Heat capacity of copolymers of chlorotrifluoroethylene and vinylidene fluoride

The heat capacities of two copolymers of chlorotrifluorethylene and vinylidene fluoride, one 30:70 mol % and the other 44:56 mol % in composition, were measured in an adiabatic calorimeter from 80 to 340 K. The glass-transition points T_g observed at 256 and 269 K for the 30:70 and 44:56 samples, respectively, closely agree with the prediction of the theory of Flory and Fox; the accompanying jump of heat capacities at these points was found to be 2.2 cal/K ‘per bead’ for both samples, in fair agreement with the ‘constant ΔC_p rule’. A small peak was observed immediately above T_g, and interpreted as a time-dependent effect arising from the lack of equilibrium in the region. The data of the heat capacities were analysed in detail in the framework of the Tarasov model and the principle of additivity, and were found to agree well ( 1–3%) with theory up to the respective glass-transition points in all cases, thus giving support to the validity of the previously published segmental values of heat capacity and of characteristic temperature θ₁.