The effect of collisions on the chemomechanics of ice-covered silica slabs: a molecular dynamics study.

Using molecular dynamics simulation and the REAX potential, we study the collision of two planar silica surfaces covered by water ice. Without the ice cover, the two surfaces stick at all velocities investigated (160-1800 m s-1), due to the formation of chemical bonds between the colliding surfaces. A narrow ice cover - here of thickness 2 nm - prevents the sticking above a characteristic velocity, the bouncing velocity νb. During the collision, reactions occur at the silica-water interface; in particular, water molecules are dissociated and silanols are formed at the surface of the silica slabs. Passivation of the silica surface by H atoms is of little consequence to the magnitude of vb but reduces the number of surface reactions occurring.

The Influence of Lubrication and the Solid-Fluid Interaction on Thermodynamic Properties in a Nanoscopic Scratching Process.

Liquid lubricants play an important role in contact processes; for example, they reduce friction and cool the contact zone. To gain better understanding of the influence of lubrication on the nanoscale, both dry and lubricated scratching processes in a model system are compared in the present work using molecular dynamics simulations. The entire range between total dewetting and total wetting is investigated by tuning the solid-fluid interaction energy. The investigated scratching process consists of three sequential movements: A cylindrical indenter penetrates an initially flat substrate, then scratches in the lateral direction, and is finally retracted out of the contact with the substrate. The indenter is fully submersed in the fluid in the lubricated cases. The substrate, the indenter, and the fluid are described by suitably parametrized Lennard-Jones model potentials. The presence of the lubricant is found to have a significant influence on the friction and on the energy balance of the process. The thermodynamic properties of the lubricant are evaluated in detail. A correlation of the simulation results for the profiles of the temperature, density, and pressure of the fluid in the vicinity of the chip is developed. The work done by the indenter is found to mainly dissipate and thereby heat up the substrate and eventually the fluid. Only a minor part of the work causes plastic deformation of the substrate.

The bouncing threshold in silica nanograin collisions.

Using molecular dynamics simulations, we study collisions between amorphous silica nanoparticles. Our silica model contains uncontaminated surfaces, that is, the effect of surface hydroxylation or of adsorbed water layers is excluded. For central collisions, we characterize the boundary between sticking and bouncing collisions as a function of impact velocity and particle size and quantify the coefficient of restitution. We show that the traditional Johnson-Kendall-Roberts (JKR) model provides a valid description of the ingoing trajectory of two grains up to the moment of maximum compression. The distance of closest approach is slightly underestimated by the JKR model, due to the appearance of plasticity in the grains, which shows up in the form of localized shear transformation zones. The JKR model strongly underestimates the contact radius and the collision duration during the outgoing trajectory, evidencing that the breaking of covalent bonds during grain separation is not well described by this model. The adhesive neck formed between the two grains finally collapses while creating narrow filaments joining the grains, which eventually tear.

Accelerated Molecular Dynamics Study of the Effects of Surface Hydrophilicity on Protein Adsorption.

The adsorption of streptavidin is studied on two surfaces, graphite and titanium dioxide, using accelerated molecular dynamics. Adsorption on graphite leads to strong conformational changes while the protein spreads out over the surface. Interestingly, also adsorption on the highly hydrophilic rutile surface induces considerable spreading of the protein. We pin down the cause for this unfolding to the interaction of the protein with the ordered water layers above the rutile surface. For special orientations, the protein penetrates the ordered water layers and comes into direct contact with the surface where the positively charged amino acids settle in places adjacent to the negatively charged top surface atom layer of rutile. We conclude that for both surface materials studied, streptavidin changes its conformation so strongly that it loses its potential for binding biotin. Our results are in good qualitative agreement with available experimental studies.

Nanoindentation of hcp metals: a comparative simulation study of the evolution of dislocation networks.

Using molecular dynamics simulation, we study the nanoindentation of three hcp metals: Mg, Ti, and Zr. Both the basal and two prismatic surface planes are considered. We focus on the characterization of the plasticity generated in the crystal. The similarities to, and the differences from, the behavior of the more commonly investigated fcc and bcc metals are highlighted. We find that hcp metals show a larger variety than the fcc and bcc metals studied up until now. The prolific emission of prismatic loops can lead to extended plastic zones. The size of the plastic zone is quantified by the ratio f of the plastic zone radius to the radius of the contact area. We find values of between 1.6 (an almost collapsed zone) and >5; in the latter case, complex dislocation networks build up which are extended in the direction of easy glide.

The elastic-plastic transition in nanoparticle collisions.

