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At least 307 records · Page 17

Development of a stoichiometric magnesium potassium phosphate cement (MKPC) for the immobilization of powdered minerals

Ordinary Portland Cement (OPC)-based materials are not systematically adapted for immobilizing industrial hazardous waste, e.g. for aluminium powder or plutonium waste sludge. In such case, Magnesium Potassium Phosphate Cements (MKPC) represent an interesting alternative. }The originality of this research is to develop a formulation of a MKPC paste for hazardous waste immobilization, which incorporates a maximum amount of such waste, preferably in powdered form. To this purpose, a stoichiometric MKPC paste is selected, and its properties are improved by powdered waste addition. }Firstly, the physico-chemical mechanisms generating expansion in stoichiometric MKPC paste are analyzed. Swelling is attributed to a pH gradient in the paste, due to the progressive sedimentation of MgO particles in the fresh mix. }Secondly, over-stoichiometric MgO is replaced by varying amounts of minerals simulating the waste, of different mineralogy and granulometry, in order to achieve sufficient workability and no swelling. An optimal formulation is proposed, which incorporates powdered fly ash at a fine-to-cement mass ratio (F/C) of 1. Its mechanical performance and endogenous dimensional changes are comparable to typical over-stoichiometric pastes, and they stabilize between 7 and 28 days.

36 MATERIALS SCIENCE↗

Comparison of liquid absorption-release of superabsorbent polymers in alkali-activated slag and Portland cement systems: An NMR study combined with additional methods

In this study, {sup 1}H low-field NMR was used to compare the liquid absorption-release behaviour of superabsorbent polymers (SAPs) in Portland cement (PC) paste, NaOH-activated slag (SH-AAS) paste, and water glass-activated slag (WG-AAS) paste. The liquid absorption of SAPs in the PC paste was lower than that in the SH-AAS paste and the WG-AAS paste. The liquid release was also faster, which was mainly due to the higher Ca{sup 2+} concentration in the pore fluid of the PC system. In the AAS system, although the Ca{sup 2+} concentration in the pore fluid was low, the Na{sup +} concentration was much higher than that in the PC system due to the activator. The Ca{sup 2+} in the PC system is an important factor affecting the swelling of SAPs, while in the AAS system, the swelling limitation of SAPs is the result of the combined effects of Ca{sup 2+} and Na{sup +}, with Na{sup +} being dominant.

36 MATERIALS SCIENCE↗

Layer size polydispersity in hydrated montmorillonite creates multiscale porosity networks

The aluminosilicate layers of the swelling clay mineral montmorillonite, and the saturated pores they delineate, control the mechanical properties and the transport of solutes in many natural and engineered environments. However, the structural basis of montmorillonite porosity remains poorly characterized due to the difficulty in visualizing hydrated samples in their native state. Here in this paper, we used cryogenic transmission electron microscopy (cryo-TEM) and cryo electron tomography (cryo-ET) to show that stacking defects within minimally altered, fully hydrated montmorillonite particles define multiscale porosity networks. Variations in layer lateral dimensions over tens to thousands of nanometers cause a range of topological and dynamic defects that generate pervasive curvature and introduce previously uncharacterized solute transport pathways. Observations of long-range rotational order between neighboring layers indicate that the layer-layer interactions that govern clay swelling involve three dimensional orienting forces that operate across nanoscale pores. These direct observations of the hierarchical structure of hydrated montmorillonite pore networks with nanoscale resolution reveal potentially general aspects of colloidal interactions in fluid-saturated clay minerals.

36 MATERIALS SCIENCE↗

Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)

In this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H 2 O 2 and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30%) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30% peroxide concentration pDODTs with M n up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10wt % H 2 O 2 and M n < 100,000 g/mol, including a sample of a fractionated polymer with starting Mn = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. In conclusion, further analysis of these interesting elastomers, available at the 20 g scale, is in progress.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lignin-based jet fuel and its blending effect with conventional jet fuel

