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At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Atomistic modeling of lanthanide diffusion in refractory body-centered cubic molybdenum

Lanthanide fission products can strongly interact with candidate cladding alloys, but their transport properties in refractory metals remain poorly understood. Here, in this work, we investigate the atomic-scale diffusion behavior of La, Ce, Pr, and Nd in body-centered cubic (bcc) molybdenum, a potential candidate for advanced nuclear cladding. Self-consistent mean-field transport modeling is performed to evaluate the fission product transport and vacancy mobility, informed by first-principles and nudged elastic band calculations of vacancy formation energies, migration barriers, and solute–vacancy binding characteristics. Compared with bcc Fe, lanthanide solutes in bcc Mo exhibit slower tracer diffusion due to higher vacancy formation and migration energies. Furthermore, the calculations reveal that the influence of fission products on migration barriers in bcc Mo are not as extensive in range compared to bcc Fe. Among the studied lanthanides, La exhibits the strongest vacancy binding while also being the fastest diffuser in Mo. These findings highlight how refractory bcc alloys can reduce fission product infiltration, offering valuable insight into the development of durable cladding systems for advanced reactors.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Microstructure and defect engineering of graphite anodes by pulsed laser annealing for enhanced performance of lithium-ion batteries

We report nanosecond pulsed laser annealing significantly improves cyclability and current carrying capacity of lithium-ion batteries (LIBs). This improvement is achieved by engineering of microstructure and defect contents present in graphite in a controlled way by using pulsed laser annealing (PLA) to increase the number density of Li + ion trapping sites. The PLA treatment causes the following changes: (1) creates surface steps and grooves between the grains to improve Li + ion charging and intercalation rates; (2) removes inactive polyvinylidene difluoride (PVDF) binder from the top of graphite grains and between the grains which otherwise tends to block the Li + migration; and (3) produces carbon vacancies in (0001) planes which can provide Li + charging sites. From X-ray diffraction data, we find upshift in diffraction peak or reduction in planar spacing, from which vacancy concentration was estimated to be about 1.0%, which is higher than the thermodynamic equilibrium concentration of vacancies. The laser treatment creates single and multiple C vacancies which provide sites for Li + ions, and it also produces steps and grooves for Li + ions to enter the intercalating sites. It is envisaged that the formation of these sites enhances Li+ ion absorption during charge and discharge cycles. The current capacity increases from an average 360 mAh/g to 430 mAh/g, and C–V shows significant reduction in SEI layer formation after the laser treatment. If the vacancy concentration is too high and charge-discharge cycles are long, then trapping of electrons by Li + may occur, which can lead to Li 0 formation and Li plating causing reduction in current capacity.

25 ENERGY STORAGE↗
DOE OSTI2020

Cluster dynamics simulation of xenon diffusion during irradiation in UO 2

Diffusion of fission gas in UO 2 nuclear fuel impacts several important performance metrics, such as fission gas release, swelling, and thermal conductivity. Current empirical models of fission gas release have significant uncertainty, some of which derives from the bulk diffusion rate and its dependence on, for example, fuel chemistry and irradiation. In this work, we have applied the previously-developed Free Energy Cluster Dynamics (FECD) methodology in the code Centipede to calculate xenon cluster concentrations in UO 2 under intrinsic (high temperature) and irradiation-enhanced (intermediate temperature) conditions in order to develop a model of the xenon diffusion coefficient based on the atomic scale mechanisms responsible for transport. While the diffusion mechanism for xenon in UO 2 is adequately described by the Xe + U 2 O vacancy cluster for intrinsic conditions, a similar process is not capable of capturing measured in-pile fission gas diffusivity at intermediate temperatures. Therefore, a different diffusion mechanism must dominate under this regime. Using calculated atomistic data, we have shown that irradiation-enhanced diffusion at intermediate temperatures occurs via the larger Xe + U 4 O y vacancy clusters, which have lower migration barriers and increase in concentration by several orders of magnitude compared to intrinsic conditions. This mechanism is enabled by the increased uranium vacancy concentration under irradiation due to Frenkel pair production. In addition, the fast migration of uranium interstitials with two attached oxygen interstitials lowers the total uranium interstitial concentration through reactions with sinks. This allows the extended defects, such as Xe + U 4 O y vacancy clusters, to maintain high concentrations by limiting annihilation with attached vacancies. Furthermore, predictions using the Xe + U 4 O y diffusion mechanism are in good agreement with experiment, albeit with some differences in the Arrhenius slope, which we believe may be related to either experimental or model parameter uncertainty. Lastly, an analytical expression suitable for application in fuel performance simulations was derived to capture the predictions of the Centipede simulations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

