arXiv subjects

Gary S. Grest

Publications and source records attributed to Gary S. Grest.

At least 55 records · Page 3Linked to original sources

arXiv2014

Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements and Crazing

Large-scale molecular simulations are performed to investigate tensile failure of polymer interfaces as a function of welding time $t$. Changes in the tensile stress, mode of failure and interfacial fracture energy $G_I$ are correlated to changes in the interfacial entanglements as determined from Primitive Path Analysis. Bulk polymers fail through craze formation, followed by craze breakdown through chain scission. At small $t$ welded interfaces are not strong enough to support craze formation and fail at small strains through chain pullout at the interface. Once chains have formed an average of about one entanglement across the interface, a stable craze is formed throughout the sample. The failure stress of the craze rises with welding time and the mode of craze breakdown changes from chain pullout to chain scission as the interface approaches bulk strength. The interfacial fracture energy $G_I$ is calculated by coupling the simulation results to a continuum fracture mechanics model. As in experiment, $G_I$ increases as $t^{1/2}$ before saturating at the average bulk fracture energy $G_b$. As in previous simulations of shear strength, saturation coincides with the recovery of the bulk entanglement density. Before saturation, $G_I$ is proportional to the areal density of interfacial entanglements. Immiscibiltiy limits interdiffusion and thus suppresses entanglements at the interface. Even small degrees of immisciblity reduce interfacial entanglements enough that failure occurs by chain pullout and $G_I \ll G_b$.

cond-mat.soft↗

arXiv2014

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those for thermal welding of homopolymer slabs. The two processes differ in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface. The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the interdiffusion is significantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of them are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and thus mechanically weaken the interface. When the interfacial strength saturates, the number of interfacial entanglements scales with the corresponding bulk entanglement density. Chain stiffness increases the density of entanglements, which increases the interfacial strength. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.

cond-mat.soft↗

arXiv2014

Coating thickness and coverage effects on the forces between silica nanoparticles in water

The structure and interactions of coated silica nanoparticles have been studied in water using molecular dynamics simulations. For 5 nm diameter amorphous silica nanoparticles we studied the effects of varying the chain length and grafting density of polyethylene oxide (PEO) on the nanoparticle coating's shape and on nanoparticle-nanoparticle effective forces. For short ligands of length $n=6$ and $n=20$ repeat units, the coatings are radially symmetric while for longer chains ($n=100$) the coatings are highly anisotropic. This anisotropy appears to be governed primarily by chain length, with coverage playing a secondary role. For the largest chain lengths considered, the strongly anisotropic shape makes fitting to a simple radial force model impossible. For shorter ligands, where the coatings are isotropic, we found that the force between pairs of nanoparticles is purely repulsive and can be fit to the form $(R/2r_\text{core}-1)^{-b}$ where $R$ is the separation between the center of the nanoparticles, $r_\text{core}$ is the radius of the silica core, and $b$ is measured to be between 2.3 and 4.1.

cond-mat.soft↗

arXiv2013

Structure and Strength at Immiscible Polymer Interfaces

Thermal welding of polymer-polymer interfaces is important for integrating polymeric elements into devices. When two different polymers are joined, the strength of the weld depends critically on the degree of immiscibility. We perform large-scale molecular dynamics simulations of the structure-strength relation at immiscible polymer interfaces. Our simulations show that immiscibility arrests interdiffusion and limits the equilibrium interfacial width. Even for weakly immiscible films, the narrow interface is unable to transfer stress upon deformation as effectively as the bulk material, and chain pullout at the interface becomes the dominant failure mechanism. This greatly reduces the interfacial strength. The weak response of immiscible interfaces is shown to arise from an insufficient density of entanglements across the interface. We demonstrate that there is a threshold interfacial width below which no significant entanglements can form between opposite sides to strengthen the interface.

cond-mat.soft↗

arXiv2013

Molecular Dynamics Simulations of Evaporation-Induced Nanoparticle Assembly

While evaporating solvent is a widely used technique to assemble nano-sized objects into desired superstructures, there has been limited work on how the assembled structures are affected by the physical aspects of the process. We present large scale molecular dynamics simulations of the evaporation-induced assembly of nanoparticles suspended in a liquid that evaporates in a controlled fashion. The quality of the nanoparticle crystal formed just below the liquid/vapor interface is found to be better at relatively slower evaporation rates, as less defects and grain boundaries appear. This trend is understood as the result of the competition between the accumulation and diffusion times of nanoparticles at the liquid/vapor interface. When the former is smaller, nanoparticles are deposited so fast at the interface that they do not have sufficient time to arrange through diffusion, which leads to the prevalence of defects and grain boundaries. Our results have important implications in understanding assembly of nanoparticles and colloids in non-equilibrium liquid environments.

