Temperature dependence of positron annihilation lifetime spectra for polyethylene: positron irradiation effects

Lifetime spectra for linear and branched polyethylene have been measured as a function of temperature. The longest lifetime, τ₃, and its intensity, I₃, are traced over a temperature range of 105–370 K. The lifetime decreases with decreasing temperature, and upon reheating the plot is retraced. I₃ has a minimum near 265 K with considerable hysteresis in the cooling/heating cycle. At the lower temperatures the increase in I₃ is attributed to source irradiation.     

Analytical application of positron lifetime spectroscopy in the characterization of binary solid solutions

Positron Lifetime Spectroscopy (LS) measurements were performed in a series of binary molecular solid solutions of the general formula M_1–x G _x L₃, where L(ligand)=acetylacetone, dipivaloylmethane, or N-benzoyl-N-phenylhydroxylamine, M=Al(III), Ga(III) or In(III), as matrix, and G=Cr(III), Mn(III), Fe(III), Co(III), Ru(III), Rh(III) and Ir(III), as guest molecules, and the corresponding mechanical mixtures. For the solid solutions, the o-Ps yield values (I ₃) decrease very rapidly with the increase of the guest mole fraction, showing a high efficient Ps inhibition process, while for the corresponding mechanical mixtures, these values decrease linearly with the increase of the guest molecule concentration, indicating the presence of two distinct phases. These results confirm our previous proposal that the LS technique is able to characterize solid solutions formed by one matrix, in whichI ₃ values are high, and one guest, in which theI ₃ values are very low.     

Thermal variation of free-volumes size distribution in polypropylenes. Probed by positron annihilation lifetime technique

Positron annihilation lifetime measurement was applied to the study of free-volume properties in three kinds of polypropylene as a function of temperature in the range of 25–180°C at thermal equilibrium. Positron lifetime data for polypropylenes were analyzed with a Laplace inversion technique in order to obtain continuous positron annihilation lifetime (PAL) distributions. At each temperature, four distinct PAL distributions were recognized. The distribution of the longest lived component was associated with a pick-off annihilation of ortho-positronium (o-Ps) trapped in free-volume of amorphous region, which grew bigger as the temperature increased. The hole radius distributions of free-volumes were estimated from the results of o-Ps lifetime distributions. A detailed analysis showed a mean radius of free volumes was 0.34 nm at room temperature and that was 0.42 nm near the melting point for each specimen. The distributions of hole radii of free volumes were found to be broader after thermal treatments. The relaxation of free volumes was attributed to the thermal equilibrium and the evacuation of included molecules in free volumes. © 1995 John Wiley & Sons, Inc.     

Study of water in Ca-montmorillonite by thermal analysis and positron annihilation lifetime spectroscopy

Journal of Thermal Analysis and Calorimetry - The aim of this study is to characterize adsorbed liquid in montmorillonite structure for different levels of adsorption by both thermoanalytical and...     

Determining the resolution of Laplace inversion spectrum

In experiments involving decaying signals, it is often desirable to analyze the data as a sum of exponential decays using the Laplace inversion method. However, Laplace inversion is an ill-conditioned problem, and it is difficult to ascertain the stability of the reconstruction method and resolution of the resulting spectrum. This paper provides an easily computed approximate bound of the resolution and offers guidelines on how to design experiments to improve the spectral resolution.     

Interpretation of positron lifetime spectra arising from micellar solutions: Determination of the ortho-positronium diffusion coefficient in the solvent

Positron lifetime spectra arising from micellar solutions of sodium dodecylsulphate (SDS) are interpreted in terms of a classical positronium diffusion model published earlier. Unlike the generally accepted assumptions, this model results in a non-exponential ortho-positronium (o-Ps) lifetime density function. A new method is presented for the simultaneous fitting of this lifetime density function to independent lifetime spectra recorded under the same experimental conditions. Among the fit parameters D_p, the diffusion coefficient of o-Ps in the solvent (i.e. heavy water) phase is studied in detail; a detailed error analysis for D_p is also given. Provided that the mean aggregation number of SDS micelles is about 60, the published D_p values show that the diffusion coefficient of o-Ps in (heavy) water at room temperature is lower than that of small ions and molecules and the Arrhenius plot indicates a strong o-Ps localization in the solvent. The hydrodynamic radius of o-Ps is calculated from the o-Ps and micellar diffusion coefficients and from the micellar radius; it is greater than that of small ions and molecules and this can be considered as an independent indirect proof for the existence of o-Ps bubble in the (heavy) water.     

