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

Net energy analysis of solar and conventional domestic hot water systems in Melbourne, Australia

It is commonly assumed that solar hot water systems save energy and reduce greenhouse gas emissions. Very rarely has the life-cycle energy requirements of solar hot water systems been analysed, including their embodied energy. The extent to which solar hot water systems save energy compared to conventional systems in Melbourne, Australia, is shown through a comparative net energy analysis. The solar systems provided a net energy saving compared to the conventional systems after 0.5 to 2 years, for electricity and gas systems respectively.<br /

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

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

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

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

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

What is the Entanglement Length in a Polymer Melt ?

We present results of molecular dynamics simulations of very long model polymer chains analyzed by various experimentally relevant techniques. The segment motion of the chains is found to be in very good agreement with the repatation model. We also calculated the plateau-modulus G_N. The predicitions of the entanglement length N_e from G_N and from the mean square displacements of the chains segments disagree by a factor of about 2.2(2), indicating an error in the prefactor in the standard formula for G_N. We show that recent neutron spin echo measurements were carried out for chain lengths which are too small for a correct determination of N_e.Comment: 5 pages, 4 figures, RevTe