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.     

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.     

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.     

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.     

On the measurement of structural relaxation in polymers using positron annihilation lifetime spectroscopy

Positron annihilation lifetime spectroscopy has been identified as an effective means of characterizing the free volume content of amorphous polymers. The lifetime and intensity of the ortho-positronium (o-Ps) pick-off annihilation has been found to correlate with the average size and density of free volume sites, respectively. Recently, PALS has been used to evaluate and monitor the physical aging and structural relaxation of polymers in terms of both initial state and evolution in state with time. However, during extended PALS measurements in insulating materials, an electric field can build up due to positron-electron annihilation and can effectively reduce the probability of positronium formation. In this paper, an observed decrease in intensity associated with the o-Ps annihilation component in the glassy polymers polycarbonate and polystyrene is found to be unrelated to structural relaxation of the materials over the time periods examined as reported earlier by others, and, instead, to be more likely a result of electric charge build-up. © 1993 John Wiley & Sons, Inc.     

Delayed formation and localisation of positronium in polymers at low temperatures

A theoretical model of the positron annihilation lifetime spectrum including the mechanisms of slow positronium (Ps) localisation and delayed Ps formation from a positron and a trapped electron was developed. The model was applied to two series of spectra for low-density polyethylene and high-density polyethylene (HDPE) collected at constant temperature (much below the glass temperature) as a function of measurement time. The Ps internal relaxation time and time of localisation of Ps in a free volume centre were determined. The results show that after long irradiation of the polymer a dominant fraction of positrons (unbound in Ps) annihilate from the trapped states. On the basis of parameters determined from the HDPE lifetime spectra, two S(t) curves (for sample in darkness and in light) were calculated. The predicted shapes of S(t) well agree with literature data obtained with the age–momentum correlation (AMOC) experiment. According to the new model the shapes of the para-Ps and the ortho-Ps (p-Ps) components are non-exponential. In spite of this, the multi-exponential decomposition of a polymer spectrum enables to determine correctly the value of the o-Ps lifetime, however the other parameters determined from the spectrum have no simple physical meaning.     

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.     

Effect of cyclic stress on structural changes in polycarbonate as probed by positron annihilation lifetime spectroscopy

Positron annihilation lifetime spectroscopy (PALS) is used to probe structural changes in glassy polycarbonate in terms of changes in the hole volume and the number density of holes during fatigue (cyclic stress) aging. The ortho-positronium (o-Ps) pickoff annihilation lifetime τ₃, as well as the intensity I₃, were measured as a function of cyclic stresses and various previous thermophysical aging histories. It is found that τ₃, the longest of the three lifetime components resolved in the PALS of glassy polycarbonate, increases when a cyclic stress is applied. These results indicate that there is a structural change during fatigue aging. The “holes” where o-Ps can localize become larger upon fatigue aging. These results also suggest that a significant distinction exists between structural changes induced by thermophysical aging and fatigue aging. The o-Ps annihilation intensity, which is a relative measure of the hole density in a material, showed a continuous decrease upon fatigue aging, indicating the possibility of hole coalescence, which could be a precursor of crazing. The interaction between thermophysical aging and fatigue aging corresponds very well with the enthalpy relaxation behavior as reported previously, viz., a well-aged sample is much more sensitive to cyclic stress. More importantly, it is hypothesized that fatigue failure initiation is probably closely related to hole size and density fluctuation.     

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.     

Temperature dependence of the free volume in polytetrafluoroethylene studied by positron annihilation spectroscopy

The temperature dependence of the free volume holes in pure polytetrafluoroethylene (PTFE) and doped with 25% glass have been studied in the temperature range (30–250 °C) using positron annihilation lifetime spectroscopy. The data clearly revealed the glass transition temperatures for pure and doped PTFE are 130 and 110 °C, respectively. As the temperature increases, the free volume distribution becomes positioned at larger free volume hole size. A good correlation between the electrical conductivity and the o-Ps parameters was achieved.     

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.     

Positron age–momentum correlation studies of free volumes in polymers

Positron age–momentum correlation (AMOC) spectroscopy, which can sensitively probe momentum distributions of positrons and positronium (Ps), was conducted for studying the pick-off process of the triplet bound state ortho-Ps (o-Ps) with electrons at the walls of the free volumes in polymers. Influences of different chemical elements forming free volume were investigated. It was found that the momentum distribution of o-Ps pick-off annihilation sensitively depends on the electronic state in the free volumes. The feasibility of the chemical analysis relevant to the free volume in polymers is discussed.     

Positron annihilation in hypercrosslinked polystyrenes

Positron annihilation in hypercrosslinked polystyrene, called CPS(0.3)150E, has been studied as a function of temperature in the range from 35 to 370 K. The positron lifetime spectra were resolved into five components using the PATFIT and MELT programs. The annihilation rate constant of the longest-lived component was found to increase linearly with increasing temperature. Remarkably, the distribution of o-Ps lifetimes resolved by MELT was shown to broaden with decreasing temperature. Moreover, an effect of the oxygen pressure on the positronium characteristics was also investigated in another hypercrosslinked polystyrene, CPS(0.3)100E. The oxygen pressure varied from vacuum to 6 atm. The annihilation rate constants of the long-lived components were observed to increase linearly as a function of the oxygen pressure, which demonstrates a dependence of the kinetic of o-Ps quenching on the pore size.     

