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At least 1,243 records · Page 69
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Roles of Vacancy/Interstitial Diffusion and Segregation in the Microchemistry at Grain Boundaries of Irradiated Fe-Cr-Ni alloys

A detailed analysis of the diffusion fluxes near and at grain boundaries of irradiated Fe–Cr–Ni alloys, induced by preferential atom-vacancy and atom-interstitial coupling, is presented. The diffusion flux equations were based on the Perks model formulated through the linear theory of the thermodynamics of irreversible processes. The preferential atom-vacancy coupling was described by the mobility model, whereas the preferential atom-interstitial coupling was described by the interstitial binding model. The composition dependence of the thermodynamic factor was modeled using the CALPHAD approach. The calculated fluxes up to 10 dpa suggested the dominant diffusion mechanism for chromium and iron is via vacancy, while that for nickel can swing from the vacancy to the interstitial dominant mechanism. The diffusion flux in the vicinity of a grain boundary was found to be greatly modified by the segregation induced by irradiation, leading to the oscillatory behavior of alloy compositions in this region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Revisiting the diffusion mechanism of helium in UO 2 : A DFT+ U study

The understanding of migration properties of helium atoms after their generation through α-decay of actinides in spent nuclear fuels is important for the safety of nuclear fuel storage and disposal. The diffusion of helium in UO 2 is revisited by using the DFT+U simulation methodology employing the “U-ramping” method to address the issue of metastable energy states. A novel diffusion mechanism by helium interstitials, the “asymmetric hop” mechanism, is reported and compared to other diffusion mechanisms including an oxygen vacancy mediated mechanism and available experimental diffusion data. We show that the new mechanism is the dominant one over a wide temperature range.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Atomistic and cluster dynamics modeling of fission gas (Xe) diffusivity in TRISO fuel kernels

TRISO fuel particles are candidates for use in next generation reactors including gas reactors, fluoride salt-cooled high temperature reactors, and micro-reactors. The UCO fuel kernel consists of a uranium dioxide (UO) and uranium carbide mixture. The addition of UC helps suppress the formation of carbon monoxide gas, which led to failures during initial TRISO development. The addition of uranium carbide alters the chemistry of the UO kernel, which is known to influence performance parameters such as fission gas diffusivity, although the impact has not been quantified and no models exist that take the change in chemistry into account. Therefore, better understanding and more accurate models of the impact of chemistry on fuel performance are of high priority. In this paper, a first-principles density functional theory (DFT) and empirical potential based multi-scale study has been carried out to model the diffusivity of fission gas xenon (Xe) in UCO TRISO fuel kernels. The focus is on the UO component in the UCO fuel kernels, as that represents the largest volume fraction of the fuel kernels. The study relies on DFT and empirical potential calculations to determine Xe and point defect properties, which are then used in thermodynamic and kinetic models to predict diffusion for intrinsic conditions. In addition, the information is utilized in cluster dynamics simulations using the Centipede code to estimate the impact of irradiation on defect transport. Additionally, the presence of UC or UC in the UCO fuel kernels is shown to have a substantial impact on the UO non-stoichiometry by inducing oxygen vacancies and driving UO sub-stoichiometric, which causes much slower Xe diffusion in UCO compared to light water reactor UO fuel. The application of this model in fuel performance simulations using the Bison code is also demonstrated.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Diffusion in undoped and Cr-doped amorphous UO 2

UO 2 fuel pellets are often doped with chromium oxide to obtain favourable properties such as higher density, improved thermal stability, large grain sizes, improved pellet-clad interaction margins, and increased fission gas retention during transients. Chromium has a low solubility limit in UO 2 , with past experimental work reporting solubility limits ranging between 0.004 to 0.06 wt.% Cr. Due to its low solubility, segregation of Cr ions to the grain boundary may occur. Further, the complexity of these boundaries may be high as observed in other ceramics resulting in disordered or amorphous regions along the boundary, affecting a range of material and operational properties of the fuel pellet. To assess these disordered regions, in this work we study amorphous undoped and Cr doped UO 2 systems (containing 10–50 at.% Cr 3+ ) that have been modelled using classical molecular dynamics methods incorporating Cr 3+ into the well-used CRG potential library. Diffusion coefficients, pre-exponential factors, and activation energies for diffusion were computed for oxygen ions, assessing the impact of structure and extrinsic species on migration. Oxygen diffusion was observed to be much faster in the undoped amorphous system compared to its crystalline counterpart. Oxygen diffusion in doped systems decreased with increasing Cr concentration, highlighting the importance of additives to retain fission products and other migratory species.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Simulations of self- and Xe diffusivity in uranium mononitride including chemistry and irradiation effects

