Rigidity of disordered networks with bond-bending forces.

At zero temperature, the elastic constants of a disordered network with bond-bending forces vanish at the geometric percolation point p(c), in contrast to networks with only central forces which lose the ability to withstand shear at a rigidity percolation point p(r). Moreover, the critical behavior of the modulus is different in the two cases. I report on extensive molecular dynamics simulations on a model system with central and bond-bending forces between the monomers over a range of temperatures T. The critical behavior of the shear modulus seems to be the same as that of a purely central-force network at finite T and consistent with a long-standing conjecture of de Gennes.

Critical behavior of entropic shear rigidity.

We report on extensive molecular dynamics (MD) simulations of a model for gels in both two and three dimensions. The model consists of randomly cross-linked monomers with a concentration p of cross-links above the percolation concentration so that the system is in the amorphous solid phase. As the concentration of cross-links approaches the percolation concentration, the entropic shear modulus vanishes as G approximately(p-p(c))(t) with t approximately 1.9 in three dimensions and t approximately 1.3 in two dimensions. These results hold whether or not the background fluid consisting of finite clusters is retained in the system. These results are also consistent with our previous calculations and with a conjecture of de Gennes but not with recent analytical results and another body of simulations.

Single-polymer Brownian motor: a simulation study.

Numerical simulation is used to study a single polymer chain in a flashing ratchet potential to determine how the mechanism of this Brownian motor system is affected by the presence of internal degrees of freedom. The polymer is modeled by a freely jointed chain with N monomers in which the monomers interact via a repulsive Lennard-Jones potential and neighboring monomers on the chain are connected by finite extensible nonlinear elastic bonds. Each monomer is acted upon by a 1D asymmetric, piecewise linear potential of spatial period L comparable to the radius of gyration of the polymer. This potential is also characterized by a localization time, t(on), and by a free diffusion time, t(off). We characterize the average motor velocity as a function of L, t(off), and N to determine optimal parameter ranges, and we evaluate motor performance in terms of finite dispersion, Peclet number, rectification efficiency, stall force, and transportation of a load against a viscous drag. We find that the polymer motor performs qualitatively better than a single particle in a flashing ratchet: with increasing N, the polymer loses velocity much more slowly than expected in the absence of internal degrees of freedom, and the motor stall force increases linearly with N. To understand these cooperative aspects of motor operation, we analyze relevant Rouse modes. The experimental feasibility is analyzed and the parameters of the model are scaled to those of lambda-DNA. Finally, in the context of experimental realization, we present initial modeling results for a 2D flashing ratchet constructed using an electrode array, and find good agreement with the results of 1D simulations although the polymer in the 2D potential sometimes briefly "detaches" from the electrode surface.

Rigidity transition in polymer melts with van der Waals interaction.

We study the onset of rigidity near the glass transition (GT) in a short-chain polymer melt modelled by a bead-spring model, where all beads interact with Lennard-Jones potentials. The properties of the system are examined above and below the GT. In order to minimize high-cooling-rate effects and computational times, equilibrium configurations are reached via isothermal compression. We monitor quantities such as the heat capacity CP, the short-time diffusion constants D, the viscosity eta , and the shear modulus; the time-dependent shear modulus Gt is compared with the shear modulus mu obtained from an externally applied instantaneous shear. We give a detailed analysis of the effects of such shearing on the system, both locally and globally. It is found that the polymeric glass displays long-time rigid behavior only below a temperature T1 , where T1 < TG. Furthermore, the linear and nonlinear relaxation regimes under applied shear are discussed.

Transport properties of incipient gels.

We investigate the behavior of the shear viscosity eta(p) and the mass-dependent diffusion coefficient D(m,p) in the context of a simple model that, as the cross link density p is increased, undergoes a continuous transition from a fluid to a gel. The shear viscosity diverges at the gel point according to eta(p) approximately (p(c)-p)(-s) with s approximately 0.65. The diffusion constant shows a remarkable dependence on the mass of the clusters: D(m,p) approximately m(-0.69), not only at p(c) but well into the liquid phase. We also find that the Stokes-Einstein relation Deta proportional, variant k(B)T breaks down already quite far from the gel point.

Model for gelation with explicit solvent effects: structure and dynamics.

We study a two-component model for gelation consisting of f-functional monomers (the gel) and inert particles (the solvent). After equilibration as a simple liquid, the gel particles are gradually cross linked to each other until the desired number of cross links have been attained. At a critical cross-link density, the largest gel cluster percolates and an amorphous solid forms. This percolation process is different from ordinary lattice or continuum percolation of a single species in the sense that the critical exponents are new. As the cross-link density p approaches its critical value p(c), the shear viscosity diverges: eta(p) approximately (p(c)-p)(-s) with s a nonuniversal concentration-dependent exponent.