Distance dependence of angular correlations in dense polymer solutions

Angular correlations in dense solutions and melts of flexible polymer chains are investigated with respect to the distance $r$ between the bonds by comparing quantitative predictions of perturbation calculations with numerical data obtained by Monte Carlo simulation of the bond-fluctuation model. We consider both monodisperse systems and grand-canonical (Flory-distributed) equilibrium polymers. Density effects are discussed as well as finite chain length corrections. The intrachain bond-bond correlation function $P(r)$ is shown to decay as $P(r) \sim 1/r^3$ for \xi \ll r \ll \r^* with $\xi$ being the screening length of the density fluctuations and $r^* \sim N^{1/3}$ a novel length scale increasing slowly with (mean) chain length $N$.Comment: 17 pages, 5 figures, accepted for publication at Macromolecule

Hyperbranched polymer stars with Gaussian chain statistics revisited

Conformational properties of regular dendrimers and more general hyperbranched polymer stars with Gaussian statistics for the spacer chains between branching points are revisited numerically. We investigate the scaling for asymptotically long chains especially for fractal dimensions $d_f = 3$ (marginally compact) and $d_f = 2.5$ (diffusion limited aggregation). Power-law stars obtained by imposing the number of additional arms per generation are compared to truly self-similar stars. We discuss effects of weak excluded volume interactions and sketch the regime where the Gaussian approximation should hold in dense solutions and melts for sufficiently large spacer chains.Comment: 13 pages, 14 figure

Stress Propagation and Arching in Static Sandpiles

We present a new approach to the modelling of stress propagation in static granular media, focussing on the conical sandpile constructed from a point source. We view the medium as consisting of cohesionless hard particles held up by static frictional forces; these are subject to microscopic indeterminacy which corresponds macroscopically to the fact that the equations of stress continuity are incomplete -- no strain variable can be defined. We propose that in general the continuity equations should be closed by means of a constitutive relation (or relations) between different components of the (mesoscopically averaged) stress tensor. The primary constitutive relation relates radial and vertical shear and normal stresses (in two dimensions, this is all one needs). We argue that the constitutive relation(s) should be local, and should encode the construction history of the pile: this history determines the organization of the grains at a mesoscopic scale, and thereby the local relationship between stresses. To the accuracy of published experiments, the pattern of stresses beneath a pile shows a scaling between piles of different heights (RSF scaling) which severely limits the form the constitutive relation can take ...Comment: 38 pages, 24 Postscript figures, LATEX, minor misspellings corrected, Journal de Physique I, Ref. Nr. 6.1125, accepte

Shear modulus of simulated glass-forming model systems: Effects of boundary condition, temperature and sampling time

The shear modulus G of two glass-forming colloidal model systems in d=3 and d=2 dimensions is investigated by means of, respectively, molecular dynamics and Monte Carlo simulations. Comparing ensembles where either the shear strain gamma or the conjugated (mean) shear stress tau are imposed, we compute G from the respective stress and strain fluctuations as a function of temperature T while keeping a constant normal pressure P. The choice of the ensemble is seen to be highly relevant for the shear stress fluctuations mu_F(T) which at constant tau decay monotonously with T following the affine shear elasticity mu_A(T), i.e. a simple two-point correlation function. At variance, non-monotonous behavior with a maximum at the glass transition temperature T_g is demonstrated for mu_F(T) at constant gamma. The increase of G below T_g is reasonably fitted for both models by a continuous cusp singularity, G(T) is proportional to (1-T/T_g)^(1/2), in qualitative agreement with some recent replica calculations. It is argued, however, that longer sampling times may lead to a sharper transition. The additive jump discontinuity predicted by mode-coupling theory and other replica calculations thus cannot ultimately be ruled out

Static Rouse Modes and Related Quantities: Corrections to Chain Ideality in Polymer Melts

Following the Flory ideality hypothesis intrachain and interchain excluded volume interactions are supposed to compensate each other in dense polymer systems. Multi-chain effects should thus be neglected and polymer conformations may be understood from simple phantom chain models. Here we provide evidence against this phantom chain, mean-field picture. We analyze numerically and theoretically the static correlation function of the Rouse modes. Our numerical results are obtained from computer simulations of two coarse-grained polymer models for which the strength of the monomer repulsion can be varied, from full excluded volume (`hard monomers') to no excluded volume (`phantom chains'). For nonvanishing excluded volume we find the simulated correlation function of the Rouse modes to deviate markedly from the predictions of phantom chain models. This demonstrates that there are nonnegligible correlations along the chains in a melt. These correlations can be taken into account by perturbation theory. Our simulation results are in good agreement with these new theoretical predictions.Comment: 9 pages, 7 figures, accepted for publication in EPJ