Pietro Riello

Nucleation and crystallization behavior of glass-ceramic materials in the Li2O-Al2O3-SiO2 system of interest for their transparency properties

Abstract We investigated the nucleation and crystallization behavior of multi-phase glass-ceramic materials (in the Li2O–Al2O3–SiO2 system to which low amounts of oxides such as TiO2, ZrO2, P2O5, BaO, Sb2O3 and ZnO were added), with interest in their transparency properties as glazes for industrial tiles with high scratch resistance. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used. XRD showed that the nucleating oxides produce, during the nucleation stage (at 953 K for 20 h), an orthorhombic ZrTiO4 phase, which maintains a similar crystallite size (about 4 nm) during the subsequent crystallization processes. We succeeded in determining the concentration of nuclei by using XRD data only. This quantity resulted close enough to the corresponding one, determined using the classical TEM method. The formation of each crystalline phase, developed during the crystallization stage, as a function of the thermal treatment, was quantitatively measured using the Rietveld method. In particular, the isothermal transformations at 1003 and 1023 K of the characteristic main phase, i.e., β-eucryptite s.s., which is richer in silica with respect to the relevant stoichiometric phase, into β-spodumene s.s., also richer in silica, were found to be consecutive solid state reactions. Moreover, this preliminary investigation aims at improving knowledge of the mechanisms leading to the development of transparent/opaque materials during the thermal treatment of Li2O–Al2O3–SiO2 glass-ceramics.

Preparation, structural characterization, and luminescence properties of Eu3+-doped nanocrystalline ZrO2.

Eu 3+ -doped zirconia nanopowders were prepared by the sol-gel technique using two different methods, based on the hydrolysis of zirconium n -propoxide, producing tetragonal and monoclinic zirconia under different preparation conditions. A detailed microstructure characterization was performed through wide angle x-ray scattering, small angle x-ray scattering, trasmission electron microscopy, and nitrogen physisorption measurements. The possible influence of the zirconia crystalline phases and particle sizes on the luminescence properties of the lanthanide ion was investigated. A detailed analysis of the emission spectra of the samples suggested that the dopant Eu 3+ ions replace the Zr 4+ ions in the zirconia crystal lattice. Moreover, samples prepared by the two different methods were characterized by different decay times of the Eu 3+ ion luminescence.

Quantitative Phase Analysis in Semicrystalline Materials Using the Rietveld Method

A new procedure to perform quantitative analysis without any internal standard has been developed within Rietveld analysis. This new approach permits solution of the problem due to the presence of an amorphous phase when its chemical composition or the global sample composition is known. The equations developed, based on a study of the global intensities diffracted by each phase in reciprocal space, reduce to the well known formula of Hill & Howard [J. Appl. Cryst. (1987), 20, 467–474] when applied to completely crystalline materials.

Top-down synthesis of multifunctional iron oxide nanoparticles for macrophage labelling and manipulation

Multifunctional iron oxide (FeOx) magnetic nanoparticles (MNPs) are promising items for biomedical applications. They are studied as theranostic agents for cancer treatment, selective probes for bioanalytical assays, controllable carriers for drug delivery and biocompatible tools for cell sorting or tissue repair. Here we report a new method for the synthesis in water of FeOx–MNPsvia a top-down physical technique consisting in Laser Ablation Synthesis in Solution (LASiS). LASiS is a green method that does not require chemicals or stabilizers, because nanoparticles are directly obtained in water as a stable colloidal system. A gamut of characterization techniques was used for investigating the structure of FeOx–MNPs that have a polycrystalline structure prevalently composed of magnetite (ca. 75%) and hematite (ca. 22%). The FeOx–MNPs exhibit very good magnetic properties if compared to what is usually reported for iron oxide nanoparticles, with saturation magnetization close to the bulk value (ca. 80 emu g−1) and typical signatures of the coexistence of ferrimagnetic and antiferromagnetic phases in the same particle. The functionalization of FeOx–MNPs after the synthesis was possible with a variety of ligands. In particular, we succeeded in the functionalization of FeOx–MNPs with carboxylated phosphonates, fluorescent alkylamines, fluorescent isothiocyanates and bovine serum albumin. Our FeOx–MNPs showed excellent biocompatibility. Multifunctional FeOx–MNPs were exploited for macrophage cell labelling with fluorescent probes as well as for cell sorting and manipulation by external magnetic fields.

Renewable H2 from Glycerol Steam Reforming: Effect of La2O3 and CeO2 Addition to Pt/Al2O3 catalysts.

