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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 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 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.

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.

Daguerreotypes are historical photographic images made on mirror-like metallic plates. These are heritage objects whose shape cannot be measured with invasive techniques, like contact probes, but the high reflectivity of their surfaces makes the use of non-invasive, 3D-measuring optical techniques challenging. Moreover, the dark areas resulting from their degradation produce a very high contrast, which add extra difficulties to their measurement. In the last few years, several strategies have been developed to overcome the limitations of optical techniques when measuring reflective metallic surfaces. Many of these solutions are not applicable to the study of cultural heritage artifacts, as they are invasive. We attempted the use of conoscopic holography in a 3D-scanning system using a double-exposure strategy. This is a promising option for 3D measuring of daguerreotypes, as we experimentally demonstrated in this work. We present the results obtained from the analyses of two 19th-century daguerreotypes with different superficial conditions. The double-exposure allowed us to obtain high-quality data from the entire object surface. This enabled the measurement of micro-scale details related to the manufacturing process and/or to the corrosion deposits. The proposed methodology can be exploited to monitor the overall health of highly reflective metallic objects but also the outcomes of some conservation treatments, such as cleaning.

Abstract Historical colour charts provide a rich and often well-dated reference materials source for studying the chemical composition of all kinds of commercial brands of artists’ paints. This article presents the results of an extensive analytical study of more than 80 paint hues from 11 colour charts that are included in the German standard book Das Deutsche Farbenbuch by H. Trillich (1925, Part II). Our research focused on the identification of synthetic organic pigments, whose quickly increasing significance for artists’ paints in the early twentieth century is impossible to evaluate by documentary source research alone. A stepwise procedure combining different non- or minimally invasive vibrational spectroscopy techniques—Normal Raman and Surface-Enhanced Raman spectroscopy as well as Metal Underlayer Attenuated Total Reflection Fourier-transform Infrared Spectroscopy—allowed the identification of 18 different organic colourants in artists’ watercolours, tempera and oil colours from six German manufacturers. In addition, micro-X-Ray Fluorescence spectroscopy was applied to determine the elemental pattern of substrates, fillers, and admixed inorganic pigments. In addition to a few traditional natural organic colourants (dark and rose madder lake, cochineal lake), most of the identified compounds comprised synthetic organic pigments or synthetic dyes from various chemical classes (indigo, anthraquinone, monoazo, ß-naphthol, xanthene, triarylcarbonium, nitroso, and azine compounds). Some of these have not or only rarely been reported in artists’ paints so far. Since the identified organic colourants have mainly poor to fair (only sometimes good) fastness to light according to modern standards and partially also to solvents typically used in conservation treatments, it is evident that works of art from this period should be treated keeping in mind the possible presence of such colourants, when planning both interventive treatments and preventive measures.

Maize stem sculptures, produced during the 16th and 17th centuries in New Spain (today, Mexico) are a clear example of the convergence of the artistic traditions from the American indigenous populations and European influence. This typology of sculptures is not limited to the Americas, as the examples found in European countries have shown. Therefore, a detailed technological investigation is required to correctly classify them. This work presents the interdisciplinary and multianalytical investigation of a 16th-century sculpture made with a maize stem preserved in Guadalajara city, Mexico. We used a set of techniques, such as CT, SEM-EDX, μ-FTIR, and μ-Raman, to study, from a macro to a micro level, the structure, the polychromy, and the modification of the sculpture. The results showed the use of maize stems, paper, and wood in the construction of the sculpture and the use of the traditional polychromy, as well as the numerous modifications that changed its appearance considerably resulting in its misclassification. We were able to associate the statue with the Cortés workshop (Mexico City region), probably produced in the decade of 1580, and track its liturgical use and historical development through the centuries.

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.

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.

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.

Fluorescence analysis of materials used as binders and coatings in artworks is often hampered by numerous factors, leading to uncertainties in data interpretation. Fluorescence lifetime (FL) measurements enable improvement of the specificity with respect to steady-state measurements by resolving the decay dynamics of the fluorophore emissions. In this work, layers of natural resin, oil, and wax—in pure form, pigmented, in mixtures, and spread on different substrates—were analyzed using a compact, portable, fiber-based FL instrument. FL data were processed via the phasor method and integrated with Raman spectroscopy to obtain complementary chemical information on the different substances. It was observed that the τ-phase of the mixtures is affected by both the pigments and the dispersing medium, and that the presence of the metal substrate contributes to changes in the FL of mixtures. The results obtained with our portable FL system combined with Raman spectroscopy pave the way for a systematic study of a larger number of materials for future in situ applications on works of art.