The structure of the free volume and its temperature dependence in poly(tetrafluoroethylene) (PTFE) and of its copolymer with perfluoro(propyl vinyl ether) (PFA) was studied by pressure-volume-temperature (PVT) experiments (T=27-380 degrees C, P=0.1-200 MPa) and positron annihilation lifetime spectroscopy (PALS, T=-173-250 degrees C, P=10(-5) Pa). From the analysis of these experiments we conclude on the volumetric properties of the mobile (MAF) and rigid amorphous fractions (RAF) in these semicrystalline polymers. The specific volumes of the MAF and RAF, V-MAF and V-RAF, were estimated assuming that V-MAF agrees with the specific volume of the melt extrapolated down to lower temperatures using the Simha-Somcynsky equation of state (S-S eos). V-RAF was then estimated from the specific volume of the entire amorphous phase, V-a, and the known V-MAF. The specific free volume V-f = V-a - V-occ was also estimated from V-a using the S-S eos hole fraction h, V-occ = (1-h)V-a. From the analysis of PALS data with the routine LT9.0 the mean volume, < v(h)>, and the width, sigma(h), of the local free volume size distribution (holes of subnanometre size) were obtained. A comparison of < v(h)> with V-f delivered the hole density N-h'. The volume parameters show that the RAF which is formed during crystallisation from the melt has a distinctly smaller specific free and total volume than the MAF. During cooling the contraction of the RAF slows down and finally, below room temperature, the RAF possesses a larger free volume than the MAF shows. Obviously, the restriction of the segmental mobility in the RAF by the crystals limits at high temperatures the free volume expansion and at low temperatures dense packing of the polymer chains. These conclusions from the analysis of the specific volume are confirmed by PALS experiments. (c) 2005 Elsevier Ltd. All rights reserved.