Effectiveness and durability of anti-graffiti products applied on ETICS: towards a compatible and sustainable graffiti removal protocol.

External Thermal Insulation Composite Systems (ETICS) are widely used constructive solutions which aim at enhancing the building thermal performance. Nevertheless, ETICS can often present anomalies (e.g., stains and microcracks) throughout their service life, and vandalism actions, as in the case of graffiti, are rather common in urban areas. The removal of undesired graffiti is generally carried out through invasive chemical-mechanical methods, which may affect the durability of the ETICS. The adoption of anti-graffiti products can be a feasible protection method; however, no comprehensive studies were already addressed on these substrates. This study aims at evaluating the effectiveness, compatibility, and durability of three anti-graffiti products (with permanent, semi-permanent, and sacrificial properties) when applied on different ETICS. The removal of aerosol graffiti paints was carried out with a low-invasive and eco-friendly removal method (i.e., low-pressure steam jet). The water transport properties, as well as color, gloss, and roughness, were evaluated before and after graffiti removal. The durability of the anti-graffiti was also assessed by artificial aging cycles. Results showed that graffiti removal was rather efficient on ETICS with acrylic-based finishing coats and when using (semi) permanent anti-graffiti products (with ΔE*ab < 5, i.e., not macroscopically visible, when comparing cleaned and reference surfaces), although these products can reduce their effectiveness after aging. Conversely, unsatisfactory graffiti cleaning was observed on ETICS with lime-based or silicate-based finishing coats (with ΔE*ab > 5), with considerable alteration also of the water transport properties (reducing water absorption and slowing down the drying kinetic).

The influence of the SO2 ageing on the graffiti cleaning effectiveness with chemical procedures on a granite substrate.

Graffiti are one of the most severe threats to Stone Cultural Heritage and are most of the times removed after long periods of environmental exposure. This research intends to evaluate the influence of the ageing of the graffitis on the effectiveness of their cleaning. So, comparative studies on unaged and on artificially SO2 aged samples were conducted. Four graffiti spray colours were applied on a granite stone and cleaned with two chemical commercial cleaners: a solution of KOH and a solution of n-butyl acetate, xylene and alcohol isobutyl. The spray paints (unaged and aged) and cleaning effectiveness were characterized by stereomicroscopy, colour spectrophotometry, adhesion tests, SEM, µEDXRF, XRD and FTIR. The cleaning effectiveness was also evaluated through surface roughness and static contact angle measurements. The alkyd graffiti paints presented greatest resistance under SO2 rich environments than the polyethylene paint. The aged polyethylene paint showed chemical modifications that resulted in graffiti losses and neo formed mineralogical phases in the surface of the paint. After ageing, the paints became more difficult to clean, showed higher global colour changes and higher residue percentages. No significant roughness variations were detected after chemical cleaning. After the cleaning procedures aged surfaces became more water repellent comparatively to unaged and reference samples. The best cleaning effectiveness was mainly achieved with the potassium hydroxide solution.

Assessing the effects of UVA photocatalysis on soot-coated TiO2-containing mortars.

The deposition of soot on building surfaces darkens their colour and leads to undesirable black crusts, which are one of the most serious problems on the conservation of built cultural heritage. As a preventive strategy, self-cleaning systems based on the use of titanium dioxide (TiO2) coatings have been employed on building materials for degrading organic compounds deposited on building surfaces, improving their durability and performance. In this study, the self-cleaning effect of TiO2-containing mortars coated with diesel soot has been appraised under laboratory conditions. The mortar samples were manufactured using lime putty and two different doses of TiO2 (2.5% and 5%). The lime mortars were then coated with diesel engine soot and irradiated with ultraviolet A (UVA) illumination for 30days. The photocatalytic efficiency was evaluated by visual inspection, field emission scanning electron microscopy (FESEM) and colour spectrophotometry. Changes in the chemical composition of the soot particles (including persistent organic pollutants) were assessed by analytical pyrolysis (Py-GC/MS) and solid state 13C NMR spectroscopy. The FESEM and colour spectrophotometry revealed that the soot-coated TiO2-containing mortars promoted a self-cleaning effect after UVA irradiation. The combination of analytical pyrolysis and 13C solid state NMR showed that the UVA irradiation caused the cracking of polycyclic aromatic structures and n-alkyl compounds of the diesel soot and its transformation into methyl polymers. Our findings also revealed that the inclusion of TiO2 in the lime mortar formulations catalysed these transformations promoting the self-cleaning of the soot-stained mortars. The combined action of TiO2 and UVA irradiation is a promising proxy to clean lime mortars affected by soot deposition.

Biodiversity of cyanobacteria and green algae on monuments in the Mediterranean Basin: an overview.

The presence and deteriorating action of micro-organisms on monuments and stone works of art have received considerable attention in the last few years. Knowledge of the microbial populations living on stone materials is the starting point for successful conservation treatment and control. This paper reviews the literature on cyanobacteria and chlorophyta that cause deterioration of stone cultural heritage (outdoor monuments and stone works of art) in European countries of the Mediterranean Basin. Some 45 case studies from 32 scientific papers published between 1976 and 2009 were analysed. Six lithotypes were considered: marble, limestone, travertine, dolomite, sandstone and granite. A wide range of stone monuments in the Mediterranean Basin support considerable colonization of cyanobacteria and chlorophyta, showing notable biodiversity. About 172 taxa have been described by different authors, including 37 genera of cyanobacteria and 48 genera of chlorophyta. The most widespread and commonly reported taxa on the stone cultural heritage in the Mediterranean Basin are, among cyanobacteria, Gloeocapsa, Phormidium and Chroococcus and, among chlorophyta, Chlorella, Stichococcus and Chlorococcum. The results suggest that cyanobacteria and chlorophyta colonize a wide variety of substrata and that this is related primarily to the physical characteristics of the stone surface, microclimate and environmental conditions and secondarily to the lithotype.

Reproducing stone monument photosynthetic-based colonization under laboratory conditions.

In order to understand the biodeterioration process occurring on stone monuments, we analyzed the microbial communities involved in these processes and studied their ability to colonize stones under controlled laboratory experiments. In this study, a natural green biofilm from a limestone monument was cultivated, inoculated on stone probes of the same lithotype and incubated in a laboratory chamber. This incubation system, which exposes stone samples to intermittently sprinkling water, allowed the development of photosynthetic biofilms similar to those occurring on stone monuments. Denaturing gradient gel electrophoresis (DGGE) analysis was used to evaluate the major microbial components of the laboratory biofilms. Cyanobacteria, green microalgae, bacteria and fungi were identified by DNA-based molecular analysis targeting the 16S and 18S ribosomal RNA genes. The natural green biofilm was mainly composed by the Chlorophyta Chlorella, Stichococcus, and Trebouxia, and by Cyanobacteria belonging to the genera Leptolyngbya and Pleurocapsa. A number of bacteria belonging to Alphaproteobacteria, Bacteroidetes and Verrucomicrobia were identified, as well as fungi from the Ascomycota. The laboratory colonization experiment on stone probes showed a colonization pattern similar to that occurring on stone monuments. The methodology described in this paper allowed to reproduce a colonization equivalent to the natural biodeteriorating process.