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

"Don't think I'm going to leave you over it": Accounts of changing hepatitis C status among couples who inject drugs.

While the health-related benefits of intimate partnership are well documented, little attention has been paid to couples exposed to high levels of social stigma and exclusion. In this project we investigated an important site of stigma for partnerships by collecting accounts of changing hepatitis C (HCV) status ("sero-change") among couples that inject drugs. We explored what these accounts reveal about the meaning of HCV for these couples, and how this understanding contributes to our collective efforts at prevention and care. Drawing from a large dataset of qualitative interviews with couples, we focussed on those containing reports of sero-change. By adopting a methodology that positioned partnerships rather than individuals as the primary unit of analysis, we addressed the commonplace tendency to either overlook or discount as dysfunctional, the sexual relationships of people who inject drugs. While some couples sought greater biomedical understanding as a means of coming to terms with sero-change, others drew on alternative logics or "rationalities" that sat firmly outside conventional biomedical discourse (privileging notions of kinship, for example). Regardless of which explanatory framework they drew on, participants ultimately prioritised the security of their relationship over the dangers of viral infection. Effectively engaging couples in HCV prevention and care requires acknowledging and working with the competing priorities and complex realities of such partnerships beyond simply the identification of viral risk. The "new era" of direct acting antiviral treatments will provide ongoing opportunities to learn to integrate biomedical information within more socially sophisticated, relationally aware approaches

Optimized cross-slot flow geometry for microfluidic extension rheometry

A precision-machined cross-slot flow geometry with a shape that has been optimized by numerical simulation of the fluid kinematics is fabricated and used to measure the extensional viscosity of a dilute polymer solution. Full-field birefringence microscopy is used to monitor the evolution and growth of macromolecular anisotropy along the stagnation point streamline, and we observe the formation of a strong and uniform birefringent strand when the dimensionless flow strength exceeds a critical Weissenberg number Wicrit 0:5. Birefringence and bulk pressure drop measurements provide self consistent estimates of the planar extensional viscosity of the fluid over a wide range of deformation rates (26 s1 "_ 435 s1) and are also in close agreement with numerical simulations performed by using a finitely extensible nonlinear elastic dumbbell model

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

Goldstone fluctuations in the amorphous solid state

Goldstone modes in the amorphous solid state, resulting from the spontaneous breaking of translational symmetry due to random localisation of particles, are discussed. Starting from a microscopic model with quenched disorder, the broken symmetry is identified to be that of relative translations of the replicas. Goldstone excitations, corresponding to pure shear deformations, are constructed from long wavelength distortions of the order parameter. The elastic free energy is computed, and it is shown that Goldstone fluctuations destroy localisation in two spatial dimensions, yielding a two-dimensional amorphous solid state characterised by power-law correlations.Comment: 7 pages, 2 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

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

Dating of the oldest continental sediments from the Himalayan foreland basin

A detailed knowledge of Himalayan development is important for our wider understanding of several global processes, ranging from models of plateau uplift to changes in oceanic chemistry and climate(1-4). Continental sediments 55 Myr old found in a foreland basin in Pakistan(5) are, by more than 20 Myr, the oldest deposits thought to have been eroded from the Himalayan metamorphic mountain belt. This constraint on when erosion began has influenced models of the timing and diachrony of the India-Eurasia collision(6-8), timing and mechanisms of exhumation(9,10) and uplift(11), as well as our general understanding of foreland basin dynamics(12). But the depositional age of these basin sediments was based on biostratigraphy from four intercalated marl units(5). Here we present dates of 257 detrital grains of white mica from this succession, using the Ar-40-(39) Ar method, and find that the largest concentration of ages are at 36-40 Myr. These dates are incompatible with the biostratigraphy unless the mineral ages have been reset, a possibility that we reject on the basis of a number of lines of evidence. A more detailed mapping of this formation suggests that the marl units are structurally intercalated with the continental sediments and accordingly that biostratigraphy cannot be used to date the clastic succession. The oldest continental foreland basin sediments containing metamorphic detritus eroded from the Himalaya orogeny therefore seem to be at least 15-20 Myr younger than previously believed, and models based on the older age must be re-evaluated