Topological versus rheological entanglement length in primitive path analysis protocols

Primitive path analysis algorithms are now routinely employed to analyze entanglements in computer simulations of polymeric systems, but different analysis protocols result in different estimates of the entanglement length, N_e. Here we argue that standard PPA measures the rheological entanglement length, typically employed by tube models and relevant to quantitative comparisons with experiment, while codes like Z or CReTA also determine the topological entanglement length. For loosely entangled systems, a simple analogy between between phantom networks and the mesh of entangled primitive paths suggests a factor of two between the two numbers. This result is in excellent agreement with reported values for poly-ethylene, poly-butadiene and bead-spring polymer melts.Comment: 3 pages, no figure

Viscoplasticity and large-scale chain relaxation in glassy-polymeric strain hardening

A simple theory for glassy polymeric mechanical response which accounts for large scale chain relaxation is presented. It captures the crossover from perfect-plastic response to strong strain hardening as the degree of polymerization $N$ increases, without invoking entanglements. By relating hardening to interactions on the scale of monomers and chain segments, we correctly predict its magnitude. Strain activated relaxation arising from the need to maintain constant chain contour length reduces the $N$ dependence of the characteristic relaxation time by a factor $\sim \dot\epsilon N$ during active deformation at strain rate $\dot\epsilon$. This prediction is consistent with results from recent experiments and simulations, and we suggest how it may be further tested experimentally.Comment: The theoretical treatment of the mechanical response has been significantly revised, and the arguments for coherent relaxation during active deformation made more transparen

Strain Hardening in Polymer Glasses: Limitations of Network Models

Simulations are used to examine the microscopic origins of strain hardening in polymer glasses. While traditional entropic network models can be fit to the total stress, their underlying assumptions are inconsistent with simulation results. There is a substantial energetic contribution to the stress that rises rapidly as segments between entanglements are pulled taut. The thermal component of stress is less sensitive to entanglements, mostly irreversible, and directly related to the rate of local plastic arrangements. Entangled and unentangled chains show the same strain hardening when plotted against the microscopic chain orientation rather than the macroscopic strain.Comment: 4 pages, 3 figure

Thermal Fluctuations and Rubber Elasticity

The effects of thermal elastic fluctuations in rubber materials are examined. It is shown that, due to an interplay with the incompressibility constraint, these fluctuations qualitatively modify the large-deformation stress-strain relation, compared to that of classical rubber elasticity. To leading order, this mechanism provides a simple and generic explanation for the peak structure of Mooney-Rivlin stress-strain relation, and shows a good agreement with experiments. It also leads to the prediction of a phonon correlation function that depends on the external deformation.Comment: 4 RevTeX pages, 1 figure, submitted to PR

Supersymmetry solution for finitely extensible dumbbell model

Exact relaxation times and eigenfunctions for a simple mechanical model of polymer dynamics are obtained using supersymmetry methods of quantum mechanics. The model includes the finite extensibility of the molecule and does not make use of the self-consistently averaging approximation. The finite extensibility reduces the relaxation times when compared to a linear force. The linear viscoelastic behaviour is obtained in the form of the ``generalized Maxwell model''. Using these results, a numerical integration scheme is proposed in the presence of a given flow kinematics.Comment: 5 pages, 2 figure

Direct optical observations of surface thermal motions at sub-shot noise levels

We measure spectral properties of surface thermal fluctuations of liquids, solids, complex fluids and biological matter using light scattering methods. The random thermal fluctuations are delineated from random noise at sub-shot noise levels. The principle behind this extraction, which is quite general and is not limited to surface measurements, is explained. An optical lever is used to measure the spectrum of fluctuations in the inclinations of surfaces down to $\sim 10^{-17}\rm rad^2/Hz$ at $1\sim10 \mu$W optical intensity, corresponding to $\sim 10^{-29} \rm m^2/\rm Hz$ in the vertical displacement, in the frequency range $1{\rm}\rm kHz\sim10 MHz$. The dynamical evolution of the surface properties is also investigated. The measurement requires only a short amount of time and is essentially passive, so that it can be applied to a wide variety of surfaces.Comment: 5pp, 5 figure

Strain-dependent localization, microscopic deformations, and macroscopic normal tensions in model polymer networks

We use molecular dynamics simulations to investigate the microscopic and macroscopic response of model polymer networks to uniaxial elongations. By studying networks with strands lengths ranging from $N_s=20$ to 200 we cover the full crossover from cross-link to entanglement dominated behavior. Our results support a recent version of the tube model which accounts for the different strain dependence of chain localization due to chemical cross-links and entanglements

Scaling of Entropic Shear Rigidity

The scaling of the shear modulus near the gelation/vulcanization transition is explored heuristically and analytically. It is found that in a dense melt the effective chains of the infinite cluster have sizes that scale sub-linearly with their contour length. Consequently, each contributes k_B T to the rigidity, which leads to a shear modulus exponent d\nu. In contrast, in phantom elastic networks the scaling is linear in the contour length, yielding an exponent identical to that of the random resistor network conductivity, as predicted by de Gennes'. For non-dense systems, the exponent should cross over to d\nu when the percolation length becomes much larger than the density-fluctuation length.Comment: 4 pages, 2 eps figure

Smectic-C tilt under shear in Smectic-A elastomers

Stenull and Lubensky [Phys. Rev. E {\bf 76}, 011706 (2007)] have argued that shear strain and tilt of the director relative to the layer normal are coupled in smectic elastomers and that the imposition of one necessarily leads to the development of the other. This means, in particular, that a Smectic-A elastomer subjected to a simple shear will develop Smectic-C-like tilt of the director. Recently, Kramer and Finkelmann [arXiv:0708.2024, Phys. Rev. E {\bf 78}, 021704 (2008)] performed shear experiments on Smectic-A elastomers using two different shear geometries. One of the experiments, which implements simple shear, produces clear evidence for the development of Smectic-C-like tilt. Here, we generalize a model for smectic elastomers introduced by Adams and Warner [Phys. Rev. E {\bf 71}, 021708 (2005)] and use it to study the magnitude of Smectic-C-like tilt under shear for the two geometries investigated by Kramer and Finkelmann. Using reasonable estimates of model parameters, we estimate the tilt angle for both geometries, and we compare our estimates to the experimental results. The other shear geometry is problematic since it introduces additional in-plane compressions in a sheet-like sample, thus inducing instabilities that we discuss.Comment: 8 pages, 5 figure

History Memorized and Recalled upon Glass Transition

The memory effect upon glassification is studied in the glass to rubber transition of vulcanized rubber with the strain as a controlling parameter. A phenomenological model is proposed taking the history of the temperature and the strain into account, by which the experimental results are interpreted. The data and the model demonstrate that the glassy state memorizes the time-course of strain upon glassification, not as a single parameter but as the history itself. The data also show that the effect of irreversible deformation in the glassy state is beyond the scope of the present model. Authors' remark: The title of the paper in the accepted version is above. The title appeared in PRL is the one changed by a Senior Assistant Editor after acceptance of the paper. The recovery of the title was rejected in the correction process.Comment: 4 pages, 4 figure