In accordo a quanto riportato precedentemente che ha individuato nelle SrFeO3 materiali interessanti per l'applicazione come elettrodi per celle reversibili e in particolare per celle simmetriche, grazie alla presenza della coppia Fe4+/Fe3+, l'attività svolta al Mese 9 del progetto ha riguardato la sintesi tramite Solution Combustion Synthesis di n. 6 composizioni a base di SrFeO3 drogate, al sito A con Ce, Y, Sm ed al sito B con Ti, Al, Mo. I suddetti materiali sono stati forniti ad ICMATE-CNR per misure elettrochimiche realizzando una cella simmetrica con elettrolita in Samarium-doped Ceria (SDC) di composizione Ce0.8Sm0.2O2-?.

Thin films based on scandium oxide (ScO) were deposited on silicon substrates to investigate the thickness effect on the reduction of work function. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), energy dispersive X-ray reflectivity (EDXR), atomic force microscopy (AFM), and ultraviolet photoelectron spectroscopy (UPS) measurements were performed on the films deposited by electron-beam evaporation with different nominal thicknesses (in the range of 2-50 nm) and in multi-layered mixed structures with barium fluoride (BaF) films. The obtained results indicate that non-continuous films are required to minimize the work function (down to 2.7 eV at room temperature), thanks to the formation of surface dipole effects between crystalline islands and substrates, even if the stoichiometry is far from the ideal one (Sc/O = 0.38). Finally, the presence of BaF in multi-layered films is not beneficial for a further reduction in the work function.

This paper presents a multipronged scientific study of mortars and plasters of the so-called Ginnasio in the Hellenistic-Roman city of Solunto (Sicily, Italy). A selection of 16 well-contextualized samples was collected to represent different functions and building phases of this private house. The results show that a variety of locally available raw materials was used as aggregates and to produce binders. The diversity of raw materials' sources and production techniques identified in this study reveals the advanced technological knowledge of the builders of Solunto, indicating a complex relationship between the settlement's cityscape and its surrounding landscape

Internal prosthesis and grafts are currently made of Ti alloys, stainless steels and Co-Cr alloys. In spite of excellent biocompatibility, they show some drawbacks that concern their mechanical properties (e.g. elastic modulus) and the need of secondary surgery for removing the implant. For this reason, a growing attention has been focused on biodegradable materials that can be absorbed into the body after tissue remodelling. In particular, Mg alloys are promising candidates for temporary implants thanks to their high biocompatibility, biodegradability and good mechanical properties that match those of human bone. In this work, the surface modifications of biodegradable AZ31 alloy were analysed after immersion for 15 days in a physiological solution (NaCl 0.09%) by using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. XPS analysis of the surface of as-supplied AZ31 alloy showed the presence of MgO, whereas after immersion in the physiological solution, only Mg (OH)(2) was detected. The result has been discussed with reference to literature data. From the photoemission spectra and quantitative analysis, a small amount of Ca (about 2 wt%) was also detected.

In the present study, micro-structural and micro-chemical investigation of archaeological bronze artefacts provided new insight about the metallurgical manufacture of defensive weapons by the Samnite's metalsmiths in central Italy from the archaic necropolis of Barrea (AQ) and Torrebruna (CH). In particular, the metallurgical features, the chemical composition and the manufacturing process of Cu-based high-tin alloys used to produce cuirass discs were investigated. These artifacts were used to protect the warrior's heart (i.e. the kardiophylaches) but were also and more importantly a distinctive sign of rank and role of warriors of the archaic age (VI BC). The Samnite cuirass discs are multi-material artifacts made of a decorated bronze central part with a complex metallurgical structure, due to the presence of different Cu-Sn phases, and a surrounding iron cladding to support the disk. These discs were studied by different surface and bulk techniques, namely Optical Microscopy (OM), Field Emission Scanning Electron Microscopy coupled with energy dispersive X-ray microanalysis (FE-SEM-EDS), X-ray Diffraction (XRD) and Infrared Spectroscopy (FTIR). The combined use of these techniques proved the high technological level of the Samnite metallurgists. In fact, their particular composition, having an uncommon high content of tin, made their manufacturing process difficult because of the intrinsic brittleness of the alloy. This work disclose the ability of Samnites people to successfully manipulate fragile high tin bronze alloys by inducing temporary phase changes and, thus, facilitating the mechanical shaping of the artifact.

