campaign of experimental and theoretical methods. Using epitaxial thin films of hematite with embedded 18O tracer layers and nanoscale atom probe tomography measurements, it is shown that anion self-diffusion is enhanced by at least 2 orders of magnitude under irradiation compared to thermal diffusion alone. Complementary scanning transmission electron microscopy of vacuum annealed specimens, reveals associated microstructural changes in the oxide films, including local phase transformation to Fe3O4 and the development of nanoscale voids from vacancy coalescence. Point defect formation and migration energies were computed from density functional theory and applied within the context of chemical rate theory to analyze contributions from both interstitial and vacancy mechanisms to self-diffusion in thermal and irradiation conditions. Comparisons are made between calculated, literature and newly measured self-diffusion values, revealing good agreement on the magnitude of radiation-enhanced anion diffusion. Further, the model suggests a transition from vacancy to interstitialcy mechanisms at low temperatures and high oxygen activity, consistent with the varied activation energies reported from prior studies.

iron oxides, isotopic tracers, atom probe tomograp↗

High temperature annealing of irradiated nuclear grade graphite

Previous work has shown that the material properties of nuclear grade graphite are substantially affected by the atomic and microstructural changes that occur during neutron-irradiation. The parameters that play a role in these changes are irradiation dose, temperature, graphite composition and the initial microstructure of the graphite. Understanding the details of how these material changes occur and exactly what the changes consists of will enable the prediction of the material property changes as a function of these variables. Other work has shown these atomic level and microstructural changes can be healed or annealed out by raising the irradiated graphite above its irradiation temperature. Here in this work, experiments were carried out to investigate how the properties of irradiated graphite recover when heated. By showing property recovery as a function of annealing temperature or energy, insight is provided into the type of damage that occurred during neutron-irradiation. The data presented here shows recovery of thermal diffusivity, coefficient of thermal expansion, Young's modulus and electrical resistivity between annealing temperatures of 500 °C and 2380 °C. Graphite grades NBG-18, IG-110 and PCEA are considered that were both stressed and unstressed during irradiation.

36 MATERIALS SCIENCE↗

AGC 4 Graphite Specimen Postirradiation Characterization Plan

This characterization plan describes the thermal, physical, and mechanical measurement techniques that will be used to characterize graphite samples being tested in the fourth Advanced Graphite Creep experiment (AGC-4). Instruments, fixtures, and methods are currently in place for both pre and postirradiation material property measurements of bulk density, thermal diffusivity, coefficient of thermal expansion, elastic modulus, and electrical resistivity. Postirradiation testing procedures used to characterize the samples are described and discussed in the plan. Where they exist, American Society for Testing and Materials (ASTM) International testing standards will apply to the tests. Any departure from ASTM International testing standards or the approved laboratory procedures are documented within this characterization plan. Deviations that occur during testing will be documented in data reports.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Time Domain Thermoreflectance and Photodeflection Signatures of He Bubbles in Metals

The mechanical properties of the steel and weldments for different components are affected by the formation of helium bubbles as a result of tritium decay. Therefore, periodic analyses of metals exposed to tritium gas are conducted to determine structural defects and temporal damage from tritium gas decay and He precipitation. Transmission electron microscopy (TEM) and autoradiography are the current analytical methods for the evaluation of metal damage. These methods are functional after several years of damage to the crystal lattice where 3He bubble formation damage can be seen with TEM. New analytical methods that can assess the damage to the crystal lattice early during the exposure to tritium are highly sought to ascertain the effects of material processing and tritium interactions. Further, simple sample preparation, compared to TEM, at a significantly reduced cost is highly desirable. A pump-probe laser technique using a femtosecond laser has been demonstrated to measure the thermal diffusivity of different materials. The time domain thermoreflectance (TDTR) laser setup can provide thermal diffusivity and phonon lifetime, which can be correlated with lattice damage. This advanced nonlinear optical technique will enable measurements of nanostructure damage in the metal before and after tritium exposure within a year. This report discusses current efforts in the design and development of the technique and the application to material characterization.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Compatibility of LaFe13−x−yMnxSiyH1.6 and Eutectic Liquid GaInSn Alloy

