Analysis of calcium acetate efflorescences formed on ceramic tiles in a museum environment

Salt crystallization is a major cause of damage in porous materials such as stone, brick and ceramics. The paper reports results of an analytical study on tiles of glazed ceramics that are seriously damaged by acetate salt crystallization. Measurements of the ionic composition of the salt mixture in the tiles and in the efflorescences were carried out. Based on the available information on the phase equilibria in the system comprising of the main constituents chloride, nitrate, acetate, calcium and sodium, the crystallization pathways of the various solid phases are traced. It is shown that a combination of qualitative XRD analysis of the phases present in the efflorescences together with a quantitative determination of the ionic composition is sufficient for the quantitative analysis of major crystalline species in the efflorescences, i.e. Ca₃(CH₃COO)₃Cl(NO₃)₂ · 7H₂O, thecotrichite, and NaCl, halite. The concentrations of these salts are obtained from a solution of the mass balance by least squares analysis. Their formation from the salt mixtures present in the tiles that are subject to acetic acid vapor attack is consistent with the solubility diagram of the above mentioned quinary system. Finally, the possibilities of preventive conservation of salt contaminated ceramics in typical museum environments are discussed.     

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.     

The evaluation of crystallization modifiers for controlling salt damage to limestone

Crystallization modifiers can significantly affect the capillary passage of dilute and concentrated solutions of sodium chloride and sodium sulfate through columns of limestone. In the absence of modifiers, sodium chloride passage through Monks Park limestone gave predominantly subflorescence with mild edge erosion while sodium sulfate mainly effloresced and severely damaged the stone column. With Texas Creme limestone, a stone of moderately higher porosity, essentially only efflorescence occurred with either salt and there was little or no stone damage. Uniquely, alkali ferrocyanides were found to impact significantly on the interaction of these solutions as they moved through the limestone. The addition of 0.10–1.00% of K₄Fe(CN)₆ to sodium chloride in Monks Park limestone experiments increased the flow rate of solutions through the stone, resulting in efflorescence in place of subflorescence, and yielded a massive formation of extended dendritic filaments without damaging the stone. This protection by additive was extended to sodium sulfate solutions, but only at lower salt concentrations. Results comparable to the effect of adding K₄Fe(CN)₆ to concentrated sodium chloride Monks Park limestone experiments were obtained with saturated sodium sulfate solutions without additives by conducting the experiments in a draft-free, high humidity environment—suggesting a potentially useful strategy for the conservation of fragile, salt-laden objects. These results are explained by factors causing evaporation of solution to occur either below or at the surface of the stone, and by the effect of modifiers on the crystal habit of the salts forming during evaporation in this region.     

Swelling damage in clay-rich sandstones used in the church of San Mateo in Tarifa (Spain)

This study shows that the sandstone used in the construction of the Church of San Mateo in Tarifa (Cádiz, Spain) is highly sensitive to processes of decay because of a combination of factors that are intrinsic and extrinsic to the material. The mineralogy, texture and porous system of the sandstone and the proximity of the church to the sea all play a part in these processes. X-ray diffraction reveals that there are interstratified chlorite/smectite clays among the minerals that make up the rock. These mixed layer clays have been shown to undergo hydric expansion. This phenomenon may be accompanied and augmented by the presence of NaCl which acts as an electrolyte in osmotic swelling processes. Two varieties of sandstone were used in the construction of the church, namely grey sandstone and brown sandstone. The latter is more porous and undergoes greater hydric expansion, showing a higher degree of deterioration. Ultrasound analysis has demonstrated that both varieties are anisotropic because they contain bedding planes and are affected by the preferred orientation of the phyllosilicates in the rock. The anisotropic nature of these stones was confirmed by capillary suction tests. The capillary front reaches a relatively low height which means that when water is absorbed, the anisotropic textural properties combined with the presence of chlorite–smectite mixed layers in the sandstone result in mechanical (shear) stress between the first few centimetres of the wet stone and the dry area behind. The latter effect favours the development of flakes, so causing the decay of the ornamental stone and the church façade.     

Physical principles and efficiency of salt extraction by poulticing

The crystallization of soluble salts plays a significant role in the deterioration of porous cultural property. A common response to salt damage problems is to undertake treatments aimed at reducing the salt content of the affected object, most typically through the application of poultices. The process of poulticing is in theory relatively simple: the wet poultice material is applied to the surface of the object to be treated, and is kept in place for some period of time before being removed. However, in practice, the efficiency of the salt extraction, or even the location of salt accumulation post treatment is more difficult to predict. This paper examines the physical principles of salt ion and moisture transport by which poultices function, and shows how depending on the application methodology, these treatments can be divided into diffusion and advection-based methods. The maximum salt extraction efficiency, the depth to which this can be achieved, and the time scale required is estimated for each type of poulticing system, to gain a better understanding of their working properties and performance. Finally, the pros, cons and limitations of desalination treatments are discussed.     

