This paper accounts for the diagnostic campaign aimed at understanding the phenomenon of black stains appeared on the passepartout close to the margins of Folio 843 of Leonardo da Vinci's Codex ...Atlanticus. Previous studies excluded microbiological deterioration processes. The study is based on a multi-analytical approach, including non-invasive imaging measurements of the folio, micro-imaging and synchrotron spectroscopy investigations of passepartout fragments at different magnifications and spectral ranges. Photoluminescence hyperspectral and lifetime imaging highlighted that black stains are not composed of fluorescent materials. μATR-FTIR imaging of fragments from the passepartout revealed the presence of a mixture of starch and PVAc glues localized only in the stained areas close to the margin of the folio. FE-SEM observations showed that the dark stains are localized inside cavities formed among cellulose fibers, where an accumulation of inorganic roundish particles (∅100-200 nm in diameter size), composed of Hg and S, was detected. Finally, by employing synchrotron μXRF, μXANES and HR-XRD analyses it was possible to identify these particles as metacinnabar (β-HgS). Further research is needed to assess the chemical process leading to the metacinnabar formation in the controlled conservation condition of Leonardo's Codex.
Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall ...paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested.
Abstract This paper introduces a novel multimodal optical microscope, integrating Raman and laser-induced photoluminescence (PL) spectroscopy for the analysis of micro-samples relevant in Heritage ...Science. Micro-samples extracted from artworks, such as paintings, exhibit intricate material compositions characterized by high complexity and spatial heterogeneity, featuring multiple layers of paint that may be also affected by degradation phenomena. Employing a multimodal strategy becomes imperative for a comprehensive understanding of their material composition and condition. The effectiveness of the proposed setup derives from synergistically harnessing the distinct strengths of Raman and laser-induced PL spectroscopy. The capacity to identify various chemical species through the latter technique is enhanced by using multiple excitation wavelengths and two distinct excitation fluence regimes. The combination of the two complementary techniques allows the setup to effectively achieve comprehensive chemical mapping of sample through a raster scanning approach. To attain a competitive overall measurement time, we employ a short integration time for each measurement point. We further propose an analysis protocol rooted in a multivariate approach. Specifically, we employ non-negative matrix factorization as the spectral decomposition method. This enables the identification of spectral endmembers, effectively correlated with specific chemical compounds present in samples. To demonstrate its efficacy in Heritage Science, we present examples involving pigment powder dispersions and stratigraphic micro-samples from paintings. Through these examples, we show how the multimodal approach reinforces material identification and, more importantly, facilitates the extraction of complementary information. This is pivotal as the two optical techniques exhibit sensitivity to different materials. Looking ahead, our method holds potential applications in diverse research fields, including material science and biology.
The European Synchrotron Radiation Facility (ESRF) has recently commissioned the new Extremely Brilliant Source (EBS). The gain in brightness as well as the continuous development of beamline ...instruments boosts the beamline performances, in particular in terms of accelerated data acquisition. This has motivated the development of new access modes as an alternative to standard proposals for access to beamtime, in particular via the "block allocation group" (BAG) mode. Here, we present the recently implemented "historical materials BAG": a community proposal giving to 10 European institutes the opportunity for guaranteed beamtime at two X-ray powder diffraction (XRPD) beamlines-ID13, for 2D high lateral resolution XRPD mapping, and ID22 for high angular resolution XRPD bulk analyses-with a particular focus on applications to cultural heritage. The capabilities offered by these instruments, the specific hardware and software developments to facilitate and speed-up data acquisition and data processing are detailed, and the first results from this new access are illustrated with recent applications to pigments, paintings, ceramics and wood.
Over the last few decades, chemical and physical studies on bowed string musical instruments have provided a better understanding of their wooden finished surface. Nevertheless, until now only a few ...of them investigated the effects of the chemical pre-treatments in the traditional making procedures. Those treatments are believed to affect wood properties, its interaction with the following treatments (i.e. varnish application) and its vibro-mechanical behaviour (that may contribute to the acoustical properties of musical instruments). In this study, two traditional alkaline treatments were applied to reference samples of spruce wood, the wood commonly used to make violins’ soundboards. An integrated analytical strategy, which combines infrared spectroscopy, analytical pyrolysis coupled to gas chromatography-mass spectrometry, and gel permeation chromatography, was employed to investigate the chemical alterations of lignocellulosic polymers (cellulose, hemicellulose, and lignin). Results have shown that the selected alkaline treatments induce the partial hydrolysis of the hemicellulose chains and a slight decrease in the crystallinity of cellulose. We could also prove: (i) the cleavage of lignin-carbohydrate complexes formed by the covalent bonds between hemicellulose and lignin in spruce wood, and (ii) the partial breaking of the hydrogen bonds network in cellulose. According to the literature, the alteration of the lignin-carbohydrate complexes is responsible for changes in wood mechanical behaviour. Hence, future perspectives of this research could outline new knowledge on the vibro-mechanical behaviour of the violin soundboard and the consequent acoustics.
