Radiation effect on positronium formation in low-temperature polyethylene

The irradiation effect of γ-rays on polyethylene (PE) has been studied by positron annihilation lifetime spectroscopy (PALS). In the case of non-irradiated PE samples, at a low temperature below the glass-transition temperature, the intensity of the long-lived component of positronium, I₃, increases due to an increase in the concentration of trapped electrons. However, the increase in I₃ obtained in a few MGy γ-irradiated samples became very small due to the effect of induced radicals. It has been observed that the trapped electrons were affected by the intensity of the positron sources used for a PALS experiment.     

Study of irradiation effect on positronium formation in polypropylene

⁶⁰Co γ-rays and positron irradiation effect on positronium (Ps) formation in the bulk and near surface region of polypropylene (PP) was studied. It is revealed that the reduction of Ps formation probability in PP bulk as a function of elapsed time may not be due to enhanced concentration of oxygen groups, and should not be ascribed to a simple accumulation of free radicals. Results indicate that Ps in PP is not formed through only one branch. That branch sensitive to the irradiation as well as the existence of sample surface seems related to relatively mobile positrons.     

Comprehensive study of positronium formation in polymer blends between polyethylene and ethylene-vinylacetate copolymer

The intensity I₃ of ortho-positronium (o-Ps) in a polymer blend system consisting of polyethylene (PE) and ethylene-vinylacetate (EVA, random copolymer with a vinylacetate content of about 14%) was measured as functions of EVA weight content (Φ=0–100%), electric field (E=0–60 kV/cm ), positron irradiation time (t=0–200 h) and temperature (T=100–300 K). It was found that the addition of small amounts of EVA to PE significantly alters the electric field, positron irradiation time and temperature dependence of I₃. Positron trapping on polar EVA is suggested to be responsible for the sensitive effects of EVA.     

Magnetic field effect on the luminescence from gamma-irradiated solutions of fluorene

The luminescence from gamma-irradiated solutions of fluorene increases when a magnetic field is applied, in agreement with recent theoretical predictions. The magnitude of the field effect is shown to be solvent dependent due to the changes in the solute ion recombination rates.     

Combining different analytical approaches to identify odor formation mechanisms in polyethylene and polypropylene

In a previous study, we identified carbonyls as highly odor-active compounds in both unprocessed and processed polypropylene (PP) with higher intensities after processing, indicating a temperature-driven forming mechanism. In the presented work, we studied whether (a) these carbonyls are the major odor drivers to the overall odor of polyolefins, (b) their formation is taking place already at moderate temperatures well below the typical processing temperatures, (c) conventional antioxidants in polyolefins can prevent or reduce their formation, and (d) whether reducing the amount of oxygen present can decrease the overall odor. One polyethylene (PE) and one PP were selected, and both stabilized and unstabilized polymer powder samples were exposed to conditions differing in oxygen concentration and aging time. The changes in the volatile fraction as well as the formation of odor-active compounds were monitored using a multidisciplinary approach by combining analytical methods based on gas chromatography (GC), multivariate data analysis, and sensory methods (GC–olfactometry and a sensory panel). Both investigated materials (PE and PP) showed similar degradation products (aldehydes, ketones, carboxylic acids, alcohols, and lactones) which increased dramatically with increasing aging time and the lack of stabilization. Oxidation products, mainly carbonyl compounds, were responsible for the odor of the investigated materials. The main odor drivers were unsaturated ketones and aldehydes with a chain length between six and nine C-atoms. Interestingly, similar odor patterns were found for both stabilized and unstabilized samples, indicating that similar formation processes take place independent of the stabilization.     

Effects of aging and oxidation on positronium formation in polyethylenes

Positron annihilation lifetimes (PAL) have been measured for polythylenes (PEs) under differenr conditions of heat treatment. It is shown that the intensity, I₃, of the long-lived component of positronium (Ps) shows hystereses between the heating and cooling processes due to aging effect. It is also shown that about half of Ps observed at low temperatures below the glass transition is inhibited after the sample is heat-treated above the melting point in the atmosphere containing oxygen. It is suggested that carbonyl groups (C=0) formed by thermal oxidation can inhibit Ps formation through trapping the precursors of Ps, e⁺ and/or e^-.     

