50 research outputs found
A study of the entanglement in systems with periodic boundary conditions
We define the local periodic linking number, LK, between two oriented closed
or open chains in a system with three-dimensional periodic boundary conditions.
The properties of LK indicate that it is an appropriate measure of entanglement
between a collection of chains in a periodic system. Using this measure of
linking to assess the extent of entanglement in a polymer melt we study the
effect of CReTA algorithm on the entanglement of polyethylene chains. Our
numerical results show that the statistics of the local periodic linking number
observed for polymer melts before and after the application of CReTA are the
same.Comment: 11 pages, 11 figure
Structure and dynamics of ring polymers: entanglement effects because of solution density and ring topology
The effects of entanglement in solutions and melts of unknotted ring polymers
have been addressed by several theoretical and numerical studies. The system
properties have been typically profiled as a function of ring contour length at
fixed solution density. Here, we use a different approach to investigate
numerically the equilibrium and kinetic properties of solutions of model ring
polymers. Specifically, the ring contour length is maintained fixed, while the
interplay of inter- and intra-chain entanglement is modulated by varying both
solution density (from infinite dilution up to \approx 40 % volume occupancy)
and ring topology (by considering unknotted and trefoil-knotted chains). The
equilibrium metric properties of rings with either topology are found to be
only weakly affected by the increase of solution density. Even at the highest
density, the average ring size, shape anisotropy and length of the knotted
region differ at most by 40% from those of isolated rings. Conversely, kinetics
are strongly affected by the degree of inter-chain entanglement: for both
unknots and trefoils the characteristic times of ring size relaxation,
reorientation and diffusion change by one order of magnitude across the
considered range of concentrations. Yet, significant topology-dependent
differences in kinetics are observed only for very dilute solutions (much below
the ring overlap threshold). For knotted rings, the slowest kinetic process is
found to correspond to the diffusion of the knotted region along the ring
backbone.Comment: 17 pages, 11 figure
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
From atomistic simulations to slip-link models of entangled polymer melts: Hierarchical strategies for the prediction of rheological properties
Segregation, clustering, and suppression of phase separation in amorphous silicon–germanium alloys
We study the problem of decomposition in amorphous Si-Ge alloys. Our Monte Carlo (MC) simulations show that phase separation is totally suppressed in the amorphous phase. Still, in the short-range structure of the network there is a tendency for clustering of homopolar bonds, as this relieves strain energy. The strain field due to the amorphous/ crystalline interface produces compositional modulations in the alloy
Effects of topological disorder on phase separation and local order in a-si1-xgex. alloys
Monte Carlo simulations show that the inherent tendency for decomposition of the Si-Ge solid mixture is totally suppressed in the amorphous phase. Yet, the distribution of Si and Ge atoms in the network is not random as in the crystal, but there is a strong tendency of homopolar bonds to cluster locally, even at high temperatures. We show that the disorder potential of the amorphous network prevents the percolation of these clusters in segregated regions under thermodynamic equilibrium. However, these homopolar clusters might act as precursors of metastable decomposed regions observed in crystallization processes