Detection of free volumes in polyaniline complexes with various acids by using positron lifetime spectroscopy

The positron lifetime spectroscopy (PLS), a non-destructive characterization method, utilizes positronium (Ps; an electron–positron bound state) as a probe and measures its lifetime in polymer free volumes. For the first time the free volumes have been estimated by PLS in polyaniline (PANI) complexes with various inorganic and organic acids. It was found that the o-Ps lifetime increases and the intensity decreases with increasing ionic radius of the counter-ions in PANI complexes. Obviously, larger counter anions result in enhanced mean size of the voids corresponding to the free volume in the bulk polymer.Electrical conductivity has been measured by conventional four-probe technique. The glass transition temperature and temperature of removal of the absorbed water have been determined by using differential scanning calorimetry. It was established fairly well correlation of the mentioned polymer parameters with the o-Ps lifetime and the free volume of PANI complexes, respectively. The greater free-volume results in a decrease of conductivity, glass transition temperature and temperature of removal of the absorbed water.     

Comments on the relation: positronium lifetime – free volume size parameters of the Tao–Eldrup model

The author is discussing the parameters appearing in the Tao–Eldrup (TE) model describing the ortho-positronium (o-Ps) lifetime dependence on the size of free volume in which Ps is trapped. Parameter values are not universal, applicable to all media. The Ps penetration to the bulk should depend on Ps work function; the o-Ps decay rate is strongly influenced by the contact density factor.     

A non-conventional method of polymer PAL spectrum analysis by the LT computer program

A new version of computer program (LT v.10) offers a new concept of polymer spectrum analysis. The theoretical model takes into account a few processes in which positron is involved: the process of slow formation and localization of positronium (Ps), delay formation of positronium from shallow trapped electrons and positron trapping in irradiation-induced centers. The model was applied to two series of spectra for LDPE and HDPE collected at constant temperature (much below the glass temperature) as a function of measurement time. The Ps internal relaxation time and time of localization of Ps in a free-volume center were determined. The results show that the trapping rate of positron is strictly correlated with the amount of the shallow trapped electrons. That suggests a coupling between the positron and electron-trapping centers.     

Study of the size and numerical concentration of the free volume of carbon filled HDPE composites by the positron annihilation method

In this paper, the size and numerical concentration of free volume of high density polyethylene/carbon black (HDPE/CB) composite were investigated by positron annihilation lifetime spectroscopy (PALS). The PALS were measured in two series of samples, one with various CB contents in the composites and the other with changing the temperature of HDPE/CB composite containing 25 phr CB. It was found that the important parameters of PALS show their fluctuation around the percolation threshold. The conductivity of HDPE/CB is controlled by CB contribution, and that can be reflected in o-Ps lifetime. The temperature dependence of positron lifetimes reveals that the existence of glass transition temperatures and the size of free volume holes increases when temperature increases above glass transition. The results observed from the second set of samples suggest that positive temperature coefficient is in some way related with free volume expansion. The experiment facts implied that the conductivity of HDPE/CB was related with not only the size of free volume holes but also the number of free volume holes. The Doppler-broadening of HDPE/CB was also investigated.     

Free volumes in solids under high pressure

A review of experimental work on ortho-positronium (o-Ps) lifetime in solids under the pressures up to 1 GPa is presented. Among the effects observed at high pressure one can mention: the disappearance of the energy level for Ps at the reduction of free volume size; pressure induced phase transitions; variation of Ps formation intensity with time; increase of o-Ps lifetime after intercalation of high pressure gas to the paraffin samples.     

Solvent and temperature effects on positronium annihilation parameters and on its quenching reactions with the free radical HTEMPO

Positron annihilation lifetime spectroscopy (LS) and the Doppler broadening of the annihilation radiation lineshape (DBARL) technique have been used in conjunction to study solvent and temperature effects on both the positronium (Ps) quenching reactions with the free-radical HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) and the annihilation parameters. A change in the nature of the quenching reaction is observed from spin conversion in benzene (Bz),N,N-dimethylacetamide (NDMA), andN-methylformamide (NMFA) to Ps oxidation inmeta cresol (m-C); it is attributed to a modification of the electron density distribution in the quenching molecule due to hydrogen bonding with them-C molecules. The data also indicate that the full-width at half-maximum of the momentum distribution associated to para-positronium (p-Ps) resulting from the spin conversion reaction is smaller by a factor of 2 than that forp-Ps directly formed in the positron spur. The ortho-positronium (o-Ps) pickoff lifetime and momentum distribution are shown to give access to physicochemical and structural properties of the solvents.     