When nanoparticles (NPs) collide with low velocities, they interact elastically in the sense that--besides their fusion caused by their mutual van-der-Waals attraction--no defects are generated. We investigate the minimum velocity, vc, necessary for generating defects and inducing plasticity in the NP. The determination of this elastic-plastic threshold is of prime importance for modeling the behavior of granular matter. Using the generic Lennard-Jones interaction potential, we find vc to increase strongly with decreasing radius. Current models do not agree with our simulations, but we provide a model based on dislocation emission in the contact zone that quantitatively describes the size dependence of the elastic-plastic transition.

Contact angle of sessile drops in Lennard-Jones systems.

Molecular dynamics simulations are used for studying the contact angle of nanoscale sessile drops on a planar solid wall in a system interacting via the truncated and shifted Lennard-Jones potential. The entire range between total wetting and dewetting is investigated by varying the solid-fluid dispersive interaction energy. The temperature is varied between the triple point and the critical temperature. A correlation is obtained for the contact angle in dependence of the temperature and the dispersive interaction energy. Size effects are studied by varying the number of fluid particles at otherwise constant conditions, using up to 150,000 particles. For particle numbers below 10,000, a decrease of the contact angle is found. This is attributed to a dependence of the solid-liquid surface tension on the droplet size. A convergence to a constant contact angle is observed for larger system sizes. The influence of the wall model is studied by varying the density of the wall. The effective solid-fluid dispersive interaction energy at a contact angle of θ = 90° is found to be independent of temperature and to decrease linearly with the solid density. A correlation is developed that describes the contact angle as a function of the dispersive interaction, the temperature, and the solid density. The density profile of the sessile drop and the surrounding vapor phase is described by a correlation combining a sigmoidal function and an oscillation term.

An atomistic study of sticking, bouncing, and aggregate destruction in collisions of grains with small aggregates.

Molecular dynamics simulations are used to study central collisions between spherical grains and between grains and small grain aggregates (up to 5 grains). For a model material (Lennard-Jones), grain-grain collisions are sticking when the relative velocity v is smaller than the so-called bouncing velocity and bouncing for higher velocities. We find a similar behavior for grain-aggregate collisions. The value of the bouncing velocity depends only negligibly on the aggregate size. However, it is by 35% larger than the separation velocity needed to break a contact; this is explained by energy dissipation processes during the collision. The separation velocity follows the predictions of the macroscopic Johnson-Kendall-Roberts theory of contacts. At even higher collision velocities, the aggregate is destroyed, first by the loss of a monomer grain and then by total disruption. In contrast to theoretical considerations, we do not find a proportionality of the collision energy needed for destruction and the number of bonds to be broken. Our study thus sheds novel light on the foundations of granular mechanics, namely the energy needed to separate two grains, the difference between grain-grain and grain-aggregate collisions, and the energy needed for aggregate destruction.

Adsorption of Diclofenac and PFBS on a Hair Keratin Dimer.

Environmental pollution by man-made toxic and persistent organic compounds, found throughout the world in surface and groundwater, has various negative effects on aquatic life systems and even humans. Therefore, it is important to develop and improve water treatment technologies capable of removing such substances from wastewater and purifying drinking water. The two substances investigated are the widely used painkiller diclofenac and a member of the class of "forever chemicals", perfluorobutanesulfonate. Both are known to have serious negative effects on living organisms, especially under long-term exposure, and are detectable in human hair, suggesting adsorption to a part of the hair fiber complex. In this study, a human hair keratin dimer is investigated for its ability to absorb diclofenac and perfluorobutanesulfonate. Initial predictions for binding sites are obtained via molecular docking and subjected to molecular dynamics simulations for more than 1 µs. The binding affinities obtained by the linear interaction energy method are high enough to motivate further research on human hair keratins as a sustainable, low-cost, and easily allocatable filtration material.

Nanoindentation into a bcc high-entropy HfNbTaTiZr alloy-an atomistic study of the effect of short-range order.

The plastic response of the Senkov HfNbTaTiZr high-entropy alloy is explored by means of simulated nanoindentation tests. Both a random alloy and an alloy with chemical short-range order are investigated and compared to the well understood case of an elementary Ta crystal. Strong differences in the dislocation plasticity between the alloys and the elementary Ta crystal are found. The high-entropy alloys show only little relaxation of the indentation dislocation network after indenter retraction and only negligible dislocation emission into the sample interior. Short-range order-besides making the alloy both stiffer and harder-further increases the size of the plastic zone and the dislocation density there. These features are explained by the slow dislocation migration in these alloys. Also, the short-range-ordered alloy features no twinning plasticity in contrast to the random alloy, while elemental Ta exhibits twinning under high stress but detwins considerably under stress relief. The results are in good qualitative agreement with our current knowledge of plasticity in high-entropy alloys.

