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).
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.
Abstract
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.
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.
Until recently, the study of drawings by old masters has been confined to the art history conservation field. More specifically, scientific investigations of Leonardo’s drawings are still very few, ...possibly due to the latter’s extreme fragility and artistic value. However, analytical data are crucial to develop a solid knowledge base of the drawing materials and techniques used by artists in the past. In this work, we report on the application of non-invasive optical techniques on a double-sided drawing by Leonardo belonging to the Uffizi Gallery (8P). We used multispectral reflectography in the visible (Vis) and near-infrared (NIR) regions to obtain a spectral mapping of the drawing materials, to be subsequently integrated with technical information provided by art historians and conservators. Morphological analysis by microprofilometry allowed for the identification of the typical wave-like texture impressed in the paper during the sheet’s manufacture, as well as of further paper-impressed traits attributable to the drawing transfer method used by Leonardo. Optical coherence tomography revealed a set of micrometric engraved details in the blank background, which lack any trace of colored material, nor display any apparent relation to the drawn landscape. The disclosure of hidden technical features allowed us to offer new insights into Leonardo’s still under-investigated graphic practices.
Raman spectroscopy (RS), for its robust analytical capabilities under constant development, is a powerful method for the identification of various materials, in particular pigments in cultural ...heritage. Characterization of the artist’s palette is of fundamental importance for the correct formulation of restoration intervention as well as for preventive conservation of artworks. Here we examine the number and variability of research studies exploiting Bravo handheld Raman spectrophotometer relying on the excitation of Raman signal with temperature-shifted diode lasers emitting at 852 and 785 nm. To this end, we explore the spectral features of common historical pigments examined as powders and in the paint layer. We show that some materials may exhibit slightly different spectra as concerns especially the relative intensity of Raman lines with 852 nm laser excitation wavelength as compared to the standard 785 nm. The aim is to provide the research community with a reference spectral database that facilitates the identification of unknown pigments using the 852 nm excitation source.
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.
The application of protective coatings is an effective preventive strategy to avoid metal corrosion. Constant monitoring of the coating’s quality is fundamental for the successful preservation of the ...metallic objects by reducing their interaction with corroding agents. Their evaluation over time helps to identify failure at early stages and promote their removal and substitution. Several methods have been employed for coating evaluation (i.e., chemical analysis, thickness and homogeneity investigation). In this paper, we compare three methods—Optical Coherence Tomography (OCT), Confocal Raman Microspectroscopy (CRM), and Eddy Currents (ECs)—to evaluate thickness values and coating integrity. The results from the two optical techniques (CRM and OCT) agree, being able to detect the inhomogeneity of the layer on a micron scale but requiring correction to account for the refraction phenomenon. The Eddy Current is a fast and efficient method for thickness estimation, providing data with millimetric lateral resolution.
The public expected color from the early photographic images, yet, daguerreotypes—the first commercially available photographic process—failed to register the natural colors. Daguerreotypists ...developed several coloring methods to solve this inconvenience after 1840. Scientific analyses of the hand-colored daguerreotypes are limited, and the primary information sources available are manuals and patents. This study aims to contribute to the knowledge of hand-coloring techniques, which impacts conservation practices, mainly the cleaning procedures and complements technical art history investigations. We studied nine colored daguerreotypes with a non-invasive methodology based on three spectroscopic techniques: X-ray fluorescence (XRF), micro-Raman spectroscopy (μ-Raman), and micro-Fourier-transform infrared spectroscopy in reflection mode (μ-rFTIR). The results revealed the different colorants and some of their mixtures employed by the colorist. It also adds information regarding the photographic production of three studios: Désiré François Millet, active in Paris between 1840 and 1868; Antoine Claudet (1797–1867), active in London; and the James E. McClees and Washington Lafayette Germon studio, operative between 1846 and 1855 in Philadelphia, USA. These technical details constitute a helpful comparison to future studies on Daguerreian studios and colored daguerreotypes.
Abstract Stratigraphic analyzes of polychrome surfaces, such as paintings, often need samples to offer consistent results regarding the sequence and composition of the layers. Non-invasive ...methodologies based on linear and nonlinear optical techniques limit material removal from the objects. Recently, optical coherence tomography (OCT) has become the preferred choice of heritage scientists because it is a safe and fast alternative for studying transparent or semi-transparent layers. Yet, nonlinear optical microscopy (NLOM)) technique in its modality of multiphoton excitation fluorescence (MPEF) has emerged as a promising tool for the same purpose. Here, we explored linear (OCT and confocal Raman microspectroscopy (CRM)) and nonlinear (NLOM-MPEF) optical methods’ capability to investigate gelatine-based layers in mock-up samples and a painting dated 1939 by an artist from the Surrealistic entourage. The optical behavior of mock-up samples that imitate the painting stratigraphy and of six painting fragments detached from the support was also investigated with fiber optics reflectance spectroscopy and laser induced fluorescence (LIF). Thickness values from the mock-ups obtained with OCT, CRM, and MPEF have provided evidence of the complementarity, from a millimetric to a micrometric scale, and the limitations (e.g. strong fluorescence emission in CRM) of the methods. Moreover, the presence of gelatine was ascertained by LIF spectroscopy applied to the painting fragments and NLOM-MPEF confirmed its suitability as a non-invasive technique for investigating gelatine-based stratigraphic systems.
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