Search

Abstract Grisaille was the first paint applied on stained-glass panels, used in Europe since the twelfth century. Historical written sources described the use of iron and copper together with a high lead-silica base glass in the grisailles production. This project aims to study the evolution of the grisaille paint composition throughout time and the changes in the raw materials used in their production using non-destructive and non-invasive techniques. To achieve this objective, 23 grisaille samples dated from the 13th to the twentieth centuries from nine different countries (Portugal, Poland, United Kingdom, Sweden, Norway, Belgium, Low Countries, Germany, and France) were studied by means of micro particle-induced X-ray emission (μ-PIXE), micro energy dispersive X-ray fluorescence (μ-EDXRF), laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF), non-linear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF) and optical microscopy (OM). The results showed that it was possible to identify compositional differences and patterns throughout the samples when compared with literature results. The preference for using copper in central and south-central European countries and the addition of new compounds (CoO, Cr2O3, MnO) as colouring agents since the nineteenth century was verified. The LIBS analyses allow the identification of boron on two samples, confirming the change of base glass components since the seventeenth century. The NLOM-MPEF showed the capability of this technique to measure the grisaille paint layers’ thickness. This non-invasive multi-analytical and complementary approach proves itself efficient in identifying changes in the grisaille’s composition throughout time, which can be interpreted as changes in the raw materials and manufacture used in the production of these paint materials.

Grisaille was the first paint applied on stained-glass panels, used in Europe since the twelfth century. Historical written sources described the use of iron and copper together with a high lead-silica base glass in the grisailles production. This project aims to study the evolution of the grisaille paint composition throughout time and the changes in the raw materials used in their production using non-destructive and non-invasive techniques. To achieve this objective, 23 grisaille samples dated from the 13th to the twentieth centuries from nine different countries (Portugal, Poland, United Kingdom, Sweden, Norway, Belgium, Low Countries, Germany, and France) were studied by means of micro particle-induced X-ray emission (μ-PIXE), micro energy dispersive X-ray fluorescence (μ-EDXRF), laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF), non-linear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF) and optical microscopy (OM). The results showed that it was possible to identify compositional differences and patterns throughout the samples when compared with literature results. The preference for using copper in central and south-central European countries and the addition of new compounds (CoO, Cr2O3, MnO) as colouring agents since the nineteenth century was verified. The LIBS analyses allow the identification of boron on two samples, confirming the change of base glass components since the seventeenth century. The NLOM-MPEF showed the capability of this technique to measure the grisaille paint layers' thickness. This non-invasive multi-analytical and complementary approach proves itself efficient in identifying changes in the grisaille's composition throughout time, which can be interpreted as changes in the raw materials and manufacture used in the production of these paint materials. [ABSTRACT FROM AUTHOR]

Nowadays, in situ pigments characterization on a cultural heritage relevant surface is possible by using combined laser spectroscopies which are suitable to detect at high resolution both molecular (Raman, LIF) and atomic sample composition (LIBS), the latter with stratigraphic capabilities and high sensitivity for trace detection. Their applications are here reported regarding the identification of historical pigments and dyes on different substrates, particularly in wall paintings, from pre-historic times up to the XIXth century when the use of synthetic substances became common. In this paper attention is focused on red colors, known since antiquity for the additional ritual and medical use. Their pictorial use along the centuries is shown and in selected cases provenances hypothesis, based on historical information, could be supported by results of composition analysis and elemental trace detection made possible by the application of laser technologies.

Nowadays scientific study of Cultural Heritage accompanies most of the time historical artistic evaluation and an assessment of the conservation state by humanistic experts and restorers. Several laboratory methods with high sensitivity are well established (ICP-MS, FTIR,...), and many methods for in situ rough characterization of large surface are widely diffused (thermovision, UV photography,...), in addition to instrumentation for punctual analysis to be applied also in field (XRF, colorimetry,...). However, the request for systems that can provide rapid detailed characterization on large surface in any storage conditions is still a hot topic. This is combined with the ever-increasing demand for digital material for documentation, fruition and study. Laser-based systems, and in particular Laser Induced Fluorescence (LIF), Laser Induced Breakdown Spectroscopy and Raman spectroscopy, due to the characteristics of these sources and the detectors to which they can be coupled, respond well to these needs. The TECFIS-DIM (Diagnostic and Metrology) Laboratory of the ENEA center of Frascati (Rome, Italy) in the last decade has put an effort to develop more and more compact and efficient laser systems for in situ material characterization on cultural heritage surfaces. Here two prototypal LIF systems have been used to characterize marble surfaces treated with ancient and modern materials and a rapid recognition and mapping method has been developed and tested thanks to the individuation of discriminant spectral features. Results are reported on test samples created in lab with known substances and in situ on real artworks. [ABSTRACT FROM AUTHOR]

The preservation of the integrity of artworks and cultural heritage items during characterization and conservation operations is of high priority, therefore, the application of non-invasive techniques is commonly suggested and recommended. Nonlinear optical microscopies (NLOM), based on the use of tightly focused pulsed femtosecond lasers, are emerging techniques for structural and chemical analysis of heritage objects with micrometric lateral and axial resolution. The results obtained with a set of optical and spectroscopic techniques for the chemical and physical characterization of grisaille paint layers on historical stained glasses, from different chronologies and provenance in Spain, are presented in this work. Optical behaviour and chemical composition were investigated by NLOM, using a laboratory set-up in the modality of Multi-Photon Excitation Fluorescence (MPEF), and by a multi-analytical combination of Field Emission Scanning Electron Microscopy-Energy Dispersive X-ray Spectrometry (FESEM-EDS), Laser Induced Breakdown Spectrosocopy (LIBS) and Laser Induced Fluorescence (LIF). Thicknesses values of the historical grisaille paint layers measured with MPEF were compared with those retrieved through FESEM, showing significant consistency and agreement. Under proper conditions, analysis via MPEF microscopy avoids the photochemical and physical damage to the examined materials, thus ensuring their preservation. This approach paves the way for future in-situ, non-invasive stratigraphic investigations on cultural heritage objects. [Display omitted] • Synergetic application of non-invasive spectroscopies and nonlinear optical microscopy for grisaille characterization. • Novel stratigraphic analysis of grisailles layers by MPEF validated through comparison with FESEM measurements. • Safe cross-sectional analysis of grisailles by MPEF ensured by control of femtosecond laser power. [ABSTRACT FROM AUTHOR]

A key first step toward probing structures and interactions of individual conformers of isolated flexible molecules is uncovering their characteristic spectral signatures. Here, conformation-specific ionization-detected stimulated Raman (IDSR) and visible-visible-ultraviolet hole-burning spectra were measured simultaneously to determine the unique signatures of the two most stable conformers of tryptamine in the gas phase. These signatures together with the comparison of the IDSR spectra to the computationally predicted Raman spectra assisted in their characterization and structural identification. This new approach offers high selectivity and is foreseen to be an improved diagnostic tool for dissection of conformers of flexible molecules.