Influence of vinylidenefluoride on the physical ageing of poly(chlorotrifluoroethylene)

The influence of vinylidenefluoride (3% composition) on the physical ageing of poly(chlorotrifluoroethylene) at 70 °C has been investigated using the positron annihilation lifetime technique. Both the ortho-positronium (o-Ps) pick-off lifetime and its intensity show a systematic variation with ageing time. The o-Ps intensity exhibits non-exponential character which can be fitted with two additive exponential decay curves and the free volume is found to exhibit the Doolittle type of free volume relaxation. The relaxation times were evaluated from the structural relaxation function and the non-exponentiality parameter was estimated using the Kohlrausch-Williams-Watts (KWW) function, which indicates the deviation from exponential relaxation. Based on the relaxation times, the activation energies calculated seems to label the different kinetic units/irregularity in the chain backbone of PCTFE structure participating in the relaxation process. Physical ageing seems to yield close packing of polymer chains.     

Column packings for high-performance liquid chromatography and positron annihilation lifetime spectroscopy

Positron annihilation measurements as a function of temperature and the length of bonded alkyl groups have been carried out on silica gel samples. Silica gel samples were bare and bonded with alkyl group from C1 up to C18. The diameters of pores were deduced from the lifetime of trapped ortho-positronium (o-Ps), and it was found that o-Ps lifetime provides reasonable information on the pore sizes for both bare and alkyl bonded silica gels.     

Positronium chemistry in porous materials

Porous materials have fascinated positron and positronium chemists for over decades. In the early 1970s it was already known that ortho-positronium (o-Ps) exhibits characteristic long lifetimes in silica gels, porous glass and zeolites. Since then, our understanding of Ps formation, diffusion and annihilation has been drastically deepened. Ps is now well recognized as a powerful porosimetric and chemical probe to study the average pore size, pore size distribution, pore connectivity and surface properties of various porous materials including thin films. In this paper, developments of Ps chemistry in porous materials undertaken in the past some 40 yr are surveyed and problems to be addressed in future are briefly discussed.     

Diffusion coefficients of positronium in polycarbonate at low temperatures

Diffusion coefficients of positronium (Ps) in polycarbonate (PC) have been determined at temperatures between 20 and 300 K by means of positron lifetime spectroscopy. 2,2-dinitrobiphenyl (DNB) was added to the polymer as a Ps quencher and the diffusion coefficients were determined from measured Ps quenching rate constants, assuming that the reaction between Ps and DNB is completely diffusion-controlled.     

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.     

Positron annihilation lifetime and differential scanning calorimetric study of immiscible NBR/PE blends

The temperature dependence of the mean size of nanoscale free‐volume holes, 〈V_h〉, in polymer blend system consisting of polar and nonpolar polymers has been investigated. The positron lifetime spectra were measured for a series of polymer blends between polyethylene (PE) and nitrile butadiene rubber (NBR) as a function of temperature from 100 to 300 K. The glass transition temperatures (T_g) for blends were determined from the ortho‐positronium (o‐Ps) lifetime τ₃ and the mean size of free‐volume holes 〈V_h〉 versus temperature as a function of wt % of NBR. The T_gs estimated from the PALS data agree very well with those estimated from DSC in view of different time scales involved in the two measurements. Both DSC and PALS results for the blends showed two clear T_gs of a two‐phase system. Furthermore, from the variation of thermal expansivity of the nanoscale free‐volume holes, the thermal expansion coefficients of glass and amorphous phases were estimated. Variations of the o‐Ps formation probability I₃ versus temperature for pure PE and blends with low wt % of NBR were interpreted on the basis of the spur reaction model of Ps formation with reference to the effects of localized electrons and trapping centers produced by positron irradiation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 227–238, 2009     

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.     

Kit development for labelling erythrocytes or leukocytes with technetium-99m in vitro

Positron lifetime spectroscopy has been applied to estimate the free-volume hole size distribution in glassy polycarbonate (PC) and polystyrene (PS) as well as in plastically deformed and undeformed, semi-crystalline polyethylene (HDPE). The hole radius density distribution is determined from the ortho-positronium lifetime distribution which is obtained via a Laplace-inversion of the positron lifetime spectrum. The hole volume density distribution and the number density distribution of holes is estimated from the hole radius density distribution. In PC and in PS all of the distributions may be well approximated by a single Gaussian. The hole radius and the hole number density distributions have centres <r> and <v _n > at 0.29 nm and 0.1 nm³ in PC, and at 0.28 nm and 0.09 nm³ in PS. The FWHM of the corresponding distributions are 0.042 nm and 0.040 nm³ (PC), and 0.039 nm and 0.34 nm³ (PS), respectively. Both, the shape and the width of the distributions correlate well with the free volume theory of BUECHE. In PE the lifetime spectra consist of four components. The o-Ps lifetime distribution is bimodal and may be attributed to o-Ps annihilation in the crystalline and in the amorphous phase of the polymer. The corresponding hole size distributions show definite changes of their position and width following plastic deformation which we attribute to homogeneous crystal lattice dilatation and/or a local disorder in the crystals and to an increase in the eccentricity of holes in the amorphous phase.     

