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1.
Stained glass windows belong to the most precious pieces of art in many European countries. Examples of heavily endangered paint on glass are reported in the literature and mainly related to condensation effects and air pollution, as stained glass windows preferably remain in their original architectural surrounding. Several surface coatings and paint treatments have been proposed to consolidate and protect degraded paint. Very often, the selection of the materials is based more on practical aspects than on scientific research. This study concerns the comparison of some traditional, modern and newly developed consolidants for the preservation of historic glass paintings. Experiments have been carried out with model painted glass samples simulating weathering phenomena of originals. Traditional materials like Paraloid B72, modern ones like SZA (proposed by the Fraunhofer-Institut für Silicatforschung, ISC), and three new consolidants prepared by the sol–gel method and based on different hybrid organic–inorganic alkyl-alkoxysilane systems have been considered. The adhesion, penetration, stability, hydrophobicity, mechanical and chemical resistance are properties and requirements tested to prove their effectiveness and range of use. The three new materials developed in this study for the consolidation of paint on glass have the potential to offer alternatives to existing materials. Nevertheless, further research is necessary before their application in restoration workshops can be recommended. A strategic approach is requested to avoid risks for these valuable historical originals and to contribute to the long-term preservation of the paint on stained glass windows in their original sites.  相似文献   

2.
In the present article we report a study on some sodium dodecyl sulphate/propylene carbonate based aqueous micellar solutions developed with the aim of setting up a nanotechnological cleaning system to remove naturally aged polymeric acrylic layers from the surface of the wall paintings in the Old Sacristy of Santa Maria della Scala in Siena (15th century). Being these systems mainly composed of water (more than 70% by weight), the cleaning of the painted surface have been performed with low environmental impact, due to the small amount of the pure organic solvents used (always less than 25% by weight). Furthermore, the aqueous phase constitutes a hydrophilic barrier to the penetration of the hydrophobic acrylic materials into the porous support. Fourier Transform InfraRed spectroscopy (FTIR), Scanning Electron Microscopy coupled with Energy Dispersive X-rays analysis (SEM/EDX) and in situ capillary water adsorption measurements indicated the efficacy of this cleaning procedure. Finally, the chemical diagnostics investigation enabled to ascertain the presence of both salts (nitrates and gypsum) and the acrylic polymeric material.  相似文献   

3.
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   

4.
The paper presents the use of laser radiation for cleaning of beeswax treated granite stone. In the early sixties, prestigious restorers decided to apply molten beeswax on the granite surface of valuable monuments with the aim of preventing the erosive action of atmospheric agents. An interesting example of this treatment is the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). With time, salt accumulation beneath the beeswax layer has caused an intense surface disintegration of granite. Conventional cleaning methods can destroy sculptured details of these emblematic monuments. For this reason, excimer laser cleaning has been chosen as a promising non contact, selective and environmentally friendly cleaning technique to be studied.The cleaning tests have been carried out using an excimer laser (ArF, 193 nm), with fluences between 0.5 and 2 J cm−2 pulse−1 and a spot area of 0.025 cm2. Samples representing beeswax films over Roan granite have been irradiated and their degree of cleaning has been studied as a function of the number of pulses and the laser fluence.Cleaning efficiency has been evaluated by FT-Raman Spectroscopy, allowing to establish the beeswax ablation threshold and the ablation rate.Excimer laser cleaning allows a progressive and controlled removal of a few tenths of micrometers of beeswax per pulse without damaging the underlying granite stone.  相似文献   

5.
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   

6.
A KrF-excimer laser operating at λ = 248 nm was used for basic studies in cleaning ancient glass surfaces. For irradiation a mask projection technique was applied. A modified optical set-up was designed using cylindrical lenses for large area removal by line scanning. Previous investigations revealed insufficient knowledge about interaction processes between UV-laser radiation and individual surface layers of encrusted historical glass. Thus, first detailed studies were carried out on special model glass samples simulating the behaviour of historical glass. The potential of removing crusts, bio layers as well as layers of different conservation materials (due to former conservation work) were examined. The avoidance of damaging material such as gel layers, paint layers or the bulk glass was of great importance. Removal rates and thresholds for the materials mentioned above were carried out. The collected data enables a comparison and evaluation of the feasibility for the removal of superficial layers from historical glass artefacts. The results indicate that in some cases a closed loop process control will be necessary to avoid over-cleaning.  相似文献   

