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.     

Consolidation of paint on stained glass windows: Comparative study and new approaches

Stained glass windows belong to the most precious pieces of art in many European countries. Examples of heavily endangered paint on glass are reported in the literature and mainly related to condensation effects and air pollution, as stained glass windows preferably remain in their original architectural surrounding. Several surface coatings and paint treatments have been proposed to consolidate and protect degraded paint. Very often, the selection of the materials is based more on practical aspects than on scientific research. This study concerns the comparison of some traditional, modern and newly developed consolidants for the preservation of historic glass paintings. Experiments have been carried out with model painted glass samples simulating weathering phenomena of originals. Traditional materials like Paraloid B72, modern ones like SZA (proposed by the Fraunhofer-Institut für Silicatforschung, ISC), and three new consolidants prepared by the sol–gel method and based on different hybrid organic–inorganic alkyl-alkoxysilane systems have been considered. The adhesion, penetration, stability, hydrophobicity, mechanical and chemical resistance are properties and requirements tested to prove their effectiveness and range of use. The three new materials developed in this study for the consolidation of paint on glass have the potential to offer alternatives to existing materials. Nevertheless, further research is necessary before their application in restoration workshops can be recommended. A strategic approach is requested to avoid risks for these valuable historical originals and to contribute to the long-term preservation of the paint on stained glass windows in their original sites.     

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.     

X-ray radiography and tomography for monitoring the penetration depth of consolidants in Opuka – the building stone of Prague monuments

Stone consolidation is one of the major restoration treatments used for historical monuments preservation. A natural stone is a complicated heterogeneous porous system making the process of consolidation dependent on many variables. In practical restoration aims, for a given stone type, the selection of a suitable consolidant and consolidation conditions therefore remains a complex issue. The impregnation depth is a key factor for the assessment of the treatment efficiency. The combination of state-of-the-art hybrid pixel semiconductor detectors with newly available micro-focus X-ray sources makes possible to apply X-ray radiography, an ideal non-destructive tool, for penetration depth monitoring. In this study, high-resolution X-ray radiography is used for monitoring the penetration depth of organosilicon consolidants in the Opuka stone. The penetration depth has been evaluated in relation to the time of consolidation, stone porosity and consolidation mixtures properties. The exact influence of the X-ray contrast agent on the consolidation depth has been investigated as well. The information obtained provides supplementary knowledge on the suitability of investigated products for the treatment of this type of stone. In our study, the capabilities of X-ray radiography have been demonstrated on X-ray radiography simple projections, high-resolution computed tomography (CT) as well as on the dynamic processes monitoring. The results thus can serve also as an instrumental and methodological example applicable for consolidation monitoring of other stone types.     

Effect of novel consolidants on mechanical and absorption properties of deteriorated wood by insect attack

The influence of chemical treatments based on novel organic products on the consolidation of deteriorated wood by insect attack was evaluated on two hardwoods and one softwood: fir (Abies alba), beech (Fagus sylvatica) and deciduous oak (Quercus sp.). Degraded and intact specimens of the three wood species were impregnated with two different chemical treatments aimed to verify the potential synergic action of the novel products on wood. Then, the specimens were subjected to bending, compression parallel to the grain, impact, hardness and water absorption tests. Untreated specimens of the same botanical species, both degraded and non-degraded, were examined for comparison purposes. The experimental results showed a different effectiveness of the proposed chemical treatments to improve the mechanical and absorption properties of degraded wood. The most effective treatment was the one assuming the concurrent use of the studied novel consolidants. The species more susceptible of the enhancement in mechanical properties were fir and beech. The observed differentiations were most likely caused by the different structure of the botanical species considered, leading to a consequent different product penetration in the wood structure. The dimensional stability in terms of water repellent and antiswelling efficiency, after a three-month immersion in deionized water, was found to improve in all the treated wood specimens. Overall, experimental results showed that the impact of the chemical treatments was higher on degraded samples than on intact ones.     

