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At least 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Enhanced gas adsorption on graphitic substrates via defects and local curvature: A density functional theory study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone–Wales defects to show the largest enhancement with respect to pristine graphene (~20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO 2 and CH 4 are similar, although CO 2 binding is generally stronger by ~4 to 5 kJ mol –1 . Furthermore, the differential between the adsorption of CO 2 and CH 4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH 4 /CO 2 flow separation and gas-selective sensors.

03 NATURAL GAS↗
DOE OSTI2021

Long-Term Structural and Chemical Stability of Carbon Electrodes in Vanadium Redox Flow Battery

Predicting the performance decay in carbon electrodes is critical to maximizing the longevity of redox flow battery (RFB) systems. This study investigates the effect of long-term cycling (over 8000 cycles) on the structural and chemical evolution of carbon electrodes. We find that the microstructural aspects such as graphitic stacking order and interlayer spacing along with overall morphological construct remains largely unchanged even after the prolonged cycling process. Conversely, significant changes in surface chemistry such as evolution of functional groups and point defects are evident from our combined multimodal spectroscopic and computational analysis. The XPS and FTIR analysis reveals chemical absorption of chloride counter anions at point defects within graphitic surface. Additionally, our results suggest that vanadium cation plays an important role in counter anion-carbon surface interaction and subsequently the surface chemistry evolutions. Our findings provide insights about surface chemical evolution that is critical for predicting electrode performance and longevity of RFB.

Modachur Sivakumar, Bhuvaneswari↗
DOE OSTI2018

Spin density stabilization of local distortions induced by a monovacancy in δ -Pu

Density functional theory calculations elucidate crystallographic and electronic structural responses of the fcc delta phase of plutonium (δ-Pu) to point defects. Discussed are responses that vary from a defect exhibiting a local structural instability common in fcc metals to an unusual defect structure that mimics properties similar to the monoclinic α phase. In the prior case, the existence of a self-vacancy when ionic relaxation is allowed induces in the fcc lattice a local tetragonal instability in nearest-neighbor atoms, slight electronic charge increase, and a spin-density decrease. However, in the latter case, after ionic relaxation, the defect is not recognizable as the structure of a vacant site common to many simple fcc metals, but is a complex extended defect involving neighboring atoms to collectively exhibit loss of lattice symmetry through formation of short Pu-Pu bonds and associated narrow bands at the Fermi energy. Partial density of states (PDOS) indicates that these narrow bands form as spectral weighting from the less energetic 6d electronic states is shifted to the 5f electronic states by means of the spin density, which occupies states at the Fermi energy. Finally, the PDOS of a 5f system exhibiting narrow bands at the Fermi energy is associated with the formation of an unusual defect structure in the lattice.

36 MATERIALS SCIENCE↗
DOE OSTI2014

First principles studies of proton conduction in KTaO{sub 3}

KTaO{sub 3} (KTO) is a useful prototypical perovskite for examining the mechanisms of proton transport in perovskites. Previously, Gomez et al. [J. Chem. Phys. 126, 194701 (2007)] reported density functional theory (DFT) calculations describing proton hopping in defect-free KTO. We use DFT calculations to extend that work in two directions, namely, understanding isotope effects in low and high temperature proton transport and the role of native point defects in KTO. At cryogenic temperatures, quantum tunneling plays a vital role in the net hopping of protons in KTO. At the elevated temperature characteristic of applications involving proton-conducting perovskites, tunneling is negligible but zero point energy effects still lead to non-negligible isotope effects for H{sup +}, D{sup +}, and T{sup +}. We also use DFT to characterize the populations of relevant point defects in KTO as a function of experimental conditions, and to examine the migration of protons that are close in proximity to these defects. This information gives useful insight into the overall transport rates of protons through KTO under a variety of external environments. We also assess the overall diffusivity of protons in KTO at various ranges of oxygen vacancy concentrations by performing kinetic Monte Carlo simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Density functional theory calculations of self- and Xe diffusion in U 3 Si 2