Mapping air pollution effects on atmospheric degradation of cultural heritage

The costs for deterioration and soiling of different materials due to air pollution are huge and the damage to culture targets endangers seriously the rich European cultural heritage. Within the sixth Framework Programme of the EU, the overall aim of the CULT-STRAT project has been to assess and predict the effects of different pollutants on materials and objects of cultural heritage in a multipollutant scenario and to identify indicators and thresholds levels of pollutants. In particular, the present paper reports one of the studies carried out in the CULT-STRAT project at city level and focused on the town of Madrid (Spain). Different maps are shown for the past, present and possible future scenarios: inventory of stock of cultural heritage for each selected material, concentration of selected pollutants (SO₂, NO₂, O₃ and PM₁₀), corrosion (cast bronze) and recession (Portland limestone), exceedance of tolerable degradation thresholds for each material and corrosion-cultural heritage overlapped maps. The model and the methodology developed could be useful if apply it to towns, regions or countries in order to quantify the percentage of Cultural Heritage at risk or to quantify the percentage of the area where corrosion/recession exceeds the established tolerable levels.     

Damage mechanism in Tournai limestone – The case of the tomb of Admiral Tromp in the Old Church of Delft (The Netherlands)

The funeral monument of Maarten Tromp, in the Old Church of Delft (the Netherlands), is partially built with Tournai stone, a grey-blackish limestone from the Wallonia region (Belgium). This stone is suffering a severe delamination and scaling, which has, in the course of the centuries, led to a considerable material loss from the surface of some of the stone elements. In order to identify the damage process and define a sound basis for the conservation of the monument, a research plan was set-up including, next to the tests and analyses on the stone, a 1-year monitoring of the microclimate in the church and the investigation of the structure of the monument as well as its connections to the adjacent walls. First of all, the stone type was identified by macroscopic features and by thin section microscopy. The moisture distribution in the monument and in the adjacent walls was gravimetrically determined on samples taken at different height and depths. The content and type of salt in the Tournai stone from the monument were determined by X-ray diffraction and ion chromatography, and the results compared to those obtained for the fresh stone. The analyses showed the presence of considerable amount of gypsum, together with a low content of soluble salts (chlorides and nitrates). The SEM-EDS observations showed that gypsum is mainly crystallizing in cracks between the layers of the material. The damage mechanism and the influence of salt on the decay were further investigated by combining hygroscopic moisture uptake, hygric dilation (RH cycles between 50% and 95% RH) measurements and SEM-EDS observations; all measurements were performed both on stone sampled from the monument and, as comparison, on fresh stone specimens. The results show that gypsum is the main salt present, but its role in the damage is not significant. The naturally thin laminated structure of the stone together with the considerable hygric dilation seem to be the main causes of the delamination observed in this stone.     

Definition of the procedure to determine the suitability and durability of an anti-graffiti product for application on cultural heritage porous materials

Anti-graffiti protection is becoming a common practice in many urban buildings, especially in areas of social decay. When Cultural Heritage objects are affected by graffiti, the application of anti-graffiti products can result not only in an unsatisfactory result but also in an irreversible damage of an invaluable cost. The materials commonly found in these constructions are very frequently porous and present different types of decay forms. For this reason, the protection of these materials should be carefully considered. This paper proposes a criterion to decide on the suitability and durability of an anti-graffiti product prior to its application in a porous surface of a protected building. Performance classifications are defined for a series of properties including colour and gloss, and hydric and durability properties, and minimum acceptable values or reductions in these properties are recommended.     

Determination of the impregnation depth of siloxanes and ethylsilicates in porous material by neutron radiography

For conservation of the built cultural heritage, the application of conservation products like consolidants or water repellents is often suggested. Their impregnation depth is a key factor for the assessment of the treatment efficiency. It will vary depending on the internal structure of the stone material and the properties of the conservation products. In this study a porous bioclastic limestone from Maastricht (the Netherlands) and a porous sandstone of Bray (Belgium) were selected for treatment with either ethylsilicate-based consolidant products or siloxane-based water repellents. We explore the potential of neutron radiography to visualize the conservation products after polymerization, since previous experiments already proved their detectability before polymerization. Additionally, water absorption by capillarity was monitored inside the samples. The experiments in this study illustrate that the ethylsilicate-based consolidants remained visible for neutrons even after the polymerization process, while the siloxane-based water repellents can only clearly be distinguished in the stone as long as they contain a certain amount of solvent. The study proves that neutron radiography can provide important additional information for the research in the built cultural heritage domain, especially as it allows to successfully visualize the impregnation depth of silicate-based consolidants inside natural building stones.     

