Search NASA⌕ Search

SEARCH · Search NASA

Results for “Defect kinetics”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Developing machine-learning potentials to study properties of the tritium formation and diffusivity in pure and defective Zircaloy-4 getters

Objective of this work was to study the formation of Sn impurity and hydride phases in Zr and study their impacts on the diffusion kinetics of 3 H by using DFT based ML approach. By implementing deep neural potential (DNP) technique, we developed potential for Zr-H and Sn impurity systems and validated the DNP by using DFT results. We found that by implementing machine learning approach, it is possible to achieve accuracy comparable to DFT level for the more realistic models by using less computational time and resources.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Interface morphology and dislocation-mediated processes during rapid solidification of thin films

Rapid solidification experiments have, in recent years, revealed a wealth of new microstructural phenomena that suggest a strong connection between the kinetics of solidification and the crystalline structures that emerge as a result. In this work, we investigate the interplay between interface morphology and defect-mediated processes during rapid solidification conditions using a Phase Field Crystal (PFC) model, enabling us to simultaneously and efficiently explore the physics of solidification and elasto-plasticity in the formalism of a single-field theory. We predict that there are two mechanisms by which dislocations emitted directly from the solid–liquid interface induce orientation gradients as well as the formation of subgrain boundaries within a single solidifying cell. We relate these mechanisms to the morphology of the moving solid–liquid interface and identify a suitable control parameter in the PFC model with which we can go between said morphologies by effectively changing the relative strength of the capillary length and kinetic coefficients of the solid–liquid interface. Thus, we are able to provide mechanistic explanations for several microstructural features (with an emphasis on orientation gradients and subgrain boundaries) observed during the rapid solidification of pure materials. We also provide a simple explanation for the formation of “jagged” subgrain boundaries, which is consistent with our experimental observations in rapidly solidified samples of Aluminum, whose mechanisms have thus far been unknown.

Interface morphology↗
DOE OSTI2024

Colloquium : Sliding and pinning in structurally lubric 2D material interfaces

A plethora of two-dimensional (2D) materials have been introduced in physics and engineering in the past two decades. Their robust, membranelike sheets permit (mostly require) deposition, giving rise to solid-solid dry interfaces whose mobility, pinning, and general tribological properties under shear stress are currently being understood and controlled, both experimentally and theoretically. Here, in this Colloquium simulated case studies of twisted graphene systems are used as a prototype workhorse tool to demonstrate and discuss the general picture of 2D material interface sliding. First highlighted is the crucial mechanical difference, often overlooked, between small and large incommensurabilities, which corresponds to, for example, small and large twist angles in graphene interfaces. In both cases, focusing on flat, structurally lubric or “superlubric” geometries, the generally separate scalings with the area of static friction in pinned states and of kinetic friction during sliding are elucidated and reviewed, tangled as they are with the effects of velocity, temperature, load, and defects. The roles of island boundaries and elasticity are also discussed, and compared when possible to results in the literature for systems other than graphene. It is proposed that the resulting picture of pinning and sliding should be applicable to interfaces in generic 2D materials that are of importance for the physics and technology of existing and future bilayer and multilayer systems.

2-dimensional systems↗
NASA NTRS1980

Radiation damage in lithium-counterdoped n/p silicon solar cells

Lithium counterdoped n+/p silicon solar cells were irradiated with 1 MV electrons and their post irradiation performance and low temperature annealing properties were compared to that of the 0.35 ohm cm control cells. Cells fabricated from float zone and Czochralski grown silicon were investigated. It was found that the float zone cells exhibited superior radiation resistance compared to the control cells, while no improvement was noted for the Czochralski grown cells. Room temperature and 60 C annealing studies were conducted. The annealing was found to be a combination of first and second order kinetics for short times. It was suggested that the principal annealing mechanism was migration of lithium to a radiation induced defect with subsequent neutralization of the defect by combination with lithium. The effects of base lithium gradient were investigated. It was found that cells with negative base lithium gradients exhibited poor radiation resistance and performance compared to those with positive or no lithium gradients; the latter being preferred for overall performance and radiation resistance.

