- Email: [email protected]
The characterization of canvas painting by the Serbian artist Milo Milunović using X-ray fluorescence, micro-Raman and FTIR spectroscopy
Radiation Physics and Chemistry 115 (2015) 135–142
Contents lists available at ScienceDirect
Radiation Physics and Chemistry journal homepage: www.elsevier.com/locate/radphyschem
Radiation Physics (Bergstrom)
The characterization of canvas painting by the Serbian artist Milo Milunović using X-ray fluorescence, micro-Raman and FTIR spectroscopy Lj. Damjanović a,n, M. Gajić-Kvaščev b, J. Đurđević a, V. Andrić b, M. Marić-Stojanović c, T. Lazić d, S. Nikolić d a
University of Belgrade-Faculty of Physical Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia University of Belgrade-Vinča Institute of Nuclear Sciences, P.O. Box 522, 11000 Belgrade, Serbia c National Museum Belgrade, Trg Republike 1a, 11000 Belgrade, Serbia d University of Arts in Belgrade-Faculty of Applied Arts, Kralja Petra 4, 11000 Belgrade, Serbia b
H I G H L I G H T S
In situ EDXRF, micro-Raman and FTIR spectroscopy were employed. Pallete of painting “The Inspiration of the poet” by Milunović has been determined. Obtained results allowed evaluation of the painter’s technique. Milo Milunović worked on the clay ground imitating Nicoals Poussin’s technique.
art ic l e i nf o Article history: Received 23 April 2015 Received in revised form 15 June 2015 Accepted 17 June 2015 Available online 25 June 2015 Keywords: Canvas painting Milo Milunović EDXRF spectroscopy Micro-Raman spectroscopy FTIR spectroscopy
a b s t r a c t A canvas painting by Milo Milunović “The Inspiration of the poet” was studied by energy dispersive X-Ray fluorescence (EDXRF), micro-Raman and Fourier transform infrared (FTIR) spectroscopy in order to identify materials used by the artist and his painting technique. Study is perfomed combining in situ nondestructive method with the preparation and study of cross-section samples and raw fragments of the samples. Milo Milunović, an eminent painter from Balkan region, made a copy of the Nicolas Poussin's original painting in Louvre in 1926/27. Obtained results revealed following pigments on the investigated canvas painting: vermilion, minium, cobalt blue, ultramarine, lead white, zinc white, cadmium yellow, chrome-based green pigment and several earth pigments – red and yellow ocher, green earth and umber. Ground layer was made of lead white mixed with calcium carbonate. & 2015 Elsevier Ltd. All rights reserved.
1. Introduction Canvas paintings are among the most heterogeneous works of art and their characterization is a demanding analytical task (Oriola et al., 2014).Traditionally, characterization of canvas painting has been mainly carried out by art-historians and restorers by naked eye and by microscopic analysis. Information obtained in this way, combined with consistent evidence of the art materials obtained by physico-chemical techniques can help conservators and restorers to select the most appropriate procedures for the purposes of restoration. The scientists always have to balance the possible risks of damage against the benefits that are gained from the investigation of n
Corresponding author. Fax: þ 381 2187 133. E-mail address: [email protected] (Lj. Damjanović).
http://dx.doi.org/10.1016/j.radphyschem.2015.06.017 0969-806X/& 2015 Elsevier Ltd. All rights reserved.
