Determination of the impregnation depth of siloxanes and ethylsilicates in porous material by neutron radiography

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.     

Combined in situ micro-XRF,LIBS and SEM-EDS analysis of base metal and corrosion products for Islamic copper alloyed artefacts from Umm Qais museum,Jordan

Selected copper alloy artefacts from the collection of the Umm Qais museum at Irbid, Jordan, were studied by SEM-EDS analysis, while in situ analyses were performed by means of portable μ-XRF and LIBS spectrometers. Analysis and characterization of base metal and corrosion products of the copper alloyed artefacts were performed in relation to the environmental conditions of the display and as part of the overall assessment of the museum environment. Findings of this study are directed towards guiding a preventive conservation strategy for the copper alloyed artefacts at the Umm Qais museum.     

The Government's Choice of Bureaucratic Organisation: An Application to Italian State Museums

Italian state museums are characterised by a rigid bureaucratic structure and are almost completely financed by government transfers. In this paper we develop a simplified two-stage model in an attempt to explain how the government's preferences for differentiated museum functions may affect museum organisation. The model shows that the government prefers that complementary functions (e.g., conservation and scientific research) be produced by a single museum, whereas it prefers that substitutable functions (e.g., conservation and access by the general public) be produced by two museums. We use this prediction for an empirical analysis of the organisational structure of Italian state museums. On the basis of the unique ISTAT census of the Italian museum system, we test with two separate probit models the probability of observing in a state museum the concentration of either scientific activities of conservation and research or promotion activities for education and the general public. Higher classes of centralisation for the state museums are also considered by means of an ordered probit model. The results seem to suggest that the Italian state museum structure, as surveyed in the early 1990s, fully reflected the traditional policy model viewing museums as institutions devoted to conservation, scientific research and education. JEL-Classification: D73, Z11     

Trans-illumination and trans-irradiation with digital cameras: Potentials and limits of two imaging techniques used for the diagnostic investigation of paintings

During the past two decades, thanks to the rapid development of solid-state-based sensor technology, digital imaging emerged as one of the most attractive research areas for the noninvasive investigation of paintings and flat artworks. In particular, the commercial availability of high-performance digital cameras opened up new perspectives to transmitted imaging techniques, such as trans-illumination and trans-irradiation, which are based on the acquisition of the visible (Vis) and near infrared (NIR) radiation, respectively, transmitted through the object. Until recently, these techniques were indeed considered to be unsuitable for applications on artefacts, because of the risks of overheating and overexposure to the light of the object under analysis. Nowadays, with the new-generation digital cameras, transmitted imaging can be reconsidered as a possible tool for noninvasive diagnostics on paintings on canvas. These techniques have been proven to be effective for the examination of hidden details, such as underlying drawing, for a study of the pictorial style or the executive techniques, as well as for assessing the state of conservation of the supports. Both trans-illumination and trans-irradiation can be easily implemented by means of professional photographic digital cameras, and therefore offer a valuable alternative to the more expensive well-established methodologies, such as X-ray radiography. In some cases, they are found to be complementary to the conventional techniques in revealing details of the underlying paint layers. Potentials and limits of transmitted imaging techniques are discussed in this paper, starting from three case studies of oil-paintings on canvas that belong to the permanent collection of the Gallery of modern art at the Pitti Palace in Florence.     

Investigation of Cheb relief intarsia and the study of the technological process of its production by micro computed tomography

Cheb relief intarsia is one of the most significant artistic techniques used in the early and middle baroque furniture manufacturing. The origin of this exceptional technique is closely tied to the city of Cheb and in a wider perspective, similarly to rondocubism or cubism applied in architecture; it is a branch of decorative arts distinctive just only for Czech lands. Here we report on the findings made on the basis of non-destructive X-ray micro computed tomography (μCT) analysis for determination of the condition and characteristics of the inner structures of an original plate of Cheb relief intarsia. The results of this analysis not only helped to clarify the manufacturing process itself, but also contributed to aim the future actions of the effective intarsia conservation in regard to the spreading internal cracks and defects in the plate discovered by μCT analysis.     

