54 research outputs found
Percolation of Immobile Domains in Supercooled Thin Polymeric Films
We present an analysis of heterogeneous dynamics in molecular dynamics
simulations of a thin polymeric film, supported by an absorbing structured
surface. Near the glass transition "immobile" domains occur throughout the
film, yet the probability of their occurrence decreasing with larger distance
from the surface. Still, enough immobile domains are located near the free
surface to cause them to percolate in the direction perpendicular to surface,
at a temperature near the glass transition temperature. This result is in
agreement with a recent theoretical model of glass transition
Glass Transition Behavior of Polymer Films of Nanoscopic Dimensions
Glass transition behavior of nanoscopically thin polymer films is
investigated by means of molecular dynamics simulations. A thin polymer film
that is composed of bead-spring model chains and supported on an idealized, fcc
lattice substrate surface is studied in this work.Comment: in review, macromolecule
Individual Entanglements in a Simulated Polymer Melt
We examine entanglements using monomer contacts between pairs of chains in a
Brownian-dynamics simulation of a polymer melt. A map of contact positions with
respect to the contacting monomer numbers (i,j) shows clustering in small
regions of (i,j) which persists in time, as expected for entanglements. Using
the ``space''-time correlation function of the aforementioned contacts, we show
that a pair of entangled chains exhibits a qualitatively different behavior
than a pair of distant chains when brought together. Quantitatively, about 50%
of the contacts between entangled chains are persistent contacts not present in
independently moving chains. In addition, we account for several observed
scaling properties of the contact correlation function.Comment: latex, 12 pages, 7 figures, postscript file available at
http://arnold.uchicago.edu/~ebn
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 . Changes in the
tensile stress, mode of failure and interfacial fracture energy 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 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 is calculated
by coupling the simulation results to a continuum fracture mechanics model. As
in experiment, increases as before saturating at the average
bulk fracture energy . As in previous simulations of shear strength,
saturation coincides with the recovery of the bulk entanglement density. Before
saturation, 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
Shear yielding of amorphous glassy solids: Effect of temperature and strain rate
We study shear yielding and steady state flow of glassy materials with
molecular dynamics simulations of two standard models: amorphous polymers and
bidisperse Lennard-Jones glasses. For a fixed strain rate, the maximum shear
yield stress and the steady state flow stress in simple shear both drop
linearly with increasing temperature. The dependence on strain rate can be
described by a either a logarithm or a power-law added to a constant. In marked
contrast to predictions of traditional thermal activation models, the rate
dependence is nearly independent of temperature. The relation to more recent
models of plastic deformation and glassy rheology is discussed, and the
dynamics of particles and stress in small regions is examined in light of these
findings
Microstructural Origins of Nonlinear Response in Associating Polymers under Oscillatory Shear
The response of associating polymers with oscillatory shear is studied through large-scale simulations. A hybrid molecular dynamics (MD), Monte Carlo (MC) algorithm is employed. Polymer chains are modeled as a coarse-grained bead-spring system. Functionalized end groups, at both ends of the polymer chains, can form reversible bonds according to MC rules. Stress-strain curves show nonlinearities indicated by a non-ellipsoidal shape. We consider two types of nonlinearities. Type I occurs at a strain amplitude much larger than one, type II at a frequency at which the elastic storage modulus dominates the viscous loss modulus. In this last case, the network topology resembles that of the system at rest. The reversible bonds are broken and chains stretch when the system moves away from the zero-strain position. For type I, the chains relax and the number of reversible bonds peaks when the system is near an extreme of the motion. During the movement to the other extreme of the cycle, first a stress overshoot occurs, then a yield accompanied by shear-banding. Finally, the network restructures. Interestingly, the system periodically restores bonds between the same associating groups. Even though major restructuring occurs, the system remembers previous network topologies
Topological changes at the gel transition of a reversible polymeric network
We investigate how the network topology of an ensemble of telechelic polymers changes with temperature. The telechelic polymers serve as “links" between “nodes", which consist of aggregates of their associating end groups. Our analysis shows that the degree distribution of the system is bimodal and consists of two Poissonian distributions with different average degrees. The number of nodes in each of them as well as the distribution of links depend on temperature. By comparing the eigenvalue spectra of the simulated gel networks with those of reconstructed networks, the most likely topology at each temperature is determined. Topological changes occur at the transition temperatures reported in our previous study (Baljo
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