The chemistry of positronium: III. Inhibition and quencing by sikver and cadmium salts

The inhibition ofpositronium formation and the quenching reactions of positronium in aqueous solutions of AgCIO₄, Cd(C10₄)₂ and AgOOC-CF₃ have been studied using the positron lifetime spectroscopy. The variations of the lifetimes of ortho-positronium (0-Ps) wiLls the concentration of the solute in water reveal peculiar features, attributed to the formation of complex ions.     

Thermal analysis techniques for characterization of polymer materials

Routine DSC and TGA techniques, used to characterise polymer thermal stability, have been further used for assessment of comparative thermal stability of various polymer materials and for prediction of material lifetimes. The following materials were investigated: (1) commercial and experimental polymer materials - results for poly(vinyl chloride) (PVC) and bisphenol A polycarbonate (PC) are presented; (2) a polydimethylsiloxane-polytetrafluoroethylene (SIL-PTFE) coating system; and (3) commercially available linear low density polyethylene (PE-LLD), unmodified and modified chemically and physically. The plot of reciprocal temperature of initial decomposition 1/T_di vs log heating rate β has been recommended for assessment of comparative thermal stability. The lifetime of polymer materials was calculated from the plots of log time-to-failure, log t_f, vs reciprocal temperature 1/T, where t_f values were obtained using T_di from TGA measurements or directly from the oxidation induction time (OIT) data as criteria for initial deterioration of polymer thermal stability. The following sequences of increasing thermal stability were found for investigated materials:

(1)

PVC ? PC;

(2)

SIL < SIL-PTFE 20% < SIL-PTFE 50% ? PTFE;

(3)

(B) PE-LLD, grafted < (A) PE-LLD, unmodified < (C) PE-LLD, filled.

The lifetime of polymer materials predicted from the plots of log t_f vs 1/T are in reasonable agreement with experimental data and users' observations, e.g. approximately 1 year for PC and unmodified PE-LLD both at 373 K (100 °C) and for PVC at temperature of outdoor conditions about 298 K (25 °C).     

Competitive positron and positronium trapping in porous media

Positron annihilation acquired acceptance for structural investigation of solids but results in porous media—where positron lifetime spectroscopy (LT) reveals substantial Ps formation—were ambiguous. Data on zeolites lead to the conclusion that Ps trapping in competing “extended free volume” sites, inhomogeneous regions and grain boundaries occurs. Furthermore, positron trapping must also be considered. Systematic errors due to incomplete time range selection are discussed, significance and importance of corrections for 3γ/2γ counting efficiency differences are shown in practice.     

Microstructural studies of electron beam-irradiated cellulose pulp

The effect of electron beam irradiation on the microstructure of cellulose has been investigated using positron annihilation lifetime spectroscopy (PALS) and electron paramagnetic resonance (EPR) Spectroscopy. PALS studies of irradiated cellulose samples showed that ortho-positronium (o-Ps) lifetime increases with an increase in dose up to 80 kGy and decreases at higher doses. The EPR signal of the irradiated cellulose matrix showed the presence of multiple radical sites. These results are discussed on the basis of chemical and physical changes occurring at the microscopic level in the cellulose due to irradiation.     

Micro-structure of gamma-ray irradiated polyethylenes studied by positron annihilation

Effects of gamma-ray irradiation on high density (HDPE) and low density (LDPE) polyethylenes were measured by positron annihilation at temperatures between 100 and 420 K. The effect of the irradiation on the intensity I₃ and the lifetime τ₃ of the longest lived component was significant below the glass transition temperature T_g, while they were little affected above T_g. For LDPE a marked minimum was observed in the I₃ vs T curve. The lower edge of the minimum, corresponding to glass II and glass I transitions, was found to shift to lower temperatures by the irradiation. In HDPE both I₃ and τ₃ decreased on irradiation mainly due to radiation induced free radicals. The gel fraction of HDPE was small when irradiated below T_m, while it rose sharply on irradiation near T_m. Positron lifetime parameters of this highly crosslinked HDPE showed a distinct difference compared to HDPE irradiated below T_m. Usefulness of the positron annihilation method is discussed in conjunction with studying micro-structure of polymers.