Enrico Sassoni

Correlation between microstructural characteristics and weight loss of natural stones exposed to simulated acid rain

The correlation between stone microstructural characteristics and material degradation (in terms of weight loss), in given environmental conditions, was investigated. Seven lithotypes, having very different microstructural characteristics, were used. Four acidic aqueous solutions were prepared to simulate acid rain (two adding H(2)SO(4) and two adding HNO(3) to deionized water, in order to reach, for each acid, pH values of 5.0 and 4.0), and deionized water at pH=5.6 was used to simulate clean rain. Stone samples were then immersed in such aqueous solutions, the surface alteration being periodically inspected and the weight loss periodically measured. After 14 days of immersion, a good correlation was found between weight loss and the product of carbonate content and specific surface area in the starting materials. This was explained considering that this product accounts for the weight loss owing to the samples fraction actually composed of calcite (the most soluble fraction) and the effective surface area exposed to dissolving solution (which depends on stone porosity and pore size distribution). Such correlation between stone microstructure and degradation may be useful for comparing the durability of different lithotypes, in given environmental conditions, and quantitatively predicting the weight loss of a lithotype, compared to another one. Hence, the correlation found in this study may be used to specifically tailor to various stone types, with different microstructural characteristics, some results that have been calculated in literature for specific stone types and then proposed as possibly representative for a broad category of stones with similar characteristics.

Consolidation of porous carbonate stones by an innovative phosphate treatment: mechanical strengthening and physical-microstructural compatibility in comparison with TEOS-based treatments

For preservation of stones used in Cultural Heritage, affected by weathering processes that threaten their cohesion and mechanical properties, the application of consolidants is a common practice. However, available consolidating products generally exhibit some drawbacks that hinder their performance, in terms of either mechanical efficacy, compatibility with the substrate and/or durability. Ethyl silicate is currently the most widely used among stone consolidants; nevertheless, its reduced efficacy on calcitic substrates, together with its temporary hydrophobicity, its tendency to crack and its common formulation with volatile organic solvent, make the research for alternative consolidants for carbonate stones necessary. In this paper, a recently proposed new consolidation treatment based on the formation of hydroxyapatite inside the stone was tested on two different porous carbonate stones (Globigerina Limestone and Giallo Terra di Siena), and compared with TEOS-based treatments, frequently used for the consolidation of these lithotypes. The results show that the hydroxyapatite treatment exhibits a good efficacy in terms of mechanical properties and, compared to TEOS, it causes less pronounced alterations in open porosity and water transport properties. This makes the new treatment a potentially valid alternative to TEOS, especially in those situations where the possible presence of water behind the consolidated layer (e.g. in case of rising damp, condensation or infiltration) might threaten the durability of the consolidation intervention.

Strengthening of Masonry Elements by FRP: Influence of Brick Mechanical and Microstructural Properties

In this paper, the effect of several brick and mortar mechanical and microstructural parameters on the maximum debonding force of the same glass fiber reinforced polymer (GFRP), applied on different bricks and on corresponding masonry panels, was investigated. GFRP sheets were bonded by epoxy resin to four different types of solid fired-clay brick and four types of masonry panels, manufactured using the same bricks and a natural hydraulic lime mortar. The reinforced specimens were subjected to bond tests to evaluate the maximum debonding force. Bricks and mortar were characterized in terms of compressive strength (in the case of bricks, along two different orthogonal directions), surface roughness and pore size distribution. Based on the results of the study, alongside brick mechanical properties in different directions, also brick microstructural parameters seem to play a very important role, which should be taken into account for fully explaining the experimental results.

Influence of sample thickness and capping on characterization of bedding mortars from historic masonries by double punch test (DPT)

For determination of compressive strength of bedding mortar used in historic masonries, a promising moderately-destructive technique is double punch test (DPT). DPT consists of loading prismatic samples of mortar (about 4×4×1 cm3) by means of two circular steel platens (typically 2 cm diameter) and then calculating mortar compressive strength as the ratio of the failure load to the cross section of the circular platens. In this study, the influence of mortar sample thickness and mortar sample capping on the reliability of results obtained by DPT was systematically investigated. The influence of sample thickness was assessed by comparing DPT results obtained for samples with 5, 10, 15 and 20 mm thickness with compressive strength determined by testing reference 4 cm-side cubes. Different mortars were considered (cement, lime-cement, natural hydraulic lime), in order to investigate a wide range of mortar mechanical characteristics. The influence of surface capping was evaluated on a lime-cement mortar by comparing compressive strength determined on reference cubes with strength obtained by DPT on proper samples, without capping and after capping with rubber, gypsum and cement. The results of the study indicate that sample thickness substantially influences mortar compressive strength determined by DPT, which may vary by up to three times depending on sample thickness. A good estimation of the actual mortar compressive strength was obtained when samples with thickness similar to the loading platens diameter were tested, which suggests that choosing the size of the loading platens for DPT based on the thickness of mortar joints under investigation may be an effective way for obtaining reliable estimations. As for the influence of surface capping, in those cases where no mortar sample regularization is possible, because of the poor quality of the mortar, the results of the study indicate that sample capping actually seems necessary in order to avoid significant underestimations of mortar compressive strength. Considering the higher practicality offered by gypsum with respect to rapid-setting cement for surface capping, the use of gypsum seems preferable.

