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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 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Investigation of oxygen point defects in cubic ZrO 2 by density functional theory

The energetics of formation and migration of the oxygen vacancy and interstitial in cubic ZrO 2 are investigated by density functional theory calculations. In an O-rich environment, the negatively charged oxygen interstitial is the most dominant defect whereas, the positively charged oxygen vacancy is the most dominant defect under O-poor conditions. Oxygen interstitial migration occurs by the interstitialcy and the direct interstitial mechanisms, with calculated migration energy barriers of 2.94 eV and 2.15 eV, respectively. For the oxygen vacancy, diffusion is preferred along the <100> direction, and the calculated energy barriers are 0.26 eV for V 2+ O , 0.27 eV for V 1+ O and 0.54 eV for V 0 O . Furthermore, these results indicate that oxygen diffusivity is higher through the vacancy-migration mechanism.

36 MATERIALS SCIENCE↗
DOE OSTI2017

First-principles study of fission gas incorporation and migration in zirconium nitride

To evaluate the effectiveness of ZrN as a diffusion barrier against fission gases, we investigate in this paper the incorporation and migration of fission gas atoms, with a focus on Xe, in ZrN by first-principles calculations. The formations of point defects in ZrN, including vacancies, interstitials, divacancies, Frenkel pairs, and Schottky defects, are first studied. Among all the defects, the Schottky defect with two vacancies as first nearest neighbor is predicted to be the most favorable incorporation site for fission gas Xe in ZrN. The migration of Xe gas atom in ZrN is investigated through two diffusion mechanisms, i.e., interstitial and vacancy-assisted diffusions. The migration barrier of Xe gas atom through the intrinsic interstitials in ZrN is considerably lower than that through vacancies. Finally, therefore, at low temperatures fission gas Xe atoms diffuse mainly through interstitials in single crystal ZrN, whereas at high temperatures Xe may diffuse in ZrN assisted by vacancies.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Impact of amorphous pockets on displacement damage evolution in silicon

Silicon has long been known to exhibit amorphization in response to heavy particle bombardment. For doses below the total amorphization threshold, partial amorphization is observed in the form of scattered amorphous pockets. While extensive research has gone into modeling the formation and evolution of amorphous pockets in response to irradiation, no studies yet investigate their impact on the evolution of other damage such as interstitial supersaturation and clustering. In this study, we survey the impact of amorphous pockets on defect evolution in silicon when treated as static sinks. MD is first used to show that amorphous pockets provide energetically favorable sites for point defects relative to the crystalline bulk, supporting the hypothesis that they act as sinks. A 0-D cluster dynamics model is then constructed, taking an interstitial clustering model from the literature and including amorphous pockets as a sink species. We conduct our survey for temperatures between 30 and 400 °C and sink strengths between 1 to 6 x 10 10 cm −2 . Both implantation- and radiation-induced damage states are investigated using interstitial and vacancy concentrations as initial condition variables. We find that, due to the differing migration rates of the interstitial and the vacancy, amorphous pockets have a non-monotonic impact on the final damage state depending on the effective sink strength of the amorphous pockets, resulting in increased damage formation in regimes of intermediate amorphization. In conclusion, this result emphasizes the important role of amorphous pockets in governing the evolution of damage in partially amorphized crystalline materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Coupled cluster and dislocation dynamics modeling of microstructure evolution in irradiated materials

We develop here a coupled cluster and dislocation dynamics framework to study the microstructure evolution of irradiated materials. The framework not only accounts for the three dimensional diffusion of radiation-generated clusters, but also their interaction with dislocation networks and the resultant climb motion of discrete dislocations within finite crystals. The framework is solved with a superposition solution scheme, and is applied to investigate the evolution of the irradiation-induced dislocation loops in zirconium (Zr), considering the effects of various bias factors including the diffusion anisotropy difference (DAD) of interstitials and interstitial clusters, the dislocation bias of defects to discrete dislocation segments, and the production bias of defects from the radiation cascade. We find that the DAD is the most critical factor influencing the kinetics of the loop evolution in Zr, while the recombination/interaction of mobile defects can induce a strong spatial dependence of the loop evolution together with the DAD. Here, the method is also adopted to study the evolution of interstitial $\langle$a$\rangle$ and vacancy $\langle$c$\rangle$ dislocation loop ensembles consistent with the microstructure observed during irradiation-induced growth of Zr. Our findings not only reveal the spatial dependence of the size and ellipticity of the dislocation loops, but also suggest a limit on the anisotropy factor of interstitials to reproduce the co-growth of $\langle$a$\rangle$ and $\langle$c$\rangle$ loops in zirconium, in good agreement with experimental observations and other simulation results.

