The Degradation of Daguerreotypes and the Relationship with Their Multi-Material Structure: A Multimodal Investigation.

Preserving and analytically examining daguerreotypes is particularly challenging because of their multi-material and multi-component structure. Various sensors have been exploited to examine mainly the image plates of the daguerreotypes even though the degradation goes beyond this component. Micro-analyses have been the preferred method due to the nanoscale structure of the image particles. In this work, we propose comprehensive multi-modal non-invasive sensing to investigate the corrosion products present in nine daguerreotypes from the Fondazione Alinari per la Fotografia (FAF, Florence, Italy). The methodology proposed includes chemical and morphological analyses: portable X-ray fluorescence spectrometry (pXRF), Raman microspectroscopy (µ-Raman), and micro-Fourier transform infrared spectroscopy in reflection mode (µ-rFTIR) for the chemical identification. For the first time, optical coherence tomography (OCT) was deployed to record the cross-sectional and morphological data of the relevant corrosion formations on daguerreotypes in a contactless way. The results allowed the characterization, in a non-invasive mode at a microscopic level, of a wide range of degradation products produced by the interaction of the different elements present in the structure of the daguerreotypes. The aim was to verify the performance of the proposed methodology and to link the chemical and physical complexity of the entire structure, disclosed by the state-of-art sensors, to the daguerreotype degradation. The results draw attention to the need to monitor not only the image condition but the whole object as a partially closed system in constant interaction internally and with the environment.

Nonlinear imaging and vibrational spectroscopic analysis of cellulosic fibres treated with COEX® flame-retardant for tapestry preservation.

Cellulose-based fabrics are widely used in the preservation and storage of historic tapestries. Their ease of flammability is a serious concern that greatly limits their applications and requires the development of effective and safe flame-retardant treatments. In this work, we analysed linen and cotton textile samples before and after COEX® treatment, a patented green technology imparting anti-flame properties by functionalizing the cellulose molecules with phosphorus and sulphur groups. Some of the samples were also exposed to photo-induced ageing after the treatment. The resulting structural and chemical changes in both fibres were characterized by nonlinear optical imaging modalities, namely Second Harmonic Generation (SHG) and Two-Photon Excited Fluorescence microscopies (TPEF), and Raman and Attenuated Total Reflection - Fourier Transform Infrared (ATR-FTIR) spectroscopies. Complementary results evidenced a reduction in microfibril crystallinity, attributed mainly to the reduction of hydrogen bonding among cellulose macromolecules, with a concomitant increase in fluorescence possibly due to the introduction of ester groups into cellulose chains and to decomposition of lignin into fluorescent by-products.

Non-invasive contactless analysis of an early drawing by Raffaello Sanzio by means of optical methods.

Studying highly valuable and fragile Renaissance drawings requires a non-invasive contactless analytical approach. In this work, we study an early drawing by Raffaello Sanzio, one of the most important artists of the Italian Renaissance, realized during his stay in Florence (1504-1508). Our analyses aimed to reveal the features of the paper support significant for its dating, identify and map the drawing media to understand the artist's technical approach, and document the drawing condition with imaging and single-sited optical methods. Reflectance Vis-NIR multispectral imaging spectroscopy elaborated with False-Colour and Principal Component Analysis provided information about the paper support and the drawing media. Laser scanning micro-profilometry and Optical Coherence Tomography allowed revealing the superficial micro-scale features of the support. The chemical composition of the different drawing materials was characterized by µ-Raman spectroscopy, which provided also some evidence of the conservation history of the drawing. Integration of spectroscopic and imaging data shows that Raffaello used different dry drawing media (carbon-based and Pb stylus) to sketch the figure and then refined the details and shadows with iron-gall ink. The paper presents a methodological approach for the analytical examination of fragile paper artworks.

Agar Gel as a Non-Invasive Coupling Medium for Reflectance Photoacoustic (PA) Imaging: Experimental Results on Wall-Painting Mock-Ups.

