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The paper reports and comments the results of several electron spin resonance investigations, performed on semiconductor oxides for gas sensing. The main aspects, related to the comparison between spectroscopic and electric data, are concerning on (i) the role of the oxide defects in interacting with the gas atmosphere; (ii) the origin of the sensing enhancement, which follows the doping of the oxide by transition metal ions; and (iii) the effects of different particle morphology and of the controlled particle shape on the sensing functionality. The electron spin resonance results have been associated, when possible, to those deriving from X-ray photoelectron spectroscopy, in order to investigate the electronic configuration of the transition metal centers. Special emphasis has been deserved to the oxide synthesis procedures, in several cases well related to the electrical response. The data have been drawn from several studies, performed in different time periods, and have been compared to suggest a possible common interpretation of the sensing mechanism, based on either electronic or morphological properties.

Photomineralization of methane in air (10.0-1,000 ppm (mass/volume) of C) at 100% relative humidity (dioxygen as oxygen donor), was systematically studied at 318 ± 3 K, in an annular laboratory-scale reactor, by photocatalytic membranes immobilising titanium dioxide and tungsten trioxide as co-photocatalysts. Kinetics of both substrate disappearance, to yield intermediates, and total organic carbon (TOC) disappearance, to yield carbon dioxide, were followed. A kinetic model was employed, from which, by a set of differential equations, four final optimised parameters, k1 and K1, k2 and K2, were calculated, able to fit the whole kinetic profile adequately. Modelling of quantum yields, as a function of substrate concentration and irradiance, as well as of concentration of photocatalysts, was carried out very satisfactorily. Kinetics of hydroxyl radicals reacting between themselves, leading to hydrogen peroxide, other than with substrate or intermediates leading to mineralization, were considered, paralleled by second competition kinetics involving superoxide radical anion. When using appropriate blends of the two photocatalysts, limiting quantum yields F∞ values increase considerably and approach the maximum allowable value for the investigated molecule, in a much wider range of irradiances than that shown by the single catalysts mainly at low irradiances. This may be interpreted by strong competition kinetics of superoxide radicals generated by the catalyst defects, in the corresponding range of high irradiances. By this way, operation at high irradiance values is possible, without losing any efficiency for the mineralization process.

ZnO nanoparticles (NPs) anchored on SiO2 (ZnO/SiO2) demonstrated to be an activator of higher efficiency in the sulfur crosslinking of isoprene rubber (IR) in comparison with conventional microcrystalline ZnO. The better performance of this innovative catalytic filler has been associated with: (i) the faster Zn reaction with stearic acid and curatives, to form the sulfurating complexes at the beginning of the curing process; (ii) the faster formation of large amounts of mono- and di- sulfide cross-linking short chains through a breaking-down mechanism of longer poly-sulfide chains, which account for the higher cross-linking density of the final cured material. In the first step of the curing reaction activated by ZnO/SiO2, the formation of a stearate bridged dimeric zinc complex has been suggested as potential highly reactive intermediate responsible for accelerating the cross-linking reaction

It is commonly accepted that the toxicity of carbonaceous particulate matter (PM) is due to the production of reactive oxygen species (ROS) which induce biological damage in the exposed cells. It is also known that PM produced during the combustion processes consists of a carbonaceous core "dressed" with other organic and/or inorganic materials. In spite of this knowledge, the role of these materials in the production of ROS has not yet been clear. This work aims at understanding whether "naked" carbonaceous particles are capable of forming ROS either in cell-free or in-cell systems. The problem has been treated based on the data collected from pure graphite samples of different sizes obtained by ball-milling pure graphite for various lengths of time. The experimental approach considered Raman, ESR (spin trapping), cell viability and fluorescence spectroscopy measurements. These techniques allowed us to carry out measurements both in cell and cell-free systems and the results consistently indicate that also pure naked carbonaceous particles can catalyze the electron transfer that produces superoxide ions. The process depends on the particle size and enlightens the role of the edges of the graphitic platelets. Evidence has been collected that even "naked" graphitic nanoparticles are capable of producing ROS and decreasing the cell viability thus representing a potential danger to human health.

The development of advanced polymer nanocomposites requires a strong filler-polymer interfacial interaction and an optimal filler nanodispersion. The incorporation of the clays into a polymer matrix frequently does not improve the composite mechanical properties, owing to both poor dispersion and macroscopic particle dimensions. In this work, pristine and organically-modified sepiolites (Sep) were structurally modified by an acid treatment, which provides nano-sized sepiolite (NS-Sep) fibers with reduced particle size and increased silanol groups on the surface layer. NS-Sep fibers were used to prepare styrene-butadiene rubber nanocomposites with enhanced mechanical properties. Dynamic-mechanical analysis of clay polymer nanocomposites demonstrated that the NS-Sep fibers provided an excellent balance between reinforcing and hysteretic behavior, compared to the large-sized pristine Sep and isotropic silica. This was related to the enhanced interfacial chemical interaction between NS-Sep and rubber, as well as to the size and self-assembly of anisotropic nanofibers to form filler network structures, as supported by transmission electron microscopy analysis. The preparation of nanocomposites, based on Sep nanofibers obtained by a simple and versatile acid treatment, can thus be considered an alternative approach for the designing of advanced clay polymer nanocomposites