Bias factors↗
DOE OSTI2016

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

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

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

Defect cluster and nonequilibrium gas bubble associated growth in irradiated UMo fuels – a cluster dynamics and phase field model

Irradiation examination shows that gas bubble swelling kinetics is much faster after irradiation-induced recrystallization than that prior recrystallization in UMo fuels. It implies that gas bubbles in coarse grains and small recrystallized grains have different growth behavior. In this work, a phase-field model of gas bubble evolution integrating microstructure dependent cluster dynamics has been developed, for the first time, to study the gas bubble swelling behavior in the recrystallization zone of UMo fuels. Generation, diffusion, reaction, sink, emission and clustering of vacancies and interstitials are described by the cluster dynamics model while a phase-field model is used to describe the evolution of non-equilibrium gas bubbles including nucleation and growth. With the coupled model, the effect of defect generation rate, clustering rate, interstitial emission and sink rates on grain boundaries on the gas bubble evolution are systematically simulated. A set of model parameters (defect generation rate, clustering rate, interstitial emission and sink rates) is determined by comparing measured and simulated gas bubble swelling kinetics. The results demonstrate that interstitial clustering is one of the important physical mechanisms which results in a fast gas bubble swelling kinetics in the recrystallization zone. The developed model can also be extended to study the associated growth of defect and second phase precipitates often observed in irradiated materials.

Hu, Shenyang↗
DOE OSTI2024

Parameterization of vacancy production rate in phase-field models of fission gas bubble evolution in nuclear fuel

Phase-field modeling has increasingly been used to study microstructural evolution in fission gas bubbles in nuclear fuel to improve understanding of fission gas release. To improve computational efficiency, often only vacancies and gas atoms are included as defect species. In this case, the net effects of vacancy and interstitial production, recombination, and biased sink absorption are included as a net vacancy source, or net vacancy source combined with an effective sink. However, there has been a lack of clarity on what parameter values should be used for these approaches to best match the more complete physical picture that includes interstitials and vacancies. Here, we compare a phase-field model of void growth to analytical models for the source-only and source plus sink approach to gain insight into how the phase-field models can be parameterized effectively. The source-only approach provides greater flexibility to match growth rates determined from the full vacancy-interstitial picture. A strategy was developed for determining the value of the net vacancy source term by comparing to an analytical model that includes vacancy and interstitial production, recombination, and biased sink absorption. Finally, this strategy can be used to parameterize phase-field models of fission gas bubble growth.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2012

Chromium incorporation into TiO{sub 2} at high pressure

Chromium incorporation into TiO{sub 2} up to 3 GPa at 1300 Degree-Sign C and 900 Degree-Sign C has been studied by XRD as well as TEM. A CaCl{sub 2} type TiO{sub 2} polymorph has been observed in the quenched samples from high pressure. Two different mechanisms of solubility occur in the recovered samples. Chromium replaces titanium on normal octahedral sites but it also occupies interstitial octahedral sites, especially in the samples recovered from higher pressures. Interstitial chromium is responsible for an orthorhombic distortion of the TiO{sub 2} rutile structure in the quenched samples and gives rise to a (1 1 0) twinned CaCl{sub 2}-structured polymorph. This phase is very likely the result of temperature quench at high pressure. The formation of this phase is directly related to the chromium content of the TiO{sub 2} grains. Chromium solubility in TiO{sub 2} increases with increasing the synthesis pressure. TiO{sub 2} is able to accommodate up to 15.3 wt% Cr{sub 2}O{sub 3} at 3 GPa and 1300 Degree-Sign C, compared to 5.7 wt% at atmospheric pressure at the same temperature. - Graphical abstract: Microstructure consisting of twins domains of recovered Cr-doped CaCl{sub 2} type TiO{sub 2} grains synthesised at high pressure. Highlights: Black-Right-Pointing-Pointer Chromium solubility in TiO{sub 2} increases at high pressure. Black-Right-Pointing-Pointer Chromium occupies substitutional and interstitial positions in the rutile structure. Black-Right-Pointing-Pointer Interstitial chromium causes a decrease of the rutile symmetry. Black-Right-Pointing-Pointer An orthorhombic CaCl{sub 2} type structure is observed in the quenched samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Synthesis, structure and electrochemical properties of layered La{sub 2}Li{sub 2x}(CO{sub 3}){sub 1−x}O{sub 2+2x}

