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

Formation and Equilibrium Properties of Living Polymer Brushes

Polydisperse brushes obtained by reversible radical chain polymerization reaction onto a solid substrate with surface-attached initiators, are studied by means of an off-lattice Monte Carlo algorithm of living polymers (LP). Various properties of such brushes, like the average chain length and the conformational orientation of the polymers, or the force exerted by the brush on the opposite container wall, reveal power-law dependence on the relevant parameters. The observed molecular weight distribution (MWD) of the grafted LP decays much more slowly than the corresponding LP bulk system due to the gradient of the monomer density within the dense pseudo-brush which favors longer chains. Both MWD and the density profiles of grafted polymers and chain ends are well fitted by effective power laws whereby the different exponents turn out to be mutually self-consistent for a pseudo-brush in the strong-stretching regime.Comment: 33 pages, 11 figues, J.Chem. Phys. accepted Oct. 199

Characterization of local dynamics and mobilities in polymer melts - a simulation study

The local dynamical features of a PEO melt studied by MD simulations are compared to two model chain systems, namely the well-known Rouse model as well as the semiflexible chain model (SFCM) that additionally incorporates chain stiffness. Apart from the analysis of rather general quantities such as the mean square displacement (MSD), we present a new statistical method to extract the local bead mobility from the simulation data on the basis of the Langevin equation, thus providing a complementary approach to the classical Rouse-mode analysis. This allows us to check the validity of the Langevin equation and, as a consequence, the Rouse model. Moreover, the new method has a broad range of applications for the analysis of the dynamics of more complex polymeric systems like comb-branched polymers or polymer blends.Comment: 6 pages, 5 figure

Development of Stresses in Cohesionless Poured Sand

The pressure distribution beneath a conical sandpile, created by pouring sand from a point source onto a rough rigid support, shows a pronounced minimum below the apex (`the dip'). Recent work of the authors has attempted to explain this phenomenon by invoking local rules for stress propagation that depend on the local geometry, and hence on the construction history, of the medium. We discuss the fundamental difference between such approaches, which lead to hyperbolic differential equations, and elastoplastic models, for which the equations are elliptic within any elastic zones present .... This displacement field appears to be either ill-defined, or defined relative to a reference state whose physical existence is in doubt. Insofar as their predictions depend on physical factors unknown and outside experimental control, such elastoplastic models predict that the observations should be intrinsically irreproducible .... Our hyperbolic models are based instead on a physical picture of the material, in which (a) the load is supported by a skeletal network of force chains ("stress paths") whose geometry depends on construction history; (b) this network is `fragile' or marginally stable, in a sense that we define. .... We point out that our hyperbolic models can nonetheless be reconciled with elastoplastic ideas by taking the limit of an extremely anisotropic yield condition.Comment: 25 pages, latex RS.tex with rspublic.sty, 7 figures in Rsfig.ps. Philosophical Transactions A, Royal Society, submitted 02/9

Copper flows in buildings, infrastructure and mobiles: a dynamic model and its application to Switzerland

During the last century, the consumption of materials for human needs increased by several orders of magnitude, even for non-renewable materials such as metals. Some data on annual consumption (input) and recycling/waste (output) can often be found in the federal statistics, but a clear picture of the main flows is missing. A dynamic material flow model is developed for the example of copper in Switzerland in order to simulate the relevant copper flows and stocks over the last 150years. The model is calibrated using data from statistical and published sources as well as from interviews and measurements. A simulation of the current state (2000) is compared with data from other studies. The results show that Swiss consumption and losses are both high, at a level of about 8 and 2kg/(capyear), respectively, or about three times higher than the world average. The model gives an understanding of the flows and stocks and their interdependencies as a function of time. This is crucial for materials whose consumption dynamics are characterised by long lifetimes and hence for relating the current output to the input of the whole past. The model allows a comprehensive discussion of possible measures to reduce resource use and losses to the environment. While increasing the recycling reduces losses to landfill, only copper substitution can reduce the different losses to the environment, although with a time delay of the order of a lifetim

Continuum limit of amorphous elastic bodies (III): Three dimensional systems

Extending recent numerical studies on two dimensional amorphous bodies, we characterize the approach of elastic continuum limit in three dimensional (weakly polydisperse) Lennard-Jones systems. While performing a systematic finite-size analysis (for two different quench protocols) we investigate the non-affine displacement field under external strain, the linear response to an external delta force and the low-frequency harmonic eigenmodes and their density distribution. Qualitatively similar behavior is found as in two dimensions. We demonstrate that the classical elasticity description breaks down below an intermediate length scale $\xi$, which in our system is approximately 23 molecular sizes. This length characterizes the correlations of the non-affine displacement field, the self-averaging of external noise with distance from the source and gives the lower wave length bound for the applicability of the classical eigenfrequency calculations. We trace back the "Boson-peak" of the density of eigenfrequencies (obtained from the velocity auto-correlation function) to the inhomogeneities on wave lengths smaller than $\xi$.Comment: 27 pages, 11 figures, submitted to Phys. Rev.

Statistical Mechanics of Stress Transmission in Disordered Granular Arrays

We give a statistical-mechanical theory of stress transmission in disordered arrays of rigid grains with perfect friction. Starting from the equations of microscopic force and torque balance we derive the fundamental equations of stress equilibrium. We illustrate the validity of our approach by solving the stress distribution of a homogeneous and isotropic array.Comment: 4 pages, to be published in PR

Impulsive correction to the elastic moduli obtained using the stress-fluctuation formalism in systems with truncated pair potential

The truncation of a pair potential at a distance r_cut is well-known to imply in general an impulsive correction to the pressure and other moments of the first derivatives of the potential. That depending on r_cut the truncation may also be of relevance to higher derivatives is shown theoretically for the Born contributions to the elastic moduli obtained using the stress-fluctuation formalism in d dimensions. Focusing on isotropic liquids for which the shear modulus G must vanish by construction, the predicted corrections are tested numerically for binary mixtures and polydisperse Lennard-Jones beads in, respectively, d=3 and d=2 dimensions

Scale-free static and dynamical correlations in melts of monodisperse and Flory-distributed homopolymers: A review of recent bond-fluctuation model studies

It has been assumed until very recently that all long-range correlations are screened in three-dimensional melts of linear homopolymers on distances beyond the correlation length $\xi$ characterizing the decay of the density fluctuations. Summarizing simulation results obtained by means of a variant of the bond-fluctuation model with finite monomer excluded volume interactions and topology violating local and global Monte Carlo moves, we show that due to an interplay of the chain connectivity and the incompressibility constraint, both static and dynamical correlations arise on distances $r \gg \xi$. These correlations are scale-free and, surprisingly, do not depend explicitly on the compressibility of the solution. Both monodisperse and (essentially) Flory-distributed equilibrium polymers are considered.Comment: 60 pages, 49 figure