Position annihilation lifetime spectroscopy PALS

Since the 1960s position annihilation lifetime spectroscopy (PALS) has been used to measure free-volume cell size and/or its content in liquids or solids. The three chapters of Part III discuss correlations between the PALS experimental values and those computed from the S-S theory. Chapter 10, by Consolati and Quasso, considers free volume in amorphous polymers Chapter 11, by Dlubek, its distribution from PALS and Chapter 12, by Jamieson et al., the free volume in heterogeneous polymer systems. These state of the art texts offer intriguing observations on the structure of polymeric systems and its variation with independent variables. In all cases, good correlation has been found between the free-volume quantity measured by PALS and its variability computed from the S-S equation of state. 

Positron Annihilation Lifetime Spectroscopy (PALS) provides a measure of free volume holes or voids, free volume, and free volume distribution, at an atomic scale. The technique exploits the fact that the positively charged positron (e" ), the antiparticle to the electron, preferentially samples regions of low positive charge density. When injected in a polymer matrix, thermalized positrons can combine with an electron to form a bound state, known as positronium (Ps). This species can only exist in a void and it rapidly annihilates on contact with the electron cloud of a molecule. For polymer studies using PALS, it is ortho-positronium (oPs, a triplet state) which is of interest. The oPs spin exchanges with electrons of opposite spin on the walls of the cavity and it is annihilated. Thus, the oPs lifetime, 13, gives a measure of the mean free volume cavity radius, whereas the relative intensity of... 

In recent years, positron annihilation lifetime (PAL) spectroscopy has been demonstrated to be a special sub-nanometer probe to determine the free-volume hole size, fraction and distribution in a variety of polymers (4-9). In this technique, measured lifetimes and relative intensities of the positron and positronium, Ps (a bound atom which consists of an electron and a positron), are related to the size and fraction of sub-nanometer holes in polymeric materials. Because of the positive-charge nature, the positron and Ps are repelled by the ion core of polymer molecules and trapped in open spaces, such as holes, free volumes, and voids. The observed... 

Positron Annihilation Spectroscopy (PALS) can investigate the free volume existing between polymer chains. The lifetime of particles (positrons) injected into a sample can thus provide information on the void structure existing in polymers and polymer blends. For immiscible polymers, free volume existing at the interface due to poor adhesion can be detected by PALS. In miscible polymers, densification due to favorable interactions may be capable of determination. This technique involves the injection of positrons into a polymeric system from a radioisotope capable of emitting positrons, such as Na. The positrons (positively charged electrons) combine with electrons to annihilate or to form a bound state called a positronium (Ps). If the spins of the positron and electron are antiparaUel, para-positroniums (pPS) with a lifetime of 0.125 ns are formed. If the spins of the positron and electrons are parallel, an orthopositronium (oPs) is formed with a lifetime of 1-5 ns. The oPs hfetime, Ts, is related to the free volume cavity in which the oPs is formed [388,389]. 

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