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Development of a new non-destructive method for analysis of the atmospheric corrosion and corrosion protection of copper and copper alloys

Exploitable results

As a contribution to the increasing efforts for the conservation of metallic historical monuments a research programme has been carried out aiming at a novel non-destructive in-situ analytical method on the basis of the photoacoustic (PAS) and photothermal deflection spectroscopies (PTDS) for in-situ control of global parameters of patina layers. Results of these methods have been interpreted by means of various microanalytical techniques applied to artificially produced patina layers on copper and bronze substrates. The project included the development of methodology and production of artificial patina layers on copper and copper-alloy and the characterization of natural and artificial patina layers by means of several microanalytical techniques: scanning electron microscopy (SEM), X-ray diffraction (XRD), colorimetry, X-ray photoelectron spectroscopy (XPS), Augerelectron spectroscopy (AES), Rutherford backscattering spectroscopy (RBS), nuclear reaction analyses (NRA), elastic recoil detection analyses (ERDA), and potentiometry. Photothermal/photoacoustic data from various samples have been measured by using laboratory scale equipment as well as miniaturized sensor units, which allowed to distinguish different copper sulphate species as well as their mixtures. The results have demonstrated successfully the applicability of these methods for non-destructive patina inspection. As the main step of the project, the photothermal/photoacoustic equipment has been miniaturized for in-situ applications. This equipment has been successfully tested with artificial samples as well as with samples from old copper roof plates. A future technical implementation aiming at a prototype device applicable for in-field measurements requires, among others, the development of battery operated electronics with integrated amplifier amd microcontroller, an improved adaptation of the PAS/PTDS sensors to fit to rough surfaces, the replacement of FTIR-PAS by FTIR-PTDS enabling measurement of depth profiles, thickness, and at the same time fingerprint spectra from both PTDS and PAS for all IR-wavelengths, and finally the implementation of the most recent portable small FTIR spectrometers.

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