Electric properties of non-irradiated and gamma-irradiated keratin

Dielectric measurements as a function of temperature and frequency are reported for non-irradiated and γ-irradiated keratin, the irradiation doses being 5 and 50 kGy. The effect of γ-irradiation on the dielectric permittivity of keratin is not observed up to 190°C. In this temperature range, the values of the relaxation time and dipole moment are similar for non-irradiated and irradiated keratin at the same temperature. The influence of irradiation is manifested as a shift of the parameter (_s−_∞) peaks associated with the process of denaturation, towards lower temperatures. This fact is supported by lower values of the dipole moment for irradiated than for non-irradiated keratin, as a result of a decrease in the number of polar groups in the side and main chains of the macromolecule in the irradiated samples.     

Effect of polymer polarity on the positronium formation

Positron annihilation lifetime spectra have been measured on styrene–methyl methacrylate, styrene–acrylonitrile, and styrene–butyl methacrylate copolymers. The results show that the longest lifetime τ₃ remains constant during extended PALS measurement in all experiment copolymers, and relative intensity I₃ decreases to a certain extent with measured time in weak polar copolymers and remain almost unchanged in strong polar copolymers as well as ST–BMA copolymers. The observed decrease in I₃ have been found to be unrelated to the microstructural change of copolymers, and, instead, to be more likely a result of the buildup of an electric field inside the copolymers during the prolonged PALS measurement. The field effect can result in the decrease of I₃ due to the increase in the positrons and electrons diffusing out of the spur, but the influence of the electric field on I₃ decrease with increasing the polarity of the copolymers and the softness of side groups of macromolecular chains in the copolymers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 435–442, 2000     

Pressure effect on positronium reactions in organic solutions

The reaction rate constants of positronium (Ps) atoms with a series of nitrobenzene derivatives and nitromethane in toluene solutions have been determined as a function of external pressure up to 1000 kg cm⁻² (about 1000 atm). The rate constants for relatively weak Ps acceptors such as p-nitroanisole, 1,3-dimethyl-2-nitrobenzene and nitromethane increased considerably with external pressure, while those for relatively strong Ps acceptors like p-dinitrobenzene or nitrobenzene either decreased or changed little with external pressure. Comparison of the experimental results on pressure effects with those on temperature effects revealed that the application of external pressure suppresses the thermal decomposition of Ps complexes which are unstable at room temperature. The effect on a solvent of the Ps reaction was also studied by determining the reactivities of Ps atoms with nitrobenzene in various solvents as a function of external pressure.     

Shearing of oriented polyethylene and polypropylene

To learn more about the out-of-plane deformation of polymer lamellae during drawing, we have measured the resistance to shear along various planes in uniaxially oriented polyethylene and polypropylene. Fissures parallel to the orientation axis in oriented materials always cause too small an experimental value for the resistance of crystal glide parallel to the chain axes, but a rough estimate for the resistance to crystal glide is obtained using the elastic anisotropy. Also, the results suggest that kinking can be easier than glide when glide is inhibited by tie molecules.     

Low-temperature formation of positronium in nonpolymer organic systems

The phenomenon of the low-temperature formation of positronium (bound electron-positron system) observed during positron irradiation of a test substance is discussed. The effect is additional relative to the formation of positronium under normal conditions and, like the principal phenomenon, is radiation-chemical in nature. This effect has been discovered and studied mainly for polymers, in which the role of weakly bound electrons and positron localization (trapping) in the intensity of manifestation of this phenomenon was revealed. This review focuses on studies concerning barely investigated nonpolymer (polar and nonpolar) organic systems, in which a relatively high mobility of molecules as compared to polymers can open an opportunity for a more pictorial manifestation of positron and electron trapping by polar centers, both belonging to separate molecules and resulting from collective orientation of the molecules.     

Electric field effect on the nematic-isotropic phase transition

Pulsed electric fields are used to study the influence of a strong field on the nematic-isotropic phase transition for cyanobiphenyl and stilbene-type liquid crystals. Deviation of the electric field-induced optical anisotropy from the Kerr law is observed and it is shown that such electric fields can shift the transition temperature substantially. The induced birefringence and the shift of the transition temperature are measured as a function of the electric field strength. The results are explained qualitatively in the context of the Landau-De Gennes theory with two order parameters. The coefficients of the phenomenological theory are calculated using the simple density functional theory of polar nematics developed in this paper and the results for the shift of the transition temperature are compared with experiment results.     

