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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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Iodine interstitials as a cause of nonradiative recombination in hybrid perovskites

The identification of deep-level defects that act as detrimental nonradiative recombination centers is critical for optimizing the optoelectronic performance of hybrid perovskites. Although extensive studies have been devoted to revealing the nature of deep-level defects in hybrid perovskites, it is still unclear what defects are responsible for the experimentally observed nonradiative recombination rates. Employing first-principles approaches, we quantitatively show that the iodine interstitial is a dominant nonradiative recombination center in methylammonium-lead iodide. Finally, this important insight points to a target for defect engineering in order to further improve the performance of hybrid perovskites.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Shear strain alters the structure and migration mechanism of self-interstitial atoms in copper

Here, we use atomistic modeling to show that externally applied shear strain causes the lowest energy self-interstitial atom (SIA) structure in copper (Cu) to change from a <100>-type dumbbell to a <110>-type dumbbell. Concurrently, SIA migration switches from the 3-D random walk characteristic of <100>-type dumbbells to a 1-D mechanism analogous to that of crowdion SIAs. Furthermore, the relative energies of these two dumbbell structures as a function of strain are well predicted using elastic dipole tensors computed at zero strain, indicating that examination of these tensors may be used to assess the likelihood of strain-induced SIA structure transitions in other materials. Changes in lowest energy SIA structures and associated migration mechanisms stand to impact predictions of SIA behavior in irradiated solids.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable CuI dihydride template [Cu 11 H 2 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] (H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P(OiPr) 2 } 6 ((C≡CPh) 6 ] + (2), and [AuCu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu 11 ] 10+ metal core, making it a two-electron superatom.

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

Creep Deformation and Dynamic Grain Growth in an Interstitial-Free Steel

Dynamic grain growth is demonstrated to be much faster than static grain growth in a body-centered-cubic, interstitial-free steel sheet material at 850°C. Dynamic grain growth occurs during concurrent plastic deformation at elevated temperature, whereas static grain growth occurs during static annealing. Grain growth during steady-state plastic flow in tension at 850°C to a true strain of 0.2 at a true-strain rate of 10 -4 s -1 doubled grain size, while static annealing for the same time produced no increase in grain size. This is described as dynamic normal grain growth (DNGG) because no abnormally large grains were observed. The recrystallized microstructure of the steel demonstrated a log-normal distribution of grain sizes. DNGG produced bimodal grain size distributions that deviate from the theoretical expectation of a simple shift to larger sizes during normal growth. The bimodal distributions contained a remnant of small grains that were not consumed during grain growth. DNGG produced a crystallographic texture that is unique from both the recrystallized material and that produced by lattice rotation alone. DNGG strengthened the {111}&lang;110&rang; and {111}&lang;112&rang; components of the strong γ-fiber component in the original recrystallization texture. Lattice rotation from tensile deformation, by contrast, strengthened the α-fiber components that intersect the original γ-fiber.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of Strain and Strain Rate on Dynamic Grain Growth and Subgrain Evolution During Plastic Deformation of an Interstitial-Free Steel at 850 ° C

Here, the effects of strain and strain rate on dynamic grain growth (DGG) and subgrain evolution are reported for an interstitial-free steel deformed at 850 ° C. Microstructures produced during tension tests at true-strain rates of 10 -4 and to 10 -3 s -1 true strains ranging from 0.02 to 0.2 were preserved following deformation. These were characterized using electron backscatter diffraction (EBSD), including the application of spherical harmonic transform indexing to produce high-angular-resolution EBSD (HR-EBSD) data. HR-EBSD data resolved the small misorientation angles of subgrain boundaries while imaging much larger data fields than possible with previously available techniques. The resulting data confirmed that steady-state flow stress is inversely proportional to the average subgrain size and that subgrain boundary misorientation angle increases with strain. The following new observations are reported. The rate of DGG increased with respect to time but decreased with respect to strain as strain rate increased. This behavior is rationalized through a simple model using separate rate parameters for the effects of time and strain. Subgrain size was not constant during steady-state deformation, but decreased slowly with increasing strain. Subgrain size distributions and subgrain boundary misorientation angle distributions were measured, and both remained approximately log-normal during steady-state deformation. Subgrain evolution demonstrated no dependence on parent grain size, crystallographic orientation, or Taylor factor. These new data suggest that steady-state flow stress is more likely controlled by the dislocation density internal to subgrains than by the spacing between subgrain boundaries.

