Synchrotron radiation X-ray diffraction computed tomography (XRDCT): a new tool in cultural heritage and stone conservation for 3D non-destructive probing and phase analysis of inorganic re-treatments.

The issue of preserving carbonatic stones of cultural heritage (CH) restored in the past that have undergone new decay phenomena is strongly emerging and conservation science has not yet found a reliable solution. In this paper, we propose the application of synchrotron radiation X-ray diffraction computed tomography (XRDCT) to explore the effects of using inorganic-mineral products (ammonium oxalate; ammonium phosphate) in sequence as a novel, compatible and effective re-treatment approach to consolidate decayed carbonatic stones already treated with inorganic-mineral treatments. High-quality XRDCT datasets were used to qualitatively/quantitatively investigate and 3D localize the complex mixture of crystalline phases formed after the conservation re-treatments within a porous carbonatic stone substrate. The XRDCT reconstruction images and the structural refinements of XRD patterns with the Rietveld methods showed that the phase composition of reaction products, their volume distribution, and weight fraction vary as a function of the treatment sequence and penetration depth. The high potential of XRDCT allows (i) assessment of peculiar trends of each treatment/treatment sequence; (ii) exploration of the reaction steps of the sequential treatments and (iii) demonstration of the consolidating effect of inorganic re-treatments, non-destructively and at the micron scale. Above all, our study (i) provides new analytical tools to support the conservation choices, (ii) showcases new analytical possibilities for XRDCT in conservation science, including in investigations of CH materials and decay processes, and (iii) opens up new perspectives in analytical chemistry and material characterisation for the non-destructive and non-invasive analysis of reactions within heterogeneous polycrystalline systems.

Synchrotron X-ray diffraction computed tomography to non-destructively study inorganic treatments for stone conservation.

The characterization of consolidating products formed by conservation treatments within Cultural Heritage (CH) materials is a burning issue and an analytical challenge, as non-destructive approaches, phase analysis, and volume distribution analysis are simultaneously required. This paper proposes the use of synchrotron X-ray diffraction computed tomography (XRDCT) to non-destructively study diammonium hydrogen phosphate (DAP) consolidating treatments for stone conservation. The mineralogical composition and localization of crystalline phases formed in a complex mixture have been explored and spatially resolved. The coexistence of hydroxyapatite and octacalcium phosphate has been finally demonstrated. The image analysis highlights the 3D distribution of calcium phosphates, their arrangement in a binding network down to the voxel scale, and their consolidating action. Above all, this study demonstrates the feasibility and high potential of XRDCT to investigate the interactions of conservation treatments with CH stone materials, and opens new analytical perspectives for XRDCT in conservation science and materials science.

Influence of speciation distribution and particle size on heavy metal leaching from MSWI fly ash.

Fly ash from municipal solid waste incineration (MSWI-FA) contains leachable heavy metals. In the present study the correlations between heavy metal content, particle size, speciation distribution with respect to water leaching are investigated, using a combination of solid-state bulk analytical techniques, leaching treatments, sequential extractions and thermodynamic geochemical modelling. Among the analyzed heavy metals, Zn and Pb are the most abundant in any grain size class, followed by Cu, Cr, Cd and Ni, with concentration that tends to increase with a decrease of the grain size. The phase composition is constituted of salt (halite, sylvite, anhydrite and syngenite), which provide the main minerals regardless of the particle size class; calcite, quartz and gehlenite occur in comparatively lower amounts, while 50% wt is composed of amorphous fraction. Heavy metal leaching is strongly correlated to speciation distribution, and in particular to the fraction (F1) associated with salt, carbonate and weak surface sorption. Leaching from speciation due to surface complexation on Al/Fe (hydr)oxide becomes relevant at acidic regime. Particle size and heavy metal content, in turn, moderately correlate with leaching. The F1-speciation as a function of particle size does not exhibit a definite trend shared by all heavy metals under investigation. This suggests that i) differences in speciation distribution, rather than bare heavy metal content or particle size, govern leaching from MSWI-FA; ii) F1 can be regarded as a marker of the potential heavy metal leaching; iii) a comparatively modest efficiency in managing MSWI-FA is expected from grain size separation strategies.

A compact and flexible induction furnace for in situ X-ray microradiograhy and computed microtomography at Elettra: design, characterization and first tests.

A compact and versatile induction furnace for in situ high-resolution synchrotron and laboratory hard X-ray microradiography and computed microtomography is described. The furnace can operate from 773 to 1723 K. Its programmable controller enables the user to specify multiple heating and cooling ramp rates as well as variable dwell times at fixed temperatures allowing precise control of heating and cooling rates to within 5 K. The instrument can work under a controlled atmosphere. Thanks to the circular geometry of the induction coils, the heat is homogeneously distributed in the internal volume of the graphite cell (ca. 150 mm3) where the sample holder is located. The thermal gradient within the furnace is less than 5 K over a height of ca. 5 mm. This new furnace design is well suited to the study of melting and solidification processes in geomaterials, ceramics and several metallic alloys, allowing fast heating (tested up to 6.5 K s-1) and quenching (up to 21 K s-1) in order to freeze the sample microstructure and chemistry under high-temperature conditions. The sample can be held at high temperatures for several hours, which is essential to follow phenomena with relatively slow dynamics, such as crystallization processes in geomaterials. The utility of the furnace is demonstrated through a few examples of experimental applications performed at the Elettra synchrotron laboratory (Trieste, Italy).

Effects of soda-lime-silica waste glass on mullite formation kinetics and micro-structures development in vitreous ceramics.

The effects of soda-lime waste glass, from the recovery of bottle glass cullet, in partial replacement of Na-feldspar for sanitary-ware ceramic production are discussed. Attention is paid to the mullite growth kinetics and to the macroscopic properties of the final output, the latter ones depending on the developed micro-structures and vitrification grade. Measurements have been performed by in situ high temperature X-ray powder diffraction, scanning electron microscopy, thermal dilatometry, water absorption and mechanical testing. Glass substituting feldspar from 30 to 50 wt% allows one (i) to accelerate the mullite growth reaction kinetics, and (ii) to achieve macroscopic features of the ceramic output that comply with the latest technical requirements. The introduction of waste glass leads to (i) a general saving of fuel and reduction of the CO2-emissions during the firing stage, (ii) a preservation of mineral resources in terms of feldspars, and (iii) an efficient management of the bottle glass refuse by readdressing a part of it in the sanitary-ware manufacturing.