Dislocation-pairing transitions in hot grain boundaries.

We report the finding of a novel grain-boundary structural phase transition in both molecular-dynamics and phase-field-crystal simulations of classical models of bcc Fe. This transition is characterized by pairing of individual dislocations with mixed screw and edge components. We demonstrate that this type of transition is driven by a combination of factors including elastic softening, core interaction, and core disordering. At high homologous temperatures the occurrence of this transition is shown to prevent premelting at misorientation angles where it would otherwise be expected.

The role of grain boundary character in solute segregation and thermal stability of nanocrystalline Pt-Au.

Nanocrystalline (NC) metals suffer from an intrinsic thermal instability; their crystalline grains undergo rapid coarsening during processing treatments or under service conditions. Grain boundary (GB) solute segregation has been proposed to mitigate grain growth and thermally stabilize the grain structures of NC metals. However, the role of GB character in solute segregation and thermal stability of NC metals remains poorly understood. Herein, we employ high resolution microscopy techniques, atomistic simulations, and theoretical analysis to investigate and characterize the impact of GB character on segregation behavior and thermal stability in a model NC Pt-Au alloy. High resolution electron microscopy along with X-ray energy dispersive spectroscopy and automated crystallographic orientation mapping is used to obtain spatially correlated Pt crystal orientation, GB misorientation, and Au solute concentration data. Atomistic simulations of polycrystalline Pt-Au systems are used to reveal the plethora of GB segregation profiles as a function of GB misorientation and the corresponding impact on grain growth processes. With the aid of theoretical models of interface segregation, the experimental data for GB concentration profiles are used to extract GB segregation energies, which are then used to elucidate the impact of GB character on solute drag effects. Our results highlight the paramount role of GB character in solute segregation behavior. In broad terms, our approach provides future avenues to employ GB segregation as a microstructure design strategy to develop NC metallic alloys with tailored microstructures.

Revealing inconsistencies in X-ray width methods for nanomaterials.

Since the landmark development of the Scherrer method a century ago, multiple generations of width methods for X-ray diffraction originated to non-invasively and rapidly characterize the property-controlling sizes of nanoparticles, nanowires, and nanocrystalline materials. However, the predictive power of this approach suffers from inconsistencies among numerous methods and from misinterpretations of the results. Therefore, we systematically evaluated twenty-two width methods on a representative nanomaterial subjected to thermal and mechanical loads. To bypass experimental complications and enable a 1 : 1 comparison between ground truths and the results of width methods, we produced virtual X-ray diffractograms from atomistic simulations. These simulations realistically captured the trends that we observed in experimental synchrotron diffraction. To comprehensively survey the width methods and to guide future investigations, we introduced a consistent, descriptive nomenclature. Alarmingly, our results demonstrated that popular width methods, especially the Williamson-Hall methods, can produce dramatically incorrect trends. We also showed that the simple Scherrer methods and the rare Energy methods can well characterize unloaded and loaded states, respectively. Overall, this work improved the utility of X-ray diffraction in experimentally evaluating a variety of nanomaterials by guiding the selection and interpretation of width methods.

New nanoscale toughening mechanisms mitigate embrittlement in binary nanocrystalline alloys.

Nanocrystalline metals offer significant improvements in structural performance over conventional alloys. However, their performance is limited by grain boundary instability and limited ductility. Solute segregation has been proposed as a stabilization mechanism, however the solute atoms can embrittle grain boundaries and further degrade the toughness. In the present study, we confirm the embrittling effect of solute segregation in Pt-Au alloys. However, more importantly, we show that inhomogeneous chemical segregation to the grain boundary can lead to a new toughening mechanism termed compositional crack arrest. Energy dissipation is facilitated by the formation of nanocrack networks formed when cracks arrested at regions of the grain boundaries that were starved in the embrittling element. This mechanism, in concert with triple junction crack arrest, provides pathways to optimize both thermal stability and energy dissipation. A combination of in situ tensile deformation experiments and molecular dynamics simulations elucidate both the embrittling and toughening processes that can occur as a function of solute content.

How grain growth stops: a mechanism for grain-growth stagnation in pure materials.

The thermodynamic equilibrium state of crystalline materials is a single crystal; however, polycrystalline grain growth almost always stops before this state is reached. Although typically attributed to solute drag, grain-growth stagnation occurs, even in high-purity materials. Recent studies indicate that grain boundaries undergo thermal roughening associated with an abrupt mobility change, so that at typical annealing temperatures, polycrystals will contain both smooth (slow) and rough (fast) boundaries. Mesoscale grain-growth models, validated by large-scale polycrystalline molecular dynamics simulations, show that even small fractions of smooth, slow boundaries can stop grain growth. We conclude that grain-boundary roughening provides an alternate stagnation mechanism that applies even to high-purity materials.

Electron-ion coupling effects on simulations of radiation damage in pyrochlore waste forms.

We have performed molecular dynamics simulations of cascade damage in the gadolinium pyrochlore Gd2Zr2O7, comparing results obtained from traditional simulation methodologies that ignore the effect of electron-ion interactions with a 'two-temperature model' in which the electronic subsystem is modeled using a diffusion equation to determine the electronic temperature. We find that the electron-ion interaction friction coefficient γ(p) is a significant parameter in determining the behavior of the system following the formation of the primary knock-on atom (PKA; here, a U³(+) ion). The mean final PKA displacement and the number of defect atoms formed is shown to decrease uniformly with increasing γ(p); however, other properties, such as the final equilibrium temperature and the oxygen-oxygen radial distribution function, show a more complicated dependence on γ(p).

Thin film compressive stresses due to adatom insertion into grain boundaries.

Atomic simulations of the growth of polycrystalline Ni demonstrate that deposited atoms incorporate into the film at boundaries, resulting in compressive stress generation. Incorporated atoms can also leave the boundaries and thus relieve compressive stress. This leads to a complex interplay between growth stress, adatom incorporation, and surface structure. A simple, theoretical model that accounts for grain size effects is proposed and is in good agreement with simulation results.

Computing the mobility of grain boundaries.

As current experimental and simulation methods cannot determine the mobility of flat boundaries across the large misorientation phase space, we have developed a computational method for imposing an artificial driving force on boundaries. In a molecular dynamics simulation, this allows us to go beyond the inherent timescale restrictions of the technique and induce non-negligible motion in flat boundaries of arbitrary misorientation. For different series of symmetric boundaries, we find both expected and unexpected results. In general, mobility increases as the grain boundary plane deviates from (111), but high-coincidence and low-angle boundaries represent special cases. These results agree with and enrich experimental observations.