Since its first reported exfoliation in 2014, the interest in 2D black phosphorus (2D BP) and its chemical functionalization has grown dramatically [1], though a satisfactory structural description of the modified materials is seldom achieved. Herein, the functionalization of 2D BP starting from molecular Pd precursors is presented, leading either to supported Pd NPs (Pd/BP) or to interlayer Pd-Pd discrete units (Pd2/BP). An in-depth solid-state characterization of the new materials was carried out by means of XPS, HAADF-STEM, XRD, NMR MAS and XAS. Remarkably, XAS analysis, backed up by DFT modelling, was crucial in revealing the existence of Pd2 moieties stacked amidst BP layers in Pd2/BP. The potential application of these heterogeneous systems as catalysts was demonstrated in distinct processes, namely the selective hydrogenation of chloronitrobenzene to chloroaniline and the hydrogen evolution reaction (HER) from acidic medium.

Quantum materials are central for the development of novel functional systems that are often based on interface specific phenomena. Fabricating controlled interfaces between quantum materials requires adopting a flexible growth technique capable to synthesize different materials within a single-run deposition process with high control of structure, stoichiometry, and termination. Among the various available thin film growth technologies, pulsed laser deposition (PLD) allows controlling the growth of diverse materials at the level of single atomic layers. In PLD the atomic species are supplied through an ablation process of a stoichiometric target either in form of polycrystalline powders or of a single crystal. No carrier gases are needed in the deposition process. The ablation process is compatible with a wide range of background pressure. We present results of thin-film growth by PLD obtained by using an Nd:YAG infrared pulsed laser source operating at its first harmonics. With respect to the traditional PLD systems-based on excimer KrF UV-lasers-optimal conditions for the growth of thin films and heterostructures are reached at large target-To-substrate distance. Merits and limitations of this approach for growing oxide and non-oxide thin films are discussed. The merits of an Nd:YAG laser to grow very high-quality thin films suggest the possibility of implementing compact in-situ setups e.g. integrated with analytical instrumentation under ultra-high vacuum conditions.

Fluorescent atomically precise Ag38(11-azido-2-ol-undecane-thiolate)24 nanoclusters are easily prepared using sodium ascorbate as a "green"reducer and are extensively characterized by way of elemental analyses, ATR-FTIR, XRD, SAXS, UV-vis, fluorescence spectroscopies, and theoretical modeling. The fluorescence and the atomically determined stoichiometry and structure, the facile and environmentally green synthesis, together with the novel presence of terminal azido groups in the ligands which opens the way to "click"-binding a wide set of molecular species, make Ag38(11-azido-2-ol-undecane-thiolate)24 nanoclusters uniquely appealing systems for biosensing, recognition and functionalization in biomedicine applications and in catalysis. This journal is

We investigated the complex interaction between a nickel layer and a 4H-SiC substrate under UV-laser irradiation since the early stages of the atomic inter-diffusion. An exhaustive description is still lacking in the literature. A multimethod approach based on Transmission Electron Microscopy, Energy Dispersive Spectroscopy and Diffraction (electron and X-ray) techniques has been implemented for a cross-correlated description of the final state of the contact after laser irradiation. They detailed the stoichiometry and the lattice structure of each phase formed as well as the Ni/Si alloy profile along the contact for laser fluences in the range 2.4-3.8 J/cm(2). To make a bridge between process conditions and post-process characterizations, time dependent ultra-fast phenomena (laser pulse approximate to 160 ns), such as intermixing driven melting and Ni-silicides reactions, have been simulated by a modified phase fields approach in the proper many-compounds formulation.

