  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. 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. The
shifts in T_g of polystyrene diluted by fully flexible short oligomers are
evaluated from the computations, along with the relative changes in the
isothermal compressibility at T_g 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 and
fragility of polymers by these molecular additives is rationalized by analyzing
the influence of the diluent's properties (cohesive energy, chain length, and
stiffness) on glass formation in diluted polymer melts. The description of
glass formation at fixed temperature that is induced upon change the fluid
composition directly implies the Angell equation for the structural relaxation
time as function of the polymer concentration, and the computed "zero mobility
concentration" scales linearly with the inverse polymerization index N.