Sustainable aviation fuels (SAFs) must demonstrate specific physical and chemical properties as well as material compatibility (i.e., seal swell) to be used as an aviation turbine fuel. Several alternative jet fuels incorporated in ASTM D7566 are comprised mainly of n/iso-alkanes and can only be blended up to 50 vol% due to material compatibility and density issues. Prior work illustrated the ability of cycloalkanes to replace aromatics’s role in material compatibility. Here, we report the first archival documentation of a feedstock and chemical process to yield a product composition able to complement existing SAF ASTM D7566 annexes. A lignin-based jet fuel (LJF) blend components is generated and composed of mostly C7-C18 mono, di, and tri-cycloalkanes. The neat LJF was blended with conventional jet fuel at 10 vol% (LJF blend) to simulate an ASTM “Fast Track” evaluation process. Fuel properties that are critical to engine operability (ATSM D4054 Tier 3 & 4) were either predicted or experimental tested based on the volume availability. All LJF blend’s critical properties fall within the experience range of conventional jet fuel, with o-ring swelling exceeding the typical range of conventional fuels. Here, these results in total support the potential use of this LJF pathway to complement other SAF pathways and achieve 100% drop-in SAF.

09 BIOMASS FUELS↗

Assessment of thermal and radiation induced creep in the dual cooled lead lithium blanket

The creep in recently designed blanket for the fusion nuclear science facility is described by decomposing it into thermal, irradiation and cavity swelling creep. Initial estimates of thermal creep using elastic high temperature rules showed that the recent heat transfer improvements at the first wall (FW) is feasible, and the FW can withstand heat flux of 0.35 MW/m 2 at 3000 hrs without rupture. A viscoplastic model that is based on Norton's power law and relies on Multiphysics coupling of solid mechanics and heat transfer modules is used to capture the inelastic deformation in the blanket. Results showed that the design peak heat flux of 0.25 MW/m 2 produced maximum thermal creep strain of 0.45 % and the relaxation of the thermal stress at the FW. Irradiation creep is prescribed to be proportional to the displacement damage dose and applied stress. The displacements from irradiation creep radially decrease from the FW to the back wall, but the maximum deformation is found at the back wall that is connected to the Helium manifold due to the high stresses at the region. In conclusion, cavity swelling creep is dominant at steady state and combined with radiation creep to produce displacement of about 8 mm at the FW.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Long-term permeability evolution of shale seal rocks with argon and scCO 2

In this work, we conducted a suite of experiments to evaluate the long-term permeability evolution of shale rocks under constant effective stress, before, during, and after interaction with supercritical carbon dioxide (scCO 2 ). To do so, we measured the time-dependent evolution of argon permeabilities for the pre- and post-reacted samples (i.e., before and after long-term interaction with scCO 2 ). In addition, we obtained permeability evolution during long-term interaction with scCO 2 . The samples showed either relatively constant permeabilities or a moderate decrease during pre reaction long-term argon tests. The permeability evolution during long-term CO 2 tests showed continuous increase, continuous decrease, or cycles of increase/decrease in permeability. The long term response of the samples to CO 2 included phenomena such as 20 (i) salt precipitation, (ii) swelling-induced cracks, and (iii) carbonate dissolution. While it is obvious that salt precipitation and swelling-induced cracks decrease and increase the permeability, respectively, the sample response to carbonate dissolution proved to be more complex and may increase or decrease the permeability. The permeability evolution during post-reaction long-term argon injection is also affected by the contribution of each of these three phenomena, during long-term interaction with CO 2 . We observe increase, decrease, and constant permeability evolution during post-reaction argon tests. Our experiments reveal that the initial permeability of the samples plays a significant role on the long-term permeability response of shales in the presence argon and scCO 2 fluids. This study shows, when shales are hydraulically fractured with CO 2 , their initial permeability has a more significant role than their permeability evolution over time.

58 GEOSCIENCES↗

Microstructural evolution of Mo-UO 2 cermets under high temperature hydrogen environments

Ceramic-metallic (cermet) materials show promise for use in nuclear thermal propulsion applications due to attractive thermophysical properties including high temperature stability and high thermal conductivity. In this work, molybdenum-uranium dioxide (Mo-UO 2 ) cermet fuel elements were fabricated by means of spark plasma sintering (SPS) and were subsequently exposed to hydrogen at high temperatures (2500 K). Mo-UO 2 samples pre- and post-exposure were characterized by means of optical microscopy, scanning electron microscopy, and X-ray diffraction (XRD). Microscopy analyses of the as-produced material displayed microscopic cracking on the interior of the spherical UO 2 fuel particles but confirmed that the fuel particles were fully encapsulated in the Mo matrix. The results further showed mass loss, macroscopic swelling, and cracking in the cermet samples which occurred during high temperature hydrogen testing. Nanoscale swelling was evidenced by XRD in the Mo matrix and UO 2 fuel structure due to the incorporation of defects and accompanied microstrain.

