Brunetto Giovanni Brunetti

In Situ Noninvasive Study of Artworks: The MOLAB Multitechnique Approach

Driven by the need to study precious and irreplaceable artworks without compromising their integrity, researchers have undertaken numerous efforts to develop noninvasive analytical tools and methodologies that can provide a chemical description of cultural heritage materials without any contact with the object. The challenge is that artworks are made of complex mixtures, often with heterogeneous and unknown layered materials. Their components must be identified over a range of size scales, from the molecular identification of constituent compounds to the mapping of alteration phases. In this Account, we review recent research in spectroscopic techniques accessible from the mobile laboratory (MOLAB). The lab is equipped with an array of state-of-the-art, portable, and noninvasive instruments specifically tailored to tackle the different issues confronted by archaeologists, curators, and conservators. The MOLAB approach is suitable for studying a variety of objects, from ceramics to manuscripts or from historical wall paintings to contemporary canvases. We begin by discussing issues related to the acquisition and interpretation of reflectance or backscattered spectra from the surface of heterogeneous materials. Then we show how the selectivity needed for the noninvasive identification of pigments in paintings, even in mixtures or in layered matrices, can be acquired by combining elemental information from X-ray fluorescence with molecular and structural insights from electronic and vibrational spectroscopies. Discriminating between original pigments and restoration retouches is possible, even when both comprise similar chromophores, as highlighted in the study of paintings by Jordaens and Raphael. The noninvasive approach permits the examination of a very large number of artworks with a virtually limitless number of measurements. Thus, unexpected and uncommon features may be uncovered, as in the case of a lead pyroantimonate yellow doped with zinc that was discovered by micro-Raman and X-ray fluorescence on an Italian Renaissance majolica. For characterizing binding media, we discuss the strengths and limitations of using mid- and near-FTIR (Fourier transform infrared) spectroscopies supported by a multivariate statistical analysis, detailing the study of organic materials in a wall painting by Perugino and a survey of the painting technique on 18 contemporary paintings by Burri. In Michelangelos David, we show how the noninvasive mapping of contaminants and alteration phases might inform decisions on preventive conservation plans. The multitechnique MOLAB approach overcomes the intrinsic limitation of individual spectroscopic methods. Moreover, the ability to analyze artworks without the need to move them is an invaluable asset in the study and preservation of cultural heritage.

Heterogeneous distribution of metal nanocrystals in glazes of historical pottery

It has been recently shown that lustre decoration of medieval and renaissance pottery consists of silver and copper nanocrystals, dispersed within the glassy matrix of the ceramic glaze. Lustre surfaces show peculiar optical effects such as metallic reflection and iridescence. In many cases, lustre appears overlapped to colored drawings. Here we report the findings of a study on glazes, pigments and lustre of several shards belonging to Deruta and Gubbio pottery of XVI century. The components of glazes and pigments have been identified. Lustre is confirmed to be characterised by silver and copper metal nanocrystals inhomogeneously dispersed in the glassy matrix of the glaze. In the case of lustre overlapped to colored decorations, we found two contradictory cases. The first consists of a lustre surface successfully applied over a blue smalt geometrical drawing. The second consists of a lustre surface, unsuccessfully applied over a yellow lead-antimonate pigment. The yellow pigment hinders the formation of lustre and removes crystals of tin dioxide, normally present in the glaze as opacifier.

FT-NIR spectroscopy for non-invasive identification of natural polymers and resins in easel paintings

In the present study, the analytical strengths and limitations of near-infrared (NIR) spectroscopy to non-invasively characterize organic components in painting materials have been investigated. In spite of the increased amount of information available today from advanced modern analytical instrumentations dedicated to cultural heritage, the non-invasive identification of materials belonging to the wide class of organic compounds historically used in paintings is still a challenging task. Near-infrared spectroscopy offers several attractive features that make this technique particularly suitable to this purpose. In fact, it is non-invasive, allows for non-contact measurements in reflectance mode, gives molecular information on complex macromolecules, and can be performed on-site by means of portable devices. First-derivative transformation of reflectance spectroscopic data has been applied to provide a simple and fast way to deduce more information from NIR spectra. This approach has allowed spectral features to be identified that can be useful to distinguish different compounds belonging to the classes of lipids, proteins, and resins. To this purpose, at first, a spectral database of pure standard has been collected. Our analytical approach was then successfully validated on pictorial models reproducing the typical stratigraphy of an easel painting. As final step, the study of a real painting has been attempted and a drying oil, animal glue, and a terpenic natural resin, as well as an earth pigment were clearly identified, as cross-validated by GC-MS analysis.

