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1.
The growing interest in the conservation of historic buildings encourages the development of water-repellent materials and methodologies to consolidate and/or protect stones. Recently, particular attention was devoted to composites of inorganic oxides nanoparticles and hybrid siloxane or silicone polymers. Here we present a study on the water repellence of a thin protective coating obtained through sol-gel process starting from Glymo and Dynasylan 40®, and loading the silicate matrix with nano-sized silica particles (Aeroxide LE1® -Degussa-Evonik). The coatings were applied to limestone, sandstone and granite samples. The silica nanoparticles have been characterized by XRD, the siloxane matrix through micro-Raman spectroscopy, while the surface morphology was examined by SEM. The efficacy of the treatments has been evaluated through static contact angle measurements and capillary water absorption. The optical appearance of the coatings was evaluated by colorimetric measurements. Nanoparticles at suitable concentration gave high values for the static contact angle (up to ∼ 150°), for all stone species even for four months exposure to atmospheric conditions. The coatings, in the water capillary absorption tests, however, behave as expected only for granite even if the long-term water direct contact reduces the hydrophobicity.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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.  相似文献   

6.
The pictorial cycle “Teodelinda's Tales” at Monza Cathedral, painted by Zavattari and his sons in 1444–1446, has been investigated by optical and SEM-EDS microscopy and microFT-IR spectroscopy. Paint layers, gildings and other metallic decorations have been analysed to elucidate the execution technique, the state of conservation and the possible retouchings in consequence of deterioration processes. Organic binders, coatings and adhesives have been also identified especially by microFT-IR spectroscopy applied directly to the sampled powders or fragments and to their solvent–soluble fractions. The obtained data offer a correct and satisfactory knowledge of the original organic and inorganic materials and those used in the subsequent retouches and restorations, their state of conservation and the painting techniques (fresco, mezzo fresco and secco).The physico-chemical investigations allowed to identify the nature and sometimes the provenance of the employed materials (i.e. ultramarine blue pigments) and some decay markers, particularly useful in understanding and describing the cycle realised by the authors and the modifications suffered along the centuries, and also to propose an integrated methodology for the scientific study of the mural paintings.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
We describe the results of electromigration desalination of two soluble salt-contaminated Galician granites. The efficacy of electromigration, which had not been previously applied to granite, was assessed for two types of granite contaminated with a 20% NaCl solution and seawater. Desalination effectiveness was evaluated as follows: (1) analysis of anode and cathode ion content during testing; (2) analysis of ions at different distances from the electrodes after testing; (3) pH assessment of the stone surfaces; and (4) evaluation of colour changes. Results were very satisfactory; by the end of testing, chloride was reduced by almost 100% in both the NaCl and seawater contaminated samples. Sulfate reduction was also significant, despite this ion's lower mobility. The granite pH values remained close to neutral and colour changes were minimal. The difference in effectiveness of the process for the two types of stone was associated with their dissimilar pore structure.  相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
Several authors or practitioners have remarked that Q-switched lasers have an immediate blackening effect on mineral pigments such as vermilion (HgS), minium (Pb3O4), white lead [2PbCO3. Pb(OH)2], malachite [Cu2CO3.(OH)2] and yellow ochre (FeOH2). A similar blackening effect can also be obtained on veined Carrara marble. This stone contains several trace elements, particularly iron and manganese. The latter is responsible for a particular response in electronic paramagnetic resonance spectroscopy (EPRS). We investigated the effect of a Q-switched Nd:YAG laser irradiation on the EPRS trace of Carrara marble. Further experiments were performed with the same analytical tool on synthetic calcite powders that had been doped with iron or manganese. It appeared that no significant change of EPRS trace could be put into evidence after laser irradiation of both bulk Carrara marble or doped calcite powders, although some samples had actually blackened. It is concluded that the blackening effect is not due to an oxidation of manganese ions. Colour measurements were also performed within the framework of this investigation. They showed that the colour shift to black is proportional to the fluence applied to the stone surface  相似文献   

