Free volume evolution in polyoxymethylene studied by positron annihilation spectroscopy

A phenomenological model linking the macroscopic volume from dilatometry with the microscopic free volume from positron annihilation lifetime spectroscopy is presented. The temperature dependences of both quantities enable to obtain the so-called initial temperature Ti at which dynamic free volume change sets in, the corresponding initial volume Vi, and subsequently, all free volume characteristics. Application of this model on the literature data of a typical low-molecular weight glass former, o-terphenyl, leads to the findings that (i) Ti ≅ TK the Kauzmann temperature and (ii) a packing fraction of the extrapolated equilibrium liquid at Ti is close to the closest regular packing of hard spheres. The published viscosity−temperature data over 12 decades of magnitude are correlated with the free volume hole fraction fh, as determined from the PALS results, via the WLF−Doolittle type equation. These findings indicate that the orthopositronium (o-Ps) is able to detect the part of the total free volume distribution which is relevant for the viscosity over the measured temperature interval from Tg up to ∼ 1.5Tg. In addition, the change of the free volume hole behavior above Tr = 1.25Tg, lying in the vicinity of the crossover temperature Tc from the idealized version of mode-coupling theory, is critically analyzed within a modified bubble concept (the equilibrium interaction of o-Ps with the soft matrix).

In this paper, a systematic study is provided of the chemical environment inside free volume holes in a series of halogenated polystyrenes (p-position), −[CH2CH C6H5X]n– (X = F, Cl, Br, I), by using positron annihilation spectroscopy. In such polymers it was determined that the chemical environment is the major effect on Doppler broadening of two 511 keV γ photons from positron–electron annihilation. Doppler broadening energy spectroscopy (DBES) and positron annihilation lifetime spectroscopy (PALS) were combined in a novel approach to study the chemical environment in a polymer system. A highly linear relationship between Doppler broadenings caused by electron kinetic energies of valence electrons and the ionization potentials of halogen elements was obtained, as well as a similar correlation with the results from ab initio molecular orbital (MO) calculations for monohalogenobenzenes, C6H5X (X = F, Cl, Br, I). The results demonstrate that the combination of DBES and PALS may provide an effective way to study the chemical environment inside free volume holes in polymers.

The microstructural evolution of a series of triazine framework-based microporous (TFM) membranes under different conditions has been explored in this work. The pristine TFM membrane is in situ fabricated in the course of polymer synthesis via a facile Brønsted-acid-catalyzed cyclotrimerizaiton reaction. The as-synthesized polymer exhibits a microporous network with high thermal stability. The free volume size of the TFM membranes gradually evolved from a unimodal distribution to a bimodal distribution under annealing, as analyzed by positron annihilation lifetime spectroscopy (PALS). The emergence of the bimodal distribution is probably ascribed to the synergetic effect of quenching and thermal cyclization reaction. In addition, the fractional free volume (FFV) of the membranes presents a concave trend with increasing annealing temperature. Vapor sorption tests reveal that the mass transport properties are closely associated with the free volume evolution, which provides an optimal condition for dehydration of biofuels. A promising separation performance with extremely high water permeability has been attained for dehydration of an 85 wt % ethanol aqueous solution at 45 °C. The study on the free volume evolution of the TFM membranes may provide useful insights about the microstructure and mass transport behavior of the microporous polymeric materials.

Free volume study of 70 MeV carbon induced modification in polymers through positron annihilation

Positron annihilation spectroscopy (PAS) is a novel method that provides molecular-level information about complex macromolecular structure in a manner different from, but complementary to, conventional physical and chemical methodology. This paper presents a perspective of PAS in polymeric systems covering 12 aspects: historical, spacial, spherical quantum model, anisotropic structure, voids, positronium chemistry, time, positron annihilation lifetime spectroscopy and data analysis, variable monoenergetic slow positron beam techniques and depth profiling, elemental analysis, multidimensional instrumentation advances in PAS, and free volume and free-volume theories.

Polymer structures have been investigated using positron annihilation lifetime spectroscopy (PALS) with a slow positron beam as well as a conventional radioactive source (22Na). The properties of the free volume holes near the polymer surface were studied as a function of the positron implantation energy. The longest lifetime was associated with ortho-positronium (o-Ps) annihilation in the free volume holes. In polytetrafluoroethylene film, the lifetime of o-Ps was observed to decrease with increasing positron implantation depth, and a significant change in the o-Ps lifetime was found at a short distance (about 10 nm) from the surface, while its intensity increased. This result implies that near the polymer surface the free volume holes become larger that in the bulk. The effect of temperature on the polymer sub-surface layers was also studied. For high molecular weight polystyrene, the glass transition temperature for the sub-surface was lower than that for the bulk and thermal expansion coefficient of the sub-surface layers was found to be larger than the bulk value.