Consolidation of Carrara Marble by Hydroxyapatite and Behaviour After Thermal Ageing

In this study, the use of hydroxyapatite (HAP), recently proposed for limestone consolidation, was investigated on unweathered and artificially weathered Carrara marble and the behaviour of HAP-treated samples towards thermal weathering was evaluated, by means of an accelerated thermal weathering test. The results of the study indicate that HAP is a very promising consolidant for marble, able to significantly improve mechanical properties without substantially altering pore size distribution and to provide some mitigation against thermal weathering.

Hydroxyapatite and Other Calcium Phosphates for the Conservation of Cultural Heritage: A Review

The present paper reviews the methods and the performance of in situ formation of calcium phosphates (CaP) for the conservation of materials belonging to cultural heritage. The core idea is to form CaP (ideally hydroxyapatite, HAP, the most stable CaP at pH > 4) by reaction between the substrate and an aqueous solution of a phosphate salt. Initially proposed for the conservation of marble and limestone, the treatment has been explored for a variety of different substrates, including sandstones, sulphated stones, gypsum stuccoes, concrete, wall paintings, archaeological bones and paper. First, the studies aimed at identifying the best treatment conditions (e.g., nature and concentration of the phosphate precursor, solution pH, treatment duration, ionic and organic additions to the phosphate solution, mineralogical composition of the new CaP phases) are summarized. Then, the treatment performance on marble and limestone is reviewed, in terms of protective and consolidating effectiveness, compatibility (aesthetic, microstructural and physical) and durability. Some pilot applications in real case studies are also reported. Recent research aimed at extending the phosphate treatment to other substrates is then illustrated. Finally, the strengths of the phosphate treatment are summarized, in comparison with alternative products, and some aspects needing future research are outlined.

Durable Self-Cleaning Coatings for Architectural Surfaces by Incorporation of TiO2 Nano-Particles into Hydroxyapatite Films

To prevent soiling of marble exposed outdoors, the use of TiO2 nano-particles has been proposed in the literature by two main routes, both raising durability issues: (i) direct application to marble surface, with the risk of particle leaching by rainfall; (ii) particle incorporation into inorganic or organic coatings, with the risk of organic coating degradation catalyzed by TiO2 photoactivity. Here, we investigated the combination of nano-TiO2 and hydroxyapatite (HAP), previously developed for marble protection against dissolution in rain and mechanical consolidation. HAP-TiO2 combination was investigated by two routes: (i) sequential application of HAP followed by nano-TiO2 (“H+T”); (ii) simultaneous application by introducing nano-TiO2 into the phosphate solution used to form HAP (“HT”). The self-cleaning ability was evaluated before and after prolonged exposure to simulated rain. “H+T” and “HT” coatings exhibited much better resistance to nano-TiO2 leaching by rain, compared to TiO2 alone. In “H+T” samples, TiO2 nano-particles adhere better to HAP (having flower-like morphology and high specific surface area) than to marble. In “HT” samples, thanks to chemical bonds between nano-TiO2 and HAP, the particles are firmly incorporated in the HAP coating, which protects them from leaching by rain, without diminishing their photoactivity and without being degraded by them.

Photocatalytic hydroxyapatite-titania nanocomposites forpreventive conservation of marble

Soiling of external surfaces is an increasing issue for conservation of architectural heritage. Providing architectural surfaces with self-cleaning ability is one of the most promising routes of preventive conservation. To this aim, several methods have been proposed in the literature, based on the use of photocatalytic TiO2 nanoparticles, either directly applied onto the surfaces or incorporated in protective coatings. However, when nano-TiO2 is directly applied onto architectural surfaces, the particles are easily removed by rain. When TiO2 is incorporated in polymeric coatings, durability issues arise as well, because the photoactivity of TiO2 nanoparticles can promote degradation of the polymer. Here, we present an innovative alternative method, based on combination of TiO2 nanoparticles and hydroxyapatite (HAP). The incorporation of nano-TiO2 into an HAP coating protects the nanoparticles from leaching by rain, thanks to the chemical bonding between TiO2 and HAP, without diminishing their photoactivity. As a result, marble treated with HAP-TiO2 composites exhibits high self-cleaning ability and high durability, with results superior to those achieve by direct application of nano-TiO2 onto the surface, as frequently performed on site.