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.     

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.     

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.     

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.     

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.     

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.     

Consolidating materials for the volcanic tuff in western Mexico

The diversity of volcanic tuff buildings standing in Western Mexico is large, therefore, it was considered relevant to evaluate and synthetize different stone consolidants that could be applied in the regional weather conditions and renew the stability of those buildings; since the commercial products are developed and tested in foreign countries, and in some cases, when applied under the weather conditions of Mexico, the results differ from those reported. For the altered tuffs from Santa Mónica's Church in Guadalajara, Mexico, the deterioration mechanism of the local tuff was determined, thus a silicate and aluminosilicate consolidants were synthesized by the sol-gel method and applied to altered tuffs in order to evaluate their performance from structural to macroscopic level.     

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.     

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.     

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.     

Organic-inorganic material for the consolidation of plaster

Organic-inorganic materials to be used as hydrophobic consolidants for plasters were synthesized starting from an inorganic precursor (Tetraethoxysilane [TEOS]), added to a polysiloxane epoxy formulation and thermally cured with Ytterbium as acid catalyst. The TEOS reduces the viscosity of the resin, contributing to the mechanical properties of the film, without causing cracking. Solvents, that are harmful for workers and environment and show some drawbacks in the practice of restoration, were not used. The film properties and the formation of silica clusters were investigated. The products were applied by brush on plaster's samples and their compatibility and effectiveness were verified. Thanks to the organic content, the products penetrate deeply, are more stable to photo-oxidative degradation, and the hydrophobicity of the resin, provided by the silicone component, is not altered.     

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.     

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.     

Review of several optical non-destructive analyses of an easel painting. Complementarity and crosschecking of the results

Five optical analyses of a given work of art are presented, using multispectral imaging, optical coherence tomography, goniophometry, UV-fluorescence emission spectroscopy and diffuse reflectance spectroscopy. All these methods are non-destructive, contactless, and implementable in situ. They all lead to results in quasi-real time. The multispectral camera allows imaging of the whole painting with very high definition and recording of 240 millions of spectra. Optical coherence tomography allows local 2D and 3D imaging with in-face and in depth stratigraphies inside the painting with a micrometric accuracy. It allows the evaluation of the pigment volume concentration inside a layer, the measurement of the thickness of one or two varnish layers, the detection and measurements of gaps inside the paint layer, the depth of varnish micro-cracks. Goniophotometry allows the measurement of the upper surface state of the painting in different locations, by quantifying the mean slope of the facets making up the surface. UV-fluorescence emission spectroscopy allows the identification of the resin, the binder and the ageing state of varnishes by use of databases of reference varnishes. Diffuse reflectance spectroscopy leads to pigment, pigment mixture and dye identifications again by use of databases. The three last methods are implemented with the same portable multi-function instrument. It allows time saving, locations on request in front of the artwork and easy use by non-scientists. Each instrument is described with its protocol and accuracy. The studied painting is a portrait of a lady painted by the Austrian artist Franz Strotszberg, chosen for its several restorations. The five kinds of results are successively detailed, analysed and compared between themselves. It is shown that the different results are complementary and their crosschecking brings thorough information. For example, the shape of the network of varnish micro-cracks detected on the surface with the multispectral camera is added to the measurement of their depth with optical coherence tomography. Another example allows connecting two different surface states of the upper varnished surface measured by goniophotometry with the identification of these varnish with UV-fluorescence and with their thicknesses measured with optical coherence tomography.     

Laser cleaning as a part of the restoration process: removal of aged oil paints from a Renaissance sandstone portal in Dresden,Germany

Laser cleaning was applied to remove aged and soiled oil paints of the 19th century from weathered, brittle sandstone surfaces. In contrast to other tested cleaning methods, the laser technique allows the removal of the oil paint layers with a minimum of material loss in brittle zones. The cleaned test areas have been investigated by optical and scanning electron microscopy as well as by colour measurements. The investigations have shown that the dirt and the oil paint layers can be removed by laser cleaning without affecting the original sandstone surface and that the pores can be opened again. The brown shade after cleaning is not caused by laser interaction with the sandstone surface but by historic impregnation with linseed oil. Immediately after cleaning, a treatment with chemical consolidants is necessary to preserve the brittle sandstone surface. Sustainable consolidation could be problematic in some areas, because the laser cleaning also preserves heavily damaged, crumbling zones of the carvings. For economic reasons, laser cleaning should be applied only in the most endangered zones of carvings and combined with classical methods (organic solvents and scalpel).     

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.     

A color image segmentation method as used in the study of ancient monument decay

In the cultural heritage area, it is of fundamental importance to characterize and classify the conservation state of the materials constituting ancient monuments, in order to study and monitor their decay. Generally, the decay diagnosis is provided by “naked eye” analysis done by expert scientists “walking around” the artifact and recording the conservation state of each individual element they observe. In this paper, a color image segmentation approach, based on histogram threshold and edge detection techniques is presented, to extract degradation regions, characterized by holes or cavities, from color images of stone-materials. The goal is to provide an aid to the decay diagnosis by segmenting degraded regions from color images, computing quantitative data, such as the area and perimeter of the extracted zones, and processing qualitative information, such as various levels of depth detected into the same zones. Since color is a powerful tool in the distinction between objects, a segmentation technique based on color, instead of intensity only, has been used to provide a clearer discrimination between regions. The study case concerns the impressive remains of the Roman Theatre in the city of Aosta (Italy). In particular, we have processed and analyzed some color images of the theatre puddingstones, acquired by a camera.     

A portable NMR device for the evaluation of water presence in building materials

The direct recording of the water presence in stone materials or in masonry provides information about their state of conservation and it can also indirectly reveal the effectiveness and durability of protection treatments or chemical interventions for rising damp reduction. Evaluating the humidity, i.e. the water content, of a building material is a problematic issue because the water is distributed in a large volume in different amounts. Usually these kinds of measures have been carried out with resistance/conductivity and thermographic systems, which are all affected by weaknesses and intrinsic restrictions. Thermographic investigations are affected by temperature differences and the evaporation–cooling effect. In the case of electric measures, the signal does not originate from the water present, but from the conductivity of the water itself, which is strictly connected to the presence of ion species that can modify it significantly. Moreover, interruptions, like air gaps or fractures, cancel the signal. For both methodologies the quantitative water evaluation is difficult. Although some minerals, like iron-based ones, could disturb the NMR measure, the signal is not influenced by the presence of most common soluble salts or pollutants in the solution (such as nitrates, chlorides or sulphates) and it is only generated by the number of water molecules present in the sensitive volume. In this paper the results, obtained in the laboratory with a portable NMR device, developed within the framework of the Eureka Project E!2214-MOUSE, are shown. The encouraging results obtained in this preliminary experiment, concern mainly the investigation of stone materials that have different porosimetric features and the calibration of the instrument under different working conditions. The experiments focused on the correlation between the content of water absorbed by capillarity and the NMR signal intensity obtained by this device. Different materials have been investigated, such as calcarenite and bricks. The experimental work will define a starting platform to successfully transfer the analytical procedure from the laboratory to in situ measurements.     

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.     

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.