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 volume of cyanate resins studied by positron annihilation

The polymerization process of bisphenol-A dicyanate (BADCy) has been studied using a positron-annihilation lifetime technique (PAL). The polymerization was conducted at 150°C, and the process was followed by PAL. Seven kinds of samples with different curing times were also formed at 150°C, and the relation between the period of the curing time and the degree of polymerization was studied. It has been shown that theo-Ps lifetime increases in samples with a higher polymerization than 85%, which is consistent with measurements of the specific volume of BADCy.     

Study on the microstructure and mechanical properties for epoxy resin/montmorillonite nanocomposites by positron

Positron annihilation lifetimes have been measured for epoxy resin/organic montmorillonite (OMMT) nanocomposites. Effects of different dispersion states of nano-layered OMMT on the positron annihilation parameters and the mechanical properties were studied. We found that the ortho-positronium (o-Ps) intensity decreased with increasing OMMT content, which indicated that the interaction between the host and nanofillers restrained the segmental motion, resulting in a decrease of the free volume. On the other hand, it is very interesting to observe a good correlation between the interfacial interaction and mechanical properties, suggesting that the dispersion states of OMMT and interfacial property between clay layers and matrix played an important role in determining the mechanical properties.     

Free volume and microstructural investigation of poly(ethylene terephthalate)-g-acrylic acid (PET-g-AA) copolymer films

Acrylic acid (AA) was grafted onto PET films by preirradiation method using a ⁶⁰Co γ-radiation source. Microstructural investigation of the PET-g-AA copolymers has been carried out by wide angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA) and positron annihilation lifetime spectroscopy (PALS) techniques. The WAXD results showed only marginal variation in the crystallinity of the graft copolymers. Dynamic mechanical analysis showed an increase in the temperature of the α-relaxation and the tan δ value of subroom temperature secondary relaxations. From the PALS results, a complex variation of the free volume parameters, i.e. the o-positronium lifetime (τ₃), its intensity (I₃), fractional free volume (f_v) and the intermediate lifetime component was observed for the graft copolymers. Multiple phenomena of the effect of secondary relaxations, additive behavior of the individual polymer free volume parameters and effects from interfacial defects have been invoked to understand the fluctuational nature of the free volume properties in the graft copolymers.     

Free volumes in liquid-crystalline main-chain polymer probed by positron annihilation

Free volumes in a copolymer consisting of p-hydroxybenzoic acid (HBA) and poly(ethylene terephthalate) (PET) were probed by positron annihilation technique. Doppler broadening profiles of the annihilation radiation and lifetime spectra of positrons were measured in the temperature range between 30 and 230°C. Above the glass transition temperature (ca. 60°C), the lifetime of ortho-positronium (o-Ps) annihilated in the free volumes and its annihilation probability were found to increase with increasing specimen temperature. These facts were attributed to the increase both in the size of the free volumes and in the concentration of such regions due to rearrangements of molecules. From the observed lifetime of o-Ps, it was found that the size of the free volumes increases from 0.05 nm³ to 0.1 nm³ in the temperature range between 30 and 230°C. At solid-mesophase transition temperature (150–220°C), the size of the free volumes monotonously increases, while the increase in the concentration of such regions saturates at 174°C. The clear relationship between the data obtained by the positron annihilation and those obtained by differential scanning calorimetry was confirmed. ©1995 John Wiley & Sons, Inc.     

Effect of conductive fillers on the cyclic stress-strain and nano-scale free volume properties of silicone rubber

The effect of carbon black(CB) and graphite(G) powders on the macroscopic and nano-scale free volume properties of silicone rubber based on poly(di-methylsiloxane)(PDMS) was studied through thermal and cyclic mechanical measurements, as well as with positron annihilation lifetime spectroscopy(PALS). The melting temperature of the composites(Tm) and the endothermic enthalpy of melting(?Hm) were estimated by differential scanning calorimetry(DSC). Tm and the degree of crystallinity(χc) of PDMS composites were found to decrease with increasing the CB content. This can be explained due to the increase in physical cross-linking which results in a decrease in the crystallite thickness. Besides, χc was found to be dependent on the filler type. Cyclic stress-strain behavior of PDMS loaded with different contents of filler has been studied. Mullins ratio(RM) was found to be dependent on the filler type and content. It was found that, RM increases with increasing the filler content due to the increase in physical cross-linking which results in a decrease in the size of free volume, as observed through a decrease of the o-Ps lifetime τ3 measured by PALS. Moreover, the hysteresis in PDMS-CB composites was more pronounced than in PDMS-G composites. Furthermore, a correlation was established between the free volume Vf and the mechanical properties of PDMS composites containing different fillers. A negative correlation was observed between Vf and RM.     

Positronium in solid phases of long-chain paraffins

The study of positronium intensity rise in long-chain alkanes shows two kinds of electron traps: the first, which are discharged at low temperature (≈200 K); the other, which remain populated up to the transition point to the rotator phase; e.g. in C₃₀H₆₂ they are still observed at 328 K.In the rigid phase of even-numbered alkanes o-Ps lifetime is shorter than that of odd-numbered ones, due to the difference in the width of gap between the molecular lamellae.