J. Cult. Heritage 1 (2000) S269 S272 ditions scientiques et me 2000 E dicales Elsevier SAS.

SAS. All rights reserved S1296- 2074( 00) 00176- X/FLA

Micro-Raman spectroscopy for standard and in situ characterisation of painting materials

Alessandra Perardi, Angela Zoppi, Emilio Castellucci*
European Laboratory for non-Linear Spectroscopy (LENS), University of Florence, Largo E. Fermi 2, 50125 Florence, Italy

Abstract Micro-Raman is a spectroscopic technique that allows the identication of painting materials even if nely grained and mixed with others, dispersed in a binder or layered on surfaces. It is used for non-destructive, in situ measurements and it is suitable for selective studies on inhomogeneous materials or surface investigations. Some examples are described of the use of this technique in the eld of art conservation and diagnostics, with regard to pigments, dyes and some products of metal alteration. Raman spectra obtained on standard painting materials were arranged in a ditions scientiques et me database and published on the Web. 2000 E dicales Elsevier SAS Keywords: micro-Raman / pigments / dyes / corrosion / non-destructivity

1. Introduction: the micro-Raman technique

Raman spectroscopy allows the identication of homogeneous materials on the basis of their molecular vibrational spectra, obtained by excitation with visible laser light. In micro-Raman spectroscopy (or Raman microscopy) the laser beam is focused by means of a microscope objective, employing a backscattering conguration; thus, the Raman scattered light is collected within the cone dened by the same objective [1]. Consequently, a much smaller area needs to be irradiated for measurements than in common Raman spectroscopy: the minimum theoretical diameter of the laser spot on the surface of the sample is represented by the diffraction limit. For a 100 magnication objective, the calculated diffraction limit is 0.63 mm with a 488 nm laser radiation, 0.66 mm for 514.5 nm, 0.83 mm for 647.1 nm. Due to the low depth of eld, only a very thin layer
* Correspondence and reprints: castel@lens.uni.it (E. Castellucci).

of the sample is irradiated, so that the resulting information comes mainly from the surface of the object, without interference from layers underneath. The technique is non-destructive and the instrumentation efciency in collecting the scattered light is such that no more than a hundred micro-watts of laser excitation power on the sample are usually required, a fact that accounts for a safe use in direct measurements on works of art. Another advantage is the scarce or lack of need for sample preparation; thus, the technique can be applied in situ, that is without any sampling of the art object to be analysed, provided it is possible to put it under the microscope objective (gure 1 ).

2. Applications
Raman microscopy has been extensively used for the characterization of organic and inorganic painting materials, such as pigments, lakes and dyes on differ-

S270

A. Perardi et al. / J. Cult. Heritage 1 (2000) S269 S272

data acquired from standard samples of known composition. As a helpful tool in this comparison, our research group has developed a database, recording Raman spectra of standard pigments and lakes, also accessible on-line at the web-site www.chim.uni.it/raman. In the following, some examples are reported of possible uses of the micro-Raman technique in the eld of art conservation and diagnostics, with regard to pigments, dyes and products of metal alteration. 2.1. Metal corrosion products An ancient iron nail from the archaeological site of Tharros, Sardinia, was examined by micro-Raman spectroscopy. This site was founded by the Phoenicians around the VIII century BC and became an important Punic harbour and one of the main trade centres in the Mediterranean; it passed later under the Roman inuence and domination. The nail probably belongs to the latter period. It underwent a severe decay during burial and the most part of the metal transformed into thin-layered crusts of iron oxides and hydroxides. The corrosion products were identied on the basis of their different crystal structure: black magnetite (Fe3O4) and maghemite (g-Fe2O3), orange lepidocrocite (g-FeOOH) and goethite (a-FeOOH). The Raman spectrum of a goethite layer is shown in gure 2. Traces of hematite (a-Fe2O3) found on the external surface of

Figure 1. Micro-Raman instrumental set-up for the study of works of art.

ent supports: canvas, parchment, paper, wood, ceramic, stone, glass, wall and so on [2]. It is also employed in the study of other materials of an artistic and historic interest, also including alteration products. For a chemical structural identication of compounds, Raman spectra recorded in the analysis of art objects are usually compared with reference

Figure 2. Raman spectrum of goethite corrosion layer on Tharros nail. Laser excitation line 647.1 nm, objective magnication 100 , monochromator entrance slit 0.1 mm, power at the sample 120 mW, acquisition time 100 s.

