Assessment of synthetic polymeric coatings for the protection and preservation of stone monuments

The performance of five synthetic coatings for the protection of stone monuments of Hellenistic and Byzantine period has been evaluated. The selected coatings included four commercially available siloxane-, siloxane/acrylic- and perfluoroether-based compositions, as well as a new composition based on newly synthesized fluoro-organosilane. The coatings were applied onto petrologically different stone substrates, such as marble, travertine, sandstone and a newly baked brick compatible with Roman period bricks, used for the restoration processes in Galerius Palace, Thessaloniki, Greece. The coatings' protective efficiency was investigated by measurement of water–stone contact angles, water vapor permeability, and water absorption by capillarity. The optical properties of the applied coatings were also investigated and they were also ranked with regard to their optical characteristics.     

Methyl–modified hybrid organic-inorganic coatings for the conservation of copper

A simple sol-gel technique for the preparation of methyl–modified silica coatings for the protection of the external surface of copper has been used in this study. Tetraethylorthosilicate (TEOS) has been used as a precursor to prepare nanosilica coatings on the surface of copper. The methyl–modified silica sols were obtained by mixing of 3% SiO₂ sol solution with trimethylchlorosilane (TMCS) or hexamethyldisilozane (HMDS) as basic materials. For comparison, the copper substrates were also coated with commercial polymers (Paraloid B 72, Plexisol P 550-40 and polyvinyl butyral (PVB)). The surface morphology changes of uncoated and coated specimens were investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The hydrophobicity of surfaces and photochemical ageing effects were evaluated by contact angle measurements. Potentiodynamic measurements were obtained in order to compare corrosion parameters of the coatings.     

Self-cleaning materials on Architectural Heritage: Compatibility of photo-induced hydrophilicity of TiO2 coatings on stone surfaces

Titanium dioxide (TiO₂) can be used to realize transparent self-cleaning coatings on stone surfaces as an active and preventive protection system, limiting cleaning and maintenance actions, reducing their costs in Architectural Heritage. This self-cleaning ability is due to photo-induced hydrophilicity on treated surfaces. The aim of this investigation is to analyze this effect, since it could bring to a greater water absorption, a potential source of damage for stone surfaces. Titania sol, obtained by sol-gel and hydrothermal processes, was deposited on travertine by spray coating, in two different ways. Water absorption by capillarity, static contact angle and a specific surface water absorption analysis were assessed before and after the TiO₂ treatments. The effects of deposited amount of titania on the characteristics of treated surfaces were evaluated. It was shown that there were no evident changes in the substrate reactivity without ultraviolet (UV) light exposure, while it seems that hydrophilicity due to UV light does not lead to higher water absorption, thus encouraging the use of TiO₂ coatings in the field of Architectural Heritage. However, before widely applying this conservative treatment, some further researches are recommended in order to better assess its durability and sustainability.     

A visible and long-wavelength photocured epoxy coating for stone protection

An epoxy coating modified by PDMS hydroxyl terminated is presented in this paper in order to evaluate its potential use as a protective of a stone surface. With a view to its use in restoration sites, visible and long-wavelength photoinitiated cationic polymerization is proposed here. The system investigated is based on a crosslinking mechanism which shows remarkable advantages for stone protection, such as the low toxicity of the products and facility of mixture preparation. Furthermore, the visible light exploitation represents the most important advantage, because it is easy to apply in a restoration site, with or without irradiation instruments. Besides coating characterization through FT-IR, DMTA analyses and contact angle measurement on glass slides, analyses were also carried out on coated plaster samples. These analyses were performed in order to evaluate the effectiveness of the protective, in relationship to hydrophobicity (contact angle measurement, capillary water absorption) and morphology surface changing (SE/SEM observations, colorimetric measurements) before and after polymer application and UV aging test of coated samples. The overall characterization makes it possible to consider it a suitable coating for stone protection.     

Effects of silica nanoparticle and GPTMS addition on TEOS-based stone consolidants

Consolidants based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying stone heritages. These products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the material. However, TEOS-based consolidants suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developed capillary force, which is typical for TEOS-based consolidants. We have prepared new consolidants TEOS-based consolidants containing flexible (3-glycidoxypropyl) trimethoxysilane (GPTMS) and silica nanoparticles in order to reduce capillary force development during gel drying, and have characterized them for the application of stone consolidants. Different sizes of silica nanoparticles were used, which were smaller than the pore size of the tested stone. The properties of the TEOS/GPTMS/nanoparticle composite solution were compared with those of the commercial products Wacker OH and Unil sandsteinfestiger OH 1:1. The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/nanoparticle solution was stable over a period of up to six months. The contact angle of the surface increased with the addition of the nanoparticle, as well as with the addition the GPTMS, which is higher than that of commercial Wacker OH. The addition of a nanoparticle, as well as GPTMS having flexible segment, provided a crack-free material, while the gels obtained from the commercial consolidants exhibited cracking.     