cond-mat.soft↗

arXiv2012

Polymer Welding: Strength Through Entanglements

Large-scale simulations of thermal welding of polymers are performed to investigate the rise of mechanical strength at the polymer-polymer interface with the welding time. The welding process is in the core of integrating polymeric elements into devices as well as in thermal induced healing of polymers; processes that require development of interfacial strength equal to that of the bulk. Our simulations show that the interfacial strength saturates at the bulk shear strength much before polymers diffuse by their radius of gyration. Along with the strength increase, the dominant failure mode changes from chain pullout at the interface to chain scission as in the bulk. Formation of sufficient entanglements across the interface, which we track using a Primitive Path Analysis is required to arrest catastrophic chain pullout at the interface. The bulk response is not fully recovered until the density of entanglements at the interface reaches the bulk value. Moreover, the increase of interfacial strength before saturation is proportional to the number of interfacial entanglements between chains from opposite sides.

cond-mat.soft↗

arXiv2012

Structure and Diffusion of Nanoparticle Monolayers Floating at Liquid/Vapor Interfaces: A Molecular Dynamics Study

Large-scale molecular dynamics simulations are used to simulate a layer of nanoparticles diffusing on the surface of a liquid. Both a low viscosity liquid, represented by Lennard-Jones monomers, and a high viscosity liquid, represented by linear homopolymers, are studied. The organization and diffusion of the nanoparticles are analyzed as the nanoparticle density and the contact angle between the nanoparticles and liquid are varied. When the interaction between the nanoparticles and liquid is reduced the contact angle increases and the nanoparticles ride higher on the liquid surface, which enables them to diffuse faster. In this case the short range order is also reduced as seen in the pair correlation function. For the polymeric liquids, the out-of-layer fluctuation is suppressed and the short range order is slightly enhanced. However, the diffusion becomes much slower and the mean square displacement even shows sub-linear time dependence at large times. The relation between diffusion coefficient and viscosity is found to deviate from that in bulk diffusion. Results are compared to simulations of the identical nanoparticles in 2-dimensions.

cond-mat.soft↗

arXiv2011

Rheology of Ring Polymer Melts: From Linear Contaminants to Ring/Linear Blends

Ring polymers remain a major challenge to our current understanding of polymer dynamics. Experimental results are difficult to interpret because of the uncertainty in the purity and dispersity of the sample. Using both equilibrium and non-equilibrium molecular dynamics simulations we have systematically investigated the structure, dynamics and rheology of perfectly controlled ring/linear polymer blends with chains of such length and flexibility that the number of entanglements is up to about 14 per chain, which is comparable to experimental systems examined in the literature. The smallest concentration at which linear contaminants increase the zero-shear viscosity of a ring polymer melt of these chain lengths by 10% is approximately one-fifth of their overlap concentration. When the two architectures are present in equal amounts the viscosity of the blend is approximately twice as large as that of the pure linear melt. At this concentration the diffusion coefficient of the rings is found to decrease dramatically, while the static and dynamic properties of the linear polymers are mostly unaffected. Our results are supported by a primitive path analysis.

cond-mat.soft↗

arXiv2011

Evaporation of Lennard-Jones Fluids

Evaporation and condensation at a liquid/vapor interface are ubiquitous interphase mass and energy transfer phenomena that are still not well understood. We have carried out large scale molecular dynamics simulations of Lennard-Jones (LJ) fluids composed of monomers, dimers, or trimers to investigate these processes with molecular detail. For LJ monomers in contact with a vacuum, the evaporation rate is found to be very high with significant evaporative cooling and an accompanying density gradient in the liquid domain near the liquid/vapor interface. Increasing the chain length to just dimers significantly reduces the evaporation rate. We confirm that mechanical equilibrium plays a key role in determining the evaporation rate and the density and temperature profiles across the liquid/vapor interface. The velocity distributions of evaporated molecules and the evaporation and condensation coefficients are measured and compared to the predictions of an existing model based on kinetic theory of gases. Our results indicate that for both monatomic and polyatomic molecules, the evaporation and condensation coefficients are equal when systems are not far from equilibrium and smaller than one, and decrease with increasing temperature. For the same reduced temperature $T/T_c$, where $T_c$ is the critical temperature, these two coefficients are higher for LJ dimers and trimers than for monomers, in contrast to the traditional viewpoint that they are close to unity for monatomic molecules and decrease for polyatomic molecules. Furthermore, data for the two coefficients collapse onto a master curve when plotted against a translational length ratio between the liquid and vapor phase.

