Sub-glassy relaxation modes in PMMA and PMMA + SiO₂ hosts of non-polar perylene derivatives

Abstract

The dielectric response of poly(methyl methacrylate) (PMMA) in solid solutions of perylene derivative laser dyes in PMMA and PMMA + SiO₂ has been studied by means of the thermally stimulated depolarization currents (TSDC) technique, with the aim to isolate molecular and phase interactions in the dye blends. The changes in characteristics of the β-relaxation mode of PMMA are interpreted with respect to the dissimilar local environments of the polar carboxy-methyl pendant groups of PMMA. An important “chemical” effect on the β relaxation mechanism recorded in the organic-inorganic composites, is the formation of hydrogen bonds between the acidic pore surfaces of SiO₂ and the acetate side-groups. Several “physical” effects produced by the chromophores and the geometrical confinement, like the modification of the monomer-to-polymer conversion rates, the polymer's free volume and the extent of the PMMA-SiO₂ interaction, are discussed.

Keywords:

• Thermally stimulated depolarization
• Dielectric relaxation
• Poly(methyl methacrylate)
• Composites
• Perylene dyes