36 MATERIALS SCIENCE↗

Phase-field simulations of intergranular fission gas bubble behavior in U 3 Si 2 nuclear fuel

U 3 Si 2 is a potential accident-tolerant fuel that shows promise due to its high thermal conductivity and higher uranium density relative to UO 2 . However, its swelling and fission gas release behavior in light water reactor (LWR) conditions is relatively unknown. To provide mechanistic insight and determine parameters for engineering-scale fuel performance modeling of pellet-form U 3 Si 2 , phase-field simulations of the growth, interconnection, and venting of intergranular fission gas bubbles were performed. The fractional coverage of the grain boundary and the fraction of bubble area that is vented were calculated as a function of time. From the simulation data, the fractional grain boundary coverage at saturation, an important parameter needed in engineering-scale modeling of swelling and fission gas release, was determined. Multiple simulations were run to determine the uncertainty in the calculated value. Finally, the effect of model assumptions and input parameters that are not well known was evaluated. Simulation results are compared to related theoretical and computational work. Based on the simulation results, a value of 0.60 for the fractional grain boundary coverage at saturation is recommended for U 3 Si 2 fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Postirradiation examination from separate effects irradiation testing of uranium nitride kernels and coated particles

An overview of postirradiation examination results for uranium nitride kernels and uranium nitride coated particles irradiated in the High Flux Isotope Reactor are presented. This is the first postirradiation examination of the MiniFuel irradiation vehicle that was recently developed to rapidly accumulate burnup during separate effects irradiation testing. In general, the burnup and fuel temperatures measured postirradiation were consistent with the design calculations. The burnup measured by mass spectrometry ranged from 5.9 to 10 MWd/kgU and was achieved after only 68 effective full-power days of irradiation. The dilatometric evaluation of passive silicon carbide thermometry indicated that the fuel was irradiated at temperatures ranging from 410 to 460 °C. Because the irradiation temperatures and burnup were low, the UN kernels showed minimal fission gas release that was within the range of the expected recoil (athermal) release. While it is possible to measure fuel swelling using x-ray computed tomography, the observed swelling was too small to quantify in this case. Extensive microstructural characterization of the irradiated fuel was performed in this study, and no significant irradiation induced changes were observed.

36 MATERIALS SCIENCE↗

Thermal properties of U-Mo alloys irradiated under high fission power density

A variety of physical and thermal property measurements made on irradiated U-Mo alloy monolithic fuel samples with a Zr diffusion barrier and clad in Al alloy 6061 are reported. These properties form the basis for additional investigations in thermal behavior of U-Mo fuel under high performance research reactor irradiation conditions. Measurements were performed on samples harvested from fuel plates irradiated under high fission power density and surface heat flux and complement previous measurements on samples subjected to moderate fission power density and surface heat flux. Specific heat capacity of irradiated monolithic U-Mo increases with increasing temperature and fission density, but carries large uncertainties associated with thickness measurements used to determine the mass fraction of the layer constituents for extraction of the U-Mo specific heat capacity, specifically the very thin and nonuniform Zr diffusion barrier. Density of irradiated monolithic U-Mo decreases with increasing fission density resulting from fission gas swelling and porosity formation. Thermal diffusivity of irradiated monolithic U-Mo increased with increasing temperature and decreased with increasing fission density. Thermal conductivity of irradiated monolithic U-Mo increased with increasing temperature, and in general, appeared to decrease and become less sensitive to temperature with increasing fission density. Thermal conductivity measurements compared to a semi-empirical model agreed within ±30%. It is suspected that the main driver in deviation between model calculations and measurements is the fission gas swelling determination, which does not account for fission power density or irradiation temperature.

uranium (U), molybdenum, nuclear fuel, thermal con↗

Effects of sample bias on adhesion of magnetron sputtered Cr coatings on SiC

Swelling of SiC at 300 C due to in-service neutron irradiation causes tensile residual stresses in coatings which are expected to adversely affect the performance of coated SiC composite fuel cladding for light water reactors. Matching the coating swelling with the substrate, a solution common for thermal expansion, is not practical in the case of neutron irradiation. Biasing samples during magnetron sputtering deposition induces compressive residual stress which may counteract this. In this study, chromium coatings were deposited on SiC by DC magnetron sputtering with no external heating at bias voltages of –50V, –75V, and –100V. The effects of the bias voltage on morphology, residual stress, microstrain, texture, and adhesion are shown. The low deposition temperature resulted in the coating microstructure evolution following an energetic particle bombardment dominated trend. Additionally, at the two lower bias voltages knock-on implantation dominated increasing the residual stress and microstrain while at the highest bias voltage, thermal spike migration allowed for defect relaxation. When the knock-on induced compressive residual stress exceeded 0.8 GPa microcrack formation in the SiC substrate decreased coating adhesion. While no microcracks formed at the lowest bias voltage, insufficient atomic mobility during coating growth lead to voids forming in the coating. A balance is needed to form void-free coatings that have high compressive residual stress.

