Automated characterization of varnishes photo-degradation using portable T-controlled Raman spectroscopy.

In this work, a portable-Raman device (excitation wavelength 1064nm) was employed for the first time for continuously monitoring the complex molecular dynamics of terpenoid resins (dammar, mastic, colophony, sandarac and shellac), which occur during their ageing under artificial light exposure. The instrumentation was equipped with a pyroelectric sensor allowing for temperature control of the sample's irradiated surface while the acquisition of spectra occurs by setting fixed maximum temperature and total radiant exposure. Resins were dropped into special pits over a dedicated rotating wheel moved by a USB motor. The rotation allowed samples sliding between the positions designated for the acquisition of the Raman spectra and that for artificial ageing. Samples were exposed to artificial light for 45-days and almost 400 spectra for each resin sample were collected. The exposure to artificial light led to significant changes allowing the characterization of the alteration process. The automated acquisition of a large number of spectra overtime during light-exposure has given the possibility to distinguish fast dynamics, mainly associated to solvent evaporation, from those slower due to resins photo-degradation processes.

A new compact instrument for Raman, laser-induced breakdown, and laser-induced fluorescence spectroscopy of works of art and their constituent materials.

A small, potentially transportable prototype instrument capable of carrying out Raman, laser-induced breakdown (LIB), and laser-induced fluorescence (LIF) spectroscopy using a single pulsed laser source was developed for the analysis of cultural heritage objects. The purpose of this instrumentation is to perform fast and reliable analysis of surfaces with minimum damage to an object. For this purpose, a compact (51 x 203 x 76 mm) nanosecond Q-switched neodymium doped yttrium aluminum garnet laser (8 ns, 20 Hz, 0.01-115 mJ/pulse) was used as an irradiation source. The use of a nanosecond-gated detector sensitive between 180 and 900 nm allows the acquisition of elemental emissions in LIB spectroscopy and can also be employed for both LIF and time-resolved Raman spectroscopy. In this work, attention is focused on the description of the instrument and its optical components, and two examples of applications for the analysis of pigments and binding media used in works of art are presented.

Spectroscopic analysis of works of art using a single LIBS and pulsed Raman setup.

A nanosecond pulsed laser setup has been optimized to perform laser-induced breakdown spectroscopy (LIBS) and pulsed Raman spectroscopy measurements in the field of cultural heritage. Three different samples of artistic/architectural interest with different typologies have been analyzed. The results from the two techniques allowed the identification of the materials used in their manufacture or contaminating them, probably coming from atmospheric pollution and biological activity. No sampling and sample preparation was required before the measurements, and no visual or structural damage was observed. Depth profiling using LIBS was performed in one of the samples, providing elemental information along the different layers composing the object and covering its surface. The quality of the results and the rather short time needed for the measurements and for switching between techniques confirmed the instrument's capabilities and specificity for dealing with objects of artistic or historical interest.

Analysis of natural and artificial ultramarine blue pigments using laser induced breakdown and pulsed Raman spectroscopy, statistical analysis and light microscopy.

Pulsed laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy were performed using a novel laboratory setup employing the same Nd:YAG laser emission at 532 nm for the analysis of five commercially available pigments collectively known as "ultramarine blue", a sodium silicate material of either mineral origin or an artificially produced glass. LIBS and Raman spectroscopy have provided information regarding the elemental and molecular composition of the samples; additionally, an analytical protocol for the differentiation between natural (lapis lazuli) and artificial ultramarine blue pigments is proposed. In particular LIBS analysis has allowed the discrimination between pigments on the basis of peaks ascribed to calcium. The presence of calcite in the natural blue pigments has been confirmed following Raman spectroscopy in specific areas of the samples, and micro-Raman and optical microscopy have further corroborated the presence of calcite inclusions in the samples of natural origin. Finally multivariate analysis of Laser induced breakdown spectra using principal component analysis (PCA) further enhanced the differentiation between natural and artificial ultramarine blue pigments.