A density functional theory and neutron diffraction study of the ambient condition properties of sub-stoichiometric yttrium hydride

Several mechanical and thermophysical properties are required as a function of non-stoichiometry for the successful implementation of YH 2-x for nuclear reactor moderator applications. Density functional theory calculations, in combination with neutron diffraction experiments, were used to study the structural and mechanical properties of YH 2-x . Point defect analysis indicated H occupation primarily at the tetrahedral site within an fcc Y sub-lattice, confirming a fluorite YH 2 structure. The small positive formation energy for H vacancies under Y-rich conditions predicted that hypo-stoichiometry is accommodated by Y+YH 2 at ambient conditions and by H vacancies in the YH 2-x single phase that is relevant to high temperatures. Neutron diffraction studies were used to confirm both the occupation of H on tetrahedral sites and the near-stoichiometric composition of the hydride phase in the two-phase Y+YH 2 region of the phase diagram that dominates at room temperature. Energy minimized special-quasirandom-structures of H vacancies were used to calculate lattice parameters, elastic constants, and several other properties as a function of composition for the single phase YH 2-x . The lattice parameter of YH 2-x decreased by only 0.004 Å with increasing H/Y for the range 1.31 ≤ H / Y ≤ 2.0 indicating a negligible effect on lattice parameters due to vacancy formation. In the two-phase region, however, calculations predicted the density of z Y + ( 1 - z ) Y H 2 - x to increase with decreasing H/Y at lower temperatures due to the increased fraction of high-density Y metal. Additionally, for the high temperature single phase, decreasing H/Y reduced the density as a consequence of the lattice expansion associated with vacancy formation. All elastic constants and moduli increased with increasing hydrogen content in single-phase YH 2-x .

36 MATERIALS SCIENCE↗
DOE OSTI2022

Engineering defect energy landscape of CoCrFeNi high-entropy alloys by the introduction of additional dopants

The concept of high-entropy alloys (HEAs) focusing on tuning the overall chemical complexity represents a novel alloy design strategy. In contrast, alloying of a metallic matrix with minor doping elements with limited and localized tunability has been a common practice to improve material performance. Combining the idea of globally engineering defect energy landscape in HEAs and the localized doping strategy in dilute alloys, in this work, we explore doping effects of minor elements in a HEA matrix to further enhance the overall and localized chemical tunability, aiming to improve its irradiation resistance. Specifically, we study the influence of minor Al, Cu, Ti, and Pd substitutional doping elements on defect energetics in a CoCrFeNi model HEA based on density-functional theory (DFT) calculations. The DFT results indicate that the formation and migration energies of vacancies can be strongly influenced when a dopant is introduced at the first nearest neighbor shells around a vacancy. On the other hand, interstitial energetics are only slightly affected. Among the four elements, Ti and Pd generally decrease vacancy formation energies and increase vacancy migration energies more significantly than Al and Cu. The doping effects become more pronounced when the concentration of the substitutional dopants increases. Based on the energy distributions obtained from DFT, we build a kinetic Monte Carlo (kMC) model to assess the impact of dopants on vacancy-mediated diffusivity in the doped HEAs. Our results suggest that Ti and Pd can lower the tracer diffusivity in the considered HEAs and act as trapping sites, whereas Cu may enhance the atomic transport. This work indicates that substitutional doping in HEAs is an effective strategy in metallurgy to further tune the defect and transport properties of complex alloys.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Understanding the effect of minor alloying elements on helium bubble formation in ferritic-martensitic steels

