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Graphene oxide (GO) with different oxidation degrees is prepared by a modified Hummers’ method varying KMnO4 amount from 0.5 to 6.0 g. X‐ray powder diffraction (XRPD), micro–Raman, thermogravimetric analysis, X‐ray photoeelectron spectroscopy, Boehm titrations, high–resolution transmission electron microscopy, and, finally, positron annihilation lifetime spectroscopy (PALS) are exploited to assess the properties of GO. Results show that increasing oxidant species can tune the interlayer gap between GO sheets up to a maximum value in the case of 4.0 g KMnO4 content. Moreover, these results validate the two‐component‐based model of GO in which, at low oxidation degree, there are unsplit/isolated graphene planes, instead at higher oxidant amounts, a five‐layer sandwiched configuration occurs comprising graphene planes having functional groups decorating the edges (bwGO), hydrated oxidative debris (OD) and “empty” spaces (revealed by PALS as the distance between (bwGO + OD) two‐component layers). In addition, by XRPD analysis, the total gap between two sheets is easily computed. In order to correlate these findings to pollutant removal capability, planar o‐toluidine adsorption is studied. Since this molecule diffuses in an aqueous environment, the obtained adsorption percentages are compared to the thickness of the hydrated OD grafted onto bwGO. A strict connection between the pollutant removal efficacy and the variation of the hydrated interlayer distance is found. Graphene oxide (GO) structures with different interlayer gaps, obtained by varying oxidant amounts, are synthesized for o‐toluidine adsorption. At low oxidation degrees GO is composed of unsplit and isolated graphene planes, whereas at higher KMnO4 content a five‐layer sandwiched configuration is appreciable.

The electron density at the positron (contact density) in the ground state positronium (Ps) formed in condensed matter is generally found to be lower than in vacuum. This is usually attributed to microscopic electric fields which polarize Ps, by acting on the two particles of the atom. In this paper we quantitatively investigate an opposite effect. It is due to the confinement of Ps in small cavities existing in the host solid (e.g. free volume in polymers), which increases the contact density. Although this phenomenon is greater, the smaller is the size of the cavity, Ps polarization seems to play anyway a predominant role.

Positronium atoms (Ps) are commonly employed as a probe to characterize nanometric or subnanometric voids or vacancies in nonmetallic materials, where Ps can end up confined. The annihilation lifetime of a trapped Ps is strongly modified by pickoff and depends on the cavity size and on the electron density in the confining cavity surface. Here, we develop a theory of the Ps annihilation in nanocavities based on the fundamental role of the exchange correlations between the Ps-electron and the outer electrons, which are not usually considered but must be considered to correctly theorize the pickoff annihilation processes. We obtain an important relation connecting the two relevant annihilation rates (for the p-Ps and the o-Ps) with the electron density, which has the property of being totally independent of the geometrical characteristics of the nanoporous medium. This general relation can be used to gather information on the electron density and on the average cavity radius of the confining medium, starting from the experimental data on PALS annihilation spectra. Moreover, by analyzing our results, we also highlight that a reliable interpretation of the PALS spectra can only be obtained if the rule of 1/3 between the intensities of p-Ps and o-Ps lifetimes can be fulfilled.

Positronium (Ps) is a valuable probe to investigate nanometric or sub-nanometric cavities in non-metallic materials, where Ps can be confined. Accessible experimental measurements concern the lifetime of trapped Ps, which is largely influenced by pick-off processes, depending on the size of the cavity as well as on the density of the electrons belonging to the surface of the host trap. Another relevant physical quantity is the contact density, that is the electron density at the positron position, which is usually found to be well below the vacuum value. Here, we review the principal models that have been formulated to account and explain for these physical properties of confined Ps. Starting with models, treating Ps as a single particle formulated essentially to study pick-off, we go on to describe more refined two-particle models because a two-body model is the simplest approach able to describe any change in the contact density, observed in many materials. Finally, we consider a theory of Ps annihilation in nanometric voids in which the exchange correlations between the electron of Ps and the outer electrons play a fundamental role. This theory is not usually taken into account in the literature, but it has to be considered for a correct theory of pick-off annihilation processes.

