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1.
The Grotta of Buontalenti (GB) was built at the end of the 1500s during the Medicean period. One of the rooms that constitutes the Grotta is decorated with mosaics composed of tesserae of stained glass. The GB underwent several restorations, which took place between the end of the 1700s and 1980s, which are poorly described and documented, leading to some uncertainties about the extent and phase(s) of restorations of the mosaics. The original tesserae and mortars of the GB were analysed for their mineralogical and chemical composition. Results indicate that glass tesserae have a common sodic base composition. Cluster analyses, however, performed considering the glass base composition (i.e. SiO2, K2O, Na2O, MgO, CaO, and Al2O3), identify three groups of samples: A, B, and C. A and B are characterised by chromophores such as Se and Cr suggesting a recent age (50–150 years) of the tesserae. On the contrary, chromophores (Fe, Mn, Cu, Co) and opacifiers (mainly SnO2, Pb2Sb2O7, Ca2Sb2O7) of the third group (C) indicate a preparation procedure known since ancient times. Based on their mineralogy and petrography, four different types of mortars were recognised. The mortars cannot be precisely dated. However, by matching their composition with that of the glass tesserae, it can be concluded that one type of mortar may be of the Medicean period, whereas the others are relatively recent, probably of this century. This evidence, in accordance with historical data, points to a Medicean age of group C tesserae. Restorations of the GB involved partial substitution of the mortars whereas the glass tesserae were largely recycled with limited addition of new materials.  相似文献   

2.
Mercury porosimetry was applied to the study of pore structure of the historic Roman cement mortars representative of different locations in Europe and time periods as well as different application techniques from architectural castings to in situ formed renders and profiles. Three categories of pores were found to coexist in the mortars. The finest pores, with diameters below 0.1 μm, are present within the hardened aged Roman cement matrix. The larger ‘air’ pores, with diameters between 0.2–2 μm, are due to the evaporation of the excess unbound water and restricted hydration. Pores larger than 2 μm are rare and, in general, can be related to microcracking induced by shrinkage drying and mortar weathering. The mortars have rarely been found to develop a dense fine-porous microstructure characteristic of the ideal conditions of moist-curing; massive architectural castings being the only exception identified. The presence of larger ‘air’ pores was, in turn, almost universally observed. The investigations of the freshly prepared Roman cement mortars have revealed that the restricted hydration could be due to the exposure of the freshly laid surface to dry real-world external environments, a high water-to-cement ratio in the original mortars, or the drawing of water from the stucco mass due to insufficient pre-wetting of the porous masonry. The insufficient reactivity of historic cements, resulting from a high content of over-burned, non-reactive cement components or coarseness of the cement grains, could be another reason for yielding poorly hydrated mortars in the past. In general, Roman cement stuccoes are in an excellent state of preservation in spite of their usual exposure to polluted urban environments for more than a century. Therefore, the coexistence of Roman cement mortars of widely different pore structures has not brought about any problems of incompatibility which field observations could reveal. The Roman cement repair materials have been found to develop pore structures similar to those of historic mortars. Therefore, they are in broad terms compatible with historic masonry or stuccoes. However, the porosity and strength of the repair materials can be controlled by a careful manipulation of the water-to-cement ratio of the mix to adapt them better to the properties of the host material.  相似文献   

3.
Two different analytical approaches have been taken into account to investigate the role of Si-rich phases in enhance hydraulic reactions of bedding mortar mixtures from San Lorenzo Church in Milan (Northern Italy) and from the Medicean Aqueduct in Pisa (Central Italy). In the first case, mortars show clear hydraulic type reactions in the form of coronal layers between the reacting additive and the binder mass. In the second one, the hydraulic reactions do not develop visible mineral phases and processes have been inferred from chemical, mineralogical analyses and mass balance calculation. The microstructural studies not always are sufficient to understand the complex dynamics of reaction attained during pre-industrial manufacturing processing of mortars and related binders. In fact, if the reacting raw materials are fine-grained and/or have remarkable chemical reactivity, no relicts are preserved by mortar microtextures.  相似文献   

4.
Two multivariate statistical tools – principal components analysis and cluster analysis – were applied to aid in the interpretation of the historical development of St. John the Baptist's church (?i?e, Slovenia). With these methods it was possible to distinguish between the types of mortar used in the Romanesque and Gothic time periods. The investigated structure is a ruin with poorly preserved fragments of historical mortars, so tracing the individual stages of its construction proved to be a demanding task. Its chemical composition was determined by inductively coupled plasma mass spectrometry (ICP-MS) and the results of the content of various oxides were statistically evaluated to interpret the age of the southern wall of the church.  相似文献   