Tailoring new fluorinated acrylic copolymers as protective coatings for marble

The protective performances of two new fluorinated acrylic copolymers (based on the monomers 1H,1H,2H,2H-perfluorodecyl methacrylate (XFDM) and 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIM) are evaluated and compared with Paraloid B72, a commercial copolymer ethyl methacrylate/methyl acrylate (EM/MA) and its partially fluorinated homologous 2,2,2-trifluoroethyl methacrylate/MA (TFEM/MA). The polymeric materials have been tested on Candoglia marble, a very low open porosity stone (<1%) used in Italian historical architecture (Milan Cathedral). The copolymers were tested according to UNI-Normal protocol. Measurements of capillary water absorption, static contact angles, colour variation and water vapour permeability were made before and after accelerated photo-ageing. FTIR spectroscopy and size exclusion chromatography (SEC) analyses were carried out on samples aged on inert substrate to assess the photostability of the copolymers themselves. The relationship between the protection efficacy and the fluorine content and distribution has been investigated. The results obtained show that the addition of a partially fluorinated co-monomer to the Paraloid B72 copolymer structure did not result in the expected improvement of the coating properties, while the fluorination of the copolymer side chain gave rise to encouraging performance.     

Use of ZnO nanoparticles for protecting oil paintings on paper support against dirt,fungal attack,and UV aging

Zinc oxide nanoparticles were prepared and used for surface treatment of oil paintings painted on paper supports. The prepared coating mixture containing 2% of ZnO nanoparticles showed excellent transparency. The effect of coating on protecting the paper support and paintings against microbial attack by Trichoderma reesei and Aspergillus niger, dirt accumulation, and UV aging was studied. Coatings containing ZnO nanoparticles enhanced the durability of linseed oil-based paintings toward UV aging regarding the change in color. Coatings containing ZnO nanoparticles improved resistance to microbial attack when subjected to inoculums containing T. reesei or A. niger fungi. In addition, coatings containing ZnO nanoparticles reduced accumulation of dirt on oil paintings when left in open air for 6 months; cleaning of paintings was quite easy compared to the non-coated paintings or those coated with the varnish without ZnO nanoparticles.     

Excimer laser removal of beeswax from galician granite monuments

The paper presents the use of laser radiation for cleaning of beeswax treated granite stone. In the early sixties, prestigious restorers decided to apply molten beeswax on the granite surface of valuable monuments with the aim of preventing the erosive action of atmospheric agents. An interesting example of this treatment is the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). With time, salt accumulation beneath the beeswax layer has caused an intense surface disintegration of granite. Conventional cleaning methods can destroy sculptured details of these emblematic monuments. For this reason, excimer laser cleaning has been chosen as a promising non contact, selective and environmentally friendly cleaning technique to be studied.The cleaning tests have been carried out using an excimer laser (ArF, 193 nm), with fluences between 0.5 and 2 J cm⁻² pulse⁻¹ and a spot area of 0.025 cm². Samples representing beeswax films over Roan granite have been irradiated and their degree of cleaning has been studied as a function of the number of pulses and the laser fluence.Cleaning efficiency has been evaluated by FT-Raman Spectroscopy, allowing to establish the beeswax ablation threshold and the ablation rate.Excimer laser cleaning allows a progressive and controlled removal of a few tenths of micrometers of beeswax per pulse without damaging the underlying granite stone.     

Testing a fluorinated compound as a protective material for calcarenite

A polyfluorinated compound was studied as a material for the specific protection of calcarenite. Water capillary absorption and vapour permeability measurements were carried out in order to evaluate efficiency as a protective agent. Particular attention was given to characterising its resistance against bio-deterioration induced by microorganisms such as blue and green algae. Chemical surface modifications were induced by UV-irradiation in a specially designed climatic chamber and were investigated through comparative tests on untreated and artificially weathered samples using X-ray photoelectron spectroscopy (XPS). This paper discusses the potential use of the compound studied as a specific coating material for the protection of calcarenite.     

