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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.
This work shows the capability of principal component analysis (PCA) to detect molecular, chemical and mineralogical changes in historic painting materials subjected to a thermal ageing test (< 250 °C). To simulate the heat-induced alterations an ageing accelerated process was performed on two sets of samples containing two mineral phases (hydroxyapatite and quartz) and two organic compounds (collagen and albumin). The chosen minerals behaved as internal standards during the tests since they are stable and chemically inert at the tested temperatures. Raman microscopy (RM) was applied to characterise one set of samples made of bone, containing ca. 70% hydroxyapatite and 30% collagen. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy was used to study the other set of samples made of four different quartz/albumin mixtures with quartz contents of 30%, 50%, 70% and 90% (w/w). The aim was to identify the ideal proportion of internal standard to be validated by ATR-FTIR and PCA, determined to be 70%. PCA analyses detected changes in the molecular structures of the organic components while the internal mineral standard remained stable. Moreover, the internal standard IR/Raman bands were constant during the tests and confirmed that the results of PCA analyses were independent of instrumental and technical factors, as well as sample collecting and handling. This demonstrates the potential benefits of our approach to study historical painting materials, which have suffered any type of heat-induced alteration.  相似文献   

4.
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   

5.
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   

6.
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   

7.
The structural and historical analysis of the aqueduct of the Alhambra is presented. In the 13th century, Muhammad I built the palatial city of the Alhambra. To provide a water supply, Muhammad I built an irrigation ditch, known as the Royal ditch. The aqueduct was reconstructed in the 18th century in ashlar masonry to replace the original one. This work analyzes the history, geometric modeling, materials and stability of the aqueduct. Due to difficulties in testing and measuring the properties and loads, the Monte Carlo analysis technique is used to analyze stability, where the input parameters are defined as probabilistic distributions. Monte Carlo analysis provides the probability of risk of collapse defined by the geometric security coefficient obtained by means of the theory of limit analysis. Additionally, this technique is used to optimize the thickness of the arch.  相似文献   

8.
The cross-linking processes of three drying oils (poppy, linseed, walnut), a class of organic compounds very important in the field of artworks, were studied by means of 1H-NMR spectroscopy, following the change of the protons signals when oils are heated at 60 °C in the presence of air or nitrogen gas. This preliminary information is particularly important to identify the presence of drying oils within a solid painting film. We demonstrated that it was possible to study these films by swollen-state NMR, an innovative spectroscopy method that can directly analyze very small semisolid samples instead of solutions. The main advantages of this method are the short time of analysis, the possibility to analyze samples without any preliminary treatment, and the small quantity of the sample required. Therefore, swollen-state NMR technique was used to characterize three real painting films: in this way, we succeeded in recognizing in real paintings specimens the presence of drying oils employed as binders, avoiding any interferences due to other organic compounds acting as binding agents, like waxes or egg-yolk media.  相似文献   

9.
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   

10.
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11.
The reliable identification of proteinaceous binders in historical mortars and plasters represents a complicated analytical problem. In this paper the possibility of peptide mass mapping (PMM) in connection with the mass spectrometry is demonstrated. The presence of milk and collagen proteins was trustworthy proved in the samples of mortars taken from the Romanesque rotunda of Saint Catherine in Znojmo (Czech Republic).  相似文献   

12.
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   

13.
The preservation of early 20th century, late 19th century albumen prints is of great concern to collection managers and conservators of photographic materials. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopic imaging is presented for the first time as analytical methodology for the study of albumen photographs. This paper shows the feasibility of obtaining FTIR images of samples from albumen photographs with a high spatial resolution using a Ge ATR objective coupled with an infrared microscope. The improved spatial resolution compared to FTIR images obtained by the reflection method is due to the high refractive index of the ATR crystal, which gives a high numerical aperture and hence, a higher spatial resolution. The technique reveals detailed information on the organic functional group distribution in the individual layers of embedded cross sections and is used complementary to visual microscopy and scanning electron microscopy/energy dispersed X-ray spectroscopy. The main results of the study are discussed with regard to their historical and artistic significance, and they are compared with data from historical and conservation literature.  相似文献   

14.
The Sos Furrighesos necropolis (Anela) is considered to be one of the most important funerary monuments in Sardinia. The hypogeum consists of various graves, called Domus de Janas, which are decorated with Neolithic mural paintings and sculptures. This work was undertaken in order to clarify which techniques were used in the past, through the identification of pigments and binding media. The samples, scraped off from the paint surface, were studied by using various analytical techniques in order to characterise both the pigments and the binding media. The main problems concerning the characterisation were due to the small sizes (1–5 mg) of the samples and their complex nature. As regards pigments, X-ray diffraction and scanning electron microscopy-energy dispersive X-ray spectrometry analyses were performed on the samples. These techniques are well suited to the characterisation of inorganic pigments and have led to the identification of the red pigment as haematite. In order to characterise the organic binders, the samples were analysed by a procedure based on a gas chromatography–mass spectrometry technique, which allows proteinaceous and lipidic media determination in the same sample. In most of the samples, the presence of egg was suggested.  相似文献   

