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At least 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Rapid solidification of high-conductivity copper alloys

The main objective was to develop improved copper alloys of high strength and high thermal and electric conductivity. Chill block melt spinning was used to produce binary alloys of Cu-Cr and Cu-Zr, and ternary alloys of Cu-Cr-Ag. By quenching from the liquid state, up to 5 atomic percent of Cr and Zr were retained in metastable extended solid solution during the rapid solidification process. Eutectic solidification was avoided and the full strengthening benefits of the large volume fraction of precipitates were realized by subsequent aging treatment. The very low solid solubility of Cr and Zr in Cu result in a high conductivity Cu matrix strengthened by second phase precipitates. Tensile properties on as-cast and aged ribbons were measured at room and elevated temperatures. Precipitate coarsening of Cr in Cu was studied by changes in electrical resistance during aging. X-ray diffraction was used to measure the lattice parameter and the degree of supersaturation of the matrix. The microstructures were characterized by optical and electron microscopy.

Bloom, Theodore Atlas↗
DOE OSTI2025

Synthesis of a series of rare-earth-based multi-anion chalcogenide iodides RE 3 Si 2 Se x S 8− x I (RE = La, Ce, Pr, and Nd) using the flux-assisted boron–chalcogen mixture method

Single crystals and polycrystalline powders of rare earth mixed chalcogenide iodides La 3 Si 2 Se 1.21 S 6.79 I, Ce 3 Si 2 Se 1.39 S 6.61 I, Pr 3 Si 2 Se 1.22 S 6.78 I, and Nd 3 Si 2 Se 1.18 S 6.82 I were prepared using the reactive flux-assisted boron–chalcogen mixture (BCM) method at 850 °C. All compounds crystallized in the monoclinic crystal system, space group C2/c (space group number 15). The series adopts the La 3 Si 2 O 8 Cl structure type, containing isolated SiQ 4 tetrahedra connected by REQ 8 (RE = La, Ce, Pr and Nd) polyhedra; this arrangement creates tunnels that are filled by I atoms. The partial substitution of S by Se was carried out to modulate the optical properties. Phase pure samples and uniform solid solutions were obtained for all compositions as determined using powder X-ray diffraction patterns. Polycrystalline powders were used for physical property measurements, including magnetic susceptibility and UV-Vis diffuse reflectance. The solid-state UV-Vis data for the polycrystalline La 3 Si 2 Se 1.21 S 6.79 I, Ce 3 Si 2 Se 1.39 S 6.61 I, and Pr 3 Si 2 Se 1.22 S 6.78 I samples revealed band gaps of E g = 2.5(1), 2.2(1), and 2.3(1) eV, typical of semiconductors. Magnetic measurements indicated that Ce 3 Si 2 Se 1.39 S 6.61 I and Nd 3 Si 2 Se 1.18 S 6.82 I exhibit paramagnetic behavior with slightly negative Weiss constants θ = −25 and −38. The photoluminescence spectrum of Ce 3 Si 2 Se 1.39 S 6.61 I exhibits a broad emission band around ∼493 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Si-Ge-metal ternary phase diagram calculations

Solution crystal growth and doping conditions of Si-Ge alloys used for high-temperature thermoelectric generation are determined here. Liquid-phase epitaxy (LPE) has been successfully employed recently to obtain single-crystalline homogeneous layers of Si-Ge solid solutions from a liquid metal solvent. Knowledge of Si-Ge-metallic solvent ternary phase diagrams is essential for further single-crystal growth development. Consequently, a thermodynamic equilibrium model was used to calculate the phase diagrams of the Si-Ge-M systems, including solid solubilities, where M is Al, Ga, In, Sn, Pb, Sb, or Bi. Good agreement between calculated liquidus and solidus data and experimental DTA and microprobe results was obtained. The results are used to compare the suitability of the different systems for crystal growth (by LPE-type process).