An oxide ion conductor, La{sub 2}Li{sub 2x}(CO{sub 3}){sub 1−x}O{sub 2+x} (x=0.15), was synthesized using a solid-state reaction, and its structure was subsequently determined by Rietveld refinement analyses of synchrotron X-ray and high-resolution powder neutron diffraction data. These analyses determined that carbonate groups are situated between (La{sub 2}O{sub 2}{sup 2+}){sub n} layers in an ordered arrangement and that both oxygen vacancies and interstitial oxygen ions exist within the carbonate layers, resulting in a composition of La{sub 2}Li{sub 0.3}(CO{sub 3}){sub 0.85}O{sub 2.3}. This material is structurally stable up to 500 °C and exhibits a conductivity of 5.5×10{sup −5} S cm{sup −1} at 450 °C. Oxide vacancies associated with carbonate anions appear to be responsible for the ionic conduction observed in this material. - Graphical abstract: Thermal ellipsoid projection of the carbonate layer viewed from the c-axis, showing oxygen migration paths: (A, blue line) interstitial hopping and (B, green line) co-operative rotation. Display Omitted - Highlights: • Lithium insertion in the structure causes the structural changes in carbonate layer. • These structural changes create oxygen vacancies within the flexible carbonate layers and introduce interstitial oxygen. • These interstitial oxygen atoms and oxygen vacancies are involved in oxide ion diffusion through the carbonate layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Electrical properties and thermal expansion of cobalt doped apatite-type lanthanum silicates based electrolytes for IT-SOFC

Graphical abstract: The figure shows the dependence of conductivity on the Co content. It can be seen that La{sub 10}Si{sub 5.2}Co{sub 0.8}O{sub 26.6} exhibits the highest ionic conductivity of 3.33 Multiplication-Sign 10{sup -2} S/cm at 800 Degree-Sign C. When x {<=} 0.8, as doping Co weakens the binding energy and aids the migration of the interstitial oxide ions, the ionic conductivity improves. On the other hand, excess dopant of Co (0.8 < x {<=} 1.5) can decrease the number of interstitial oxide ions and reduce the ionic conductivity. Highlights: Black-Right-Pointing-Pointer The unit volumes of La{sub 10}Si{sub 6-x}Co{sub x}O{sub 27-x/2} increase with increasing cobalt content. Black-Right-Pointing-Pointer Doping Co can increase the thermal expansion because of the larger radius of Co{sup 3+} ion. Black-Right-Pointing-Pointer Conductivities of La{sub 10}Si{sub 6-x}Co{sub x}O{sub 27-x/2} first increase and then decrease with cobalt content. Black-Right-Pointing-Pointer Above 550 Degree-Sign C, La{sub 10}Si{sub 6-x}Co{sub x}O{sub 27-x/2} shows low activation energies of around 0.7 eV. -- Abstract: The thermal expansion and conductivities have been investigated for Co{sup 3+} doped lanthanum silicates. The apatite-type lanthanum silicates with formula La{sub 10}Si{sub 6-x}Co{sub x}O{sub 27-x/2} (x = 0.2, 0.4, 0.6, 0.8, 1.0, 1.5) were synthesized by sol-gel process. The thermal expansion coefficient (TEC) of La{sub 10}Si{sub 6-x}Co{sub x}O{sub 27-x/2} was improved with increasing cobalt content because of the lower valence and larger radius of Co{sup 3+} ion compared to Si{sup 4+}. Analysis of AC impedance spectroscopy showed that conductivity increased first and then decreased with increasing cobalt content. There is an optimum doping amount of cobalt and La{sub 10}Si{sub 5.2}Co{sub 0.8}O{sub 26.6} exhibits the highest conductivity of 3.33 Multiplication-Sign 10{sup -2} S/cm at 800 Degree-Sign C. When x {<=} 0.8, the local distortion caused by doping with Co{sup 3+} can significantly affect the oxygen channels and assist the migration of the interstitial oxide ions, resulting in the improvement of ionic conductivity. However, excess Co{sup 3+} dopant (0.8 < x {<=} 1.5) reduced the number of interstitial oxide ions and decreased the conductivity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Formation of large loop-hydrogen complexes and related effects on mechanical properties of Zirconium investigated with molecular dynamics method

