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1.
The present work aims to investigate the morphology and composition of natural patina formed after long-term atmospheric exposure (∼100 years) on the bronze screws used in assembling the statuary group of Mathias Rex, placed in the center of Cluj-Napoca, Romania. The chemical composition of the bronze and of the natural patina, formed on the screws’ surface were determined by X-ray fluorescence analysis, and the morphology of the latter was determined by SEM - EDX cartographies.  相似文献   

2.
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.  相似文献   

3.
Bab Agnaou is one of the most beautiful gates of the 12th century town walls of Marrakech (Morocco). It is faced with poorly preserved stone, which has recently been subjected to preliminary laboratory studies for the purpose of collecting data useful for its restoration. The results of such studies indicate the presence of two macroscopically similar grey stones, classified as slates, which were probably sourced from quarries situated not far from the city of Marrakech. The schistosity of such stones, namely their laminated fabric, has much influenced the morphology of deterioration. The causes and mechanisms of decay have been investigated and connected to the presence of soluble salts, mainly chlorides and sulphates deriving from the mortar used to fix the stone blocks to the wall, and to local air pollution. Their concentration in the bottom 3 m of the gate due to rising damp has produced strong exfoliation and flaking phenomena through rapidly repeating crystallization/dissolution cycles. A minor contribution to the overall deterioration is due to hydrolytic phenomena partly responsible for the formation of natural brown patinas on the stone surface. Another brown patina formed of Ca-oxalates and with residual proteinaceous matter was also detected and is probably due to partly mineralized protection-treatments made with natural products such as animal glue. General indications for the restoration of the gate, based on these results, are proposed.  相似文献   

4.
At the instigation of the Musée du Louvre's Department of Egyptian Antiquities, an intensive programme to study black bronze has been carried out at the Centre de Recherche et de Restauration des Musées de France. Systematic research has been undertaken on the museum's collection to identify objects that might have an intentional black patina.The same experimental protocol has been applied to all the objects, alllowing this study to be one of the most important coherent investigation on this type of bronze decoration. It involves the use of non-invasive analytical methods in order to obtain the maximum amount of information possible about the chemical nature and structure of the surface layer. The protocol makes it possible to compare objects and to propose an interpretation of how this decorative technique evolved during the Egyptian period.Based on previous stylistic investigations (by J. Cooney, 1966) and personal observation, sixteen objects dating from the Middle Kingdom to the Late Period were selected. Thanks to elemental analyses, twelve of them were identified as being intentionally patinated. Only ten of these could be described as hmty-km, because the base patinated alloy contains small amounts of gold and/or silver and the black patina is made up mainly of cuprous oxide Cu2O (cuprite). Among the four other objects, one patina is very close to the black bronze patina, but contains neither gold nor silver. Three other pieces have an unusual patina. A lack of other comparable examples makes it very difficult to determine whether the patinas are of ancient origin.  相似文献   

5.
Multivariate statistics is a well-known and invaluable tool in archaeological science but its use is limited in monument restoration. The aim of this work is to demonstrate the effectiveness of Principal Component Analysis (PCA) on the characterization, technology and weathering condition investigation of building materials from historical monuments.Towards this aim, three examples are given:The first one is a provenance and technology investigation of the Aghia Sophia (Istanbul, Turkey) bricks, some of which had to be replaced due to weathering, during recent restoration works. It was proved by PCA that the original clay, used for the construction of the bricks, is not similar to the clay of other contemporary constructions in Istanbul but presents high similarity to the raw material of the bricks from a contemporary church in the island of Rhodes (Dodecanese, Greece). Additionally, the technology of the bricks was studied by mercury intrusion porosimetry, strength tests and Scanning Electron Microscopy. The use of PCA gives a very comprehensive way to present the difference in the technology of the dome bricks.The second presents a classification of mortars from medieval (Byzantine) monasteries, based on their microstructural characteristics (porosity, reverse hydraulicity ratio) and strength measurements. The PCA grouping gives an illustrative diagram depicting the correlation between mortar syntheses and resulting characteristics.The third case shows an example of the correlation between environmental pollution data and data from the weathering layers of marble surfaces (patina composition, orientation of the monument surface, etc.).  相似文献   

6.
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   

7.
A heavily corroded Egyptian bronze figurine of the god Osiris was examined and shown to have been originally gilt with gold leaf and inlaid with blue glass. Detailed formal comparison between this Osiris figure and the known corpus of bronze and stone sculpture leads to the inference that the statuette dates to the time between the Third Intermediate Period and the fourth century BC, with a greater probability of originating from the Third Intermediate Period through to the 26th Dynasty, or even possibly as late as the fourth century on the basis of stylistic similarities. An extensive corrosion crust of atacamite and chalconatronite completely obscures inlaid glass decoration, found during the investigation, together with remnants of a gilded surface. Analysis of the glass by electron microprobe showed a composition consistent with early Egyptian blue glass with high sodium oxide and low potassium oxide content. The solid cast bronze is a leaded tin bronze, and the gold is a gold foil applied to the bronze surface, originally alternating in decoration with the blue glass. The chalconatronite and atacamite patina appear to be closely associated in the development of the unusual but extensive chalconatronite crust that now covers part of the surface, as a natural corrosion process in this case, not derived from subsequent conservation treatment. The loss of the light blue corrosion crust was prevented by consolidation with Paraloid B72, as examination over several months showed no sign of continued chemical instability.  相似文献   

