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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
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 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 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 OSTI2017

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopic ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10 –14 cm 2 /s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Relative Size of the Polymer and Nanoparticle Controls Polymer Diffusion in All-Polymer Nanocomposites

The dynamics of polymers in an all-polymer nanocomposite that are composed of soft cross-linked polystyrene nanoparticles and linear polystyrene have been examined. In this article, we describe how the relative size of the nanoparticle to that of the polymer chain and its rigidity impact the linear polymer chain diffusion. The results of the in situ neutron reflectivity experiments show three distinct regimes in the linear polymer diffusion. The results indicate that the inclusion of soft nanoparticles increases the amount of topological constraints and confinement effects for low matrix molecular weight polymer. At modest molecular weights where the size of the nanoparticle and polymer chain are similar, the soft nanoparticles neither inhibit nor enhance the linear polymer diffusion, while at the highest polymer matrix molecular weight, the linear polymer diffusion increases due to an increase in the constraint release mechanism by the soft nanoparticles. Thermal analysis demonstrates that the nanoparticles do not increase the free volume of the system nor do they behave as a plasticizing agent. These results are interpreted to indicate that the competition between a topological barrier effect and enhancing constraint release defines the behavior of a given all-polymer nanocomposite.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Impact of Microporous Layer Roughness on Gas-Diffusion-Electrode-Based Polymer Electrolyte Membrane Fuel Cell Performance

This study explores the role of the gas diffusion media microporous layer (MPL) surface structure on the electrochemical properties of gas-diffusion-electrode (GDE)-based membrane electrode assemblies (MEAs). It has been shown that a thin ionomer layer on top of the GDE and hot pressing is needed to create good contact between the catalyst layer and the membrane. In this study, gas diffusion media with different MPL surface roughness were applied to fabricate GDE-based MEAs to understand how MPL roughness impacts the amount of ionomer overlayer required for maximum performance. Electron microscopy was employed to investigate MPL/catalyst layer and catalyst layer/membrane interfaces. In-situ performance testing was used to assess the impact of MPL roughness and ionomer overlayer on catalyst utilization and air polarization performance. We find that a smoother MPL surface required a thinner ionomer overlayer than gas diffusion media (GDM) with a rougher MPL surface to achieve a performance comparable to direct-coated catalyst-coated-membrane MEAs.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH) 3 ) Crystallization from Alkaline Aqueous Solution

Understanding molecular-scale factors governing the precipitation of aluminum hydroxides, such as gibbsite, under alkaline conditions is important for the formation of laterite deposits, as well as aluminum processing. However, mechanisms enabling tetrahedral aluminate ions to assemble into octahedral sites of the gibbsite lattice remain unclear. Formation of oligomeric complexes has been hypothesized as a critical intermediate step. Here, we report a study of gibbsite solubility in highly alkaline solutions using deuterium substitution to probe equilibrium and kinetic factors that could affect oligomeric intermediate formation, including the reactivity and the diffusivity of aluminate ions. When substituting sodium hydroxide with sodium deuteroxide, solution analysis shows a nearly 40% and 50% increase in gibbsite solubility in 2.4 and 3.3 mol·kg –1 total sodium solutions, respectively. Raman spectroscopy indicated that monomeric aluminate ions are the predominant species in solution irrespective of deuteration. However, both 27 Al and 23 Na nuclear magnetic resonance (NMR) spectroscopy revealed significant differences in chemical shifts in deuterated solutions, and analysis of 1 H, 23 Na, and 27 Al diffusion coefficients with pulsed-field gradient, stimulated echo NMR spectroscopy shows a decrease in ion diffusivity with increasing total deuterium in solution, consistent with the notion of increasing strength in the hydrogen/deuterium bonding network. In conclusion, because the relative change in 1 H diffusion coefficients are commensurate with the difference in apparent solubility constants, there is evidence for an oligomeric intermediate whose steady-state concentration is maintained by the collision frequency of aluminate ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Spatially Mapping the CO 2 Alkaline Sorbent Diffuse Microenvironment Using Operando Raman Spectroscopy