Fleurial, J. P.↗
DOE OSTI2015

Phase Stability for the Pd-Si System. First-Principles, Experiments, and Solution-Based Modeling

Relative stabilities of the compounds in the binary Pd-Si system were assessed using first-principles calculations and experimental methods. Calculations of lattice parameters and enthalpy of formation indicate that Pd 5 Si-μ, Pd 9 Si 2 -α, Pd 3 Si-β, Pd 2 Si-γ, and PdSi-δ are the stable phases at 0 K (-273 °C). X-ray diffraction analyses (XRD) and electron probe microanalysis (EPMA) of the as-solidified and heat-treated samples support the computational findings, except that the PdSi-δ phase was not observed at low temperature. Considering both experimental data and first-principles results, the compounds Pd 5 Si-μ, Pd 9 Si 2 -α, Pd 3 Si-β, and Pd 2 Si-γ are treated as stable phases down to 0 K (-273 °C), while the PdSi-δ is treated as being stable over a limited range, exhibiting a lower bound. Using these findings, a comprehensive solution-based thermodynamic model is formulated for the Pd-Si system, permitting phase diagram calculation. Moreover, the liquid phase is described using a three-species association model and other phases are treated as solid solutions, where a random substitutional model is adopted for Pd-fcc and Si-dia, and a two-sublattice model is employed for Pd 5 Si-μ, Pd 9 Si 2 -α, Pd 3 Si-β, Pd 2 Si-γ, and PdSi-δ. Model parameters are fitted using available experimental data and first-principles data, and the resulting phase diagram is reported over the full range of compositions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Carbonation and Sulfidation of Mg- and Ni-Containing Solutions: Implications for Carbon Mineralization and Critical Element Recovery

Carbonation of alkaline earth metals ( e.g. , magnesium (Mg)) and sulfidation of nickel (Ni) are promising methods to achieve concurrent carbon mineralization and selective Ni recovery. However, the coexistence of alkaline earth metals and Ni from silicate ores or mining wastewater complicates the carbonation and sulfidation owing to cation coprecipitation. To better understand simultaneous metal carbonation and Ni-sulfide formation, we used Mg- and Ni-containing solutions and systematically investigated the Mg and Ni coprecipitates’ phase transformation during sequential/concurrent carbonation and sulfidation. During a single carbonation process, hydromagnesite dehydrated and formed magnesite over time. Nickel bicarbonate formed and became a Mg–Ni carbonate solid solution because of their similar ionic radii. During a single sulfidation process, the pH did not affect Ni-sulfide formation, but it controlled Mg behavior. Specifically, at pH 9.6, brucite formed, while at pH 7.8, Mg 2+ remained in the solution. For the sequential carbonation–sulfidation process, Ni-carbonate formed during carbonation converted to Ni-sulfide because of the low Ni-sulfide K sp . For the sulfidation–carbonation process, Ni-sulfide remained the same even after carbonation and Mg-carbonate precipitates. For the concurrent carbonation and sulfidation process, Mg-carbonate and Ni-sulfide formed simultaneously. Finally, this study develops a scientific foundation of carbonation and sulfidation processes, benefiting coupled CO 2 storage and sulfide-enabled resource recovery.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Ab-initio Cu alloy design for high-gradient accelerating structures

Operation of normal conducting accelerator structures at high accelerating gradients is beneficial for many accelerator applications in basic science, industry, medicine, and National Security. RF breakdown is the major factor that limits the achievable accelerating gradients. Previous experiments on copper (Cu) have demonstrated that RF breakdown probability can be significantly decreased by hardening the material and alloying Cu with solutes such as silver (Ag). In this paper, we propose a figure-of-merit (FOM) that characterizes the ability of Cu alloys to withstand high-gradients. The FOM represents a trade-off between hardening through solid solution strengthening and the additional thermal stress induced by incremental RF pulse heating resulting from changes in electronic properties induced by alloying. We performed high-throughput ab initio calculations and computed the FOM for a large number of binary Cu alloys. Several promising candidate alloys for high-gradient accelerating structures were identified, such as CuAg, CuCd, CuHg, CuAu, CuIn, and CuMg. CuAg alloys have previously exhibited low RF breakdown rates in experiments. The results provide guidance for selecting alloys for the future high-gradient normal conducting accelerating structures operating at very high gradients.

