Monitoring the Restoration of a Seventeenth-Century Wooden Artwork Using Laser-Induced Fluorescence and Digital Image Analysis.

The present paper is aimed at demonstrating the capabilities of digital image analysis (DIA) to support conservation of painted artwork. Laser-induced fluorescence (LIF) imaging has been usually used in the diagnosis of wall paintings. In this case, LIF is applied to the case study of a painted wooden canopy, and most successful data processing techniques are presented in the discussion of results. The Jesús del Gran Poder canopy, completed by Francisco Ruiz Gijón in 1692, is an oil panel painting on wood. Eight panels of the canopy have been study by LIF. This technique is capable of remotely acquiring hyperspectral images operating in fluorescence mode following ultraviolet laser excitation. LIF spectra combined with principal component analysis, spectral angle mapper, and DIA provide a chemical mapping of the treated wooden surface of the panels. Besides, LIF spectrum is as a fingerprint of the panels that allows stablishing differences between them. LIF imaging analysis has proven to be a very useful tool for mapping retouching work, tracking previous restorations, and detecting chemicals on the wood in order to monitor restorations.

Sample Preparation for Repeated Measurements on a Single Liquid Droplet Using Laser-Induced Breakdown Spectroscopy.

We studied changes in laser-induced breakdown spectroscopy (LIBS) signal intensity with the thickness of a liquid layer placed on a solid substrate, where an easily evaporating methanol sample was used. For a certain optimal liquid film thickness we obtained a manifold increase of the LIBS signal from methanol. Progressive liquid film thinning leads to a reduction and a successive disappearance of laser-induced splashes; the latter condition drastically reduces the sample consumption and allows measurements to be repeated many times on a single liquid droplet. In following, we developed two methods for actively controlled deformation, i.e., thinning of a liquid droplet (volume ∼10 µl) prior to its sampling by LIBS. Control of the droplet's height was achieved on a Si-SiO2 wafer substrate by electro-wetting in the case of water solutions or by target rotation in the case of viscous liquids. The chosen substrate also has the advantages of low cost, easy manipulation, and very high purity, thus minimizing interference with analytes. Through the droplet deformation, in a single-pulse excitation at moderate laser energy (70 mJ), we clearly detected Fe and Mn in peanut oil, which represent trace elements in edible oils (∼ 1 part per billion), according to results published in the literature.

Theoretical modeling of laser ablation of quaternary bronze alloys: case studies comparing femtosecond and nanosecond LIBS experimental data.

A model, formerly proposed and utilized to understand the formation of laser induced breakdown spectroscopy (LIBS) plasma upon irradiation with nanosecond laser pulses at different fluences and wavelengths, has been extended to the irradiation with femtosecond laser pulses in order to control the fractionation mechanisms which heavily affect the application of laser-ablation-based microanalytical techniques. The model takes into account the different chemico-physical processes occurring during the interaction of an ultrashort laser pulse with a metallic surface. In particular, a two-temperature description, relevant to the electrons and lattice of the substrate, respectively, has been introduced and applied to different ternary and quaternary copper-based alloys subjected to fs and ns ablation both in the visible (527 nm) and in the UV (248 nm). The model has been found able to reproduce the shorter plasma duration experimentally found upon fs laser ablation. Kinetic decay times of several copper (major element) emission lines have been examined together with those relevant to the main plasma parameters. The plasma experimental temperature, derived assuming a Boltzmann distribution, and the electron density following the Saha equation have been compared with the corresponding theoretical data. A satisfactory description of plasma parameters and main matrix constituent composition has been obtained in the time window where local thermal equilibrium was assumed for LIBS data analysis. Improved analytical capabilities are predicted upon delayed detection of plasma emission in femtosecond LIBS, in relation to the better LOD achieved and to the improved data reproducibility expected. Results support the utilization of ultrafast laser sources for trace detection, despite the residual fractionation occurring in the examined range of fluences which affects the linearity of experimental calibration curves built for tin and lead after internal standardization on copper. The validation of model results by experimental data allowed highlighting, from first principles, of the ablation mechanisms for the two temporal regimes and information on how this affects the accurate microanalysis of Cu-based alloys.