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Gustavo A Schwartz

Publications and source records attributed to Gustavo A Schwartz.

3 recordsLinked to original sources

Describing the component dynamics in miscible polymer blends: towards a fully predictive model.

We have recently proposed [D. Cangialosi et al., J. Chem. Phys. 123, 144908 (2005)] an extension of the Adam-Gibbs [J. Chem. Phys. 43, 139 (1965)] theory, combined with the concept of self-concentration, to describe the temperature dependence of the relaxation time for the component segmental dynamics in miscible polymer blends. Thus, we were able to obtain the dynamics of each component in the blend starting from the knowledge of the dynamic and thermodynamic data of the pure polymers, with a single fitting parameter (alpha) which had to be obtained from the fitting of the experimental data. In the present work we demonstrate that this model is also suitable to describe the polymer segmental dynamics in concentrated polymer solutions. From this result we have developed a new route for determining the value of the alpha parameter associated with any given polymer. Once this value is known for the two components of a possible polymer blend, our model for polymer blends dynamics becomes fully predictive.

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Glass transition and relaxation processes in supercooled water.

Many of water's peculiar physical properties are still not well understood, and one of the most important unresolved questions is its glass transition related dynamics. The consensus has been to accept a glass transition temperature (T(g)) around 136 K, but this value has been questioned and reassigned to about 165 K. We find evidence that the dielectric relaxation process of confined water that has been associated with the long accepted T(g) of water (130-140 K) must be a local process which is not related to the actual glass transition. Rather, our data indicate a glass transition at 160-165 K for bulk water and about 175 K for confined water (depending on the confining system).

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Relaxation dynamics of a polymer in a 2D confinement.

The molecular dynamics of oligomeric poly(propylene glycol) (PPG) liquids (MW=1000, 2000, and 4000 g/mol) confined in a two-dimensional layer-structured Na-vermiculite clay has been studied by broadband dielectric spectroscopy. The alpha-relaxation and the normal mode relaxation processes were studied for all samples in bulk and confinement. The most prominent experimental observation was that for the normal mode process: the relaxation rate in the clay is drastically shifted to lower frequencies compared to that of the bulk material. This slowing down is probably caused by the strongly reduced number of accessible chain conformations in two dimensions. Also the temperature dependence of the relaxation time for the normal mode process is strongly affected by the confinement. In contrast, for the alpha-relaxation of the confined polymers we observed only a slight increase of the relaxation rate at high temperatures compared to the corresponding bulk samples, and a decrease of its relaxation strength relative to the beta relaxation. Thus, the glass transition is unaffected by the 2D confinement, suggesting that the underlying phenomena responsible for the glass transition is the same as in bulk. Moreover, in the clay the intensity of the normal mode is stronger than that of the alpha-process, in contrast to the bulk samples where the opposite behavior is observed.

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