Revealing the hidden structure of disordered materials by parameterizing their local structural manifold.

Durable interest in developing a framework for the detailed structure of glassy materials has produced numerous structural descriptors that trade off between general applicability and interpretability. However, none approach the combination of simplicity and wide-ranging predictive power of the lattice-grain-defect framework for crystalline materials. Working from the hypothesis that the local atomic environments of a glassy material are constrained by enthalpy minimization to a low-dimensional manifold in atomic coordinate space, we develop a generalized distance function, the Gaussian Integral Inner Product (GIIP) distance, in connection with agglomerative clustering and diffusion maps, to parameterize that manifold. Applying this approach to a two-dimensional model crystal and a three-dimensional binary model metallic glass results in parameters interpretable as coordination number, composition, volumetric strain, and local symmetry. In particular, we show that a more slowly quenched glass has a higher degree of local tetrahedral symmetry at the expense of cyclic symmetry. While these descriptors require post-hoc interpretation, they minimize bias rooted in crystalline materials science and illuminate a range of structural trends that might otherwise be missed.

Critical Analysis of an FeP Empirical Potential Employed to Study the Fracture of Metallic Glasses.

An empirical potential that has been widely used to perform molecular dynamics studies on the fracture behavior of FeP metallic glasses is shown to exhibit spinodal decomposition in the composition range commonly studied. The phosphorous segregation induces a transition from ductility to brittleness. During brittle fracture the atomically sharp crack tip propagates along a percolating path with higher P concentration. This embrittlement is observed to occur over a wide range of chemical compositions, and toughness decreases linearly with the degree of compositional segregation over the entire regime studied. Stable glass forming alloys that can be quenched at low quench rates do not, as a rule, exhibit such thermodynamically unstable behavior near to or above their glass transition temperatures. Hence, the microstructures exhibited in these simulations are unlikely to reflect the actual microstructures or fracture behaviors of the glassy alloys they seek to elucidate.

Local yield stress statistics in model amorphous solids.

We develop and extend a method presented by Patinet, Vandembroucq, and Falk [Phys. Rev. Lett. 117, 045501 (2016)PRLTAO0031-900710.1103/PhysRevLett.117.045501] to compute the local yield stresses at the atomic scale in model two-dimensional Lennard-Jones glasses produced via differing quench protocols. This technique allows us to sample the plastic rearrangements in a nonperturbative manner for different loading directions on a well-controlled length scale. Plastic activity upon shearing correlates strongly with the locations of low yield stresses in the quenched states. This correlation is higher in more structurally relaxed systems. The distribution of local yield stresses is also shown to strongly depend on the quench protocol: the more relaxed the glass, the higher the local plastic thresholds. Analysis of the magnitude of local plastic relaxations reveals that stress drops follow exponential distributions, justifying the hypothesis of an average characteristic amplitude often conjectured in mesoscopic or continuum models. The amplitude of the local plastic rearrangements increases on average with the yield stress, regardless of the system preparation. The local yield stress varies with the shear orientation tested and strongly correlates with the plastic rearrangement locations when the system is sheared correspondingly. It is thus argued that plastic rearrangements are the consequence of shear transformation zones encoded in the glass structure that possess weak slip planes along different orientations. Finally, we justify the length scale employed in this work and extract the yield threshold statistics as a function of the size of the probing zones. This method makes it possible to derive physically grounded models of plasticity for amorphous materials by directly revealing the relevant details of the shear transformation zones that mediate this process.

Predicting Shear Transformation Events in Metallic Glasses.

Shear transformation is the elementary process for plastic deformation of metallic glasses, the prediction of the occurrence of the shear transformation events is therefore of vital importance to understand the mechanical behavior of metallic glasses. In this Letter, from the view of the potential energy landscape, we find that the protocol-dependent behavior of shear transformation is governed by the stress gradient along its minimum energy path and we propose a framework as well as an atomistic approach to predict the triggering strains, locations, and structural transformations of the shear transformation events under different shear protocols in metallic glasses. Verification with a model Cu_{64}Zr_{36} metallic glass reveals that the prediction agrees well with athermal quasistatic shear simulations. The proposed framework is believed to provide an important tool for developing a quantitative understanding of the deformation processes that control mechanical behavior of metallic glasses.

Tribochemical Wear of Diamond-Like Carbon-Coated Atomic Force Microscope Tips.

