Defect and structural evolution under high-energy ion irradiation informs battery materials design for extreme environments.

Understanding defect evolution and structural transformations constitutes a prominent research frontier for ultimately controlling the electrochemical properties of advanced battery materials. Herein, for the first time, we utilize in situ high-energy Kr ion irradiation with transmission electron microscopy to monitor how defects and microstructures evolve in Na- and Li-layered cathodes with 3d transition metals. Our experimental and theoretical analyses reveal that Li-layered cathodes are more resistant to radiation-induced structural transformations, such as amorphization than Na-layered cathodes. The underlying mechanism is the facile formation of Li-transition metal antisite defects in Li-layered cathodes. The quantitative mathematical analysis of the dynamic bright-field imaging shows that defect clusters preferentially align along the Na/Li ion diffusion channels (a-b planes), which is likely governed by the formation of dislocation loops. Our study provides critical insights into designing battery materials for extreme irradiation environments and understanding fundamental defect dynamics in layered oxides.

Theoretical prediction and atomic kinetic Monte Carlo simulations of void superlattice self-organization under irradiation.

Nano-structured superlattices may have novel physical properties and irradiation is a powerful mean to drive their self-organization. However, the formation mechanism of superlattice under irradiation is still open for debate. Here we use atomic kinetic Monte Carlo simulations in conjunction with a theoretical analysis to understand and predict the self-organization of nano-void superlattices under irradiation, which have been observed in various types of materials for more than 40 years but yet to be well understood. The superlattice is found to be a result of spontaneous precipitation of voids from the matrix, a process similar to phase separation in regular solid solution, with the symmetry dictated by anisotropic materials properties such as one-dimensional interstitial atom diffusion. This discovery challenges the widely accepted empirical rule of the coherency between the superlattice and host matrix crystal lattice. The atomic scale perspective has enabled a new theoretical analysis to successfully predict the superlattice parameters, which are in good agreement with independent experiments. The theory developed in this work can provide guidelines for designing target experiments to tailor desired microstructure under irradiation. It may also be generalized for situations beyond irradiation, such as spontaneous phase separation with reaction.

Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics.

Oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation, and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo method has been used to investigate the kinetics of oxygen transport in UO2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable off-stoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO(2-x), oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO(2+x), oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that di-interstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence, and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing an explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.

Strain effects on oxygen transport in tetragonal zirconium dioxide.

Temperature accelerated dynamics and molecular dynamics simulations are used to investigate the strain effects on oxygen interstitial and vacancy migration in tetragonal zirconium dioxide. At zero external strain, the anisotropic migration mechanisms of oxygen defects are characterized. At non-zero strains, both the crystal structure and defect migration barriers are modified by strain. Under compressive strains, the defect migration barrier increases with the increasing strain for both interstitials and vacancies. The crystal structure transforms from a tetragonal to a nearly cubic fluorite structure. Accordingly, the defect migration becomes nearly isotropic. Under dilative strains, the migration barrier first decreases then increases with increasing strain for both types of defects. The tetragonal phase transforms to a lower symmetry structure that is close to the orthorhombic phase. In turn, the defect migration becomes highly anisotropic. Under both compressive and dilative strains, interstitials respond to strain more strongly than vacancies. At small dilative strains, an oxygen interstitial has comparable diffusivity to a vacancy, suggesting that both types of defects can contribute to oxygen transport, if they are present. Although currently no previous result is available to validate oxygen interstitial diffusion behavior, the trend of strain effects on oxygen vacancy diffusion is in good agreement with available experimental and theoretical studies in the literature.

Point defect-grain boundary interactions in MgO: an atomistic study.

The way in which point defects interact with grain boundaries in oxides is important for understanding radiation damage evolution, sintering, and many other technologically important applications. Here, we examine how vacancies interact with three different grain boundaries in MgO, chosen as a model oxide ceramic. Further, we compare the vacancy interaction with both pristine (as constructed) and 'damaged' boundaries, in which excess interstitials are placed in the boundary plane to mimic the structure after a damage event. We find that the excess interstitials significantly change the interaction of the vacancies with the boundaries and that this change is sensitive to the atomic structure of the boundary. We further observe that complex electrostatic effects arise that can dominate the interaction. These results show that, as boundaries absorb defects, their interaction with other defects will change dramatically.

Influence of point defects on grain boundary mobility in bcc tungsten.

Atomistic computer simulations were performed to study the influence of radiation-induced damage on grain boundary (GB) sliding processes in bcc tungsten (W), the divertor material in the ITER tokamak and the leading candidate for the first wall material in future fusion reactors. In particular, we calculated the average sliding-friction force as a function of the number of point defects introduced into the GB for a number of symmetric tilt GBs. In all cases the average sliding-friction force at fixed shear strain rate depends on the number of point defects introduced into the GB, and in many cases introduction of these defects reduces the average sliding-friction force by roughly an order of magnitude. We have also observed that as the number of interstitials in the GB is varied, the direction of the coupled GB motion sometimes reverses, causing the GB to migrate in the opposite direction under the same applied shear stress. This could be important in the microstructural evolution of polycrystalline W under the harsh radiation environment in a fusion reactor, in which high internal stresses are present and frequent collision cascades generate interstitials and vacancies.

Migration mechanisms of oxygen interstitial clusters in UO2.

