RESUMO
Volatile Binding Media (VBM) are waxy solids that can be used for temporary consolidation of heritage artifacts and architectural surfaces thanks to their spontaneous sublimation at room temperature. They are used to temporary shelter, consolidate or protect materials during high-risk operation, such as excavation, transportation, water-based treatments, etc. Although they are employed since the 1990s, research focused almost entirely on one of them, cyclododecane (CDD), which is by far the most used in onsite applications. However, CDD exhibits some drawbacks, including a fixed sublimation speed that hardly fits into all the possible applications and climates, hence the development of new VBM is strongly needed. In recent years, a certain attention was addressed to menthol as a possible alternative, but the research on other possible substitutes is still lacking. In this paper, a range of different VBM for temporary consolidation of cultural heritage materials was prepared and investigated, including five pure compounds (CDD, cyclododecanol, cyclododecanone, menthol and camphene) and fifteen mixes. These new materials are expected to provide tunable properties in terms of melting temperatures and sublimation rates, allowing their use in a variety of climatic contexts and applications, and to exhibit better properties for onsite applications compared to CDD, such as lower flash point, lower hazard for conservators' health and/or higher availability.
RESUMO
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.
RESUMO
Reversibility is a mandatory requirement for materials used in heritage conservation, including hydrophobic protectives. Nevertheless, current protectives for stone are not actually reversible as they remain on the surfaces for a long time after their hydrophobicity is lost and can hardly be removed. Ineffective and aged coatings may jeopardise the stone re-treatability and further conservation interventions. This paper aims at investigating the performance of PHAs-based coatings for stone protection, their main potential being the 'reversibility by biodegradation' once water repellency ended. The biopolymer coatings were applied to three different kinds of stone, representative of lithotypes used in historic architecture: sandstone, limestone and marble. Spray, poultice and dip-coating were tested as coating techniques. The effectiveness and compatibility of the protectives were evaluated in terms of capillary water absorption, static and dynamic contact angles, water vapour diffusion, colour alteration and surface morphology. The stones' wettability after application of two commercial protectives was investigated too, for comparison. Finally, samples were subjected to artificial ageing to investigate their solar light stability. Promising results in terms of efficacy and compatibility were obtained, although the PHAs-based formulations developed here still need improvement for increased durability and on-site applicability.
RESUMO
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 sample's 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.
