An introduction to the statistical theory of polymer network formation

A short but detailed introduction to the statistical theory of polymer network formation is given, including gel formation, gel structure, and sol fraction. Focus is put on the use of probability generating functions, and results that are of interest for polymer network elasticity are emphasized. Detailed derivations are supplied, and a simple 6-step procedure is provided, so that the reader is able to adapt and apply the theory to his own chemical systems, even if examples are given on polyurethanes essentially

Physical interpretation of the Mullins softening in a carbon-black filled SBR

A 40 phr carbon-black filled styrene butadiene rubber has been submitted to several experiments in order to identify the physical damage responsible for the mechanical softening recorded upon first stretch. Damage in the rubber matrix was determined by swelling. The filler structure alteration was monitored by electrical conductivity measurements. Both damages are shown to be of minor importance compared to the substantial mechanical softening undergone by the material. Degradation at the rubber-filler interface may be recovered by exposing the material at high temperatures in vacuo. The chain mobility in such storage conditions promotes free chain adsorption at the filler surface. The existence of a layer of polymer whose movements are hindered adds to the filler reinforcement and its desorption creates Mullins softening

A statistical theory of polymer network degradation

A statistical theory was proposed for the degradation (random scission of chains) of a network having f-functional nodes in the case where all chains contain equireactive groups and a chain scission event does not create new groups or suppress more than one group. Closedform relations were established between the conversion ratio of the degradation process and the crosslink density. Emphasis was put on the value of the conversion ratio for which the gel disappears. Some limited cases already considered in the literature were recovered, but a general solution was proposed for networks having any number of reactive groups per chain, be it uniform or not, and for conversion ratios up to the degelation point. The results were applied successfully to recent experiments regarding the hydrolysis of a polyester

Direct experimental evidence of time-temperature superposition at finite strain for an amorphous polymer network

The time-temperature superposition property of an amorphous polymer acrylate network is characterized at infinitesimal strain by standard dynamic mechanical analysis tests. Comparison of the shift factors determined in uniaxial tension and in torsion shows that both tests provide equivalent time-temperature superposition properties. More interestingly, finite strain uniaxial tension tests run until break at constant strain rate show that the acrylate network exhibits the same time-temperature superposition property at finite strain as at infinitesimal strain. Such original experimental evidence provides new insight for finite strain constitutive modelling of polymer amorphous networks.ANR REFORM 10-JCJC-091

The effect of moisture-induced swelling on the absorption capacity of transversely isotropic elastic polymer-matrix composites

The interaction between humid air and transversely isotropic fiber-reinforced composites with swelling polymeric matrix is considered. A model is proposed for the water saturation level in a polymer when stresses are applied, that uses directly obtainable material parameters only. In a composite, the reinforcements modify the water uptake of the polymer matrix because of the internal stresses that are induced by its restricted swelling, and this effect is evaluated. As a consequence of the coupling between stresses and absorption capacity, the sorption isotherm of a composite is ruled by the (nonlinear) Langmuir equation when the unreinforced matrix obeys the (linear) Henry’s law

Radiochemical 'degelation' of polymethyl methacrylate networks

Methyl methacrylate-ethylene glycol dimethacrylate networks were synthetized and submitted to radiochemical degradation, with ageing monitored by means of sol-gel analysis. The networks were shown to undergo chain scission predominantly, which leads to their degelation, i.e., the recovery of a thermoplastic-like behavior with loss of all elastically active chains. The degelation dose was shown to increase with crosslink density and the corresponding critical conversion ratio was discussed regarding a recent and general statistical theory that covers radiochemical as well as chemical chain scissions

Homogenization estimates for texture evolution in halite

In this work, the recently developed “second-order” self-consistent method [Liu, Y., Ponte Castaneda, P., 2004a. Second-order estimates for the effective behavior and field fluctuations in viscoplastic polycrystals. J. Mech. Phys. Solids 52 467–495] is used to simulate texture evolution in halite polycrystals. This method makes use of a suitably optimized linear comparison polycrystal and has the distinguishing property of being exact to second order in the heterogeneity contrast. The second-order model takes into consideration the effects of hardening and of the evolution of both crystallographic and morphological texture to yield reliable predictions for the macroscopic behavior of the polycrystal. Comparisons of these predictions with full-field numerical simulations [Lebensohn, R.A., Dawson, P.R., Kern, H.M., Wenk, H.R., 2003. Heterogeneous deformation and texture development in halite polycrystals: comparison of different modeling approaches and experimental data. Tectonophysics 370 287–311], as well as with predictions resulting from the earlier “variational” and “tangent” self-consistent models, included here for comparison purposes, provide insight into how the underlying assumptions of the various models affect slip in the grains, and therefore the texture predictions in highly anisotropic and nonlinear polycrystalline materials. The “second-order” self-consistent method, while giving a softer stress-strain response than the corresponding full-field results, predicts a pattern of texture evolution that is not captured by the other homogenization models and that agrees reasonably well with the full-field predictions and with the experimental measures

Testing some implementations of a cohesive-zone model at finite strain

This study shows how the results given by a cohesive-zone model at finite strain may depend strongly on its numerical implementation. A two-dimensional four-node cohesive element is considered, which includes several variants depending on a part of the strain-displacement matrix, on the quadrature rule applied, and on the configuration chosen to perform integration. Finite element simulations combine these variants with a very simple, bilinear, cohesive-zone model, in two tests. The first test involves a single element and illustrates some features of the various implementations. The other test simulates the peeling of an elastomer strip from a rigid substrate

Some features of the PPR cohesive-zone model combined with a linear unloading/reloading relationship

A loading/unloading/reloading process is applied to a cohesive zone where the model proposed by Park, Paulino and Roesler in 2009 is combined with a linear unloading/reloading relationship. The applied loading and unloading use the same mixed mode and reloading is in mode I. When the amplitude of preloading is varied, several features are evidenced: jumps of the dissipated energy, reversibility maintained after a traction peak, nonlinear traction variations during unloading, increasing traction during unloading, finite traction after a fracture criterion has been fulfilled, different traction values at the beginning of unloading and when dissipative reloading begins. Moreover, the results depend strongly on the path followed during unloading. Simple modifications of the model allow none of these questionable features to appear