Initial results on laser cleaning at the Victoria & Albert Museum,Natural History Museum and Tate Gallery

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.     

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).     

Spectroscopic analyses of Hellenistic painted plasters from 2nd century B.C., Sicily (South Italy)

In the present work, an analytical characterization of painted plaster samples coming from ancient buildings dated back to 2nd cent. B.C., located in Licata (Sicily, Southern Italy), has been carried out. The investigation has been performed through different spectroscopic techniques: X-ray fluorescence (XRF) using an handheld energy-dispersive XRF analyzer, scanning electron microscopy equipped with an Energy Dispersive Spectrometry microanalysis detector (SEM-EDS) and Fourier transform infrared absorbance spectroscopy (FT-IR). The main goal is to identify the plaster and pigments material. In particular, the XRF investigation of surfaces is the first step for a preliminary elemental characterization. Then, through SEM-EDS measurements, a quantitative analysis of the chemical composition of the plaster and the pigmenting agents along with eventual components related to deterioration processes has been obtained. Finally, FT-IR absorbance spectra have proven to be a useful tool to investigate the molecular nature of the used materials.     

Identification of natural dyes in historical textiles from Romanian collections by LC-DAD and LC-MS (single stage and tandem MS)

In this study, the dyes present in five 17th- to 18th-century textiles from the National Museum of Art of Romania, three religious embroideries and two brocaded velvets, are characterized and discussed, together with earlier results on textiles from Romanian collections obtained by the same research group. Dye analyses were performed using two methods: the well-established liquid chromatography-diode array detection (LC–DAD) and a recently developed liquid chromatography-mass spectrometry (LC–MS) analytical protocol. The examination of very small historical samples by both techniques allows a better insight in the advantages and limitations of the two approaches to real analyses to be obtained. LC–MS data interpretation is based entirely on the results accumulated for dye standards. Electrospray ionization (ESI) was used in the negative ion mode and an ion trap served as mass analyzer. Both single stage (MS) and tandem (MS/MS) mass spectrometric approaches were considered. The dyes and natural sources identified by both analytical techniques are discussed in the historical context of the textiles, with respect to earlier results collected for similar Romanian objects. The study showed that the dye sources found in the 17th- and 18th-century Romanian velvets and embroideries were produced using a wide variety of dye sources, suggesting influences from Europe as well as from Asia Minor. Dye sources imported from New World have been also detected. The range of biological sources is in very good correspondence with earlier results obtained from textiles in the Romanian Collections. LC-MS (single stage and tandem MS) approaches have been demonstrated to be valuable tools for dye identification in small-scaled samples from historical textile objects only if sufficient knowledge on the dyes and their biological sources is first accumulated within experiments performed on standard dyes and standard dyed fibers.     

Noninvasive physicochemical characterization of two 19th century English ferrotypes

The present work was one of the first attempts to analyze the conservation status of two ferrotypes, ancient photographic plates realized on a support made of iron. The photographic material was constituted of collodion as binder for the photosensitive silver halides grains. The two ferrotypes studied belonged to a private collection of a family from Durham, UK, and were made at the end of the 19th century. The analytical techniques used for the morphological and physicochemical characterization were noninvasive. The surface morphology was studied by means of optical microscopy (OM) and environmental scanning electron microscopy (ESEM) coupled with an energy dispersive X-rays (EDX) system for the elemental analysis. These techniques, together with microreflectance Fourier transform infrared spectroscopy (μ-FTIR) and contact angle, allowed to obtain information on both the chemical – elemental – composition of the materials constituting the ferrotypes, and the conservation status of these photographic plates. The study showed that the physicochemical diagnostics allowed to characterize the two ferrotypes that, despite their similar age and provenance, showed different conservation status, surface properties, and elemental composition.     

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.     

Material structure and constructive history

The features of materials and of constructive techniques have been singled out and recorded through techniques already experimented in the archaeological field (stratigraphy and typologies comparisons); it led to determining the constructive history, the alterations and the restorations of the building on a wide scale which goes from the margin walling of the Arsenal to the colours of walls. Every single piece of the building can be associated to the general constructive history and can be representative of the whole body of materials and constructive techniques used in the different historical periods of construction and use of tesone 105.     

Ancient materials specificities for their synchrotron examination and insights into their epistemological implications

The synchrotron characterisation of archaeological and heritage materials has undergone a steep development in the past years, among a range of other advanced characterisation techniques. For synchrotron techniques alone, close to a hundred articles were published in 2011 on such materials, prompting new developments at large scale facilities. However, few publications have discussed the speci?c characteristics of heritage materials in their advanced spectroscopic and imaging study. Here, we suggest that a greater consideration be put on the speci?cities of ancient materials and their theoretical implications on the analytical process. In particular, we discuss the importance of the a posteriori framework of the study of heterogeneous materials considered in their historicity as structuring parameters of their study. Major implications are the relevance of trace analyses, those of majors and we suggest, more importantly, the dynamics between both endpoints. The on-going development of multimodal spectral imaging appears as a way to better address corresponding difficulties. Epistemologically, we suggest that a re?exive approach be developed to explain, structure and possibly contribute to narrowing down the ?eld of possible methodological research.     