36 MATERIALS SCIENCE↗
DOE OSTI2020

The lattice parameter – composition relationship of the body centered cubic uranium-niobium alloys

In this paper, in-situ time-of-flight neutron diffraction experiments were performed on uranium-niobium alloy with 6 wt% Nb to study the lattice parameter-composition relationship for the body centered cubic (bcc) alloys. Based on lattice-parameter measurements of Nb-supersaturated γs phase over the range of 450 – 790 °C, an improved Vegard's-type relationship was established for determination of Nb concentrations at elevated temperatures. Neutron diffraction data were also collected as a function of aging time over the 450 - 600 °C range when γs phase decomposed isothermally into the mixture of orthorhombic α-U and Nb-rich bcc phase, as well as at room-temperature on the alloys aged ex-situ at 500 °C up to five years. From these measurements, the average Nb concentrations in the bcc phase were determined based on the Rietveld refinements of weight fraction and mass conservation relations (lever rule). Over the 15at% – 78at% range of Nb concentrations that correspond to different experimental aging times, the lattice parameters at constant temperatures exhibit a nonlinear S-shaped variation with Nb concentration, and the associated excess volumes of mixing can be described by a subregular solution model of the Redlich–Kister type of polynomial. Over the full range of composition the S-shaped deviation from Vegard's law can be modeled using a combination of an elastic continuum model and a perturbation to the radii of the solute atoms in the solvent, suggesting that electronic interactions between solute and solvent atoms could play an important role in the compositional dependence of lattice parameter for the γ-phase U-Nb alloys. While Vegard's law is a straightforward and reasonably good approximation for the bcc solid solutions in the U-Nb system, the Nb concentrations determined from the weight fraction refinements of diffraction data provide internally consistent, mass-conserving estimates of solute redistribution for the monotectoid reaction.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Engineering Multi-scale B2 Precipitation in a Heterogeneous FCC Based Microstructure to Enhance the Mechanical Properties of a Al0.5Co1.5CrFeNi1.5 High Entropy Alloy

While ordered L12 or gamma prime precipitates in face centered cubic (FCC) based microstructures have been extensively used for strengthening Nickel or Cobalt base superalloys, and more recently in high entropy alloys (HEAs) or complex concentrated alloys (CCAs), the possibility of exploiting ordered B2 precipitates in FCC-based systems has been relatively less investigated. The present study shows the propensity of developing a heterogeneous microstructure, consisting of two different distributions of FCC grain sizes, and two different size scales of B2 precipitates, within an FCC-based Al0.5Co1.5CrFeNi1.5 HEA/CCA. This alloy composition has been designed using solution thermodynamics-based modeling such that it has a high phase fraction and solvus temperature of the B2 phase. The resulting heterogenous microstructure exhibited an approximately 400% increase in yield strength with respect to the single-phase FCC solid solution condition of the same alloy while maintaining very good tensile ductility ~20 %.

Dasari, Sriswaroop↗
DOE OSTI2024

Systematic discovery of new nano-scale metastable intermetallic eutectic phases in laser rapid solidified Aluminum-Germanium alloy

