Excess specific heats of different binary blends involving different levels
of relatively strong specific interactions have been deter mined from spec
ific heats of the pure components and those of the blends. A heat-flux (Cal
vet) calorimeter and a step-by-step methodology have been used. Blends of p
oly(hydroxy ether of bisphenol A) (phenoxy resin) with polyesters and polye
thers, where specific interactions are supposed to play a role in miscibili
ty, and blends with stronger hydrogen-bond interactions, such as poly(vinyl
phenol)/poly(methyl methacrylate) (PVPh/PMMA), have been included in the s
tudy. Only the experimental excess specific heat for the PVPh/PMMA blend is
negative, whereas those relative to phenoxy blends are all positive. These
results have been analyzed on the basis of an association model specifical
ly designed for polymer blends in which miscibility is mainly caused by hyd
rogen bonding. The model predicts, in all cases, a continuous decrease of t
he enthalpy of mixing with temperature, i.e., a negative value of Delta C-p
. Equation of state effects have been included in the theoretical simulatio
ns, giving modified trends of the enthalpy of mixing with temperature in a
more reasonable agreement with the experimental results.