dynamic grain growth↗
DOE OSTI2023

Effect of free surfaces on localized plastic deformation in single-crystal nickel containing helium bubbles and radiation-induced self-interstitial atom clusters

This paper presents molecular dynamics (MD) simulations of plastic deformation in single-crystal Ni models containing internal distributions of helium (He) bubbles and self-interstitial atom (SIA) clusters corresponding to experimental characterization of ex-service Inconel X-750 components. Here, we simulate single crystals with and without free surfaces at room temperature and 588K, the latter temperature corresponding to the Inconel X-750 service conditions. Both models are deformed under multiple slip to a maximum deviatoric strain of ~10 %. A dislocation slip band forms in the model without free surfaces, but not in the model with free surfaces. However, the latter exhibits nano-twin nucleation from surfaces. Helium (He) bubbles that overlap with a slip band or a nano-twinned region deform more severely than other bubbles in the model. Nevertheless, the bubbles do not link up and do not form configurations that resemble incipient cracks.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hydrogen bond network and bond valence analysis on uranyl sulfate compounds with organic-based interstitial cations

Seven new uranyl sulfate compounds with organic charge-balancing cations have been synthesized and structurally characterized. The structural unit topologies of the two chains and five sheets have been previously reported in uranyl sulfate crystal chemistry, although they were synthesized using different organic molecules. With the inclusion of six of these structures to the 48 previously published uranyl sulfate compounds, a total of 54 known uranyl sulfate compounds with organic charge-balancing cations were compiled and analyzed. A graphical approach was used to compare the structural unit topologies, and a bond valence approach was used to quantify the hydrogen bond networks that exist between the interstitial cationic and solvent species to the uranyl sulfate anionic structural units. Finally, this analysis helped elucidate which oxygen atoms in the structural unit receive hydrogen bonds and how the organic cations stabilize the overall crystal structures in this subclass of U(VI) materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Unfaulting mechanisms of interstitial Frank loops in fluorite-structured ThO 2

Unfaulting of Frank loops in irradiated fluorite-structured oxides is of significance for understanding microstructural evolution. However, the mechanisms have not yet been directly observed. To this end, we utilize molecular dynamics to reveal the atomistic details related to the unfaulting process of interstitial Frank loops in ThO 2 , which involve a single pair or multiple pairs of co-propagating Shockley partials to annihilate the stacking faults. Here, we find that the unfaulting is achieved via a synchronous shear of the partial pairs to remove the extrinsic stacking fault in the cation sublattice and the intrinsic stacking fault in the anion sublattice. The high mobility of oxygen at the dislocation core may reduce the activation barriers of dislocation nucleation and migration. These findings provide a fundamental understanding of the transformation of faulted loops in irradiated ThO 2 , and could be transferable to other fluorite-structured oxides.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Toggling Stereochemical Activity through Interstitial Positioning of Cations between 2D V 2 O 5 Double Layers