Nanoscale wear is a critical issue that limits the performance of tip-based nanomanufacturing and nanometrology processes based on atomic force microscopy (AFM). Yet, a full scientific understanding of nanoscale wear processes remains in its infancy. It is therefore important to quantitatively understand the wear behavior of AFM tips. Tip wear is complex to understand due to adhesive forces and contact stresses that change substantially as the contact geometry evolves due to wear. Here, we present systematic characterization of the wear of commercial Si AFM tips coated with thin diamond-like carbon (DLC) coatings. Wear of DLC was measured as a function of external loading and sliding distance. Transmission electron microscopy imaging, AFM-based adhesion measurements, and tip geometry estimation via inverse imaging were used to assess nanoscale wear and the contact conditions over the course of the wear tests. Gradual wear of DLC with sliding was observed in the experiments, and the tips evolved from initial paraboloidal shapes to flattened geometries. The wear rate is observed to increase with the average contact stress, but does not follow the classical wear law of Archard. A wear model based on the transition state theory, which gives an Arrhenius relationship between wear rate and normal stress, fits the experimental data well for low mean contact stresses (<0.3 GPa), yet it fails to describe the wear at higher stresses. The wear behavior over the full range of stresses is well described by a recently proposed multibond wear model that exhibits a change from Archard-like behavior at high stresses to a transition state theory description at lower stresses.

Multibond Model of Single-Asperity Tribochemical Wear at the Nanoscale.

Single-asperity wear experiments and simulations have identified different regimes of wear including Eyring- and Archard-like behaviors. A multibond dynamics model has been developed based on the friction model of Filippov et al. [Phys. Rev. Lett. 92, 135503 (2004)]. This new model captures both qualitatively distinct regimes of single-asperity wear under a unified theoretical framework. In this model, the interfacial bond formation, wearless rupture, and transfer of atoms are governed by three competing thermally activated processes. The Eyring regime holds under the conditions of low load and low adhesive forces; few bonds form between the asperity and the surface, and wear is a rare and rate-dependent event. As the normal stress increases, the Eyring behavior of wear rate breaks down. A nearly rate-independent regime arises under high load or high adhesive forces, in which wear becomes very nearly, but not precisely, proportional to sliding distance. In this restricted regime, the dependence of wear rate per unit contact area is nearly independent of the normal stress at the point of contact. In true contact between rough elastic surfaces, where contact area is expected to grow linearly with normal load, this would lead to behavior very similar to that described by the Archard equation. Detailed comparisons to experimental and molecular dynamics simulation investigations illustrate both Eyring and Archard regimes, and an intermediate crossover regime between the two.

Coarse graining atomistic simulations of plastically deforming amorphous solids.

The primary mode of failure in disordered solids results from the formation and persistence of highly localized regions of large plastic strains known as shear bands. Continuum-level field theories capable of predicting this mechanical response rely upon an accurate representation of the initial and evolving states of the amorphous structure. We perform molecular dynamics simulations of a metallic glass and propose a methodology for coarse graining discrete, atomistic quantities, such as the potential energies of the elemental constituents. A strain criterion is established and used to distinguish the coarse-grained degrees-of-freedom inside the emerging shear band from those of the surrounding material. A signal-to-noise ratio provides a means of evaluating the strength of the signal of the shear band as a function of the coarse graining. Finally, we investigate the effect of different coarse graining length scales by comparing a two-dimensional, numerical implementation of the effective-temperature description in the shear transformation zone (STZ) theory with direct molecular dynamics simulations. These comparisons indicate the coarse graining length scale has a lower bound, above which there is a high level of agreement between the atomistics and the STZ theory, and below which the concept of effective temperature breaks down.

Connecting Local Yield Stresses with Plastic Activity in Amorphous Solids.

In model amorphous solids produced via differing quench protocols, a strong correlation is established between local yield stress measured by direct local probing of shear stress thresholds and the plastic rearrangements observed during remote loading in shear. This purely local measure shows a higher predictive power for identifying sites of plastic activity when compared with more conventional structural properties. Most importantly, the sites of low local yield stress, thus defined, are shown to be persistent, remaining predictive of deformation events even after fifty or more such plastic rearrangements. This direct and nonperturbative approach gives access to relevant transition pathways that control the stability of amorphous solids. Our results reinforce the relevance of modeling plasticity in amorphous solids based on a gradually evolving population of discrete and local zones preexisting in the structure.

ZT > 0.1 Electron-Carrying Polymer Thermoelectric Composites with In Situ SnCl2 Microstructure Growth.

An n-type pyromellitic diimide polymer composite with in situ microstructure growth of the common element compound SnCl2 reaches power factor of 50-100 µW m-1 K-2, the highest purely n-type polymer composite power factor yet reported. The composite has a gigantic Seebeck coefficient between -4000 and -5000 µV K-1, many times higher than other polymer composites.

Soft spots and their structural signature in a metallic glass.

In a 3D model mimicking realistic Cu64Zr36 metallic glass, we uncovered a direct link between the quasi-localized low-frequency vibrational modes and the local atomic packing structure. We also demonstrate that quasi-localized soft modes correlate strongly with fertile sites for shear transformations: geometrically unfavored motifs constitute the most flexible local environments that encourage soft modes and high propensity for shear transformations, whereas local configurations preferred in this alloy, i.e., the full icosahedra (around Cu) and Z16 Kasper polyhedra (around Zr), contribute the least.