the art-work. Hence, the risk of damage/information ratio should be considered and optimized carefully for each investigation (Dredge et al., 2003; Ortega-Avilés et al., 2005). Significant progress in this area is made by continuous advances in non-invasive experimental techniques (Adriaens, 2005; Miliani et al., 2010; Alfeld and Broekaert, 2013). In the cases where samples are available, amounts of obtained material are usually in micro or submicro range containing different analytes. These complex mixtures most often include organic and inorganic compounds, thus use of different analytical techniques is required for a complete characterization of the investigated samples (Doménech-Carbó et al., 2001). In this work we present multianalytical study of canvas painting “The inspiration of the poet” made by Milo Milunović (1897– 1967), a distinguished painter from Balkan region. He studied art in Florence under the apprenticeship of Antonio Augusto Giacometti (1912–1914), and later in Paris (1919–22; 1926–32). During
136
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
his stay in Paris, he developed friendships with many artists such as Chaim Soutine, Massimo Campigli, AntoineBourdelle (who bought several Milunović's paintings, which are now in the Bourdelle Museum in Paris – two paintings are included in the permanent exhibition). With two colleagues, Milo Milunović founded the Academy of Fine Arts in Belgrade, Serbia in 1937, where he worked as a professor. He was also cofounder of School of Fine Arts in Cetinje, Montenegro in 1947. Milo Milunović's artistic importance and regional influence is manifested through domestic and international exibitions: 45 independent (e.g. Paris, Cardot Gallery, 1928– 29, 1932) and over 320 group (e.g. Salon des Tuileries, 1927 and Galerie Bernheim Jeune, 1931) exhibitions. His creative work is described in monographies, prefaces of catalogs, books and encyclopedias (Trifunović, 1973; Ćelić-Simeonović and Milunović, 1997; Jovanović, 2001). Almost consistently following the beliefs of Cezanne, who was his great inspiration, that “The Louvre is a book from which we learn to read” and that “One should do Poussin all over from Nature” Milunović copied the Nicolas Poussin's painting “The inspiration of the poet” in the Louvre in 1926/27. “The Inspiration of the poet” painted by Milunović is 2.18 m 1.80 m large. The painting was firstly in the possession of Milunović's brother at Cetinje, Montenegro till 1931, when it was sent to Belgrade to his friend Kosta Hakman. The painting was sold to the French Club in Belgrade in 1935 where it stayed till the beginning of the World War II. It is not known where the painting was till 1967 when it was displayed again in the hall of the Craftsman Workhouse building in Belgrade. Since 1990 it has been permanently exhibited in the hall of the Faculty of Fine Arts in Belgrade. This painting was brought to the Faculty of Applied Arts in Belgrade for restoration, which provided a unique opportunity for a scientific investigation. This is the first scientific study of Milo Milunović's artwork and it was perfomed combining in situ non-destructive energy dispersive X-Ray fluorescence (EDXRF) spectroscopy, which has been proven to be efficient in the study of canvas painting materials (Rosi et al., 2009; Campos et al., 2014; Van de Voorde et al., 2014), with the preparation and study of cross-section samples as well as raw fragments of the samples. In-house developed portable EDXRF spectrometer was used for investigation of well-preserved regions of the painting, while paint chips taken from the edges of the damaged regions were investigated by optical microscopy, microRaman and FTIR spectroscopy. The aim of this study was to gather information about materials (pigments and ground layer) and painting technique used by the artist, combining data obtained by different analytical techniques.
2. Experimental Portable in-house developed EDXRF spectrometer was used for the non-invasive and non-destructive analysis of the painting. The excitation X-ray tube (Oxford, Rh anode, max voltage 50 kV, max current 1 mA, air cooled) is mounted on a motorized platform which allows easy movement along all three axes. The construction allows precise movement of 1 mm in each direction. The detection of the characteristic X-rays was made by compact X-ray spectrometer (X123, Amptek Inc.) with Si-PIN detector (6 mm2/500 μm, Be window 12.5 μm thickness and 1.5 in. detector extension) which is mounted on the excitation X-ray protection box together with two laser pointers which enable alignment of the measuring system at the desired point to be analyzed. The energy resolution of used detector was 160 eV at 5.89 keV. The excitation X-ray beam has been collimated passing through especially designed collimator mounted at the end of the tube. The
Fig. 1. Photographs of Milo Milunović's canvas painting “The Inspiration of the poet”: (a) front side-EDXRF spectra were collected at the points labeled 1–39, samples were taken from the areas labeled MM-1 to MM-6; (b) backside-EDXRF spectra were collected at the points labeled 40–45. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