Ancient covering plaster mortars from several convents and Islamic and Gothic palaces in Palma de Mallorca (Spain). Analytical characterisation

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.     

The identification of organic additives in traditional lime mortar

Organic-inorganic lime mortars were widely used in many ancient buildings due to their good performance in some fields (such as caking property, water repellency, weatherability, etc.). However, many ancient buildings and sites are suffering from various degrees of damage with the development of the economy and society and appropriate conservation and restoration are needed. The application of traditional construction materials, such as organic-inorganic lime mortars, attracts more and more attention in the conservation and restoration of ancient buildings in the recent years. So, the understanding of the components of original lime mortar which remained in ancient sites is of fundamental significance. In this work a set of analytical procedures to identify the organic additives in lime mortars by classical chemical analysis is proposed. The results show that using iodine-potassium iodide reagent, Benedict's reagent, reduction phenolphthalein reagent, Coomassie brilliant blue and sodium periodate oxidation glycerin acetyl acetone method could effectively detect a small amount of starch, reducing sugar, blood, protein and fatty acid ester that remained in ancient buildings’ lime mortars, respectively. These analytical methods are easy to operate with low detection limit, high accuracy and some other advantages.     

The effect of Nd:YAG laser radiation on medieval pigments

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.     

An analysis of building methods: chemical-physical and archaeological analyses of micro-layer coatings on medieval facades in the centre of Genoa

The present research is an attempt to create a link among different disciplines and to confirm stratigraphic observations through chemical analyses. It involved detailed colorimetric examination and in-depth chemical-physical study of the samples taken from the historical centre of Genoa, which enabled connections to be made among many data. This led to the creation of an analytical method that is applicable to various geographical sites. Examinations involved several experimental techniques: X-ray diffractometry, scanning electron microscopy, optical microscopy and infrared spectroscopy; the data were compared with those from the stratigraphic examination. A detailed investigation of the Ligurian climate, including data kindly supplied by the Environment Department of the Provincia di Genova, allowed us to explain the presence of particular chemical substances and suggested how they might have been formed.     

The characterization of commercial artists’ alkyd paints

There is little information in the conservation literature with respect to artists’ alkyd paints; thus, artists and conservators are somewhat at a loss about how to use and treat alkyds. Recently, analytical methods have been developed to identify the components in these polymers (oil modified polyesters), rates of cross-linking and mechanical properties. Presented in this paper are some of the characterization results of artists’ alkyd paints using THM (thermally assisted hydrolysis and methylation) gas chromatography– mass spectrometry (THM–GC/MS) and Fourier transform infrared spectroscopy–attenuated total reflectance (FTIR–ATR). Four brands of artists’ alkyd paints containing alkyd resin have been analysed; one containing a phthalic anhydride and pentaerythritol based alkyd resin, two containing isophthalic acid and pentaerythritol based alkyd resins, and the final one containing both phthalic anhydride and isophthalic acid and pentaerythritol based resins among the colours studied.     

What do plastics emit? HS-SPME-GC/MS analyses of new standard plastics and plastic objects in museum collections

In recent years, plastics are designated as a source of indoor pollution and particular attention has thus been devoted to the identification of emitting low molecular weight compounds. Headspace-solid phase microextraction-gas chromatography coupled with mass spectrometry (HS-SPME-GC/MS) has been already successfully applied for screening emissions from synthetic materials. This analytical tool being also non-invasive, it has been already successfully applied in the field of cultural heritage science for the identification of volatile organic compounds (VOCs) emitted from various museum objects made of natural materials. In this research, we aimed at assessing the use of HS-SPME-GC/MS as an in situ non-invasive analytical tool for a better knowledge of the volatile organic compounds emitted by plastics in collections. The possibility of characterizing plastics based on their emission signatures was also evaluated. Twelve new standard plastic samples, belonging to seven main polymer families widely present in museum collections as well as three naturally aged museum objects, were investigated. In this paper, we provide a survey of the VOCs emitted, and the use of HS-SPME-GC/MS for identifying volatile marker compounds, degradation products, additives, and monomer residues of the plastic synthesis is evaluated. More than 200 different VOCs were identified from the new standard samples. Two categories of VOCs were distinguished: “non-specific” and “specific” ones. We showed that based on the “specific” VOCs, it was possible to identify the nature of the polymeric matrix itself or at least to unambiguously distinguish a plastic by family. Emissions from the museum objects were then characterised, and main volatile degradation compounds considered as degradation markers of the natural deterioration of polymeric matrices, were identified. This identification procedure could be further exploited for the characterization of VOCs emitted by objects made of multiple synthetic polymers. Complementary to other techniques, this analytical tool is an interesting way to assess the risk for the objects stored in the vicinity of emitting plastics.     