Mechanism of enhanced positronium formation in low-temperature polymers

An enhanced positronium (Ps) formation in low-temperature polymers has been widely observed. The additional positronium formation is due to shallow trapped electrons in them. Positron annihilation lifetime spectroscopy was applied to investigate the Ps formation in a series of polymers, such as low-density polyethylene, ethylene-methyl methacrylate copolymers with various methyl methacrylate contents, and pure poly(methyl methacrylate) at low temperature. An analysis of the experimental data based on simple kinetic equations enables one to understand the Ps formation mechanism in polymers during low-temperature positron annihilation experiments as functions of the temperature and elapsed time. Good fittings of the experimental data were obtained. The fitting parameters seemed to show clear physical meanings.     

Mixed spherulites of alpha and gamma phases in gamma-irradiated and thermal-treated isotactic polypropylene

Samples of commercial bulk gamma irradiated i-PP are recrystallized at various temperatures. Optical microscopy, (SALS), and (DSC) are used. All common types of PP spherulites are observed. Investigation shows that number of dendritic spherulites and their positive birefringences increase with doses. It is supposed that spherulites observed consist of twins built up of triclinic and monoclinic crystallites of i-PP. A mechanism of their growth is proposed.     

Electric field induced instability and pattern formation in thin liquid films

Electrostatic field induced instability, morphology, and patterning of a thin liquid film confined between two electrodes with an air gap are studied on the basis of nonlinear 3D simulations, both for spatially homogeneous and heterogeneous fields. In addition to the spinodal flow resulting from the variation of field because of local thickness changes, a heterogeneous imposed field also moves the liquid from the regions of low field to high field, thus allowing a more precise control of pattern. Hexagonal packing of liquid columns is observed for a spatially homogeneous electric field, which is in accord with the e-field experiments on thin polymer films (Schaffer et al. Nature 2000, 403, 874). For a large liquid volume fraction in the gap, varphi > or = 0.75, the coalescence of columns causes a phase inversion, leading to the formation of air columns or cylindrical holes trapped in the liquid matrix (air-in-liquid dispersion). Locally ordered aligned patterns are formed by imposing a spatial variation of the electrostatic field by using a topographically patterned electrode. For example, multiple rows/lines of liquid columns are formed near the edge of a step-like heterogeneity of the electrode and annular rings of ordered columns or concentric ripples are formed around a heterogeneous circular patch. Simulations predict that the electrode pattern is replicated in the film only when the pattern periodicity, L(p), exceeds the instability length scale on the basis of the minimum interelectrode separation distance, L(p) > or = lambda(m)-d(min). Thus, the formation of secondary structures can be suppressed by employing an electrode with deep grooves and stronger field gradients, which produces almost ideal templating. The number density of the electric field induced patterns can be altered by tuning the mean film thickness (or the volume fraction of liquid in the gap), periodicity and depth (amplitude) of the grooves on the top electrode, and the applied voltage. The implications are in electrostatic lithography, pattern replication in soft materials, and the design and interpretation of thin film experiments involving electric fields.     

Electric and dielectric properties of some gamma-irradiated cabal glasses

Electrical conductivity and dielectric properties have been studied for the glass system CaO---B₂O₃---Al₂O₃ in the temperature range 40–200°C. The substitution of 5% B₂O₃ by CaO or replacing 5% CaO by Na₂O or MgO cause a decrease in the conductivity, but the decrease obtained by soda is greater than that of magnesia. The activation energies of the tested glasses were calculated. All the glasses investigated showed a dielectric constant almost independent of temperature at fixed frequency. The effect of subjecting the glass to a constant dose of gamma-rays changes both the electrical conductivity and dielectric constant. The experimental results were discussed in relation to the specific conduction mechanism in such glasses. Also the effect of varying glass composition or temperature on the mobility or migration of current carrier was considered. The possible creation of induced defects in glass on irradiation was evaluated.     

Recycled injection-molded and fibre-reinforced polyethylene/polypropylene

In this presentation, we are concerned with the fabrication and characterization of samples of compression-molded and injection-molded recycled polyethylene, with, in some cases, addition of cellulose fibre. We wish to know what is the performance of such plastics, as compared to the virgin materials and what is the effect of added fibre in both molding modes.