A practical perspective on the implementation of hyperdynamics for accelerated simulation.

Consideration is given to several practical issues arising during the implementation of hyperdynamics, a methodology that extends the time scale of the conventional molecular dynamics simulation potentially by orders of magnitude. First, the methodology is reformulated in terms of the transition rate based on the buffer region approach (buffer rate), which can describe transitions in more general contexts than the transition state theory (TST). It will be shown that hyperdynamics can exactly preserve the buffer rate as well as the TST rate, which broadens the scope of the method. Next, the originally proposed scheme to compute the boost factor on-the-fly is reviewed and some alternative methods, one of which uses the umbrella sampling method, are presented. Finally, the methodology is validated in the context of a 1-dimensional example potential and a 3-dimensional simulation of the motion of an atomic force microscope tip moving along a surface.

Cavitation in amorphous solids.

Molecular dynamics simulations of cavitation in a Zr(50)Cu(50) metallic glass exhibit a waiting time dependent cavitation rate. On short time scales nucleation rates and critical cavity sizes are commensurate with a classical theory of nucleation that accounts for both the plastic dissipation during cavitation and the cavity size dependence of the surface energy. All but one parameter, the Tolman length, can be extracted directly from independent calculations or estimated from physical principles. On longer time scales strain aging in the form of shear relaxations results in a systematic decrease of cavitation rate. The high cavitation rates that arise due to the suppression of the surface energy in small cavities provide a possible explanation for the quasibrittle fracture observed in metallic glasses.

An energy basin finding algorithm for kinetic Monte Carlo acceleration.

We present an energy basin finding algorithm for identifying the states in absorbing Markov chains used for accelerating kinetic Monte Carlo (KMC) simulations out of trapping energy basins. The algorithm saves groups of states corresponding to basic energy basins in which there is (i) a minimum energy saddle point and (ii) in moving away from the minimum the saddle point energies do not decrease between successive moves. When necessary, these groups are merged to help the system escape basins of basins. Energy basins are identified either as the system visits states, or by exploring surrounding states before the system visits them. We review exact and approximate methods for accelerating KMC simulations out of trapping energy basins and implement them within our algorithm. Its flexibility to store varying numbers of states, and ability to merge sets of saved states as the program runs, allows it to efficiently escape complicated trapping energy basins. Through simulations of vacancy-As cluster dissolution in Si, we demonstrate our algorithm can be several orders of magnitude faster than standard KMC simulations.

Evaluation of the disorder temperature and free-volume formalisms via simulations of shear banding in amorphous solids.

Molecular dynamics simulations of shear band development over 1000% strain in simple shear are used to test whether the local plastic strain rate is proportional to exp(-1/chi), where chi is a dimensionless quantity related to the disorder temperature or free volume that characterizes the structural state of the glass. Scaling is observed under the assumption that chi is linearly related to the local potential energy per atom. We calculate the potential energy per atom corresponding to absolute zero disorder temperature and the energy needed to create a shear transformation zone.

Strain localization and percolation of stable structure in amorphous solids.

Spontaneous strain localization occurs during mechanical tests of a model amorphous solid simulated using molecular dynamics. The degree of localization depends upon the extent of structural relaxation prior to mechanical testing. In the most rapidly quenched samples higher strain rates lead to increased localization, while the more gradually quenched samples exhibit the opposite strain rate dependence. This transition coincides with the k-core percolation of atoms with quasi-crystal-like short range order. The authors infer the existence of a related microstructural length scale.

Shear softening and structure in a simulated three-dimensional binary glass.

Three-dimensional model binary glasses produced by quenching from a range of liquid temperatures were tested in shear over a range of strain rates using molecular-dynamics techniques. Tests were performed under constant volume and constant pressure constraints. The simulations revealed a systematic change in short-range order as a function of the thermal and strain history of the glass. While subtle signs of differences in short-range order were evident in the pair distribution function, three-body correlations were observed to be markedly more sensitive to the changes in structure. One particular structural parameter, the number of aligned three-atom clusters, was analyzed as a function of the degree of supercooling, the strain and the strain rate. The glasses quenched from the supercooled liquid regime were observed to contain an initially higher number of such clusters, and this number decreased under shear. Those quenched from high-temperature equilibrium liquids contained lower numbers of such clusters and these increased or remained constant under shear. The glasses quenched from the supercooled liquid regime showed higher strength, more marked shear softening, and an increased propensity toward shear localization. The evolution of this structural parameter depended both on its initial value and on the imposed shear rate. These results were observed to hold for simulations performed under both constant density and constant pressure boundary conditions.