Physical and chemical effects on the dynamics of the β-relaxation of PMMA in Rhodamine 6G+PMMA+SiO2 matrices

Abstract

The Thermally Stimulated Depolarization (TSD) Current technique has been used to reveal confinement effects on the β-relaxation process of PMMA polymerized in-situ SiO2 in the presence of the laser dye Rhodamine 6G/Cl– (Rh6G). The TSD current band of the β process, associated with the rotational relaxation of the mobile carboxymethyl side groups of PMMA, presents a drastic low temperature shift with the introduction of Rh6G or the confinement of PMMA in the nanometric silica substrate. By using the fractional polarization technique we have decomposed this band into single current signals. Irrespective of the initiator type used in the polymerization process, the broad activation energy distribution associated with the β process is nearly identical in the Rh6G+PMMA+SiO2 materials and bulk PMMA. The increase of the dye concentration enlarges the band shift, without any significant modification in the TSD current spectrum (i.e. distinct bands from the polar chromophore). The changes in the molecular dynamics of the polar carboxymethyl side groups of PMMA are discussed in terms of the hydrogen-bond interactions between the silicic acid pore surface and the basic side-groups of PMMA and the decrease of the polymer chain entanglements due to pore directed propagation of polymerization. The relative importance of the various types of interactions between the two chemically identifiable phases in the presence of the dye is discussed.