Contact sponge method: Performance of a promising tool for measuring the initial water absorption

Porous limestone and mortar are able to absorb large quantities of water. This phenomenon will accelerate the deterioration of the material. In such cases, the material might be treated with a hydrophobic product, which creates a superficial layer that hampers the penetration of water. In order to decide if such a treatment should be applied or not, the water absorbing behaviour of the material should be measured. With the same measuring technique the efficiency of the hydrophobic barrier can be evaluated. Moreover, it allows the monitoring of such barriers as a function of time. At the same time, the water absorption of porous stone material is an indication of the degree of deterioration and its sensitivity to future deterioration. Up to now, two different measuring techniques exist, but one can only be used in laboratory and the other, which can be operated in laboratory as well as in situ, is not always reliable for in situ analyses. This article proposes an alternative method: the contact sponge method. This recently developed method was tested on non-treated porous stone materials in a laboratory environment in order to evaluate its performance in comparison with the two existing methods.     

Environmentally-induced stone decay: the cumulative effects of crystallization–hydration cycles on a Lincolnshire oopelsparite limestone

An investigation has been undertaken at St Andrew’s church, Walpole St Andrew, Norfolk, to establish the underlying causes of the observed stone decay to the upper parts of the six stone piers. The stone decay was first recorded in the early 1930s. The salt-contaminated masonry within the church has been shown to undergo severe salt decay during the summer, with little damage occurring over the winter months. The south aisle piers have been shown to decay 2.5 times faster than the north aisle piers. Although crystallization–hydration cycles have been identified, the rate of decay is at its greatest when the cycling is relatively infrequent. This was not the expected trend. Furthermore, it has been shown that during extended periods where the ambient relative humidity is less than 75%, the rate of decay reaches a maximum. It is the length of this ‘drying’ period that apparently has the greatest influence on the rate of decay and could explain the significant difference in the rate of decay between the south and north aisle piers. The results have serious implications for passive conservation, where it is often recommended to lower the ambient relative humidity to well below the equilibrium relative humidity of the salt contaminant, to avoid crystallization–hydration cycles. Since, at the time of building, the church was situated on the coast, it is possible that the sodium chloride contamination occurred during the building process (1440–1520), particularly since the area was prone to sea-flooding at this time. Alternatively, the salt could have been applied as a treatment during the general restoration of 1897. Whatever the source of the salt, it seems likely that the ambient environment was changed by the insertion of a sealed floor in 1897, which could account for the onset of the salt decay.     

Rising moisture,salts and electrokinetic effects in ancient masonries: From laboratory testing to on-site monitoring

The investigation of capillary water rise mechanisms in old masonries is of great practical interest, as well as the investigation of the electrical effects accompanying such phenomenon. In fact, moisture presence facilitates all the decay processes in porous building materials and strongly threatens the preservation of materials in architectural heritage. Previous papers have shown that performing a correct and accurate measurement of spontaneous electric potential in masonries is very challenging due to several variables influencing these phenomena, such as materials microstructure, soluble salts nature and amount. In this paper, the influence of mortar joints on the capillary water rise and on the related electrokinetic effects was investigated on laboratory assemblies; then, the same measuring procedure was applied on site to a real XVI Cent. masonry building affected by rising damp.     

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.     

Particle-modified consolidants: A study on the effect of particles on sol–gel properties and consolidation effectiveness

In this paper, we have performed a systematic characterization of sol and gel properties for particle-modified silica consolidants filled with titania (TiO₂-PMC), alumina (Al₂O₃-PMC), and silica (SiO₂-PMC) particles. Viscosity of the sol is not increased much by loading with particles, especially for TiO₂-PMC and SiO₂-PMC. Composites show a strong reduction of silicate network shrinkage. Also, the incorporation of oxide particles into the matrix increases the elastic modulus while decreasing the thermal expansion. In agreement with the improvement of bulk gel properties, we observed better performance of PMCs against unfilled silicate upon consolidation of Ohio Massilian sandstone. Notably, the sulfate crystallization test has less effect on PMC-treated than on silica-treated samples.     

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.     

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.     