Uranium silicide, U 3 Si 2 , has been proposed as an advanced nuclear fuel to be used in light water reactors (LWRs). Development of this alternative to the predominant current fuel, UO 2 , is motivated by enhanced accident tolerance as a result of higher thermal conductivity as well as improved fuel cycle economics through increased uranium density. In order to accurately model the fuel performance of U 3 Si 2 , the diffusion rate of point defects, which is related to self-diffusion, and of fission gas atoms must be determined. DFT calculations are used to predict the U and Si point defect concentrations, the corresponding self-diffusivities, the preferred Xe trap site and the Xe diffusivity. Effects of irradiation are not considered. A low defect formation energy and a high entropy for Si interstitials give rise to Si-rich non-stoichiometry at elevated temperatures. Both U and Si self-diffusion and Xe diffusion are anisotropic as a consequence of the tetragonal crystal structure of U 3 Si 2 . Si diffusion occurs by interstitial mechanisms in both the a-b plane and along the c axis, while the U c axis diffusion rate is controlled by a vacancy mechanism. Interstitial diffusion of U is very fast in the a-b plane of the U 3 Si 2 crystal structure. Xe atoms prefer to occupy U vacancy trap sites. The highest Xe diffusion rate occurs by a vacancy mechanism in both the a-b plane and along the c axis. The diffusion rate is similar in the a-b plane and along the c axis. U and Si self-diffusion and Xe diffusion are all faster in U3Si2 than intrinsic U and Xe diffusion in conventional UO 2 nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Experimental confirmation of first-principles thermal conductivity in Zirconium-doped ThO 2

The degradation of thermal conductivity in advanced nuclear fuels due to the accumulation of fission products and irradiation-induced defects is inevitable, and must be considered as part of safety and efficiency analyses of nuclear reactors. Here, this study examines the thermal conductivity of a zirconium-doped ThO 2 crystal, synthesized via the hydrothermal method using a spatial domain thermoreflectance technique. Zirconium is one of the soluble fission products in oxide fuels that can effectively scatter heat-carrying phonons in the crystalline lattice of fuel. Thus, thermal property measurements of zirconium-doped ThO 2 single crystals provide insights into the effects of substitutional zirconium doping, isolated from extrinsic factors such as grain boundary scattering. The experimental results are compared with first-principles calculations of the lattice thermal conductivity of ThO 2 , employing an iterative solution of the Peierls-Boltzmann transport equation. Additionally, the non-perturbative Green's function methodology is utilized to compute phonon-point defect scattering rates, accounting for local distortions around point defects, including mass difference changes, interatomic force constants, and structural relaxation. The congruence between the predicted results from first-principles calculations and the measured temperature-dependent thermal conductivity validates the computational methodology. Furthermore, the methodologies employed in this study enable systematic investigations of thermal conductivity reduction by fission products, potentially leading to the development of more accurate fuel performance codes.

36 - MATERIALS SCIENCE↗
DOE OSTI2026

A foundation model for non-destructive defect identification from vibrational spectra

Defects are ubiquitous in solids and strongly influence materials’ functional properties. However, non-destructive characterization and quantification of defects, especially when multiple types coexist, remain a long-standing challenge. Here, we introduce DefectNet, a foundation machine learning model that predicts the chemical identity and concentration of substitutional point defects with multiple coexisting elements directly from vibrational spectra, specifically phonon density-of-states (PDoS). Trained on over 16,000 simulated spectra from 2,000 semiconductors, DefectNet employs a tailored attention mechanism to identify up to six distinct defect elements at concentrations ranging from 0.2% to 25%. The model generalizes well to unseen crystals across 56 elements and can be fine-tuned on experimental data. Validation using inelastic scattering measurements of SiGe alloys and MgB 2 superconductor demonstrates its accuracy and transferability. Furthermore, our work establishes vibrational spectroscopy as a viable, non-destructive probe for bulk point defect quantification, and highlights the promise of foundation models in data-driven defect engineering.

artificial intelligence↗
DOE OSTI2014

Lattice constant prediction of defective rare earth titanate perovskites

Engineering defective structures in an attempt to modify properties is an established technique in materials chemistry, yet, no models exist which can predict the structure of perovskite compounds containing extrinsic point defects such as vacancies. An empirically derived predictive model, based solely on chemical composition and published ionic radii has been developed. Effective vacancy sizes were derived both empirically from an existing model for pseudocubic lattice-constants, as well as experimentally, from average bond lengths calculated from neutron diffraction data. Compounds of lanthanum-doped barium titanate and strontium-doped magnesium titanate were synthesized with vacancies engineered on the A and B sites. Effective vacancy sizes were then used in empirical models to predict changes in lattice constants. Experimentally refined bond lengths used in the derivation of an effective vacancy size seemed to overestimate the effect of the point defects. Conversely, using calculated vacancy sizes, derived from a previously reported predictive model, showed significant improvements in the prediction of the pseudocubic perovskite lattice. - Graphical abstract: Atomistic model of Sr{sub 0.3}Nd{sub 0.7}Mg{sub 0.35}Ti{sub 0.65}O{sub 3} and Rietveld refinement of neutron diffraction data. - Highlights: • Defective perovskites were synthesized using the organic steric entrapment method. • Oxygen tilt systems were solved through X-ray, electron, and neutron diffraction. • An effective vacancy size for the cations was calculated from experimental bond lengths. • Discrepancies between Shannon radii and experimental measurements are explored. • An empirical model for predicting a{sub pc}, with an absolute error of 0.20%, was developed.