Hermann, A. M.↗
DOE OSTI2021

Phase Stability of Yttrium Titanium Oxide

This proposed study aims at elevating Idaho National Laboratory (INL)’s portfolio in nuclear material research on two major fronts: 1) expanding INL’s material characterization capabilities to provide holistic microstructural and microchemical characterization ranging from atomic scale to millimeter scale, and 2) filling the knowledge gap on the effect of microstructural evolution on material phase stability at extreme conditions resembling those inside nuclear reactors, using Yttrium-Titanium-Oxide (YTO) as a model material. Previous research indicated the kinetics of phase transition of YTO materials varies between bulk samples and powder samples, suggesting that microstructural characteristics such as defect, micro-strain, and crystallite size could play a significant role in phase transition. The effect of crystallite size on the thermodynamics of phase transition has been well documented for other ceramic materials at nanometer crystallite size, with potential impacts from surface and strain energy and defects. In this proposed study, we will perform microstructural (micro-strain, crystallite size, defects, phase) and microchemical (elemental mapping) analyses through in-situ high temperature measurements using X-ray diffraction (XRD; at millimeter scale for powder and bulk samples) and transmission electron microscopy (TEM, at nanometer scale and atomic scale for powder and thin foil samples), to provide a comprehensive view of the effect of microstructural and microchemical evolution on phase transition and phase stability of YTO materials. These findings will also establish a roadmap and provide new insights on the phase stability of other materials that are critical to nuclear energy and other renewable energy infrastructure. Besides advancing our understanding of this fundamental material science question, this project will also enable the development of state-of-the-art material characterization capabilities at INL/MFC for microstructural and microchemical analysis at high temperature conditions. The new collaboration between the High-Resolution Materials Characterization group at INL and the Electron Microscopy group at the University of Florida (UF) in this project will open the possibilities for more fruitful and synergetic cutting-edge nuclear material research in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Defect evolution in Ni and solid-solution alloys of NiFe and NiFeCoCr under ion irradiation at 16 and 300 K

Single-phase concentrated solid-solution alloys (SP-CSAs) have shown unique chemical complexity at the levels of electrons and atoms, and their defect evolution is expected to be different from conventional dilute alloys. Single crystals of Ni, NiFe and NiFeCoCr are chosen as model systems to understand the chemical complexity on defect formation and damage accumulation in SP-CSAs under ion irradiation. The high-quality crystals were irradiated at 16 and 300 K to different ion fluences, to form irradiated region with little to heavy damages. Additionally, the ion-induced damage was determined using Rutherford backscattering spectrometry technique along a channeling direction (RBS/C) and the level of lattice damage in irradiated Ni and SP-CSAs was quantified from Monte Carlo (MC) simulations. The results are interpreted using the Multi Step Damage Accumulation model to reveal material damage accumulation kinetics. Key findings of the study are that in case of room temperature irradiations the damage level measured for complex alloys at the highest irradiation fluence of 2 × 10 15 cm -2 (~3 dpa) is significantly higher than that obtained for pure nickel samples and suggest two-step damage accumulation process with a defect transformation taking place at a fluence of about 1.5 × 10 15 cm -2 . Furthermore, structural and damage kinetic differences clearly imply that, with increasing degree of chemical complexity and high solid-solution strengthening effects from Ni to NiFe and to NiFeCoCr, the enhanced lattice stiffness resists to randomization of atomic configurations and inhibits the growth of extended defects.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Diffuse scattering from dynamically compressed single-crystal zirconium following the pressure-induced α → ω phase transition

The prototypical α → ω phase transition in zirconium is an ideal test bed for our understanding of polymorphism under extreme loading conditions. After half a century of study, a consensus had emerged that the transition is realized via one of two distinct displacive mechanisms, depending on the nature of the compression path. However, recent dynamic-compression experiments equipped with diffraction diagnostics performed in the past few years have revealed new transition mechanisms, demonstrating that our understanding of the underlying atomistic dynamics and transition kinetics is in fact far from complete. We present classical molecular dynamics simulations of the α → ω phase transition in single-crystal zirconium shock compressed along the [0001] axis using a machine-learning-class potential. The transition is predicted to proceed primarily via a modified version of the two-stage Usikov-Zilberstein mechanism, whereby the high-pressure ω phase heterogeneously nucleates at boundaries between grains of an intermediate β phase. We further observe the fomentation of atomistic disorder at the junctions between β grains, leading to the formation of highly defective interstitial material between the ω grains. We directly compare synthetic x-ray diffraction patterns generated from our simulations with those obtained using femtosecond diffraction in recent dynamic-compression experiments, and show that the simulations produce the same unique, anisotropic diffuse scattering signal unlike any previously seen from an elemental metal. Our simulations suggest that the diffuse signal arises from a combination of thermal diffuse scattering, nanoparticlelike scattering from residual kinetically stabilized α and β grains, and scattering from interstitial defective structures. Published by the American Physical Society 2024

