Mesoscopic theory of the viscoelasticity of polymers

We have advanced our previous static theory of polymer entanglement involving an extended Cahn-Hilliard functional, to include time-dependent dynamics. We go beyond the Gaussian approximation, to the one-loop level, to compute the frequency dependent storage and loss moduli of the system. The three parameters in our theory are obtained by fitting to available experimental data on polystyrene melts of various chain lengths. This provides a physical representation of the parameters in terms of the chain length of the system. We discuss the importance of the various terms in our energy functional with respect to their contribution to the viscoelastic response of the polymeric system.Comment: Submitted to Phys. Rev.

Influence of supercoiling on the disruption of dsDNA

We propose that supercoiling energizes double-stranded DNA (dsDNA) so as to facilitate thermal fluctuations to an unzipped state. We support this with a model of two elastic rods coupled via forces that represent base pair interactions. Supercoiling is shown to lead to a spatially localized higher energy state in a small region of dsDNA consisting of a few base pairs. This causes the distance between specific base pairs to be extended, enhancing the thermal probability for their disruption. Our theory permits the development of an analogy between this unzipping transition and a second order phase transition, for which the possibility of a new set of critical exponents is identified

Onset of entanglement

We have developed a theory of polymer entanglement using an extended Cahn-Hilliard functional, with two extra terms. One is a nonlocal attractive term, operating over mesoscales, which is interpreted as giving rise to entanglement, and the other a local repulsive term indicative of excluded volume interactions. We show how such a functional can be derived using notions from gauge theory. We go beyond the Gaussian approximation, to the one-loop level, to show that the system exhibits a crossover to a state of entanglement as the average chain length between points of entanglement decreases. This crossover is marked by critical slowing down, as the effective diffusion constant goes to zero. We have also computed the tensile modulus of the system, and we find a corresponding crossover to a regime of high modulus.Comment: 18 pages, with 4 figure

Phonons in random alloys: the itinerant coherent-potential approximation

We present the itinerant coherent-potential approximation(ICPA), an analytic, translationally invariant and tractable form of augmented-space-based, multiple-scattering theory in a single-site approximation for harmonic phonons in realistic random binary alloys with mass and force-constant disorder. We provide expressions for quantities needed for comparison with experimental structure factors such as partial and average spectral functions and derive the sum rules associated with them. Numerical results are presented for Ni_{55} Pd_{45} and Ni_{50} Pt_{50} alloys which serve as test cases, the former for weak force-constant disorder and the latter for strong. We present results on dispersion curves and disorder-induced widths. Direct comparisons with the single-site coherent potential approximation(CPA) and experiment are made which provide insight into the physics of force-constant changes in random alloys. The CPA accounts well for the weak force-constant disorder case but fails for strong force-constant disorder where the ICPA succeeds.Comment: 19 pages, 12 eps figures, uses RevTex

ELEMENTARY APPROACH TO SELF-ASSEMBLY AND ELASTIC PROPERTIES OF RANDOM COPOLYMERS

The authors have mapped the physics of a system of random copolymers onto a time-dependent density functional-type field theory using techniques of functional integration. Time in the theory is merely a label for the location of a given monomer along the extent of a flexible chain. We derive heuristically within this approach a non-local constraint which prevents segments on chains in the system from straying too far from each other, and leads to self-assembly. The structure factor is then computed in a straightforward fashion. The long wave-length limit of the structure factor is used to obtain the elastic modulus of the network. It is shown that there is a surprising competition between the degree of micro-phase separation and the elastic moduli of the system

A Flow Reactor for the Flow Supercritical Water Oxidation of Wastes to Mitigate the Reactor Corrosion Problem

We have designed a flow tube reactor for supercritical water oxidation of wastes that confines the oxidation reaction to the vicinity of the axis of the tube. This prevents high temperatures and reactants as well as reaction products from coming in intimate contact with reactor walls. This implies a lessening of corrosion of the walls of the reactor. We display numerical simulations for a vertical reactor with conservative design parameters that illustrate our concept. We performed our calculations for the destruction of sodium nitrate by ammonium hydroxide In the presence of supercritical water, where the production of sodium hydroxide causes corrosion. We have compared these results with that for a horizontal set-up where the sodium hydroxide created during the reaction ends up on the floor of the tube, implying a higher probability of corrosion