7.
Titanium dioxide (TiO2) can be used to realize transparent self-cleaning coatings on stone surfaces as an active and preventive protection system, limiting cleaning and maintenance actions, reducing their costs in Architectural Heritage. This self-cleaning ability is due to photo-induced hydrophilicity on treated surfaces. The aim of this investigation is to analyze this effect, since it could bring to a greater water absorption, a potential source of damage for stone surfaces. Titania sol, obtained by sol-gel and hydrothermal processes, was deposited on travertine by spray coating, in two different ways. Water absorption by capillarity, static contact angle and a specific surface water absorption analysis were assessed before and after the TiO2 treatments. The effects of deposited amount of titania on the characteristics of treated surfaces were evaluated. It was shown that there were no evident changes in the substrate reactivity without ultraviolet (UV) light exposure, while it seems that hydrophilicity due to UV light does not lead to higher water absorption, thus encouraging the use of TiO2 coatings in the field of Architectural Heritage. However, before widely applying this conservative treatment, some further researches are recommended in order to better assess its durability and sustainability.  相似文献   

8.
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   

9.
The growing interest in the conservation of historic buildings encourages the development of water-repellent materials and methodologies to consolidate and/or protect stones. Recently, particular attention was devoted to composites of inorganic oxides nanoparticles and hybrid siloxane or silicone polymers. Here we present a study on the water repellence of a thin protective coating obtained through sol-gel process starting from Glymo and Dynasylan 40®, and loading the silicate matrix with nano-sized silica particles (Aeroxide LE1® -Degussa-Evonik). The coatings were applied to limestone, sandstone and granite samples. The silica nanoparticles have been characterized by XRD, the siloxane matrix through micro-Raman spectroscopy, while the surface morphology was examined by SEM. The efficacy of the treatments has been evaluated through static contact angle measurements and capillary water absorption. The optical appearance of the coatings was evaluated by colorimetric measurements. Nanoparticles at suitable concentration gave high values for the static contact angle (up to ∼ 150°), for all stone species even for four months exposure to atmospheric conditions. The coatings, in the water capillary absorption tests, however, behave as expected only for granite even if the long-term water direct contact reduces the hydrophobicity.  相似文献   

10.
The development of laser cleaning as a conservation treatment has imposed a need for the evaluation and assessment of other cleaning techniques. The use of more traditional methods like abrasive cleaning, steam cleaning and chemical cleaning has relied so far on visual assessment, unlike much of the research applied to laser cleaning. A conscientious use of these cleaning methods requires their assessment as well as the need for a comparison based on a common methodology. A topographical assessment of laser cleaning, abrasive cleaning, steam cleaning and chemical cleaning (using hydrofluoric acid, ammonium carbonate and EDTA) is presented. Topographical variations induced on marble, oolitic limestone and architectural terracotta surfaces are assessed by means of light interferometry, showing the potential of this non-contact and non-destructive technique for surface studies in conservation. The comparison between cleaning treatments is based upon key parameters associated with cleaning surfaces. The aesthetic impact of these treatments is verified by means of optical microscopy and quantified by colour measurement. Chemical analysis of the cleaned surface (EDS) is performed to investigate the removal of surface pollutants and the presence of residues. Finally, petrographical analysis was used to investigate the removal of pollutant layers and its effect on surface texture.  相似文献   

11.
Very often traces of paint and pigment have been found on medieval sculpture. Presently, little is known about the effects of laser radiation on polychromy. It is important to protect and preserve these traces during any cleaning or restoration process. The absorption properties of polychrome materials are likely to be different from those of the underlying stone or substrate and as a result special care must be taken to avoid any damaging or discolouring phenomena associated with laser cleaning. Spectroscopic methods (XPS, AES, reflectance spectroscopy) together with optical microscopy, digital photography and X-ray diffraction analysis have been used in a series of experiments on simulated samples of common medieval pigments (vermilion, red and white lead and ochres in linseed oil) on limestone plates, in order to study the reaction of these materials to infrared laser radiation.  相似文献   