The influence of dibutyl phthalate (DBP) plasticizer on poly(vinyl acetate) (PVAc) degradation was investigated. A multi-analytical approach (combining FTIR and Fluorescence spectroscopy, NMR and DSC ...analyses) was used to study how thermal- and photo-oxidative ageing treatments act on the polymer and assess the role of the additive in the degradation pattern. Standard and plasticized PVAc films were artificially aged at 60 °C in a thermal regime and irradiated at wavelengths above 290 nm in a photo-oxidative ageing regime, with exposure between 100 and 2000 h. The two types of ageing differ mainly in the formation of CC double bonds along the polymer backbone, enhanced by thermal ageing, and the formation of aldehydic structures, following photo-oxidative treatment and in the degree to which plasticizer is lost. The integration of results from different analytical methods highlights the utility in combining complementary analyses for the study of PVAc degradation.
In conservation, science semiconductors occur as the constituent matter of the so-called semiconductor pigments, produced following the Industrial Revolution and extensively used by modern painters. ...With recent research highlighting the occurrence of various degradation phenomena in semiconductor paints, it is clear that their detection by conventional optical fluorescence imaging and microscopy is limited by the complexity of historical painting materials. Here, we illustrate and prove the capabilities of time-resolved photoluminescence (TRPL) microscopy, equipped with both spectral and lifetime sensitivity at timescales ranging from nanoseconds to hundreds of microseconds, for the analysis of cross-sections of paint layers made of luminescent semiconductor pigments. The method is sensitive to heterogeneities within micro-samples and provides valuable information for the interpretation of the nature of the emissions in samples. A case study is presented on micro samples from a painting by Henri Matisse and serves to demonstrate how TRPL can be used to identify the semiconductor pigments zinc white and cadmium yellow, and to inform future investigations of the degradation of a cadmium yellow paint.
In conservation science, the identification of painting materials is fundamental for the study of artists’ palettes, for dating and for understanding on-going degradation phenomena. For these ...purposes, the study of stratigraphic micro-samples provides unique information on the complex heterogeneity of the pictorial artworks. In this context, we propose a combined-microscopy approach based on the application of time-resolved photoluminescence (TRPL) micro-imaging and micro-Raman spectroscopy. The TRPL device is based on pulsed laser excitation (excitation wavelength = 355 nm, 1 ns pulse width) and time-gated detection, and it is suitable for the detection of photoluminescent emissions with lifetime from few nanoseconds to hundreds of microseconds. In this work, the technique is beneficially applied for identifying different luminescent semiconductor and mineral pigments, on the basis of their spectral and decay kinetic emission properties. The spatial heterogeneities, detected in the micro-sample, are investigated with Raman spectroscopy (785-nm in CW mode) for a further identification of the paint composition on basis of the molecular vibrations associated with the crystal structure. The effectiveness and limits of the proposed combined method is discussed through analysis of a corpus of stratigraphic micro-samples from Russian Avant-garde modern paintings. In the selected samples, the method allows the identification of modern inorganic pigments such as cadmium-based pigments, zinc white, titanium white, chrome yellow, ultramarine and cinnabar.
The historical knowledge inherited from house paint documents and the experimental research on synthetic pigments show that production methods have an important role in the performance of paint. In ...this regard, this work investigates the links existing between the optical emission, crystal defects and photocatalytic activity of zinc white pigment from different contemporary factories, with the aim of elucidating the effects of these characteristics onto the tendency of the pigment to induce paint failures. The analysed samples display highly similar crystallite structure, domain size, and specific surface area, whilst white pigments differ from pure ZnO in regards to the presence of zinc carbonate hydrate that is found as a foreign compound. In contrast, the photoluminescence measurements categorize the analysed samples into two groups, which display different trap-assisted emissions ascribed to point crystal defects introduced during the synthesis process, and associated to Zn or O displacement. The photocatalytic degradation tests infer that the emerged defective structure and specific surface area of ZnO-based samples influence their tendency to oxidize organic molecules under light irradiation. In particular, the results indicate that the zinc interstitial defects may be able to promote the photogenerated electron-hole couples separation with a consequent increase of the overall ZnO photocatalytic activity, negatively affecting the binding medium stability. This groundwork paves the way for further studies on the link between the photoluminescence emission of the zinc white pigment and its tendency to decompose organic components contained in the binding medium.
The deterioration of cadmium yellow paints in artworks by Joan Miró (1893–1983) and in painting materials from his studios in Mallorca (Spain) was investigated. Analysis of samples from Miró’s ...paintings and from paint tubes and palettes showed that degraded paints are composed of poorly crystalline cadmium sulfide/zinc cadmium sulfide (CdS/Cd
1−x
Zn
x
S) with a low percentage of zinc, in an oil binding medium. Cadmium sulfates were identified as the main deterioration products, forming superficial white crusts detected using SR µXANES and µXRD techniques. Time-resolved photoluminescence measurements demonstrated that highly degraded samples display a pink/orange emission from the paint surface with a microsecond lifetime, a phenomenon observed in other degraded cadmium yellow paints. In agreement with recent studies on altered cadmium paints, these results suggest that the stability of the paint is related to its manufacturing method, which affects the degree of crystallinity of the resulting pigment. This, together with the environmental conditions in which artworks have been exposed, have induced the degradation of yellow paints in Miró’s artworks. It was finally noted that the paints exhibiting alteration in the analysed Miró artworks have a chemical composition that is very similar to the tube paint ‘Cadmium Yellow Lemon No. 1’ produced by
Lucien Lefebvre-Foinet
. Indeed, paint tubes from this brand were found in the studio, linking the use of this product with Miro’s degraded artworks.
PDF