Positron annihilation lifetime spectroscopy (PALS) is a valuable technique to investigate defects in solids, such as vacancy clusters and grain boundaries in metals and alloys, as well as lattice imperfections in semiconductors. Positron spectroscopy is able to reveal the size, structure and concentration of vacancies with a sensitivity of 10−7. In the field of porous and amorphous systems, PALS can probe cavities in the range from a few tenths up to several tens of nm. In the case of polymers, PALS is one of the few techniques able to give information on the holes forming the free volume. This quantity, which cannot be measured with macroscopic techniques, is correlated to important mechanical, thermal, and transport properties of polymers. It can be deduced theoretically by applying suitable equations of state derived by cell models, and PALS supplies a quantitative measure of the free volume by probing the corresponding sub-nanometric holes. The system used is positronium (Ps), an unstable atom formed by a positron and an electron, whose lifetime can be related to the typical size of the holes. When analyzed in terms of continuous lifetimes, the positron annihilation spectrum allows one to gain insight into the distribution of the free volume holes, an almost unique feature of this technique. The present paper is an overview of PALS, addressed in particular to readers not familiar with this technique, with emphasis on the experimental aspects. After a general introduction on free volume, positronium, and the experimental apparatus needed to acquire the corresponding lifetime, some of the recent results obtained by various groups will be shown, highlighting the connections between the free volume as probed by PALS and structural properties of the investigated materials.

Graphene oxide (GO) is conveniently prepared from expandable graphite using a simplified Hummers’ method. The product is thoroughly characterized by usual techniques (UV-vis, Fourier-transform infrared (FTIR) and Raman spectroscopies, zeta potential, electron microscopy, X-ray diffraction, nitrogen adsorption) to confirm the success of synthesis. Positron annihilation lifetime spectroscopy (PALS) is then used to extract information on the microenvironment in between the layers of graphene oxide.

Meeting the increasing demand of clean water requires the development of novel efficient adsorbent materials for the removal of organic pollutants. In this context the use of natural, renewable sources is of special relevance and sepia melanin, thanks to its ability to bind a variety of organic and inorganic species, has already attracted interest for water purification. Here we describe the synthesis of a material obtained by the combination of sepia melanin and poly(ethylene-alt-maleic anhydride) (P(E-alt-MA)). Compared to sepia melanin, the resulting hybrid displays a high and fast adsorption efficiency towards methylene blue (a common industrial dye) for a wide pH range (from pH 2 to 12) and under high ionic strength conditions. It is easily recovered after use and can be reused up to three times. Given the wide availability of sepia melanin and P(E-alt-MA), the synthesis of our hybrid is simple and affordable, making it suitable for industrial water purification purposes.

The sensitivity of positron annihilation characteristics to changes in the molecular packing in network-forming polymers has been demonstrated since the early 1980s. Positron annihilation lifetime spectroscopy (PALS) is a unique technique that can provide direct information on the free volume in polymers through the experimental parameters of the free volume hole distribution, their mean value, and volume fraction. This knowledge is currently applied for PALS investigations on the main processes that govern the molecular organization in some green polymers when subjected to different synthesis procedures or environmental conditions (humidity, physical aging, temperature). In this article, which includes a wide repertoire of works published in the last two decades, results of PALS studies on eco-sustainable polymer systems based on starch, chitosan, or vegetable oils, are analyzed and discussed. Many examples are taken from the direct experience of the authors.

Polymer blends are a versatile playground for studying phase separation and its effect on the development of morphology and mechanical properties of the resulting materials. Blends obtained from two immiscible polymers, ethyl cellulose (EC) and poly(vinyl pyrrolidone) (PVP), are especially relevant for their practical applications as coatings for pharmaceutical preparations and controlled drug release. Here, films of EC–PVP blends are studied by means of thermal analysis, dynamic-mechanical analysis as well as positron annihilation lifetime spectroscopy. The morphology of the microstructures generated by phase separation is investigated by means of scanning electron microscopy. The effect of both components’ ratio and of molecular mass of PVP on the final properties of the blends is determined in a systematical way. The results obtained are not only of theoretical interest but will prove useful for the optimization of industrial formulations based on these polymers. Graphical abstract

The free volume fraction of a macromolecular structure can be assessed theoretically by using a suitable model; however, it can also be evaluated from experimental data obtained from dilatometry and positron annihilation lifetime spectra. In this second case, a regular geometry of the sub-nanometric cavities forming the free volume has to be assumed, although in fact they are irregularly shaped. The most popular approach is to guess spherical holes, which implies an isotropic growth of these last with temperature. In this work, we compared the free volume fraction, as obtained from experiments in a set of polybutadiene and polyisoprene cured rubbers and their blends, with the analogous quantity expected by using the lattice-hole model. The results allowed us to obtain insights on the approximate shape of the holes. Indeed, a cylindrical flattened geometry of the cavities produced a better agreement with the theory than the spherical shape. Furthermore, the best fit was obtained for holes that expanded preferentially in the radial direction, with a consequent decrease of the aspect ratio with temperature.