Multiphoton Excitation Fluorescence Microscopy and Spectroscopic Multianalytical Approach for Characterization of Historical Glass Grisailles.

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.