Laser Induced Breakdown Spectroscopy (LIBS) applied to stratigrafic elemental analysis and Optical Coherence Tomography (OCT) to damage determination of cultural heritage Brazilian coins

摘要

This work presents a compositional characterization of 1939's Thousand "Reis" and 1945's One "Cruzeiro" Brazilian coins, forged on aluminum bronze alloy. The coins were irradiated by a Q-switched Nd:YAG laser with 4 ns pulse width and energy of 25mJ emitting at 1064nm reaching 3.10~(10)Wcm~(-2) (assured condition for stoichiometric ablation), forming a plasma in a small fraction of the coin. Plasma emission was collected by an optical fiber system connected to an Echelle spectrometer. The capability of LIBS to remove small fraction of material was exploited and the coins were analyzed ablating layer by layer from patina to the bulk. The experimental conditions to assure reproductivity were determined by evaluation of three plasma paramethers: ionization temperature using Saha-Boltzmann plot, excitation temperature using Boltzmann plot, plasma density using Saha-Boltzmann plot and Stark broadening. The Calibration-Free LIBS technique was applied to both coins and the analytical determination of elemental composition was employed. In order to confirm the Edict Law elemental composition the results were corroborated by Neutron Activation Analysis (NAA). In both cases the results determined by CF-LIBS agreed to with the Edict Law and NAA determination. Besides the major components for the bronze alloy some other impurities were observed. Finally, in order to determine the coin damage made by the laser, the OCT (Optical Coherence Tomography) technique was used. After tree pulses of laser 54μg of coin material were removed reaching 120μm in depth.