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

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

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

Models of stress fluctuations in granular media

We investigate in detail two models describing how stresses propagate and fluctuate in granular media. The first one is a scalar model where only the vertical component of the stress tensor is considered. In the continuum limit, this model is equivalent to a diffusion equation (where the r\^ole of time is played by the vertical coordinate) plus a randomly varying convection term. We calculate the response and correlation function of this model, and discuss several properties, in particular related to the stress distribution function. We then turn to the tensorial model, where the basic starting point is a wave equation which, in the absence of disorder, leads to a ray-like propagation of stress. In the presence of disorder, the rays acquire a diffusive width and the angle of propagation is shifted. A striking feature is that the response function becomes negative, which suggests that the contact network is mechanically unstable to very weak perturbations. The stress correlation function reveals characteristic features related to the ray-like propagation, which are absent in the scalar description. Our analytical calculations are confirmed and extended by a numerical analysis of the stochastic wave equation.Comment: 32 pages, latex, 18 figures and 6 diagram

Vibrations of amorphous, nanometric structures: When does continuum theory apply?

Structures involving solid particles of nanometric dimensions play an increasingly important role in material sciences. These structures are often characterized through the vibrational properties of their constituent particles, which can be probed by spectroscopic methods. Interpretation of such experimental data requires an extension of continuum elasticity theory down to increasingly small scales. Using numerical simulation and exact diagonalization for simple models, we show that continuum elasticity, applied to disordered system, actually breaks down below a length scale of typically 30 to 50 molecular sizes. This length scale is likely related to the one which is generally invoked to explain the peculiar vibrational properties of glassy systems.Comment: 4 pages, 5 figures, LATEX, Europhysics Letters accepte

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

Stress in frictionless granular material: Adaptive Network Simulations

We present a minimalistic approach to simulations of force transmission through granular systems. We start from a configuration containing cohesive (tensile) contact forces and use an adaptive procedure to find the stable configuration with no tensile contact forces. The procedure works by sequentially removing and adding individual contacts between adjacent beads, while the bead positions are not modified. In a series of two-dimensional realizations, the resulting force networks are shown to satisfy a linear constraint among the three components of average stress, as anticipated by recent theories. The coefficients in the linear constraint remain nearly constant for a range of shear loadings up to about .6 of the normal loading. The spatial distribution of contact forces shows strong concentration along ``force chains". The probability of contact forces of magnitude f shows an exponential falloff with f. The response to a local perturbing force is concentrated along two characteristic rays directed downward and laterally.Comment: 8 pages, 8 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