Laser surface remelting of as-cast Al-Ge eutectic alloy is shown to produce ultrafine lamellar eutectic morphology with interlamellar spacing refined up to ∼60 nm and composed of FCC Al solid solution and unusual Al x Ge y intermetallic phases that do not form during near-equilibrium solidification. The microstructures are characterized and analyzed using a combination of selected area electron diffraction, high-resolution scanning transmission electron microscopy, energy dispersive X-ray spectroscopy to obtain high-resolution elemental maps, and atomistic modeling using density functional theory followed by atomic-scale image simulation. Depending on the local solidification conditions, the crystallography of the Al x Ge y intermetallic phases in the eutectic microstructure is either monoclinic (C 2/c) or monoclinic (P 2 1 ), with high densities of defects in both cases. This is in sharp contrast to the as-cast alloys that showed nominally pure Al and Ge phases with significant solute partitioning and equilibrium FCC and diamond cubic crystal structures, respectively. Corresponding kinetic phase diagrams are proposed to interpret the evolution of nano-lamellar eutectic morphologies with equilibrium Al and metastable Al x Ge y phases, and to explain increased solid solubility in the Al phases manifested by precipitation of ultrafine clusters of Ge. Furthermore, the reasons for the formation of these metastable eutectics under laser rapid solidification are discussed from the perspective of the competitive growth criterion.

Al-Ge eutectic↗
NASA NTRS2004

Semiconductor Crystal Growth in Static and Rotating Magnetic fields

Magnetic fields have been applied during the growth of bulk semiconductor crystals to control the convective flow behavior of the melt. A static magnetic field established Lorentz forces which tend to reduce the convective intensity in the melt. At sufficiently high magnetic field strengths, a boundary layer is established ahead of the solid-liquid interface where mass transport is dominated by diffusion. This can have a significant effect on segregation behavior and can eliminate striations in grown crystals resulting from convective instabilities. Experiments on dilute (Ge:Ga) and solid solution (Ge-Si) semiconductor systems show a transition from a completely mixed convective state to a diffusion-controlled state between 0 and 5 Tesla. In HgCdTe, radial segregation approached the diffusion limited regime and the curvature of the solid-liquid interface was reduced by a factor of 3 during growth in magnetic fields in excess of 0.5 Tesla. Convection can also be controlled during growth at reduced gravitational levels. However, the direction of the residual steady-state acceleration vector can compromise this effect if it cannot be controlled. A magnetic field in reduced gravity can suppress disturbances caused by residual transverse accelerations and by random non-steady accelerations. Indeed, a joint program between NASA and the NHMFL resulted in the construction of a prototype spaceflight magnet for crystal growth applications. An alternative to the suppression of convection by static magnetic fields and reduced gravity is the imposition of controlled steady flow generated by rotating magnetic fields (RMF)'s. The potential benefits of an RMF include homogenization of the melt temperature and concentration distribution, and control of the solid-liquid interface shape. Adjusting the strength and frequency of the applied magnetic field allows tailoring of the resultant flow field. A limitation of RMF's is that they introduce deleterious instabilities above a critical magnetic field value. Growth conditions in which static magnetic fields rotational magnetic fields, and reduced gravitational levels can have a beneficial role will be described.

Volz, Martin↗
NASA NTRS1995

Preparation and Thermoelectric Properties of IR(sub x)Co(sub 1-x)Sb(sub 2) Alloys

The preparation and characterization of the binary arsenopyrite compounds CoSb2 and IrSb2 and IrxCo1-xSb2 alloys is reported. Single crystals of CoSb2 were grown by the vertical gradient freeze technique from solution rich in antimony. Polycrystalline samples of IrSb2 and IrxCo1-xSb2 alloys were prepared by hot-pressing of prereacted elemental powders. Samples were investigated by X-ray diffractometry, microprobe analysis and density measurements. It was found that a range of solid solution exist in the system IrxCo1-xSb2 for 0.1<x<0.8. Samples were also characterized by high temperature electrical resistivity, Seebeck coefficient and thermal conductivity measurements. All materials have p-type conductivity and are semiconductors. A band gap of about 0.98 eV was calculated for IrSb2. Preliminary measurements of the thermoelectric properties of these materials showed that their potential for thermoelectric applications is limited.