Ferritic-martensitic steels are promising structural materials for advanced nuclear reactors. To minimize long-term radioactivity, reduced-activation ferritic-martensitic steels have been developed by substituting high-activation elements like Ni and Mo with low-activation elements such as W. However, the impact of these alloying modifications on helium bubble formation, which plays a key role in material swelling, remains unclear. Here, in this study, we compared helium bubble formation in ferritic-martensitic steel T91 and reduced-activation ferritic-martensitic steel F82H. Both materials were irradiated with sequential 100 keV, 150 keV, and 200 keV helium ions to a dose of 0.5 dpa and a helium concentration of 9,000 appm at 500°C. The helium bubbles in F82H exhibited a larger average size and a lower density than those in T91, suggesting differences in minor alloying elements may influence the bubble growth. Here, to investigate the effects of these alloying elements, we characterized radiation-induced segregation near bubbles and grain boundaries. Prominent Ni-Mn-Si enriched clusters were found near bubbles in T91, while only Mn-Si enriched clusters were found near bubbles in F82H. In addition, the obvious Cr enrichment near grain boundaries was absent around bubbles in both steels. The different segregation trends among elements revealed the variations in element diffusion mechanisms and the different sink biases between bubbles and grain boundaries. Cr enrichment near grain boundaries is mostly driven by interstitial-mediated diffusion. However, since bubble growth relies on net vacancy flux, vacancy-mediated diffusion plays a dominant role in controlling element segregation near bubbles. Therefore, Cr enrichment was not found near bubbles. Because of preferential vacancy-drag diffusion for Ni, Si and Mn, these elements were enriched near bubbles. Due to the strong binding energies of vacancies with these solute atoms, the vacancy diffusivity can be reduced near these solutes. Therefore, the more prominent Ni-Si-Mn clustered near helium bubbles in T91 lead to stronger suppression of helium bubble growth compared to F82H.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Maintaining a Flat Li Surface during the Li Stripping Process via Interface Design

Electroplating has been the main focus in mitigating the dendrite growth on the Li-metal electrode; however, the stripping process is equally critical, since the nonsmooth Li surface during stripping will lead to nonuniform local current density, planting the seeds for dendrite growth. In this paper, density functional theory (DFT) and kinetic Monte Carlo (KMC) techniques were combined to investigate the vacancy evolution in Li interfaced with different solid–electrolyte interphase (SEI) materials. It was found that the lithiophilic interface, such as Li/Li 2 O, repels vacancies into the bulk Li, so Li atoms can quickly fill the Li vacancies near the Li/Li 2 O interface and maintain a smooth Li surface. In contrast, the lithiophobic interface, such as Li/LiF, traps Li vacancies toward the interface, and the accumulated Li vacancies form voids and roughen the surface. The predicted critical stripping current density, below which a smooth Li surface will be maintained, is therefore much faster at the lithiophilic interface than that at the lithiophobic interface. It was further revealed that the lithiophilicity at different SEI or coating materials can be ranked as Li/Li 2 O > Li/LiPON > Li/Li 2 CO 3 > Li/LiF based on the calculated interfacial adhesion and accumulation of electron density at the interface. Furthermore, this suggests that interface and coating design at nanoscale can be effective for maintaining a smooth Li surface during the stripping process, solving another challenge to achieving a dendrite-free Li-metal electrode in both liquid and solid electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Determining the Oxygen Stoichiometry of Cobaltite Thin Films

Transition metal oxides (TMO) are promising materials to realize low-power neuromorphic devices. Their physical properties critically depend on their oxygen vacancy concentrations, whose experimental determination remains a challenging task. Here we focus on cobaltites, in particular La 1-x Sr x CoO 3-d (LSCO), and we present a strategy to identify fingerprints of oxygen vacancies in X-ray absorption (XA) spectra. Using a combination of experiment and theory, we show that the variation of the oxygen vacancy concentration in the perovskite phase of LSCO is correlated with the change of the relative peak positions of the O K-edge XA spectra. Furthermore, we also identify an additional geometrical fingerprint that captures both the changes of the Co-O bond length and Co-O-Co bond angle in the material due to the presence of oxygen vacancies. Finally, we predict the oxygen vacancy concentration of experimental samples and show how the resistivity of the oxide material may be tuned as a function of the defect concentration present in the system.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Insights into the Interaction of Redox Active Organic Molecules and Solvents with the Pristine and Defective Graphene Surfaces from Density Functional Theory