The present invention regards a solid master elastomeric compn. (masterbatch, MB) comprising silicate fibers with needle-shaped morphol. of nanometric size, characterized by high fiber content and uniformity, a process advantageous for the prepn. thereof and its use in manufg. tyres for vehicles. Advantageously the present elastomeric compn. allows minimizing the drawbacks assocd. with the handling of the powdery fibers in the manufg. of compds. for tyres, without altering the final performances thereof

The mechanical properties of rubber can be highly increased thanks to the vulcanization process, leading to the formation of sulfur cross-linking between polymer chains. To improve the rate and efficiency of this process, several catalysts, including zinc oxide nanoparticles (ZnO NPs) are generally added to the matrix. However, the high hydrophilicity of ZnO hinders a fine distribution of ZnO that tends to agglomerate in the hydrophobic polymer, thus creating non-homogeneous islands of vulcanized rubber and requiring the addition of high zinc content to the matrix. Besides, an environmental issue has been recently connected to zinc release during the life cycle of rubber materials, especially in connection with tyres application. In this scenario, with the aim of reducing the amount of ZnO and improve the vulcanization efficiency, a new vulcanization catalyst has been developed [1], in which ZnO NPs are dispersed onto the surface of silica particles (ZnO/SiO2); as silica is a common reinforcing agent, the supported catalyst behaves as a “double function filler”. A laboratory scale synthetic procedure has been studied in detail, based on a sol-gel procedure, that allows the formation of amorphous ZnO NPs on silica surface and lead to an improved vulcanization efficiency, with half of the amount of zinc employed. Besides, the production of higher reinforced materials with reduced zinc content was achieved on a preindustrial scale (TRL5). Thus, ZnO/SiO2 has showed to be a good candidate to substitute the conventional catalyst in the vulcanization process. As a next step, the development of the large-scale production of the material is under examination, in order to get a low-cost production process, maintaining at the same time the initial catalytic properties and to allow its further commercialization.

The present study provides a comprehensive investigation at the micro and nanoscale of the interface between hybrid SiO2@POSS nanofiller, where silica nanoparticles (NPs) and POSS nanocages are intimately interconnected, and Styrene Butadiene Rubber (SBR). SEM and AFM inspection and, more in depth, solid state 1H NMR revealed a remarkable fraction of rigid rubber close to the SiO2@POSS surfaces, which increases with the curing temperature. Instead, a reduced amount of immobilized rubber was detected for SBR/SiO2+POSS nanocomposites, obtained by simply mixing SBR, SiO2 and POSS. The results allowed us to propose a model for the network formation in C-SBR/SiO2@POSS. This is based on the progressive activation by dicumylperoxide (DCP) of the methacryl functionalities of POSS nanounits which, being closely connected to SiO2 NPs in SiO2@POSS, promote crosslinking in proximity of the filler surfaces, and lead to the generation of a tight network strongly bonded to the rubber chains

Organic–inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs

Environmentally persistent free radicals (EPFRs) are toxic products deriving from incomplete combustion and are able to generate DNA damage and pulmonary dysfunction. They are formed on particulate matter through interaction with aromatic hydrocarbons, catalyzed by transition metal oxides, and produce reactive oxygen species (ROS) in aquatic media. The processes are already described for substituted aromatic molecules, for example, phenol, but not for unsubstituted aromatic systems, such as benzene. This Article reports on the reaction of benzene with molecular oxygen in the presence of CuxO/SiO2, suggesting a mechanism based on cluster and periodic computational models. The activation of O2 by interaction with silica coordinated Cu(I) centers leads to a peroxy species that yields the phenoxy radical upon reaction with benzene. Dissociation of OH• radical eventually allows for the recovery of the catalyst. The experimental characterization of the CuxO/SiO2 catalyst regarded morphology, crystal structure, copper electronic state, and crystal field around Cu(II). Electron paramagnetic resonance (EPR) spectroscopy revealed the formation of phenoxy radical entrapped in the catalyst upon reaction between benzene and CuxO/SiO2. Moreover, EPR investigation of ROS in aqueous solution evidenced the generation of OH• radicals by benzene-contacted CuxO/SiO2. All of the experimental results nicely fit the outcomes of the computational models.

A novel hybrid nanofiller, SiO2@POSS, where the silica nanoparticles (NPs) and the POSS belong to the same functional structure, has been synthesized by grafting different loadings of OctaMethacrylPOSS onto silanized commercial SiO2, using a surface reaction mediated by dicumylperoxide (DCP). The peroxide, besides anchoring the nanocages onto the silica surface, ensures the presence of methacryl functionalities in the final structure, which are still available for cross-linking reactions with a polymer host. The hybrid SiO2@POSS NPs were used to prepare, by ex situ blending, SBR nanocomposites. The dynamic-mechanical analysis performed on the cured SBR/SiO2@POSS composites indicated that the presence of POSS induces a remarkable increase of modulus either at low or at high strain, and a considerable decrease of hysteresis. This has been associated with the peculiar hybrid structure of the SiO2@POSS filler, in which silica NP aggregates are partially interconnected and surrounded by a thin shell of POSS nanounits which, thanks to their high number of reactive functionalities, promote the formation of "sticky regions" among the silica aggregates and, consequently, a tight filler network wherein rubber is immobilized. This grants a relevant reinforcement and increased hysteretic properties, suggesting SiO2@POSS as a promising filler system for decreasing the energy loss under strain and for leading to a potential reduction of filler utilization in rubber composite formulations.