A positron lifetime and Doppler-broadening study of positron states and free volume in polyethylene

Positron lifetime (LT) and Doppler-broadening (DB) studies of polyethylene have been performed simultaneously in the temperature range between 80 and 300 K. The LT spectra have been analysed assuming four exponential components. Two long-lived components appear, which were attributed too-Ps pick-off annihilation in crystalline regions (₃ = 0.9 to 1.2 ns) and at free-volume holes in the amorphous phase ( to 2.8), The variation in ₄ correponds to an increase of the mean hole size from 0.053 nm³ at 80 K to 0.188 nm³ at 300 K. From the data the glass transition temperature (T _g=195 K), the coefficient of thermal expansion of holes in the glassy and rubbery phase ( _{h, g} = 14.5 · 10^–4 K^–1 and _{h, r} = 189 · 10^–4 K^–1) and the fractional free volume (2.8% to 10.4%) were estimated. The DB curves were fitted by a sum of three Gaussians, the narrowest of which is assumed to represent the self-annihilation ofp-Ps localised at holes. The intensity of the narrow component,I _n, varies between 0 and 7.3% in a similar way as the LT intensityI _4/3 varies. From this it was concluded that other Ps reactions beside pick-off are not important. Further, it was shown that the average positron lifetime is dominated by theo-Ps component,T _{4 g}, while the behaviour of the DB peak height is mainly affected by thep-Ps narrow componentI _n .     

The application of normal coordinate analysis to INS spectra

The limitations, advantages and methodology of NCA applied to INS are presented. Additional effects due to harmonics and molecular recoil are discussed with some examples. The ability to find the best molecular model using INS is exemplified and some recent examples of this are discussed. Future possibilities and extensions are also suggested.     

A positron annihilation lifetime study of isotactic polypropylene

Positron lifetime studies were performed on well-characterized annealed and quenched samples of isotactic polypropylene. The positron experiments were conducted from ?20 to 110°C as a function of both heating and cooling. Of the three decaying exponential components resolved from the lifetime spectra, only the long-lifetime ortho-positronium (o-Ps) pickoff component was affected by the changes in temperature. The behavior of both the lifetime and intensity of the o-Ps component was interpreted with the aid of x-ray diffraction, densitometry, and optical microscopy examinations and results from previously reported investigations of the thermal transition behavior of polypropylene. The present experiments demonstrate that o-Ps lifetimes were similar for both the annealed and quenched samples, independent of thermal cycling, while the o-Ps component intensity was significantly larger for the quenched material during heating, with both sample types exhibiting a significant hysteresis upon cooling. These results suggest that the mean free-volume cavity size is independent of prior thermal treatment, while the density of free-volume sites is a sensitive function of structure and prior thermal history. The variations of lifetime and of intensity with temperature have provided insight into polypropylene's glass transition phenomena.     

Study of solid-state polymerization by positron lifetime measurements

The positron lifetime measurement technique was applied to analyze the structural changes occurring in solid-state polymerization of acrylamide and trioxane. Positronium (Ps) parameters, τ₂ and I₂, which show a marked change as a function of the γ-ray irradiation dose, signaled the presence of three clearly defined stages in the polymerization process: initiation, propagation, and saturation. The initial increase in τ₂, may very well be the result of efficient trapping of Ps in vacancies created around the polymer nuclei. The complicated behavior of I₂ may be explained as a chemical reaction between Ps precursors and the radiolysis products of this polymerization process.     

Molecular weight dependence of positron lifetime parameters in PEEK samples

Positron lifetime measurements have been performed on differently manufactured PEEK samples of different molecular weights. Our measurements confirmed an old assumption: the o-Ps lifetime changes linearly with the molecular weight of the polymer. We have found that both the size of the free volumes and their number increase with increasing molecular weight of the investigated polymers.     

The buildup of the electric field during positron annihilation lifetime spectroscopy measurement

Positron annihilation lifetime spectra were measured on pure polystyrene (PS) and PS samples whose film surfaces were coated with gold, graphite (GR‐PS), or M_oS₂. The results showed the longest lifetime remained constant with measured time in all experimental samples, whereas the corresponding intensity decreased with time at different rates. The experimental phenomena were associated with the buildup of an electric field inside the polymer during extended positron annihilation lifetime spectroscopy (PALS) measurement. The decrease in the rate was attributed to the presence of conductive film causing the neutrality between positive charges and negative charges, thereby reducing the buildup of the electric field. Additionally, we also performed PALS measurement on GR‐PS under different experimental conditions, such as the conductive film being grounded or not grounded or the presence of an external electric field. These results further indicated that the buildup of the electric field was responsible for the decrease in the intensity with time. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 332–336, 2001     

Nano-free volume characterization by positron annihilation lifetime technique in flame-retardant poly (vinyl chloride) after thermal treatment

The flammability tests are performed on flame-retardant poly (vinyl chloride) (FRPVC) material that has been used in cable insulation and jacketing construction for multi-purpose reactor (MPR) at Atomic Energy Authority of Egypt, as well as carbon-black FRPVC (CB-FRPVC) material produced by Egyptian Electrical Cable Company (EECC).The temperature variation of thermal conductivity, thermal expansion coefficients, and nano-size free volumes by means of positron annihilation lifetime (PAL) technique are determined. Correlation of positron annihilation and thermal conductivity has been discussed in terms of phonons as the main heat carriers.     