When designing a chemical process, the local balance of transport and kinetics, collectively referred to as the diffuse microenvironment, plays a critical role in performance but is difficult to directly observe. This work demonstrates a method of two-dimensional spatial chemical mapping of the diffuse microenvironment in the context of alkali metal hydroxide direct air capture of carbon dioxide using a custom operando gas-absorption flow cell along with confocal Raman spectroscopy. Notably, we observe the concentration boundary layer near the gas–liquid interface and elucidate the interplay of carbonate and bicarbonate ions within it while inferring local hydroxide depletion through continuum modeling. These first of their kind observations provide a technique to compare the performance of direct air capture solvents based on diffuse microenvironment dynamics while also providing metrics important for air contactor design such as boundary layer thickness. Overall, this work showcases a new experimental platform to study interfacial diffuse microenvironments in and outside of the field of direct air capture of carbon dioxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Large Exciton Diffusion Coefficients in Two Dimensional Covalent Organic Frameworks with Different Domain Sizes Revealed by Ultrafast Exciton Dynamics

Large singlet exciton diffusion lengths are a hallmark of high performance in organic-based devices such as photovoltaics, chemical sensors, and photodetectors. In this study, exciton dynamics of a two-dimensional covalent organic framework, 2D COF-S, is investigated using ultrafast spectroscopic techniques. After photoexcitation, the COF-S exciton decays via three pathways: (1) excimer formation (4 +/- 2 ps), (2) excimer relaxation (160 +/- 40 ps), and (3) excimer decay (>3 ns). Excitation fluence-dependent transient absorption studies suggest that COF-5 has a relatively large diffusion coefficient (0.08 cm(2)/s). Furthermore, exciton-exciton annihilation processes are characterized as a function of COF-S crystallite domain size in four different samples, which reveal domain-size-dependent exciton diffusion kinetics. These results reveal that exciton diffusion in COF-S is constrained by its crystalline domain size. These insights indicate the outstanding promise of delocalized excitonic processes available in 2D COFs, which motivate their continued design and implementation into optoelectronic devices.

Flanders, Nathan C.↗
DOE OSTI2019

Real Time Monitoring of the Dynamic Intracluster Diffusion of Single Gold Atoms into Silver Nanoclusters

Alloying metal materials with heterometal atoms is an efficient way to diversify the function of materials, but in-depth understanding of the dynamic heterometallic diffusion inside the alloying materials is rather limited, especially at the atomic level. Here, we report the real-time monitoring of the dynamic diffusion process of a single gold (Au) atom into an atomically precise silver nanocluster (Ag NC), Ag 25 (MHA) 18 (MHA = 6-mercaptohexanoic acid), by using in situ UV–vis absorption spectroscopy in combination with mass and tandem mass spectrometry. We found that the Au heteroatom first replaces the Ag atom at the surface Ag 2 (MHA) 3 motifs of Ag 25 (MHA) 18 . After that, the Au atom diffuses into the surface layer of the icosahedral Ag 13 kernel and finally occupies the center of the alloy NCs to form the thermodynamically stable [email protected] 24 (MHA) 18 product. Density functional theory (DFT) calculations reveal that the key thermodynamic driving force is the preference of the Au heteroatom for the central site of alloy NCs. Furthermore, the real-time monitoring approach developed in this study could also be extended to other metal alloy systems to reveal the reaction dynamics of intracluster diffusion of heteroatoms, as well as the formation mechanisms of metal alloy nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Role of Solvation on Diffusion of Ions in Diblock Copolymers: Understanding the Molecular Weight Effect through Modeling

Salt-doped diblock copolymers with microphase-separated domains of both an ion conductive and a mechanically strong polymer have been extensively studied due to their potential in transport applications. Several unusual or counterintuitive trends regarding their transport properties have been observed experimentally, such as increasing ion conduction as a function of molecular weight. A vital feature of these systems is the strong solvation of ions in the conducting microphase due to its higher dielectric constant. Herein, we perform molecular dynamics simulations using a coarse-grained model that includes a 1/r 4 potential form to generically represent ion solvation, allowing us to reproduce experimentally observed trends and explore their molecular underpinnings. We find that increasing ion concentration can increase or decrease ion diffusion, depending on solvation strength. We further show that the trend of increasing diffusion with molecular weight becomes more dramatic as ions are solvated in one polymer block more strongly or as the ion-ion interactions get stronger. In contrast to expectations, the interfacial width or the overlap of ions with the nonconductive polymer block do not adequately explain this phenomenon; instead, local ion agglomeration best explains reduced diffusion. Interfacial sharpening, controlled by the Flory chi parameter and molecular weight, tends to allow ions to spread more uniformly, and this increases their diffusion.

36 MATERIALS SCIENCE↗