Paola Meloni

Use of admixtures in organic-contaminated cement-clay pastes

In this work microstructure, porosity and hydration degree of cement-based solidified/stabilized wasteforms were studied before assessing their leaching behaviour. 2-Chloroaniline was chosen as a model liquid organic pollutant and included into cement pastes, which were also modified with different admixtures for concrete: a superplasticizer based on acrylic-modified polymer, a synthetic rubber latex and a waterproofing agent. An organoclay, modified with an ammonium quaternary salt (benzyl-dimethyl-tallowammonium, BDMTA), was added to the pastes as pre-sorbent agent of the organic matter. All the samples were dried up to constant weight in order to stop the hydration process at different times during the first 28 days of curing, typically, after 1 day (1d), 7 days (7d) and 28 days. Then, the microstructure of the hardened cement-clay pastes was investigated by powder X-ray diffraction (XRD). The hydration degree and porosity were studied by thermal analysis (TG/DTA) and mercury intrusion porosimetry (MIP), respectively. For samples cured for 28 days a short-term leach test set by Italian regulation for industrial waste recycling (D.M. 5 February 1998) was performed. The best results showed a 5% release of the total initial amount of organic pollutant.

Synthesis, characterization and DFT-modeling of novel agents for the protection and restoration of historical calcareous stone substrates

The ammonium salts of oxamate (AmOxam) and monomethyloxalate (AmMeox), structurally related to ammonium oxalate (AmOx), were synthesized and characterized as protecting agents/filler for calcareous stone substrates. Both compounds featured an improved solubility in water and alcoholic-water mixtures with respect to AmOx. While AmOxam is stable in aqueous solution and reacts with calcite to afford the corresponding insoluble calcium oxamate (CaOxam), AmMeox spontaneously undergoes hydrolysis to give ammonium monohydrogen oxalate hemihydrate (AmBiox) and calcium oxalate (CaOx). Both compounds have been tested for the restoration of naturally weathered marble and biomicritic limestone. The formation of a superficial layer of CaOxam and CaOx was observed on stone samples treated with AmOxam and AmMeox, respectively, depending on the solvent mixture. A quantum-mechanical study was carried out at DFT level in order to investigate the nature of the interactions occurring between the lithic substrate (calcite) and the passivating agents, showing how the structural modifications on oxalic acid derivatives can be exploited to fine-tune their interaction with the calcite surface.

Binders alternative to Portland cement and waste management for sustainable construction—part 1:

This review presents “a state of the art” report on sustainability in construction materials. The authors propose different solutions to make the concrete industry more environmentally friendly in order to reduce greenhouse gases emissions and consumption of non-renewable resources. Part 1—the present paper—focuses on the use of binders alternative to Portland cement, including sulfoaluminate cements, alkali-activated materials, and geopolymers. Part 2 will be dedicated to traditional Portland-free binders and waste management and recycling in mortar and concrete production.

Crime art on the stone: graffiti vandalism on cultural heritage and the anti-graffiti role in its surfaces protection

Apparently perceived like an easy thing commonly used, spray paint is a very complex product composed by substances strongly penetrating particularly into the porous materials. This characteristic is very hazardous for our cultural heritage. The problem concerning the surfaces protection from paints and signs is very hard to solve, both for the difficulty to remove these substances and for the variety of the materials that react in a different manner to the various paints and cleaning treatments because of their different physical-chemical characteristics. With the aim to evaluate the damages originated by the spray paints on the stones and the efficacy of anti-graffiti products, some laboratory tests have been carried out. Two different limestones have been selected like supports: a little porous, polishable wakestone and a very porous bio-calcarenite with very scarce mechanical properties. Both these limestones are used as coverings and structural elements of buildings and monuments around Mediterranean basin. Concerning the spray paint cans, the most popular Montana mtn94 has been used, and two commercial anti-graffiti have been applied as protective products. Using Scanning Electron Microscope, Infrared Spectrometry, Colorimetry, Mercury Intrusion Porosimetry and Contact Angle Analysis the interactions stone-paint, stone-anti-graffiti and paint-anti-graffiti have been investigated. In order to evaluate the real efficacy of the anti-graffiti, some cleaning and removal paint tests have been carried out. The research highlights that the anti-graffiti cause variations concerns the colour and/or the wettability in both limestones. Their effects are strictly related to the stonework and their microstructure but also the interaction with the paint is influent too.

Water Absorption Properties of Cement Pastes: Experimental and Modelling Inspections

An intermingled fractal units’ model is shown in order to simulate pore microstructures as pore fraction and pore size distribution. This model is aimed at predicting capillary water absorption coefficient and sorptivity values in cement pastes. The results obtained are in good agreement with the experimental ones. For validating this model, a comparison with other procedures has been shown. It is possible to establish that the newly proposed method matches better with the experimental results. That is probably due to the fact that pore size distribution has been considered as a whole. Moreover, even though the proposed model is based on fractal base units, it is able to simulate and predict different properties as well as nonfractal porous microstructure.