measurements were performed without additional filtering of the excitation beam. Measuring system is mounted on the cantilever which enables portability, sufficient stability, easy movement and handling, even during analysis of large scale paintings like the one analyzed in this study. Geometry of the experimental setup for all measurements was the same: distance between surface of the painting and the end point of the collimator was 16 mm, distance between analyzed surface and detector window was 21 mm and angle between detector and X-ray tube axes was 45°. The X-ray tube voltage was altered to give excitation of 40 keV. In this experimental setup, with detection path in the air, only elements heavier than Si can be detected. For all the measurements filament current was set at 300 μA and acquisition time was 40 s since only qualitative analysis was performed. For the spectra acquisition and processing ADMCA software was used (Amptek Inc.). Total of 45 points (see Fig. 1) were analyzed. Analyzed points were selected to represent particular colors on the surface layer of the painting. Few points on the backside of the painting were also analyzed for the characterization of preparation layer. Investigated canvas painting was well-preserved. Hence it was
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
possible to take only small number of samples. In total 6 samples of paint chips were taken from the edges of existing damaged regions of the painting: 3 samples were taken from painted canvas which was folded under the frame and 3 samples from the front of the painting (see Fig. 1a, samples denoted “MM”). Samples of approximately 1 mm2 or even smaller were removed by sharp and clean scalpel. Cross sections of 6 samples were recorded by optical Olympus BX51M microscope equipped with UV lamp Olympus U-RFL-T and U-MWUS3 and U-MWBS3 filters. Micro-Raman spectra were recorded in situ from cross-sections of 6 samples on a DXR Raman Microscope (Termo Scientific). The 532 nm line of a diode-pumped solid state high brightness laser was used as the exciting radiation and the power of illumination at the sample surface ranged between 3 and 10 mW. Collection of the scattered light was made through an Olympus microscope with infinity-corrected confocal optics, 25 mm pinhole aperture, standard working distance objective 50 , gratings of 900 lines/mm and 1800 lines/mm, and resolution of 2 cm 1. Acquisition time was 2 s with 15 scans. The laser spot diameter on the sample was 1 mm. Thermo Scientific OMNIC software was used for spectra collection and manipulation. The identification of pigments was performed by comparison of recorded spectra with spectra of
137
pigments from homemade database or from literature (Bell et al., 1993; Bikiaris et al., 2000). The FTIR spectra of 6 samples of paint chips, which were grounded to a powder, were recorded on a FTIR Nicolet 6700 spectrometer using KBr pellets technique, in the wavenumber range from 4000 to 400 cm 1.
3. Results and discussion Milo Milunović's canvas painting “The Inspiration of the poet” investigated in this work is shown in Fig. 1. The surface of the painted layer was covered with a thin layer of dust and dirt, which notably changed its color. Parts of the painting were cleaned before this study and investigated points in cleaned areas are: 10, 12, 13, 15, 16, 17, 24, 29, 30, 31, 32, and 34 (see Fig. 1a). The excess canvas is folded and fixed with metal nails to the slats of the blind frame. The surface of the excess canvas is covered with a uniform layer of preparation, indicating that the canvas was prepared before stretching. According to restorers, this feature together with the fact that the format of the painting is large with a uniformly applied preparation suggests that the canvas was
Fig. 2. The EDXRF spectra recorded at: (a) red sections of paint layer-points 14, 19 and 38; (b) white sections of paint layer-points 17, 32 and 34; (c) brown sections of paint layer-points 8, 23 and 36; (d) backside of painting – points 40–43. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
138
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
industrially prepared. 3.1. EDXRF spectroscopy Qualitative EDXRF spectroscopy analysis of paint layer of investigated canvas painting was performed at 39 points shown at Fig. 1a. The detected elemental composition at the measuring points allowed identification of following pigments used by the artist. 3.1.1. Red pigments The EDXRF spectra recorded at red sections of paint layer, at points 14, 19 and 38, are shown at Fig. 2a. Three different red pigments were identified: vermilion (HgS), red ochre (Fe2O3 þclayþsilica) and minium (Pb3O4). According to the tone and hue of the color it can be assumed that minium is probably used in mixture with red ochre (Van der Snickt et al., 2010). 3.1.2. Green pigments In all EDXRF spectra recorded at green sections of paint layer (points 1, 24–28) intensive Fe peak has been detected indicating presence of green earth (hydrous aluminosilicate of iron, magnesium and potassium). Characteristic trace elements for green earth, K, Ti, and Mn, were also detected confirming use of this pigment (Bevilacqua et al., 2010). Lighter hues of green color have been obtained by mixing with lead white (basic lead carbonate, 2PbCO3 Pb(OH)2) and zinc white (ZnO). Particular hues (points 24, 27 and 28) have been the most probably obtained by addition of cadmium yellow (CdS). Several EDXRF spectra recorded at green sections of paint layer show presence of Cr. Precise distinction between use of chrome green, Cr2O3, and viridian, Cr2O3 2H2O, at these points is not possible by used analytical technique. Based on the art historians' knowledge, the most likely artist has used viridian for intense dark hues of green color (point 26). Another possibility is that chrome green has been used for olive green tone or that viridian has been mixed with cadmium yellow to achieve such tone (points 24 and 28). 