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

Optimizing proton conductivity in zirconates through defect engineering

The alkaline-earth zirconates (CaZrO 3 , SrZrO 3 , and BaZrO 3 ) are under active investigation as solid-state electrolytes in hydrogen fuel cells. Their performance as proton conductors depends critically on the properties of acceptor dopants. Here, we use first-principles calculations to study the role of acceptors and point defects in incorporating protons through an oxygen-vacancy-mediated process. For CaZrO 3 , we find that Zr Ca antisites suppress formation of oxygen vacancies. Other intrinsic point defects are shown not to hinder performance. Common unintentional impurities, such as C and N, are not good acceptors but can incorporate in other configurations. Our results show that the effectiveness of common dopants such as Sc and Y is limited by self-compensation due to their incorporation on the "wrong" cation site, where they act as donors. We demonstrate that using alkali metal dopants overcomes this problem, as the formation energy of compensating donors is very high. Alkali metal dopants also have low binding energies for protons, reducing their tendency to act as traps and hence enhancing proton conductivity. As a result, our guidelines for choosing acceptor dopants and optimizing synthesis conditions can greatly improve the efficacy of these proton-conducting oxides as solid-state electrolytes.

08 HYDROGEN↗
DOE OSTI2016

Nonlinear Impedance Analysis of La 0.4 Sr 0.6 Co 0.2 Fe 0.8 O 3-δ Thin Film Oxygen Electrodes

Here, linear and nonlinear electrochemical impedance spectroscopy (EIS, NLEIS) were used to study 20 nm thin film La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF-6428) electrodes at 600°C in oxygen environments. LSCF films were epitaxially deposited on single crystal yttria-stabilized zirconia (YSZ) with a 5 nm gadolinium-doped ceria (GDC) protective interlayer. Impedance measurements reveal an oxygen storage capacity similar to independent thermogravimetry measurements on semi-porous pellets. However, the impedance data fail to obey a homogeneous semiconductor point-defect model. Two consistent scenarios were considered: a homogeneous film with non-ideal thermodynamics (constrained by thermogravimetry measurements), or an inhomogeneous film (constrained by a semiconductor point-defect model with a Sr maldistribution). The latter interpretation suggests that gradients in Sr composition would have to extend beyond the space-charge region of the gas-electrode interface. While there is growing evidence supporting an equilibrium Sr segregation at the LSCF surface monolayer, a long-range, non-equilibrium Sr stratification caused by electrode processing conditions offers a possible explanation for the large volume of highly reducible LSCF. Additionally, all thin films exhibited fluctuations in both linear and nonlinear impedance over the hundred-hour measurement period. This behavior is inconsistent with changes solely in the surface rate coefficient and possibly caused by variations in the surface thermodynamics over exposure time.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Synthesis, characterization and effect of low energy Ar ion irradiation on gadolinium oxide nanoparticles

