A Combined Atomic and Molecular Probe Characterization of Aromatic Hydrocarbons via PALS and ESR: Methylbenzene

A combined study of one of the simplest aromatic hydrocarbons, i.e., methylbenzene (toluene) (TOL), via the annihilation of an ortho-positronium (o-Ps) probe via positron annihilation lifetime spectroscopy (PALS) and the rotation dynamics of nitroxide spin probe 2,2,6,6-tetramethyl-piperidinyl-1-oxy (TEMPO) using electron spin resonance (ESR) over a wide temperature range, 10–300 K, is reported. The o-Ps lifetime, τ3, and the relative o-Ps intensity, I3, as a function of temperature exhibit changes defining several characteristic PALS temperatures in the slowly and rapidly cooled samples. Similarly, the spectral parameter of TEMPO mobility in TOL, 2Azz‘, and its correlation time, τc, reveal several effects at a set of the characteristic ESR temperatures, which were determined and compared with the PALS results. Finally, the physical origins of the changes in free volume expansion and spin probe mobility are revealed. They are reflected in a series of the mutual coincidences between the characteristic PALS and ESR temperatures and appropriate complementary thermodynamic and dynamic techniques.

Features of the Gas-Permeable Crystalline Phase of Poly-2,6-Dimethylphenylene Oxide

Poly-2,6-dimethylphenylene oxide (PPO) film samples with varying degrees of crystallinity (from 0 to 69%) were obtained by means of different techniques. The films were studied by various physicochemical methods (Fourier-transform infrared spectroscopy, positron annihilation lifetime spectroscopy, X-ray diffraction, and 1H nuclear magnetic resonance relaxation). Solubility coefficients of gases in the PPO samples were measured via sorption isotherms of gases by volumetric technique with chromatographic detection. The apparent activation energy of permeation and the activation energy of diffusion of all gases were estimated based on temperature dependences of gas permeability and diffusivity for amorphous and semi-crystalline PPO in the range of 20–50 °C. The peculiarities of free volume, density, and thermal properties of gas transport confirm the nanoporosity of the gas-permeable crystalline phase of PPO. So, the PPO can be included in the group of organic molecular sieves.

Water intake of cellulose materials monitored by positron annihilation lifetime spectroscopy

In this study, for the first time, the experimental technique of positron annihilation lifetime spectroscopy (PALS) has been applied to monitor in situ the microstructural changes of cellulose-based materials, i.e. paper, during water intake. For three different cellulose samples, bleached fine paper without filler, Kraft paper without filler, and a viscose fiber sheet, the mean positron lifetime $$\Delta \tau _{\mathrm {mean}}$$ Δ τ mean showed a strong increase with time in humid atmosphere, but exhibiting different trends depending on the type of sample. For all the cellulose samples investigated, the mean positron lifetime $$\Delta \tau _{\mathrm {mean}}$$ Δ τ mean shows an initial strong increase simultaneously occurring (t<10 h) to the mass increase of the samples due to water intake. Interestingly, the variations of $$\Delta \tau _{\mathrm {mean}}$$ Δ τ mean of the viscose fiber sheet and the Kraft paper sample both show a second increase on longer timescales (t>60 h in humid atmosphere) during which the mass increase of these samples has already been saturated. The results of this study show that by the means of PALS, water transport in paper can be reliably followed over a long timespan and it is even possible to distinguish between different types of cellulose materials. The second stage increase of the mean positron lifetime after long times in humid atmosphere for the Kraft paper sample and the pure viscose sheets even suggest that not only water intake itself can be monitored but also further atomistic processes in the material are accessible.

Positron Annihilation Lifetime Spectroscopy Insight on Free Volume Conversion of Nanostructured MgAl2O4 Ceramics

Herein we demonstrate the specifics of using the positron annihilation lifetime spectroscopy (PALS) method for the study of free volume changes in functional ceramic materials. Choosing technological modification of nanostructured MgAl2O4 spinel as an example, we show that for ceramics with well-developed porosity positron annihilation is revealed through two channels: positron trapping channel and ortho-positronium decay. Positron trapping in free-volume defects is described by the second component of spectra and ortho-positronium decay process by single or multiple components, depending on how well porosity is developed and on the experimental configuration. When using proposed positron annihilation lifetime spectroscopy approaches, three components are the most suitable fit in the case of MgAl2O4 ceramics. In the analysis of the second component, it is shown that technological modification (increasing sintering temperature) leads to volume shrinking and decreases the number of defect-related voids. This process is also accompanied by the decrease of the size of nanopores (described by the third component), while the overall number of nanopores is not affected. The approach to the analysis of positron annihilation lifetime spectra presented here can be applied to a wide range of functional nanomaterials with pronounced porosity.

