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1.
Optical and SEM-EDS microscopy, X-ray powder diffraction and micro FT-IR spectroscopy investigations of the funerary klinai (couches) of Tomb 1 from Amphipolis and a stone sarcophagus from ancient Tragilos—two painted monuments made by Macedonian craftsmen of the Early Hellenistic period—identified the original materials and painting technique, as well as synthetic materials used as consolidants during past restoration treatments. The original organic binders and the superficial modern coatings have been identified by micro FT-IR spectroscopy applied directly to the sampled powders or tiny fragments and to their solvent—soluble fractions. The pigments identified on the couch of Amphipolis are: red and yellow ochre, cinnabar, Madder lake, paratacamite and antlerite, carbon black, calcium carbonate, kaolin and gypsum. The identification of egg and animal glue confirms the application of tempera and secco techniques. The detection of polymers such as polydimethylsiloxane, polyvinyl acetate and alkyd resins, is related to modern restoration products. The pigments attested on the paintings of the Tragilos' sarcophagus are: red and yellow ochre, Egyptian blue, malachite, carbon black, calcium carbonate and gypsum. The absence of organic binders combined with the constant presence of calcium carbonate in all the examined samples suggests the use of lime as the binding medium in the painted decoration of the sarcophagus. The presence of Paraloid B72 is related to recent conservation treatments.  相似文献   

2.
This paper reports results derived from a chemico-physical characterisation study undertaken on an important ensamble of early 20th century stained glass windows from Madrid and signed by the prestigious and well-known Maumejean Fréres company. The study is part of an on-going project of restoration and conservation carried out by the National Glass Centre Foundation (FCNV, La Granja de San Ildefonso, Segovia, Spain). The basic aim of the research was to assess their current state of conservation and to study the degree of damage suffered throughout the last century by different materials employed in their production, namely colourless and coloured glasses, grisailles, lead cames, and putties used to fix glass pieces into the lead cames. Selected samples from these materials were characterised through optical microscopy (OM), X-ray fluorescence (XRF), scanning electron microscopy (SEM), energy dispersive X-ray microanalysis (EDX), VIS spectrophotometry, and X-ray diffraction (XRD). As a general rule, most of them presented an acceptable state of conservation, without any of the known degradation phenomena of more ancient stained glasses (e.g. Medieval, Renaissance, etc.). However, some remarkable alterations were observed. Important deposits of soot and dirt particles coming from a polluted urban environment were detected, producing a slow blackening of the panels. Resulting data have been useful to design and optimise a combined conservation and restoration strategy in the recovery of this valuable legacy of early 20th century stained glass windows from Madrid.  相似文献   

3.
A collaborative project between the Materials Department of Imperial College, the Victoria & Albert Museum, Natural History Museum and the Tate Gallery was initiated with the objective of introducing laser cleaning in these London-based museums and establishing a long-term research collaboration. An access to these material conservation departments means that materials like traditional statuary materials, heavily corroded metals, ivory, palaeontological samples, textiles, stained glass, plaster and some modern materials can be used to investigate the usefulness of laser cleaning and study their effects using a wide range of analytical techniques.  相似文献   

4.
The experimental procedures and most important conclusions of the first on-site Raman study of the stained glass windows in the upper chapel of the Sainte-Chapelle, Paris are discussed. Some of the windows suffered damage during/after the French Revolution and were partly restored in the 19th century. Measurements were performed with a new portable Raman instrument on colourless, blue and green stained glasses. We illustrate how the Raman signature of the glass makes it possible to distinguish between medieval K/Ca or 19th century restored Na/Ca-based silicates and to determine their weathering degree. This is achieved by means of the extraction of vibrational parameters and then processing them, using chemometric approaches, principal components and cluster variation analyses with varying degrees of complexity. The Raman scattering intensity of weathered glasses is used to determine their relative age. The results differ from those presented in the Corpus Vitrearum Medii Aevi (obtained by visual inspection) and therefore demonstrate the need for updating these reports with modern methods such as in situ Raman spectroscopy.  相似文献   