Graphical abstract: . The figure depicts Raman spectra of (A) unirradiated and (B) 80 keV Ar ion irradiated nanoscale gadolinium oxide (Gd{sub 2}O{sub 3}) systems. Intense Raman signals corresponding to two B{sub g} modes at 288 and 384 cm{sup -1} are observed for irradiated sample along with the evolution of a new peak at 202 cm{sup -1} due to surface defects. Highlights: {yields} Gadolinium oxide nanoparticles are synthesized via a selective reduction route. {yields} 80 keV Ar ion-irradiated specimen showed better symmetric emission than pristine. {yields} Irradiation led point defect contribution was studied through spectroscopic means. -- Abstract: In this work, we report on the surfactant assisted synthesis of gadolinium oxide (Gd{sub 2}O{sub 3}) nanoparticles and their characterization through various microscopic and spectroscopic tools. Exhibiting a monoclinic phase, the nanoscale Gd{sub 2}O{sub 3} particles are believed to be comprising of crystallites with an average size of {approx}3.2 nm, as revealed from the X-ray diffraction analysis. The transmission electron microscopy has predicted a particle size of {approx}9 nm and an interplanar spacing of {approx}0.28 nm. Fourier transform infrared spectroscopy studies show that Gd-O inplane vibrations at 536.8 and 413.3 cm{sup -1} were more prominent for 80-keV Ar-ion irradiated Gd{sub 2}O{sub 3} nanosystem than unirradiated system. The photoluminescence (PL) spectra of irradiated specimen have revealed an improvement in the symmetry factor owing to significant enhancement of surface-trap emission, compared to the band-edge counterpart. Irradiation induced creation of point defects (oxygen vacancies) were predicted both from PL and electron paramagnetic resonance (EPR) studies. Further, the Raman spectra of the irradiated sample have exhibited notable vibrational features along with the evolution of a new peak at {approx}202 cm{sup -1}. This can be ascribed to an additional Raman active vibrational response owing to considerable modification of the nanostructure surface as a result of ion bombardment. Probing nanoscale defects through prime spectroscopy tools would find a new avenue for precise tuning of physical properties with generation and annihilation of defects.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of sink strength on coherency loss of precipitates in dilute Cu-base alloys during in situ ion irradiation

In situ irradiations with 1 MeV Kr ions at 50~613 K up to a fluence of 6.25 × 10 14 ions/cm 2 (~1.25 displacements per atom, dpa) have been performed on pre-aged dilute Cu-0.9%Co, Cu-0.9%Fe and Cu-0.8%Cr alloys containing uniform matrix dispersions of coherent precipitates in order to study the effects of initial precipitate sink strength, damage dose and irradiation temperature on radiation-induced coherency loss of precipitates. Coherent precipitates with different point defect sink strengths (2πNd, where N and d are the precipitate density and diameter) were used in this work to examine potential differences in atomic relaxation during absorption of point defects. In all cases, irradiation to low doses (<~1 dpa) was very effective at inducing loss of precipitate coherency. At low sink strengths (~10 13 m -2 ), loss of precipitate coherency could be induced for doses ~0.01 dpa. This suggests there might be an efficient preferential medium-range strain-induced bias for absorption of interstitial defects due to tensile strains emanating from the undersized precipitates, which induces relatively rapid loss of coherency at low precipitate sink strengths. High precipitate sink strength (~10 14 m -2 ) conditions were relatively resistant to the radiation-induced loss of coherency (requiring higher doses approaching ~1 dpa) and this might be due to nearly equal numbers of interstitial and vacancy defects arriving at the precipitate interface for such high sink strength conditions. The precipitate coherency loss was observed to have a weak dependence on irradiation temperature. Molecular dynamics simulations confirm a strong effect of precipitate sink strength on the probability of interstitial absorption at precipitates.

36 MATERIALS SCIENCE↗
DOE OSTI2015

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively. The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O,the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.

Yildirim, Handan↗
DOE OSTI2016

Equivalent radiation damage in zirconium irradiated in various reactors - 2016-0101

The physical properties and in-reactor performance of core components made from zirconium alloys are a function of the radiation-induced atomic displacements that occur during service. The vacancy and interstitial point defects and their clusters created by the atomic displacements modify the microstructure, and therefore physical properties such as strength and ductility, by forming dislocation loops. The rate of production of point defects also affects time-dependent properties such as creep and diffusion (mass transport). To simulate the effect of irradiation on core components, researchers have used materials test reactors for many years to irradiate and test materials. Such reactor tests can target an accumulated displacement damage dose to simulate the state of a material at a given stage in reactor life but at an accelerated rate. Each nuclear reactor has a specific neutron energy spectrum that also depends on the in-reactor location. Therefore, to use test reactor data to determine the effect of radiation damage on power reactor materials, one must convert the accumulated dose into a unit that is common in its effect on the material properties. For many property changes in nuclear reactor cores, this unit is displacements per atom. This paper compares the damage production for zirconium irradiated under differing neutron energy spectra in various power and test reactors. The damage rates as a function of different measures of neutron flux were used to relate atomic displacements in various materials test reactors to CANDU and light-water reactor conditions. (authors)

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ultrahigh temperature in situ transmission electron microscopy based bicrystal coble creep in Zirconia II: Interfacial thermodynamics and transport mechanisms