The identification of organic additives in traditional lime mortar

Organic-inorganic lime mortars were widely used in many ancient buildings due to their good performance in some fields (such as caking property, water repellency, weatherability, etc.). However, many ancient buildings and sites are suffering from various degrees of damage with the development of the economy and society and appropriate conservation and restoration are needed. The application of traditional construction materials, such as organic-inorganic lime mortars, attracts more and more attention in the conservation and restoration of ancient buildings in the recent years. So, the understanding of the components of original lime mortar which remained in ancient sites is of fundamental significance. In this work a set of analytical procedures to identify the organic additives in lime mortars by classical chemical analysis is proposed. The results show that using iodine-potassium iodide reagent, Benedict's reagent, reduction phenolphthalein reagent, Coomassie brilliant blue and sodium periodate oxidation glycerin acetyl acetone method could effectively detect a small amount of starch, reducing sugar, blood, protein and fatty acid ester that remained in ancient buildings’ lime mortars, respectively. These analytical methods are easy to operate with low detection limit, high accuracy and some other advantages.     

A methodological approach in the evaluation of the efficacy of treatments for the dimensional stabilisation of waterlogged archaeological wood

The aim of the work is to set up a methodological approach to verify the effectiveness of the treatments of decayed waterlogged archaeological wood and to point out the proper thermo-hygrometric conditions for its preservation after treatment. The treatments were performed on wood samples of maritime pine (Pinus pinaster Aiton), oak (Quercus sp. caducifolia), elm (Ulmus cf. minor) and strawberry tree (Arbutus unedo L.), obtained from stems pertaining to the original vegetation found in the excavation site of the Ancient Ships in Pisa (Italy), and dated from seventh century BC to second century AD The utilised products were: Polyethylene Glycols (PEG) of various molecular weights, a Polypropylene Glycol (PPG 425), Trehalose (α-D-glucopyranosyl-α-D-glucopyranoside), and their mixtures, and also a Hydroxypropylcellulose (Klucel). The main objective to be pursued by the treatments was considered the stabilisation of the original size and shape of samples. The various steps of this approach were: the execution of a preliminary diagnostic survey on untreated samples; the characterisation of treatment solutions ‘as such’ to establish the property to be monitored during the treatment; the evaluation of the main physical characteristics of wood after the treatment were determined. Among the latter, the coefficient of dimensional stability during the exposure to a series of selected thermo-hygrometric conditions and the retention of consolidants after the treatment. These two measurements allowed the definition of the ‘efficacy of a treatment’, φ_T, a new parameter firstly utilised in this work. It measures the stabilisation capability of the percent unit of retained product, and its value permits to put in evidence the consolidants that stabilise wood with the lowest amount of product. Conversely, it was not possible to measure the Anti-Shrink Efficiency (ASE), one of the most utilised parameters for the evaluation of treatments, because of the serious distortions and fractures observed in all the heavily degraded untreated samples.     

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.     

Nanolime suspensions applied on natural lithotypes: The influence of concentration and residual water content on carbonatation process and on treatment effectiveness

Ca(OH)2 particles with submicrometric dimensions (nanolimes) are recently introduced in cultural heritage conservation, in order to improve lime treatments. Lime nanoparticles are typically produced by a chemical precipitation process in supersaturated aqueous solutions of the reactants (calcium chloride [CaCl₂] and sodium hydroxide [NaOH]); water is then partially substituted with 2-propanol in order to improve stability and to reduce a random orientation of the particles. Aim of the present work is to analyse the influence of the nanolime suspensions concentration on the carbonatation process, in relation to the residual water content too. The obtained lime nanoparticles are characterised by X-rays diffraction (XRD) and profile analysis. Afterwards, the influence of the suspension concentration on stones protective treatments is evaluated: alcoholic nanolime suspensions, characterised by different concentration values, are applied on several natural lithotypes. Standard tests are performed to estimate the superficial consolidation and the protective treatment effectiveness: “Scotch tape test” (STT) and capillarity test. Porosimetric investigations are performed too.     