A combination of density functional theory and empirical potential atomic scale simulations have been used to determine a model for defect stability and mobility in uranium mononitride (UN), as a function of temperature (T) and N 2 partial pressure (p N 2 ). Using the model, predictions of hypo-stoichiometry under U-rich conditions compare favorably to CALPHAD calculations using the TAF-ID database. Furthermore, our predictions of U and N self-diffusivity are in good agreement with experiments carried out as a function of T at specific partial pressures under thermal equilibrium. The validated atomic scale data have then been implemented within a cluster dynamics method to simulate irradiation-enhanced defect concentrations. All defects and clusters studied have significantly enhanced concentrations, with respect to thermal equilibrium, as T is lowered. The irradiation-enhanced Xe diffusivity is compared to post-irradiation annealing and in-pile experiments. In conclusion, the contributions of various defects and clusters to non-stoichiometry, self-diffusivity, and Xe diffusivity are discussed.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Radiation induced athermal diffusivity in uranium mononitride

Uranium mononitride (UN) is one of the ceramic nuclear fuel alternatives to oxide fuel considered for light water reactors and advanced reactor designs. Properties like self- and fission gas diffusivity need to be better understood, given that they influence key fuel performance phenomena such as fission gas swelling and release. In particular, the radiation induced athermal (D 3 ) diffusivity remains challenging to accurately predict and has only been sparsely characterized in UN, despite its importance as it likely governs diffusion at the low temperatures this high-thermal-conductivity fuel form may operate. Molecular Dynamics simulations are used to estimate the mean square displacement induced by a primary knock-on atom (PKA) with a given kinetic energy. These results are combined with the PKA energy distributions obtained from binary collision approximation calculations to obtain the displacement due to a particular fission fragment. Finally, this is combined with experimental fission fragment yields to determine the displacement due to an average fission event and, thus, express the athermal diffusivity as a function of the fission rate density. These results are in excellent agreement with available experimental data. In conclusion, a particular importance is given to the understanding and the quantification of the variability of these results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Grain boundary self-diffusion and point defect interactions in α -U via molecular dynamics

Though metallic U-Zr fuel has been used in nuclear reactors since the 1960s, many of its fundamental and thermodynamic properties are still unknown. The a-U phase, which has a highly anisotropic crystal structure and physical properties, is present in U-Zr fuel. The character and behavior of a-U grain boundaries will strongly impact fuel thermophysical performance under irradiation. Here, we study the interaction of point defects with grain boundaries, diffusion along grain boundaries, and the predicted diffusional creep behavior of a-U via molecular dynamics. We calculate the segregation energy of vacancies and interstitials to grain boundaries and quantify the biased sink strength of the grain boundaries, and observe that this sink strength is not strongly dependent on the grain boundary orientation. We also find that grain boundary diffusivity is strongly dependent on the grain boundary energy and grain boundary orientation. The presence of point defects within the grain boundary can induce diffusion in grain boundaries with low formation energies and can enhance diffusion in high-energy grain boundaries. We also find that diffusional creep of a-U at prototypical metallic fuel operation conditions is extremely high and could help explain observed metallic fuel swelling behaviors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Modeling Ni redistribution in the hydrogen electrode of solid oxide cells through Ni(OH) 2 diffusion and Ni-YSZ wettability change

Ni redistribution in the hydrogen electrodes of solid oxide cells is an important degradation mechanism. Its driving force is still under debate. This work focuses on the interplay between Ni(OH) 2 diffusion and Ni-YSZ wettability change. With a Ni(OH) 2 diffusion model developed in our previous work, we further employ three models for the Ni-YSZ contact angle to quantify the Ni-YSZ wettability change. The microstructure evolutions in a reconstructed Ni-YSZ electrode are simulated under selected experimental operating conditions. It is shown that the phenomenological model can capture the driving force of Ni spreading/detachment on YSZ surface and the Ni migration reported in experiments can be qualitatively reproduced through the competition between Ni(OH) 2 diffusion and Ni-YSZ wettability change. It is also found that the initial microstructure of the active layer and the microstructure characteristics in the support layer can strongly affect the distribution of steam partial pressure and overpotential, hence the Ni redistribution, in the active layer, which may explain the inconsistencies in experiments. Further, our results show that there are two missing pieces in current theory of Ni redistribution: a mechanism of fast Ni diffusion under humid atmosphere and the physical reason behind the Ni spreading/detachment.