A Bacillus subtilis cell fraction (BCF) inducing calcium carbonate precipitation: Biotechnological perspectives for monumental stone reinforcement

Monumental stone decay is a consequence of the weathering action of physical, chemical and biological factors, which induce a progressive increase in porosity. To cope this degradation, bacterial calcium carbonate mineralization has been proposed as a tool for the conservation of monumental calcareous stones. The advantage of this kind of treatment is to obtain a mineral product similar to the stone substrate, mimicking the natural process responsible for stone formation. In this work, the possibility to induce CaCO₃ mineralization by a bacteria-mediated system in absence of viable cells was investigated and tested on stone. Our results showed that Bacillus subtilis dead cells as wells as its bacterial cell wall fraction (BCF) can act as calcite crystallization nuclei in solution. BCF consolidating capability was further tested in laboratory on slab stones, and in situ on the Angera Church, a valuable 6th century monumental site. New crystals formation was observed inside pores and significant decrease in water absorption (up to 16.7%) in BCF treated samples. A little cohesion increase was observed in the treated area of the Angera Church, showing the potential of this application, even though further improvements are needed.     

Evaluation of the effectiveness of treatment products in improving the quality of ceramics used in new and historical buildings

Ceramic samples made with a mixture of 70% ball clay and 30% quartz sand were moulded and then fired at 900 °C in an electric kiln. Samples were then treated with different products and analyses and tests were performed to evaluate the physical changes induced by the application of these products and their effects on the quality of the ceramics. A petrographic study indicated that the ceramics were composed of quartz, small amounts of mullite and sanidine and traces of hematite. Mineral clays (i.e. kaolinite) disappeared during firing. Two consolidating products (Paraloid B72 and Tegovakon V) and one water repellent (Silo 111) were applied to samples by capillarity, and physical changes (colour, water flow, porosity and pore size distribution) were measured. Finally, we carried out salt crystallization tests in order to determine which product improved the quality of the ceramics. Treated samples registered a decrease in porosity and a general increase in pore size. The application of Silo 111 drastically reduced water absorption by immersion and by capillarity. This product was also responsible for a decrease in pore interconnection. Samples treated with Tegovakon V performed better in terms of their overall hydric behaviour. Silo 111 was the only product that did not modify the colour of samples when compared with untreated ones, and after accelerated aging tests, samples treated with this product hindered the absorption of saline solution into ceramic pores and prevented their decay. Paraloid B72 did not improve any of the properties of the ceramics.     

Study on some sorption properties of treated bentonites for their potential use as a moisture regulating system for the preservation of historical wooden elements

We report the first results of a research study aimed at developing a new strategy for the conservation of wooden structural elements present in historical buildings, based on moisture regulating systems. As has been happening for artefact preservation in museums, the idea is to develop systems based on the ability of some highly hygroscopic materials to moderate variations in relative humidity. These materials could adsorb and release moisture to reduce the extreme values of humidity in the micro-climate, for example between wooden beams and masonry. In order to experimentally verify this possibility using current, low cost and easy handling building materials, 5 bentonite samples were laboratory processed to improve their adsorbing properties by means of treatment with sodium carbonate at 3 concentrations: 2, 3 and 4% by weight. The effectiveness of ion exchange between sodium carbonate and bentonite was controlled by measuring the swelling volume of the bentonites. All the samples (n = 15) were tested for their hygroscopic properties. Adsorption isotherms were measured at 25 °C, using desiccators with silica gel, saturated salt solutions and bi-distilled water. A comparison between isotherms of one of the lower hygroscopic treated sample of bentonite and of a sample of wood and of a sample of brick and some numerical analyses with the Delphin code were made in order to evaluate the potential use of this bentonite as a moisture regulating system for the preservation of historical wooden elements. Results show that it seems to be possible to use bentonites as a moisture buffering material in order to reduce moisture content in wooden beams at least during their adsorption phase. It remains to investigate their desorption phase and their behaviour if they be in a saturation condition. Further studies are currently under way.     

Assessment of the state of conservation of stone artworks after laser cleaning: comparison with conventional cleaning results on a two-decade follow up

The utilization of laser light to produce fine and selective cleaning of superficial deposits and encrustation from stones was originally proposed more than 20 years ago by John Asmus who performed pioneering trials of laser cleaning on stone façades in Venice, Cremona and Padua. The opportunity to collect stone samples from these sites allowed us to carry out an original study aimed at evaluating the conservation state of stone surfaces cleaned 10–20 years ago by means of three different techniques: Nd:YAG laser radiation, micron sandblasting and chemical pads. Samples of various stone types, as Istria limestone, Botticino limestone and Nanto sandstone were collected and examined by means of optical and SEM microscopy, FT/IR, and EDAX analyses. The results provided preliminary indications that the state of conservation of stone surfaces previously subjected to laser cleaning is generally better in comparison with those which concurrently underwent mechanical and chemical cleaning.