Photocrosslinking of poly(N-vinylcarbazole): Implementing a complementary set of techniques to characterize the three-dimensional network formation

The crosslinking of poly(N-vinylcarbazole) PVK resulting from UV irradiation (λ > 300 nm) was studied by combining various techniques including infrared spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), swelling ratio, positron annihilation spectroscopy (PAS) and thermoporosimetry. The results obtained from all of these techniques were correlated and allowed a complete monitoring of the crosslinking during irradiation, from the creation of the first crosslinks to the formation and densification of the three-dimensional network. From SEC analysis and determination of swelling ratios, it was demonstrated that crosslinking was the predominant mechanism during the first stages of irradiation. PAS and DSC analyses revealed a good correlation between variations of free volume and increase of glass transition (T_g) of the bulk material. In addition, the development of the polymer architecture shown by the growth of T_g was nicely correlated with the modifications of the chemical structure observed by infrared analysis. Thermoporosimetry allowed the determination of the mesh size distributions within the polymer for the longest irradiation times. Numerical relationships were established and their validity was checked.     

Diffusivity enhancement of water vapor in poly(vinyl alcohol)–fumed silica nano-composite membranes: Correlation with polymer crystallinity and free-volume properties

The diffusion coefficients of water vapor in poly(vinyl alcohol)–fumed silica (PVA–FS) nano-composite membranes were determined using the gravimetric method. Water vapor was observed to diffuse more rapidly in membranes with increased FS content. The vapor diffusion coefficient was determined as 1.2 × 10⁻¹³ m²/s in pure PVA and was observed to increase to 3.0 × 10⁻¹³ m²/s in PVA composites containing 30% FS nano-particles. The free-volumes of PVA–FS membranes were characterized using positron annihilation lifetime (PAL) spectroscopy. PAL results showed that both the ortho-positronium (o-Ps) lifetime and intensity increased with the addition of FS. The intensity (I₃) was found to be higher than the estimated value determined from the linear combination of the data from pristine PVA and FS, and correlated excellently with the polymer amorphous content. The PAL results indicate that a higher FS content in PVA increases the free-volume hole size (a volume increase from 40 to 55 Å³) and free-volume hole density (an I₃ increase from 23 to 28%), resulting in a higher fractional free-volume in the nano-composites. The increase in the relative polymer free-volume with higher FS content was associated with a decrease in the PVA crystallinity, as determined from differential scanning calorimetry measurements. It is postulated that the incorporated FS nano-particles interrupt polymeric chain packing and retard crystallization during membrane formation. More crystalline segments were transformed into amorphous regimes in the nano-composites containing more FS. A correlation between water diffusivity and the fractional free-volume was obtained, and the water diffusivity was successfully expressed by the free-volume theory.     

Synthesis and characterization of magnesium oxide nanocrystallites and probing the vacancy-type defects through positron annihilation studies

Magnesium oxide nanocrystallites exhibit certain abnormal characteristics when compared to those of other wide band gap oxide semiconductors in the sense they are most prone to water absorption and formation of a hydroxide layer on the surface. The problem can be rectified by heating and pure nanocrystallites can be synthesized with controllable sizes. Inevitably the defect properties are distinctly divided between two stages, the one with the hydroxide layer (region I) and the other after the removal of the layer by annealing (region II). The lattice parameters, the optical band gap and even the positron annihilation characteristics are conspicuous by their distinct behavior in the two stages of the surface configurations of nanoparticles. While region I was specific with the formation of positronium-hydrogen complexes that drastically altered the defect-specific positron lifetimes, pick-off annihilation of orthopositronium atoms marked region II. The vacancy clusters within the nanocrystallites also trapped positrons. They agglomerated due to the effect of the higher temperatures and resulted in the growth of the nanocrystallites. The coincidence Doppler broadening spectroscopic measurements supported these findings and all the more indicated the trapping of positrons additionally into the neutral divacancies and negatively charged trivacancies. This is apart from the Mg²⁺ monovacancies which acted as the dominant trapping centers for positrons.     

Positron trapping defects in free-volume investigation of Ge–Ga–S–CsCl glasses

Evolution of free-volume positron trapping defects caused by crystallization process in (80GeS₂–20Ga₂S₃)_100−х(СsCl)_x, 0 ≤ x ≤ 15 chalcogenide-chalcohalide glasses was studied by positron annihilation lifetime technique. It is established that CsCl additives in Ge–Ga–S glassy matrix transform defect-related component spectra, indicating that the agglomeration of free-volume voids occurs in initial and crystallized (80GeS₂–20Ga₂S₃)_100−х(СsCl)_x, 0 ≤ x ≤ 10 glasses. Void fragmentation in (80GeS₂–20Ga₂S₃)₈₅(СsCl)₁₅ glass can be associated with loosing of their inner structure. Full crystallization in each of these glasses corresponds to the formation of defect-related voids. These trends are confirmed by positron-positronium decomposition algorithm. It is shown, that CsCl additives result in white shift in the visible regions in transmission spectra. The γ-irradiation of 80GeS₂–20Ga₂S₃ base glass leads to slight long-wavelength shift of the fundamental optical absorption edge and decreasing of transmission speaks in favor of possible formation of additional defects in glasses and their darkening.     

