Handheld new technology Raman and portable FT-IR spectrometers as complementary tools for the in situ identification of organic materials in modern art.

A non-invasive approach has been carried out to characterize painting materials used in modern artworks conserved in the art collection of Carandente's museum at Palazzo Collicola in Spoleto (Italy). This work is focused on the cross-validation of the handheld BRAVO Raman spectrometer, that uses a sequentially Shifted Excitation (SSE) to mitigate fluorescence, for the characterization specifically of organic materials. The analytical procedure, combining XRF, Raman and reflection infrared spectroscopy, allowed a complete characterization of the artists' palettes; particularly eight different synthetic dyes belonging to the class of pigment red (PR) and pigment yellow (PY.), synthetic and traditional binders, such as alkyd resin and lipids have been easily identified.

[1]  Francesca Casadio,et al.  Ad-hoc surface-enhanced Raman spectroscopy methodologies for the detection of artist dyestuffs: thin layer chromatography-surface enhanced Raman spectroscopy and in situ on the fiber analysis. , 2009, Analytical chemistry.

[2]  H. Edwards,et al.  Fast detection of sulphate minerals (gypsum, anglesite, baryte) by a portable Raman spectrometer , 2009 .

[3]  Costanza Miliani,et al.  On the Use of Overtone and Combination Bands for the Analysis of the CaSO4—H2O System by Mid-Infrared Reflection Spectroscopy , 2010, Applied spectroscopy.

[4]  Costanza Miliani,et al.  Interpretation of mid and near-infrared reflection properties of synthetic polymer paints for the non-invasive assessment of binding media in twentieth-century pictorial artworks , 2016 .

[5]  V. Farmer The Infrared spectra of minerals , 1974 .

[6]  P. Vandenabeele,et al.  The role of mobile instrumentation in novel applications of Raman spectroscopy: archaeometry, geosciences, and forensics. , 2014, Chemical Society reviews.

[7]  M. Carvalho,et al.  Application of spectroscopic techniques to the study of illuminated manuscripts: A survey , 2012 .

[8]  Costanza Miliani,et al.  Reflection infrared spectroscopy for the non-invasive in situ study of artists’ pigments , 2012 .

[9]  Costanza Miliani,et al.  In situ noninvasive study of artworks: the MOLAB multitechnique approach. , 2010, Accounts of chemical research.

[10]  Koen Janssens,et al.  Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods. 2. Original paint layer samples. , 2011, Analytical chemistry.

[11]  S. Sánchez‐Cortés,et al.  Assessment of a multi-technical non-invasive approach for the typology of inks, dyes and pigments in two 19th century's ancient manuscripts of Morocco , 2014 .

[12]  C. Miliani,et al.  Non-invasive identification of metal-oxalate complexes on polychrome artwork surfaces by reflection mid-infrared spectroscopy. , 2013, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[13]  Sarah Marshall,et al.  Spatially compressed dual-wavelength excitation Raman spectrometer. , 2014, Applied optics.

[14]  C. Colombo,et al.  Portable Sequentially Shifted Excitation Raman spectroscopy as an innovative tool for in situ chemical interrogation of painted surfaces. , 2016, The Analyst.

[15]  A. Berger,et al.  Early Viridian Pigment Composition CHARACTERIZATION OF A (HYDRATED) CHROMIUM OXIDE BORATE PIGMENT , 2009 .

[16]  J. Madariaga,et al.  Vibrational Spectroscopic Techniques for the Analysis of Artefacts with Historical, Artistic and Archaeological Value , 2006 .

[17]  Luc Moens,et al.  A decade of Raman spectroscopy in art and archaeology. , 2007, Chemical reviews.

[18]  Z. Dohcevic-Mitrovic,et al.  Infrared study of laser synthesized anatase TiO2 nanopowders , 2005 .

[19]  Philippe Colomban,et al.  The on‐site/remote Raman analysis with mobile instruments: a review of drawbacks and success in cultural heritage studies and other associated fields , 2012 .

[20]  B. Doherty,et al.  A vibrational spectroscopic and principal component analysis of triarylmethane dyes by comparative laboratory and portable instrumentation. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[21]  R. Frost,et al.  Raman spectroscopy of selected lead minerals of environmental significance. , 2003, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[22]  A. Durán,et al.  Comparison between micro-Raman and micro-FTIR spectroscopy techniques for the characterization of pigments from Southern Spain Cultural Heritage , 2009 .

[23]  R Siddall,et al.  Pigment Compendium: A Dictionary of Historical Pigments , 2007 .

[24]  J. Chalmers,et al.  Handbook of vibrational spectroscopy , 2002 .

[25]  P. Vandenabeele,et al.  Contribution to the identification of α-, β- and ε-copper phthalocyanine blue pigments in modern artists' paints by X-ray powder diffraction, attenuated total reflectance micro-fourier transform infrared spectroscopy and micro-Raman spectroscopy , 2012 .

[26]  L. Rintoul,et al.  Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes , 2000 .

[27]  V. Crupi,et al.  Spectroscopic investigation of Roman decorated plasters by combining FT-IR, micro-Raman and UV-Raman analyses , 2016 .

[28]  Mohamed Abdelkader,et al.  Sequentially Shifted Excitation Raman Spectroscopy: Novel Algorithm and Instrumentation for Fluorescence-Free Raman Spectroscopy in Spectral Space , 2013, Applied spectroscopy.

[29]  Barbara Salvadori,et al.  Spectroscopic Techniques in Cultural Heritage Conservation: A Survey , 2005 .

[30]  Costanza Miliani,et al.  An integrated spectroscopic approach for the non-invasive study of modern art materials and techniques , 2010 .

[31]  S. Gunasekaran,et al.  Raman and infrared spectra of carbonates of calcite structure , 2006 .

[32]  M. Llusar,et al.  Colour analysis of some cobalt-based blue pigments , 2001 .

[33]  M. Seery,et al.  Spectroscopic Investigation of the Anatase-to-Rutile Transformation of Sol−Gel-Synthesized TiO2 Photocatalysts , 2009 .

[34]  Steven Saverwyns,et al.  Identification of synthetic organic pigments: the role of a comprehensive digital Raman spectral library† , 2012 .

[35]  U. Panne,et al.  Raman spectroscopy of synthetic organic pigments used in 20th century works of art , 2008 .

[36]  C. Miliani,et al.  FT-NIR spectroscopy for non-invasive identification of natural polymers and resins in easel paintings , 2009, Analytical and bioanalytical chemistry.

[37]  P. Vandenabeele,et al.  Characterisation of a portable Raman spectrometer for in situ analysis of art objects. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[38]  R. Fontana,et al.  Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies , 2016, Heritage Science.

[39]  G. Socrates,et al.  Infrared and Raman characteristic group frequencies : tables and charts , 2001 .

[40]  Lucia Toniolo,et al.  The analysis of polychrome works of art: 40 years of infrared spectroscopic investigations , 2001 .

[41]  R. Das,et al.  Raman spectroscopy: Recent advancements, techniques and applications , 2011 .