25 ENERGY STORAGE↗
DOE OSTI2020

Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy

Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at -20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (~30 nm in diameter) inside a ceria grain is reduced to the C-type CeO 1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO 2 , Ce 0.94 Sm 0.06 O 1.97 , Ce 0.89 Sm 0.11 O 1.945 , and Ce 0.8 Sm 0.2 O 1.9 , respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT) calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Influence of Sulfide Nanoparticles on Dissolved Mercury and Zinc Quantification by Diffusive Gradient in Thin-Film Passive Samplers

Diffusive gradient in thin-film (DGT) passive samplers are frequently used to monitor the concentrations of metals such as mercury and zinc in sediments and other aquatic environments. The application of these samplers generally presumes that they quantify only the dissolved fraction and not particle-bound metal species that are too large to migrate into the sampler. However, metals associated with very small nanoparticles (smaller than the pore size of DGT samplers) can be abundant in certain environments, yet the implications of these nanoparticles for DGT measurements are unclear. The objective of this study was to determine how the performance of the DGT sampler is affected by the presence of nanoparticulate species of Hg and Zn. DGT samplers were exposed to solutions containing known amounts of dissolved Hg(II) and nanoparticulate HgS (or dissolved Zn(II) and nanoparticulate ZnS). The amounts of Hg and Zn accumulated onto the DGT samplers were quantified over hours to days, and the rates of diffusion of the dissolved metal (i.e., the effective diffusion coefficient D) into the sampler’s diffusion layer were calculated and compared for solutions containing varying concentrations of nanoparticles. The results suggested that the nanoparticles deposited on the surface of the samplers might have acted as sorbents, slowing the migration of the dissolved species into the samplers. The consequence was that the DGT sampler data underestimated the dissolved metal concentration in the solution. In addition, X-ray absorption spectroscopy was employed to determine the speciation of the Hg accumulated on the sampler binding layer, and the results indicated that HgS nanoparticles did not appear to directly contribute to the DGT measurement. Overall, our findings suggest that the deployment of DGT samplers in settings where nanoparticles are relevant (e.g., sediments) may result in DGT data that incorrectly estimated the dissolved metal concentrations. Models for metal uptake into the sampler may need to be reconsidered.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Excited-State Diffusion Monte Carlo Calculations: A Simple and Efficient Two-Determinant Ansatz

We perform excited-state variational Monte Carlo and diffusion Monte Carlo calculations using a simple and efficient wave function ansatz. This ansatz follows the recent variation-after-response formalism, accurately approximating a configuration interaction singles wave function as a sum of only two nonorthogonal Slater determinants and further including important orbital relaxation. The ansatz is used to perform diffusion Monte Carlo calculations with large augmented basis sets, comparing to benchmarks from near-exact quantum chemical methods. Here, the significance of orbital optimization in excited-state diffusion Monte Carlo is demonstrated, and the excited-state optimization procedure is discussed in detail. Diffuse excited states in water and formaldehyde are studied, in addition to the formaldimine and benzonitrile molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Diffusivity of Carbon Dioxide in Aqueous Solutions under Geologic Carbon Sequestration Conditions

Accurate assessment of the long-term security of geologic carbon sequestration requires knowledge of the mobility of carbon dioxide in brines under pressure and temperature conditions that prevail in subsurface aquifers. In this paper, we report Raman spectroscopic measurements of the rate of CO 2 diffusion in water and brines as a function of pressure, salinity, and concentration of CO 2 . In pure water at 50 ± 2 °C and 90 ± 2 bar, we find the diffusion coefficient, D, to be (3.08 ± 0.03) × 10 –9 m 2 /s, a value that is consistent with a recent microfluidic study but lower than earlier PVT measurements. Under reservoir conditions, salinity affects the mobility of CO 2 significantly and D decreased by 45% for a 4 M solution of NaCl. We find significant differences of diffusivity of CO 2 in brines (0–4 M NaCl), in both the absolute values and the trend compared to the Stokes–Einstein prediction under our experimental conditions. Finally, we observe that D decreases significantly at the high CO 2 concentrations expected in subsurface aquifers (~15% reduction at 0.55 mol/kg of CO 2 ) and provides an empirical correction to the commonly reported D values that assume a tracer concentration dependence on diffusivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Extremely Slow Diffusion of Gold Nanoparticles under Confinement in Mesoporous Silica

Here, we report an X-ray photon correlation spectroscopy (XPCS) study of the mobility of colloidal gold nanoparticles with a diameter of approximately 4 nm in glycerol under confinement within the channels of SBA-15 mesoporous silica with pore diameters of approximately 6 and 12 nm. The XPCS correlation functions result from an effective heterodyne signal due to the mixing of the coherent scattering from the nanoparticles and the mesoporous silica. Over the range of wave vectors and hence length scales probed, the nanoparticle dynamics are well described by one-dimensional diffusion. The nanoparticle diffusivity varies with temperature in a manner expected based on the temperature-dependent viscosity of glycerol; however, the magnitudes of the diffusion coefficients are several orders of magnitude smaller than those of the nanoparticles in bulk glycerol. We consider mechanisms that might contribute to this reduction in diffusivity including enhancement in hydrodynamic drag under confinement, effects of nanoparticle adsorption to the pore walls, and slowing structural dynamics in glycerol due to the combination of the nanometer-scale confinement and the presence of the nanoparticles.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modeling of Diffusivity for 2D Vacancy Nanopits and Comparison with 2D Adatom Nanoislands on Metal(100) Surfaces Including Analysis for Ag(100)