3.1.3. Blue pigments Blue sections of paint layer (points 6, 10 and 13) were made by cobalt blue pigment (CoO Al2O3). Blue tones at points 2, 20 and 21 were obtained by mixtures of iron based pigments: Prussian blue, Fe4[Fe(CN)6]3, or green earth with ultramarine, (Na8–10[Al6Si6O24]S2–4). Neither Prussian blue nor ultramarine can be unambiguously determined by this analytical technique (Korolija-Crkvenjakov et al., 2012). 3.1.4. White pigments The most intense hue of white color (point 32) has been obtained with lead white. Zinc white was added for particular tone (points 34 and 35) (Brostoff et al., 2009). Green earth was used in the mixture with lead white and zinc white for gray tones (points 12, 15, 17 and 18). Representative EDXRF spectra recorded at white sections of paint layer are shown at Fig. 2b. 3.1.5. Yellow pigments Yellow sections from the dress (points 3–5, 29–31) were made of iron-based pigment-yellow ochre (Fe2O3 H2O or FeOOH þclayþ silica). Different hues were obtained by addition of zinc white, although presence of lead white in this mixture cannot be excluded. 3.1.6. Other pigments The precise determination of pigments used for flesh tones (points 9, 11, 16, 22 and 39) was difficult because the surface of paint layer was covered with dirt. The most probably lead white
was used with addition of zinc white and iron based pigment (red or yellow ochre). Brown sections of paint layer (points 7, 8, 23, 36 and 37) were made of earth pigment umber (iron oxides with 6– 15% of MnO2) which was identified by the presence of strong peak of Fe and peak of Mn in the EDXRF spectra (Bevilacqua et al., 2010). Representative EDXRF spectra recorded at brown sections of paint layer are shown at Fig. 2c. Cadmium based pigment has also been determined. Since Cd was detected at sections of paint layer which are not yellow, it can be assumed that cadmium yellow was mixed with green, yellow and brown pigments. 3.1.7. Ground layer In order to obtain information about ground layer, EDXRF spectra of the painting's backside were recorded (Fig. 1b). EDXRF spectra obtained at points 40 to 43, shown in Fig. 2d, were identical. This finding indicates that the ground layer was homogeneously applied on the canvas which strongly supports assumptions of restorers that canvas was bought with already prepared ground layer. EDXRF spectrum recorded at the excess canvas with no paint layer folded under the frame, point 44, showed presence of only Pb and Ca, while Zn and Fe were not detected. This finding leads to the conclusion that lead white mixed with calcium carbonate (CaCO3) was used for the ground layer. However, this part of the canvas was exposed to external influences over time therefore it is difficult to eliminate with certainty presence of Zn in the ground layer.The possible interpretation of obtained results is that Zn and Fe originate from paint layer, but it cannot be distinguished precisely by EDXRF spectroscopy. The traces of tiny white splashes can be observed on the entire surface of the back of the canvas and the slats of the blindframe. EDXRF spectrum recorded at one of those white spots (point 45) showed presence of Pb, Zn, Ca, Fe, Ba and Sr. The chemical composition at this point differs from results obtained for ground layer indicating that these traces appeared at a later stage, due to improper storage. 3.2. Optical microscopy Optical microscopy provides information about the sequence and the thickness of the paint layer and it allows a preliminary characterization of the materials in the paint film and the ground layer. Optical micrographs and fluorescence photographs under UV light of 6 samples taken from the investigated painting are shown in Table 1. Ground layer appeared as a single, thick and consistent layer in all investigated samples. No fluorescence under UV light has been detected in ground layer of all 6 samples. This finding supports results obtained by EDXRF spectroscopy that zinc white was not used for ground layer. Optical micrographs of samples MM-1, MM-2, MM-3, MM-4 and MM-6 show three paint layers, while there are two layers of paint in the case of sample MM-5. Thin layer of red color applied on the ground layer is clearly visible in the cross sections of samples MM-2, MM-3 and MM-4 indicating that additional thick paint layers were painted over thin one. It is known that during 17th and 18th century painters were making several preparatory layers prior to beginning of painting. This was usually done with the combination of red, yellow and brown earths with lead white or minium. One of the examples is the painting the “The inspiration of the poet” by Nicolas Poussin made in Italy between 1627 and 1629, which has a brown ground layer with red grains (Duval, 1992). It appears that Milo Milunović was imitating this technique at the part of canvas with the darker colors in order to obtain similar effects as Poussin.
