The micelles formed by sodium dodecyl sulfate (SDS) are studied in aqueous solutions at 294 K as a function of nominal SDS concentration (C) using positron lifetime spectroscopy. In a four-component analysis of the data, it appears that the lifetime (τ 3 ) of the positronium triplet state (o-Ps) in the aqueous phase decreases significantly with increasing C. Preliminary results on sodium methanesulfonate solutions show that this compound does not result in any significant Ps lifetime quenching. Thus, the changes in the lifetime are attributed to the trapping of Ps from the aqueous to the organic micellar phase. On the basis of simple diffusion-controlled kinetics, the observed linearity of 1/τ 3 with C indicates that the ratio of the micelle core radius (R mic ) to the aggregation number (N ag ) is about constant over the concentration range investigated, in agreement with information from other studies. Quantitatively, on the hypothesis of a constant value of N ag ) 64, the use of the simple model, or of a more rigorous one, for Ps diffusion and trapping leads to R mic ) 1.50 and 1.19 nm, respectively. Both values are lower than 1.84 nm as expected from other studies on the total SDS aggregate radius at 298 K. However, taking account of the size of the polar sulfate groups and of some slight variation of N ag with C, the most complete model leads to R mic ) 1.75 nm, in satisfactory agreement with the 1.84 nm value. Examination of the intensities of the two longest-lived components, related to o-Ps in the aqueous and micellar phases, shows that, as was the case for reverse micelles, most of the Ps formation occurs in the former. The aggregated SDS molecules display a very low inhibiting power toward Ps formation, with an inhibition constant of 0.01 M -1 , in agreement with the low ability of alkyl sulfates and sulfonates to scavenge electrons. The trapping of Ps in the micelles is confirmed by the continuous increase with C of the intensity of the longest-lived component, related to o-Ps in the organic phase.

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The interaction of positronium with molecular oxygen dissolved in liquids is experimentally investigated. A computer software has been developed for fitting the positron annihilation lifetime spectra using parameters with clear physical meaning.

This chapter reviews the following items: 1. Energy deposition and track structure of fast positrons: ionization slowing down, number of ion-electron pairs, typical sizes, thermalization, electrostatic interaction between e + and its blob, effect of local heating;2. Positronium formation in condensed media: the Ore model, quasifree Ps state, intratrack mechanism of Ps formation;3. Fast intratrack diffusion-controlled reactions: Ps oxidation and ortho-para conversion by radiolytic products, reaction rate constants, interpretation of the PAL spectra in water at different temperatures; 4. Ps bubble models. "Non-point" positronium: wave function, energy contributions, relationship between the pick-off annihilation rate and the bubble radius.

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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.

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