This work uses a combination of stress dependent single grain boundary Coble creep and zero-creep experiments to measure interfacial energies, along with grain boundary point defect formation and migration volumes in cubic ZrO 2 . These data, along with interfacial diffusivities measured in a companion paper are then applied to analyzing two-particle sintering. The analysis presented here indicates that the large activation volume, v * = v f + v m primarily derives from a large migration volume and suggests that the grain boundary rate limiting defects are delocalized, possibly due to electrostatic interactions between charge compensating defects. The discrete nature of the sintering and creep process observed in the small-scale experiments supports the hypothesis that grain boundary dislocations serve as sources and sinks for grain boundary point defects and facilitate strain during sintering and Coble creep. Model two-particle sintering experiments demonstrate that initial-stage densification follows interface reaction rate-limited kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electronic and protonic conduction in LaFeO 3

Perovskite-type LaFeO3 has promising applications as a negative-electrode material for Ni/metal-hydride batteries. To further improve electrode performance, a thorough understanding of its charge-transport mechanisms is required. We use hybrid density functional theory to investigate the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects and polarons on charge transport. Electronic charge localizes in the form of small hole and electron polarons; this self-trapping occurs in the bulk and also in the vicinity of point defects and impurities. We find that oxygen vacancies act as deep donors, while Fe and La vacancies are acceptors with the induced holes trapped as small polarons. Hydrogen interstitials and Ge and Ti impurities, on the other hand, act as donors that can trap small electron polarons. Hydrogen binds strongly to the La and Fe vacancies and hence these defects are detrimental to protonic conduction. We also elucidate how doping with Sr enhances the electrode performance of LaFeO3:Sr impurities substituting on La sites act as acceptors and enable electronic conductivity through hole polarons, with a hopping barrier of 0.39 eV. In addition, Sr impurities suppress the formation of cation vacancies, thereby enhancing proton conductivity.

Zhu, Zhen↗
DOE OSTI2024

First-principles study of the Stark shift effect on the zero-phonon line of the NV center in diamond

Point defects in semiconductors are attractive candidates for quantum information science applications owing to their ability to act as spin-photon interface or single-photon emitters. However, the coupling between the change of dipole moment upon electronic excitation and stray electric fields in the vicinity of the defect, an effect known as Stark shift, can cause significant spectral diffusion in the emitted photons. In this work, using first principles computations, we revisit the methodology to compute the Stark shift of point defects up to the second order. The approach consists of applying an electric field on a defect in a slab and monitoring the changes in the computed zero-phonon line (i.e., difference in energy between the ground and excited state) obtained from constraining the orbital occupations (constrained-DFT). Here, we study the Stark shift of the negatively charged nitrogen-vacancy (NV) center in diamond using this slab approach. We discuss and compare two approaches to ensure a negatively charged defect in a slab and we show that converged values of the Stark shift measured by the change in dipole moment between the ground and excited states (Δ⁢μ) can be obtained. We obtain a Stark shift of Δ⁢μ = 2.68⁢D using the semilocal GGA-PBE functional and of Δ⁢μ = 2.23⁢D using the HSE hybrid functional. These values are in good agreement with experimental results. We also show that modern theory of polarization can be used on constrained-DFT to obtain Stark shifts in very good agreement with the slab computations.

36 MATERIALS SCIENCE↗
NASA NTRS1996

Defect Structure of Beta NiAl Using the BFS Method for Alloys

The semiempirical BFS method for alloys is generalized by replacing experimental input with first-principles results thus allowing for the study of complex systems. In order to examine trends and behavior of a system in the vicinity of a given point of the phase diagram a search procedure based on a sampling of selected configurations is employed. This new approach is applied to the study of the beta phase of the Ni-Al system, which exists over a range of composition from 45-60 at.% Ni. This methodology results in a straightforward and economical way of reproducing and understanding the basic features of this system. At the stoichiometric composition, NiAl should exist in a perfectly ordered B2 structure. Ni-rich alloys are characterized by antisite point defects (with Ni atoms in the Al sites) with a decrease in lattice parameters. On the Al-rich side of stoichiometry there is a steep decrease in lattice parameter and density with increasing Al content. The presence of vacancies in Ni sites would explain such behavior. Recent X-ray diffraction experiments suggest a richer structure: the evidence, while strongly favoring the presence of vacancies in Ni sites, also suggests the possibility of some vacancies in Al sites in a 3:1 ratio. Moreover, local ordering of vacant sites may be preferred over a random distribution of individual point defects.

Bozzolo, Guillermo↗