The new reflectance set-up configuration extended the applicability of the photoacoustic (PA) imaging technique to art objects of any thickness and form. Until now, ultrasound gel or distilled water have been necessary as coupling mediums between the immersion-type transducer and the object's surface. These media can compromise the integrity of real artwork; therefore, known applications of reflectance PA imaging have been limited to only experimental mock-ups. In this paper, we evaluate an alternative non-invasive PA coupling medium, agar gel, applied in two layers of different consistency: first, rigid-for the protection of the object's surface, and second, fluid-for the transducer's immersion and movement. Agar gel is widely used in various conservation treatments on cultural heritage objects, and it has been proven to be safely applicable on delicate surfaces. Here, we quantify and compare the contrast and signal-to-noise ratio (SNR) of PA images, obtained in water and in agar gel on the same areas, at equal experimental conditions. The results demonstrate that the technique's performance in agar is comparable to that in water. The study uncovers the advanced potential of the PA approach for revealing hidden features, and is safely applicable for future real-case studies.

Portable Sequentially Shifted Excitation Raman Spectroscopy to Examine Historic Powders Enclosed in Glass Vials.

Raman spectroscopy (RS) is a powerful non-invasive tool for the characterization of materials. However, the fluorescence effect often hampers the detectability of the relatively weak vibrational Raman signal. Several approaches were exploited to overcome this limit. This work, in particular, evaluates the performance of an in situ portable sequentially shifted excitation (SSE™) Raman spectrometer applied to the examination of artistic historical pigment powders enclosed in glass vials. The explored handheld spectrometer employs a dual, temperature-shifted, 785 nm and 852 nm laser excitation to optimize both spectral coverage and fluorescence subtraction. The study demonstrates the feasibility of the SSE RS approach for non-invasive identification of art materials, and its applicability in complex situations where the examined material cannot be removed from its container. Laboratory measurements using benchtop dispersive micro-Raman spectroscopy at 785 nm are reported for comparison.

Revealing Underdrawings in Wall Paintings of Complex Stratigraphy with a Novel Reflectance Photoacoustic Imaging Prototype.

Revealing precious hidden features by a completely non-invasive approach is one of the crucial issues in the Heritage Science field. In this regard, concealed fresco paintings still represent an analytical challenge. This paper addresses the specific issue in wall painting diagnostics by the photoacoustic (PA) imaging technique, already proven to be efficient in revealing underdrawings and internal stratigraphy in movable paintings on paper and canvas. A newly set-up reflection PA prototype was applied here for the first time to probe the charcoal, graphite and sinopia hidden sketch drawings in concealed (gypsum, limewash, overpainted) wall paintings. The results presented here push forward the frontiers of the PA imaging technique and point to its potential effectiveness of revealing hidden underdrawings in historical wall paintings with complex stratigraphy.

Revealing Hidden Features in Multilayered Artworks by Means of an Epi-Illumination Photoacoustic Imaging System.

Photoacoustic imaging is a novel, rapidly expanding technique, which has recently found several applications in artwork diagnostics, including the uncovering of hidden layers in paintings and multilayered documents, as well as the thickness measurement of optically turbid paint layers with high accuracy. However, thus far, all the presented photoacoustic-based imaging technologies dedicated to such measurements have been strictly limited to thin objects due to the detection of signals in transmission geometry. Unavoidably, this issue restricts seriously the applicability of the imaging method, hindering investigations over a wide range of cultural heritage objects with diverse geometrical and structural features. Here, we present an epi-illumination photoacoustic apparatus for diagnosis in heritage science, which integrates laser excitation and respective signal detection on one side, aiming to provide universal information in objects of arbitrary thickness and shape. To evaluate the capabilities of the developed system, we imaged thickly painted mock-ups, in an attempt to reveal hidden graphite layers covered by various optically turbid paints, and compared the measurements with standard near-infrared (NIR) imaging. The obtained results prove that photoacoustic signals reveal underlying sketches with up to 8 times improved contrast, thus paving the way for more relevant applications in the field.

Multisensorial Assessment of Laser Effects on Shellac Applied on Wall Paintings.