5.
In order to conserve the archeological site of Olynthos, a systematic study of materials preceded. The analysis of mortar samples taken from the remains of ancient Olynthos (400 BC) showed that different qualities of mortars were used for different purposes. Almost impermeable mortars were found in contact with draining canals. This was the initiative to start a combined analysis of mortars by determining their physical and chemical characteristics in order to find the textural features and the alterations of the structure in order to understand their resistance to weathering.The paper focuses on the interrelation of findings from the above-referred examinations. The use of reactive siliceous materials in combination with lime as well as the excellent gradation of aggregates used seems to be the secrets of the good performance of the ancient mortars.  相似文献   

6.
This research focuses on the characterization of historical mortars collected from a covered dockyard, called tezone 105, erected in the Arsenal of Venice during the XVI century. The mortars date back to different building phases. A stratigraphical analysis of tezone 105 has proposed a chronology of building interventions. The building phases recognized by the stratigraphical analysis belong to the original structure (XVI century) and to later interventions from XVI to XX century. Mortar samples are investigated by granulometric analysis, infrared spectroscopy (FT-IR), simultaneous thermal analysis (DSC/TG) and X-ray diffraction analysis (XRD) in order to identify the technology peculiar of each building phase. Mortar sampling was carried out on indoor masonry and foundation. Masonry mortars appeared to be characterized by the application of air-hardening binders, whereas foundation mortars were characterized by hydraulic binders.  相似文献   

7.
The knowledge of the morphological and mechanical properties of masonry walls is very important for the refurbishment of ancient buildings, particularly when the requirements of both structural safety and historical preservation must be fulfilled. The masonry is not of homogenous material: its mechanical properties depend on stones, mortar, and texture which are very variable due to their dependence on the historical periods and the geographical area of the erection. For this reason, a deep knowledge of masonries built in different sites and historical periods is essential in order to evaluate both the capacities of bearing vertical load and the seismic vulnerability of the masonry structure. Three fundamental typologies of tuff masonry have been defined: they are the characteristics of different historical periods from the XVI to the XX century. The models are in full-scale in order to reproduce the three defined chronotypes. Original tuff stones quarried in the corresponding historical period, mortars similar to the original ones, reproduced according to ancient documents and original constructive techniques have been used for the construction of the specimens. Compression tests performed in displacement control have been carried out on the masonry models in order to determine the maximum resistance of the material and the corresponding strain, the ultimate strain and corresponding residual strength. In this paper, the procedure used for making the specimens and for experimentally evaluating the mechanical properties of post-medieval Neapolitan yellow tuff masonry are illustrated and the obtained results, even in terms of plastic capacity of these kinds of masonry, are reported.  相似文献   

8.
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.  相似文献   

9.
The study of the interaction between silica glass and saturated Ca(OH)2 solutions can be a useful approach to resolve the problem of the adhesion between lime-sand mortar and clay bricks. Since it is reasonable that the silica–calcium hydroxide system well simulates a brick–mortar system, experimental observations concerning the interaction of silica glass and this strong basic solution should be of value for the comprehension of the chemical reactions that could take place at the mortar–brick interface, maybe affecting the adhesion between the two building materials. We demonstrated the effects of saturated Ca(OH)2 solutions on commercial pure silica glass (fused silica) and on silica films obtained via a sol–gel process by means of dip-coating. Silica samples were dipped in the solutions at different temperatures (room temperature, 60 and 80 °C) and at different time intervals (1 and 21 h) and then they were analysed by means of surface techniques: X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and atomic force microscopy (AFM). It has been shown that Ca(OH)2 reacts with the silica glass network. The experimental results clearly show a very different behaviour of sol–gel silica with respect to fused silica, probably because of their different nanostructure. Many problems concerning the interaction of silica and Ca(OH)2 are still to be solved, but the results of this research strengthen the idea that adhesion between lime-sand mortar and clay bricks is caused not only by carbonation of calcium hydroxide contained in the mortar, but even by some chemical reactions involving the brick constituents and calcium hydroxide itself. The final products, calcium silicates, may induce a chemical continuity between lime-sand mortar and clay bricks.  相似文献   

10.
The use of a scanning electron microscope equipped with a microanalytical system is proposed for characterising ancient mortars. A calculation procedure is presented that allows a determination of the binder and aggregate compositions (including volatile components) from microprobe data collected on the binder, and chemical, mineralogical, petrographical and physical data collected on the mortar bulk sample. The proposed procedure is applied to 11 mortar samples from three historical monuments built in Pisa throughout the Middle Ages. The binder of the analysed samples consists of a carbonate crystalline fraction and an amorphous carbonate-free fraction that makes up from 20 to 60 % by weight of the binder. The aggregate composition, on average, is close to that of the Arno River sands.  相似文献   

