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This paper proposed a multianalytical, non-invasive, accessible and expensive (compared to traditional ones) approach for the characterization of pictorial surfaces. A set of 18 pigments and 37 mixtures widely used in the Middle Ages in the Apulia (Italy) artistic and archaeological contexts was considered, and corresponding replicas were produced. Pigments were first characterized by X-ray powder diffraction (XRPD), then replicas were studied by optical microscopy using a portable instrument, colorimetry and fiber optic reflectance spectroscopy (FORS). The investigation provided encouraging results, which allowed the creation of a library including diagnostic microscopic, colorimetric and reflectance markers of each pigment and the identification of the mixtures’ components.

In the field of historical buildings, the wide use of lime as a binder in various contexts of application emerges from a series of artistic and archaeological evidence in the Apulia (Italy) from the 4th century BCE to the 15th century CE. The large availability of carbonate rocks in the geological substratum from Daunian Subappennines to Salento areas strongly influenced the material culture of the region. In this paper, significant study cases were presented to bring to light the technological complexity, almost completely cancelled by the widespread presence of industrial products, in the use of lime over the centuries. Through examples of use from antiquity to the modern age in Apulia (Egnatia, Lamapopoli, Tertiveri, Siponto, Lucera and Monopoli sites), technological solutions indicating an ecological dimension of production were discussed, bearing witness to technologies on a human scale and sustainability. The comparison of petrographical (POM, SEM-EDS) and mineralogical (XRPD) results indicated the technological trend and custom for lime production in the Apulian region that starts from the choice of the stone to be calcined and the aggregates and passes through the modalities of lime hydration and preparation of the mixture up to the laying.

Water potabilization sludges (WPS) are a heterogeneous waste generated from the coagulation–flocculation process of drinking water production, whose composition is highly dependent on the geological context of reservoirs, the composition and volume of treated water, and the types of coagulants used. For this reason, any feasible approach for reusing and valorising of such waste cannot be disregarded from the detailed investigation of its chemical and physical characteristics and they have to be evaluated at a local scale. In this study, WPS samples from two plants serving the Apulian territory (Southern Italy) were subjected for the first time to a detailed characterization with a view to evaluating their recovery and reuse at a local scale as a raw material for producing alkali activated binders. WPS samples were investigated by X-ray fluorescence (XRF), X-ray powder diffraction (XRPD) including phase quantification by the combined Rietveld and reference intensity ratio (RIR) methods, thermogravimetric and differential thermal analysis (TG-DTA), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX). Samples showed aluminium–silicate compositions with up to 37 wt% of Al2O3 and up to 28 wt% of SiO2. Small amounts of CaO were also found (6.8 and 4 wt%, respectively). The mineralogical investigation indicates the presence of illite and kaolinite as clayey crystalline phases (up to 18 wt% and 4 wt%, respectively), in addition to quartz (up to 4 wt%) and calcite (up to 6wt%) and a large amorphous fraction (63 wt% and 76 wt%, respectively). WPS were subjected to heating from 400 °C to 900 °C and mechanical treatment by high energy vibro-milling in order to determine the best pre-treatment condition in view of their use as solid precursors to prepare alkali-activated binders. Alkali activation (8M NaOH solution; room temperature curing) was attempted on untreated WPS, on 700 °C heated and on 10-minute high-energy milled samples, which were considered the most suitable based on the preliminary characterization. Investigations of alkali-activated binders confirmed the geopolymerisation reaction occurrence. Variations in gel features and compositions depended on the amount of reactive SiO2, Al2O3 and CaO available in the precursors. WPS heated at 700 °C led to the most dense and homogeneous microstructures, due to a greater availability of reactive phases. The results of this preliminary study demonstrate the technical feasibility of preparing alternative binders from the investigated Apulian WPS, paving the way for a local reuse of these waste products, leading to economic and environmental benefits.

This work deals with the investigation of alkaline binders obtained from binary mixtures of carbonate-rich illitic clay from deposits in southern Italy and two industrial by-products with very different total composition and calcium content, i.e., blast furnace slag and type F fly ash, respectively. To improve the reactivity, the selected clay was ground in a ball miller and heated to 700 °C. The binary mixtures were alkali activated with NaOH solution at 4 M and 8 M, and the activated pastes were cured at room temperature and relative humidity >90% in a climatic chamber. Heat flow, total heat and compressive strength (2, 7 and 28 days) were determined. The hardened pastes were characterized by X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX). Results show that the main reaction product in all samples is a gel or mixture of C-A-S-H/(N, C)-A-S-H type gel depending on the calcium content in the precursors. The paste, made up of a 1:1 weight proportion of carbonate-rich illitic clay and blast furnace slag, showed the formation of a more compact matrix than that observed in each individually activated component, achieving the considerable mechanical strength value of 45 MPa after 28 days, which suggests a very positive interaction between the two calcium-rich solid precursors. The binary mixture of carbonate-rich illitic clay and F fly ash showed relatively low compressive strength (below 15 MPa), which has been related to the poor reaction potential of fly ash regarding the alkali activation at room temperature. The modification of curing parameters is expected to improve the reaction of carbonate-rich illitic clay/fly ash blend. The clay activation method used in this study has been demonstrated to be suitable for larger scale industrial pre-treatment set-ups.