8.
The performance of five synthetic coatings for the protection of stone monuments of Hellenistic and Byzantine period has been evaluated. The selected coatings included four commercially available siloxane-, siloxane/acrylic- and perfluoroether-based compositions, as well as a new composition based on newly synthesized fluoro-organosilane. The coatings were applied onto petrologically different stone substrates, such as marble, travertine, sandstone and a newly baked brick compatible with Roman period bricks, used for the restoration processes in Galerius Palace, Thessaloniki, Greece. The coatings' protective efficiency was investigated by measurement of water–stone contact angles, water vapor permeability, and water absorption by capillarity. The optical properties of the applied coatings were also investigated and they were also ranked with regard to their optical characteristics.  相似文献   

9.
The use of the artificial calcium oxalate treatment providing a protective patina to marble sculptures and a mural façade has been investigated. The longevity of the protective method is controlled at a distance of 3–4 years from its application on two diversely externally exposed Florentine monuments. Micro samples were analysed by optical microscopy (OM), scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX) and MicroRaman spectroscopy to characterize products of deterioration and the efficacy of the applied treatment.Decay is predominately noted at a superficial level and in all cases the calcium oxalate is still present, thus the protective action of the treatment is confirmed and moreover, a consolidant effect is also considered. Both statues present fractures and cavities filled with calcium oxalate residues and various degradation products such as gypsum, lichens and pollution particles. This study contributes to ascertain that artificial calcium oxalate prevents further decay of carbonate materials in urban polluted environments.  相似文献   

10.
Two issues of great interest in the field of lasers in artwork conservation are the so-called yellowing effect and the discoloration of pigments. We have viewed these issues from a comprehensive point of view, considering all our present experimental results as well as ongoing modeling and theoretical calculations. The first concern to be discussed is the yellowing effect in laser cleaning of marble or stone artifacts. Although, in most cases, a yellowish layer exists underneath the black encrustation, the so-called ‘patina’, it has become clear that there are situations where yellowing cannot be attributed to an existing layer. In the present study, a light scattering model that may account for the yellowing is presented. This model considers a thin absorbent layer and the surface roughness and/or created voids and accounts for the reflectance spectra measured by (i) hyper-spectral imaging and (ii) integrating sphere. Additional experimental data, such as the absence of yellowing when the third harmonic of a Q-swihed Nd:YAG laser is used, support this model. A thorough understanding of the quantitative characteristics of pigment discoloration, on the other hand, has been attempted by means of X-ray diffraction and theoretical studies. The model developed suggests a nucleation process for cinnabar resulting in a structural modification within the volume of a pigment’s crystal or particle close to the ‘ablation front’, which extends for a few nanometers from its surface.  相似文献   

11.
The hewn sandstone and ornamental figures of the Albertino Chancel, built around the mid-14th century, are covered with black encrustations of plaster and carbon deposits, often several millimetres thick. Their removal constitutes one of the main objectives in the conservation of the precious materials of the cathedral. The Nd:YAG laser method cleans the original surface of hardened encrustations without damaging or affecting the old coloured plasters and without affecting the centuries-old patina. Laser-Tech GmbH, founded by two expert restorers from Austria and Italy, is specialised in large-scale projects and, regarding the present project for the chancel, has managed to combine the sensitivity of the preserver with the laser technology applied to large surfaces. The present project concerning St. Stephen's Church comprises over 2000 m2 of stone surface treated only with laser systems, by groups of qualified restorers trained at Altech to use such instrumentation on artistic historic surfaces.  相似文献   

12.
The susceptibility to weathering of eleven carbonate and evaporitic Spanish building rocks was studied by means of dissolution experiments. Mineralogy, petrology, geochemistry and porosity of the rocks were also characterized in order to determine the potential relationships between these properties of the rocks and their dissolution rates. Rock slabs were submerged in a 0.1 M HCl acid solution for 72 h and the amounts of Ca, Mg and S released were measured, as well as the weight loss of the samples during the acid attack. Alabasters, which presented very low porosity, were dissolved to a lesser extent than limestones and dolostones in the time of the experiment. A significant positive correlation was found for connected with the weight loss of the rocks during dissolution and with the kinetic rate of Ca dissolution. Overall, the results highlight the influence of the porous network in the degradability of building stones by controlling their rate of dissolution. There is a positive correlation for all the rocks between weight loss along acidic attack and connected porosity, but no relationship between mineralogical and petrographical composition and susceptibility to dissolution.  相似文献   