Ion implantation of sulphur into GaAs,GaP and ge monocrystals

The possibility of using ion implantation to form high concentration junctions in semiconductors has been explored for the specific case of sulphur in GaAs, GaP and Ge. The effects of ion dose, ion energy, crystal orientation and target temperature have been investigated by means of radiotracers and sectioning techniques.

It is shown that high concentration junctions can be formed using an incident ion having high electronic stopping cross-section and implanted along the <110< channeling directions of the crystals. A large increase in junction concentration may be obtained when the GaAs and GaP crystals are maintained at 150 °C during the implantation process, but this is not the case with Ge. Rutherford back-scattering of 1 MeV He⁺ ions has been used to measure the ion-bombardment induced damage in the crystals and to show how this damage can be annealed by heating the crystal during the implantation. The annealing, at temperatures up to 150 °C, is most effective in GaAs and least effective in Ge.     

Investigation of microstructure thermal evolution in nanocrystalline Cu

The microstructure of nanocrystalline Cu prepared by compacting nanoparticles (50-60 nm in diameter) under high pressures has been studied by means of positron lifetime spectroscopy and X-ray diffraction. These nanoparticles were produced by two different methods. We found that there are order regions interior to the grains and disorder regions at the grain boundaries with a wide distribution of interatomic distances. The mean grain sizes of the nanocrystalline Cu samples decrease after being annealed at 900 °C and increase during aging at 180 °C, which are observed by X-ray diffraction, revealing that the atoms exchange between the two regions. The positron lifetime results clearly indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder grain growth when the samples age at 180 °C, and the vacancy clusters inside the disorder regions, which are related to Cu₂O, need longer aging time to decompose. The disorder regions remain after the heat treatment in this work, in spite of the grain growth, which will be good for the samples keeping the properties of nanocrystalline material.     

Structural changes of poly(ethylene isophthalate) subjected to gamma irradiation

The results of studies of the physico-chemical changes of a polyester, poly(ethylene isophthalate), subjected to gamma irradiation up to 1 MGy, are reported. Viscometric measurements were carried out to monitor variations of the molecular weight. Changes in the amorphous fraction of the polymer were observed by means of differential scanning calorimetry. Positron annihilation lifetime spectroscopy was used to show possible modifications of the free volume as a consequence of irradiation. The results allow us to conclude that the polymer shows a good resistance to radiation damage.     

The exact solution of the diffusion trapping model of defect profiling with variable energy positrons

We report an exact analytical solution of so-called positron diffusion trapping model. This model have been widely used for the treatment of the experimental data for defect profiling of the adjoin surface layer using the variable energy positron (VEP) beam technique. However, up to now this model could be treated only numerically with so-called VEPFIT program. The explicit form of the solutions is obtained for the realistic cases when defect profile is described by a discreet step-like function and continuous exponential-like function. Our solutions allow to derive the analytical expressions for typical positron annihilation characteristics including the positron lifetime spectrum. Latter quantity could be measured using the pulsed, slow positron beam. Our analytical results are in good coincidence with both the VEPFIT numerics and experimental data. The presented solutions are easily generalizable for defect profiles of other shapes and can be well used for much more precise treatment of above experimental data.     

Sexual dimorphism in the human brain: evidence from neuroimaging

In recent years, more and more emphasis has been placed on the investigation of sex differences in the human brain. Noninvasive neuroimaging techniques represent an essential tool in the effort to better understand the effects of sex on both brain structure and function. In this review, we provide a comprehensive summary of the findings that were collected in human neuroimaging studies in vivo thus far: we explore sexual dimorphism in the human brain at the level of (1) brain structure, in both gray and white matter, observed by voxel-based morphometry (VBM) and diffusion tensor imaging (DTI), respectively; (2) baseline neural activity, studied using resting-state functional magnetic resonance imaging (rs-fMRI) and positron emission tomography (PET); (3) neurochemistry, visualized by means of neuroreceptor ligand PET; and (4) task-related neural activation, investigated using fMRI. Functional MRI findings from the literature are complemented by our own meta-analysis of fMRI studies on sex-specific differences in human emotional processing. Specifically, we used activation likelihood estimation (ALE) to provide a quantitative approach to mapping the consistency of neural networks involved in emotional processing across studies. The presented evidence for sex-specific differences in neural structure and function highlights the importance of modeling sex as a contributing factor in the analysis of brain-related data.     

Temperature dependence of free volume in atactic polypropylene

Positron annihilation lifetime spectroscopy data are often used to get information on the typical sizes of sub nanometric holes forming the free volume in polymers. To this purpose, the cavities are modelled as spheres or, more generally, using geometries which assume an isotropic expansion with the temperature. However, this guess could be unrealistic owing to the irregular shape of holes and the constrained movements of the macromolecules.In this work positron and dilatometric data are used to estimate the free volume fraction in atactic polypropylene. Comparison with the prediction of the Simha–Somcynsky theory supplies information on the thermal dependence of the volume of holes, whose behaviour can be interpreted in terms of anisotropic expansion.