Interaction of positronium with dissolved oxygen in liquids.

The interaction of positronium (Ps) with molecular oxygen dissolved in liquids is experimentally investigated. Computer software has been developed for fitting the positron annihilation lifetime spectra in liquids using parameters with clear physical meaning: rate constants of the Ps chemical reactions, annihilation rate constants of the different positron states, probability of Ps formation in a quasi-free state, typical formation time of a Ps nanobubble. Such processing of the spectra allowed identification of the dominant interaction of the Ps atom with dissolved oxygen. It turns out to be mainly ortho-para-conversion (Ps → 1/4 p-Ps + 3/4 o-Ps), but not oxidation (Ps + O2→ e+ + O2-). Values of the reaction rate constants are obtained.

Positronium as a probe in natural polymers: decomposition in starch.

Ortho-positronium (o-Ps) is used as a probe in positron annihilation lifetime spectroscopy (PALS) experiments, to characterise the behaviour of free volumes in natural starch samples, as a function of temperature (T). Up to about 540 K, the o-Ps intensity, I(3), remains constant at 26.2% while its lifetime, tau(3), is found to increase linearly. Both parameters undergo a decrease above this T, due to the onset of decomposition, which results in a shrinking of the sample pellets. The results indicate that the glass transition temperature should be above 501 K. Data from thermal gravimetry analysis (TGA) measurements are well described by supposing a first order process for the survival probability (p) of the starch lattice, with an activation energy, E(act) = (1.52 +/- 0.05) eV, and a frequency factor, ln(k(0), s(-1)) = 25.3 +/- 0.4. In the decomposition region, the PALS data show the unexpected correlation (tau(3n))(3) = I(3n), linking the normalised values of tau(3), tau(3n), and of I(3), I(3n). This is explained by considering that the changes in I(3) with T arise from those in the surviving volume fraction of the lattice, p, whereas the changes in tau(3) reflect the shrinking of the radius of the free volumes, the latter decreasing in proportion to p(1/3). Quantitative approaches on these bases lead to satisfactory fitting of all PALS data, yielding an activation energy, E(act) = (1.53 +/- 0.03) eV, and frequency factor, ln(k(0), s(-1)) = 25.4 +/- 0.2, in excellent agreement with the values derived from TGA.