Concentration and temperature dependence of diluent dynamics studied by line shape experiments on a phosphate ester...

31P Hahn spin echo line shape and proton line shape experiments are reported on bisphenol A polycarbonate (BPAPC)-tris(2-ethylehexyl)phosphate (TOP) systems to study the concentration and temperature dependence of the local dynamics. In an earlier 31P line shape study a lattice model was presented as a framework to interpret the plasticization and antiplasticization behavior of the diluent based on a fractional population given by the type of nearest neighbor contacts in the mixed polymer-diluent glass. In this study, 31P spin echo line shapes of BPAPC, with 5%, 10% and 15% TOP, which monitor the diluent dynamics, at different temperatures and echo delay times are simulated in terms of fast- and slow-moving components, and the resulting fractional populations are compared with that predicted by the lattice model. Comparisons with the lattice model calculations are also made in the simulation of the 1H line shapes on BPAPC with 5% and 10% TOP, which probes both the polymer and diluent dynamics, and on BPAPC with 5% and 10% perdeuterated trioctylphosphate (DTOP), which detects only the polymer motion. Fairly good line shape simulations and agreement between the lattice model and the fitting results at low diluent concentrations are obtained in all cases. Restricted cone motion best describes the slow-moving component in the 31P line shape fittings. For the fast component, rotational Brownian diffusion with a distribution of correlation times corresponding to a stretched exponential function is used. An activation energy Ea of 56 kJ/mol and an exponent alpha of 0.7 for the fractional exponential correlation function are obtained and used to calculate the mechanical loss peak which was compared with the experimental loss data. The plateau character of the fractional population as a function of temperature can also be interpreted and understood in terms of the lattice model.