COF-1 has a structure with rigid 2D layers composed of benzene and BO rings and weak van der Waals bonding between the layers. The as-synthesized COF-1 structure contains pores occupied by solvent molecules. A high surface area empty-pore structure is obtained after vacuum annealing. High-pressure XRD and Raman experiments with mesitylene-filled (COF-1-M) and empty-pore COF-1 demonstrate partial amorphization and collapse of the framework structure above 12-15 GPa. The ambient pressure structure of COF-1-M can be reversibly recovered after compression up to 10-15 GPa. Remarkable stability of highly porous COF-1 structure at pressures at least up to 10 GPa is found even for the empty-pore structure. The bulk modulus of the COF-1 structure (11.2(5) GPa) and linear incompressibilities (k=111(5) GPa, k=15.0(5) GPa) were evaluated from the analysis of XRD data and cross-checked against first-principles calculations.

Shape setting is a crucial step of the production route of shape memory alloys (SMAs) elements for fixing their functional properties. For thin SMA wires, this peculiar setting can be performed by a laser beam scanning the wire length. In the present work the correlation among the functional properties, such as stress-strain curves, the microstructural properties and the laser power was studied on 100 ?m pseudoelastic NiTi wire. A comparison between the performances of the laser treated and the commercial wires was discussed. It can be stated that the wire responses can be modulated as a function of the laser power; the optimal laser condition can induce functional properties at least comparable to the ones of the wire conventionally treated in a furnace. Laser induced superelasticity was obtained at room temperature and the corresponding microstructure suggests a texture effect associated with the directional and fast heating induced by the laser beam scan. A favorable condition for extended stress induced plateau lengths, compared to the one of the commercially available furnace treated wires, was induced by the laser scan.

Giulio Monteverde (1837-1917) was one of the major and most important sculptors of the early 1900s, both in Italy and at a worldwide level. Monteverde is mainly known for the artworks he realized in stone and metal, but he still remains almost unacknowledged for his plaster statues. Until today, neither the manufacture, nor the chemical composition of these sculptures was ever studied. In this paper, we have performed a preliminary investigation of the morphological and chemical composition of the gypsum plaster that Monteverde used to create his artwork in stone "Idealità e Materialismo", today in the National Gallery of Modern Art in Rome. Micro-samples of the sculpture were characterized by scanning electron microscopy (SEM), analytical microprobe (EDX), Fourier transform infrared spectroscopy (FTIR), and X-ray powder diffraction (XRD). This enabled the identification of both the chemical composition of the material used by the artist and the steps adopted to realize his sculptures. The analyzed samples have shown the presence of a thin finishing layer, as a "skin", covering the whole artwork. This layer consists mainly of Gypsum, Calcite and Anhydrite and has, consequently, a different chemical composition than the inner bulk, which is made of pure gypsum. Such outer layer results in a marble-like surface of the sculpture with increased hardness and reduced porosity, which results in a higher resistance to external environmental conditions. This may also explain why Monteverde's plaster sculptures are so well preserved over time.

In the frame of the HERACLES (HEritage Resilience Against CLimate Events on Site) project, a set of cultural heritage sites was studied to improve their resilience against climate events. The mediaeval Town Walls of Gubbio, in the centre of Italy, are among these. Over the centuries, several factors including environmental actions and structural and material repairs have produced different criticalities, involving both structure and materials. A severe problem consists in the progressive degradation of the mortars binding the masonry. Since the wall body structure behaves/reacts properly only if the cohesion between mortar and stones is sufficiently large, it follows that mortars degradation represents a quite significant issue that deserves a special attention. The present work focuses on the characterization of the mortars sampled in various parts of the Walls, corresponding to different historical periods, restoration measures and interventions. They were characterized to determine the corresponding mineralogical and chemical compositions along with morphological features and to investigate their mechanical properties. For that purpose, penetrometric and sclerometric tests on site and ex situ laboratory techniques, such as X-ray diffraction, polarized light microscopy, scanning electron microscopy, thermogravimetry and differential thermal analysis, were used to examine the weathering effects on mortars and more generally their degradation state, in order to plan appropriate restoration and repair actions.