The heat transfer rate of magnetocaloric regenerators is a topic of extensive research and the cyclability of these regenerators is critical to the operation of systems with a high coefficient of performance (e.g., potentially >22, significantly higher than typical vapor compression cooling technologies). To enable a high operating frequency that will result in a high specific cooling power, the heat transfer fluid should have high thermal conductivity and lower specific heat, i.e., higher thermal diffusivity. Eutectic metal alloys possess these qualities, such as gallium–indium–tin (Galinstan), whose thermal diffusivity has been found to be approximately an order of magnitude higher than water. For this study, the effects of eutectic liquid Galinstan exposure on the phase stability of LaFe13−x−yMnxSiyH1.6 magnetocaloric powders in an active magnetic regenerator device were investigated. The powders were characterized before and after exposure to Galinstan using X-ray diffraction, in which the phases were determined using the Rietveld refinement technique and X-ray fluorescence. It was found that after Galinstan exposure, hydrogen containing phases were present in the powder, suggesting that the hydrogen was lost from the magnetocaloric phase. The magnetocaloric phase degradation indicates that the powder was incompatible with the Galinstan metal in an environment with moisture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MESOSCALE THERMAL TRANSPORT MEASUREMENTS OF MULTI-PHASE AND POROUS NUCLEAR FUELS USING A SQUARE-WAVE PULSE THERMOREFLECTANCE TECHNIQUE

The safe and efficient operation of nuclear reactors require accurate knowledge of peak temperatures in the fuel assemblies. The temperature profiles are governed by the thermal transport properties of the fuel, namely the thermal conductivities (k) and thermal diffusivities (D). These values can be very difficult to measure as they are known to vary considerably from the measured bulk values of the fresh fuel, and quickly degrade with increasing burnup [1 -3] . Laser-based techniques have been effectively used for non-destructive and non-contact thermal transport measurements of a wide variety of materials, including nuclear materials [4-6] that would otherwise prove too hazardous or difficult to measure otherwise. In this study, a new thermoreflectance technique known as square-pulse transient thermoreflectance (SPTR) is described and used to determine the mesoscale thermal diffusivity of both uranium sesquisilicide (U3Si2) and uranium nitride (UN) phases in a composite fuel with micron level spatial resolution [7]. This technique employs a rapid train of square-wave pulses from an excitation laser to create a periodic heat flux on a gold coated sample surface. Surface adsorption results in transient film temperatures and hence rapid fluctuations in thermoreflectance that can be measured via a detection laser coupled with a digital oscilloscope. The lasers are coaxially focused on the sample surface, allowing for a sample measurement area of a single convolved laser spot size (~2 µm). A sensitivity analysis was conducted to identify key measurement parameters of this technique using reference materials with a range of thermal conductivities comparable to those of both ceramic, composite, and metal nuclear fuel types (1.4 – 27.2 W/m-K). The reference materials were measured using the new technique as well as a spatial-domain thermoreflectance technique (SDTR) previously reported for a comparison [8]. Additionally, measurements of several U3Si2 and UN phase regions of a polished UN/U3Si2 (70/30 vol.%) sample were taken, and the resulting calculated D values are reported, with both techniques showing excellent agreement between samples. This technique was used to scan a multiphase region at 5 micron increments to generate a local diffusivity map, demonstrating the utility of the techniques for measuring thermal transport properties in specimens with precipitates and secondary phases. Furthermore, the technique is currently being applied to measure thermal properties of Fast Flux Test Reactor (FFTR) irradiated metal fuel specimens whose porous microstructure make it very difficult to measure using other techniques. Comparison of the local scale measurements are compared with the pre-irradiated fuel samples to show the degradation of thermal transport in fuels due to pores from fission gas bubbles and other irradiation induced defects.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrothermal Phenomena in Ferroelectrics

Physical properties of lead-zirconate-titanate (PZT) ceramics change according to the initial electric poling process and electrical boundary conditions. This paper reports the electrothermal, piezothermal, and piezoelectric coupling phenomena in ferroelectrics from thermodynamics viewpoints, in particular, thermal property differences between unpoled and poled PZT’s in the poling direction for open circuit and short circuit conditions. We propose a new terminology, “secondary electrothermal” coupling factor kλ, which is analogous to the electromechanical coupling factor k, relating the elastic compliances under short- and open-circuit conditions, in order to explain the fact that the short-circuit condition exhibited the larger thermal diffusivity than the open-circuit condition. On the other hand, the unpoled specimen exhibits the lowest thermal diffusivity. This tutorial paper was authored for providing comprehensive knowledge on equilibrium and time-dependent thermodynamics in ferroelectrics.