The free volume of octaphenyl polyhedral oligomeric silsesquioxane (OPS) modified polyurethane prepared from different dispersion method was investigated using Positron annihilation lifetime spectroscopy (PALS). The relationships of free volume and mechanical property were analyzed. Our results showed that OPS decreased the original free volume hole size and fraction, but varied with the dispersion method. For the sonication dispersion samples, the tensile was conform to the free volume fraction, while the elongation at break was against the free volume hole size. In the high shear dispersion process, the tensile increased and no apparent change was seen on the elongation at break.

The PULSTAR is a 1-MWth nuclear research reactor located at North Carolina State University. It is fueled by uranium dioxide assemblies enriched to 4% or 6% in U-235 and is currently under licensing for operation at 2-MWth power. The PULSTAR is a center for irradiation testing and pre/post irradiation examination of materials. Among its unique capabilities are positron annihilation spectroscopy (PAS) and neutron powder diffraction (NPD) facilities. The PAS facility provides an intense positron beam reaching 6 × 108 e+/s, which drives two spectrometers; the e+-PAS and the Ps-PAS, used for studies of defects in thin film materials. A Na-22 bulk PAS system is also operational, which is used for studying millimeter scale materials. All spectrometers are capable of performing Doppler Broadening Spectroscopy (DBS) and Positron Annihilation Lifetime Spectroscopy (PALS). To date, the PAS systems have been used to characterize various materials (unirradiated and irradiated) that include graphite, soft matter, and metal-organic frameworks (MOF). The NPD facility uses a double focusing single crystal silicon rotating monochromator producing neutron beams with different energies. A position sensitive detection bank covers a scattering angle of 5°-125°. The facility is used in the examination of unirradiated and irradiated materials including graphitic materials, magnetic materials without rare-earth elements, and anode materials used in lithium batteries. The collected diffraction patterns can be processed to produce atomic pair distribution functions. The PAS and NPD facilities are available through user programs including the US DOE’s Nuclear Science User Facilities (NSUF) and the US NSF’s Research Triangle Nanotechnology Network (RTNN).

Positron annihilation lifetime spectroscopy (PALS) was used to investigate the phase transitions, mainly the glass transition, of poly(ethylene terephthalate) (PET) and nylon-6 during the thermal treatment of these polymers. The longest-lived component lifetime and intensity, indicative of ortho-positronium pick-off, exhibit thermal dependencies that can be attributed to the free-volume changes associated with structural transitions. Glass transition temperatures and the volume of intermolecular-space holes among polymer chains were obtained from the lifetime, τ3 and intensity of formation, I3, of the long-lived component of ortho-positronium. For PET, the free-volume fraction and thermal expansion coefficients related to the free-volume fraction were also obtained. Double glass transition behavior was noted in the analyzed polymers, which was consistent with their semicrystalline nature as revealed by differential scanning calorimetry. Increases in the slope of the lifetime-temperature plots for nylon-6 and PET were interpreted to suggest that glass transitions are followed by an increased free-volume cavity expansion as temperature is increased. The intensity response for PET was consistent with the association of glass transition with the reduction of crystalline consraint on segmental mobility in the amorphous phase. In contrast, the intensity behavior during the thermal treatment of nylon-6 seems to be governed more by the electronic effects occurring when the polymer chains acquire mobility than by free-volume changes. Since the sensitivity of PALS is in the order of nanometers, it is expected to give an alternative novel technique to estimate phase transitions and relaxations in polymers from the point of view of the free volume. © 1996 John Wiley & Sons, Inc.