13.
Biodeterioration of Incralac used for the protection of bronze monuments   总被引：2，自引：0，他引：2  
Outdoor bronze sculptures are highly susceptible to corrosion in many environments and organic coatings are widely used for their protection. The purpose of this study was to determine the susceptibility of the commonly used coating Incralac to biodeterioration by microorganisms. A yeast was isolated from a bronze statue treated with Incralac and its ability to degrade Incralac was determined using growth curves, scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The organism grew slowly on Incralac in liquid culture, but SEM images demonstrated its ability to adhere to Incralac coated metal. Additionally, the yeast caused a rapid drop in the low frequency impedance of Incralac coated metal that was not observed under sterile conditions, indicating that the organism accelerated deterioration of the coating. The potential for microbial growth to accelerate deterioration of Incralac should be considered when developing a maintenance strategy for the protection of outdoor metal monuments.  相似文献   

14.
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   

15.
The present study dealt with the characterisation of marble surfaces coated by three kinds of polymeric material usually employed in stones conservation and with the evaluation of the removal of these coatings from the surfaces by means of new nanocontainer aqueous systems constituted of micellar solutions (MS) and oil-in-water microemulsions (MC). The polymeric coatings were also subjected to accelerated artificial ageing in order to detect possible effects associated to natural photochemical ageing. The aim of the work was the assessment of the performance of such nanocontainer aqueous systems taking acetone (Ac) as a reference “traditional” solvent for the removal procedure. The characterisation was carried out by means of Scanning Electron Microscopy (SEM) and Environmental Scanning Electron Microscopy (ESEM), Fourier Transform Infra-Red (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopies and the results obtained showed that the performance of these innovative methods based on nanocontainer aqueous systems can be considered highly promising in the view of a “green approach” to the conservation of cultural heritage.  相似文献   

16.
The glazed tile decorative art was one of the widely used ornamental techniques for the monumental buildings during the Mughal period, in Pakistan. Coloured tile samples from Jahangir tomb were analyzed to know the glaze composition and to identify the colouring phases used at that time. The study was performed using light microscopy (OM), scanning electron microscopy equipped with energy dispersive X-ray analyzer (SEM-EDS), Raman spectroscopy (RS) and electron microprobe analysis (EMPA). These complementary analytical techniques allowed characterizing the samples as alkali glazes made from plant ashes. The results indicated the use of lead-tin yellow type II for yellow glazes, cobalt and copper for blue glazes, mixtures of yellow and blue glazes for the green glazes, manganese for purple glazes, and a transparent glaze layer for white glazes.  相似文献   

17.
This work reports mainly the results of an X-ray Absorption Spectroscopy (XAS) study carried out on coloured glass tesserae from the palaeo-Christian mosaic which decorated the votive chapel of St. Prosdocimus (Padova) until its replacement with the current frescoes of Renaissance age, and which is one of the only two known mosaics in the Veneto region (Italy). The study aims at clarifying how the different local structure, oxidation state and quantity of copper influenced colour. Analysis of high-resolution Cu-K edge X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectra showed that copper is present as cuprite (Cu2O) in orange samples and as metallic copper in red and brown ones. These phases are responsible for both the colour and opacity of the samples. In addition, Cu1+ ions linked to the oxygen atoms of the glass framework were identified in ratios of about 60% and 30% of total copper in orange and red/brown samples, respectively. In blue and green samples, copper is dispersed in the glass matrix as a mixture of Cu1+ and Cu2+ ions, and no crystalline phases are visible. In this context, the Cu1+ and Cu2+ contents in glass were also quantified thanks to suitable standards, demonstrating that, when Cu2+ is the main chromophorous ion, colour intensity is directly correlated to its content in the glass. In particular, in green and blue samples, coloured by copper, Cu2+ content varies from 26% to 56% of total copper, and the higher contents of Cu2+ are shown by more intensely coloured samples. It should be stressed here that the green colour of the analysed tesserae is given by the physical interaction of blue colour, due to Cu2+ ions, and yellow colour, due to Pb antimonates used as opacifiers.  相似文献   

18.
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.  相似文献   

19.
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20.
The chemical composition of 11 glass panes originating from two 13th century non-figurative windows were analyzed by means of Scanning Electron Microscopy–Energy Dispersive X-ray system (SEM-EDX). The windows were discovered in the back-wall of the triforium during the restoration of the choir of the cathedral St. Michael and St. Gudule in Brussels (Belgium). In order to determine if these windows were fabricated with glass of different origin or not, the compositional difference between the panes were compared with the variation in composition as a result of the following causes: (1) compositional fluctuation between panes cut from the same sheet of glass, (2) compositional fluctuation caused when panes are cut from different sheets that were made with the same batch, (3) compositional fluctuation caused when the glass is made from different batches at the same production center, and (4) compositional fluctuation as a result of glass produced at different fabrication centers.  相似文献   

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