36 MATERIALS SCIENCE↗

High radiation tolerance of an ultrastrong nanostructured NiCoCr alloy with stable dispersed nanooxides and fine grain structure

The present paper reports the irradiation behavior of nanostructured NiCoCr medium entropy alloy enhanced by Y-Hf-O nanooxides and fine grains produced by powder metallurgy. Ion beam irradiation to a peak dose of 130 dpa at 580°C produced neither detectable void swelling nor irradiation-induced hardening, in contrast to significant void swelling and property degradation of single phase NiCoCr concentrated solid-solution alloy under the similar irradiation condition. The dispersed nanooxides and high density of grain boundaries act as defect sinks that effectively annihilate irradiation-induced interstitials and vacancies. Furthermore, high-density nanooxides maintain their crystalline structures and stabilize the grain boundaries during irradiation.

36 MATERIALS SCIENCE↗

Characterization of radiation damage in 3D printed SiC

The SiC fuel matrix for advanced gas-cooled high temperature reactors as part of the Transformational Challenge Reactor program serves as the fuel particle container structure, a barrier to fission gas release, and a heat transfer medium. Its performance is particularly important because the fuel matrix must demonstrate good structural stability and thermal behaviors. An additive manufacturing methodology combining a binder jet 3D printing process with chemical vapor infiltration (CVI) for the production of SiC was recently developed. In this study, post irradiation examination by transmission electron microscopy shows that defect accumulation within the printed particles is very similar to other forms of high-purity SiC. However, damage accumulation was not directly observed in the CVI matrix because black spot damage and dislocation loops are difficult to image within the nanoscale highly faulted CVI matrix and because interstitial defects may rapidly annihilate at the stacking faults. Therefore, electron energy loss spectroscopy (EELS) analysis was used to analyze defect swelling in both the printed particles and the CVI matrix. The EELS analysis helped reveal that the radiation-induced swelling in the CVI matrix is similar to that of the printed SiC particles. This work shows that 3D printed SiC has behavior that is comparable to SiC processed by other means and that 3D printing could serve as a suitable processing technique for high-purity SiC for nuclear applications.

36 MATERIALS SCIENCE↗

Properties and microstructure evolution of silicon nitride and zirconium nitride following Ni ion irradiation

We report that silicon nitride and zirconium nitride have been proposed as potential materials for multiple nuclear applications (inert matrix fuels, accident tolerant fuels, space nuclear power, fusion reactor design), yet knowledge on their behavior under irradiation remains limited. Ion irradiations were performed using 15 MeV Ni 5+ ions on Si 3 N 4 and ZrN samples, with midrange doses (around 3 µm) from 1 to 50 dpa and temperatures from 300 to 700°C. Volumetric lattice swelling was determined by grazing incidence X-ray diffraction, defect production and evolution were tracked using Transmission Electron Microscopy, and nanoindentation was performed to quantify the ceramics’ mechanical properties evolution. The results from these irradiation studies on nitride ceramics help fill the current gap present in the literature. Behavior consistent with past work on irradiated Si 3 N 4 was observed with respect to mechanical properties and defect formation up to 15 dpa and 500°C. Failure of the grain boundary sintering aid in Si 3 N 4 was observed above these conditions. Different behavior was observed in both nitrides at 50 dpa and 700°C, where lattice swelling increased past potential saturation values. Unreported cavity formation was witnessed in both materials under all irradiation conditions, with stable number density and slight size increase above 15 dpa. The mechanism for the cavity formation remains to be determined.