Thermoelectric Properties↗
DOE OSTI2019

Self-regulating surface chemistry for more robust highly durable solid oxide fuel cell cathodes

Solid oxide fuel cells (SOFCs) offer direct conversion of hydrogen or hydrocarbon fuels to electricity with high energy conversion efficiency (>50%). Impurities that block active reaction sites on the electrode surface can markedly degrade the oxygen exchange rate, and lead to a reduction in long term durability of such devices. In this work, we propose to develop electrodes that are tolerant to Si which is one of the most prevalent cathode impurities. This work draws on our recent method to fully recover oxygen exchange kinetics following Si induced aging of ceria containing cathodes. We take advantage of elements, which over time during SOFC operation, are released by exsolution to actively trap (i.e. getter) Si impurities in a self-regulating chemical fashion. The objective is to evaluate impurity scavenging by added reactive elements that are intentionally exsolved from the SOFC cathode electrode during operation. In this study, we chose to focus our effort on one cathode material: Pr doped ceria (PCO). This material has the advantage of not containing strontium, an element known to segregate to the surface of the well-known perovkite based cathodes materials, thereby degrading their performance. As for the Si getter, we choose to focus on lanthanum, which is added in PCO in solid solution.

03 NATURAL GAS↗
NASA NTRS1994

Silica-merrihueite/roedderite-bearing chondrules and clasts in ordinary chondrites: New occurrences and possible origin

Merrihueite (K,Na)2(Fe,Mg)5Si12O30 (na less than 0.5, fe greater than 0.5, where na = Na/(Na + K), fe = Fe/(Fe + Mg) in atomic ratio) is a rare mineral described only in several chondrules and irregularly-shaped fragments in the Mezo-Madaras L3 chondrite (Dodd et al., 1965; Wood and Holmberg, 1994). Roedderite (Na,K)2(Mg,Fe)5Si12O30 (na greater than 0.5, fe less than 0.5) has been found only in enstatite chondrites and in the reduced, subchondritic silicate inclusions in IAB irons (Fuchs, 1966; Rambaldi et al., 1984; Olsen, 1967). We described silica-roedderite-bearing clasts in L/LL3.5 ALHA77011 and LL3.7 ALHA77278, a silica-roedderite-bearing chondrule in L3 Mezo-Madaras, and a silica-merrihueite-bearing chondrule in L/LL3.5 ALHA77115. The findings of merrihueite and roedderite in ALHA77011, ALHA77115, ALHA77278 and Mezo-Madaras fill the compositional gap betweeen previously described roedderite in enstatite chondrites and silicate inclusions in IAB irons and merrihueite in Mezo-Madaras, suggesting that there is a complete solid solution of roedderite and merrihueite in meteorites. We infer that the silica- and merrihueite/roedderite-bearing chondrules and clasts experienced a complex formational history including: (a) fractional condensation in the solar nebular that produced Si-rich and Al-poor precursors, (b) melting of fractionated nebular solids resulting in the formation of silica-pyroxene chondrules, (c) in some cases, fragmentation in the nebula or on a parent body, (d) reaction of silica with alkali-rich gas that formed merrihueite/roedderite on a parent body, (e) formation of fayalitic olivine and feerosilite-rich pyroxene due to reaction of silica with oxidized Fe on a parent body, and (f) minor thermal metamorphism, possibly generated by impacts.

Krot, Alexander N.↗
NASA NTRS1986

Heat capacity, enthalpy of mixing, and thermal conductivity of Hg(1-x)Cd(x)Te pseudobinary melts

Heat capacity and enthalpy of mixing of Hg(1-x)Cd(x)Te pseudobinary melts were calculated assuming an associated solution model for the liquid phase. The thermal conductivity of the pseudobinary melts for x = 0, 0.05, 0.1, and 0.2 was then calculated from the heat capacity values and the experimental values of thermal diffusivity and density for these melts. The thermal conductivity for the pseudobinary solid solution is also discussed.