Study of the interactions of atomic and molecular oxygen with O2 and N2 by scattering data

Absolute total scattering cross sections for the O2–O2, O2–N2, O–N2, and O–O2 systems are measured in the thermal energy range. A glory structure is present for O2–O2, O2–N2, and O–N2. For O–N2 this structure appears to be partially quenched due to the anisotropy of the 3P oxygen atom. For O–O2 the structure is almost completely quenched because of the presence of a manifold of interactions. From the analysis of the cross section data, information about the interaction potential of all these systems of atmospheric interest is obtained. For O2–O2 a potential able to reproduce also the spectroscopic and thermophysical data is proposed.

Non-invasive identification of organic materials in wall paintings by fiber optic reflectance infrared spectroscopy: a statistical multivariate approach

The aim of this study is to develop a method for the non-invasive and in situ identification of organic binders in wall paintings by fiber optic mid-FTIR reflectance spectroscopy. The non-invasive point analysis methodology was set-up working on a wide set of wall painting replicas of known composition and using statistical multivariate methods, in particular principal component analysis (PCA), for the interpretation, understanding, and management of data acquired with reflectance mid-FTIR spectroscopy. Results show that PCA can be helpful in managing and preliminary sorting of the large amount of spectra typically collected during non-invasive measurement campaigns and highlight further avenues for research. The developed PCA model was finally applied to the case of a Renaissance wall painting by Perugino assessing it predictability as compared to the interpretation of the single spectrum.

Velocity dependence of the cross section for Penning and associative ionization of argon atoms by metastable neon atoms

Relative cross sections for Penning and associative ionization in Ne*(3P2,0)–Ar collisions have been measured, in a crossed beam experiment, as a function of the collision velocity, in the thermal energy range. The total ionization cross sections have been analyzed, together with other experimental results, obtaining a best fit resonance width function. The analysis of the associative to Penning ionization cross section ratios shows that, in the high collision energy range, the ionization occurs predominantly through the 2Σ1/2 ground state of NeAr+ ion. Some considerations on the role played by the interaction anisotropy in these ionization processes are reported.

Fiber-Optic Fourier Transform Mid-Infrared Reflectance Spectroscopy: A Suitable Technique for in Situ Studies of Mural Paintings

A prototypical in situ noninvasive study of ancient mural painting materials has been carried out using an easily manageable fiber-optic Fourier transform mid-infrared (mid-FT-IR) reflectance spectrophotometer. The reported object of the study is the Renaissance fresco by Pietro Vannucci, called il Perugino, located in the church of Santa Maria delle Lacrime (1521, Trevi, Perugia Italy). For the first classification and interpretation of infrared spectra, principal components analysis was used. Spectral artifacts due to lacunas, restoration materials, or alteration products have been identified, as well as two different secco refinements bound in a tempera medium. For the characterization of inorganic pigments, mid-FT-IR spectra have been integrated with other data obtained through in situ X-ray fluorescence (XRF) elemental analysis. This complementary noninvasive approach led to the characterization of Peruginos pigments, even in the presence of complex mixtures. The mid-FT-IR noninvasive technique, in combination with XRF, is thus recommended as a valuable first approach for the examination of mural paintings, permitting the assessment of the execution technique as well as contributing to the evaluation of the conservation state.

Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods : 3 : synthesis, characterization, and detection of different crystal forms of the chrome yellow pigment

The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO(4) and PbCr(1-x)S(x)O(4), that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO(4) and PbCr(1-x)S(x)O(4), permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Goghs Portrait of Gauguin (Van Gogh Museum, Amsterdam).

Noninvasive nuclear magnetic resonance profiling of painting layers

In this work we demonstrate the potential of single-sided nuclear magnetic resonance (NMR) sensors to access deeper layers of paintings noninvasively by means of high-resolution depth profiles spanning several millimeters. The performance of the sensor in resolving painting structures was tested on models for which excellent agreement with microscopy techniques was obtained. The depth profiling NMR technique was used in situ to investigate old master paintings. The observation of differences in NMR relaxation times of tempera binders from these paintings and from artificially aged panels raises the possibility to differentiate between original and recently restored areas.

On the use of overtone and combination bands for the analysis of the CaSO4-H2O system by mid-infrared reflection spectroscopy.

With the aim of characterizing ground preparations of paintings by infrared reflection spectroscopy, the CaSO4–H2O system (gypsum/bassanite/anhydrite) has been re-investigated, evaluating and assigning the SO42- and OH overtone and combination bands, respectively, in the ranges 1900–2700 cm−1 and 5000–6000 cm−1 resulting from reflection and high concentration transmission spectra. The second-order modes have been proven to be highly specific, reliable, and less affected by overlap with bands of organic binders and can hence be exploited for the identification of the sulfate hydration phase using infrared (IR) reflection spectroscopy. Subsequently, the characterization and identification of hydration phases in unknown sulfate-based ground preparations on authentic artworks have been carried out noninvasively by fiber-optic reflection IR spectroscopy and on cross-sections by infrared reflection micro-spectroscopy. The spectroscopic data collected both on standards and artworks have been cross-validated by X-ray diffraction.