We assess the nature of the chemical environment of free volume “holes” in polymers of
different chemical compositions using positronium annihilation spectroscopy. After the subtraction of a
narrow parapositronium component obtained from a three-Gaussian fit from the conventional Doppler
broadened annihilation energy line, the remaining broad distribution can be related to the nature and
density of the chemical species in the vicinity of the holes. Element specific information on the annihilation
site can be expressed in terms of an integral parameter, e.g., the normalized peak height. This method
has an advantage in that it can be used as a fast and routine method.