12.
The removal of a brass-based paint (purpurin) used in painting gilded wood to cover losses of gold leaf, represents today a difficult task to conservators, who may have to resort to toxic chemical solvents in order to clean the painted surface. This action, due to its nature, is unsuitable for both the conservator and the artwork itself. In this study, a Q-switched Nd:YAG laser system outputting 1 064 nm (infrared), 532 nm (visible, green) and 266 nm (ultra-violet) radiation was used to study the interaction of these wavelengths in a gilded sample surface painted with purpurin. All tested wavelengths interacted differently with the tested surface and, also, the several layers that form the gilded surface (purpurin, varnish and gold) showed different interactions to each wavelength. The ultra-violet radiation (266 nm), in a multi-pulse mode at low fluences, was found to be the most efficient wavelength in cleaning the painted gilded surface.  相似文献   

13.
The Carrera del Darro is a street within the city of Granada, Spain, which is emblematic owing to the architectural value of its buildings, to its significance for the urban structure of the city and to the implications it has for the surroundings of the Alhambra. Our study concerns the chemical analysis of the mural paintings on four façades, corresponding to numbers 23, 25, 27 and 29 of the Carrera del Darro. From the analysis of the mortar, it may be concluded that the composition is very similar, though not identical, in the four paintings studied: a limestone mortar. Ochre, white, black and red were used for the decoration of the four façades; green pigment was also observed in the second decoration of no. 29. The results of the morphological examination and EDX microanalysis of the paint samples are shown. By means of the thermogravimetric analysis we established the existence of an organically derived compound. After the existence of an oleaginous binder had been discounted by gas chromatography/mass spectrometry (GC/MS) analysis, we continued with the extraction and determination of proteins by spectrophotometry analysis, detecting low levels of proteins in the paint on the four façades analysed. The study was completed by evaluating the influence on the deterioration of the paintings by the possible surface presence of salts (such as nitrates or chlorides) and organic compounds.  相似文献   

14.
Porous limestone and mortar are able to absorb large quantities of water. This phenomenon will accelerate the deterioration of the material. In such cases, the material might be treated with a hydrophobic product, which creates a superficial layer that hampers the penetration of water. In order to decide if such a treatment should be applied or not, the water absorbing behaviour of the material should be measured. With the same measuring technique the efficiency of the hydrophobic barrier can be evaluated. Moreover, it allows the monitoring of such barriers as a function of time. At the same time, the water absorption of porous stone material is an indication of the degree of deterioration and its sensitivity to future deterioration. Up to now, two different measuring techniques exist, but one can only be used in laboratory and the other, which can be operated in laboratory as well as in situ, is not always reliable for in situ analyses. This article proposes an alternative method: the contact sponge method. This recently developed method was tested on non-treated porous stone materials in a laboratory environment in order to evaluate its performance in comparison with the two existing methods.  相似文献   

15.
The stele of Axum was brought to Rome in 1937, broken in five pieces. The erection of the stele in Rome, in Porta Capena square, required re-joining the pieces with mortar joints and bronze bolts. To give back the stele to the Ethiopian authorities, following an Italian/Etiopian agreement, it was impossible to send the stele as it was, it required separation into three pieces so that the load and dimension of each piece was compatible with the aircraft characteristics. This operation was very delicate, as for cultural reasons it was not acceptable to cut the stone (granite) of the stele with a saw; therefore the only option was to disarticulate the stele in two of the joints. To do that, as the material was weakened by microcracks and decay, it was foreseen to provisionally protect the stone with a carbon-fibre and epoxy fabric and then to apply tension forces to open the joints with a system of jacks.  相似文献   