White bronzes are electrodeposited coatings applied on brass as surface finishes. We report a comparative study on the corrosion resistance in chloride aqueous environment of two white bronzes, a Zn-bearing and a Zn-free. Corrosion tests showed that both materials provide protection to brass, but the Zn-free is more cathodic and performs better in the test environment, following a different corrosion mechanism. We also explored the effect of the coating thickness on the corrosion parameters. We found that the more cathodic OCPs were achieved with coatings exceeding 1 ?m, while the 0.5 ?m coatings show OCPs closer to the brass substrate.

During the Classical Period (300 BC-400 AD), the Indian Ocean emerged as one of the largest hubs of ancient international trade. For a long period, these contacts were described from a Rome-centric point of view, looking at the connections between Rome and India. However, recent studies have demonstrated that the Roman-Indo connection was only one of the vast medium and short distance trade routes involving numerous regions and populations, exchanging goods and culture. Current archaeological investigations have demonstrated that several minor trade dynamics formed the primary connective tissue of the Indian Ocean. This study attempts to trace these mid-range connections by focusing on the transport of torpedo jars, recently found in several settlements throughout the Indian Ocean. Two archaeological sites were considered: Al Hamr al-Sharqiya 1 (Inqitat, southern Oman), and the port of Alagankulam (southern India). An analytical protocol based on thin sections analysis, SEM-EDS, XRD and GC/MS was applied to a selection of fragments from the two archaeological sites. The analytical investigation carried out on these vessels identified three different ceramic compositions, which distributed differently in the two sites, characterized by a black coating due to a similar bitumen source. The location of the production sites and comparative studies between these vessels and reference materials available in the literature enabled us to cast new light on the routes followed by the torpedo jars, from Mesopotamia to India and Oman.

We investigated the adsorption of heavy metal ions on a nanostructured coating of zinc-aluminum layered double hydroxides (Zn-Al LDHs) grown on aluminum foam by one-step hydrothermal process. This approach aimed to increase the interactive surface and provide a more practical medium for removal of toxic heavy metals from aqueous media. The foam coated with LDH was characterized by using scanning electron microscopy and X-ray diffraction. After immersion in a copper-rich water solution, X-ray photoelectron spectroscopy demonstrated the occurrence of adsorbed copper on the LDH-coated foam with two oxidation states: particles of metallic copper Cu(0)with oxidized surface Cu+1. X-ray diffraction showed the presence of Cu(+2)in the LDH structure.

Stable palladium oxide nanoparticles were prepared in aqueous suspension with a very simple procedure, by dissolving palladium nitrate in water at a concentration around 10(-4) M. UV-visible absorption spectroscopy was adopted to follow the formation of these nanoparticles, which were characterized by TEM microscopy, along with XRD, XPS and Raman measurements. DFT calculations allowed to interpret the Raman data and to clarify the species present at the surface of the nanoparticles. The catalytic activity of the latter was evaluated by monitoring the reduction of p-nitrophenol to p-aminophenol. This investigation paves the way to the use of these colloidal nanoparticles in processes of heterogeneous catalysis, in particular those concerning the catalytic degradation of aromatic derivatives that represent a serious danger for the environment as pollutants, as in the case of p-nitrophenol.

The development of sustainable building materials is essential in view of meting worldwide requirements of the green and sustainable economy; this aspect is crucial in cement concrete, in which commercial demand is increasing day by day. Superior quality concretes can be produced by using natural additives, such as biopolymers, being them harmfully respect to the environment. In this investigation, bio-additives prepared from cactus extract with varying concentrations was mixed into cement concrete mixtures for the manufacturing of sustainable concretes. The modified concretes were evaluated for their fresh and hardened state properties. The interaction of cactus extract with cement particles during hydration reactions was also examined by Fourier Transform Infrared Spectroscopy (FT-IR); the microstructural properties of the modified cement concrete was also studied through X-ray Diffraction (XRD) and Thermo Gravimetric Analysis (TGA). As a result, FT-IR evidenced that the additives containing polysaccharides enhanced the water retention of the concrete, preventing the early drying of the concrete mix and thereby reducing shrinkage cracks. Cactus extract enhances the viscosity property of the concrete mix and thereby improves the workability of the concrete mix. The results of the investigation also evidenced that modified concretes exhibit enhanced mechanical properties and durability characteristics. In particular, polysaccharides influence the strength characteristics of the additive modified concrete while proteins and fats have an impact on the workability and durability of modified concrete. Hence, the tested bio-additive could be considered as an eco-friendly, cheaper natural additive that could develop sustainable cement composites with upgraded workability, mechanical and durability characteristics.

