Atomistic Simulations of Integranular Fracture in Symmetric-Tilt Grain Boundaries

Fracture experiments on symmetric-tilt grain boundaries in Cu are interpreted using the Peierls-Nabarro continuum model of dislocation nucleation as a starting point. Good agreement is found only when the continuum model is modified according to the results of atomistic simulations. The same experiments are also reproduced by direct Molecular Dynamics simulations of fracture propagation and dislocation emission from a microcrack placed in the interface plane of the symmetric-tilt (221)(221) grain boundary in fcc Cu. Direction-dependent fracture response is observed, namely the microcrack advancing by brittle fracture along the [11 ] direction and being blunted by dislocation emission along the opposite [ 4] direction. Moreover, the simulations allow us to establish important differences with respect to the continuum-model predictions due to the shielding of the stress field at the crack-tip and to the presence of the residual stress at the interface.     

The growth and modification of materials via ion–surface processing

A wide variety of gas phase ions with kinetic energies from 1–10⁷ eV increasingly are being used for the growth and modification of state-of-the-art material interfaces. Ions can be used to deposit thin films; expose fresh interfaces by sputtering; grow mixed interface layers from ions, ambient neutrals, and/or surface atoms; modify the phases of interfaces; dope trace elements into interface regions; impart specific chemical functionalities to a surface; toughen materials; and create micron- and nanometer-scale interface structures. Several examples are developed which demonstrate the variety of technologically important interface modification that is possible with gas phase ions. These examples have been selected to demonstrate how the choice of the ion and its kinetic energy controls modification and deposition for several different materials. Examples are drawn from experiments, computer simulations, fundamental research, and active technological applications. Finally, a list of research areas is provided for which ion–surface modification promises considerable scientific and technological advances in the new millennium.     

Block copolymer adsorption from a homopolymer melt to an amine-terminated surface

Using neutron reflectometry, the adsorption of diblock copolymers from a neutral polystyrene (PS) matrix is studied as a function of substrate type and non-adsorbing block degree of polymerization. The block copolymer is poly(deutero styrene)-block-poly(methyl methacrylate) and the substrates are silicon oxide, SiO_x, and SiO_x functionalized with (3-aminopropyl)triethoxysilane (APTES). We have determined the equilibrium volume fraction-depth profiles for such films, and compared them with volume fraction profiles generated by self-consistent mean-field (SCMF) theory and find good agreement between the experimental and theoretical data. SCMF calculations show that the segmental interaction energy between PS matrix chains and APTES is two orders of magnitude stronger than that between PS and SiO_x.     

Intranuclear-Cascade model calculation of photofission probabilities for actinide nuclei

We have calculated the fission probabilities for ²³⁷Np, ^{233, 235, 238}U, ²³²Th, and ^natPb following the absorption of photons with energies from 68 MeV to 3.77 GeV using the RELDIS Monte Carlo code. This code implements the cascade-evaporation-fission model of intermediate-energy photonuclear reactions. It includes multiparticle production in photoreactions on intranuclear nucleons, pre-equilibrium emission, and the statistical decay of excited residual nuclei via competition of evaporation, fission, and multifragmentation processes. The calculations show that in the GeV energy region the fission process is not solely responsible for the entire total photoabsorption cross-section, even for the actinides. The fission probabilities are 80-95% for ²³³U, ²³⁵U, and ²³⁷Np, 70-80% for ²³⁸U, and only 55-70% for ²³²Th. This is because certain residual nuclei that are created by deep photospallation at GeV photon energies have relatively low fission probabilities. The results of those model calculations are in reasonable agreement (at the 10% level) with recent experimental data on relative photofission cross-sections for ²³⁷Np and ^{233, 235, 238}U (but not for ²³²Th or ^natPb) from the Saskatchewan and Jefferson Laboratories over a very wide range in photon energy. Using our calculated fission probabilities plus the total photoabsorption cross-sections per nucleon, estimated from previous cross-section data for nuclei from C to Pb, we can infer absolute photofission cross-sections for the actinide nuclei and compare them with the SAL and JLab results. The resulting discrepancies, however, clearly demonstrate the need for direct measurement of the total photoabsorption cross-sections for the heavy actinides.     

