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1.
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   

2.
Although Venice is regarded as being one of the most important centres of glass manufacture and trade in Western Europe, little is known about the origins of the Venetian glassmaking. Some archaeologists suggest there is a continuity in the history of glass making, in its transplantation from the Roman centres of the mainland (Altino and Aquileia), first to some islands of the lagoon, and later to the town. Some others, instead, think that there was no continuity at all and that the art of glassmaking was imported in Venice from the Islamic glass factories of the Middle East. Of great help in answering this and other technological questions is the information about the composition of ancient glass from well-dated excavations that allows to conclude on the early technology, sources of raw materials and long-distance trade. Some significant glass findings, including fragments of pots used for glass melting, were found on the island of Torcello and, more recently, in two emergency excavations in the historic centre of Venice. In this paper, the chemical composition of a large set of glass findings (and related materials) from the Venetian lagoon dating from the 7th to the 13th centuries is determined by X-ray microanalysis in order to throw new light on the glassmaking technology in the early centuries of the Venetian tradition. The results show that in this period there occurred a gradual transition from the Roman technique (a two-ingredient formulation with silica-lime sand and natron as a fluxer), towards the use of silica sand and soda plant ash. There is evidence, therefore, for a production continuity with the Roman period (melting pots and glass scraps with a natron-based composition), yet restricted to transparent blown items. No evidence was found for a local production of glass tesserae for the mosaics of the church of St. Maria Assunta in Torcello.  相似文献   

3.
The mosaics covering the floors of the rooms of the domus dei Coiedii at Suasa (Ancona, Italy) may be dated archaeologically and artistically between the late republican-Augustan age (end of the first century B.C.-beginning of first century A.D.) and the second century A.D.-first half of third century A.D. The floors were made mostly in opus tessellatum, only one in opus sectile. Tesserae used in opus tessellatum are made mainly of local stones, belonging to the so-called Umbro-Marchigiana Sedimentary Sequence: the white to pinkish and reddish tesserae consist prevalently of limestones belonging to the ‘Scaglia Rosata’ Formation (Late Turonian-Middle Eocene), and subordinately to the ‘Calcare Massiccio del Burano’, which is part of the ‘Calcare Massiccio s.l.’ Formation (Late Triassic-Early Lias). Most dark to black tesserae are composed of not fossiliferous marls and marly clays, which probably derive from the local ‘Marne a Fucoidi’ Formation; a number of them are made of very fine grained sandstones, which are found as pebbles in the alluvial sediments of the Cesano river close to Suasa, and, some, of aphyric leucite-bearing basanites from the potassic Quaternary magmatic province of central-southern Italy. Artificial glasses (red and green, rich in Pb and low in Sb; light blue, low in Pb and high in Sb), containing microliths of Pb-rich phase(s) and of wollastonite, were also used in some floors. The stones used in opus sectile are (1) sedimentary: nodular limestones belonging to the ‘Rosso Ammonitico’, which occurs in the Umbro-Marchigiana Sedimentary Succession; black marls and marly clays similar to those used in opus tessellatum; onyx marble; (2) magmatic: porphyrites (‘porfido verde antico’) and gabbros (ophite); (3) marbles: different kinds of coloured marbles, comprising ‘marmo cipollino’, ‘rosso antico’, ‘pavonazzetto’, ‘portasanta’, ‘giallo antico’, ‘bigio antico’, ‘brecce coralline’. White marbles from Marmara and Carrara were also employed.  相似文献   

4.
The vaults of the Saint Peter basilica in Vatican (Rome) are decorated with mosaics whose realisation is dated to the end of the 16th century. The mortar layers beneath the mosaics are realised with the so-called “Roman stucco”, a kind of mastic specifically employed as a binder in the mosaic's supporting layers. Its empirical recipe was known and reported by 18th century authors, accounting for the use of lime, travertine powder added to a mixture of herbs and linseed oil. A recent restoration of the mosaics has allowed to characterise the mortars from a compositional point of view by individuating the inorganic mineralogical fraction and by chemically characterising the organic components. The study of stucco samples has been performed through polarising microscope observations, X-ray diffraction (XRD) analyses, thermal analyses (TA) (thermodifferential-DTA and termogravimetric-TGA analysis), Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy, pyrolysis-gascromatography (PY-GC)–mass spectrometry. The analyses have allowed to distinguish between original stucco, produced and utilized at the same time of the realisation of the mosaics, and other mortars, presumably employed in later times during restoration interventions. The outcomes of the mineralogical investigation and TA indicate the presence of four different types of stuccos, here considered as four characteristic groups. The mineralogical analyses indicate that all the samples are constituted of two main phases: calcite and vaterite and the TA, beyond the quantification of the calcium carbonate content, have shown the presence of organic components in the stucco. The organic fraction was characterised by PY-GC–mass spectrometry, confirming the presence of the linseed oil cited in the ancient recipes. The very interesting outcome of this study is the occurrence of the rare calcium carbonate polymorph vaterite. The ATR-FTIR spectroscopy on the stucco gives further contribution to a better understanding of the FTIR spectrum of the rare mineral and an explanation of its formation is tentatively given.  相似文献   