36 MATERIALS SCIENCE↗
DOE OSTI2021

Insights into Defect-Mediated Nucleation of the Equilibrium B2 Phase in Face-Centered Cubic High-Entropy Alloys

A fine scale second phase distribution is important for strengthening metallic materials. High precipitate density is often difficult to achieve due to sluggish precipitation kinetics and limited nucleation sites. Based on the CALPHAD predictions, transition element-based complex concentrated alloys (CCAs)/ High Entropy Alloys (HEAs), have a highly stable face-centered cubic (FCC) phase and intermetallic B2 phase. The precipitation of the strengthening B2 phase is often limited to low fractions in these alloys due to a high nucleation barrier in the FCC matrix. Here, by illustrating in three different alloys, we present a defect mediated nucleation of a high fraction equilibrium B2 phase. The degree of cold work is used to manipulate the phase fraction, morphology, and distribution of B2 precipitates. Our approach synergistically improves the strength and ductility of these alloys and is widely applicable to many other complex alloys.

Sharma, Abhishek↗
DOE OSTI2024

Flash healing of laser-induced graphene

The advancement of laser-induced graphene (LIG) technology has streamlined the fabrications of flexible graphene devices. However, the ultrafast kinetics triggered by laser irradiation generates intrinsic amorphous characteristics, leading to high resistivity and compromised performance in electronic devices. Healing graphene defects in specific patterns is technologically challenging by conventional methods. Herein, we report the rapid rectification of LIG’s topological defects by flash Joule heating in milliseconds (referred to as F-LIG), whilst preserving its overall structure and porosity. The F-LIG exhibits a decreased I D /I G ratio from 0.84 – 0.33 and increased crystalline domain from Raman analysis, coupled with a 5-fold surge in conductivity. Pair distribution function and atomic-resolution imaging delineate a broader-range order of F-LIG with a shorter C-C bond of 1.425 Å. The improved crystallinity and conductivity of F-LIG with excellent flexibility enables its utilization in high-performance soft electronics and low-voltage disinfections. Notably, our F-LIG/polydimethylsiloxane strain sensor exhibits a gauge factor of 129.3 within 10% strain, which outperforms pristine LIG by 800%, showcasing significant potential for human-machine interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Activation of Transition Metal (Fe, Co and Ni)-Oxide Nanoclusters by Nitrogen Defects in Carbon Nanotube for Selective CO 2 Reduction Reaction

The electrochemical carbon dioxide reduction reaction (CO2RR), which can produce value-added chemical feedstocks, is a proton-coupled-electron process with sluggish kinetics. Thus, highly efficient, cheap catalysts are urgently required. Transition metal oxides such as CoO x , FeO x , and NiO x are low-cost, low toxicity, and abundant materials for a wide range of electrochemical reactions, but are almost inert for CO 2 RR. Here, we report for the first time that nitrogen doped carbon nanotubes (N-CNT) have a surprising activation effect on the activity and selectivity of transition metal-oxide (MO x where M = Fe, Ni, and Co) nanoclusters for CO 2 RR. MO x supported on N-CNT, MOx/N-CNT, achieves a CO yield of 2.6–2.8 mmol cm -2 min -1 at an overpotential of -0.55V, which is two orders of magnitude higher than MO x supported on acid treated CNTs (MOx/O-CNT) and four times higher than pristine N-CNT. The faraday efficiency for electrochemical CO 2 -to-CO conversion is as high as 90.3% at overpotential of 0.44V. Both in-situ XAS measurements and DFT calculations disclose that MO x nanoclusters can be hydrated in CO 2 saturated KHCO 3 , and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions, which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

In Situ Electrochemistry of Buried Interfaces in Metal Halide Perovskites: Probing Energy Bands, Halide Redox Activity, and Kinetics

Control over charge injection and extraction processes across buried interfaces is fundamental for all (opto)electronic multilayer device platforms, necessitating detailed understanding of local structural and chemical differences that promote defect formation, distort energetic band-edge alignments, and alter charge transport processes. Herein, the implementation of a low-cost electroanalytical methodologies’ tool suite is described to quantitatively characterize buried interfaces and redox reactions in printable, mixed electrical–ionic, and redox-active metal halide perovskites and a prototypical hole-transporting nickel oxide (NiO x ) thin film. The objective is to demonstrate the power of electrochemical methodologies to improve the nanoscale understanding of complex interfaces within optoelectronic devices by providing case studies on how to: i) differentiate between electronic and chemical properties in NiO x contacts; ii) measure changes in reversibility of halide redox reactions via NiO x surface states; iii) assess energy alignment and charge transport across (modified) buried interfaces; and iv) quantify defects at buried interfaces that change with modifiers and differences in perovskite processing, including increasing defect concentrations when films are slot-die-coated versus spin-cast. The collective approach addresses major challenges in understanding the precise energy landscape and interface reactivity under relevant electric fields that mimic operando conditions (away from equilibrium) and across length scales in thin film device formats.