Su, Ching-Hua↗
DOE OSTI2019

Theoretical constraints on the effects of added cations on clumped, oxygen, and carbon isotope signatures of dissolved inorganic carbon species and minerals

Carbonate clumped isotope thermometry has emerged as a useful tool for the reconstruction of precipitation temperatures for minerals from surface and subsurface environments. Few studies have examined the impact of variable solution chemistry and mineral chemistry on clumping. Therefore, we used theoretical calculations to predict the impact of the presence of cations in a solution on the equilibrium clumped, oxygen ( 18 O/ 16 O and 17 O/ 16 O, θ and κ), and carbon isotopic ( 13 C/ 12 C) compositions of dissolved inorganic carbon species (DIC), and the impact of cation type and stoichiometry on carbonate mineral composition within the calcite-dolomite-magnesite solid solution. We examined the impact of the presence of Mg 2+ , K + , Na + , and Ca 2+ on equilibrium Δ 63 values of carbonate ion groups in DIC species and the composite DIC pool using the B3LYP/6-311++G(2d, 2p) model. We developed new cluster models for dolomite, magnesite, and high-magnesium calcite (Ca 0.83 Mg 0.17 )CO 3 and (Ca 0.67 Mg 0.33 )CO 3 ) and examined the effect of extraneous cations substituted into the crystal lattices of the carbonate minerals. We find the presence of added cations in the DIC pool increases equilibrium Δ 63 values slightly, depending upon their solution concentrations. For the cations examined, the identity of the added cation does not seem to be significant. Cumulative effects may account for small-scale differences (<0.02‰) but are unlikely to be substantial unless cation/anion association and ion pairing are important in the solution that carbonates are growing from. We also find that at a given temperature, stoichiometric dolomite and magnesite Δ 63 values are similar to calcite and less than aragonite. Surprisingly, substitution of an extraneous cation into a carbonate mineral (e.g., as observed in high-magnesium calcite) generally lowered Δ 63 by a slight amount, which suggests that high and low-magnesian calcites may have resolvable differences in equilibrium clumped isotope signatures, potentially providing an explanation for observations of different Δ 47 values in slow-growing minerals. These results imply the cationic composition of the solution may be a minor factor that should be considered for crystals that rapidly grow from solution, and that cationic substitution into carbonate mineral lattices will influence equilibrium compositions of carbonate minerals. Solution chemistry effects on mineral composition are likely to be observed at high growth rates. In contrast, equilibrium isotope compositions arising from cationic substitution in minerals, such as differences between high-Mg calcite and low-Mg calcite, or high-Mg calcite and dolomite, would likely be observed at slow growth rates.

58 GEOSCIENCES↗
DOE OSTI2020

Progress in Understanding the Origins of Excellent Corrosion Resistance in Metallic Alloys: From Binary Polycrystalline Alloys to Metallic Glasses and High Entropy Alloys

Some of the factors responsible for good corrosion resistance of select polycrystalline and emerging alloys in chloride solutions are discussed with a goal of providing some perspectives on the current status and future directions. Traditional metallic glass alloys, single phase high entropy alloys (HEAs), early metallic glasses, and high entropy metallic glasses are all emerging corrosion-resistant alloys (CRAs) that utilize traditional strategies for improved corrosion resistance as well as take advantage of some other novel beneficial attributes. These materials enjoy many degrees of freedom as far as choice of both composition and structure, providing great flexibility in the pursuit of superior corrosion resistance. The new materials depart from classical solvent-solute type polycrystalline binary or ternary alloys. Thus, such emerging materials provide significant opportunities to achieve even greater improvements in corrosion resistance in harsh environments. Several examples of the unique corrosion properties of selected materials in the context of modern theories of corrosion are discussed herein. Discussion is restricted to solid-solution binary or ternary polycrystalline alloys, several metallic glass alloys, and single phase HEAs. A common feature of many CRAs is that composition and microstructure often affect both passivity and resistance to localized corrosion that can be divided into initiation, stabilization, and propagation stages. Enormous complexities in protective oxide structures and chemistries and the large number of combinatorial possibilities in newer materials such as HEAs preclude trial-and-error approaches and perhaps even combinatorial experimental design. Computational materials methodologies will be required in the search for new corrosion-resistant alloys in these material classes. The search must consider the best scientific insights available regarding how major and minor alloy additions, as well as various microstructural attributes, contribute to corrosion mitigation. Additional scientific insights, as they emerge, will enable choices beyond the reliance on high concentrations of alloying elements that are known to affect passivity breakdown and pit stabilization. A challenge is to connect the “basic attributes” of an alloy with its properties. The strength of this connection will likely require new scientific principles enabling deep multiphysics insights in order to link feature(s) such as composition and metallurgical phases to the desired corrosion properties. Application of data informatics will likely also play a role given the plethora of variables that are important in corrosion and the difficulty in assessing all relationships. Here, the opportunity exists to accelerate the design of emerging materials for high corrosion resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Report on the effect of dopants on FLASH sintering of enhanced UO 2