5.
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   

6.
Historical evidence on the use of mortars to meet several needs has existed for millennia. With reference to the characteristic historical periods of the city of Rhodes, mortar sampling was performed on historical constructions, masonry and architectural surfaces. In the present work the different mortar technologies are investigated aiming to answer questions regarding their finality, i.e. whether their differences arise mainly from the various historical periods of construction or from the purposes they had to serve, imparting to the mortars the properties required by their function in the structure. Mineralogical, chemical, physical and mechanical investigations have been performed on characteristic samples after gradation. The exponentially declining function of the ratio CO2/H2O structurally bound to the CO2 content shows a continuous evolution of the kinetics governing the various mechanisms of carbonation of the binder or the formation of hydraulic components during setting, hardening and ageing of the mortars. The grouping of mortars in well-distinct ‘hydraulic levels’ is ascribed to the physico-chemical cohesion and adhesion bonds developed at the matrix and matrix/aggregate interfaces, respectively, allowing for the mortars to either bear continuous stresses and strains as joint mortars or provide compact impermeable renderings which harden even more on contact with water. Hence, parameters determining the diversification of the resulting mortar/matrix types concern the raw materials employed as binding materials and the production processing.  相似文献   

7.
The room-temperature photoluminescence spectra of various samples of Egyptian blue (CaCuSi4O10) are presented, discussed and compared with those of recently synthesized compounds corresponding to the ancient pigments Han blue (BaCuSi4O10) and Han purple (BaCuSi2O6). All the samples of Egyptian blue show identical spectra, in spite of their very different origin. The spectra of Han blue and Han purple are significantly different. Since the Cu2+ ion may be considered the only luminescent centre in the spectral range under investigation, the differences between the spectra of the various pigments are ascribed to a ligand-field change. This can be related to the larger size of the Ba2+ ion with respect to Ca2+. The use of PL spectra for the identification of these pigments in works of art is proposed.  相似文献   

8.
Fifteenth century porcelains and celadons are the most interesting ancient Vietnamese ceramics, both from the material and aesthetic points of view. This paper reports on composition, microstructure and technological processing of the Chu Ðâu-My Xa (Hai Duong province) ceramics. Samples come either from the kiln site or from the Cù Lao Chàm (Hôi An) shipwreck. Chemical analysis, scanning electron microscopy, EDX analysis, X-ray diffraction, Raman spectroscopy, thermal expansion/shrinkage and open porosity measurements were systematically performed. The results show the Ca (+K)-based glaze, high-temperature-fired bodies, by one- or multi-step firings. Mullite phase (3Al2O3·2SiO2) was formed in large amount indicating the true porcelain quality of the samples under study. The matrices used for overglaze colouring (e.g., the green, red and metallic-lustre) are lead-based low-firing-temperature glasses. Comparison was made for the structural elements and fluxing agents between the 15th century Vietnamese porcelains and the time-corresponding Chinese ones.  相似文献   

9.
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   

10.
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   

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.
In this paper, we have performed a systematic characterization of sol and gel properties for particle-modified silica consolidants filled with titania (TiO2-PMC), alumina (Al2O3-PMC), and silica (SiO2-PMC) particles. Viscosity of the sol is not increased much by loading with particles, especially for TiO2-PMC and SiO2-PMC. Composites show a strong reduction of silicate network shrinkage. Also, the incorporation of oxide particles into the matrix increases the elastic modulus while decreasing the thermal expansion. In agreement with the improvement of bulk gel properties, we observed better performance of PMCs against unfilled silicate upon consolidation of Ohio Massilian sandstone. Notably, the sulfate crystallization test has less effect on PMC-treated than on silica-treated samples.  相似文献   

13.
The costs for deterioration and soiling of different materials due to air pollution are huge and the damage to culture targets endangers seriously the rich European cultural heritage. Within the sixth Framework Programme of the EU, the overall aim of the CULT-STRAT project has been to assess and predict the effects of different pollutants on materials and objects of cultural heritage in a multipollutant scenario and to identify indicators and thresholds levels of pollutants. In particular, the present paper reports one of the studies carried out in the CULT-STRAT project at city level and focused on the town of Madrid (Spain). Different maps are shown for the past, present and possible future scenarios: inventory of stock of cultural heritage for each selected material, concentration of selected pollutants (SO2, NO2, O3 and PM10), corrosion (cast bronze) and recession (Portland limestone), exceedance of tolerable degradation thresholds for each material and corrosion-cultural heritage overlapped maps. The model and the methodology developed could be useful if apply it to towns, regions or countries in order to quantify the percentage of Cultural Heritage at risk or to quantify the percentage of the area where corrosion/recession exceeds the established tolerable levels.  相似文献   

