Most applications of positron beams require knowledge of the implantation characteristics for an appropriate interpretation of the experimental data. In this work, the median implantation depth as a function of implantation energy, z 1/2 (E), of 3-18 keV positrons and their implantation profile P(z,E) in a total of 13 thin films of atactic polystyrene, poly͑styrene-co-acrylonitrile͒, and polymethylmethacrylate spin coated onto a silicon substrate were determined from positron lifetime measurements using a pulsed, low-energy positron beam. z 1/2 (E) and P(z,E) were determined from the measurement of the ortho-positronium yield obtained from the intensity I 3 of the long lifetime. z 1/2 (E) was parametrized with the commonly used power-law fit z 1/2 (E) ϭ(A/)E n , with and E in units of g cm Ϫ3 and keV, respectively, yielding Aϭ2.81(Ϯ0.2) g cm Ϫ2 and n ϭ1.71(Ϯ0.05). Excellent agreement between amorphous polymer and literature data on Al and Cu suggests that the median implantation depth of positrons for low-to medium-Z materials in the studied energy range is independent of structure and only a function of mass density. Fitting of the Makhovian implantation profile to the experimental data suggested that the value of the parameter m varies between 1.7 and 2.3, systematically increasing with z at constant implantation energy, but is independent of the implantation energy. Using an equation proposed by Baker et al., the experimental data of 12 of the 13 studied polymer films could be described with a slightly better agreement than the Makhovian equation.

Density gradient widths at the polymer−vacuum surfaces of poly(methyl methacrylate), styrene-co-acrylonitrile, and styrene-co-maleic anhydride were quantified to 2, 5, and 4 nm, respectively, by use of a pulsed low-energy positron lifetime beam and to approximately 1.5 nm for all three polymers on the basis of theoretical predictions from pressure−volume−temperature (PVT) data, making use of the Cahn−Hilliard theory of inhomogeneous systems in conjunction with the Sanchez−Lacombe lattice fluid theory. Excellent agreement between the two methods was found for the homopolymer, whereas for the copolymers, the former method gave larger density gradient widths, a result attributed to the surface orientation of the less polar polymer segments, which the theoretical predictions did not take into account. As has been previously proposed, the discrepancy between the depth ranges of the surface effects on density and the glass transition temperature (T g) is suggested to result from a coupling between the dynamics of adjoining polymer segments, canceling a direct relationship between local density profile ρ(z) and local T g(z) as a function of distance z from the free surface.

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The free volume properties of a poly(methyl methacrylate)−azobenzene copolymer were for the first time directly probed by use of a low-energy positron lifetime beam with in-situ excitation capabilities, showing that the free volume cavity size was not appreciably influenced by photoisomerization and thermal isomerization in the temperature range 34−180 °C. Isomerization is therefore suggested to occur without any molecular rearrangement of the glassy polymer matrix, which would also account for the lack of any shift to shorter wavelengths for the photoisomerization occurring in a glassy polymer in comparison to a chloroform solution. A decrease in the thermal isomerization rate at room temperature caused by the glassy polymer is explained in terms of a model in which only a fraction of the azobenzene is free to isomerize. The cis-azobenzene was found to be an efficient inhibitor of positronium formation, which enabled measurements of thermal isomerization rates and changes in the steady-state concentration of cis-azobenzene for an illuminated sample as a function of temperature.