A. Perardi et al. / J. Cult. Heritage 1 (2000) S269 S272

S271

2.2. Textile dyes Micro-Raman spectroscopy was used to identify dyes in a late 1400 Medici silk stole from Volterra. Florentine heraldry had a great inuence on textile design in the XV century, and the Medici family among others made extensive use of their coat of arms in architectonic decoration and art objects. The fabric under study is attributed to a factory working in Florence in the second half of 1400; just in those years, Volterra was entering the sphere of inuence of Florentine policy. The cloth was originally a vestment, turned inside out and reused to make a stole at the end of the XIX century. The pattern, gold and blue on red satin, has two borders with fruits, pearls and the Medici shield; the centre is decorated with leaves and a composition of cherubs surrounding the family coat of arms. The analysis of red warp and blue woof silk threads gave the spectra of kermesic acid and indigo [4], obtained under resonance conditions; the resonance effect can result in a strong enhancement of some Raman bands, which helps in identifying even tiny amounts of material [5]. Figure 3 reports the spectrum of a blue indigo thread, with three strong Raman bands assigned to total-symmetric vibrations. 2.3. Frescoes An extensive study was performed on XV century early Renaissance frescoes painted by Michele di Matteo, Lorenzo di Pietro (Vecchietta) and Benvenuto di Giovanni in the baptistery of the Cathedral in Siena. They are located inside the apse and represent scenes from the Passion of Christ and from the life of Saint Anthony [6]. Cross-sections of the frescoes were analysed and the following pigments identied: red ochre, lead tin yellow (type I), malachite, azurite, red lead. Figure 4 shows the spectrum obtained for azurite; this compound was identied by comparison with a standard. Azurite, a copper carbonate with the formula 2CuCO3.Cu(OH)2, has the characteristic carbonate band at 1 099 cm 1, though this is not the main peak, which is instead observed at 406 cm 1 and corresponds to a stretching of the Cu O bond [7].

Figure 3. Raman spectrum of blue silk thread (indigo). Laser excitation line 647.1 nm, objective magnication 100 , monochromator entrance slit 0.01 mm, power at the sample 280 mW, acquisition time 300 s, baseline subtraction.

Figure 4. Identication of azurite in fresco cross-section. Laser excitation line 514.5 nm, objective magnication 100 , monochromator entrance slit 0.1 mm, power at the sample 250 mW, acquisition time 60 s 5 accumulations, baseline subtraction.

the nail have been recognized as coming from the iron-rich soil of the site. It is interesting to note that the black compounds are bad scatterers and their Raman spectra are rather weak, while, on the other hand, goethite, lepidocrocite and hematite give rise to strong and sharp bands. For these analyses a low laser power was used, in order to avoid the danger of thermal degradation of the sample pointed out by many authors [3]: at high temperature, transformation of magnetite and maghemite into hematite occurs, and dehydration of goethite and lepidocrocite leads to hematite and maghemite.

3. Conclusions
The above examples clearly illustrate the possible applications of Raman microscopy in the eld of cultural heritage and how this versatile technique

272

A. Perardi et al. / J. Cult. Heritage 1 (2000) S269 S272

can be adapted to the study of many different objects and materials. The microscope objective focuses analysis on particles of a few micrometres in size: pigment grains in painting layers, thin corrosion layers, the surface of a single thread. Thus, they can be better isolated from interference from the surrounding environment. The main problems in the use of this technique arise from possible local burning (or thermal decomposition, as mentioned before) due to the focalization of the laser light and from the excitation of uorescence emission, which can conceal the Raman spectrum. To avoid excessive heating, low laser powers are usually employed in sample excitation; as to uorescence, when it is not possible to avoid it by focusing the laser on isolated non-luminescent particles, it may be of help choosing a laser excitation wavelength outside the absorption spectral range. In some cases, anyway, a moderate absorption of radiation can enhance the Raman response, with a resonance effect: in fact, we took advantage of this enhancement in the analysis of the textile dyes.

nail; Dr S. Di Blasi and Dr L. Ciampini for the silk stole; Dr M. Matteini, OPD Firenze, for the fresco cross-sections.

References
[1] Turrell G., Dhamelincourt P., Micro-Raman spectroscopy, in: Laserna J.J. (Ed.), Modern Techniques in Raman Spectroscopy, Wiley, New York, 1996, pp. 109 142. [2] Coupry C., Lautie A., Revault M., Dulho J., Contribution of Raman spectroscopy to art and history, J. Raman Spectrosc. 25 (1994) 89 94. [3] De Faria D.L.A., Vena ncio Silva S., de Oliveira M.T., Raman microspectroscopy of some iron oxides and oxyhydroxides, J. Raman Spectrosc. 28 (1997) 873 878. [4] Coupry C., Sagon G., Gorguet-Ballesteros P., Raman spectroscopic investigation of blue contemporary textiles, J. Raman Spectrosc. 28 (1997) 85 89. [5] Bussotti L., Castellucci E., Matteini M., The microRaman technique in the studies for the conservation of art works: identication of lakes in paints, Sci. Technol. Cult. Heritage 5 (1996) 13 19. [6] Alessi C. et al., Le pitture murali della zona presbiteriale del battistero di Siena: Storia, studi e restauri, OPD Restauro 4 (1992) 9 27. [7] Guineau B., Analyse non destructive des pigments par microsonde Raman laser : exemples de lazurite et de la malachite, Stud. Conserv. 29 (1984) 35 41.

Acknowledgements. The authors would like to thank persons and institutions who provided the samples: Dr L. Ruatta, Politecnico di Torino, for the