(spectro)electrochemistry↗
DOE OSTI2021

Effect of Helium Flux on Near-surface Helium Accumulation in Plasma-Exposed Tungsten

We report results of object kinetic Monte Carlo (OKMC) simulations aimed at understanding the effect of helium flux on the near-surface helium accumulation in plasma-facing tungsten, which is initially defect-free and has a W(100) surface orientation. These OKMC simulations are performed at 933 K for fluxes ranging from 10 22 to 4 × 10 25 He/m 2 s, with 100 eV helium atoms impinging on a W(100) surface up to a maximum fluence of 4×10 19 He/m 2 . In the near-surface region, helium clusters interact elastically with the free surface. The interaction is attractive and results in the drift of mobile helium clusters towards the surface as well as increased trap mutation rates. The associated kinetics and energetics of the above-mentioned processes obtained from molecular dynamics simulations are also considered. The OKMC simulations indicate that as the flux decreases, the retention of implanted helium decreases, and its depth distribution shifts to deeper below the surface in initially pristine tungsten. Furthermore, the fraction of retained helium diffusing into the bulk increases as well, so much so that for 10 22 He/m 2 s, almost all of the retained helium diffused into the bulk with minimal/negligible near-surface helium accumulation. At a given flux, with increasing fluence, the fraction of retained helium initially decreases and then starts to increase after reaching a minimum. The occurrence of the retention minimum shifts to higher fluences as the flux decreases. Although the near-surface helium accumulation spreads deeper into the material with decreasing flux and increasing fluence, the spread appears to saturate at depths between 80 and 100 nm. Finally, we present a detailed analysis of the influence of helium flux on the size and depth distribution of total helium and helium bubbles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Precision Calcination Mechanism of CaCO 3 to High-Porosity Nanoscale CaO CO 2 Sorbent Revealed by Direct In Situ Observations

Deploying energy storage and carbon capture at scale is hindered by the substantial endothermic penalty of decomposing CaCO 3 to CaO and CO 2 , and the rapid loss of CO 2 absorption capacity by CaO sorbent particles due to sintering at the high requisite decomposition temperatures. The decomposition reaction mechanism underlying sorbent deactivation remains unclear at the atomic level and nanoscale due to past reliance on postmortem characterization methods with insufficient spatial and temporal resolution. Thus, elucidating the important CaCO 3 decomposition reaction pathway requires direct observation by time-resolved (sub-)nanoscale methods. Here, chemical and structural dynamics during the decomposition of CaCO 3 nanoparticles to nanoporous CaO particles comprising high-surface-area CaO nanocrystallites are examined. Comparing in situ transmission electron microscopy (TEM) and synchrotron X-ray diffraction experiments gives key insights into the dynamics of nanoparticle calcination, involving anisotropic CaCO 3 thermal distortion before conversion to thermally dilated energetically stable CaO crystallites. Time-resolved TEM uncovered a novel CaO formation mechanism involving heterogeneous nucleation at extended CaCO 3 defects followed by sweeping reaction front motion across the initial CaCO 3 particle. These observations clarify longstanding, yet incomplete, reaction mechanisms and kinetic models lacking accurate information about (sub-)nanoscale dynamics, while also demonstrating calcination of CaCO 3 without sintering through rapid heating and precise temperature control.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Positron stopping in multilayer materials

Positron annihilation spectroscopy provides a sensitive toolset for defect characterization. In beam based studies of single-layer targets, the form of implantation profiles is well established, depending on the kinetic energy and angle of incident positrons relative to the target surface and the density and average atomic number of the target. For multilayer systems, the difference in density and across the layers makes derivation of an analytical form difficult. To date, the determination of positron stopping profiles in multilayer targets has primarily involved Monte Carlo simulations. We present here an alternative approach that estimates the energy distribution dN/dE of those positrons transmitted past each layer boundary, by fitting the remaining tail of the stopping profile after each layer with a basis set comprised of calculated stopping profiles in the same material they are transmitted through. The stopping profile in the next layer is then found by summing a series of stopping profiles in the new medium in proportion to the determined distribution dN/dE. The results of our model are compared with simulation results in a system of alternating layers of Al and Au and find reasonable agreement in the predicted profile and excellent agreement in the predicted mean implantation depth. Finally, we derived a simple formula-based approach for the calculation of the mean implantation depth in two-layer systems that provides results in excellent agreement with the full model.