11.
Black crusts formed on limestone built into the King's Gate represent the most important process in stone deterioration that is occurring in this part of the monumental complex of the Belgrade Fortress (Serbia). Of special importance is the association of salts (namely gypsum and syngenite). Syngenite is a common secondary deposit on granite monuments and on medieval stained glass (i.e., on K-containing materials). However, its appearance over calcareous substrates is not apparent, particularly in cases where cement mortar was not used for bounding. The origins of the potassium and sulphate ions required for syngenite formation are related to meteoritic water, which penetrates the soil above the arch of King's Gate. Water dissolves some soil components and becomes enriched with various ions before coming into contact with the limestone blocks. Enriched water contains two times more K+ and SO42? ions than pristine meteoritic water does. The source of the required ions is potassium-sulphate that is present in agricultural fertilisers that are used above the monument. The proposed mechanism for syngenite formation was additionally supported with laboratory experiment. The results of X-ray diffractometry and SEM-EDS analyses of limestone treated with potassium-sulphate solution and sulphuric acid suggest the possibility that the syngenite was formed over calcite:CaCO3 + K2SO4 + H2SO4 → K2Ca(SO4)2 H2O + CO2↑However, the complex mechanisms of gypsum and syngenite formation under natural conditions (variable concentration of potassium and sulphate ions, intermediates phases, temperature changes, humidity, the amount of disposable water etc.) do not exclude the possibility of syngenite formation over gypsum.  相似文献   

12.
This paper presents the most comprehensive study conducted so far for evaluating the corrosion levels related to air quality and the seasonal pollutant (NO2, SO2, and O3) exposure levels over 50 monitoring stations distributed on the historical peninsula of Istanbul. Istanbul has been one of the most important as well as most populated major cities in the world during all the ages. Today, owing to its historical and cultural structures, the historical peninsula of Istanbul has become an attraction point of tourism and is one of the most unique and ancient urban settlement areas in the world. However, the cultural heritage stocks in the peninsula are under the risk of corrosion and critical air pollution level exposure caused by chemical reactions under the multi-pollutant situation of the air pollutants, principally SO2, NO2, and O3, as well as meteorological factors, e.g. humidity and temperature. In the present study, seasonal exposure of NO2, SO2, and O3 pollutants were monitored using passive samplers, and corrosion attack values were calculated using dose-response functions. The geostatistical analyst tool of ArcGIS® 9.1 was then used for generating GIS-based surface pollution and corrosion distribution maps. Subsequently, two hotspots were clearly identified, the tip of the peninsula and the area around the Ataturk Bridge, which fall under serious corrosion risks for copper, cast bronze, and carbon steel materials. However, no significant risk was identified for cultural heritage materials made of limestone in the peninsula.  相似文献   

13.
Very few scientific studies have been performed so far on ancient and modern hydraulic mortars. The effects of atmospheric multi-pollutants on hydraulic mortars used in monuments and historic buildings in urban areas, especially those linked to dry and wet carbon and sulphur deposition, remain in need of thorough investigation. In the literature, studies on damage typology identification, composition and origin and relative quantitative data are both scarce and rather poor in quality. While the sulphate source from marine spray deposition and water capillary rising are known, atmospheric sulphur effects on mortars still require elucidation. Ancient and modern hydraulic mortars have been collected from the Arsenal of Venice. The original material characterisation and the evaluation of the surface damage due to atmospheric pollution are presented along with a comparison of the data obtained for the cement and cocciopesto mortars.  相似文献   

14.
Interactions of lead-based pigments with a number of inorganic salts, one of the most dangerous degradation agents of wall paintings, were studied under laboratory conditions. The results were used to interpret colour changes observed in 11th century frescoes from the church of Saint George in Kostoľany pod Tríbečom, the oldest preserved wall paintings in Slovakia. Interactions of selected pigments (lead white, massicot, red lead) with different salt solutions were performed within long-term laboratory experiments. We used a selection of naturally occurring salts (Na2SO4, MgSO4, CaSO4, NaCl, NaNO3, Ca(NO3)2, Na2CO3, K2CO3 and urea) and, additionally, a range of synthetic salts that are often applied to the wall paintings during their cleaning and conservation (NaHCO3, KHCO3, (NH4)2CO3, NH4HCO3). The reaction products were identified by X-ray powder diffraction. Red lead (Pb3O4) has a tendency to darken in all salt solutions containing dissolved atmospheric CO2 due to disproportionation to plattnerite (PbO2) and cerussite (PbCO3). Massicot (PbO) in a wet state reacts with atmospheric CO2 to form hydrocerussite and finally cerussite. Lead white (PbCO3 and Pb2CO3(OH)2) reacts with sulphates, carbonates and chlorides to form their respective salts in high yield and, sometimes, without any apparent colour change. Samples taken from the dark brown parts of the wall paintings in Saint George's church were analysed using laboratory X-ray powder microdiffraction. The presence of hydrocerussite, cerussite, plattnerite and lead magnesium carbonate was revealed. According to the results of laboratory experiments, the original lead-based pigment of the now darkened parts was red lead.  相似文献   