The assessment of five different laser treatments in the conservation of wall paintings was devised on the basis of the surface temperature monitoring by infrared thermography (IRT), ultraviolet-induced fluorescence-visible (UV-VIS) imaging, and optical coherence tomography (OCT). A series of yttrium-aluminum-garnet (YAG) lasers were tested for removal of shellac layers from wall painting mock-ups. The mock-ups were realized as buon fresco with different mineral based pigments (earths and iron oxide) on a lime- and sand-based mortar. After the carbonatation process, all the samples were treated with shellac (5% in ethanol). The effects of neodymium (Nd):YAG, holmium (Ho):YAG, and erbium (Er):YAG laser sources, in different operative modes, on average temperature of the surface, color, and morphology were inspected with complementary sensors. The results show the necessity to adopt a combined approach in establishing safe laser operating conditions to avoid any undesired effects induced on the artefacts by the laser treatments. We demonstrate, for the first time, the performance of the Ho:YAG laser in the removal of a conservation treatment.

Synchronized Hardware-Registered VIS-NIR Imaging Spectroscopy and 3D Sensing on a Fresco by Botticelli.

We discuss a synchronised sensing technique for the analysis of painted surfaces of frescos. Specifically, the performance of Visible-Near Infrared (VIS-NIR) Reflectance Imaging Spectroscopy (RIS) synchronized with three-dimensional (3D) acquisition is demonstrated in the study of a detached mural painting by Alessandro Botticelli. Synchronized sensing generates georeferenced data for simplified data treatment and interpretation. We show how such output data can provide key information to interpret important fresco surface and subsurface features (e.g., painting technique, material composition, pentimenti).

Spectral Imaging and Archival Data in Analysing Madonna of the Rabbit Paintings by Manet and Titian.

A concise insight into the outputs provided by the latest prototype of visible-near infrared (Vis-NIR) multispectral scanner (National Research Council-National Institute of Optics, CNR-INO, Italy) is presented. The analytical data acquired on an oil painting Madonna of the Rabbit by É. Manet are described. In this work, the Vis-NIR was complemented with X-ray fluorescence (XRF) mapping for the chemical and spatial characterization of several pigments. The spatially registered Vis-NIR data facilitated their processing by spectral correlation mapping (SCM) and artificial neural network (ANN) algorithm, respectively, for pigment mapping and improved visibility of pentimenti and of underdrawing style. The data provided several key elements for the comparison with a homonymous original work by Titian studied within the ARCHive LABoratory (ARCHLAB) transnational access project.

Using Optical Coherence Tomography to Reveal the Hidden History of The Landsdowne Virgin of the Yarnwinder by Leonardo da Vinci and Studio.

Optical coherence tomography (OCT) was used for non-invasive examination of a well-known, yet complex, painting from the studio of Leonardo da Vinci in combination with routine imaging in various bands of electromagnetic radiation. In contrast with these techniques, OCT provides depth-resolved information. Three post-processing modalities were explored: cross-sectional views, maps of scattering from given depths, and their 3D models. Some hidden alterations of the painting owing to past restorations were traced: retouching and overpainting with their positioning within varnish layers as well as indications of a former transfer to canvas.

Close to the diffraction limit in high resolution ATR FTIR mapping: demonstration on micrometric multi-layered art systems.

This paper is aimed at demonstrating the potentiality of high resolution Attenuated Total Reflection Fourier Transform Infrared micro-mapping (micro-ATR-FTIR) to reconstruct the images of micrometric multi-layered systems. This method can be an effective analytical alternative when the layer thickness requires high lateral resolution, and fluorescence or thermal effects prevent the deployment of conventional analytical techniques such as micro-Raman spectroscopy. This study demonstrates the high micro-ATR-FTIR setup performances in terms of lateral resolution, spectral quality and chemical image contrast using a new laboratory instrument equipped with a single element detector. The method has been first validated on mock-ups and then successfully applied on cross-sectional samples from real artworks: Leonardo da Vinci's mural painting, characterised by a few micrometers thin sequence of organic and inorganic layers, and an outdoor marble statue, with a complex sequence of decay products on its surface. This study paves the way to a new investigation modality of micrometric systems, combining high lateral resolution with excellent spectral quality, essential in the field of Cultural Heritage as well as in the wider area of materials and forensic sciences.