Jones, A. C. L. [Arizona State University, Tempe, ↗
NASA NTRS1993

Quartz dissolution. I - Negative crystal experiments and a rate law. II - Theory of rough and smooth surfaces

The range of the measured quartz dissolution rates, as a function of temperature and pOH, extent of saturation, and ionic strength, is extended to cover a wider range of solution chemistries, using the negative crystal methodology of Gratz et al. (1990) to measure the dissolution rate. A simple rate law describing the quartz dissolution kinetics above the point of zero charge of quartz is derived for ionic strengths above 0.003 m. Measurements were performed on some defective crystals, and the mathematics of step motion was developed for quartz dissolution and was compared with rough-face behavior using two different models.

Gratz, Andrew J.↗
DOE OSTI2022

The Potential Energy Hotspot: Effects of Impact Velocity, Defect Geometry, and Crystallographic Orientation

In energetic materials, the localization of energy into “hotspots” is known to dictate the initiation of chemical reactions and detonation. Recent all-atom simulations have shown that more energy is localized as internal potential energy (PE) than can be inferred from the kinetic energy (KE) alone. The mechanisms associated with pore collapse and hotspot formation are known to depend on pore geometry and dynamic material response such as plasticity. Therefore, we use molecular dynamics (MD) simulations to characterize shock-induced pore collapse and the subsequent formation of hotspots in 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), a highly anisotropic molecular crystal, for various defect shapes, shock strengths, and crystallographic orientations. We find that the localization of energy as PE is consistently larger than the KE in cases with significant plastic deformation. Additionally, an analysis of MD trajectories reveals the underlying molecular- and crystal-level processes that govern the effect of orientation and pore shape on PE localization. We find that the regions of highest PE relate to the areas of maximum plastic deformation, while KE is maximized at the point of impact. Comparisons against octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) reveal less energy localization in TATB, which could be a contributing factor to the latter’s insensitivity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Leveraging Exchange Kinetics for the Synthesis of Atomically Precise Porous Catalysts

Metal-organic frameworks (MOFs) have attracted significant attention as porous catalyst platforms due to the synthetic modularity of these materials and the diversity of lattice-confined catalytic active sites that are readily embedded within periodic crystalline frameworks. MOFs offer platforms to heterogenize molecular catalysts, stabilize novel coordination motifs, and leverage confinement effects in catalysis. Crystallinity allows diffraction-based methods to be employed in the characterization of these catalysts. Access to crystalline MOFs typically requires reversible construction of the metal-ligand (M-L) bonds that connect the SBUs, which provides a mechanism to anneal defects during crystallization. While the required M-L bond reversibility is often promoted by synthesis at elevated temperature, access to crystalline materials based on either transition metals with characteristic slow exchange kinetics or highly basic donor ligands remains a synthetic challenge. Here in this paper, we highlight synthetic strategies that leverage M-L exchange kinetics to access MOFs based on kinetically inert ions and extensions of these strategies to the assembly of atomically precise multimetallic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Combined density functional theory/kinetic Monte Carlo investigation of surface morphology during cycling of Li-Cu electrodes

In this work, we employed a combined density functional theory and kinetic Monte Carlo approach in order to investigate the nanoscale behavior of lithium stripping and plating on lithium-copper nanoalloys. Density functional theory calculations were used to develop an atom-by-atom understanding of the nucleation behavior of lithium on copper surfaces with different surface morphologies. We found that nanometric pits resulted in significantly more favorable lithium deposition when compared to pristine or lightly-defective Cu surfaces, which is in agreement with previous experimental studies. We then used density functional theory and constrained ab initio molecular dynamics to develop interaction and reaction parameters for a larger-scale kinetic Monte Carlo model in order to provide insight into the stripping and plating behavior of nanostructured Li-Cu nanoalloy anodes. Substantial losses in capacity and strong indications of morphological change were observed for a wide range of Cu:Li ratios over 100 cycles. We observed a complex relationship between the nanoparticle composition and the properties of the formed solid-electrolyte interphase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