Desalination characteristics for ceramics excavated from Taean shipwreck,Korea

The ceramic artefacts, excavated from ancient shipwrecks, are generally saturated with soluble salts, mainly NaCl, within the porous structure of ceramics. The salinity contents typically exhibit ionic and osmotic pressures to the ceramic microstructures, thus causing significant damages to the integrity of ceramic artefacts. While the utilisation of aqueous soaking methods is commonly accepted for effective desalination processes of ceramics, the relationships between the structural characteristics of ceramics and the desalination efficiency have not been demonstrated. In this study, we examined the desalination processes of various ceramics excavated from the Taean shipwrecks in South Korea to identify major controlling factors for the desalination processes. Our results indicated that the physical properties of ceramics including the water absorption and the pore size distribution greatly influence on the desalination process time and efficiency. It is also found that the surface condition of ceramic samples such as microstructural cracks on the glaze layer is a crucial component of the desalination characteristics. Nevertheless, the small residue of salts such as NaCl crystals were found in the microstructures of some ceramics after prolonged desalination periods. Therefore, it is important to control the humidity and temperature in the conservation environment for desalinated ceramic artefacts even after desalination.     

Protein identification and localization using mass spectrometry and staining tests in cross-sections of polychrome samples

The identification and localization of the proteinaceous binders are essential issues in studies of painting materials and techniques, for further proposing valid restoration and conservation treatments of the painted or polychrome works of art. The challenge for analytical chemists and conservation scientists is the availability of methods able to simultaneously identify and map the presence of the binders in the multilayered structure of a sample and the possibility to use a very low amount of sample from the studied art object (considering also the criteria of minimum sampling). These methods should be fast, reproducible in different artefacts and in case of mixture of protein-based binders with other non-proteinaceous constituents (oils, resins, waxes, gums etc.) and also economical (both in terms of materials and time consume). In this context, the present paper proposes an innovative protocol of investigation using two complementary techniques – Matrix-Assisted Laser Desorption/Ionisation – Time of Flight Mass Spectrometry (MALDI-TOF MS) and staining tests (one visible and one fluorescent stain) assisted by Optical Microscopy (OM) on cross-section of samples – for the simultaneous identification and mapping of protein – and oil-based binders in paint materials. The novelty is based on the use of MALDI-TOF MS on cross-sections of paints together with a fluorescent stain for protein identification and mapping (mainly used in the area of proteomics) complementing the use of a traditional visible stain for oil-based material identification. The protocol was successfully applied on several samples taken from a Czech medieval polychrome sculpture, entitled “The Mourning of Jesus Christ” (16th century) belonging to the Moravian Gallery (Brno).     

Process for the 3D virtual reconstruction of a microcultural heritage artifact obtained by synchrotron radiation CT technology using open source and free software

Computer tomography (CT) technology has greatly contributed to the feasibility and convenience of detecting and visualizing the internal material constitution and geometrical fabrication of museum artifacts. This paper presents a case study of 3D virtual reconstruction for the CT-acquisition-based study of a cultural heritage artifact. It documents the complete procedure, including the preprocessing, segmentation and visualization of the data by providing coarse interactive exploration and integrated high-quality renderings. A parallel aim achieved was to use open source tools and free software for segmentation and visualization, thus providing full transparency of the adopted methodology and 3D visualization methods, and a cost effective solution for ordinary CPU-based PC users. Furthermore, the challenges of the large data volumes involved have been addressed using preprocessing, a segmentation scheme and linked front-to-back management to keep interaction and high-quality rendering available, thus achieving corresponding demands.     

The impact of heating, lighting and people in re-using historical buildings: a case study

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.     

Effective biocide to prevent microbiological contamination during PEG impregnation of wet archaeological iron-wood artefacts

A new conservation process was developed for archaeological iron-wood artefacts. Metal part protection was achieved by adding a corrosion inhibitor (Hostacor IT^®) in the polyethylene glycol (PEG) soaking solutions. Nevertheless, a significant microbiological growth was observed in the baths and around the objects. From the different soaking solutions, 23 bacterial strains and 12 strains of filamentous fungi were isolated. Adding compatible biocide has been absolutely essential to allow the PEG and Hostacor IT^® to be effective. Among biocides tested, Dowicide^®A that contains sodium o-phenylphenate is the most efficient. As shown by electrochemical measurements (corrosion potential, intensity and polarization resistance), this biocide does not destabilize the formation of protective film created by Hostacor IT^®. There is no competition of adsorption between Hostacor IT^® and Dowicide^®. In the presence of Dowicide^®, Hostacor IT^® acts more quickly and in a significant way.At the concentration of 3000 ppm, Dowicide^® is effective to protect the aqueous solutions of PEG 400+ Hostacor IT^® from the development of the selected microorganisms. Adding the biocide at the beginning of the object impregnation was the most effective way to prevent bacterial and fungal growth. Tests in real conditions showed that after two months of impregnation, solutions reminded clear and no biofilm was observed around artefacts.     