Determination of thickness of thin turbid painted over-layers using micro-scale spatially offset Raman spectroscopy.

We present a method for estimating the thickness of thin turbid layers using defocusing micro-spatially offset Raman spectroscopy (micro-SORS). The approach, applicable to highly turbid systems, enables one to predict depths in excess of those accessible with conventional Raman microscopy. The technique can be used, for example, to establish the paint layer thickness on cultural heritage objects, such as panel canvases, mural paintings, painted statues and decorated objects. Other applications include analysis in polymer, biological and biomedical disciplines, catalytic and forensics sciences where highly turbid overlayers are often present and where invasive probing may not be possible or is undesirable. The method comprises two stages: (i) a calibration step for training the method on a well characterized sample set with a known thickness, and (ii) a prediction step where the prediction of layer thickness is carried out non-invasively on samples of unknown thickness of the same chemical and physical make up as the calibration set. An illustrative example of a practical deployment of this method is the analysis of larger areas of paintings. In this case, first, a calibration would be performed on a fragment of painting of a known thickness (e.g. derived from cross-sectional analysis) and subsequently the analysis of thickness across larger areas of painting could then be carried out non-invasively. The performance of the method is compared with that of the more established optical coherence tomography (OCT) technique on identical sample set.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.

Portable Raman versus portable mid-FTIR reflectance instruments to monitor synthetic treatments used for the conservation of monument surfaces.

This study aims to evaluate the relevance of portable Raman and portable mid-Fourier transform infrared (FTIR) reflectance instruments in monitoring the synthetic treatments applied on plaster substrates, a crucial issue in a conservation work. Some polymeric consolidants and protectives have a relatively short life owing to their degradation, and after some years the surface should be retreated. It follows that any information about the presence and composition of the products applied, their chemical transformations and their distribution on the surfaces is essential. For these purposes, conservation scientists should seek and test new in situ methods, and this is of utmost importance especially in the case of buildings, considering their large dimensions and consequent extensive mapping. The effectiveness of portable Raman and portable mid-FTIR reflectance instruments has been compared by analysing a set of laboratory specimens prepared and treated with variable amounts of products belonging to three classes of polymers; the spectroscopic investigation highlighted, for the first time, the limits and the advantages of portable Raman and portable mid-FTIR reflectance instruments in the detection of small amounts of products commonly employed for the conservation of plasters.

Non-destructive and non-invasive analyses shed light on the realization technique of ancient polychrome prints.

Five polychrome prints representing famous painters, such as Albrecht Dürer, were analyzed using a non-destructive and non-invasive methodology as required by the artwork typology. The diagnostic strategy includes X-ray fluorescence (XRF), reflectance micro-infrared (microFTIR) and micro-Raman (microRaman) spectroscopy. These prints were realized with a la poupée method that involves application of the polychrome inks on a single copper plate, before the printing process. A broad range of compounds (i.e., cinnabar, red lead, white lead, umber earth, hydrated calcium sulfate, calcium carbonate, amorphous carbon, and Prussian blue) was employed as chalcographic inks, using linseed oil as a binding medium. Gamboge was identified in the delicate finishing brush touches realized in watercolor.

Phase separation in class II organically modified silicate films as probed by phase-imaging atomic force microscopy.

Phase imaging tapping mode atomic force microscopy has been used to examine the presence and extent of phase separation in organically modified silicate films. A total of seven films were prepared using two different synthetic routes (cohydrolysis/condensation and separate hydrolysis/condensation) with three different organoalkoxysilanes and tetraethoxysilane. Films made from separately hydrolyzed sols were rougher and had larger phase separated domains compared to films prepared from cohydrolyzed sols. Likewise, films prepared from sols containing organoalkoxysilanes with nonpolar bulky substituents, such as ethyl and isobutyl, were significantly rougher and more phase separated relative to those prepared from a more miscible nitrile alkoxysilane.