Large grained UO 2 can be achieved through the addition of dopants such as, Cr, Al, Nb and Mg. The enhanced microstructure can enable slower fission gas release that reduces pressure build up in the fuel rods and better mechanical properties that can alter the pellet cracking behavior and, therefore, limit accident prone pellet cladding loading. UO 2 fuel is sintered through conventional sintering methods that require high temperatures and long sintering times. Field assisted sintering techniques like flash sintering use current and voltage to enable sintering of ceramics at low temperatures and short times. Flash sintering has been demonstrated for sintering UO 2 to high densities. In this work, this technique has been applied to Cr-doped UO 2 to assess the feasibility of the technique for grain enhancement. Doped UO 2 samples below and above the solubility limit of Cr into UO 2 have been assessed. The results show that grain enhancement was not possible in either case and this was attributed to the low temperatures and sintering times that make flash sintering attractive. For the Cr-doped sample below or near the solubility of Cr, it is postulated that the temperatures were not high enough to actually dissolve it into solution in the UO 2 lattice. For the Cr-doped sample above the solubility limit of Cr, secondary phases were identified via SEM and EDS, as expected. Follow up work should be carried out to assess if flash sintering can produce grain enlargement for UO 2 feedstocks with dopants already in solid solution such as UO 2 produced via sol-gel or modified direct denitration method.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

An Assessment of the Safeguards Implications of Particle and Alloy Formation in MSRs

Molten salt reactors (MSRs) present unique challenges for applying safeguards measures and differ significantly from traditional nuclear reactors. Although the special fissionable materials within MSRs principally exist as dissolved species within the fuel salt, key actinides of interest may also be converted to solid phases including alloys and precipitated oxides via chemical and electrochemical reactions. These solid-phase components will complicate the nuclear material accounting and control (NMAC) approaches that have, so far, primarily targeted measurements of the liquid salt itself. For example, most of the proposed monitoring and characterization methods for MSRs are reliant on homogeneity of the salt and the ability to maintain accountable materials in solution. Solid deposits and particulates could invalidate the assumption of homogeneity and necessitate the use of new models and measurement tools to permit a full accounting of all nuclear material in an MSR. To address this, the likelihood of solids formation in MSRs, estimated the rate at which these solids could form, and assessed the monitoring tools that are available to account for the presence of these materials were examined. Specifically, three solid forming mechanisms were investigated, including (1) the accumulation of actinides within the MSR’s structural materials due to alloying, (2) the accumulation of actinides within noble metal fission product particulates, and (3) the generation of actinide oxides from interactions with salt impurities. These modeling-informed studies were completed with considerations to both fluoride- and chloride-containing salts. It was determined that, although measurable amounts of special fissionable material were expected to alloy with the structural elements and fission products, the predicted amounts were below levels considered as significant quantities (SQ) by the International Atomic Energy Agency (IAEA). However, it was determined that sufficiently large oxygen concentrations could potentially lead to significant quantities of special fissionable material being converted to solid oxide phases. As such, a comparative study of technologies that are commercially available to assist in monitoring and accountancy of this material was presented. Policy implications, design recommendations, and suggestions for follow-on experimental work were also presented to further assist reactor vendors in designing and controlling the fuel salt chemistry to address potential safeguards considerations.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