cond-mat.soft↗

arXiv2011

Molecular Dynamics Simulation Study of Nonconcatenated Ring Polymers in a Melt: I. Statics

Molecular dynamics simulations were conducted to investigate the structural properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N=1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. For the rings, the radius of gyration squared was found to scale as N to the 4/5 power for an intermediate regime and N to the 2/3 power for the larger rings indicating an overall conformation of a crumpled globule. However, almost all beads of the rings are "surface beads" interacting with beads of other rings, a result also in agreement with a primitive path analysis performed in the following paper (DOI: 10.1063/1.3587138). Details of the internal conformational properties of the ring and linear polymers as well as their packing are analyzed and compared to current theoretical models.

cond-mat.soft↗

arXiv2011

Molecular Dynamics Simulation Study of Nonconcatenated Ring Polymers in a Melt: II. Dynamics

Molecular dynamics simulations were conducted to investigate the dynamic properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N=1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. The ring melts were found to diffuse faster than their linear counterparts, with the self-diffusion coefficient for both architectures scaling as approximately N to the -2.4 power for large N. The mean-square displacement of the center-of-mass of the rings follows a sub-diffusive behavior for times and distances beyond the mean-square gyration radius, neither compatible with the Rouse nor the reptation model. The rings relax stress much faster than linear polymers and the zero-shear viscosity was found to vary as approximately N to the 1.4 power which is much weaker than the N to the 3.4 power of linear chains, not matching any commonly known model for polymer dynamics when compared to the observed mean-square displacements. These findings are discussed in view of the conformational properties of the rings presented in the preceding paper (DOI: 10.1063/1.3587137).

cond-mat.soft↗

arXiv2010

End Grafted Polymer Nanoparticles in a Polymeric Matrix: Effect of Coverage and Curvature

It has recently been proposed that the miscibility of nanoparticles with a polymer matrix can be controlled by grafting polymer chains to the nanoparticle surface. As a first step to study this situation, we have used molecular dynamics simulations on a single nanoparticle of radius R ($4σ\le$R$\le 16σ$, where $σ$ is the diameter of a polymer monomer) grafted with chains of length 500 in a polymer melt of chains of length 1000. The grafting density $Σ$ was varied between $0.04$-$0.32$ chains/$σ^2$. To facilitate equilibration a Monte Carlo double-bridging algorithm is applied - new bonds are formed across a pair of chains, creating two new chains each substantially different from the original. For the long brush chains studied here, the structure of the brush assumes its large particle limit even for $R$ as small as 8$σ$, which is consistent with recent experimental findings. We study autophobic dewetting of the melt from the brush as a function of increasing $Σ$. Even these long brush and matrix chains of length $6$ and $12$ $N_e$, respectively, (the entanglement length is $N_e \sim 85$) give somewhat ambiguous results for the interfacial width, showing that studies of two or more nanoparticles are necessary to properly understand these miscibility issues. Entanglement between the brush and melt chains were identified using the primitive path analysis. We find that the number of entanglements between the brush and melt chains scale simply with the product of the local monomer densities of brush and melt chains.

cond-mat.soft↗

arXiv2010

Stress Relaxation in Entangled Polymer Melts

We present an extensive set of simulation results for the stress relaxation in equilibrium and step-strained bead-spring polymer melts. The data allow us to explore the chain dynamics and the shear relaxation modulus, $G(t)$, into the plateau regime for chains with $Z=40$ entanglements and into the terminal relaxation regime for $Z=10$. Using the known (Rouse) mobility of unentangled chains and the melt entanglement length determined via the primitive path analysis of the microscopic topological state of our systems, we have performed parameter -free tests of several different tube models. We find excellent agreement for the Likhtman-McLeish theory using the double reptation approximation for constraint release, if we remove the contribution of high-frequency modes to contour length fluctuations of the primitive chain.