15.
The concentrations of CO2, CO, formaldehyde (H2CO) and water vapour were simultaneously monitored in various sections of a mountain church situated in the village of Rocca Pietore in the Italian Alps. The performance of a conventional, hot-air heating system and a novel design for heating the church, consisting of low-temperature heating elements, such as electrically heated pews and carpets, were compared for the supply, transport and removal of gases, the deposition and/or transformation of which may affect the preservation of displayed works of art. Experiments with sulphur hexafluoride (SF6) tracer-gas showed a considerable influx of external air through the hot air carrier ducts of the old heating system, and also the leakage of the internal air mostly via the apertures of the doors. The ventilation rates for the total volume of the church with the hot-air heating system (on for 1.5 h), the new heating system (on for 2 h), and without heating were calculated to be 0.25, 0.18, and 0.13 h−1, respectively. Without heating, a nearly homogeneous distribution of gases has been observed along both the horizontal and the vertical cross-sections of the church. Immediately after switching on the hot-air heating system, the levels of CO2 and water vapour showed a sharp increase. After turning this system off, the levels of gases showed a slow fall and they developed a highly non-homogeneous spatial distribution indoors for many hours. In the upper region of the church, being airtight, higher concentrations of the pollutants could be detected. The low levels of CO and H2CO, mostly originating from incense burning during services, were correlated to that of CO2. The hot-air heating system has been proved to present a potential deterioration risk to artworks, as it increases the supply, transport and deposition probability of air pollutants. On the other hand, the novel, symmetrical heating system eliminates these undesirable effects, thus its application is advantageous to all churches involved in the preservation of works of art.  相似文献   

16.
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.  相似文献   

17.
Analysis of historic mortars including Islamic, Gothic and later ones taken from palaces, convents and mansions in Palma de Mallorca has been carried out. Scanning electron microscopy (SEM) coupled to energy dispersive X-ray spectrometer (EDX), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) techniques were used to characterise the morphology and analytical composition of the samples analysed. Generally, covering plaster mortars presented a low percentage of small size aggregate. The reported results show that mixed and lime mortars have been used, thus, the establishment of a relationship between the type of mortar employed and its age is not feasible. In the painted mortars, polychromy has also been studied. The most common pigments to be found are natural earths.  相似文献   

18.
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   

19.
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   

20.
The application of a new class of organogels as cleaning tools for painted surfaces is described. It combines some of the most attractive features of cleaning liquids and normal gels while diminishing the deleterious characteristics of both. Thus, the ‘latent’ gellant, polyethyleneimine (PEI), reacts with CO2 at room temperature in solutions of several organic liquids to produce an ammonium carbamate form (PEICO2). This charged species organizes itself into 3D polymer networks which immobilize the liquids as gels. The properties of the original solution (i.e. a free-flowing liquid) are re-established immediately after addition of a small amount of a weak acid which displaces the CO2 molecules and makes the PEI chains positively charged. The visual changes are substantiated by rheological analyses. Results from analytical tests to determine the utility of these gels as cleaning tools for painted surfaces of historical and artistic interest, have been obtained from contact angle and FTIR measurements as well as visual comparisons of the surfaces before and after application of the gels. The analyses indicate that the PEICO2-based organogels were very effective in removing different surface patinas from painted supports. A surface layer of dammar was completely removed from a test canvas with oil paint, an aged painting from the XIX century, and a XV century oil-on-wood panel attributed to Mariotto di Cristoforo. Finally, a surface acrylic polymeric resin (used in a restoration performed during the 1960s) was also successfully removed from Renaissance wall paintings decorating the Santa Maria della Scala Sacristy in Siena, Italy. The isothermally rheoreversible gel approach described in this work represents a new, highly versatile, and very efficient method for removing aged surface patinas from works of art.  相似文献   

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