A granular mechanics model study of the influence of non-spherical shape on aggregate collisions.

Collisions between granular aggregates influence the size distribution of dust clouds. Granular aggregates may possess non-spherical shapes as a result of, for instance, previous collision processes. Here, we study aggregate collisions using a granular mechanics simulation code. Collisions between spherical aggregates are compared to collisions of ellipsoidal aggregates of equal mass. As the most prominent result, we find that the growth velocity, i.e., the velocity above which the post-collision aggregates are smaller than before collision, is generally reduced for ellipsoidal aggregates. The reason hereto lies in the less compact structure of ellipsoids which allows for a larger degree of fragmentation in a 'rim peel-off' mechanism. On the other hand, relative fragment distributions are only little influenced by aggregate shape.

Adsorption of Diclofenac and Its UV Phototransformation Products in an Aqueous Solution on PVDF: A Molecular Modeling Study.

The presence of pharmaceuticals in drinking water has generated considerable scientific interest in potential improvements to polymeric membranes for water purification at the nanoscale. In this work, we investigate the adsorption of diclofenac and its ultraviolet (UV) phototransformation products on amorphous and crystalline poly(vinylidene difluoride) (PVDF) membrane surfaces at the nanoscale using molecular modeling. We report binding affinities by determining the free energy landscape via the extended adaptive biasing force method. The high binding affinities of the phototransformation products found are consistent with qualitative experimental results. For diclofenac, we found similar or better affinities than those for the phototransformation products, which seems to be in contrast to the experimental findings. This discrepancy can only be explained if the maximum adsorption density of diclofenac is much lower than that of the products. Overall, negligible differences between the adsorption affinities of the crystalline phases are observed, suggesting that no tuning of the PVDF surfaces is necessary to optimize filtration capabilities.

Strain-rate-dependent plasticity of Ta-Cu nanocomposites for therapeutic implants.

Recently, Ta/Cu nanocomposites have been widely used in therapeutic medical devices due to their excellent bioactivity and biocompatibility, antimicrobial property, and outstanding corrosion and wear resistance. Since mechanical yielding and any other deformation in the patient's body during treatment are unacceptable in medicine, the characterization of the mechanical behavior of these nanomaterials is of great importance. We focus on the microstructural evolution of Ta/Cu nanocomposite samples under uniaxial tensile loading conditions at different strain rates using a series of molecular dynamics simulations and compare to the reference case of pure Ta. The results show that the increase in dislocation density at lower strain rates leads to the significant weakening of the mechanical properties. The strain rate-dependent plastic deformation mechanism of the samples can be divided into three main categories: phase transitions at the extreme strain rates, dislocation slip/twinning at lower strain rates for coarse-grained samples, and grain-boundary based activities for the finer-grained samples. Finally, we demonstrate that the load transfer from the Ta matrix to the Cu nanoparticles via the interfacial region can significantly affect the plastic deformation of the matrix in all nanocomposite samples. These results will prove useful for the design of therapeutic implants based on Ta/Cu nanocomposites.

Spin-lattice-dynamics analysis of magnetic properties of iron under compression.

Compression of a magnetic material leads to a change in its magnetic properties. We examine this effect using spin-lattice dynamics for the special case of bcc-Fe, using both single- and poly-crystalline Fe and a bicontinuous nanofoam structure. We find that during the elastic phase of compression, the magnetization increases due to a higher population of the nearest-neighbor shell of atoms and the resulting higher exchange interaction of neighboring spins. In contrast, in the plastic phase of compression, the magnetization sinks, as defects are created, increasing the disorder and typically decreasing the average atom coordination number. The effects are more pronounced in single crystals than in polycrystals, since the presence of defects in the form of grain boundaries counteracts the increase in magnetization during the elastic phase of compression. Also, the effects are more pronounced at temperatures close to the Curie temperature than at room temperature. In nanofoams, the effect of compression is minor since compression proceeds more by void reduction and filament bending-with negligible effect on magnetization-than by strain within the ligaments. These findings will prove useful for tailoring magnetization under strain by introducing plasticity.

Simulated nanoindentation into single-phase fcc Fe[Formula: see text]Ni[Formula: see text] alloys predicts maximum hardness for equiatomic stoichiometry.

