[en] This work deals with the synthesis and Rietveld structure refinement of a zirconium-praseodymium yellow pigment prepared either by a traditional ceramic process route and by an unconventional synthesis method based on SHS (self-propagating high-temperature synthesis). In order to confirm the effective formation of the solid solutions, SEM imaging and EDS analysis, and leaching tests have also been performed. The results proved the applicability of the unconventional processing route for obtaining yellow solid solutions. (orig.)

[en] Cement-asbestos is the main asbestos containing material still found in most of the European countries such as Italy. Man- and weathering-induced degradation of the cement-asbestos slates makes them a source of dispersion of asbestos fibres and represents a priority cause of concern. This concern is the main prompt for the actual policy of abatement and disposal of asbestos containing materials in controlled wastes. An alternative solution to the disposal in dumping sites is the direct temperature-induced transformation of the cement-asbestos slates into non-hazardous mineral phases. This patented process avoids the stage of mechanical milling of the material before the treatment, which improves the reactivity of the materials but may be critical for the dispersion of asbestos fibres in working and life environment. For the first time, this paper reports the description of the reaction path taking place during the firing of cement-asbestos slates up to the complete transformation temperature, 1200 deg. C. The reaction sequence was investigated using different experimental techniques such as optical and electron microscopy, in situ and ex situ quali-quantitative X-ray powder diffraction. The understanding of the complex reaction path is of basic importance for the optimization of industrial heating processes leading to a safe recycling of the transformed product. For the recycling of asbestos containing materials, the Italian laws require that the product of the crystal chemical transformation of asbestos containing materials must be entirely asbestos-free, and should not contain more than 0.1 wt% fraction of the carcinogenic substances such as cristobalite. Moreover, if fibrous phases other than asbestos (with length to diameter ratio >3) are found, they must have a geometrical diameter larger than 3 μm. We have demonstrated that using an interplay of different experimental techniques, it is possible to safely verify the complete transformation of asbestos minerals in this temperature-induced process. The product of transformation of cement-asbestos (CATP) has a phase composition similar to that of a natural or a low temperature clinker with the exception of having a larger content of aluminium, iron and magnesium. This product can be safely recycled for the production of stoneware tile mixtures. The addition of 3-5 mass% of CATP does not bear significant variations to the standard parameters of white porcelain tile mixtures

[en] Titanium dioxide exists in a large number of polymorphs, the most common ones being, in order of abundance, rutile, anatase and brookite. Recently, there has been an increasing degree of attention on TiO₂, due to its photocatalytic and antibacterial properties. In this work, titania nanopowders synthesized via an aqueous sol–gel method were modified with silver and/or tungsten, with potential application as photocatalysts and antibacterial agents. The dried gels were thermally treated at two temperatures, and the occurrence of amorphous phase—in both dried and calcined gels—was obtained using the Rietveld method. In powders calcined at 600 °C, the crystal structure of rutile was determined with the Rietveld method on the full profile fitting of the X-ray powder diffraction patterns, while microstructural information was achieved by means of Williamson–Hall plots and line broadening analysis methods. The photochromic property of the Ag and W/Ag modified samples—when subjected to both UV- and visible-light irradiation and for different time exposures—was also investigated via UV–Vis spectroscopy. Powders were shown to possess a tuneable photochromism due to the surface plasmon resonance of the added silver, depending on the firing temperature, light (and time) exposure, and on whether or not tungsten was present in the nanopowders

[en] Titanium dioxide (TiO_2) is a popular photocatalyst used for many environmental and anti-pollution applications, but it normally operates under UV light, exploiting ∼5% of the solar spectrum. Nitrification of titania to form N-doped TiO_2 has been explored as a way to increase its photocatalytic activity under visible light, and anionic doping is a promising method to enable TiO_2 to harvest visible-light by changing its photo-absorption properties. In this paper, we explore the insertion of nitrogen into the TiO_2 lattice using our green sol–gel nanosynthesis method, used to create 10 nm TiO_2 NPs. Two parallel routes were studied to produce nitrogen-modified TiO_2 nanoparticles (NPs), using HNO_3+NH_3 (acid-precipitated base-peptised) and NH_4OH (totally base catalysed) as nitrogen sources. These NPs were thermally treated between 450 and 800 °C. Their true phase composition (crystalline and amorphous phases), as well as their micro-/nanostructure (crystalline domain shape, size and size distribution, edge and screw dislocation density) was fully characterised through advanced X-ray methods (Rietveld-reference intensity ratio, RIR, and whole powder pattern modelling, WPPM). As pollutants, nitrogen oxides (NO_x) are of particular concern for human health, so the photocatalytic activity of the NPs was assessed by monitoring NO_x abatement, using both solar and white-light (indoor artificial lighting), simulating outdoor and indoor environments, respectively. Results showed that the onset of the anatase-to-rutile phase transformation (ART) occurred at temperatures above 450 °C, and NPs heated to 450 °C possessed excellent photocatalytic activity (PCA) under visible white-light (indoor artificial lighting), with a PCA double than that of the standard P25 TiO_2 NPs. However, higher thermal treatment temperatures were found to be detrimental for visible-light photocatalytic activity, due to the effects of four simultaneous occurrences: (i) loss of OH groups and water adsorbed on the photocatalyst surface; (ii) growth of crystalline domain sizes with decrease in specific surface area; (iii) onset and progress of the ART; (iv) the increasing instability of the nitrogen in the titania lattice. - Graphical abstract: Nitrogen modified TiO_2 synthesised via a green aqueous sol–gel method showed to degrade nitrogen oxides (NO_x) under visible white-light (indoor artificial lighting), with a photocatalytic activity double than that of the standard P25 TiO_2 NPs. - Highlights: • N–TiO_2 synthesised via a green aqueous sol–gel method. • Advanced X-ray methods used to detect both crystalline and amorphous contents. • Microstructure fully addressed via XRPD and whole powder pattern modelling. • Photocatalytic NO_x removal assessed using both solar and visible-light lamps.