Chinese archaeological artefacts: Microstructure and corrosion behaviour of high-leaded bronzes

Metallographic features of ancient bronze artefacts often hide peculiar micro-chemical processes and corrosion behaviours, which are worth to be studied as they can provide conservators and archaeologists with valuable tools and information. It is widely documented that Chinese bronzes were cast and the way to adjust their properties was to change the alloy composition. In particular, addition of lead, which is insoluble in the bronze matrix, results in the formation of inclusions or globules, which undergo oxidation processes leading to their conversion into corrosion products. The mechanisms through which this occurs were still poorly investigated. The present work was conducted to further study the corrosion behaviour of high-leaded bronze, especially focusing on the behaviour of lead globules. To this aim, a collection of Chinese archaeological bronzes, showing intermediate steps of degradation, were selected and investigated. The use of combined microscopy-based, molecular and elemental, analytical techniques allowed the characterization as well as the precise location of corrosion products, thus enabling us to propose a degradation pathway basing on thermodynamic data provided by Pourbaix diagram. The achieved results will be useful for researchers involved in these kinds of studies to better interpret data obtained.     

Enhancing the examination workflow for Byzantine icons: Implementation of information technology tools in a traditional context

In the interdisciplinary domain of conservation science, a critical and selective eye is required in order to allow researchers to choose the most effective combination of analytical techniques for each project and, more importantly, to process and analyze the resulting volume of diverse data. The current essay attempts to combine a more traditional workflow for the examination of painted objects with techniques borrowed from the domain of computer science in order to yield the maximum amount of information and make that added knowledge more accessible to the researcher. The project was approached as a case study, regarding a post-Byzantine icon. Three-dimensional digitization with a laser scanning system, X-ray radiography and optical microscopy were applied for the determination of several structural characteristics of the painted surface and the icon's state of preservation. Multispectral imaging was used for the collection of surface spectral data, which were subsequently processed by means of cluster analysis in a novel approach to map the composition of the painted surface. Finally, micro-X-Ray Fluorescence (μ-XRF) was chosen as the primary source for surface pointwise elemental composition data while Fourier Transform Infrared Spectroscopy (FTIR) and Gas Chromatography coupled with Mass Spectroscopy (GC-MS) provided additional assistance in the characterization of materials based on their molecular structure. A custom platform was developed to address the issue of multilevel visualization and assessment of the data, designed to act as a tool for viewing and combining the acquired information. Via this integrated approach valuable information regarding the icon was revealed, including the verification of a prior conservation attempt and partial overpainting, the recording and quantification of the warping of the wooden panel and, finally, the identification of the constituent materials and their spatial distribution.     

Characterisation of 15 century red and black pastes used for wall decoration in the Qijmas El-Eshaqi mosque (Cairo, Egypt)

The use of coloured pastes for inlaying marble and limestone wall panels is one of the ornamental techniques that were widely used during the Mamluk period in Egypt (1250–1516 AD). Red and black pastes from Qijmas El-Eshaqe mosque (1482 AD) in Cairo were studied to identify their main components. The study of the samples involved the identification of the pigments, additive materials and organic binding media. The study was performed using various analytical methods such as polarising microscopy (PLM), scanning electron microscopy equipped with energy dispersive X-ray analyser (SEM-EDX), inductively-coupled plasma (ICP-AES), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). These complementary analytical techniques provide precise identification of inorganic and organic substances used in the pastes. The results indicated that the red pigment is mainly obtained from red ochre containing hematite, whereas amorphous carbon (bone black and charcoal) was used to obtain the black colour. Both samples contain calcium sulphate, which was used to give some hardness to the pastes. Beeswax was used as an organic medium in both pastes. The study provides the information required for the conservation of the coloured paste ornaments.     

Daily natural heat convection in a historical hall

The use of numerical simulation methods for the Cultural Heritage is of increasing importance for the analysis, conservation, restoration and appreciation of works of art. This is particularly important when their preservation and planned maintenance is the primary aim. Today museums, and particularly historical buildings converted to museums, should be considered as places where precious artefacts should have first-rate protection and conservation. It is a question of solving the compromise between protection, conservation and comfort for works of art and/or visitors, with the consequence that preservation and planned maintenance criteria must prevail over use requirements. Refurbishment and conservation of a building, and requirements for visitor presence and works of art need different thermo-physical indoor parameter values. The present paper concerns the thermal and air velocity analysis of the Salone dei Duecento (the Hall of the Two Hundred of the Palazzo Vecchio (Old Palace)) in Florence. In this paper an appropriate transient 3D model by Computational Fluid Dynamics (CFD) software based on the finite element method (FEM) was used. Variations and interaction between indoor and outdoor microclimatic conditions, and thermo-physical behaviour of the building connected to lighting, visitor presence and cooling–heating fan coils system were considered. The 3D modelling method provided by the present paper can be applied to several situations where there is interaction between outdoor and indoor climate variations and the building structure. It can be very useful for defining measures to preserve tapestries, understanding deterioration processes, and developing new conservation techniques and strategies for care and exhibition.     