Diffusion coefficients, D N , for 2D vacancy nanopits are compared with those for 2D homoepitaxial adatom nanoislands on metal(100) surfaces, focusing on the variation of DN with size, N. Here, N is measured in missing atoms for pits and adatoms for islands. Analysis of D N is based on kinetic Monte Carlo simulations of a tailored stochastic lattice-gas model, where pit and island diffusion are mediated by periphery diffusion, i.e., by edge atom hopping. Precise determination of D N versus N for typical parameters reveals a cyclical variation with an overall decrease in magnitude for increasing moderate O(10 2 ) ≤ N ≤ O(10 3 ). Monotonic decay, D N ~ N -β , is found for N ≥ O(10 2 ) with effective exponents, β = β eff , for both pits and islands, both well below the macroscopic value of βmacro = 3/2. D N values for vacancy pits are significantly lower (higher) than for adatom islands for moderate N in the case of low (high) kink rounding barrier. However, D N values for pits and islands slowly merge, and β eff → 3/2 for sufficiently large N. The latter feature is expected from continuum Langevin formulations appropriate for large sizes. Finally, we compare predictions from our model incorporating appropriate energetic parameters for Ag(100) with different sets of experimental data for diffusivity at 300 K, including assessment of β eff , for experimentally observed sizes N from ~100 to ~1000.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Monovalent versus Divalent Cation Diffusion in Thiospinel Ti2S4

Diffusion coefficients (D) for both Li+ and Mg2+ in Ti2S4 were measured using the galvanic intermittent titration technique (GITT) as a function of both ion concentration (x) and temperature. During discharge at 60 degrees C, D-Li descends gradually from 2 X 10(-8) cm(2)/s at x(Li) approximate to 0 to 2 X 10(-9) cm(2)/s at x(Li) approximate to 1.9. In contrast, D-Mg decreases sharply from 2 X 10(-8) to 1 x 10(-12) cm(2)/s by x(Mg) approximate to 0.8. This kinetic factor limits the maximum practical discharge capacity of MgxTi2S4. The difference in behavior vis a vis Li+ implies that either increasing Mg2+ occupation of the tetrahedral site at x(Mg) > 0.6 and/or interactions between diffusing cations play a larger role in mediating the diffusion of divalent compared to monovalent cations. Diffusion activation energies (E-a) extracted from the temperature-dependent data revealed that E-a,E-Mg (540 +/- 80 meV) is about twice that of E-a,E-Li (260 +/- 50 meV), explaining the poorer electrochemical performance of MgxTi2S4 at room temperature.

Bonnick, Patrick J.↗
DOE OSTI2024

Molecular Dynamics Study of the Effect of Grafting Density on Ion Diffusivity in a MARTINI Coarse-Grained Strong Polyelectrolyte Brush

Because surface-grafted polyelectrolyte brushes (PEBs) are responsive to external stimuli, such as electric fields and ionic strength, PEBs are attractive for applications ranging from drug delivery to separation technologies. Essential to PEB utilization is understanding how critical parameters like grafting density (σ) impact the PEB structure and the dynamics of the PEB and counterions. To study the effect of σ on PEB and the counterion structure and dynamics, we fine-tune a coarse-grained model that retains the chemical specificity of a strong polyelectrolyte, poly[(2-(methacryloyloxy)ethyl) trimethylammonium chloride] (PMETAC), using the MARTINI force field. Using “salt-free” conditions where the counterion concentration balances the charge on the brush, we build coarse-grained (CG) molecular dynamics simulations for MARTINI PMETAC brushes (N = 150 monomers; M W = 31.2 kg/mol) at experimentally relevant values of σ = 0.05, 0.10, 0.20, and 0.40 chains/nm 2 . Using 5 μs simulations, we investigate the effects of grafting density on the PEB structure, ion dissociation dynamics, polymer mobility, and counterion diffusivity. Results show that competition between electrostatic interactions, steric hindrance, and polymer mobility controls counterion diffusivity. Finally, the interplay of these factors leads to diffusivity that depends non-monotonically on σ, with counterion diffusivity peaking at an intermediate σ = 0.10 chains/nm 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2015

The role of nanoparticle rigidity on the diffusion of linear polystyrene in a polymer nanocomposite

The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanoparticle rigidity or softness on the impact of the presence of that nanoparticle on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of 10 nm soft nanoparticles in a polymer matrix (R g ~ 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transition temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Furthermore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.

36 MATERIALS SCIENCE↗