We investigate by molecular dynamics simulation the mechanical behavior of concentrated alloys under nanoindentation for the special example of single-phase fcc Fe[Formula: see text]Ni[Formula: see text] alloys. The indentation hardness is maximum for the equiatomic alloy, [Formula: see text]. This finding is in agreement with experimental results on the strength of these alloys under uniaxial strain. We explain this finding with the increase of the unstable stacking fault energy in the alloys towards [Formula: see text]. With increasing Fe content, loop emission from the plastic zone under the indenter becomes less pronounced and the plastic zone features a larger fraction of screw dislocation segments; simultaneously, the length of the dislocation network and the number of atoms in the stacking faults generated in the plastic zone increase. However, the volume of twinned regions in the plastic zone is highest for the elemental solids and decreases for the alloys. This feature is explained by the fact that twinning proceeds by the glide of dislocations on adjacent parallel lattice planes; this concerted motion is less efficient in the alloys. Finally, we find that surface imprints show increasing pile-up heights with increasing Fe content. The present results will be of interest for hardness engineering or generating hardness profiles in concentrated alloys.

Why nanoprojectiles work differently than macroimpactors: the role of plastic flow.

Atomistic simulation data on crater formation due to the hypervelocity impact of nanoprojectiles of up to 55 nm diameter and with targets containing up to 1.1×10(10) atoms are compared to available experimental data on µm-, mm-, and cm-sized projectiles. We show that previous scaling laws do not hold in the nanoregime and outline the reasons: within our simulations we observe that the cratering mechanism changes, going from the smallest to the largest simulated scales, from an evaporative regime to a regime where melt and plastic flow dominate, as is expected in larger microscale experiments. The importance of the strain-rate dependence of strength and of dislocation production and motion are discussed.

Bouncing and spinning of amorphous Lennard-Jones nanoparticles under oblique collisions.

Collisions of Lennard-Jones nanoparticles (NPs) may be used to study the generic collision behavior of NPs. We study the collision dynamics of amorphous NPs for oblique collisions using molecular dynamics simulation as a function of collision velocity and impact parameter. In order to allow for NP bouncing, the attraction between atoms originating from differing NPs is reduced. For near-central collisions, a finite region of velocities - a 'bouncing window' - exists where the 2 NPs bounce from each other. At smaller velocities, energy dissipation and - at larger velocities - also NP deformation do not allow the NPs to surpass the attractive forces such that they stick to each other. Oblique collisions of non-rotating NPs convert angular momentum into NP spin. For low velocities, the NP spin is well described by assuming the NPs to come momentarily to a complete stop at the contact point ('grip'), such that orbital and spin angular momentum share the pre-collision angular momentum in a ratio of 5:2. The normal coefficient of restitution increases with impact parameter for small velocities, but changes sign for larger velocities where the 2 NPs do not repel but their motion direction persists. The tangential coefficient of restitution is fixed in the 'grip' regime to a value of 5/7, but increases towards 1 for high-velocity collisions at not too small impact parameters, where the 2 NPs slide along each other.

Collisions between CO, CO[Formula: see text], H[Formula: see text]O and Ar ice nanoparticles compared by molecular dynamics simulation.

Molecular dynamics simulations are used to study collisions between amorphous ice nanoparticles consisting of CO, CO[Formula: see text], Ar and H[Formula: see text]O. The collisions are always sticking for the nanoparticle size (radius of 20 nm) considered. At higher collision velocities, the merged clusters show strong plastic deformation and material mixing in the collision zone. Collision-induced heating influences the collision outcome. Partial melting of the merged cluster in the collision zone contributes to energy dissipation and deformation. Considerable differences exist-even at comparable collision conditions-between the ices studied here. The number of ejecta emitted during the collision follows the trend in triple-point temperatures and increases exponentially with the NP temperature.

A nanodispersion-in-nanograins strategy for ultra-strong, ductile and stable metal nanocomposites.

Nanograined metals have the merit of high strength, but usually suffer from low work hardening capacity and poor thermal stability, causing premature failure and limiting their practical utilities. Here we report a "nanodispersion-in-nanograins" strategy to simultaneously strengthen and stabilize nanocrystalline metals such as copper and nickel. Our strategy relies on a uniform dispersion of extremely fine sized carbon nanoparticles (2.6 ± 1.2 nm) inside nanograins. The intragranular dispersion of nanoparticles not only elevates the strength of already-strong nanograins by 35%, but also activates multiple hardening mechanisms via dislocation-nanoparticle interactions, leading to improved work hardening and large tensile ductility. In addition, these finely dispersed nanoparticles result in substantially enhanced thermal stability and electrical conductivity in metal nanocomposites. Our results demonstrate the concurrent improvement of several mutually exclusive properties in metals including strength-ductility, strength-thermal stability, and strength-electrical conductivity, and thus represent a promising route to engineering high-performance nanostructured materials.