15.
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).  相似文献   

16.
The “marble” Portasanta from Caldana (Grosseto, Italy) takes its name from the strict resemblance to the ancient Marmor Chium (also this called Portasanta) coming from the island of Chios in Greece. In this work, a complete characterization of the Italian Portasanta was made: chemical (X-ray fluorescence and isotopic analyses), mineralogical (X-ray diffraction on the bulk sample and on insoluble residue after acid attack), physical (water accessible porosity and imbibition coefficients), petrographical (optical microscopy) and mechanical (compressive strength test) analyses have been carried out in order to obtain a better distinction between Italian and Greek “marble”, sometimes mistaken. The Portasanta from Caldana (Italy) was quarried surely in the sixteenth century, but a possible use of this material during Roman time is still in doubt. The study of samples from some Tuscan archaeological sites (Torraccia di Chiusi, Siena and Roselle, Grosseto) allows us to confirm the use of Portasanta from Chios for the Torraccia site and that of Caldana for Roselle.  相似文献   

17.
This work describes the quantitative analysis of mercury present in the ink used to colour some books of XVIII century. The mercury content was determined by Energy Dispersive X-ray Spectrometry. This is a non-destructive technique which allows elemental identification and quantification (Z > 13) by atomic physics processes. The organic pigments cannot be identified by this technique, taking into account that its composition is mainly C, O and H. Levels of 2 wt.% and 4.5 wt.% were measured in 1756 and 1753 books respectively. No significant amount of mercury was observed in other red books, on a total of 11, all from XVIII century: 1720, 1732, 1753, 1756, 1780, 1798, 1800. More than one book for each year were analysed. The studied books belong to a private collection, and were selected taking into account the age and the reddish colour of their external parts. High content on Fe were observed in some of the books. This work highlights the application of a physics technique in a very important aspect for art and cultural heritage conservation and restoration, considering that high levels of toxic elements might be found in ancient documents. It is of great importance that preliminary elemental analyses are performed on ancient documents before handling them, because they might constitute some danger for restorers, conservators and collectors. This work highlights, for the first time, the danger of some ancient books. They might contain a very high concentration of mercury, which is toxic for the organism. This is also a particularly important problem of public health never mentioned in literature before.  相似文献   

18.
Transylvanian glass icons are very specific heritage items of Romanian folk art, produced from the middle of 18th century until now. The present research reports the results of a study on the organic components of the paint layers, analyzing the binding media of a series of glass icons belonging to three important icon making centers: Nicula, Olt County (?ara Oltului) and Brasov area (?cheii Bra?ovului). The analysis of the binding media has been done by means of gas chromatography coupled with mass spectrometry (GC/MS). The applied analytical procedure allowed the characterization of the proteinaceous, polysaccharide and lipid-resinous content of the binding media starting from a unique microsample. Results showed that a wide range of materials were used by the icons painters, mostly applied as mixtures of a proteinaceous material and a lipid one. The proteinaceous component proved to be mainly egg, though animal glue and casein were ascertained too, and proteins were often mixed; the lipid material was identified as linseed oil. In some of the icons pine resin and saccharide material were found. Data also highlighted that though the materials used in all the glass icons under study are similar, some particularities could be observed in the painting technique of the studied producing centers and icon painters.  相似文献   

19.
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   

20.
Piperno, a Late Quaternary magmatic rock cropping out on the eastern side of the Campi Flegrei (Italy), is probably the most important building stone of Naples, used over a time-span from at least the Roman age until the beginning of the 20th century. Despite its wide diffusion in the monumental architecture of Naples, very little is known about this rock, as regards its technical features, as well as the geological aspects. This paper aims at providing a first overall contribution towards a rediscovery of this long-time-used material, in view of careful restoration works, which nowadays at Naples only take into account the proper geological features of the stone in a few peculiar cases. Thus, it seems of extreme importance to understand the basic parameters of Piperno and, above all, its response to weathering agents. Main mineralogical, petrographical and engineering–geological properties are presented here for the first time, with specific reference to two sampling areas, located at Pianura and Soccavo, in the western sector of the Neapolitan urban area. As far as many of its physico–mechanical features are concerned, Piperno extends over a wide range of values, which allow different varieties of the rock to be identified. This preliminary result is seemingly in accordance with data from old historical literature, which stated the existence of six horizons in the Piperno formation.  相似文献   

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