Evolution of Free Volumes in Polycrystalline BaGa2O4 Ceramics Doped with Eu3+ Ions

BaGa2O4 ceramics doped with Eu3+ ions (1, 3 and 4 mol.%) were obtained by solid-phase sintering. The phase composition and microstructural features of ceramics were investigated using X-ray diffraction and scanning electron microscopy in comparison with energy-dispersive methods. Here, it is shown that undoped and Eu3+-doped BaGa2O4 ceramics are characterized by a developed structure of grains, grain boundaries and pores. Additional phases are mainly localized near grain boundaries creating additional defects. The evolution of defect-related extended free volumes in BaGa2O4 ceramics due to the increase in the content of Eu3+ ions was studied using the positron annihilation lifetime spectroscopy technique. It is established that the increase in the number of Eu3+ ions in the basic BaGa2O4 matrix leads to the agglomeration of free-volume defects with their subsequent fragmentation. The presence of Eu3+ ions results in the expansion of nanosized pores and an increase in their number with their future fragmentation.

Semi-insulating GaAs detectors degraded by 8 MeV electrons up to 1500 kGy

Radiation degradation of semi-insulating GaAs detectors by 8 MeV electrons up to doses of 1500 kGy is studied in this paper. The influence of irradiation on GaAs material parameters and on spectrometric and electrical properties of fabricated detectors is evaluated. The detector material was degraded before contact preparation, which ensured separation of radiation degradation solely to the bulk material, excluding the contact degradation. The positron annihilation lifetime spectroscopy (PALS) was involved to characterize the substrate material together with galvanometric measurements. Radiation-induced mono-vacancies were clearly identified by PALS in the irradiated materials with increasing concentration up to 2.8 × 1016 cm−3 at maximal applied dose. In correlation with defect concentration the electron Hall mobility decreased with dose down to 3270 cm2 V−1 s−1 and resistivity increased up to 5.22 × 108 Ω cm at 1500 kGy. The bulk material properties influenced the parameters of fabricated detectors. The detectors lost their current blocking behaviour at 1000 kGy according to current-voltage measurements. The charge collection efficiency during alpha-particle and gamma ray measurements almost exponentially decreased with applied dose from initial 40% down to 5% at 1500 kGy in the case of alpha spectrometry and from 48% to 12% at 500 kGy for gamma spectrometry.

Defect engineering on V2O3 cathode for long-cycling aqueous zinc metal batteries

Defect engineering is a strategy that is attracting widespread attention for the possibility of modifying battery active materials in order to improve the cycling stability of the electrodes. However, accurate investigation and quantification of the effect of the defects on the electrochemical energy storage performance of the cell are not trivial tasks. Herein, we report the quantification of vanadium-defective clusters (i.e., up to 5.7%) in the V2O3 lattice via neutron and X-ray powder diffraction measurements, positron annihilation lifetime spectroscopy, and synchrotron-based X-ray analysis. When the vanadium-defective V2O3 is employed as cathode active material in an aqueous Zn coin cell configuration, capacity retention of about 81% after 30,000 cycles at 5 A g−1 is achieved. Density functional theory calculations indicate that the vanadium-defective clusters can provide favorable sites for reversible Zn-ion storage. Moreover, the vanadium-defective clusters allow the storage of Zn ions in V2O3, which reduces the electrostatic interaction between the host material and the multivalent ions.

Relationship between the Microstructure and Performance of Graphene/Polyethylene Composites Investigated by Positron Annihilation Lifetime Spectroscopy

The quantitative characterization of microstructure is most desirable for the establishment of structure-property relationships in polymer nanocomposites. In this work, the effects of graphene on the microstructure, mechanical, electrical, and thermal properties of the obtained graphene/polyethylene (PE) composites were investigated. In order to reveal the structure-performance relationship of graphene/PE composites, especially for the effects of the relative free volume fraction (fr) and interfacial interaction intensity (β), positron annihilation lifetime spectroscopy (PALS) was employed for its quantitative description. The relative free volume fraction fr gives a good explanation of the variation for surface resistivity, melting temperature, and thermal stability, and the variation of tensile strength and thermal conductivity agree well with the results of interfacial interaction intensity β. The results showed that fr and β have a significant effect on the properties of the obtained graphene/PE composites, and the effect on the properties was revealed.

Physical Testing and Surface Morphology Studies of Stainless Steel Irradiated with Xe Ions

6 MeV Xe ions were used to irradiate austenitic stainless steel at room temperature. Three displacement damage levels of 2,7 and 15 dpa were selected. Microstructure and surface morphology were characterized by transmission electron microscopy (TEM), positron annihilation lifetime spectroscopy (PLS) and atomic force microscope (AFM). PLS indicated that vacancy defects were introduced by ions irradiation. Vacancy clusters containing Xe will reduce the positron annihilation lifetime. High density of dislocation loops were observed by TEM. The dislocation loops size and density saturates after 7 dpa and the nature of dislocation loops can be deduced by its distribution. A surface step was detected by AFM measurements between irradiated region (uncovered) and unirradiated region (covered with nickel mesh). This indicate that the irradiation swelling phenomenon occur and swelling is closely related to irradiation damage. According to the step height, the volume swelling is about 1.7% and 4.2% after irradiated to 7 and 15 dpa.