J. Phys. IV France
Volume 03, Numéro C4, Septembre 1993
4th International Workshop on Positron and Positronium Chemistry
Page(s) C4-265 - C4-270
4th International Workshop on Positron and Positronium Chemistry

J. Phys. IV France 03 (1993) C4-265-C4-270

DOI: 10.1051/jp4:1993441

Temperature dependence of free volume distributions in polymers studied by positron lifetime spectroscopy


1  Institute of Physics, Slovak Academy of Sciences, 84228 Bratislava, Slovakia
2  Polymer Institute, SAS, 84228 Bratislava, Slovakia

The temperature dependence of mean ortho-positronium lifetime ([MATH]) and intensity (I3) was measured in the range between 60 and 293 K for polycarbonate and polyoxymethylene samples. The values of [MATH] and I3 are a constant below T = 127 K. Above this temperature the [MATH] as well as I3 are a linear function of T. Annihilation lifetime measurements have also been performed to deduce the free-volume hole distributions in the polycarbonate and polyoxymethylene polymer samples at temperature of 70 and 293 K. Lifetime spectra were analysed using the Laplace transform and the hole volume distributions are determined from the results of o-Ps lifetime distributions using the particle in a spherical box theory. The free-volume hole radii of polycarbonate at 293 K are distributed between 2.1 and 3.9 Å with a maximum at (2.83 ± 0.02). Free volumes spread out between 40 and 230 Å3 with a maximum at (92 ± 2) Å3. In the case of polyoxymethylene, the free volume hole radii at 293 K are peaked at (3.10 ± 0.07) Å inside (2.0 - 4.6)Å interval. Free volumes are distributed between 35 and 350 Å3 with a maximum at (125 ± 8) Å3. At [MATH]75 K the distributions are quite different. They are narrower and shifted to lower values of R (V). In the case of polyoxymethylene, mean value of radius is (2.06 ± 0.02) Å and mean free volume is (35 ± 2) Å3. In the case of polycarbonate, mean radius is (2.5 ± 0.05) Å and the mean free volume is (70 ± 4) Å3.

© EDP Sciences 1993