The 5/6s 2 lone-pair electrons of p-block cations in their lower oxidation states are a versatile electronic and geometric structure motif that can underpin lattice anharmonicity and often engender electronic and structural instabilities that underpin the function of active elements in nonlinear optics, thermochromics, thermoelectrics, neuromorphic computing, and photocatalysis. In contrast to periodic solids where lone-pair-bearing cations are part of the structural framework, installing lone-pair-bearing cations in the interstitial sites of intercalation hosts provides a means of a systematically modulating electronic structure through the choice of the group and the period of the inserted cation while preserving the overall framework connectivity. The extent of stereochemical activity and the energy positioning of lone-pair-derived mid-gap states depend on the cation identity, stoichiometry, and strength of anion hybridization. V 2 O 5 polymorphs are versatile insertion hosts that can accommodate a broad range of s-, p-, and d-block cations. However, the insertion of lone-pair-bearing cations remains largely underexplored. In this article, we examine the implications of varying the 6s 2 cations situated in interlayer sites between condensed [V 4 O 10 ] n double layers. Systematic modulations of lattice distortions, electronic structure, and magnetic ordering are observed with increasing strength of stereochemical activity from group 12 to group 14 cations. We compare and contrast p-block-layered M x V 2 O 5 (M = Hg, Tl, and Pb) compounds and map the significance of local off-centering arising from the stereochemical activity of lone-pair cations to the emergence of filled antibonding lone-pair 6s 2 –O 2p-hybridized mid-gap states mediated by second-order Jahn–Teller distortions. Crystallographic studies of cation coordination environments and the resulting modulation of V–V interactions have been used in conjunction with variable-energy hard X-ray photoelectron spectroscopy measurements, first-principles electronic structure calculations, and crystal orbital Hamilton population analyses to decipher the origins of stereochemical activity. Magnetic susceptibility measurements reveal antiferromagnetic signatures for all the three compounds. However, the differences in V–V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 160 and 260 K for Hg 0.5 V 2 O 5 and δ-Tl 0.5 V 2 O 5 , respectively, as compared to 7 K for δ-Pb 0.5 V 2 O 5 . In δ-Pb 0.5 V 2 O 5 , the strong stereochemical activity of electron lone pairs and the resulting electrostatic repulsions enforce superlattice ordering, which strongly modifies the electronic localization patterns along the [V 4 O 10 ] slabs, resulting in disrupted magnetic ordering and an anomalously low ordering temperature. The results demonstrate a versatile strategy for toggling the stereochemical activity of electron lone pairs to modify the electronic structure near the Fermi level and to mediate superexchange interactions.

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

Simulating the mechanisms of serrated flow in interstitial alloys with atomic resolution over diffusive timescales

Abstract The Portevin-Le Chatelier (PLC) effect is a phenomenon by which plastic slip in metallic materials becomes unstable, resulting in jerky flow and the onset of inhomogeneous deformation. The PLC effect is thought to be fundamentally caused by the dynamic interplay between dislocations and solute atoms. However, this interplay is almost always inaccessible experimentally due to the extremely fine length and time scales over which it occurs. In this paper, simulations of jerky flow in W-O interstitial solid solutions reveal three dynamic regimes emerging from the simulated strain rate-temperature space: one resembling standard solid solution strengthening, another one mimicking solute cloud formation, and a third one where dislocation/solute coevolution leads to jerky flow as a precursor of dynamic strain aging. The simulations are carried out in a stochastic framework that naturally captures rare events in a rigorous manner, providing atomistic resolution over diffusive time scales using no adjustable parameters.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Sample spinning to mitigate polarization artifact and interstitial-vacancy imbalance in ion-beam irradiation

Accelerator-based ion-beam irradiation has been widely used to mimic the effects of neutron radiation damage in nuclear reactors. However, ion radiation is most often monodisperse in the incoming ions’ momentum direction, leading to excessive polarization in defect distribution, while the scattering under neutron irradiation is often more isotropic and has less radiation-induced polarization. Mitigation of the excess-polarization as well as the damage non-uniformity artifact might be crucial for making the simulation of neutron radiation by ion-beam radiation more realistic. In this work, a general radiation polarization theory in treating radiation as external polar stimuli is established to understand the natural material responses in different contexts, and the possibility to correct the defect polarization artifact in ion-beam irradiation. Inspired by Magic Angle Spinning in Nuclear Magnetic Resonance, we present a precise sample spinning strategy to reduce the point-defect imbalance effect in ion-beam irradiation. It can be seen that with optimized surface inclination angle and the axis of sample rotation, the vacancy-interstitial population imbalance, as well as the damage profile non-uniformity in a designated region in the target are both reduced. It is estimated that sample spinning frequency on the order of kHz should be sufficient to scramble the ion momentum monodispersity for commonly taken ion fluxes and dose rates, which is experimentally feasible.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Re-examining the silicon self-interstitial charge states and defect levels: A density functional theory and bounds analysis study