Uchino, Kenji (ORCID:0000000316517912)↗

Mechanical characterization of fine-grain dispersion-strengthened tungsten as a plasma facing material

Field-Assisted Sintering Technology (FAST) was used to produce fine-grained, dispersion-strengthened tungsten (W) materials. Investigated materials 4138, 4353, and 4355 composed of 3 wt% ZrC sintered at 1800 °C, 5 wt% ZrC sintered at 1800 °C, and 3 wt% ZrC sintered at 2000 °C, respectively. They were compared against ITER-grade W. A series of mechanical and thermal property testing and microstructure studies were conducted to study them as a potential plasma facing material (PFM) for fusion reactors. Hardness testing showed that manufacturing conditions substantially altered hardness. Material 4355 had an average HV10 value of 497.2 ± 16.8, slightly higher than ITER-grade at 378.5 ± 40.3. However, material 4353 was substantially higher with an HV10 value of 738.9 ± 31.7 over the investigated temperature range. Electron Backscatter Diffraction (EBSD) analysis showed that FAST produced substantially smaller grains than the hot-rolled ITER-grade W material, offering notable control over grain size. Materials 4353 and 4355 had grain sizes of 0.44 ± 0.20 µm and 3.67 ± 0.89 µm, respectively, whereas ITER-grade 27.14 ± 19.76 µm at room temperature. The fine grain structures showed no net coarsening after 1 hr. anneals up to 1800 °C, several hundred degrees above the 1100 – 1500 °C recrystallization range reported for conventional W. Inverse application of the Zener pinning relationship to the measured grain sizes indicates that these two FAST sintering conditions produce markedly different effective dispersoid populations, with effective particle diameters of approximately 90 nm at a peak sintering temperature of 1800 °C and approximately 460 nm at 2000 °C, respectively. This result demonstrates that the FAST thermal condition itself, and not the nominal ZrC content alone, governs the pinning effectiveness of the dispersion. Thermal diffusivity measurements support this finding independently. Materials of identical composition sintered at different temperatures differ by approximately 19% in measured thermal diffusivity with statistically indistinguishable density, while materials of different composition and sintering temperature converge to within approximately 2%. At a representative divertor heat flux of 10 MW/m², the lower thermal conductivity of the fine-grained materials corresponds to approximately 28 to 33 °C per millimeter of armor thickness relative to ITER-grade W, traded against a substantially larger margin to recrystallization-driven degradation. While high temperature tensile testing revealed likely contamination that motivates refinement of the manufacturing process, FAST-produced, fine-grained, dispersion-strengthened W offers process-controlled microstructural stability well above the operating temperatures of conventional W and supports its continued development as a PFM for economically viable commercial fusion power.

Parker, Gabe [ORNL] (ORCID:0000000190394100)↗

The Thermal Response of a Packed Bed Thermal Energy Storage System upon Saturated Steam Injection Using Distributed Temperature Sensing

The effectiveness of a thermal energy storage (TES) system is typically characterized with the help of thermal stratification or temperature gradients along the direction of heat injection, which is typically the flow direction of heat transfer fluid. The steepness of temperature gradients are a direct indicator of the effectiveness or efficiency of the heat storage or dispatch process. The temperature gradient evolution along the packed bed of ceramic particles upon saturated steam injection is presented in this work. Distributed temperature sensing based on optical frequency domain reflectometry was deployed in a packed bed of ceramic particles to capture the thermal front evolution in the axial direction. The physical processes accompanying steam injection in packed beds are complex due to phase change, transitioning two-phase flow, and changes in condensate accumulation. Therefore, the variation of thermal response of the TES system for various steam injection flow rates was experimentally studied using a high-resolution distributed temperature sensing system in a chemically inert alumina particle-packed bed. Distinct zones of different heat transfer modes were observed during the steam injection experiments. A distinct conduction zone, evident from diffuse thermal fronts, was observed at low flow rates, and these thermal gradients became sharper as the flow rate increased. The diffuse thermal fronts in the heat storage media suggest a low exergy efficiency of the TES system, as energy losses started initiating before a significant fraction of the bed was saturated with steam.