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
139
Table 1 Optical micrographs and fluorescence photographs under UV light; magnification 100x. Sample Visible color of the sample before cleaning MM-1
Red with brown hue
MM-2
Blue
MM-3
Dark green
MM-4
Dark green
MM-5
Dark green
MM-6
Light blue
Optical micrographs
3.3. Micro-Raman spectroscopy Micro-Raman spectroscopy can yield detailed information about compounds present in different layers. In this study microRaman analysis is performed on the cross sections of samples taken from the investigated painting, thus it was possible to determine pigments used in specific layers. The red color in the top paint layer of sample MM-1 originates from hematite, the main colorant of red ochre, identified by
Fluorescence photographs under UV light
characteristic Raman shifts at 220, 240 and 290 cm 1, as shown in Fig. 3a (Bikiaris et al., 2000). Micro-Raman analysis of yellow pigment grains identified cadmium yellow, by characteristic peaks at 297 and 600 cm 1, in the top paint layer of sample MM-1, as shown in Fig. 3b (Bell et al., 1993). Raman spectra of thin red layer of paint applied over the ground layer (see optical micrographs in Table 1) were recorded for samples MM-3 and MM-4 and shown in Fig. 4. In the case of
140
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
Fig. 3. Raman spectra of pigments in a top paint layer of sample MM-1: (a) red (hematite-He) and (b) yellow (cadmium yellow-Cd-y).
sample MM-3 lead white was identified by characteristic Raman shift at 1050 cm 1, anatase by characteristic peak at 144 cm 1 and minium was identified by characteristic Raman shift at 550 cm 1 (Bell et al., 1993). Presence of goethite is confirmed by Raman shifts at 393 and 296 cm 1, Fig. 4a (Bikiaris et al., 2000). Red color in the case of sample MM-4originates from hematite identified by its characteristic Raman shifts at 220, 240, 290, 403 and 605 cm 1, Fig. 4b (Bikiaris et al., 2000). Peak at 144 cm 1 originates from anatase (Bell et al., 1993) which is usually present as a constituent of red ochre (Hradil et al., 2003). Presence of iron oxides and anatase in thin layer applied over ground layer indicate that it was made of ochres – red and yellow, with addition of lead white and minium for particular hue (Hradil et al., 2003). This finding is in accordance with EDXRF spectroscopy results obtained at the backside of the painting where Fe is detected homogenously distributed on the canvas. Moreover, it proves that Milo Milunović was imitating Poussin's technique in preparation of ground layer. Results obtained by EDXRF spectroscopy indicate presence of two blue pigments in the paint layer of the investigated canvas. Micro-Raman spectroscopy analysis identified ultramarine as blue
Fig. 4. Raman spectra of the thin red layer of paint applied over the ground layer of samples: (a) MM-3 and (b) MM-4; Abbreviations: Pb-w-lead white, Mi-minium, Go-goethite, An-Atanase, He-hematite.
pigment in a middle paint layer of sample MM-4, as shown in Fig. 5a. Blue pigment used in paint layer of the sample MM-6 is cobalt blue, as shown in Fig. 5b, which confirms EXDRF spectroscopy finding that cobalt blue was used at blue section of the paint layer. 3.4. FTIR spectroscopy FTIR analyses of 6 samples taken from the investigated canvas have been performed. These samples are mixtures of pigments, binders and extenders. Obtained FTIR spectra are shown in Fig. 6. IR absorption bands are relatively broad due to the overlapping of vibrational modes of different compounds in investigated samples. But it is possible to identify different materials by means of a few characteristic absorption bands. Characteristic bands for Si–O stretching vibrations appear as a broad signal between 1150 and 900 cm 1, indicating presence of earth pigments in all investigated samples (La Russa et al., 2014). Lead white is identified
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
141
Fig. 6. FTIR spectra of samples taken from the investigated canvas; vertical lines represent the positions of characteristic bands of lead white.
Fig. 5. Raman spectra of: (a) blue pigment in a middle paint layer of sample MM-4 and pure ultramarine; (b) blue pigment in the paint layer of sample MM-6 and pure cobalt blue.
minium, cobalt blue, ultramarine, lead white, zinc white, cadmium yellow, chrome-based green pigment and several earth pigments – red and yellow ochre, green earth and umber. Lead white and calcite were used for ground layer. Milunović was imitating Poussin's technique in prepration of ground layer. The first scientific study of Milo Milunović's artwork revealed several important findings. (a) Pallete which artist used during his so called “French period” has been reconstructed; these data can be sucesfully used for investigation of other paintings which artist created in the same period but also for comparison with materials that Milunović used during his other phases. (b) Unambiguos determination of used materials allowed insight into artist's painting technique. This is particulary important to art historians for interpretation of Milunović's artwork, specially during his intesive interaction with French painters. (c) Applied analytical methodology provided substantial amount of data with minimal damage by sampling of precious artwork. (d) Last, but not least, the conclusions derived based on EDXRF spectra were confirmed by other applied analytical techniques, thus proving that EDXRF spectroscopy, as a qualitative method, is a viable tool in examinations of objects of art.