A systematic study is reported on the interaction of two representative redox active organic molecules and two solvent molecules with pristine and defective graphene surfaces as a model of an electrode surface of a redox flow battery (RFB). The redox active molecules include a catholyte, 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB), and an anolyte molecule, benzothiadiazole (BTZ), and the solvent molecules include acetonitrile (MeCN) and ethylene carbonate (EC). The graphene defects investigated include a single vacancy, double vacancy, zigzag step edge, and armchair step edge. Computations suggest that the interactions of all molecules with a pristine graphene surface are relatively weak (0.2 to 0.8 eV) and dominated by van der Waals effects; therefore, these molecules are chemically stable upon interacting with pristine nondefective graphene. The BTZ, DDB, MeCN, and EC molecules interact strongly (1.5 to 5.5 eV) with the single vacancy and zigzag step edges of graphene that leads to the possible decomposition of the molecules with strength of interaction in the order of MeCN > BTZ > DDB > EC and MeCN > EC > BTZ > DDB, respectively. Calculations show that the BTZ, DDB, MeCN, and EC molecules interact less strongly (0.2 to 1.4 eV) to the double vacancy and armchair step edge than to the single vacancy and zigzag step edge. The binding energies of the molecules were significantly reduced when interacting with the passivated defects, suggesting that the passivation of the defects could help prevent unwanted chemical interactions between the neutral molecules and the electrode surface. In all organic RFBs, one of the crucial bottlenecks is the stability of the constituent molecules with the electrode material, and this study provides insights into the chemical interaction of selected candidate species with a model carbon electrode.

Howard, Jason D.↗
DOE OSTI2020

Site-dependent reactivity of MoS2 nanoparticles in hydrodesulfurization of thiophene

The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Substituted SrFeO 3 as robust oxygen sorbents for thermochemical air separation: correlating redox performance with compositional and structural properties

Thermochemical air separation via cyclic redox reactions of oxide-based oxygen sorbents has the potential to achieve high energy efficiency. Although a number of promising sorbents have been investigated, further improvements in sorbent performance through a fundamental understanding of the structure–performance relationships are highly desirable. In this study, we systematically investigated the effects of A and B site dopants on the oxygen uptake/release properties (i.e., vacancy formation energy, reduction enthalpy, oxygen release temperature, and oxygen capacity) of the SrFeO 3 family of perovskites as oxygen sorbents. A monotonic correlation between DFT calculated oxygen vacancy formation energy and oxygen release temperature demonstrates the effectiveness of DFT for guiding sorbent selection. Combining vacancy formation energy with stability analysis, dopants such as Ba and Mn have been identified for tuning the redox property of SrFeO 3 sorbents, and increasing the oxygen capacity for temperature and pressure swings when compared to undoped SrFeO 3 . The Mn doped sample proved to be highly stable, with less than a 3% decrease in capacity over 1000 cycles. Although the dynamic nature of the redox process makes it difficult to use a single vacancy formation energy as the descriptor, a systematic approach was developed to correlate the oxygen storage capacities with the sorbents’ compositional properties and vacancy formation energies. The combination of DFT calculations with experimental studies from this study provides a potentially effective strategy for developing improved sorbents for thermochemical air separation.

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

Pressure-induced order–disorder transitions in β-In 2 S 3 : an experimental and theoretical study of structural and vibrational properties

We report this joint experimental and theoretical study of the structural and vibrational properties of β-In 2 S 3 upon compression shows that this tetragonal defect spinel undergoes two reversible pressure-induced order–disorder transitions up to 20 GPa. We propose that the first high-pressure phase above 5.0 GPa has the cubic defect spinel structure of α-In 2 S 3 and the second high-pressure phase ($\phi$-In 2 S 3 ) above 10.5 GPa has a defect α-NaFeO 2 -type (R$\bar{3}$) structure. This phase, related to the NaCl structure, has not been previously observed in spinels under compression and is related to both the tetradymite structure of topological insulators and to the defect LiTiO 2 phase observed at high pressure in other thiospinels. Structural characterization of the three phases shows that α-In 2 S 3 is softer than β-In 2 S 3 while $\phi$-In 2 S 3 is harder than β-In 2 S 3 . Vibrational characterization of the three phases is also provided, and their Raman-active modes are tentatively assigned. Our work shows that the metastable α phase of In 2 S 3 can be accessed not only by high temperature or varying composition, but also by high pressure. On top of that, the pressure-induced β–α–$\phi$ sequence of phase transitions evidences that β-In 2 S 3 , a B III 2 X V 3 compound with an intriguing structure typical of A II B III 2 X VI 4 compounds (intermediate between thiospinels and ordered-vacancy compounds) undergoes: (i) a first phase transition at ambient pressure to a disordered spinel-type structure (α-In 2 S 3 ), isostructural with those found at high pressure and high temperature in other B III 2 X V 3 compounds; and (ii) a second phase transition to the defect α-NaFeO 2 -type structure ($\phi$-In 2 S 3 ), a distorted NaCl-type structure that is related to the defect NaCl phase found at high pressure in A II B III 2 X VI 4 ordered-vacancy compounds and to the defect LiTiO 2 -type phase found at high pressure in A II B III 2 X VI 4 thiospinels. This result shows that In 2 S 3 (with its intrinsic vacancies) has a similar pressure behaviour to thiospinels and ordered-vacancy compounds of the A II B III 2 X VI 4 family, making β-In 2 S 3 the union link between such families of compounds and showing that group-13 thiospinels have more in common with ordered-vacancy compounds than with oxospinels and thiospinels with transition metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Identity of the reversible hole traps in InP/ZnSe core/shell quantum dots