The self-interstitial atom (SIA) is one of two fundamental point defects in bulk Si. Isolated Si SIAs are extremely difficult to observe experimentally. Even at very low temperatures, they anneal before typical experiments can be performed. Given the challenges associated with experimental characterization, accurate theoretical calculations provide valuable information necessary to elucidate the properties of these defects. Previous studies have applied Kohn–Sham density functional theory (DFT) to the Si SIA, using either the local density approximation or the generalized gradient approximation to the exchange-correlation (XC) energy. The consensus of these studies indicates that a Si SIA may exist in five charge states ranging from -2 to +2 with the defect structure being dependent on the charge state. This study aims to re-examine the existence of these charge states in light of recently derived “approximate bounds” on the defect levels obtained from finite-size supercell calculations and new DFT calculations using both semi-local and hybrid XC approximations. We conclude that only the neutral and +2 charge states are directly supported by DFT as localized charge states of the Si SIA. Within the current accuracy of DFT, our results indicate that the +1 charge state likely consists of an electron in a conduction-band-like state that is coulombically bound to a +2 SIA. Furthermore, the -1 and -2 charge states likely consist of a neutral SIA with one and two additional electrons in the conduction band, respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal gradient effect on helium and self-interstitial transport in tungsten

First-wall materials in a fusion reactor are expected to withstand harsh conditions, with high heat and particle fluxes that modify the materials microstructure. These fluxes will create strong gradients of temperature and concentration of diverse species. Besides the He ash and the hydrogenic species, neutron particles generated in the fusion reaction will collide with the material creating intrinsic defects, such as vacancies, self-interstitials atoms (SIAs), and clusters of such point defects. These defects and the He atoms will then migrate in the presence of the aforementioned gradients. In this study, we use nonequilibrium molecular dynamics to analyze the transport of He and SIAs in the presence of a thermal gradient in tungsten. We observe that, in all cases, the defects and impurity atoms tend to migrate toward the hot regions of the tungsten sample. The resulting species concentration profiles are exponential distributions, rising toward the hot regions of the sample, in agreement with irreversible thermodynamics analysis. For both He atoms and SIAs, we find that the resulting species flux is directed opposite to the heat flux, indicating that species transport is governed by a Soret effect (thermal-gradient-driven diffusion) characterized by a negative heat of transport that drives species diffusion uphill (from the cooler to the hot regions of the sample). Here, we demonstrate that the steady-state species profiles obtained accounting for the Soret effect vary significantly from those where temperature-gradient-driven transport is not considered and discuss the implications of such a Soret effect on the response to plasma exposure of plasma-facing tungsten.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Impact of nitrogen and oxygen interstitials on niobium SRF cavity performance

Superconducting radio frequency (SRF) cavities are the leading technology for highly efficient particle acceleration, and their performance can be significantly enhanced through the controlled introduction of interstitial impurities into bulk niobium. Nitrogen doping has demonstrated a substantial reduction in surface resistance, which improves the quality factor of the cavities. More recently, oxygen doping has emerged as a promising alternative, demonstrating comparable reductions in surface resistance. In this study, we combine cavity measurements on 1.3 GHz niobium SRF cavities subjected to a range of nitrogen- and oxygen-based treatments with material characterizations performed on cavity cutouts processed under identical conditions. This approach allows us to quantitatively assess the contribution of each impurity to the reduction of surface resistance. We find that nitrogen is ten times more effective than oxygen in reducing surface resistance at 16 MV/m. We also observe an additive effect of O and N impurities in reducing RT. We discuss these results in the context of field-dependent nonequilibrium superconductivity, gap enhancement, and hydrogen trapping mechanisms.