Effects of montmorillonite (MMT) content on the free volume hole and miscibility were first investigated for polyurethane/epoxy resin (PU/EP) interpenetrating polymer network (IPN) nanocomposites by positron annihilation lifetime spectroscopy (PALS), X‐ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). An exfoliated (IPN/MMT1), a coexistence of exfoliated and intercalated (IPN/MMT3), and an intercalated (IPN/MMT5) structures were confirmed by XRD. Influences of two kinds of hydrogen bonding interactions including both between carbonyl group and N‐H group, and the other between urethane group and silicate layers have been discussed. PALS results reveal that the size of the free volume holes decreases after the MMT loaded due to the increase of chain packing efficiency. The large difference between IPN/MMT1 and IPN/MMT5 in the free volume distribution was observed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Silicone rubber is widely used as an insulating material. In this article, silicone rubber samples were prepared by varying the content of crosslinker (2,5-bis(tert-butyl-peroxy)-2,5-dimethylhexane, DBPMH), and the free volume holes in the samples were investigated by means of positron annihilation lifetime spectroscopy (PALS) measurement. The surface chemical structure, surface micromorphology and water diffusion of the samples after corona discharge treatment were studied by FTIR, SEM and EIS measurements, respectively. As the crosslinker weight ratio increased from 0.2 wt.% to 1.5 wt.%, the mean free volume hole size first decreased and then remained unchanged. However, the concentration of free volume holes did not vary as the crosslinker weight ratio increased. SEM morphologies show that surface cracks were produced on samples having high crosslinking levels after corona treatment. The water diffusion coefficient of samples after corona treatment increased from 3.13 × 10−10 cm2 s−1 to 17.68 × 10−10 cm2 s−1 in the initial immersion period, as the crosslinker weight ratio increased from 0.2 wt.% to 3.0 wt.%. The results indicated that deterioration of samples with high crosslinking levels were more serious and water repellency more easily lost. The corona resistance ability of low crosslinking level silicone rubber stems from internal low molecular weight molecules.

Positron/positronium annihilation as a probe for chemical environments of free volume holes in fluoropolymers

Positron annihilation spectroscopy characterization results for neutron-irradiated $3C$-SiC are described here, with a specific focus on explaining the size and character of vacancy clusters as a complement to the current understanding of the neutron irradiation response of $3C$-SiC. Positron annihilation lifetime spectroscopy was used to capture the irradiation temperature and dose dependence of vacancy defects in $3C$-SiC following neutron irradiation from 0.01 to 31 dpa in the temperature range from $380{\phantom{\rule{0.16em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$ to $790{\phantom{\rule{0.16em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$. The neutral and negatively charged vacancy clusters were identified and quantified. The results suggest that the vacancy defects that were measured by positron annihilation spectroscopy technique contribute very little to the transient swelling of SiC. In addition, coincidence Doppler broadening measurement was used to investigate the chemical identity surrounding the positron trapping sites. It was found that silicon vacancy-related defects dominate in the studied materials and the production of the antisite defect ${\mathrm{C}}_{\mathrm{Si}}$ may result in an increase in the probability of positron annihilation with silicon core electrons.

La espectroscopía de aniquilación de positrones (PAS) ha demostrado ser una poderosa herramienta para el estudio de defectos en sólidos ya que posee características únicas debido a su alta sensibilidad a la presencia de defectos tales como vacancias, aglomerados de vacancias o nanohuecos. Asimismo, PAS posibilita la identificación y caracterización de cada uno de estos defectos. Existen diferentes variantes experimentales de PAS tales como la espectrometría temporal positrónica, que permite identificar y cuantificar los distintos tipos de defectos, y el ensanchamiento Doppler que brinda información no solo sobre los defectos sino, también, sobre las especies atómicas que decoran los sitios de atrapamiento de los positrones. Estas técnicas, acopladas a un haz de positrones lentos permiten estudiar, además, defectos sub-superficiales en materiales con espesores inferiores al micrómetro, films y coatings. En este trabajo, se presentan dos ejemplos que ponen de manifiesto la potencialidad de PAS para el estudio de defectos sub-superficiales en: i) vidrios de sílice implantados con iones de oro y ii) oro rugosado.

Different definitions of the free volumes are discussed and related to the total specific volume and to the local free (hole) volume. Positron lifetime measurements are reported for polyethylene, polytetrafluoroethylene, and CR39-copolymers. Two long-lived components appear in polyethylene and polytetrafluoroethylene, which were attributed to o-Ps annihilations in crystalline regions and in holes of the amorphous phase. From a relation between the coefficients of the thermal expansion of macroscopic and hole volume, the fractional hole volume h and from this the number of holes, N, is estimated. Values of Tg = 195 K, hg = 4.5% (polyethylene) and 5.7% (polytetrafluoroethylene) and Ng = 0.73 nm -3 (polyethylene) and 0.36 nm -3 (polytetrafluoroethylene) were obtained. In semicrystalline polymers these values agree with estimates obtained from the densities of the crystalline and amorphous phases. The effect of cross-linking on the free-volume properties of CR39-copolymer networks was studied. The comparison of the hole volume with the specific volume allowed us to estimate the number density of holes to = 1 nm -3 . PACS numbers: 61.41.+e, 65.70.+y, 78.70.—g