Temperature and pressure dependence of secondary process in an epoxy system.

Dielectric spectroscopy as a function of temperature and pressure was used to study the secondary relaxation in poly [(phenyl glycidyl ether)-co-formaldehyde] at hydrostatic pressure up to 600 MPa and at different temperatures between 315 and 243 K. From the analysis of the isothermal measurements, we observe that the activation volume of the secondary relaxation has nonmonotonic temperature dependence with a maximum at the temperature of the glass transition at ambient pressure. An interpretation in terms of mean hole volume dispersion is proposed based on literature data. Moreover, from isobaric data, we studied the effect of pressure on activation entropy and enthalpy of the secondary relaxation evidencing its local nature but also the presence of a certain complexity of the motion, which supports the idea that this process reflects the motion of a large part of the molecule.

Relaxation dynamics in tert-butylpyridine/tristyrene mixture investigated by broadband dielectric spectroscopy.

We investigated, by means of dielectric spectroscopy, the relaxation dynamics of glass forming binary mixtures composed by the quite rigid polar molecules tert-butylpyridine dissolved in the apolar solvent tristyrene. By changing the relative concentration of the components we observed a transition from a relaxation scenario with a structural process and an excess wing to that with a structural process and a well resolved secondary process. Another relaxation process, slower than the latter, was observed, well below Tg. Our detailed analysis evidenced that the secondary relaxation with shorter relaxation time can be identified as the Johari-Goldstein relaxation for all the mixtures, whereas the new relaxation process was attributed to a different type of motion of tert-butylpyridine needing a larger amount of free volume for the molecular rotation.

Influence of a reduced mobility layer on the structural relaxation dynamics of aluminum capped ultrathin films of poly(ethylene terephthalate).

The structural dynamics of ultrathin polymer films of poly(ethylene terephthalate) capped between aluminum electrodes have been investigated by dielectric relaxation spectroscopy. A deviation from bulk behavior, appearing as an increase of the relaxation time at a fixed temperature, is observed for films of thickness below 35 nm. The slowing down acts as a constant shift factor independent from the temperature, and the fragility is constant. The interfacial energy between aluminum and poly(ethylene terephthalate) is calculated to be 3 mJ/m2, confirming a strong interaction between polymer and substrate, which leads to the presence of a layer characterized by a reduced mobility at their interfaces. We proposed a mathematical schematization of a multylayer model that allowed qualitative reproduction of the observed thickness dependences of the static and dynamic properties. In terms of such a model, the upper limit for the thickness of the reduced mobility layer was estimated as 20 nm. The conditions to extend the proposed model to different observables are finally suggested.