Laser-induced emission, fluorescence and Raman hybrid setup: A versatile instrument to analyze materials from cultural heritage

Abstract The aim of this research project was the development of a hybrid system in laboratory coupling together three analytical techniques, namely laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF) and Raman spectroscopy in a single instrument. The rationale for combining these three spectroscopies was to identify a material (molecular and elemental analysis) without any preliminary preparation, regardless of its organic or inorganic nature, on the surface and in depth, without any surrounding light interference thanks to time resolution. Such instrumentation would allow characterizing different materials from cultural heritage. A complete study on LIBS-LIF-Raman hybrid was carried out, from its conception to instrumental achievement, in order to elaborate a strategy of analysis according to the material and to be able to address conservation issues. From an instrumental point of view, condensing the three spectroscopies was achieved by using a single laser for excitation and two spectrometers (time-integrated and not time-integrated) for light collection. A parabolic mirror was used as collecting system, while three excitation sources directed through this optical system ensured the examination of a similar probe area. Two categories of materials were chosen to test the hybrid instrumentation on cultural heritage applications (copper corrosion products and wall paintings). Some examples are reported to illustrate the wealth of information provided by the hybrid, thus demonstrating its great potential to be used for cultural heritage issues. Finally, several considerations are outlined aimed at further improving the hybrid.

[1]  I. Osticioli,et al.  Analysis of natural and artificial ultramarine blue pigments using laser induced breakdown and pulsed Raman spectroscopy, statistical analysis and light microscopy. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[2]  Paraskevi Pouli,et al.  Measuring the thickness of protective coatings on historic metal objects using nanosecond and femtosecond laser induced breakdown spectroscopy depth profiling , 2005 .

[3]  F. Weritz,et al.  A combined laser-induced breakdown and Raman spectroscopy Echelle system for elemental and molecular microanalysis , 2009 .

[4]  Demetrios Anglos,et al.  Spectroscopic analysis using a hybrid LIBS-Raman system , 2006 .

[5]  Raymond E. Arvidson,et al.  Combined remote mineralogical and elemental identification from rovers: Field and laboratory tests using reflectance and laser‐induced breakdown spectroscopy , 2002 .

[6]  Demetrios Anglos,et al.  Laser-Induced Breakdown Spectroscopy in Art and Archaeology , 2001 .

[7]  Nathaniel R. Gomer,et al.  Remote Raman Spectroscopy for Planetary Exploration: A Review , 2012, Applied spectroscopy.

[8]  Vincent Detalle,et al.  Novel approach of signal normalization for depth profile of cultural heritage materials , 2017 .

[9]  P. Vandenabeele,et al.  Comparative study of mobile Raman instrumentation for art analysis. , 2007, Analytica chimica acta.

[10]  R. Barlow,et al.  A Comparison of CMC and PDF Modelling Predictions with Experimental Nitric Oxide LIF/Raman Measurements in a Turbulent H2 Jet Flame , 1995 .

[11]  Vincent Detalle,et al.  Evaluation of the standard normal variate method for Laser-Induced Breakdown Spectroscopy data treatment applied to the discrimination of painting layers , 2015 .

[12]  R. Barlow,et al.  The structure of turbulent nonpremixed flames revealed by Raman-Rayleigh-LIF measurements , 1996 .

[13]  Antonio Sansonetti,et al.  Versatile pulsed laser setup for depth profiling analysis of multilayered samples in the field of cultural heritage , 2009 .