Location of solubilizate in water-AOT-isooctane systems using positron lifetime spectroscopy

In the present work, positrons have been used as a probe to locate the interaction site of the additive molecules in a membrane mimetic system similar to reverse micelles. The systems investigated are water-AOT Aerosol OT [Sodium bis(2-ethylhexyl) sulfosuccinate)-isooctane solutions. Positron lifetime measurements have been performed in water-AOT-isooctane solutions containing chloroform and dichloromethane, respectively, as additives. The choice of these additives is based on their physiological importance. A comparison of the behavior of positron annihilation parameters in surfactant solutions containing the additives with that in systems without them has been made. It has provided some information about the location of the interaction site of the additive molecules in these solutions. In chloroform, the additive molecules tend to migrate from the bulk solvent to the aggregates and are adsorbed either at the interface or close to it. The dichloromethane molecules, on the other hand, tend to get distributed near the hydrocarbon tail of the AOT molecules closer to the bulk solvent.     

Regularized inversion of the Laplace transform for series of experiments

Not only in low-field nuclear magnetic resonance, Laplace inversion is a relevant and challenging topic. Considerable conceptual and technical progress has been made, especially for the inversion of data encoding two decay dimensions. Distortion of spectra by overfitting of even moderate noise is counteracted requiring a priori smooth spectra. In this contribution, we treat the case of simple and fast one-dimensional decay experiments that are repeated many times in a series in order to study the evolution of a sample or process. Incorporating the a priori knowledge that also in the series dimension evolution should be smooth, peak position can be stabilized and resolution improved in the decay dimension. It is explained how the standard one-dimensional regularized Laplace inversion can be extended quite simply in order to include regularization in the series dimension. Obvious improvements compared with series of one-dimensional inversions are presented for simulated as well as experimental data. For the latter, comparison with multiexponential fitting is performed.     

Study of molecular motions in alkyl cyanobiphenyls using positron lifetime spectroscopy

Positron lifetime measurements have been carried out in two liquid-crystal-forming homologues of alkyl cyanobiphenyls, 7CB and 10CB. In each of these two compounds measurements were performed during the heating cycle of samples prepared either by quenching or by slow cooling from the respective liquid crystalline phase. In both compounds, the behavior of quenched and slow-cooled samples is found to be different. Unlike the slow-cooled sample, the material in the quenched sample seems to have transformed into a glassy solid. Theo-Ps pick-off lifetime in the quenched sample exhibits a strong temperature dependence. In each case, its value exhibits six broad peaks at various characteristic temperatures which have been ascribed to various motions associated with the molecules of these compounds. The quenched samples of 7CB and 10CB exhibit glass transitions at 268 and 266 K, respectively. The present work demonstrates an interesting application of positron lifetime spectroscopy (PLS).     

The scavenging of the precursors of the solvated electron from the positron lifetime spectroscopy and the doppler broadening of annihilation line shape technique

The electron scavenging properties of aqueous solutions of two series of solutes are investigated, using the positron as a probe. For a better interpretation of the data, both lifetime spectroscopy and the Doppler broadening of annihilation line shape technique are used. All solutes inhibit the positronium (Ps) formation, by the scavenging of electrons. The first series consists of the halate ions, that should follow the Hunt linear relation between the rate constant for reaction with the solvated electrons, k_(e^?aq+S), and that for its precursor(s), 1/C₃₇. The Ps inhibition constants, k, are 0.14, 1.44 and 3.45 M^?1 for ClO^?₃, BrO^?₃ and IO^?₃, respectively. This sequence is quantitatively consistent with that of the respective k_(e^?eq+S). The second series includes the SeO⁼₄, Te(OH)₆ and BrO^?₄ species, and the Ps inhibition constants are 5.62, 10.5 and 14.3 M^?1 respectively. These values are much higher than expected from the k_(e^?aq+S) constants, on basis of the Hunt relation, in agreement with previous results from pulse radiolysis experimets.     

Computational aspects of Laplace transform inversion of thermal unimolecular rate constant

The thermal limiting high-pressure unimolecular rate constant k∞ represents, operationally, the Laplace transform of the product of microcanonical rate constant for decomposition of molecules having specified energy E [k(E)] and the density of states [N(E)]. By inversion, it is possible to recover k(E)N(E), from which one can obtain the energy dependence of k(E) and the pressure dependence of k_uni, the thermal general-pressure unimolecular rate constant. This article examines numerical aspects of three methods of inversion, their reliability and dependence on sampling, i.e., on the number of available experimental data points, by comparing exact k(E) and k_uni with those obtained by inversion. It turns out that the method of steepest descents is the best all-round performer.     

A positron annihilation lifetime study of isothermal structural relaxation in bisphenol-A polycarbonate

Positron annihilation lifetime spectroscopy has been used to study the isothermal relaxation response of compression molded bisphenol-A polycarbonate at temperatures of 263, 273, and 303 K. The temperature dependence of both the lifetime and intensity of the ortho-Positronium (o-Ps) pickoff component is discussed in terms of ductile-to-brittle transition behavior and free volume theory. An additive exponential model and the Williams–Watt model were used to analyze the relaxation as a function of temperature and provided results consistent with the anticipated molecular mobility of polycarbonate at sub-T_g temperatures.