Here, using molecular dynamics (MD) method, interaction between hydrogen (H) atoms and interstitial or vacancy dislocation loops in Zr is extensively studied. The results show that the binding of hydrogen atoms to dislocation loops is anisotropic (attractive or repulsive), depending on the position of the hydrogen atoms with respect to the loop’s core. The anisotropy is governed by excess volume and stress field induced by the loop. For a 1/3[$2\bar1$$\bar1$$0$] interstitial dislocation loop, hydrogen atoms preferentially segregate near the outside of the loop and close to the decomposition knots of the loop. While for a 1/3[$2\bar1$$\bar1$$0$] or 1/6[$20$$\bar2$$3$] vacancy loop, hydrogen atoms prefer to segregate near the inside of the loop. The present work indicates large loop-hydrogen complexes could form in Zr. The binding of hydrogen to loops is stable up to 600 K, while dissociation is observed at 900 K. Formation of loop-hydrogen complexes affect the activation of slip system, resulting in higher yield stress of Zr. The effect increases with the increasing ratio of H to vacancies or interstitials in the vacancy or interstitial loops. The results imply the effects of large loop-hydrogen complexes should be considered to fully understand radiation damage in Zr.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Structure, Stability, and Electronic Properties of Boron Suboxide: A Density Functional Theory Study

Boron suboxide (B 6 O) is a boron-rich compound derived from the α-rhombohedral boron lattice with extreme hardness and unusual semiconducting properties. In this work, density functional theory (DFT) was used to show that unit cell volume, mechanical strength, band gaps, and thermodynamic stabilities of B 6 O were influenced by the interstitial elements and point defects at the icosahedral sites. While the hexagonal unit cell volume (HUCV) varies with interstitial occupancy, it is the icosahedral defect that weakens the intrinsic bulk modulus of B 6 O. Using the hybrid HSE functional, we confirmed that the perfect B 6 O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. The formation free energies calculated over a wide range of temperatures (0–2500 K) and pressures (0–80 GPa) predict that formations of interstitial defects become favorable only at higher temperatures (ca. 1800 K) in bulk B 6 O lattices. The nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barrier of 0.16 eV. More complex B diffusion paths involving the reorganization of icosahedral boron atoms incur higher barriers (>1 eV). In contrast, the diffusion of interstitial O atoms is facile with a barrier of 0.4 eV. Lastly, successive O insertions into the α-B lattice were performed using DFT to generate a basic understanding of the oxidation process. Furthermore, these calculations provide fundamental atomistic insights into the growth of B 6 O crystals and control of their point defects.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Directing Polymorphism of Colloid Crystals Using Conformational Entropy of Polymer Chains

Controlling the polytypes of close-packed structures of spherical colloids is still a challenging problem despite their wide occurrence. Here, in this work, we show that systematic engineering of the polytype structures of close-packed colloids is possible by using the conformational entropy of polymer chains confined in the interstitial space of colloid crystals. Our interstitial space analysis shows that the hexagonal close-packed (HCP) structures offer larger local interstitial space domains, and the structure director chains in favor of HCP counteract the entropic advantages of the face-centered cubic (FCC) lattices. Using model block copolymer colloids and the known lattice entropy of FCC, a proportionality parameter, β CP = 1.91 × 10 –3 ± 3.67 × 10 –4 , for quantifying the conformational entropy contribution toward HCP structures is extracted. This work demonstrates that the interstitial space of colloid crystals serves as a new structure engineering tool for the self-assembly of colloids.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Small-Angle Twist Grain Boundaries as Sinks for Point Defects

It is known that grain boundaries (GBs) provide sinks for defects induced into a solid by irradiation. At the same time radiation can change the atomic structure and chemistry of GBs, which in turn impacts the ability of GBs to continue absorbing defects. Although a number of studies have been reported for tilt GBs acting as defect sinks, the questions of how twist GBs evolve to absorb non-equilibrium concentrations of defects and whether GBs saturate as defect sinks for typical irradiation conditions have remained largely unanswered. Here, we used a combination of molecular dynamics and grand canonical Monte Carlo simulations to determine how twist GBs accommodate point defects. We used SiC and {001} and {111} twist GBs as model systems. We found that diffusion of defects along GBs in this material is slow and for most experimentally relevant conditions point defects will accumulate at twist GBs, driving structural and chemical evolution of these interfaces. During irradiation, screw dislocations within GB planes absorb interstitials by developing mixed dislocation segments that climb. Formation of mixed dislocations occurs either by nucleation of interstitial loops or by faulting/unfaulting of stacking faults. Furthermore both types of twist GBs can accommodate a high density of interstitials without losing the crystalline structure, irrespectively of the interstitial flux.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Nanoscale Engineering Of Radiation Tolerant Silicon Carbide

