Didier R. Long

Mechanical properties of thin confined polymer films close to the glass transition in the linear regime of deformation: theory and simulations.

Over the past twenty years experiments performed on thin polymer films deposited on substrates have shown that the glass transition temperature Tg can either decrease or increase depending on the strength of the interactions. Over the same period, experiments have also demonstrated that the dynamics in liquids close to the glass transition temperature is strongly heterogeneous, on the scale of a few nanometers. A model for the dynamics of non-polar polymers, based on percolation of slow subunits, has been proposed and developed over the past ten years. It proposes a unified mechanism regarding these two features. By extending this model, we have developed a 3D model, solved by numerical simulations, in order to describe and calculate the mechanical properties of polymers close to the glass transition in the linear regime of deformation, with a spatial resolution corresponding to the subunit size. We focus on the case of polymers confined between two substrates with non-negligible interactions between the polymer and the substrates, a situation which may be compared to filled elastomers. We calculate the evolution of the elastic modulus as a function of temperature, for different film thicknesses and polymer-substrate interactions. In particular, this allows to calculate the corresponding increase of glass transition temperature, up to 20 K in the considered situations. Moreover, between the bulk Tg and Tg + 50 K the modulus of the confined layers is found to decrease very slowly in some cases, with moduli more than ten times larger than that of the pure matrix at temperatures up to Tg + 50 K. This is consistent with what is observed in reinforced elastomers. This slow decrease of the modulus is accompanied by huge fluctuations of the stress at the scale of a few tens of nanometers that may even be negative as compared to the solicitation, in a way that may be analogous to mechanical heterogeneities observed recently in molecular dynamics simulations. As a consequence, confinement may result not only in an increase of the glass transition temperature, but in a huge broadening of the glass transition.

Dielectric relaxation of thin films of polyamide random copolymers.

We investigate the relaxation behavior of thin films of a polyamide random copolymer, PA66/6I, with various film thicknesses using dielectric relaxation spectroscopy. Two dielectric signals are observed at high temperatures, the α process and the relaxation process due to electrode polarization (the EP process). The relaxation time of the EP process has a Vogel-Fulcher-Tammann type of temperature dependence, and the glass transition temperature, T(g), evaluated from the EP process agrees very well with the T(g) determined from the thermal measurements. The fragility index derived from the EP process increases with decreasing film thickness. The relaxation time and the dielectric relaxation strength of the EP process are described by a linear function of the film thickness d for large values of d, which can be regarded as experimental evidence for the validity of attributing the observed signal to the EP process. Furthermore, there is distinct deviation from this linear law for thicknesses smaller than a critical value. This deviation observed in thinner films is associated with an increase in the mobility and/or diffusion constant of the charge carriers responsible for the EP process. The α process is located in a higher-frequency region than the EP process at high temperatures but merges with the EP process at lower temperatures near the glass transition region. The thickness dependence of the relaxation time of the α process is different from that of the EP process. This suggests that there is decoupling between the segmental motion of the polymers and the translational motion of the charge carriers in confinement.

Fatigue crack growth dynamics in filled natural rubber

Abstract We present fatigue experiments performed on filled natural rubber and study the correlations between crack growth dynamics and fracture morphologies imprinted by an irregular crack path. Slow crack growth dynamics is obtained by cyclic fatigue in a pure shear test. We will show that an unstable crack growth regime exists for high loads. We will also discuss the appearance of sawtooth striations which follow a scenario that significantly differs from previous results reported in the literature.

Long-time damage under creep experiments in disordered materials: Transition from exponential to logarithmic fracture dynamics

Abstract.Some materials, and in particular some polymer materials, can display an important range of stress levels for which slow and progressive damage can be observed before they finally break. In creep or fatigue experiments, final rupture can happen after very long times, during which the mechanical properties have progressively decayed. We model here some generic features of the long-time damage evolution of disordered elastic materials under constant load, characterized by a progressive decrease of the elastic modulus. We do it by studying a two-dimensional electric random fuse network with quenched disorder and thermal noise. The time evolution of global quantities (conductivity or, equivalently, elastic modulus) is characterized by different regimes ranging from faster than exponential to slower than logarithmic, which are governed by the stress level and the relative magnitude of disorder with respect to temperature. A region of widely distributed rupture times exists where the modulus decays (more slowly than) logarithmically for not too small values of the disorder and for not too large values of the load. A detailed analysis of the dynamical regimes is performed and presented through a phase diagram.Graphical abstract