Efflorescence on thin sections of calcareous stones

Limestone and marble, still frequently used as building materials are especially vulnerable to the destructive effects of efflorescence. The effect of interaction between five different calcareous stones and corrosive atmospheres has been investigated. A novel technique of stone degradation analysis has been used where thin sections of fresh stone materials were exposed in a corrosion chamber under controlled conditions (temperature, relative humidity (RH), SO₂ and NO₂ concentration). Following 1-week’s exposure; observations of the initial crystallisation were studied by light microscopy, scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD). The results obtained from the surface analysis clearly showed sulphation of the samples and formation of gypsum. Observations of the initial corrosion indicated differences in the location of efflorescence and its shape among and within the samples. The mineralogy, grain shape and size, mineral defects and existence of cracks and pores, all influenced the substrate’s reactivity. The most vulnerable areas and the places where the corrosion started on the calcitic stones were the triple grain junctions followed by grain boundaries, and on the dolomitic marble cracks and pores.     

Integrated reflectography and thermography for wooden paintings diagnostics

The need of inspecting a masterpiece of fine art without affecting it led to develop non destructive methods of investigation. In the field of art conservation, several diagnostic techniques are being widely used to inspect works of art, giving different but complementary results. The present work deals with two of these methods, reflectography and thermography, both techniques examining objects in the infrared spectrum but in different wavelength bands. Their integrated data potentially provide a powerful tool for mapping hidden features and alterations of artworks. This was confirmed during the inspections of a 13th century panel painting under restoration at the Opificio delle Pietre Dure laboratories (Florence, Italy). A graphical user interface was also designed to aid operators in the field of conservation dealing with the results of the two IR methods. Many options such as image adjustment, comparison, overlaying and transparency variation, in addition to thermographic elaborations, have been made available to users. Imaging data integration provides a multi-layered and multi-spectral representation of the painting that yields a comprehensive diagnosis confirms the anomalies individuation and reduces the ambiguities of information coming from a single diagnostic method.     

Technological features of the ‘Cotto Variegato’: a petrological approach

The ‘Cotto Variegato’ are tiles used in Lombardy, between the XVII and XIX centuries as flooring for several historical buildings. Tiles are produced by the processing of two compositionally distinct clays. The main stylistic character of these tiles is a banded texture producing a veined aspect, in which white and red bands are also folded. The artefacts were hand crafted using two clayey raw materials of different composition, that are only partially mixed before the firing. The colour differences are produced during the firing. In all samples white and red portions are always composed of Ca-rich and Ca-poor clay, respectively. The multi-layered texture was obtained by a multiple folding and pressing process of the mixture. The interference of fold limbs with the tile surface gives the ‘variegato’ style to tiles. The paper explains how basic petrological knowledge can be applied to the study of ceramic artefacts in order to define provenance of the raw material, firing technology and how ancient craftsmen transformed the natural clayey materials into floor tiles. The methodological approach is that commonly applied to the study of the rocks and consists of textural analyses, at a different observational scale, combined with X-ray powder diffraction, X-ray fluorescence and microprobe analyses.     

A color image segmentation method as used in the study of ancient monument decay

In the cultural heritage area, it is of fundamental importance to characterize and classify the conservation state of the materials constituting ancient monuments, in order to study and monitor their decay. Generally, the decay diagnosis is provided by “naked eye” analysis done by expert scientists “walking around” the artifact and recording the conservation state of each individual element they observe. In this paper, a color image segmentation approach, based on histogram threshold and edge detection techniques is presented, to extract degradation regions, characterized by holes or cavities, from color images of stone-materials. The goal is to provide an aid to the decay diagnosis by segmenting degraded regions from color images, computing quantitative data, such as the area and perimeter of the extracted zones, and processing qualitative information, such as various levels of depth detected into the same zones. Since color is a powerful tool in the distinction between objects, a segmentation technique based on color, instead of intensity only, has been used to provide a clearer discrimination between regions. The study case concerns the impressive remains of the Roman Theatre in the city of Aosta (Italy). In particular, we have processed and analyzed some color images of the theatre puddingstones, acquired by a camera.     

ATR-FTIR imaging of albumen photographic prints

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.     

Neorenaissance/Neobaroque stained glass windows from Madrid: a characterisation study on some panels signed by the Maumejean Fréres company

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.