The thermodynamic properties of polytetrafluoroethylene

Polytetrafluoroethylenes of different crystallinity were analyzed between 220 and 700 K by differential scanning calorimetry. A new computer coupling of the standard DSC is described. The measured heat capacity data were combined with all literature data into a recommended set of thermodynamic properties for the crystalline polymer and a preliminary set for the amorphous polymer (heat capacity, enthalpy, entropy, and Gibbs energy; range 0–700 K). The crystal heat capacities have been linked to the vibrational spectrum with a θ 3 of 54 K, and θ 1 of 250 K, and a full set of group vibrations. C v to C p conversion was possible with a Nernst–Lindemann constant of A = 1.6 × 10 −3 mol K/J. The glass transition was identified as a broad transition between 160 and 240 K with a Δ C p of 9.4 J/K mol. The room‐temperature transitions at 292 and 303 K have a combined heat of transition of 850 J/mol and an entropy of transition of 2.90 J/K mol. The equilibrium melting temperature is 605 K with transition enthalpy and entropy of 4.10 kj/mol and 6.78 J/K mol, respectively. The high‐temperature crystal from is shown to be a condis crystal (conformationally disordered), and for the samples discussed, the crystallinity model holds.