Plasticization and antiplasticization of polymer melts diluted by low molar mass species.

An analysis of glass formation for polymer melts that are diluted by structured molecular additives is derived by using the generalized entropy theory, which involves a combination of the Adam-Gibbs model and the direct computation of the configurational entropy based on a lattice model of polymer melts that includes monomer structural effects. Our computations indicate that the plasticization and antiplasticization of polymer melts depend on the molecular properties of the additive. Antiplasticization is accompanied by a "toughening" of the glass mixture relative to the pure polymer, and this effect is found to occur when the diluents are small species with strongly attractive interactions with the polymer matrix. Plasticization leads to a decreased glass transition temperature T(g) and a "softening" of the fragile host polymer in the glass state. Plasticization is prompted by small additives with weakly attractive interactions with the polymer matrix. However, the latter situation can lead to phase separation if the attractive interactions are sufficiently strong. The shifts in T(g) of polystyrene diluted by fully flexible short oligomers (up to 20% mass of diluent) are evaluated from the computations, along with the relative changes in the isothermal compressibility at T(g) (a softening or toughening effect) to characterize the extent to which the additives act as antiplasticizers or plasticizers. The theory predicts that a decreased fragility can accompany both antiplasticization and plasticization of the glass by molecular additives. The general reduction in the T(g) of polymers by molecular additives is rationalized by analyzing the influence of the diluent's properties (cohesive energy, chain length, and stiffness) on glass formation in fluid mixtures and the variation of fragility is discussed in relation to changes in the molecular packing in diluted polymer melts. Our description of constant temperature glass formation upon increasing the diluent concentration directly leads to the Angell equation (tau(alpha) approximately A exp{B/(phi(0,p)-phi(p))}) for the structural relaxation time as function of the polymer concentration, where the extrapolated "zero mobility concentration" phi(0,p) calculated from the theory scales linearly with the inverse polymerization index N.