16.
An archaeological excavation has been carried out at Pisa (Italy), unearthing an ancient metallurgical workshop. Since archaeological burnt materials provide important records of direction and intensity of the Earth's magnetic field in the past and they can be used to better improve geomagnetic secular variation curves (SVCs), an archaeomagnetic study has been performed. This small copper-alloy furnace presents a circular concave shape covered with a thin layer of mortar, with some traces of heated clay surrounding the feature that confirms the high temperature reached inside it. Archaeological context dating points to the last firing of the furnace between the last quarter of the 13th century and the first quarter of 14th century AD, when then the metallurgical workshop was transformed in a warehouse. Archaeomagnetic sampling has been performed using the modified Thellier method, by collecting several, large and independently oriented aliquots of heated clay, forming the bottom part of the circular wall of the structure. Laboratory treatments have been conducted at the IGG-CNR ARCHEO_LAB (Pisa, Italy) and at St. Maur Palaeomagnetic laboratory (Paris, France). Analytical measurements of the thermo-remanent magnetization index acquired from the samples have been performed using a large cell induction magnetometer for large samples, and the characteristic remanent magnetization (ChRM) has been successfully isolated after an alternate field demagnetization cleaning procedure for each sample. The final mean archaeomagnetic direction has been calculated at sampling site (D = 6.9°; I = 52.8°; N = 9; k = 305; α95 = 2.6°) following the Fisher Statistics, and it exhibits a perfect agreement with some coeval already published directions obtained from Mt. Arso lava flows, these latter being an important anchor point in the preliminary Italian secular variation curve. Comparison with the preliminary Italian SVC, the French SVC and the SCHA.DIF.3K archaeomagnetic regional model have permitted to define an archaeomagnetic absolute age confirming the conventional archaeological age, underlining the importance of this result into the Italian archaeomagnetic data set.  相似文献   

17.
This paper presents the first extensive investigation of the composition of both the organic and inorganic media used by Lorenzo Lotto, one of the outstanding artists of the Italian Renaissance in the early 16th century. By investigating four paintings from The State Hermitage Museum collection (Saint-Petersburg, Russia), new insights into the artist's painting techniques were obtained, which contribute to our understanding of the transition from egg tempera to oil painting techniques that took place in Italian paintings between the 15th to the mid 16th century. Inorganic materials were determined using SEM-EDX and PLM, revealing information on the artist's palette. Of particular note was the powdered colourless glass found in the priming layer of the Madonna delle Grazie, which was most likely used as dryer. Organic materials were analysed in individual paint layers using GC-MS, and revealed a mature use of drying oils as paint binders, skilfully mixed with other organic materials and inorganic driers, to obtain the desired aesthetical and technical qualities of the paint. The study revealed that Lotto used the tempera grassa technique through most of his creative life.  相似文献   

18.
Optical microscopy, cross-section and fragment Micro-FTIR spectroscopic techniques along with microchemical tests were used for the identification of pigments in two different samples of an icon. Representing the Last Judgement, and painted by the Greek master Ioannis from the village of Kapesovo in the year 1771, the kneeling desk icon under investigation is a noteworthy contribution to the study of materials in post-Byzantine visual arts. The main components found in the ground layer of both samples were gypsum, beeswax and a proteinaceous material. Cinnabar, Prussian blue and cerussite were identified on the paint layers. The binding medium on the paint layers was weddelite. The materials used in the painting and ground layers were characterized in order to clarify the painting technique. Proteinaceous materials have been identified as binders for the pigments, indicating a tempera painting technique.  相似文献   

19.
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   

20.
The artist Jordi Teixidor is one of the leading exponents of twentieth century Spanish abstract art. In recent years, he has used a synthetic polymer as a support for his art work, namely polypropylene. The behaviour of this material in combination with layers of oil paint has not been studied until now. One of the objectives of this study was to chemically characterise the material present in Jordi Teixidor's work, using FT-IR spectroscopy, in order to be able to examine the behaviour of this set of materials after undergoing cycles of accelerated aging. After subjecting the samples to temperature and relative humidity cycles and ultraviolet radiation, their physico-mechanical behaviour was determined via tensile and bend tests, with the results being processed further by means of spectroscopic techniques and colour measurements. It was found that the possible migration of the additives present in the PP support and the gradual degradation of the materials could affect the adherence between the paint layers in the future.  相似文献   

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