The scientific investigation for the study and conservation of the wooden model of S. Maria della Consolazione's church (Todi,Italy)

The focus of this work is the wood polychrome model of the church of S. Maria della Consolazione in Todi, an artefact whose author and historical events are not completely known except a general reference to the construction period of the church (1508–1607 AD). In this study, original and additional materials were examined in order to provide a deeper understanding of the painting and assembly techniques, and a greater awareness of how well preserved the object is, as well as an analysis of previous preservation and conservation interventions. The samples from the painted surfaces were examined by means of micro-Raman spectroscopy, fourier transform infrared (FTIR) spectrometry and internal microstratigraphic analysis. Thin sections of the wood samples were examined under an optical transmission light microscope in order to identify the botanical species. The results shown in this paper suggest the possibility that the original painted layers are made of calcium carbonate white, red ochre and indigo and they were applied by protein binder without any ground layer. Some non-original pigments were found on the model surface like Prussian blue and chrome yellow. Concerning wood components, poplar was characterized both in the original and non-original parts of the model whereas pine species were detected only in the restoration elements.     

Manufacturing expedients in medieval ceramics in Apulia

A group of 51 shards of medieval polychrome glazed pottery, coming from Canosa castle archaeological site (Bari, Italy), has been investigated through surface analytical techniques, such as Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) and elemental ones, such as Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP–OES) and Absorption Atomic Spectroscopy (AAS) by flame and electro-thermal atomisation. The investigation was aimed at defining the elemental composition of pottery findings, identifying pigments and clarifying glaze types. The results of the analytical characterization allowed the identification of materials and technological expedients used for pottery manufacturing, highlighting original features in the production of the investigated pottery.The quantitative analysis performed on ceramic paste, glaze and painted decorations provided a significant number of results, thus enabling their effective exploitation for multivariate statistical techniques, in order to find out possible groups of pottery items with defined similarity within the samples.     

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.     

A survey on the light-fastness properties of organic-based Alaska Native artifacts

A series of light-fastness tests were conducted on a group of ethnographic objects that will be on exhibit at the Smithsonian Institution Arctic Studies Center, a recent addition to the Anchorage Museum at Rasmuson Center in Alaska. The objects surveyed belong to the collections of the Smithsonian National Museum of Natural History and the Smithsonian National Museum of the American Indian. This work was designed as a feasibility study on the use of a micro-fading tester as a non-contact and non-destructive technique to evaluate the light-stability of materials present in ethnographic collections. A broad range of objects containing a wide variety of materials were selected for the study. The materials investigated included a variety of dyes applied on silk, cotton, and wool substrates along with some unusual materials such as tanned skin and seal gut skin. The results from this investigation have allowed establishing exhibition recommendations taking into consideration the sensitivity of each object, light levels in the museum building, and estimated light exposures based on the duration of the exhibit. The micro-fading tester has proven to be a very useful tool for determining the light-stability of ethnographic materials without causing any harm to the objects. Objects containing equivalent materials are usually classified under a general category based on their probable sensitivity to light. However, micro-fading test results have permitted the detection of dissimilarities among some of these objects, which could be associated to variations in prior fading histories, the quality of raw materials, and different preparation methods.     

The case study of an Italian contemporary art object: Materials and state of conservation of the painting “Ragazzo seduto” by Remo Brindisi

This paper deals with the scientific survey of Remo Brindisi's painting “Ragazzo seduto” (Seated boy), made at the end of the 1950s, that is a symbolic figure of both his personal artistic solitude and the crisis of values determined by the economic boom in the post-war period. In a period of great changes and economic regrowth, the need to find a new style that could be the most authentic and personal as possible pressed the artist to experiment innovative products, including non-conventional support. Photographic and analytical techniques demonstrated the use of innovative products as an experimentation tendency, that pressed the artist to use non-conventional support, industrially treated with plasticized PVC and primed with acrylate polymers and to paint with traditional and industrial pigments mixed with an oil-modified alkyd resin. In the span of a few years, an unexpected and extended degradation on the whole surface of the painting took place, with the consequent formation of lifting and detachment of the paint film. The detected alteration is mainly due to the fast ageing of the employed polymeric materials, actually responsible of the impermanence of many contemporary works of arts. Clarifying the unknown aspects of the Remo Brindisi's stylistic choices together with the deterioration processes of the employed painting materials, this paper highlights the general problems related to the conservation of contemporary art, a neglected area of research in Italy, where more efforts are committed to the enormous and more ancient cultural heritage.