Smart surfaces for architectural heritage: Preliminary results about the application of TiO2-based coatings on travertine

The development and application of self-cleaning treatments on historical and architectural stone surfaces could be a significant improvement in conservation, protection and maintenance of Cultural Heritage. In this paper, a TiO₂-based coating has been investigated in order to evaluate its possible use as a self-cleaning treatment. This coating was obtained by a sol-gel and a hydrothermal (134 °C) processes and then it was applied on travertine (a limestone often used in historical and monumental buildings) in two ways, obtaining a single-layer and a three-layer treatment, respectively. In order to verify its potential use in the field of Cultural Heritage, the maintenance of appearance properties of the treated travertine surfaces was monitored by colour and gloss analyses. Besides, de-pollution and soiling removal tests were carried out under ultraviolet-light exposure to evaluate photo-induced effects and self-cleaning efficiency. Results seem to allow the use of TiO₂-based treatments on historical and architectural surfaces made up by travertine, where de-pollution and self-cleaning photo-induced effects are well evident, maintaining their original visual appearance. Anyway, before applying TiO₂-based coatings as conservative treatments, further tests are needed especially on their durability, that is mandatory for Cultural Heritage applications. On-site test in an urban environment and accelerated test by weatherometer are currently under way.     

The use of hydroxyapatite as a new inorganic consolidant for damaged carbonate stones

The feasibility and the effectiveness of using hydroxyapatite (HAP) formed by reacting limestone with a solution of diammonium hydrogen phosphate (DAP) in mild conditions, as a consolidant for carbonate stones were investigated. Firstly, a novel method for predamaging limestone was developed. Then, the effects of DAP solution concentration and reaction duration were evaluated to define the best treatment conditions, and the strengthening effect was evaluated on artificially damaged Indiana Limestone samples. Treated samples exhibit a significant increase in the dynamic elastic modulus and tensile strength, which is attributed to microcrack reduction and pore filling consequent to formation of calcium phosphate phases at grain boundaries, as assessed by SEM/EDS and ESEM/EBSD. Consequent to a slight reduction of coarser pores, as revealed by MIP, the sorptivity of treated samples is only slightly reduced, so that water and water vapor exchanges with the environment are not significantly blocked.     

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.     

Structural evaluation of restoration processes with holographic diagnostic inspection

Implementation of laser technology in art conservation has resulted in an increased consideration of intervention restoration processes. Skepticism is raised regarding the side effects of interactions that could induce either short- or long-term irreversible physical alterations. Herein, an integrated laser-optic module based on the principles of holographic interferometry (HI) has been developed to study existent structural condition and probable alterations. The experimental procedure involved allows repeatable data acquisition in long-term monitoring. The tested system and methodology overcome a fragmented structural approach imposed in art conservation diagnostics by existing instruments and practices, and a full field response offering a detailed source of information is obtained. The controlled procedures by which interference fringes are formed by laser cleaned surfaces permit their long-term comparison. The results urged studies on the fundamental mechanical behavior of defects. Thus, the high resolution of HI recording was used to study the dynamics of deterioration by detecting the potential of existing defects’ natural propagation, which for the first time is described here. The study can form the basis to distinguish natural from artificially induced alterations. Comparative evaluation during conventional conservation consolidation processes was performed on an early El Greco painting which resulted in a direct evaluation of the restoration action. The results thus far were acquired in laboratory facilities. A custom-developed system was next transported to the museum floor and a significant outcome of on-field holography complementing established structural conservation diagnostics was accomplished.     

Epoxy monomers consolidant for lime plaster cured via a redox activated cationic polymerization

Epoxy resins, widely used in conservation, still remain controversial materials. Considering some of the drawbacks that currently limit the application of epoxy consolidants, we present the application of the cationic ring opening polymerization as a novel method to cure the epoxy monomer in the restoration field. The cationic polymerization was carried out through a redox system based on the reduction of the iodonium salt in the presence of ascorbic acid catalyzed by a copper salt. The use of this initiator system for carrying out a suitable consolidant for lime plaster is considered. First, the film properties of the cured films were investigated. Then, the formulation was applied on a sample of plaster and its compatibility was verified. Its effectiveness as a consolidant product is explored through the evaluation of chromatic changes, mechanical strength, morphology of the re-aggregated material, and changes of the surface properties.     