Consolidation and protection by nanolime: Recent advances for the conservation of the graffiti,Carceri dello Steri Palermo and of the 18th century lunettes,SS. Giuda e Simone Cloister,Corniola (Empoli)

Nanolime dispersed in 2-propanol was extensively used for the consolidation of wall paintings. The knowledge of the advances of this methodology dealing with all the possible effects associated with the nanolime new material in conservation is fundamental to assess and improve the technique. In this paper, four different dispersions of Ca(OH)₂ nanoparticles were characterised by Small Angle X-rays Scattering technique (SAXS) and Transmission Electron Microscopy (TEM) in order to achieve information on size, shape, polydispersity, agglomeration, and crystal structure (by SAED patterns) of the particles. Once characterised, the dispersions were tested in two different case studies, the Carceri dello Steri in Palermo with their graffiti and the 18th century lunettes at the SS. Giuda e Simone Cloister, Corniola (Empoli) with their lime-based mural paintings. The treated samples were characterised in relationship to either their morphology and surface chemical composition by Scanning Electron Microscopy coupled with Energy Dispersive X-rays spectroscopy (SEM-EDX), or their water absorption and mechanical properties (resistance to material abrasion). The results obtained showed that all the dispersions were nanometrically structured and their application succeeded in recovering the mechanical properties of the painting or graffito layers, not altering their permeability to water and keeping perfectly the wall transpiration. However, the dispersions constituted of the nanoparticles obtained via a synthesis able to control size and shape of the Ca(OH)₂ particles resulted in a better performance in situ, even if the differences found by SAXS and TEM were slight.     

Combined tannate/decanoate coatings

This study focused on tannate and decanoate coatings on iron surfaces and their potential combinations. The properties of the coatings were evaluated using a broad range of methods: spectrophotometry, contact angles measurement, impedance spectroscopy, mass gain, glow discharge optical emission spectroscopy (GD-OES), resistometry, and exposure experiments complete with digital image analysis. A decanoate coating was superior in a humid environment (low wettability and water vapour permeability) than tannate. A combined coating, with tannate deposited initially and then sealed in a decanoate bath, appeared to provide an ideal coating.     

Consolidation of carbonate stones: Influence of treatment procedures on the strengthening action of consolidants

This article demonstrates the importance of treatment application procedures on the consolidation effectiveness obtained by comparison of the results obtained using three different consolidants on four carbonate stone types, and proposes a general methodology for assessing the potential effectiveness of consolidants in laboratory conditions. It stresses the relevance of taking into account the treatment methodology, given the influence application protocols can have on the overall behaviour of the consolidated material. Several mechanical properties were assessed to demonstrate this influence on the performance of the consolidant. The results demonstrate that the strengthening action achieved with a specific product can only be defined in a strict relation to the treatment protocol used to produce it. The results also contribute towards the definition of standard testing protocols on stone consolidation. The application of a consolidant by direct contact capillary absorption is a reliable procedure and the results are easier to interpret than others obtained by brushing or by full immersion, thus making this procedure a good candidate for an eventual standard laboratory assessment method of the consolidation action of any specific stone/consolidant combination. This study also showed that the best test method to assess the strengthening action of stone consolidants in soft stones is DRMS (Drilling Resistance Measuring System). Moreover, the collection of longitudinal ultrasound velocity profiles determined in stones specimens treated by contact capillary absorption was shown to be a useful non-destructive method to assess the depth of the strengthening action achieved.     

Effectiveness of antigraffiti treatments in connection with penetration depth determined by different techniques

The elimination of spray paint using traditional (chemical and mechanical) methods inevitably entails altering surface characteristics. Hence, the impact and deterioration caused by graffiti in heritage buildings and monuments have led to the development and application of preventive systems in the form of antigraffiti coatings (which prevent paint from seeping into the pores of the surface material and facilitate cleaning). The effectiveness of two of these treatments, a commercial product (fluoroalkyl siloxane, protectosil, marketed by Degussa) and a hybrid organic-inorganic material (Ormosil), was evaluated in five construction materials (limestone, granite, cement mortar, lime mortar and brick), in terms of their penetration into the substrate. A number of techniques were used to determine the penetration depth (SEM/EDX, micro-Raman and LIBS), because a comparative analysis showed that none was universally valid for all types of treatments. The results show that the presence of the coating on the surface of less porous materials only ensures effective cleaning when the surface is fairly smooth. In granite, for instance, the CF₃ terminals in the fluorinated treatment hinder spray paint bonding more effectively than Ormosil, but not efficiently enough to ensure complete removal of the paint from granite surfaces.     

