Comparative laser spectroscopy diagnostics for ancient metallic artefacts exposed to environmental pollution.

Metal artworks are subjected to corrosion and oxidation processes due to reactive agents present in the air, water and in the ground that these objects have been in contact with for hundreds of years. This is the case for archaeological metals that are recovered from excavation sites, as well as artefacts exposed to polluted air. Stabilization of the conservation state of these objects needs precise diagnostics of the accrued surface layers and identification of original, historical materials before further protective treatments, including safe laser cleaning of unwanted layers. This paper presents analyses of the chemical composition and stratigraphy of corrosion products with the use of laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy. The discussion of the results is supported by material studies (SEM-EDS, XRF, ion-analyses). The tests were performed on several samples taken from original objects, including copper roofing from Wilanów Palace in Warsaw and Karol Poznanski Palace in LódY, bronze decorative figures from the Wilanów Palace gardens, and four archaeological examples of old jewellery (different copper alloys). Work has been performed as a part of the MATLAS project in the frames of EEA and Norway Grants (www.matlas.eu) and the results enable the comparison of the methodology and to elaborate the joint diagnostic procedures of the three project partner independent laboratories.

Characterization of Laser Cleaning of Artworks.

The main tasks of conservators of artworks and monuments are the estimation and analysis of damages (present condition), object conservation (cleaning process), and the protection of an object against further degradation. One of the physical methods that is becoming more and more popular for dirt removal is the laser cleaning method. This method is non-contact, selective, local, controlled, self-limiting, gives immediate feedback and preserves even the gentlest of relief - the trace of a paintbrush. Paper presents application of different, selected physical sensing methods to characterize condition of works of art as well as laser cleaning process itself. It includes, tested in our laboratories, optical surface measurements (e.g. colorimetry, scatterometry, interferometry), infrared thermography, optical coherent tomography and acoustic measurements for "on-line" evaluation of cleaning progress. Results of laser spectrometry analyses (LIBS, Raman) will illustrate identification and dating of objects superficial layers.