5.
The German Federal Foundation for the Environment (Deutsche Bundesstiftung Umwelt) is one of Europe's largest organizations of its kind. It supports innovative, exemplary projects for the protection of the environment and of national historic monuments and cultural landscapes. All projects are set up to provide a platform for researchers, craftsmen and restorers to find a common solution to difficult problems in conservation practice. More than 360 projects have been funded since 1990. Two recent projects deal with laser cleaning, one for stone and the other one for stained glass windows, the latter being presented here. This publication gives an overview on cleaning problems on stained glass windows and the project methodology. The interdisciplinary approach of the project provides the possibility of including experts in different fields to examine perspectives and limits of laser cleaning for stained glass windows. Two other publications in this issue (LACONA III) give selected results on cleaning experiments achieved within this project.  相似文献   

6.
The methodology of protecting the European stained glass windows against environmental risk (e.g. meteorological factors, air pollution, microorganisms) by means of an external glazing is not new. In spite of many scientific studies carried out in the last 20 years, some questions were still up for discussion. The European VIDRIO (2002–2005) project gave an answer to these questions. The research carried out by the different project partners established a new multidisciplinary approach aimed at evaluating the efficiency of the protective glazing systems and their effects on stained glass windows conservation, and finally at assessing the most appropriate strategy to preserve stained glass windows. Scientific results showed that the so-called isothermal glazing (i.e. ventilation by the air coming from the inside of the building) protected efficiently the ancient stained glass window from environmental attack (i.e. rain, pollutants, condensation, thermal shocks) with very limited secondary effects. The scientific research highlighted that its efficiency was strongly related to the technical design of the protective system. In particular, the ventilation and the size of the interspace had to be carefully considered. The research developed within the VIDRIO project was turned into general recommendations to the owners and practitioners on the best practice for the stained glass windows future conservation.  相似文献   

7.
A significant number of archaeological finds of the 13th–16th century from the Tuscan sites of Germagnana and Gambassi in Valdelsa—FI, was studied by different physico-chemical investigations (SEM–EDS, ICP, Mössbauer spectroscopy, XRD, XRF, TG-DTA) in order to contribute to clarify the production methodology and the pre-industrial glass manufacture technology. The studied samples are mainly non-vitreous finds as production waste, refractory materials, crucibles and raw materials; also vitreous finds as frits, skims, glasses (glass masses, glass working waste and finished products) have been taken into consideration. The obtained petrographic and physico-chemical data strongly suggest that both Gambassi and Germagnana glass manufactures were strictly connected with the sources of vitrifiable materials, situated in Tuscan sand quarries. In particular a comparison between sands from the neighbouring quarries and appropriate finds of the two archaeological sites evidences that the employed vitrifiable materials possibly belong to La Casina La Cava resort. The archaeological classification, based on macroscopic observation and stratigraphic position, was compared and verified with the scientific classification of the examined finds of Germagnana and Gambassi sites based on their composition, morphology and physico-chemical properties.  相似文献   

8.
The oil painting “La Medusa” executed by Caravaggio at the end of the XVI century on a wooden shield, was investigated by integrated physical–chemical and analytical methodologies in order to obtain scientific data capable of elucidating the state of conservation and the painting technique. Optical (OM) and electronic (SEM-EDS) microscopy, micro-FT-IR spectroscopy, gas chromatography–mass spectrometry (GC–MS) and pyrolysis GC–MS were applied on two microfragments and some organic samples obtained by solvent extraction using the swab cleaning technique. The obtained results indicated that Caravaggio probably reused an old shield as a previous gypsum preparation layer has been detected under the original painting layers. He used white lead, natural earths, verdigris and lead–tin yellow type I mixed with drying oils to paint. The considerable amount of amorphous particles of copper chlorides found in the green pigment verdigris suggests that it could have been produced according to the ancient recipe of verde salsum described by Theophilus. Mordant gilding has been identified on the upper part of the shield that can be related to an abandoned experiment to give the painting a mirror-like reflecting effect. Three different varnishes layers have been detected above the painted surface. The original and restoration varnishes have been identified and they contain a mixture of drying oil, mastic and turpentine and some beeswax. Cleaning tests, performed with different organic solvents, suggest the use of isopropyl alcohol as cleaning agent because it is less efficient in comparison to others solvents; thus it ensures a careful and controlled removal of the varnishes.  相似文献   

