Application of positron annihilation to the characterization of polymer structure

Positron annihilation has been applied to study characteristics of polymers last many years. Positron behaves as a nano-meter probe and brings out information of chemical structures, geometric structures, and momentum of electrons through the annihilation gamma-rays. Positrons injected in polymers tends to form positronium, which is similar structure to hydrogen atom and consists of electron and positron. Positronium diffuses through polymer structures and preferentially trapped by intermolecular spaces, if there is not any strong polar group in the chemical structure. Inside the spaces positronium annihilates through pick-off annihilation with electrons constituting walls of the spaces. Thus the pick-off annihilation brings out information about the interaction with electrons on the walls forming the spaces. These information can be measured by the positron annihilation lifetime spectroscopy (PALS) and Doppler broadening spectroscopy: from the former lifetimes and intensities of positronium can be measured and from the latter energy spectrum of the positron annihilation gamma-rays. The lifetimes are connected with the nano-meter size of the spaces and, using an empirical formula, the pore size can be estimated quantitatively. However the intensities bring out many kinds of information. Knowing the sample chemical structures, the values can be simply connected with the amount of spaces and often reflect the polar effect and temperature effect. In the positron annihilation technique, the energy distribution of-positron annihilation gamma-rays plays important role in the investigation of positron interaction with atoms constituting polymer chemical structures. The energy distribution can be measured using a high pure Ge detector. Although the spectrum obtained by one Ge detector has a large peak to back-ground ratio, using a coincidence technique of two Ge detectors, the coincidence Doppler broadening spectrum (CDBS) can improve the ratio from the order of 10-2 to 10-7. The high resolution of CDBS can be used for the study of the interaction of positrons with core electrons of the constituent atoms and the information is useful to investigate the minute elements in samples: thus CDBS can be used as the minute chemical-analysis. The information of the momentum distribution of core electrons is also useful to study the bond structures: i.e., pi and sigma bonds. In this talk, the application of CDBS and PALS to polymer will be discussed.