36 MATERIALS SCIENCE↗

Computational determination of a primary diffusion mode in γ U-10Mo under irradiation

Low enriched uranium (< 20 % 235 U)-molybdenum (U-Mo) monolithic fuel is the primary candidate for high performance research and test reactors, and is in the process of being qualified to replace highly enriched uranium (≥ 20 % 23 5U) fuel. As part of the qualification process, it is critical to understand and predict the behavior of fission gas bubbles under irradiation, which affects fuel swelling and fuel failure. Mechanistic fuel models are being developed that can both reproduce the existing experimental data for fuel swelling, and be further applied to irradiation conditions beyond the experimental scope. Diffusion of species under irradiation conditions is an important parameter in the mechanistic fuel models; however, no temperature-relevant experimental diffusion data exists. In the present work, radiation-enhanced diffusion coefficients of U, Mo, and Xe in λU-10wt.%Mo were calculated in the temperature range between 300 K and 1400 K via rate-theory models and molecular dynamics simulations with an embedded-atom method interatomic potential for the U-Mo-Xe system. Accordingly, total diffusion coefficients under relevant irradiation conditions are determined using previously obtained intrinsic thermal diffusion and radiation-driven diffusion coefficients, as well as the newly calculated radiation-enhanced diffusion coefficients presented herein. Radiation-enhanced diffusion of U and Mo was dominant in the intermediate temperature range, whereas radiation-enhanced diffusion of Xe did not significantly contribute to total diffusion of Xe at the relevant fission rate densities. Radiation-enhanced diffusion of Xe became faster than both intrinsic thermal diffusion and radiation-driven diffusion at a fission rate density of 5 x 10 22 fissions/m 3 /s, which is higher than the typical fission rate density range in research reactors. The temperature regime that radiation-enhanced diffusion of each element dominated was dependent on the fission rate density. Finally, the total diffusion coefficients of U, Mo, and Xe, updated in this work, will be utilized as parameters in the mechanistic fuel models to help predict the behavior of fission gas bubbles under irradiation more accurately.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Porosity evolution in proton irradiated microfine-grained POCO graphite

This work investigated the porosity evolution of POCO ZXF-5Q graphite that has been irradiated by 340 kW, 120 GeV protons inside NT02 target system in Fermilab's NuMI beamline. This POCO graphite has undergone direct bulk dimensional swelling at low dose irradiation and its local microstructural change is still not well-understood during this process. In this work, the (sub-) micrometre scale porosity from six locations across proton beam fluence and temperature gradients have been studied using focused ion beam-scanning electron microscopy (FIB-SEM) tomography. Here, a deep learning-based tomographic image segmentation technique has been established and implemented for porosity segmentation and quantification. It has been found that there is a decrease in the total volumetric percentage of the porosity at proton beam centre (~ 8 – 8.4 vol.%), by comparing to un-irradiated POCO (~ 12 – 13vol.%) and to beam 2σ and 5σ radii (~ 12vol.%). This decrease in porosity volume percentage was found to be caused by the reduction in pores with volumes > 0.1 μm 3 induced by material bulk dimensional swelling at proton beam centre area. The porosity reduction in relation to dimensional change and irradiation creep was discussed among with other contributing factors, and further investigations through well-controlled irradiation experiment are still needed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Post-irradiation examination of AGR-3/4 TRISO fuel compacts using three-dimensional X-ray computed tomography

The AGR-3/4 irradiation tests combined the third and fourth planned irradiation experiments in the US Department of Energy’s Advanced Gas Reactor (AGR) testing campaign of tri-structural isotropic (TRISO) fuel compacts. In this article, we present post-irradiation examination (PIE) using X-ray computed tomography (XCT) of two unirradiated and two irradiated compacts from the AGR-3/4 irradiation tests. The irradiated compacts studied (compact 7–1 and compact 12–4) represent the upper and lower limit of burnup within the AGR-3/4 irradiation experiment. This article presents a detailed quantitative analysis on the post-irradiation structure of TRISO fuel compacts. Various quantitative parameters including shape, size, and packing of kernels, and their spatial distribution, were utilized to gain insights into the structural changes caused by irradiation. The equivalent diameter and sphericity were found to increase and decrease, respectively, in irradiated compact 7–1 due to its higher burnup. Nearest neighbor distance between fuel kernels decreased after irradiation, suggesting irradiation-induced shrinkage of graphitic matrix. Furthermore, each compact in AGR-3/4 irradiation tests contained 20 designed-to-fail (DTF) fuel particles that were meant to act as a source of fission product release to the experiment test train. Furthermore, in the present work, all DTF fuel particles in the four compacts studied were identified, and it was found that they exhibited larger kernel swelling in compact 12–4 and smaller kernel swelling in compact 7–1, compared to the driver particles.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