Abstract: Positron annihilation lifetime spectroscopy (PALS) has widely been used for probing open volume defects in various materials. PALS is in principle non-destructive, yet conventional PALS is not strictly non-destructive because cutting out of two specimens from the material is required. Recently we developed a novel method of PALS, which is potentially applicable to non-destructive, onsite material inspection. In order to explore the possibility of onsite monitoring of polymer degradation by this novel method of PALS, we studied variations of positron lifetime and mechanical properties of ultra high molecular weight polyethylene (UHMWPE) subjected to γ-irradiation. Correlations were found between the mechanical properties and ortho-positronium lifetimes, suggesting the feasibility of non-destructive, onsite monitoring of polymer degradation by PALS. The effect of γ-irradiation on positronium formation is discussed.
Abstract: Ortho-positronium pick off annihilation lifetime gives the information of the microscopic free volume of polymers. Polyimide polymers such as Kapton are applied in many fields, but it was impossible to apply the positron lifetime method for free volume investigation because of no positronium formation. Here, we apply the idea of the free positron annihilation probability that is sum of the probability of annihilation by the positron and electrons on the molecular chain where the positron localized and that for the annihilation with the electrons on the neighboring molecular chains. The second term is probably affected by the free volume change. We have successfully shown the temperature dependence and the electron beam irradiation effect on the free volume change by observing the free positron annihilation lifetime for Kapton.
Abstract: The Poly N-Isopropyl acrylamide (PNIPA) gels were prepared in different synthesis media by crosslinking with acrylate monomers with varying chain length. The microstructural characterization in terms of the free volume fractions and distributions were studied using positron annihilation lifetime spectroscopy (PALS). The equilibrium swelling of the PNIPA in distilled water was measured. An attempt has been made to understand the correlations between microscopic free volumes and the equilibrium swelling of the gels. The free volume fraction of the gels prepared in Dimethyl formamide (DMF) was directly correlated with swelling while it varied inversely with chain length of the crosslinker. The microstructure of the gels was found to be very sensitive to the solvent/medium used for polymerization. Our studies show that the swelling property is influenced by the free volumes, chain relaxation as well as the chemical nature of the cross linkers.
Abstract: Polypropylene (PP) derivatives, prepared with different α-olefin comonomers of hexane and hexenol, were investigated using the positron annihilation lifetime technique. The free-volume hole sizes for the present polymers were quantified from the long-lived ortho-positronium (o-Ps) lifetimes. In contrast to the case of nonpolar, introduction of the polar hexenol into PP reduced the o-Ps lifetimes and the hole sizes derived from them. This indicates that the interchain interaction due to the hydrogen bonds in the amorphous region is much stronger than the enhancement of the segmental motion due to the butyl long branch. A comparison of the o-Ps lifetimes with the corresponding tensile strength suggested significant contribution of the subnanostructure in the amorphous region to the mechanical property.
Abstract: The microstructure of the polypropylenes (PP) irradiated by gamma ray was studied by positron lifetime technique and differential scanning calorimetry (DSC). Lifetime measurement shows o-Ps intensity decreases with increasing γ irradiation dose. The crystallinity of irradiated samples was detected by DSC method. The correlation between o-Ps intensity and crystallinity indicates γ-ray can induce higher crystallinity in the polypropylene at low irradiation dose.
Abstract: The subnanoscopic structures of polyrotaxanes, prepared from α-cyclodextrins, poly(ethylene glycol), and bulky adamantane end groups, were examined by means of the positron annihilation lifetime technique, in consideration of the free-volume hole, quantified from the long-lived ortho-positronium (o-Ps) lifetimes. The influence of the chemical structure on the temperature dependence of the o-Ps lifetimes are discussed.
Abstract: The new organic-inorganic materials, based on polyether chains covalently linked to a silica framework through urea bridges, referred as ureasilicates or ureasils, and semiconducting As2S3-ureasil composites are investigated using positron annihilation lifetime spectroscopy (PALS) and scanning electron microscopy (SEM) techniques. The results obtained show that incorporation of the As2S3 clusters into ureasil affects on the ortho-positronium (o-Ps) intensity or positronium formation probability and micro-/nanoscopic structure compared to the pure polymer, the effect is more essential as the loading fraction of As2S3 increases.
Abstract: Depth profile of subsurface chemical composition and free volume in segmented polyurethane-urea/clay nanocomposites was studied by angle resolved X-ray photoelectron spectroscopy (ARXPS) and Doppler broadening energy spectroscopy (DBES) using slow positron beam. The ARXPS studies revealed increasing N/C atomic ratio (hard segment to soft segment ratio) at any given depth for the clay loaded samples compared to the neat polymer. DBES study revealed significant microstructure modification with clay loading. Self segregation of hard and soft segments in neat polymer and their interspersing with clay loading was observed from DBES measurements.
Abstract: In this work positron annihilation lifetime spectroscopy (PALS) is employed to study the ortho-Positronium lifetime parameters τ3>, σ3 and I3 in two structurally simple amorphous polymers 1,2-poly(butadiene) and cis-1,4-poly(isoprene). The ortho-Positronium mean lifetime parameter τ3> is compared with dynamics data from broadband dielectric spectroscopy (BDS) and electron spin resonance (ESR) experiments. Coincidences of characteristic temperatures from PALS with BDS and ESR experiments show close relationships between positron lifetime and dynamics of polymers.
Abstract: In this contribution a generalized picture of the cavity number behavior is obtained by means of molecular dynamics simulations and consequent free volume analysis. The cavity number obtained for free volume cavities defined by different probe radii shows a complex behavior with the temperature. The number of cavities determined by small probes drops with the temperature. The number of cavities determined by large probes increases. This complex behavior of the cavity number can be discussed with the distinct behavior of the relative intensity, as observed in the experiment, and a support for the most basic of assumptions, that the cavity number relates to the relative intensity, is given.