GPR survey to study the restoration of a Roman monument

This paper describes the ground-penetrating radar (GPR) survey carried out on the Roman theatre of Sagunto (Valencia, Spain) following recent restoration work in 1991. The structure has been substantially altered a number of times: it was remodelled during the Roman and Moorish periods, partially destroyed during the Peninsular War (1808–1814) and the Carlist War (1833–1839), and extensively modified during the 1930s and 1950s. Major reconstruction work was carried out in 1991 to convert the building into a working theatre. The GPR survey was performed to detect the possible effects of the 1991 remodelling on the historical remains and to identify the point of contact between the present-day modifications and the Roman remains. We took several on-site measurements of the wave velocity in the different materials in known areas to determine as accurately as possible the depth of the contact point. The velocity was calculated by measuring the depth in these areas and the two-way travel time of the wave. The measurements were taken from the walls and the tiers as the thicknesses of the materials were known in these areas. The recorded values were compared with the velocities reported by other authors and with the information from diffraction hyperbolas recorded in the radar data, which are caused by small objects inserted in the medium. We used these velocities to determine the exact point of contact between the Roman remains and the materials used in later restorations. The contact points cause the reflections that can be seen in the GPR data. The results also reveal considerable variations in the surface of the Roman tiers, which can be attributed to partial erosion in these areas caused mainly by water.     

The origin of syngenite in black crusts on the limestone monument King's Gate (Belgrade Fortress,Serbia) – the role of agriculture fertiliser

Black crusts formed on limestone built into the King's Gate represent the most important process in stone deterioration that is occurring in this part of the monumental complex of the Belgrade Fortress (Serbia). Of special importance is the association of salts (namely gypsum and syngenite). Syngenite is a common secondary deposit on granite monuments and on medieval stained glass (i.e., on K-containing materials). However, its appearance over calcareous substrates is not apparent, particularly in cases where cement mortar was not used for bounding. The origins of the potassium and sulphate ions required for syngenite formation are related to meteoritic water, which penetrates the soil above the arch of King's Gate. Water dissolves some soil components and becomes enriched with various ions before coming into contact with the limestone blocks. Enriched water contains two times more K⁺ and SO₄^2? ions than pristine meteoritic water does. The source of the required ions is potassium-sulphate that is present in agricultural fertilisers that are used above the monument. The proposed mechanism for syngenite formation was additionally supported with laboratory experiment. The results of X-ray diffractometry and SEM-EDS analyses of limestone treated with potassium-sulphate solution and sulphuric acid suggest the possibility that the syngenite was formed over calcite:CaCO₃ + K₂SO₄ + H₂SO₄ → K₂Ca(SO₄)₂ H₂O + CO₂↑However, the complex mechanisms of gypsum and syngenite formation under natural conditions (variable concentration of potassium and sulphate ions, intermediates phases, temperature changes, humidity, the amount of disposable water etc.) do not exclude the possibility of syngenite formation over gypsum.     

Investigation of the technology of historic mortars

Historical evidence on the use of mortars to meet several needs has existed for millennia. With reference to the characteristic historical periods of the city of Rhodes, mortar sampling was performed on historical constructions, masonry and architectural surfaces. In the present work the different mortar technologies are investigated aiming to answer questions regarding their finality, i.e. whether their differences arise mainly from the various historical periods of construction or from the purposes they had to serve, imparting to the mortars the properties required by their function in the structure. Mineralogical, chemical, physical and mechanical investigations have been performed on characteristic samples after gradation. The exponentially declining function of the ratio CO₂/H₂O structurally bound to the CO₂ content shows a continuous evolution of the kinetics governing the various mechanisms of carbonation of the binder or the formation of hydraulic components during setting, hardening and ageing of the mortars. The grouping of mortars in well-distinct ‘hydraulic levels’ is ascribed to the physico-chemical cohesion and adhesion bonds developed at the matrix and matrix/aggregate interfaces, respectively, allowing for the mortars to either bear continuous stresses and strains as joint mortars or provide compact impermeable renderings which harden even more on contact with water. Hence, parameters determining the diversification of the resulting mortar/matrix types concern the raw materials employed as binding materials and the production processing.     

Effect of the addition of hydroxyl-terminated polydimethylsiloxane to TEOS-based stone consolidants

Hybrid stone consolidants prepared from tetraethoxysilane (TEOS) and α,ω-hydroxyl-terminated polydimethylsiloxane (PDMS-OH) have been considered as one of the most promising approaches to improve the effectiveness of traditional alkoxysilane-based formulations. They have emerged as response to the negative reports commonly found in the literature: the resulting silica gel phase (SiO₂) tends to develop fractures and fissures inside the stone as the gel shrinks during the drying stage. In this work, we employed SEM, solid-state ²⁹Si NMR spectroscopy and compressive tests to characterize SiO₂-PDMS hybrid gels. We report the morphological characteristics exhibited by gels prepared in vitro and in situ. It was found an appreciable reduction of gel fracture for hybrids prepared from 5% w/w of PDMS. As TEOS polycondenses, PDMS-OH is chemically incorporated into the gel matrix via Si-O-Si bonds. The inclusion of these elastic chains provides the necessary flexibility to resist the stress imposed by capillary pressure. Additionally, an important hydrophobic character is imparted to the stone.     

