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

Glassy states and microphase separation in cross-linked homopolymer blends

The physical properties of blends of distinct homopolymers, cross-linked beyond the gelation point, are addressed via a Landau approach involving a pair of coupled order-parameter fields: one describing vulcanisation, the other describing local phase separation. Thermal concentration fluctuations, present at the time of cross-linking, are frozen in by cross-linking, and the structure of the resulting glassy fluctuations is analysed at the Gaussian level in various regimes, determined by the relative values of certain physical length-scales. The enhancement, due to gelation, of the stability of the blend with respect to demixing is also analysed. Beyond the corresponding stability limit, gelation prevents complete demixing, replacing it by microphase separation, which occurs up to a length-scale set by the rigidity of the network, as a simple variational scheme reveals.Comment: 7 pages, 6 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

‘‘Lozenge’’ contour plots in scattering from polymer networks

We present a consistent explanation for the appearance of “lozenge” shapes in contour plots of the two dimensional scattering intensity from stretched polymer networks. By explicitly averaging over quenched variables in a tube model, we show that lozenge patterns arise as a result of chain material that is not directly deformed by the stretch. We obtain excellent agreement with experimental data

Random solids and random solidification: What can be learned by exploring systems obeying permanent random constraints?

In many interesting physical settings, such as the vulcanization of rubber, the introduction of permanent random constraints between the constituents of a homogeneous fluid can cause a phase transition to a random solid state. In this random solid state, particles are permanently but randomly localized in space, and a rigidity to shear deformations emerges. Owing to the permanence of the random constraints, this phase transition is an equilibrium transition, which confers on it a simplicity (at least relative to the conventional glass transition) in the sense that it is amenable to established techniques of equilibrium statistical mechanics. In this Paper I shall review recent developments in the theory of random solidification for systems obeying permanent random constraints, with the aim of bringing to the fore the similarities and differences between such systems and those exhibiting the conventional glass transition. I shall also report new results, obtained in collaboration with Weiqun Peng, on equilibrium correlations and susceptibilities that signal the approach of the random solidification transition, discussing the physical interpretation and values of these quantities both at the Gaussian level of approximation and, via a renormalization-group approach, beyond.Comment: Paper presented at the "Unifying Concepts in Glass Physics" workshop, International Centre for Theoretical Physics, Trieste, Italy (September 15-18, 1999

Dynamical signatures of the vulcanization transition

Dynamical properties of vulcanized polymer networks are addressed via a Rouse-type model that incorporates the effect of permanent random crosslinks. The incoherent intermediate scattering function is computed in the sol and gel phases, and at the vulcanization transition between them. At any nonzero crosslink density within the sol phase Kohlrausch relaxation is found. The critical point is signalled by divergence of the longest time-scale, and at this point the scattering function decays algebraically, whereas within the gel phase it acquires a time-persistent part identified with the gel fraction.Comment: 4 page

Universality and its Origins at the Amorphous Solidification Transition

Systems undergoing an equilibrium phase transition from a liquid state to an amorphous solid state exhibit certain universal characteristics. Chief among these are the fraction of particles that are randomly localized and the scaling functions that describe the order parameter and (equivalently) the statistical distribution of localization lengths for these localized particles. The purpose of this Paper is to discuss the origins and consequences of this universality, and in doing so, three themes are explored. First, a replica-Landau-type approach is formulated for the universality class of systems that are composed of extended objects connected by permanent random constraints and undergo amorphous solidification at a critical density of constraints. This formulation generalizes the cases of randomly cross-linked and end-linked macromolecular systems, discussed previously. The universal replica free energy is constructed, in terms of the replica order parameter appropriate to amorphous solidification, the value of the order parameter is obtained in the liquid and amorphous solid states, and the chief universal characteristics are determined. Second, the theory is reformulated in terms of the distribution of local static density fluctuations rather than the replica order parameter. It is shown that a suitable free energy can be constructed, depending on the distribution of static density fluctuations, and that this formulation yields precisely the same conclusions as the replica approach. Third, the universal predictions of the theory are compared with the results of extensive numerical simulations of randomly cross-linked macromolecular systems, due to Barsky and Plischke, and excellent agreement is found.Comment: 10 pages, including 3 figures (REVTEX