cond-mat.soft↗

arXiv2010

Effect of Particle Shape and Charge on Bulk Rheology of Nanoparticle Suspensions

The rheology of nanoparticle suspensions for nanoparticles of various shapes with equal mass is studied using molecular dynamics simulations. The equilibrium structure and the response to imposed shear are analyzed for suspensions of spheres, rods, plates, and jacks in an explicit solvent for both charged and uncharged nanoparticles. For the volume fraction studied, ?$ϕ_{vf}=0.075$, the uncharged systems are all in their isotropic phase and the viscosity is only weakly dependent on shape for spheres, rods, and plate whereas for the jacks the viscosity is an order of magnitude larger than for the other three shapes. The introduction of charge increases the viscosity for all four nanoparticle shapes with the increase being the largest for rods and plates. The presence of a repulsive charge between the particles decreases the amount of stress reduction that can be achieved by particle reorientation.

cond-mat.soft↗

arXiv2009

Forces between functionalized silica nanoparticles in solution

To prevent the flocculation and phase separation of nanoparticles in solution, nanoparticles are often functionalized with short chain surfactants. Here we present fully-atomistic molecular dynamics simulations which characterize how these functional coatings affect the interactions between nanoparticles and with the surrounding solvent. For 5 nm diameter silica nanoparticles coated with poly(ethylene oxide) (PEO) oligomers in water, we determined the hydrodynamic drag on two approaching nanoparticles moving through solvent and on a single nanoparticle as it approaches a planar surface. In most circumstances, acroscale fluid theory accurately predicts the drag on these nano-scale particles. Good agreement is seen with Brenner's analytical solutions for wall separations larger than the soft nanoparticle radius. For two approaching coated nanoparticles, the solvent-mediated (velocity-independent) and lubrication (velocity-dependent) forces are purely repulsive and do not exhibit force oscillations that are typical of uncoated rigid spheres.

cond-mat.mes-hall↗

arXiv2007

Viscoelasticity and primitive path analysis of entangled polymer liquids: From f-actin to polyethylene

We combine computer simulations and scaling arguments to develop a unified view of polymer entanglement based on the primitive path analysis (PPA) of the microscopic topological state. Our results agree with experimentally measured plateau moduli for three different polymer classes over a wide rangeof reduced polymer densities: (i) semi-dilute theta solutions of synthetic polymers, (ii) the corresponding dense melts above the glass transition or crystallization temperature, and (iii) solutions of semi-flexible (bio)polymers such as f-actin or suspensions of rodlike viruses. Together these systems cover the entire range from loosely to tightly entangled polymers. In particular, we argue that the primitive path analysis renormalizes a loosely to a tightly entangled system and provide a new explanation of the successful Lin-Noolandi packing conjecture for polymer melts.

cond-mat.soft↗

arXiv2007

Application of Ewald summations to long-range dispersion forces

We present results illustrating the effects of using explicit summation terms for the $r^{-6}$ dispersion term on the interfacial properties of a Lennard-Jones fluid and SPC/E water. For the Lennard-Jones fluid, we find that the use of long-range summations, even with a short ``crossover radius,'' yields results that are consistent with simulations using large cutoff radii. Simulations of SPC/E water demonstrate that the long-range dispersion forces are of secondary importance to the Coulombic forces. In both cases, we find that the ratio of box size $L_{\parallel}$ to crossover radius $r_{\rm c}^{\mathbf k}$ plays an important role in determining the magnitude of the long-range dispersion correction, although its effect is secondary when Coulombic interactions are also present.

cond-mat.mtrl-sci↗

arXiv2007

Stresses in Smooth Flows of Dense Granular Media

The form of the stress tensor is investigated in smooth, dense granular flows which are generated in split-bottom shear geometries. We find that, within a fluctuation fluidized spatial region, the form of the stress tensor is directly dictated by the flow field: The stress and strain-rate tensors are co-linear. The effective friction, defined as the ratio between shear and normal stresses acting on a shearing plane, is found not to be constant but to vary throughout the flowing zone. This variation can not be explained by inertial effects, but appears to be set by the local geometry of the flow field. This is in agreement with a recent prediction, but in contrast with most models for slow grain flows, and points to there being a subtle mechanism that selects the flow profiles.

cond-mat.soft↗