Consolidating preservative-treated wood: Combined mechanical performance of boron and polymeric products in wood degraded by Coniophora puteana

When timber elements in heritage buildings are moderately degraded by fungi and assuming underlying moisture problems have been solved, two actions can be taken: i) use a biocide to stop fungal activity; ii) consolidate the degraded elements so that the timber keeps on fulfilling its structural and decorative functions. The aim of this work is to investigate the mechanical performance of maritime pine wood degraded by fungi after being treated with a biocide followed by impregnation with a polymer product. Three commercially available products were used: a boron water-based biocide, an acrylic consolidant and an epoxy-based consolidant. Treated and consolidated specimens were subjected to mechanical tests: axial compression test (NP 618), static surface hardness (ISO 3350) and bending test (NP 619). Sets of replicates were subjected to an evaporation ageing test (EN 73) after application of the products and also tested for mechanical behaviour. An increase in mechanical strength was observed for both consolidants with no significant influence from the previous use of biocide product. The specimens subjected to ageing showed a slightly better general mechanical performance.     

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.     

Surface changes upon high-frequency plasma treatment of heritage photographs

Recent research, concerning the application of high-frequency cold plasma in restoration and preservation of the cultural heritage, has included the objects derived from organic materials, which are highly sensitive to microclimate factors. Historical photographs made on paper base and covered with various emulsions belong to this category of heritage objects, and make the purpose of the present study. Plasma treatment was used to enhance the aesthetic aspect of the photographs by a cleaning treatment involving either physical and/or chemical etching, which did not cause major physicochemical changes on the plasma-treated surface. The photographs before and after plasma treatments were analysed by optical and atomic force microscopy, scanning electron microscopy with energy-dispersive X-ray microanalysis, Fourier transform infrared spectroscopy, colour, gloss and contact angle measurements.     

The funerary klinai of tomb 1 from Amphipolis and a sarcophagus from ancient Tragilos, eastern Macedonia: a physico-chemical investigation on the painting materials

Optical and SEM-EDS microscopy, X-ray powder diffraction and micro FT-IR spectroscopy investigations of the funerary klinai (couches) of Tomb 1 from Amphipolis and a stone sarcophagus from ancient Tragilos—two painted monuments made by Macedonian craftsmen of the Early Hellenistic period—identified the original materials and painting technique, as well as synthetic materials used as consolidants during past restoration treatments. The original organic binders and the superficial modern coatings have been identified by micro FT-IR spectroscopy applied directly to the sampled powders or tiny fragments and to their solvent—soluble fractions. The pigments identified on the couch of Amphipolis are: red and yellow ochre, cinnabar, Madder lake, paratacamite and antlerite, carbon black, calcium carbonate, kaolin and gypsum. The identification of egg and animal glue confirms the application of tempera and secco techniques. The detection of polymers such as polydimethylsiloxane, polyvinyl acetate and alkyd resins, is related to modern restoration products. The pigments attested on the paintings of the Tragilos' sarcophagus are: red and yellow ochre, Egyptian blue, malachite, carbon black, calcium carbonate and gypsum. The absence of organic binders combined with the constant presence of calcium carbonate in all the examined samples suggests the use of lime as the binding medium in the painted decoration of the sarcophagus. The presence of Paraloid B72 is related to recent conservation treatments.     

Tracing of decay profiles and evaluation of stone treatments by means of microdrilling techniques

The recent development of a new drilling machine in the framework of the EU project HARDROCK brought some interesting perspectives for the characterisation of decay profiles, for tracing old consolidating treatments and for evaluating new consolidants. The equipment executes a drill hole, typically 5 mm in diameter, down to 5 cm, under precisely defined and controlled drilling conditions. The output is a graph of force versus depth. The instrument can be transported and operated in situ. The operator defines the drilling rotation speed and the advancing rate and the instrument registers the force required for executing the hole under those strictly defined conditions. This paper presents some data taken from a laboratory study on consolidants which demonstrate that the equipment has a very high discriminating power for detecting the presence of consolidants. Clear differences among some typical consolidants were detected, both in the strength increase and in the penetration depth. They also show that the average drilling forces present a fairly good correlation with bending strength, in spite of the fact that full consolidation of the tested specimens was not possible with all consolidants. The in situ study of Porta Especiosa has shown that the instrument was able to identify the presence of decay events at several depths, in a way that no other known method can do. The identification of the presence of old treatments was demonstrated with total guarantee.