Andrea Macchia

XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments

Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate.In this work we have analysed samples from two modern limestone monuments in Rome, the Botticino surfaces of the ‘Vittoriano’ (by G.Sacconi, 1885-1911- Piazza Venezia) and the travertine basement of the ‘Statua dello Studente’ (by A.Cataldi, 1920- University city, La Sapienza), and focussed our investigation on the chemical composition of the copper-stained zones using XPS (X-ray Photoelectron Spectroscopy) as a surface-specific technique.Based on observations reporting on the structure and bonding at the calcite surfaces we have identified copper complexes and mixed calcium/copper carbonates associated with the stains, as well as the chemical state of other elements therein included, and related the compositional changes with differences in chromatic characteristics and sampling locations.

Marine Antifouling for Underwater Archaeological Sites: TiO2 and Ag-Doped TiO2

Marine fouling plays a crucial role in the degradation of underwater archaeological sites. Limitation of fouling activity and its damages are one of the most critical issues for archaeologists and conservators. The common cleaning procedure, consisting in the manual removal of fouling, requires a continuous maintenance, while a proper inhibition of biological colonisation would provide a long-time protection against biofouling. On the other hand, the most used antifouling paints, especially for ship hulls, show considerable toxicity level. Since submerged archaeological sites are often included in environmental protected areas, more eco-friendly products must be used. We have explored the possibility to use titanium dioxide and Ag-doped titanium dioxide as antifouling agents. For this purpose, they have been synthetized by sol-gel method, and then XRD, XPS, and reflectance spectroscopy measurements have been carried out to gain structural information. The powders have been dispersed in a polymer and then applied to marble surface to evaluate the chromatic alteration induced by the treatments. By means of biological tests, it was possible to assess their behaviour as biofouling agents. Results show a decreasing of biofouling activity on treated stony surfaces.

New insights on the consolidation of salt weathered limestone: the case study of Modica stone

The deterioration of a stone material is related to its pore structure, which affects the interaction between surface and environmental agents. Indeed, salt crystallization is one of the most dangerous weathering agents in porous building materials. The crystallization pressure of salt crystals, growing in confined pores, is found to be the main cause for damage. The consolidation of such degraded stone materials represents a crucial issue in the field of restoration of cultural heritage. This paper presents the results of a laboratory experimentation carried out on Modica stone, a limestone largely used in the Baroque architecture of eastern Sicily. Several specimens, collected from a historical quarry near the city of Modica, were artificially degraded by salt crystallization tests. Then, degraded samples were treated with three different consolidating products: a suspension of nanolime in alcohol, a suspension of nanosilica in water, and ethyl silicate dispersed in white spirit. A systematic approach, including mercury intrusion porosimetry, peeling tests and point load test, was used to evaluate the correlation between the salt crystallization and the micro-structural features of the limestone, as well as the efficacy of treatments. The consolidating behavior of the tested products was also appraised by repeating salt crystallization tests after consolidation, in order to assess the resistance of treated stone to further salt crystallization phenomena. Results showed that nanolime provides a good resistance to the stone; conversely, ethyl silicate, although inducing an enhancement of stone cohesion, leads to an increase of the crystallization pressure, which generates dangerous susceptibility to weathering.

Calcium hydroxide nanoparticles and hypogeum environment: test to understand the best way of application

For a long time the conservation of archaeological artefacts has been based on the principles of compatibility and minimal intervention. This involves a series of partially unsolved problems, concerning the products used for deteriorated structures consolidation. The choice of materials depends on several factors such as: microclimatic conditions, application methods, and reaction time of products. Recently the employment of nanolime in the consolidation treatments of decorative carbonate matrix surfaces had a great development, thanks to multifunctional use in calcium standard-sized particles treatments. However, while the use of the nanostructured materials is described in several specialized papers, the information about the best conditions of applicability of the nanolime and its related potentiality for the consolidation in hypogeum environment is rarely considered. The present work is devoted to represent a case study with the aim to give useful elements in order to evaluate the application of nanolime. The funerary inscriptions coming from St. Callixtus Catacombs have been the object of the research carried out in situ and in laboratory, checking indirectly in the short run and in the long run the porosity variation in the materials. The present study intends to indicate the best suspension concentration on consolidation in relationship with hypogeum environment.

Surface and volume non-invasive methods for the structural monitoring of the bass-relief 'Madonna con Bambino' (Gorizia, Northern Italy).

Abstract Structural analysis of marble statues, carried out by non-invasive and in situ methods, is crucial to define the state of conservation of the artworks and to identify the deterioration phenomena that can affect them. In this work, we combined in situ non-destructive techniques, ultrasonic tomography (US), ultraviolet-induced visible fluorescence (UV-IF) and X-ray fluorescence (XRF) to study the bass-relief ‘Madonna con Bambino’ (Gorizia, Italy). The US revealed the presence of some metallic pivots, associated with areas of high sound velocity; moreover, a more degraded area has been identified in the lower part of the bass-relief. The acquired UV-IF image confirmed the presence of surface degradation, allowing a preliminary evaluation of the extension of a fracture, from surface to bulk. In addition, the different materials (both original and/or integrations) that compose the studied surface have been identified. The XRF has contributed to define the nature of the inorganic materials applied during undocumented previous restoration works on the surface as filler for lacunae.

Evaluation of the consolidant efficiency of nanosilica based products on Neapolitan Yellow Tuff

The consolidation of stone materials used in the Cultural Heritage represents a critical issue because of their restoration and conservation. In this regard, Yellow Neapolitan Tuff is not only one of the most used rock but also one of the most affected by degradation phenomena. For this reason, it needs to individuate suitable strategies to preserve efficaciously this material. The consolidant efficiency of innovative nano-silica products was tested in this paper to evaluate their possible use in the conservation of stones employed in Cultural Heritage. The mixtures realized with tuff fragments and consolidants as binder at different concentrations were undergone peeling and point load tests. The results achieved exhibit the suitability of nanosilica products as consolidant in the tuff, suggesting their possible next use in the preservation of stone materials employed in Cultural Heritage.

White zinc in linseed oil paintings: chemical, mechanical and aesthetic aspects

The interest of this research derived from the request for a scientific investigation of the observed phenomenon from by few contemporary artists who, in some occasions, observed the formation of crequalure in rethinking areas where a paint layer of different colour was over imposed to a zinc white layer, on commercial canvases. To investigate this phenomenon several investigations to characterized chemical and physical proprieties of commercial white zinc pigments are carried out: XRD, ICP/OES, SEM/EDS, FTIR, GC-MS. Moreover, to several tests were performed in order to evidence the different behavior of the various white pigments referring to the miscibility and to the drying times. The paper shows how the size of the pigment particles affects the formation and the type of the craquelure.