Oxamate salts as novel agents for the restoration of marble and limestone substrates: case study of ammonium N-phenyloxamate

The ammonium salt of N-phenyloxamic acid (AmPhOxam) was synthesised, characterised by FT-IR, FT-Raman, UV-Vis, 1H-NMR spectroscopic methods and single crystal X-ray diffraction, and evaluated as a protective and consolidating agent for calcareous stone substrates under mild conditions. Hydro-alcoholic solutions of AmPhOxam were tested for the treatment of naturally weathered white marble and biomicritic limestone. Mercury intrusion porosimetry, FT-NIR spectroscopy measurements and SEM microscopy showed the formation of a superficial protective layer of crystals of the corresponding monohydrated calcium salt, CaPhOxam, on both treated stones.

Multi analytical technique study of human bones from an archaeological discovery

In 1953, during the building restoration of San Michele church (Bono, Sardinia, 16th-19th Century), a high number of disarticulated skeletons were recovered. From a group of 412 hip bones, two of these, affected by several pathological lesions, were analysed. The two coxal bones can be referred to the same individual, an adult man. A multi-analytical study, started with the purpose of investigating the bone pathology, was extended to characterize the mineral components of a large representative set of bones from the same ossuary, all attributed to adult men who lived in the region four-two centuries ago. A quantitative ICP-AES analysis for Ca, Fe, Mg, Mn, Na, Pb and Zn was executed, and a chemometric investigation on the results was performed. This approach gave evidence of the effects of diagenesis, allowed some hypothesis of the incidence of the known dietary habits on bone composition, and completely differentiated the pathological bones from those of a normal population on the basis of the mineral composition. Moreover, porosity, crystallinity and FT-IR analysis were conducted on both non- and pathological sample.

Pigments and materials across Sardinia’s walls: contribution on the Tomba dei Pesci e delle Spighe in Cagliari

Sardinia is an ancient island where it is possible to find signs and symbols, decorative engraved and colored traces of men and history. In 1997 an ancient tomb in Cagliari has been discovered: it is located in the necropolis of Tuvixeddu, an old and spread necropolis dating from Punic to Roman times now located in the urban texture. The tomb, consisting of only one chamber, is dated by archaeologists a few centuries A.D. The name, Tomba dei Pesci e delle Spighe, is related to the painted decorations that were clearly visible on the walls and roof of the burial chamber, not so easily distinguishable anymore because of natural decay processes. Wall paintings appear severely damaged owing to the darkening of some areas, the detachments of others and a widespread presence of superficial concretions on the roof surfaces. This contribution aims to characterize pigments and the painting technique used in this burial chamber and compare them to the roman tradition. The site is confined, with evident problems of conservation because of the critical microclimatic conditions. High humidity and degradation are compromising the legibility of the decorative schemes. Samples of constituting materials and concretions have been collected and analyzed using x-rays diffraction (XRD) and IR spectroscopy (µFTIR-ATR). Preparatory layers supporting the pictorial have inorganic nature: diffractograms showed the presence of gypsum and calcite. IR spectroscopy (µFTIR) and scanning electron microscopy coupled with an energy dispersive system (SEM-EDS) were used to investigate the nature of pigments. Samples of blue, red and yellow pigments have been investigated. Egyptian blue, cinnabar and earth pigments have been detected. Proteinaceous materials have been identified as possible binders for the pigments.

Density functional theory modelling of protective agents for carbonate stones: a case study of oxalate and oxamate inorganic salts

Sulphur and nitrogen oxide pollutants cause acid rain that can eventually lead to the dissolution of calcite in marble and limestones. Calcium oxalate is an inorganic protective agent, which is obtained by treatment with ammonium oxalate. The functionalization of oxalic acid to give monoesters and monoamides (oxamates) allows tailoring the solubility of the relevant ammonium and calcium salts. In this context, theoretical calculations carried out at the Density Functional Theory (DFT) level were exploited to investigate the capability of oxalate, methyloxalate, phenyloxalate, oxamate, methyloxamate, and phenyloxamate to interact with the calcium carbonate lattice. An in-depth validation based on the structural data showed that DFT calculations with the PBE0 functional along with a single or triple-zeta def2 basis set allow understanding the different reactivity of the oxalate and oxamate derivatives and their efficiency in interacting with stones containing calcium carbonate, such as Carrara marble and biomicritic limestones.

Contrasting decay of historical building stone: relationships between petrophysical features and frontal polymerization treatment suitability on medieval buildings of north Sardinia, Italy

Textural, physical–mechanical, and mineralogical–chemical properties influence the degradation of building stone. These properties also control the efficacy of different preventative treatments to inhibit degradation. In this study, several historic buildings in northern Sardinia, Italy, constructed with a wide variety of building stones were examined in order to contrast degradation effects with and without frontal polymerization. Different types of degradation were observed in carbonate and volcanic lithologies, which compromise their durability and toughness. Among the different lithotypes tested, four revealed a good response to the polymerization treatment. Textural and physical–mechanical evidences show that open porosity and capillary absorption control the suitability of this treatment. Laboratory tests on both untreated and treated specimens revealed a strong reduction of parameters directly related to decay (e.g., open porosity and water absorption), as well as an improvement on crush strength. Moreover, the polymerization treatment retains a residual porosity sufficient to enable the rock to equilibrate with the ambient environmental humidity.