Transition of elastomers from a rubber to glassy state under laser shock conditions.

The mechanical behaviour of polycarbonate and polydimethylsiloxane (Sylgard184) is studied in this work under laser shock conditions that induce high pressure and strain rates. Laser shock, usually used to reinforce metals, is chosen here because of its capacity to produce strain rates in the 106 s1 range and pressures of GPa order. The pressure and strain rates produced are extracted from the backface velocity profiles and reproduced with the FEM simulation on Abaqus for each laser shot. These two parameters lead to a glass transition shift in the polymers that can induce significant behaviour modifications. We show that Sylgard184, an elastomer with a glass transition temperature of 147 K, exhibits glassy behaviour under such laser shock conditions. By contrast, polycarbonate is already a glassy polymer in its normal state with a glass transition temperature of 415 K; no drastic change in behaviour under shock is evidenced. To discuss these findings in relation to the different mobility domains of the polymer chains under extreme conditions, dielectric relaxation spectroscopy (DRS) measurements are performed to characterize the limits of the rubbery and glassy behaviour for both polymers. As a result, the coupling of the two techniques provides a deeper understanding of the contribution of both the strain rate and pressure to the dynamic glass transition in polymers and thus expands the experimental study range of the two polymers to a strain rate that had not previously been reached.

Cooperativity length scale in nanocomposites: interfacial and confinement effects.

Interfacial and confinement effects on the evolution of cooperativity on approaching the glass transition have been studied in poly(propylenecoethylene) functionalized with diethylmaleate, polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol and their nanocomposites with montmorillonite. A small increase of the structural dynamic cooperativity, a weak alteration of the temperature dependence of the characteristic relaxation frequency, and no changes in the glass transition temperature observed in poly(propylenecoethylene)-based samples can be rationalized in terms of interfacial interactions between polymer and exfoliated clay. On the other hand, confinement of polymer chains in the galleries of clay (intercalated nanocomposite) produces a strong reduction of cooperativity, of the temperature dependence of the characteristic relaxation frequency, and of the glass transition temperature in polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol samples. Finally, by investigating the temperature dependence of a generalized fragility and of cooperativity, we evidenced that fragility of glass formers is determined not only by cooperativity.

Temperature dependence of the characteristic length scale for glassy dynamics: combination of dielectric and specific heat spectroscopy.

The temperature dependence of characteristic length scales associated to the glass transition such as the cooperativity length scale introduced by Adam and Gibbs [cooperative rearranging region (CRR)] or the dynamic heterogeneity as estimated from the four point correlation function chi4, is at the center of large interests. Broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry allow to study the CRR size temperature dependence in the temperature range of ergodicity loss for glass-forming liquids, starting from the onset of cooperativity in the crossover region down to the glass transition temperature. Furthermore, the correlation between these two techniques allows to explore a large frequency range (from 1 mHz to 10 MHz). The goal of this work is to follow the cooperativity evolution along the Arrhenius plot for two different polymeric systems: poly(ethylene 1,4-cyclohexylenedimethylene terephthalate glycol) and poly(bisphenol A carbonate).