14.
Nanolime dispersed in 2-propanol was extensively used for the consolidation of wall paintings. The knowledge of the advances of this methodology dealing with all the possible effects associated with the nanolime new material in conservation is fundamental to assess and improve the technique. In this paper, four different dispersions of Ca(OH)2 nanoparticles were characterised by Small Angle X-rays Scattering technique (SAXS) and Transmission Electron Microscopy (TEM) in order to achieve information on size, shape, polydispersity, agglomeration, and crystal structure (by SAED patterns) of the particles. Once characterised, the dispersions were tested in two different case studies, the Carceri dello Steri in Palermo with their graffiti and the 18th century lunettes at the SS. Giuda e Simone Cloister, Corniola (Empoli) with their lime-based mural paintings. The treated samples were characterised in relationship to either their morphology and surface chemical composition by Scanning Electron Microscopy coupled with Energy Dispersive X-rays spectroscopy (SEM-EDX), or their water absorption and mechanical properties (resistance to material abrasion). The results obtained showed that all the dispersions were nanometrically structured and their application succeeded in recovering the mechanical properties of the painting or graffito layers, not altering their permeability to water and keeping perfectly the wall transpiration. However, the dispersions constituted of the nanoparticles obtained via a synthesis able to control size and shape of the Ca(OH)2 particles resulted in a better performance in situ, even if the differences found by SAXS and TEM were slight.  相似文献   

15.
Due to sensitivity of historic papers and their conservation importance, it is necessary to produce appropriate environment condition for preservation purposes. TiO2 nanoparticles have been evaluated for multiple applications in the conservation of paper because of TiO2 nanoparticles special characteristics for UV filtration, decomposing of air pollutants and their antifungal and antibacterial properties. Firstly, TiO2 nanoparticles synthesized in sol-gel process, and then have been coated on glass surface with spray-pyrolysis method. Then, coated glass used for preparing display box for protecting paper-art-works. Also, non-coated glass was used as a blank sample and assessments have been done on the filter paper (Whatman®) as a standard for paper-art-works. Temperature, humidity and light accelerated aging were done on samples in both coated and uncoated boxes. Results showed more tension strength and lower oxidation of paper and also, lower growth of fungi and bacteria in coated glassy box. Furthermore, madder dyed papers into coated box showed lower fading after UV exposure.  相似文献   

16.
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   

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.
The conditions that led to the deterioration of the Madara Horseman sculpture, a relief carved in a sandy limestone cliff in north-east Bulgaria, were studied, with most emphasis on the chemical weathering at the stone–atmosphere interface. Total deposition sampled close to the monument contains high concentrations of NH4+ and K+, which shows the influence of the dense vegetation in the area, and Ca2+, which reflects the cliffˈs weathering products. Ca2+ is also one of the most important constituents (next to aluminosilicates) of the atmospheric particulate collected at the monument. S-rich particles are the most abundant particles in the size range < 0.5 μm. High amounts of biogenic particles (K-P-S-rich) were found, especially for particles < 1.0 μm. The chemical, mineralogical and petrographic characteristics of the stratum that holds the monument were studied down to a depth of 20 cm. Two distinctive processes are active at the stone–atmosphere interface. Firstly, a weathering crust (ca. 2 mm thickness), consisting mainly of calcite and gypsum and enriched with Cl–, K+ and NO3–, is formed in the rain-sheltered areas of the monument. Secondly, karstic dissolution in the interior of the rock substrate leads to the formation of a hard carbonate crust at the surface of the sculpture. This natural surface hardening leads to a state of ‘auto-conservationˈ of the monument. The atmospheric composition seems to have only a limited influence on the deterioration of the Madara Horseman. Far more important are the micro-climatic conditions and the action of lichens.  相似文献   

19.
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   

20.
Based on both a historic and documentary and a physicochemical approach, the study is attempting to codify well-adapted antique, medieval and traditional textile dyeing recipes; to reconstruct them through a detailed sequence of simple and reproducible operations; and to optimize the methodology at all stages, i.e. extraction of the colouring principles, as well as mordanting and dyeing; the latter being evaluated through standard light and wash fastness assessments, and on the basis of systematically obtained colorimetric data. As colouring agents are considered saffron, turmeric, weld, Persian berries, henna, safflower, dyer's bugloss, madder, scale insects, sappan and Brazil wood. A variety of mordants, namely FeCl3, SnCl2, K2Cr2O7, ZnCl2, CuSO4, and KAl(SO4)2·12H2O, is anticipated to meet both early and rather recent options, while being easily available. Based on a large collection of ancient proposals and optimized by means of methodical assessments, the standardized dyeing processes proposed are simple, reproducible, and perfectly reliable for use in the preservation of the relevant tangible heritage, and the revival of traditional arts and crafts; and are consequently beneficial to artistic weavers, as well as conservators and restorers of textile products.  相似文献   

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