Hu, H. [Chicago U.; Fermilab] (ORCID:0009000330621↗
DOE OSTI2023

Migration of Ga vacancies and interstitials in β – Ga 2 O 3

Pathways and energy barriers for the migration of Ga vacancies (V Ga ) and Ga interstitials (Ga i ) in β–Ga 2 O 3 are explored using hybrid functional calculations and the nudged elastic band method. Considering β–Ga 2 O 3 as primarily being an n-type semiconductor, we focus on defect charge states relevant under such conditions: $V^{3 –}_{Ga}$, Ga$^{3+}_{i}$, and Ga$^{+}_{i}$. Notably, we describe a mechanism by which V Ga can transform between its different split configurations. In all cases, the intermediate state consists of a vacancy split between three Ga sites—a three-split vacancy—which enables passage over a significantly lower energy barrier. This is because it avoids the unfavorable simple vacancy at the tetrahedral Ga site. The proposed mechanism lowers the overall barrier for $V^{3–}_{Ga}$ diffusion along the [001] crystal direction from 1.73 to 0.97 eV, whereas the 2.08 eV barrier for the [100] and [010] directions is unaffected. For Ga$^{3+}_{i}$, we obtain similar overall migration barriers of 0.72, 0.80, and 1.02 eV for the [010], [001], and [100] directions, respectively. Ga$^{+}_{i}$ exhibits a strong preference for diffusion within the large eight-sided channel; the overall migration barrier is 0.92 eV for the [010] direction, and 2.16 eV for the [001] and [100] directions. The limiting step for the two latter directions involves ionization of Ga$^{+}_{i}$ followed by a jump to an adjacent large eight-sided channel as Ga$^{3+}_{i}$. Finally, our results are discussed in light of experimental observations of thermally activated recovery processes in irradiated material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr 1−x Ln x ) 2 NiO 4 (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study

Praseodymium nickelate, Pr 2 NiO 4 (PNO), is a promising electrode to promote oxygen reduction reaction (ORR) in a solid oxide fuel cell, but it exhibits phase transformation during electrochemical operation. The origin of the simultaneous phase transformation and high electrochemical performance remains obscure. We carried out a systematic density functional theory study to elucidate the mechanism for this conjugated phenomenon. Charge, electronic structure, and normal-mode analysis suggest the presence of peroxide. Our study shows that the formation of peroxide (O 2 2– ) is attributed to both oxygen interstitials and Pr vacancies. The peroxide species limits the oxygen ion migration due to the additional energy required to break its O–O bond, which leads to a decrease in ORR activity. Subsequently, we investigate the diffusion paths of Pr-ions while comparing them with those of other Ln 3+ ions (La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) in PNO. The formation energies for various Ln 3+ cation occupancies are calculated, as well as segregation energies in CeO 2 (111) surfaces. Lastly, criteria for effective Ln 3+ dopants are developed. La, Nd, and Pm are proposed as potential substituents in PNO to obtain a stable structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Methods of controllable interstitial oxygen doping in niobium

A method for vacuum heat treating Nb, such as is used in superconducting radio frequency cavities, to engineer the interstitial oxygen profile with depth into the surface to conveniently optimize the low-temperature rf surface resistance of the material. An example application is heating of 1.3 GHz accelerating structures between 250-400° C. to achieve a very high quality factor of 5×1010 at 2.0 K. With data supplied by secondary ion mass spectrometry measurements, application of oxide decomposition and oxygen diffusion theory was applied to quantify previously unknown parameters crucial in achieving the oxygen alloy concentration profiles required to optimize the rf surface resistance. RF measurements of vacuum heat treated Nb superconducting radio frequency cavities confirmed the minimized surface resistance (higher Q0) previously expected only from 800° C. diffusive alloying with nitrogen.

Palczewski, Ari D.↗