25 ENERGY STORAGE↗

Slides for MS&T2022: Carbon-Carbon Composites from 3D Printed Preforms Graphitized by Electric Field Assisted Sintering

Formation of Carbon-Carbon (C-C) composite materials requires putting a carbon fiber preform through a cycle of densification, carbonization, and graphitization. This cycle is then repeated until the desired properties are achieved. The graphitization phase is particularly energy demanding as it involves heating the components to in excess of 2000°C. In traditional furnaces this is also quite time consuming as typical heating rates are low, and the actual heat treatment may be limited by component dimensions, as heat is conducted throughout the part primarily by thermal diffusion. Joule heating by means of Electric Field Assisted Sintering (EFAS) systems enables high heating rates and causes the part to be heated from the inside, which eliminates the thermal diffusion time constraint. In our process, C-C composites are formed by pyrolyzation of 3D-printed carbon fiber preforms, vacuum infiltration of naphthalene based mesophase pitch, and carbonization. The part is then graphitized in the EFAS system. By this method graphitization of the composite matrix was achieved in less than an hour. A part density of greater than 1.6g/cc (up to 1.9g/cc demonstrated) was achieved after only two rounds of infiltration and a single graphitization. Overall the process took less than a week which is significantly faster than traditional methods. Optical microscopy and XRD results are discussed to elucidate the internal porosity and characterize the degree of graphitization. Testing was performed showing the impact on fiber direction to electrical and thermal properties of the final part.

36 MATERIALS SCIENCE↗

U 3 Si 2 and UO 2 composites densified by spark plasma sintering for accident-tolerant fuels

This work reports the synthesis and characterization of the U 3 Si 2 and UO 2 composites sintered by spark plasma sintering (SPS) with controlled microstructures for accident-tolerant fuel application. The U 3 Si 2 and UO 2 composites with different silicide and oxide ratios were synthesized by SPS at temperatures from 1000 to 1300 °C for 5 minutes. The microstructure and phase composition of the SPS densified composite fuels were characterized with scanning electron microscopy, X-ray diffraction (XRD), and energy dispersed spectroscopy (EDS). A systematic study of the thermal and mechanical properties was conducted using microhardness testing and laser flash apparatus, along with oxidation resistance measurements using thermogravimetric analysis (TGA). The results show that the synthesis of composite fuels can be achieved with a 90% theoretical density (TD) at 1000 °C and over 95% TD when sintered at 1300 °C. XRD and EDS results confirmed that the dominant phases in the composites are U 3 Si 2 and UO 2 . Improved physical density generally leads to improved hardness, fracture toughness, thermal diffusivity, and onset temperature during the oxidation process. U 3 Si 2 was found to play a dominant role in determining the mechanical and oxidation properties of the composite fuels, whereas UO 2 had a more important impact on controlling the thermal diffusivity of the composites. The composite with 50 wt% UO 2 sintered at 1300 °C displayed the onset oxidation temperature of 500 °C by dynamic oxidation testing using TGA at a ramp degree of 10 °C/min. The composite also achieved a high fracture toughness of ~3.5 MPa m ½ . Finally, these results highlight the potential of composite fuel forms densified by SPS with simultaneously enhanced fissile element density, fracture toughness, thermal transport properties, and oxidation resistance.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

FY20 Status Report on Photothermal Radiometry Development

This report documents FY20 progress in the development of a benchtop photothermal radiometry (PTR) instrument for the measurement of thermal diffusivity. A PTR system incorporating Off-Axis Parabolic (OAP) mirrors was designed and tested. Additionally, a novel analysis technique that accounts for systematic errors that affect measurement accuracy was implemented. Measurements on samples with a range of thermal diffusivities using the PTR setup along with the new analysis technique resulted in improved accuracy and repeatability. Areas for future development work are set forth.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A model to separate conduction and radiation in high temperature laser flash measurements for semi-transparent materials

Laser flash analysis (LFA) is a widely used technique in the scientific and industrial communities for measuring the thermal diffusivity and conductivity of materials. However, traditional fitting methods based solely on heat conduction do not account for radiation heat transfer in transparent and semi-transparent materials, which becomes significant at high temperatures. In this study, we have developed a coupled radiation-conduction model that considers the optical properties of materials to accurately extract thermal diffusivity from LFA measurements. We conducted LFA measurements on fused silica glass samples of varying thicknesses and within the temperature range of 25 to 1000 °C and fitted the data with the model. Since the coupled model requires optical properties as input parameters, which are often unavailable for new materials, we have also proposed a modified transparent model. Compared to the coupled model, results from the modified transparent model generally overestimate thermal conductivity, but the errors are acceptable in silica glass with small thickness. Here, we also investigated the applicability of the modified transparent model with materials of different optical properties.

14 SOLAR ENERGY↗