9.
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   

10.
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   

11.
The binding media of the polychromy of Qin Shihuang's Terracotta Army   总被引：2，自引：0，他引：2  
The “Terracotta Army” is a worldwide known archaeological finding in China. It is a part of the burial complex of the emperor Qin Shihuangdi (259–210 BC), which is still under excavation and study. The fact that the sculptures, chariots and weapons of the First Chinese Emperor's Terracotta Army were originally all painted in bright colours is still not widely known. The chemical characterisation of the paint medium was performed through an analytical procedure based on GC-MS. The proteinaceous binder was identified for the first time through a desalting procedure used in proteomics. The identification of egg as a paint binder is extremely interesting in terms of the historical significance of the work of art itself and important in terms of the method of conservation. Moreover it represents one of the first steps towards an understanding of the painting technique used on ancient sculptures in China, of which – despite their fame – nothing is yet known.  相似文献   

12.
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   

13.
The scientific approach to the restoration and monitoring of mural paintings, at S. Girolamo Chapel – SS. Annunziata Church in Florence, is reported as a fruitful example of the synergic collaboration between restorers and scientists in the planning and development of conservative interventions. Before restoration, the painting technique and the state of preservation of the pictorial cycle have been investigated firstly by close examination of the painted surfaces and then by optical and/or SEM-EDS microscopy and μFT-IR spectroscopy on appropriately selected samples. In particular, the original constituent materials and those belonging to subsequent restorations were characterized together with those originating from decay processes. In this mural painting cycle, a peculiar “fresco” technique has been used although an auxiliary binder for pigment distemper has been also employed. The use of this technique, sometimes in an improper way together with uncorrected restoration interventions, are the main responsible of the unsatisfactory state of conservation of many painted areas. Preliminary conservation trials and scientific studies were carried out to design the most convenient restoration intervention and to verify the correctness and non-invasive of the necessary operations. Special attention was devoted to cleaning procedures, continuously monitored by a physico-chemical methodology, mainly based on microinvasive, microscopic and spectroscopic investigations, to evaluate the efficiency, advantages and drawbacks of the proposed cleaning procedures and define the most appropriate ones. Finally, specific decay markers have been recognized, by a comparison of the results obtained from the detached samples with those deriving from artificially aged models, to be used for a correct future monitoring and maintenance of the wall paintings.  相似文献   

14.
For conservation of the built cultural heritage, the application of conservation products like consolidants or water repellents is often suggested. Their impregnation depth is a key factor for the assessment of the treatment efficiency. It will vary depending on the internal structure of the stone material and the properties of the conservation products. In this study a porous bioclastic limestone from Maastricht (the Netherlands) and a porous sandstone of Bray (Belgium) were selected for treatment with either ethylsilicate-based consolidant products or siloxane-based water repellents. We explore the potential of neutron radiography to visualize the conservation products after polymerization, since previous experiments already proved their detectability before polymerization. Additionally, water absorption by capillarity was monitored inside the samples. The experiments in this study illustrate that the ethylsilicate-based consolidants remained visible for neutrons even after the polymerization process, while the siloxane-based water repellents can only clearly be distinguished in the stone as long as they contain a certain amount of solvent. The study proves that neutron radiography can provide important additional information for the research in the built cultural heritage domain, especially as it allows to successfully visualize the impregnation depth of silicate-based consolidants inside natural building stones.  相似文献   

15.
The application of lasers for the removal of superficial deposits from historic stained glass is a comparatively new field of scientific interest. Experimental studies concerning the behaviour of glass substrates and the corresponding superficial deposits towards different laser wavelengths were carried out. The experiments were performed using wavelengths of λ = 193 nm (ArF-Excimer), 308 nm (XeCl-Excimer), 355 nm (Nd:YAG third harmonic) and 1 064 nm (Nd:YAG fundamental) in comparison to λ = 248 nm (KrF-Excimer). This comparison is due to the fact that the present knowledge is based on the 248 nm wavelength. Specially prepared model glass samples representing the original fragments and samples of organic polymers (formerly used as a protective material for historic stained glasses) were used to study the effects of laser radiation and were subsequently characterised by optical microscopy.  相似文献   