15.
基于历史档案资料,追述了伦敦大火后英国圣保罗大教堂重建时期石材采运的历史,揭示了各类石材的开采与运输方式、建造中引发的问题,并首次对石材的供应情况进行了定量分析,呈现了石材采运如何成为圣保罗大教堂的重建历时35年之久的主要原因之一。圣保罗大教堂的石材采运问题并非独特案例,同类型的石材在同时期其他建筑中曾被广泛运用,因此对研究那个时代的砖石建筑具有更普遍的参考意义。  相似文献   

16.
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.  相似文献   

17.
The use of phase change materials (PCMs) in civil buildings as an effective thermal energy storage solution has been well documented in literature and proven in the field. When applied to Cultural Heritage, PCMs’ technology needs to be adapted to specific requirements. Besides the important objectives of economic return and human comfort, the indoor microclimatic conditions have to be suitable for conservation purposes. The application of PCMs’ technology to Cultural Heritage has been investigated within the European MESSIB (Multi-source Energy Storage System Integrated in Buildings) project. Firstly, several methodologies of incorporation of PCMs in different materials were studied and tested. The thermal properties of gypsum panels and silicon coatings incorporating micro-encapsulated PCMs in the form of powder and emulsion were analysed in the laboratory. Then, PCMs incorporated in gypsum panels in contact with a wooden panel were tested and their effect on the thermal behaviour of the wooden panel was evaluated under thermal cycles in a climatic chamber. PCMs incorporated in silicon coatings in contact with a painting were also tested. Moreover, gypsum panels containing PCMs were tested in the S. Croce Museum in Florence, Italy, where the microclimatic monitoring has shown thermal conditions potentially dangerous for the works of art preserved. The research performed both in the laboratory and on the field confirmed the effectiveness of the PCMs as thermal storage solutions, but also gave evidence on an important drawback when the material incorporating PCMs is in direct contact with an object of art.  相似文献   

18.
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.  相似文献   

19.
The presence of a diffuse biodeterioration phenomena can be observed across large areas of the outer surface of the limestone walls of the Church of the Virgin in Martvili. A differential erosion phenomenon was detected, suggesting a possible association with biological colonization. The erosion phenomenon is characterized by a circular discoloration leading progressively to the detachment of flakes of limestone at its center. Since the aforementioned process has not been described in the literature until now, the present study was focused on the interpretation of its origin and evolution. Three sides of the Church are affected by a variety of occurrences of circular differential erosion which display different stages of the process, whereas the western side is affected by epilithic growths across its entire surface. Surveys of the petrographic, mineralogical and physical features of the stone were made, and parameters such as density and porosity were recorded. Samples were analyzed by optical microscopy and SEM analysis in order to detected the presence of microorganisms whose species were then identified by means of morphological and molecular examinations. The study of cross-sections stained using the PAS method has confirmed the causal connection between microorganisms and the deterioration phenomena, providing information about their spread of penetration into the substrate and their substantial potential for causing damage. Dryness appears to be the main ecological condition favoring endolithic rather than epilithic growth. The most common isolated microorganisms were cyanobacteria (Chroococcales) and, to a lesser extent, meristematic fungi. The characteristics of the stone, and especially some endogenous discontinuities related to the accumulation of sedimentary layers and to the action of stone carving tools, might explain why the same differential erosion phenomenon occurs in specific areas of the block stones. The development of the differential erosion phenomenon shows a variety of stages of biological colonization. The progressive evolution of the deterioration process has been observed in detail: (a) firstly, white circular discolorations appear on the stone, which darken over time eventually becoming almost black; (b) circular perforations appear around the perimeter; (c) and finally a flake detaches from the center, leaving a deep depression in the stone.  相似文献   

20.
The penetration of water in rock materials is the main cause of deterioration of stone surfaces exposed to rainfall. Their protection is generally achieved using water-repellents, in order to reduce the absorption of water. Nuclear Magnetic Resonance Imaging (MRI) provides a new tool to visualize the presence of water inside the stone and, hence, the performance of hydrophobic treatments. This technique can also give indirect information on the distribution of the hydrophobic product inside the rock.  相似文献   

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