No abstract

Free‐volume hole sizes, fractions, and distributions in a series of polycarbonate‐based polymers are measured by using positron annihilation lifetime (PAL) spectroscopy. Correlations between the obtained free‐volume hole properties and gas diffusion coefficients are observed. © 1995 John Wiley & Sons, Inc.

Existing positron annihilation lifetime spectroscopy (PALS) uses the orthopositronium components, lifetimes, and intensities observed in molecular substrates, such as in polymers, to determine free-volume properties based on an infinitive potential spherical model originally proposed by Tao in 1972. However, in many molecular systems, positronium is either quenched or inhibited by interacting with chemical functional groups and leads to no or nearly no orthopositronium component in PALS. In this Article, a newly modified equation is developed by following the Tao’s quantum model using the positron component (not orthopositronium) of PALS. This modified equation is examined by fitting free-volume results obtained from o-Ps lifetimes with the positron lifetimes in pressure- and temperature-dependent data in polymers and calibrated with known or calculated cavity sizes in zeolite materials. A newly modified positron lifetime-free volume correlation equation is established for the determination of free volumes up to the mean radius of 5 Å in polymeric systems, where no orthopositronium component is observed in PALS.

Positron annihilation lifetime and Doppler broadening of annihilation radiation experiments are performed in a polyurethane film using the mono-energetic slow positron probe as a function of positron energies. Significant variations of positron annihilation signals are observed at a short distance from the surface (<100 nm). The ortho-positronium lifetime in the polymer increases near the surface, while its intensity decreases. The intensity results are consistent with the description of a free-volume hole model for positronium formation proposed by Brandt, Berko and Walker. This study further confirms that positron annihilation spectroscopy is a sensitive probe for the characterization of physical properties of sub-nanometre defects, such as free volumes and holes for polymeric materials.

The degradation of polymer coating systems due to UV irradiation is studied using positron annihilation spectroscopy. Doppler broadened spectra of positron annihilation are measured as a function of slow positron implantation energy in a series of polymer coating systems which were exposed to UV irradiation for up to 2000 h. The S parameters from the Doppler broadened energy spectra vs positron energy show an increase at very low positron energy (<575 eV) and then a decrease to about 8 keV, followed by a slight increase up to 50 keV. The UV irradiation systematically decreases the S parameter as a function of exposure duration. The significant S parameter decrease is interpreted as the degradation of polymers and the change of the sub-nanometer defect profiles due to UV irradiation. These interpretations are supported by the data from the atomic force microscope, UV absorption, Fourier transform infrared, and profilometry measurements.