Density functional theory calculations are combined with time-resolved photoluminescence experiments to identify the species responsible for reversible trapping of holes following photoexcitation of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) having excess indium in the shell. Several possible assignments are considered, and a substitutional indium adjacent to a zinc vacancy, In 3+ /V Zn 2- , is found to be the most likely. This assignment is consistent with the observation that trapping occurs only when the QD has excess indium and is supported by experiments showing that the addition of zinc oleate or acetate decreases the extent of trapping, presumably by filling some of the vacancy traps. We also show that addition of alkyl carboxylic acids causes increased trapping, presumably by creation of additional zinc vacancies. The calculations show that either a single In 2+ ion or an In 2+ -In 3+ dimer is much too easily oxidized to form the reversible traps observed experimentally, while In 3+ is far too difficult to oxidize. Additional experimental data on InP/ZnSe/ZnS QDs synthesized in the absence of chloride demonstrates that the reversible traps are not associated with Cl - . Furthermore, a zinc vacancy adjacent to a substitutional indium is calculated to have its highest occupied orbitals about 1 eV above the top of the valence band of bulk ZnSe, in the appropriate energy range to act as reversible traps for quantum confined holes in the InP valence band. The associated orbitals are predominantly composed of p orbitals on the Se atoms adjacent to the Zn vacancy.

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

Doping a bad metal: Origin of suppression of the metal-insulator transition in nonstoichiometric VO 2

Rutile ( R ) phase VO 2 is a quintessential example of a strongly correlated bad metal, which undergoes a metal-insulator transition (MIT) concomitant with a structural transition to a V-V dimerized monoclinic ( M 1 ) phase below T MIT ~ 340 K . It has been experimentally illustrated that one can control this transition by doping VO 2 . In particular, doping with oxygen vacancies ( V O ) has been shown to completely suppress this MIT without any structural transition. We explain this suppression by elucidating the influence of oxygen vacancies on the electronic structure of the metallic R phase VO 2 , explicitly treating strong electron-electron correlations using dynamical mean-field theory (DMFT) as well as diffusion Monte Carlo (DMC) flavor of quantum Monte Carlo (QMC) techniques. DMC calculations show a gap closure in the M 1 phase when vacancies are present, suggesting that when vacancies are introduced in the high-temperature rutile phase, the dimerized insulating phase cannot be reached when temperature is lowered. Both DMFT and DMC calculations of nonstoichiometric metallic rutile phase shows that this tendency not to dimerize in the presence of vacancies is because V O 's tend to change the V - 3 d filling away from its nominal half-filled value, with the e g π orbitals competing with the otherwise dominant a 1 g orbital. Loss of this near orbital polarization of the a 1 g orbital is associated with a weakening of electron correlations, especially along the V-V dimerization direction. This removes a charge-density wave (CDW) instability along this direction above a critical doping concentration, which further suppresses the metal-insulator transition. Our research further suggests that the MIT is predominantly driven by a correlation-induced CDW instability along the V-V dimerization direction.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Computational study of Li3BO3 and Li3BN2 I: Electrolyte properties of pure and doped crystals