16.
Consolidants based on tetraethoxysilane (TEOS) have been widely used for the consolidation of decaying stone heritages. These products polymerize within the porous structure of the decaying stone, significantly increasing the cohesion of the material. However, TEOS-based consolidants suffer from practical drawbacks, such as crack formation of the gel during the drying phase due to the developed capillary force, which is typical for TEOS-based consolidants. We have prepared new consolidants TEOS-based consolidants containing flexible (3-glycidoxypropyl) trimethoxysilane (GPTMS) and silica nanoparticles in order to reduce capillary force development during gel drying, and have characterized them for the application of stone consolidants. Different sizes of silica nanoparticles were used, which were smaller than the pore size of the tested stone. The properties of the TEOS/GPTMS/nanoparticle composite solution were compared with those of the commercial products Wacker OH and Unil sandsteinfestiger OH 1:1. The gelation time was similar to that of commercial consolidants, and the TEOS/GPTMS/nanoparticle solution was stable over a period of up to six months. The contact angle of the surface increased with the addition of the nanoparticle, as well as with the addition the GPTMS, which is higher than that of commercial Wacker OH. The addition of a nanoparticle, as well as GPTMS having flexible segment, provided a crack-free material, while the gels obtained from the commercial consolidants exhibited cracking.  相似文献   

17.
The aim of the work is to set up a methodological approach to verify the effectiveness of the treatments of decayed waterlogged archaeological wood and to point out the proper thermo-hygrometric conditions for its preservation after treatment. The treatments were performed on wood samples of maritime pine (Pinus pinaster Aiton), oak (Quercus sp. caducifolia), elm (Ulmus cf. minor) and strawberry tree (Arbutus unedo L.), obtained from stems pertaining to the original vegetation found in the excavation site of the Ancient Ships in Pisa (Italy), and dated from seventh century BC to second century AD The utilised products were: Polyethylene Glycols (PEG) of various molecular weights, a Polypropylene Glycol (PPG 425), Trehalose (α-D-glucopyranosyl-α-D-glucopyranoside), and their mixtures, and also a Hydroxypropylcellulose (Klucel). The main objective to be pursued by the treatments was considered the stabilisation of the original size and shape of samples. The various steps of this approach were: the execution of a preliminary diagnostic survey on untreated samples; the characterisation of treatment solutions ‘as such’ to establish the property to be monitored during the treatment; the evaluation of the main physical characteristics of wood after the treatment were determined. Among the latter, the coefficient of dimensional stability during the exposure to a series of selected thermo-hygrometric conditions and the retention of consolidants after the treatment. These two measurements allowed the definition of the ‘efficacy of a treatment’, φT, a new parameter firstly utilised in this work. It measures the stabilisation capability of the percent unit of retained product, and its value permits to put in evidence the consolidants that stabilise wood with the lowest amount of product. Conversely, it was not possible to measure the Anti-Shrink Efficiency (ASE), one of the most utilised parameters for the evaluation of treatments, because of the serious distortions and fractures observed in all the heavily degraded untreated samples.  相似文献   

18.
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   

19.
The impact of lighting, heating and people in re-using historical buildings are discussed for the case study concerning the ceremony room (i.e. the Giant Hall) of a mediaeval palace in Padova. The Hall has substantially four major problems for conservation: (i) the impact of heating, lighting and people when the room is used; (ii) many cracks on the oak panels of the coffered ceiling; (iii) the soiling by dust and soot particles deposited on the frescoes; (iv) the stained glass windows. A microclimate study was performed to know the impact of the environmental variables, and the use of the room, on the artworks preserved inside. The study has proved the impact of the lamps (both incandescence and compact fluorescent lamps) on the ceiling, the penetration of external air in the room, the heat and the moisture released by people, the impact of sunshine through windows and the scatter diagram of the daily cycles in temperature (T) and relative humidity (RH). During winter concerts, the strips of lead which are wrapped round the edge of the cut glass pieces in stained glass windows easily drop below the dew point and form condensation, starting corrosion. A discussion concerns the allowed variability, which should not exceed risk thresholds. A safe interval can be established within the area determined by the most frequent T and RH natural cycles. In fact, both of the cycles were compatible with the artefacts, or the artefacts were already damaged to allow the exceeding dimensional changes. Attention should be paid in the variability external to this area, especially approaching or exceeding a limit equal to twice the mode of the natural variability.  相似文献   

20.
The stained glass windows of the Pavia Carthusian Monastery are an important testimony of medieval glass making in which a wood-ash flushing component was used. Glass surfaces reveal alteration processes extending to depth, with evidence of microbial corrosion. Electron microprobe analyses coupled with EDS data allow the identification of different steps in the alteration process. Microbial attack occurs in an early stage and determines component leaching of the glass, with the development of reactions in which the crystallisation of gypsum is favoured.  相似文献   

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