Glycerol is the main byproduct of biodiesel production and its increased production volume derives from the increasing demand for biofuels. The conversion of glycerol to hydrogen-rich mixtures presents an attractive route towards sustainable biodiesel production. Here we explored the use of Pt/Al(2)O(3)-based catalysts for the catalytic steam reforming of glycerol, evidencing the influence of La(2)O(3) and CeO(2) doping on the catalyst activity and selectivity. The addition of the latter metal oxides to a Pt/Al(2)O(3) catalyst is found to significantly improve the glycerol steam reforming, with high H(2) and CO(2) selectivities. A good catalytic stability is achieved for the Pt/La(2)O(3)/Al(2)O(3) system working at 350 degrees C, while the Pt/CeO(2)/Al(2)O(3) catalyst sharply deactivates after 20 h under similar conditions. Studies carried out on fresh and exhausted catalysts reveal that both systems maintain high surface areas and high Pt dispersions. Therefore, the observed catalyst deactivation can be attributed to coke deposition on the active sites throughout the catalytic process and only marginally to Pt nanoparticle sintering. This work suggests that an appropriate support composition is mandatory for preparing high-performance Pt-based catalysts for the sustainable conversion of glycerol into syngas.

Enhanced low-temperature protonic conductivity in fully dense nanometric cubic zirconia

The authors report on the consolidation of nanostructured bulk cubic zirconia with a grain size of about 15nm and a relative density greater than 98%. This material exhibits a change in the conduction mechanism with considerable protonic conductivity when exposed to moisture. The marked reduction of the resistivity of zirconia at low temperatures brings it to a level comparable to that typical of other protonic conductors, but with the advantage of superior mechanical and chemical stabilities.

Encapsulation of submicrometer-sized silica particles by a thin shell of poly(methyl methacrylate)

Polymer encapsulation of submicrometer-sized silica particles by synthesis of the polymer shell, poly(methyl methacrylate) under static conditions in a reaction medium free of surfactants and stabilizing agents is described. The Stöber method, a base-catalyzed hydrolysis and condensation of tetraethyl orthosilicate is used for the synthesis of the monodisperse colloidal dispersion of silica particles. The silica particles are subsequently modified in situ with the surface grafting of the silane coupling agent, 3-(trimethoxysilyl)propyl methacrylate. Encapsulation is achieved using tetraethyl orthosilicate as a reaction medium, in which a thermally initiated radical polymerization of methyl methacrylate is promoted in the presence of the modified particles by a seeding method which leads to a thin coating of poly(methyl methacrylate), and hence silica core-shell particles. The complete encapsulation of individual silica spheres by poly(methyl methacrylate) is visually evidenced by TEM microscopy which reveals the presence of a polymer shell coating up to 10 nm. Evidence for the presence of a poly(methyl methacrylate) shell is further corroborated by DSC/TGA, DRIFT-IR and NMR measurements.

Coexistence of plasmonic and magnetic properties in Au89Fe11 nanoalloys

We describe an environmentally friendly, top-down approach to the synthesis of Au89Fe11 nanoparticles (NPs). The plasmonic response of the gold moiety and the magnetism of the iron moiety coexist in the Au89Fe11 nanoalloy with strong modification compared to single element NPs, revealing a non-linear surface plasmon resonance dependence on the iron fraction and a transition from paramagnetic to a spin-glass state at low temperature. These nanoalloys are accessible to conjugation with thiolated molecules and they are promising contrast agents for magnetic resonance imaging.

Physicochemical properties of thermally prepared Ti-supported IrO2+ ZrO2 electrocatalysts

Abstract Thermally prepared mixed-oxide IrO2 + ZrO2 films have been studied by Rutherford backscattering spectrometry (RBS), wide-angle X-ray scattering (WAXS) and cyclic voltammetry. Concentration depth profiling by RBS has shown that electrode films containing less than 50 mol.% of iridium dioxide have layered structures where noble metal oxide and zirconium oxide enrichments alternate. The outermost layer is enriched with iridium oxide. By WAXS analysis it was possible to prove the existence of an IrO2 and a ZrO2 phase. From cell parameters, very limited solubility could be ascertained, restricted at the two limits of the composition coordinate. In the range 0–20 mol.% of iridium dioxide, a tetragonal ZrO2 phase is formed. For samples richer in IrO2, the ZrO2 phase becomes amorphous. The microstructural features of the tetragonal IrO2-rich phase do not change significantly with the film composition. The effective surface area of the samples, as determined by cyclic voltammetry, exhibits a maximum in the composition range 50–80 mol.% IrO2. This result has been interpreted on the basis of WAXS and RBS data.

Wustite as a new precursor of industrial ammonia synthesis catalysts

Contradictory results about the best oxidic precursor of Fe ammonia synthesis catalyst prompted the present comparative investigation on wustite- and magnetite-based catalysts. Many physical (density, porous texture, crystalline phases, reduction rate, metal surface, abrasion loss) and catalytic (kinetic constants, thermoresistancy) properties have been determined on both catalysts. The wustite-based catalyst proved to be much more active, especially at lower temperatures, approaching the performances of Ru/C catalyst, except at high conversion. Possible reasons for such a behavior of the wustite-based catalyst are discussed, suggesting that a reconsideration of the present consolidated knowledge on Fe ammonia synthesis catalyst might be convenient.