Understanding the migration kinetics of radiation-induced point defects and defect clusters is key to predicting the microstructural evolution and mass transport in nuclear fuels. Although the diffusion kinetics of point defects in UO(2) is well explored both experimentally and theoretically, the kinetics of defect clusters is not well understood. In this work the migration mechanisms of oxygen interstitial clusters of size one to five atoms (1O(i)-5O(i)) in UO(2) are investigated by temperature-accelerated dynamics simulations without any a priori assumptions of migration mechanisms. It is found that the migration paths of oxygen interstitial clusters are complex and non-intuitive, and that multiple migration paths and barriers exist for some clusters. It is also found that the cluster migration barrier does not increase with increasing cluster size and its magnitude has the following order: 2O(i) < 3O(i) < 1O(i) < 5O(i) < 4O(i). Possible finite-size effects are checked with three systems which are of different sizes. The results show good agreement with other available experimental and theoretical data. The cluster migration sequence might explain the interesting relationship measured experimentally between the oxygen diffusivity and stoichiometry in UO(2+x).

Defects in rutile and anatase polymorphs of TiO2: kinetics and thermodynamics near grain boundaries.

The direct consequence of irradiation on a material is the creation of point defects-typically interstitials and vacancies, and their aggregates-but it is the ultimate fate of these defects that determines the material's radiation tolerance. Thus, understanding how defects migrate and interact with sinks, such as grain boundaries, is crucial for predicting the evolution of the material. We examine defect properties in two polymorphs of TiO(2)-rutile and anatase-to determine how these materials might respond differently to irradiation. Using molecular statics and temperature accelerated dynamics, we focus on two issues: how point defects interact with a representative grain boundary and how they migrate in the bulk phase. We find that grain boundaries in both polymorphs are strong sinks for all point defects, though somewhat stronger in rutile than anatase. Further, the defect kinetics are very different in the two polymorphs, with interstitial species diffusing quickly in rutile while oxygen defects-both interstitials and vacancies-are fast diffusers in anatase. These results allow us to speculate on how grain boundaries will modify the radiation tolerance of these materials. In particular, grain boundaries in rutile will lead to a space charge layer at the boundary and a vacancy-rich damage structure, while in anatase the damage structure would likely be more stoichiometric, but with larger defects consisting primarily of Ti ions.

Efficient annealing of radiation damage near grain boundaries via interstitial emission.

Although grain boundaries can serve as effective sinks for radiation-induced defects such as interstitials and vacancies, the atomistic mechanisms leading to this enhanced tolerance are still not well understood. With the use of three atomistic simulation methods, we investigated defect-grain boundary interaction mechanisms in copper from picosecond to microsecond time scales. We found that grain boundaries have a surprising "loading-unloading" effect. Upon irradiation, interstitials are loaded into the boundary, which then acts as a source, emitting interstitials to annihilate vacancies in the bulk. This unexpected recombination mechanism has a much lower energy barrier than conventional vacancy diffusion and is efficient for annihilating immobile vacancies in the nearby bulk, resulting in self-healing of the radiation-induced damage.

Comparing crystal-melt interfacial free energies through homogeneous nucleation rates.

In this work, we compared several available crystal-melt interfacial free energies via homogeneous nucleation rates in a pure Lennard-Jones model system using both model fitting and numerical methods. We examined the homogeneous nucleation temperature obtained from the classical nucleation theory using the available interfacial free energies from three different methods as inputs, i.e. the free energy integration method, the interface fluctuation method and the classical nucleation theory based method. We found that the critical temperature obtained by using the interfacial free energy calculated recently (Bai and Li 2006 J. Chem. Phys. 124 124707) is in better agreement with that obtained from spontaneous crystallization in an independent molecular dynamics simulation. The discrepancies among the interface energies are discussed in light of these results.

Nucleation and melting from nanovoids.

Melting in solids containing nanovoids is studied via molecular dynamics simulation, and the finite size effects are treated with different size systems. For the first time, we have found four typical stages in void melting that are different from the melting of bulk materials and nanoparticles. Melting in each of the stages is governed by the interplay among different thermodynamic mechanisms arising from the changes in the interfacial free energies, the curvature of the interface, and the elastic energy induced by the density change at melting. As a result, the local melting temperatures show a strong dependence on the void size, which is the root cause of the observed complex hierarchical melting sequence.

Calculation of solid-liquid interfacial free energy: a classical nucleation theory based approach.

We present a simple approach to calculate the solid-liquid interfacial free energy. This new method is based on the classical nucleation theory. Using the molecular dynamics simulation, we employ spherical crystal nuclei embedded in the supercooled liquids to create an ideal model of a homogeneous nucleation. The interfacial free energy is extracted by fitting the relation between the critical nucleus size and the reciprocal of the critical undercooling temperature. The orientationally averaged interfacial free energy is found to be 0.302+/-0.002 (in standard LJ unit). The temperature dependence of the interfacial free energy is also obtained in this work. We find that the interfacial free energy increases slightly with increasing temperature. The positive temperature coefficient of the interfacial free energy is in qualitative agreement with Spaepen's analysis [Solid State Phys. 47, FS181 (1994)] and Turnbull's empirical estimation [J. Appl. Phys. 21, 1022 (1950)].

Differences between solid superheating and liquid supercooling.

The thermodynamic and kinetic behaviors for solid superheating and liquid supercooling were critically examined and compared via molecular-dynamics simulations. It is shown that the large elastic energy associated with internal melting and solid-liquid interface disorder play important roles in superheating. The growth rate is anisotropic for supercooling, but isotropic for superheating. Supercooling can be well described by the classical nucleation theory, whereas superheating shows many exceptions. The underlying mechanisms for these differences are discussed.

Test of classical nucleation theory via molecular-dynamics simulation.

A direct test of classical nucleation theory (CNT) is made using molecular-dynamics simulations. The relation between critical nucleus size and undercooling temperature is extracted and the result yields the solid-liquid interfacial energy. It is shown that the CNT, within the assumptions made for spherical nucleus in supercooled liquid, is valid in the critical regime of nucleation for a large range of undercooling and nucleus size.