Free‐volume variation in polyethylenes of different crystallinities: Positron lifetime, density, and X‐ray studies

Abstract

AbstractHigh‐quality positron lifetime measurements (70 million total counts) are reported for polyethylenes (PEs) of different crystallinities (Xc = 3–82%). The specific volumes of the crystalline and amorphous phases (Vc and Va, respectively) were estimated from density and wide‐angle X‐ray scattering (WAXS) experiments. Some samples (those with low values of Xc) were branched PEs, and those with high values of Xc were linear PEs for which Xc was varied with changes in the crystallization temperature. Both Vc and Va increase with decreasing Xc in the range 0% ≤ Xc ≤ 56% (the branched PEs) but are constant for Xc ≥ 56% (the linear PEs). The lifetime spectra were analyzed with the MELT and LIFSPECFIT routines. Artifacts that can appear in the spectrum analysis were checked via an analysis of computer‐generated spectra. Four lifetime components appeared in all of the PEs; the two long‐lived ones are attributed to pick‐off annihilation of ortho‐positronium (o‐Ps) in crystalline regions (τ3) and in holes of the amorphous phase (τ4). With increasing Xc, τ3 decreases from about 1.2 to 1 ns, τ4 decreases from 3.0 to 2.5 ns, and the intensity I4 decreases from 29 to 0%. An increase in I3 from 6 to 12% was observed. A comparison with simulations shows that the true I3 value approaches 0 for Xc → 0%. The decrease in I4 is weaker than the increase in Xc; this leads to the conclusion that the apparent specific o‐Ps yield in the amorphous phase I4Xc increases with Xc. Possible reasons for this surprising results are discussed. The fractional free hole volume [h = (Va − Vocc)/Va, where Vocc is the crystalline occupied volume] was estimated from density and WAXS results. Between Xc = 0 and 56%, h decreases from 0.151 to 0.090, but it does not change further above Xc = 56%. The mean size (v) of the local free volumes (holes) estimated from τ4 decreases from 200 to 150 Å3. The number density of holes (Nh) calculated from these values (Nh = h/v) also decreases from 0.8 to 0.6 nm−3 in the range 0% ≤ Xc ≤ 56%. The values of Va, Vc, h, and Nh increase with an increasing degree of branching but do not vary for linear PEs. The possible influence of a crystalline–amorphous interfacial phase (three‐phase model) on the observed lifetime parameters is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 65–81, 2002