Both Li3BO3 and Li3BN2 materials have promising properties for use in all-solid-state batteries and other technologies dependent on electrolytes with significant ionic conductivity. As the first of a two-part study, this paper reports the analysis of detailed simulations of Li ion diffusion in the monoclinic forms of these materials. Using both NEB and MD methods, it is clear that Li ion migration via vacancy mechanisms provides the most efficient ion transport in each material. While the results suggest that interstitial defects in these materials do not play a direct role in Li ion migration, their relative stability seems to enhance vacancy production via the formation of Frenkel-type defects. This may partially explain why the Li ion conductivities computed from MD simulations of samples initially containing a single Li ion vacancy are in reasonable agreement with measured values of this work for Li3BO3 and those reported in the literature for poorly crystalline samples of both materials. The possibility of increasing vacancy concentrations by substitutional doping (F for O in Li3BO3 and C for B in Li3BN2) is also examined, finding simulated conductivities comparable to those of the ideal vacancy model.

Li, Yan↗
DOE OSTI2024

Generalized rate theory for void and bubble swelling and its application to δ -plutonium

A rate theory for void and bubble swelling is derived that allows both vacancies and self-interstitial atoms to be generated by thermal activation at all sinks. In addition, they can also be produced by displacement damage from external and internal radiation. This generalized rate theory (GRT) is applied to swelling of gallium-stabilized δ-plutonium in which α-decay causes the displacement damage. Since the helium atoms produced also become trapped in vacancies, a distinction is made between empty and occupied vacancies. The growth of helium bubbles observed by transmission electron microscopy in weapons-grade and in material enriched with Pu238 is analyzed, using different values for the formation energy of self-interstitial atoms (SIA) and two different sets of relaxation volumes for the vacancy and for the SIA. One set allows preferential capture of SIA at dislocations, while the other set gives equal preference to both vacancy and SIA. It is found that the helium bubble diameters observed are in better agreement with GRT predictions if no preferential capture occurs at dislocations. Therefore, helium bubbles in δ-plutonium will not evolve into voids. Furthermore, the helium density within the bubbles remains sufficiently high to cause thermal emission of SIA. Based on a helium density between two to three helium atoms per vacant site, the sum of formation and migration energies must be around 2.0 eV for SIA in δ-plutonium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

A new mechanism for void-cascade interaction from nondestructive depth-resolved atomic-scale measurements of ion irradiation–induced defects in Fe

The nondestructive investigation of single vacancies and vacancy clusters in ion-irradiated samples requires a depth-resolved probe with atomic sensitivity to defects. The recent development of short-pulsed positron beams provides such a probe. Here, we combine depth-resolved Doppler broadening and positron annihilation lifetime spectroscopies to identify vacancy clusters in ion-irradiated Fe and measure their density as a function of depth. Despite large concentrations of dislocations and voids in the pristine samples, positron annihilation measurements uncovered the structure of vacancy clusters and the change in their size and density with irradiation dose. When combined with transmission electron microscopy measurements, the study demonstrates an association between the increase in the density of small vacancy clusters with irradiation and a remarkable reduction in the size of large voids. This, previously unknown, mechanism for the interaction of cascade damage with voids in ion-irradiated materials is a consequence of the high porosity of the initial microstructure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

First-Principles Study of Tritium Trapping by Point Defects in Fe-Al Aluminide Coating Phases

Density functional theory simulations have been carried out to investigate the potential for tritium trapping by metal vacancies in five different Fe-Al aluminide coating phases. It was found that tritiation of Fe and Ni vacancies is generally less favorable than the tritiation of Al vacancies. However, for the first tritiation, a trend in the defect formation energy can be obtained such that metal defects in the Fe 2 Al x family of materials (i.e., Fe 2 Al 4 , Fe 2 Al 5 , and Fe 2 Al 6 ) trap tritium species more favorably than metal vacancies in Fe 4 Al 13 and FeNiAl 5 . Further investigations using ab initio thermodynamics calculations confirmed that trend for a range of tritium partial pressure at a temperature of 700 K. Especially, it was shown that the energy difference between tritiated and non-tritiated metal vacancies is smaller and more favorable for the Fe 2 Al x family, followed by Fe 4 Al 13 , and FeNiAl 5 . While this study shows that tritium interacts differently in the various Fe-Al aluminide phases, it also suggests that tritium trapping and retention could be more efficient if metal defects are present in some Fe-Al phases.

36 MATERIALS SCIENCE↗