Deacidification of paper using dispersions of Ca(OH)2 nanoparticles in isopropanol. Study of efficiency

The efficiency of a recently described non-aqueous method for paper deacidification using Ca(OH)₂ nanoparticles in isopropanol was evaluated by pH and colorimetric measurements and by the analysis of the degree of polymerization (DP). Samples of plain paper and paper with iron gall ink were tested. The results were compared with non treated samples and samples submitted to the traditional treatment with saturated aqueous Ca(OH)₂ solution. By comparing the two conservation methods, the aqueous one shows higher neutralization reaction kinetics than the non-aqueous one. The iron gall ink samples maintain their coloration closer to the original after the non-aqueous Ca(OH)₂ nanoparticles treatment, in contrary to the aqueous treatment that changes the ink aesthetics considerably. Artificial aging tests revealed a general increase in the aging stability of deacidified paper samples. The Ca(OH)₂ nanoparticles treatment can be an alternative for papers who can not be treated by the classical aqueous treatment, e.g. papers with water soluble components.     

Silica glass interaction with calcium hydroxide: a surface chemistry approach

The study of the interaction between silica glass and saturated Ca(OH)₂ solutions can be a useful approach to resolve the problem of the adhesion between lime-sand mortar and clay bricks. Since it is reasonable that the silica–calcium hydroxide system well simulates a brick–mortar system, experimental observations concerning the interaction of silica glass and this strong basic solution should be of value for the comprehension of the chemical reactions that could take place at the mortar–brick interface, maybe affecting the adhesion between the two building materials. We demonstrated the effects of saturated Ca(OH)₂ solutions on commercial pure silica glass (fused silica) and on silica films obtained via a sol–gel process by means of dip-coating. Silica samples were dipped in the solutions at different temperatures (room temperature, 60 and 80 °C) and at different time intervals (1 and 21 h) and then they were analysed by means of surface techniques: X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and atomic force microscopy (AFM). It has been shown that Ca(OH)₂ reacts with the silica glass network. The experimental results clearly show a very different behaviour of sol–gel silica with respect to fused silica, probably because of their different nanostructure. Many problems concerning the interaction of silica and Ca(OH)₂ are still to be solved, but the results of this research strengthen the idea that adhesion between lime-sand mortar and clay bricks is caused not only by carbonation of calcium hydroxide contained in the mortar, but even by some chemical reactions involving the brick constituents and calcium hydroxide itself. The final products, calcium silicates, may induce a chemical continuity between lime-sand mortar and clay bricks.     

On the use of ASTM closed vessel tests in accelerated ageing research

The ASTM D6819-02e3 standard for testing the accelerated ageing of paper, published in 2002, recommends using closed glass vials in order to keep the degradation products in contact with the paper and thus permitting a better simulation of the natural ageing conditions inside closed books. In the present study, the actual conditions and their stability inside closed vessels have been evaluated. The necessity of assuring a very high sealing performance (tightness) of the systems in order to avoid leakage of water vapour is the main drawback of this ageing method. Systematic studies presented in this publication tried to monitor this tightness and have provided data that helped to answer the question of what circumstances could lead to achieving its improvement. Both gravimetric monitoring of water content in vials and “in situ” IR measurements of the aged paper humidity have been applied for this purpose. As a result, better sealing materials (gaskets and caps) than those recommended by the ASTM standard, have been found. Additionally, application of a dynamometric spanner for closing the vials is recommended, as this is a guarantee of reasonably high and recurring tightness of the systems used in tests. Nevertheless, the systematic, linear with time, loss of moisture for all used vials was observed. A 9% loss of the initial moisture content in samples of the aged paper was observed for the tested conditions (14 days at 90 °C). Therefore, it seems that including some kind of gravimetric control for ageing tests performed in closed vessels is of essential importance.Kinetic studies of accelerated ageing in both closed and open systems, as monitored by DP and breaking length measurements, unexpectedly show that no statistically meaningful difference of degradation rates can be observed. On the other hand, the pH and whiteness index values reveal a meaningful difference between the rates of ageing in these systems, thus confirming the basic assumption of the ASTM test concerning the interaction of paper degradation products with the paper itself.