Radiation tolerance is determined by how effectively the microstructure can remove point defects produced by irradiation. Engineered nanocrystalline SiC with a high-density of stacking faults (SFs) has significantly enhanced recombination of interstitials and vacancies, leading to selfhealing of irradiation-induced defects. While single crystal SiC readily undergoes an irradiationinduced crystalline to amorphous transformation at room temperature, the nano-engineered SiC with a high-density of SFs exhibits more than an order of magnitude increase in radiation resistance. Molecular dynamics simulations of collision cascades show that the nano-layered SFs lead to enhanced mobility of interstitial Si atoms. The remarkable radiation resistance in the nano-engineered SiC is attributed to the high-density of SFs within nano-sized grain structures that significantly enhance point defect annihilation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2013

Effects of interface bonding and defects on boron diffusion at Si/SiO{sub 2} interface

We perform first-principles density functional calculations to find the migration pathway and barrier for B diffusion at the Si/SiO{sub 2} interface. For various interface models, in which crystalline α-quartz or amorphous silica (a-SiO{sub 2}) is placed on Si, we examine stable and metastable configurations of B-related defects which play a role in B diffusion. While a substitutional B alone is immobile in Si, it tends to diffuse to the interface via an interstitialcy mechanism in the presence of a self-interstitial and then changes into an interstitial B in oxide via a kick-out mechanism, leaving the self-interstitial at the interface. At the defect-free interface, where bridging O atoms are inserted to remove interface dangling bonds, an interstitial B prefers to intervene between the interface Si and bridging O atoms and subsequently diffuses through the hollow space or along the network of the Si-O-Si bonds in oxide. The overall migration barriers are calculated to be 2.02–2.12 eV at the Si/α-quartz interface, while they lie in the range of 2.04 ± 0.44 eV at the Si/a-SiO{sub 2} interface, similar to that in α-quartz. The migration pathway and barrier are not significantly affected by interface defects such as suboxide bond and O protrusion, while dangling bonds in the suboxide region can increase the migration barrier by about 1.5 eV. The result that the interface generally does not hinder the B diffusion from Si to SiO{sub 2} assists in understanding the underlying mechanism for B segregation which commonly occurs at the Si/SiO{sub 2} interface.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Mechanism of vacancy formation induced by hydrogen in tungsten

We report a hydrogen induced vacancy formation mechanism in tungsten based on classical molecular dynamics simulations. We demonstrate the vacancy formation in tungsten due to the presence of hydrogen associated directly with a stable hexagonal self-interstitial cluster as well as a linear crowdion. The stability of different self-interstitial structures has been further studied and it is particularly shown that hydrogen plays a crucial role in determining the configuration of SIAs, in which the hexagonal cluster structure is preferred. Energetic analysis has been carried out to prove that the formation of SIA clusters facilitates the formation of vacancies. Such a mechanism contributes to the understanding of the early stage of the hydrogen blistering in tungsten under a fusion reactor environment.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo

We have applied the many-body ab initio diffusion quantum Monte Carlo (DMC) method to study Zn and ZnO crystals under pressure and the energetics of the oxygen vacancy, zinc interstitial, and hydrogen impurities in ZnO. We show that DMC is an accurate and practical method that can be used to characterize multiple properties of materials that are challenging for density functional theory (DFT) approximations. DMC agrees with experimental measurements to within 0.3 eV, including the band-gap of ZnO, the ionization potential of O and Zn, and the atomization energy of O{sub 2}, ZnO dimer, and wurtzite ZnO. DMC predicts the oxygen vacancy as a deep donor with a formation energy of 5.0(2) eV under O-rich conditions and thermodynamic transition levels located between 1.8 and 2.5 eV from the valence band maximum. Our DMC results indicate that the concentration of zinc interstitial and hydrogen impurities in ZnO should be low under n-type and Zn- and H-rich conditions because these defects have formation energies above 1.4 eV under these conditions. Comparison of DMC and hybrid functionals shows that these DFT approximations can be parameterized to yield a general correct qualitative description of ZnO. However, the formation energy of defects in ZnO evaluated with DMC and hybrid functionals can differ by more than 0.5 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