In the present study were studied the ferromagnetic La1-xSrx (Mn1-yCoy)(z)O-3 (LSMCO) films with Co content y = 0 to 0.18, grown on LaAlO3 substrates by advantageous pulsed-injection metalorganic chemical vapor deposition technique. The LSMCO films exhibit negative colossal magnetoresistance effect; therefore, they are interesting as potential material for the applications in magnetic field sensing. The changes of lattice volume in the investigated LSMCO films were monitored by X-ray diffraction measurements revealing a transition from tensile to compressive strain with increase of Co content. Additionally, from the atomic force microscopy images, the surface smoothening with increase of y was determined. Despite the reduction of the out-of-plane lattice parameter of LSMCO, the increase of lattice volume in the whole Co-doping range was observed. The X-ray photoelectron spectroscopy combined with Ar+ ion sputtering was used for the investigation of chemical composition of the LSMCO films and demonstrated the change and redistribution of oxidation states of Mn and Co on the surface and in the volume of the films. Regardless of the structural changes and charge distribution of Co and Mn cations, epitaxial LSMCO exhibits ferromagnetic properties and magnetoresistance values increases with augmenting Co content in the range of y = 0 to 0.18.

A novel black organoammonium iodoplumbate semiconductor, namely phenyl viologen lead iodide CHN(PbI) (PhVPI), was successfully synthesized and characterized. This material showed physical and chemical properties suitable for photovoltaic applications. Indeed, low direct allowed band gap energy (E = 1.32 eV) and high thermal stability (up to at least 300 °C) compared to methylammonium lead iodide CHNHPbI (MAPI, E = 1.5 eV) render PhVPI potentially attractive for solar cell fabrication. The compound was extensively characterized by means of X-ray diffraction (performed on both powder and single crystals), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), UV-photoelectron spectroscopy (UPS), FT-IR spectroscopy, TG-DTA, and CHNS analysis. Reactivity towards water was monitored through X-ray powder diffraction carried out after prolonged immersion of the material in water at room temperature. Unlike its methyl ammonium counterpart, PhVPI proved to be unaffected by water exposure. The lack of reactivity towards water is to be attributed to the quaternary nature of the nitrogen atoms of the phenyl viologen units that prevents the formation of acid-base equilibria when in contact with water. On the other hand, PhVPI's thermal stability was evaluated by temperature-controlled powder XRD measurements following an hour-long isothermal treatment at 250 and 300 °C. In both cases no signs of decomposition could be detected. However, the compound melted incongruently at 332 °C producing, upon cooling, a mostly amorphous material. PhVPI was found to be slightly soluble in DMF (~5 mM) and highly soluble in DMSO. Nevertheless, its solubility in DMF can be dramatically increased by adding an equimolar amount of DMSO. Therefore, phenyl viologen lead iodide can be amenable for the fabrication of solar devices by spin coating as actually done for MAPI-based cells. The crystal structure, determined by means of single crystal X-ray diffraction using synchrotron radiation, turned out to be triclinic and consequently differs from the prototypal perovskite structure. In fact, it comprises infinite double chains of corner-sharing PbI octahedra along the a-axis direction with phenyl viologen cations positioned between the columns. Finally, the present determination of PhVPI's electronic band structure achieved through UPS and UV-Vis DRS is instrumental in using the material for solar cells.