Complex formation between a nanoparticle and a weak polyelectrolyte chain: Monte Carlo simulations

Understanding the complexation processes between nanoparticles and polyelectrolytes is an essential aspect in many branches of nanotechnology, nanoscience, chemistry, and biology to describe processes such as nanoparticle stabilization/destabilization and dispersion, water treatment, microencapsulation, complexation with biomolecules for example, and evolution of the interface of many natural and synthetic systems. In view of the complexity of such processes, applications are often based on empirical or semiempirical observations rather than on predictions based on theoretical or analytical models. In this study, the complex formation between an isolated weak polyelectrolyte and an oppositely charged nanoparticle is investigated using Monte Carlo simulations with screened Coulomb potentials in the grand canonical ensemble. The roles of the nanoparticle surface charge density , solution pH and ionic concentration C_i are systematically investigated. The phase diagrams of complex conformations are also presented. It is shown that the polyelectrolyte conformation at the surface of the nanoparticle is controlled by the attractive interactions with the nanoparticle but also by the repulsive interactions between the monomers. To bridge the gap with experiments titration curves are calculated. We clearly demonstrate that an oppositely charged nanoparticle can significantly modify the acid/base properties of a weak polyelectrolyte.     

Correlation between host-guest binding and host amplification in simulated dynamic combinatorial libraries

We present a versatile computer model of diverse dynamic combinatorial libraries, and examine how molecular recognition between library members and a template can be used to amplify the best binders. The correlation between host-guest binding and amplification was examined for a set of 50 libraries with >300 components each over a wide range of template and building block concentrations. Depending on these concentrations correlations vary from poor (when using a large excess of template) to good (for very dilute libraries and/or substoichiometric template concentrations), highlighting the need to choose the experimental conditions for dynamic combinatorial libraries thoughtfully.     

Nonlinear mobility of a driven system: Temperature and disorder effects

We consider the dissipative nonlinear dynamics of a model of interacting atoms driven over a substrate potential. The substrate parameters can be suitably tuned in order to introduce disorder effects starting from two geometrically opposed ideal cases: commensurate and incommensurate interfaces. The role of temperature is also investigated through the inclusion of a stochastic force via a Langevin molecular dynamics approach. Here, we focus on the most interesting tribological case of underdamped sliding dynamics. For different values of the chain stiffness, we evaluate the static friction threshold and consider the depinning transition mechanisms as a function of the applied driving force. As experimentally observed in QCM frictional measurements of adsorbed layers, we find that disorder operates differently depending on the starting geometrical configuration. For commensurate interfaces, randomness lowers considerably the chain depinning threshold. On the contrary, for incommensurate mating contacts, disorder favors static pinning destroying the possible frictionless (superlubric) sliding states. Interestingly, thermal and disorder effects strongly influence also the occurrence of parametric resonances inside the chain, capable of converting the kinetic energy of the center-of-mass motion into internal vibrational excitations. We comment on the nature of the different dynamical states and hysteresis (due to system bi-stability) observed at different increasing and decreasing strengths of the external force.     

Optimal conditions for submonolayer nanoisland growth in ion beam assisted deposition

We study the optimal conditions for nanoisland growth in ion beam assisted deposition (IBAD). This situation occurs when adatom islands remain small enough to prevent the onset of three-dimensional growth, while at the same time preventing ion-induced surface erosion. To this end, we develop a rate equation model of IBAD, which embodies continuous deposition of adatoms and creation of vacancies, recombination of vacancies at adatom island edges, as well as recombination of adatoms at vacancy island edges. These rate equations are solved by numerical simulations based on the particle coalescence method. To determine the optimal growth condition, we find the largest mean size of the vacancy islands leading to their survival. We show that at this onset between the rough and smooth layer-by-layer growth regimes there is a simple exponential relation between the largest size of the vacancy islands and the external control parameters of the growth.     

Height and roughness distributions in thin films with Kardar-Parisi-Zhang scaling

We study height and roughness distributions of films grown with discrete Kardar-Parisi-Zhang (KPZ) models in a small time regime which is expected to parallel the typical experimental conditions. Those distributions are measured with square windows of sizes 8 ? r ? 128 gliding through a much larger surface. Results for models with weak finite-size corrections indicate that the absolute value of the skewness and the value of the kurtosis of height distributions converge to 0.2 ? ∣S∣ ? 0.3 and 0 ? Q ? 0.5, respectively. Despite the low accuracy of these results, they give additional support to a recent claim of KPZ scaling in oligomer films. However, there are significant finite-size effects in the scaled height distributions of models with large local slopes, such as ballistic deposition, which suggests that comparison of height distributions must not be used to rule out KPZ scaling. On the other hand, roughness distributions of the same models show good data collapse, with negligible dependence on time and window size. The estimates of skewness and kurtosis for roughness distributions are 1.7 ? S ? 2 and 3 ? Q ? 7. A stretched exponential tail was found, which seems to be a particular feature of KPZ systems in 2 + 1 dimensions. Moreover, the KPZ roughness distributions cannot be fitted by those of 1/f^α noise. This study suggests that the roughness distribution is the best option to test KPZ scaling in the growth regime, and provides quantitative data for future comparison with other models or experiments.