by bands at 3535, 1407 and 680 cm 1 originating from a hydroxyl stretching vibration, antisymmetric stretching vibrations and the rocking deformations of CO3 groups, respectively (Meilunas et al., 1990). In all FTIR spectra characteristic bands originating from the CH2 and CH3 stretching vibrations appear at 2925 cm 1 and 2850 cm 1 as well as carbonyl (C ¼O) stretching band at 1740 cm 1 (Derrick et al., 1999) revealing presence of organic matter probably used as a binder, but obtained results cannot be used for precise identification of compound from which these signals originate.
The authors gratefully acknowledge the financial support provided by Ministry of Education, Science and Technological Development, Republic of Serbia within the framework of projects OI177021, OI177012 and TR37021.The authors would also like to thank Prof. Ivanka Holclajtner-Antunović for help with micro-Raman spectroscopy experiments.
4. Conclusion
References
Spectroscopic study of Milo Milunović's canvas painting “The Inspiration of the poet” showed that painter has used a variety of pigments which, mixed in different combinations, produced a complex palette. Combining results obtained by different experimental techniques materials used by the artist were successfully determined. Following pigments were identified: vermilion,
Acknowledgments
Adriaens, A., 2005. Non-destructive analysis and testing of museum objects: an overview of 5 years of research. Spectrochim. Acta Part B 60, 1503–1516. Alfeld, M., Broekaert, J.A.C., 2013. Mobile depth profiling and sub-surface imaging techniques for historical paintings – a review. Spectrochim. Acta Part B 88, 211–230. Bell, I.M., Clark, R.J.H., Gibbs, P.J., 1993. Raman spectroscopy library of natural and synthetic pigments (pre 1850 AD). Spectrochim. Acta Part A 53, 2159–2179.
142
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
Bevilacqua, N., Borgioli, L., AdroverGracia, I., 2010. Matteini, M. (Ed.), I Pigmentinell’arte. Dalla Preistoria Alla Rivoluzione Industrilae. Il Prato, Saonara, Italy. Bikiaris, D., Daniilia, S., Sotiropoulou, S., Katsimbiri, O., Pavlidou, E., Moutsatsou, A. P., 2000. Ochre-differentiation through micro-Raman and micro-FTIR spectroscopies: application on wall paintings at Meteora and Mount Athos, Greece. Spectrochim. Acta Part A 56, 3–18. Brostoff, L., Maynor, C., Speakman, R., 2009. Preliminary study of a Georgia O'Keeffe pastel drawing by XRF and mXRD. Powder Diffr. J. 24, 116–123. Campos, P.H.O.V., Kajiya, E.A.M., Rizzutto, M.A., Neiva, A.C., Pinto, H.P.F., Almeida, P. A.D., 2014. X-ray fluorescence and imaging analyses of paintings by the Brazilian artist Oscar Pereira Da Silva. Radiat. Phys. Chem. 95, 362–367. Ćelić-Simeonović, I., Milunović, Milo, 1997. Boundless Striving Towards the Essence of the Painter’s Matter and Colour. SANU, Belgrade. Derrick, M.R., Stulik, D., Landry, J.M., 1999. Infrared Spectroscopy in Conservation Science. The Getty Conservation Institute, USA. Doménech-Carbó, M.T., Casas-Catalán, M.J., Doménech-Carbó, A., Mateo-Castro, R., Gimeno-Adelantado, J.V., Bosch-Reig, F., 2001. Analytical study of canvas painting collection from the Basilica de la Virgen de los Desamparados using SEM/EDX, FT-IR, GC and electrochemical techniques. Fresenius' J. Anal. Chem. 369, 571–575. Dredge, P., Wuhrer, R., Phillips, M.R., 2003. Monet's painting under the microscope. Microsc. Microanal. 9, 139–143. Duval, A.R., 1992. Les préparations colorées des tableaux de l'Ecole Française des dix-septième et dix-huitième siècles. Stud. Conserv. 37, 239–258. Hradil, D., Grygar, T., Hradilova, J., Bezdička, P., 2003. Clay and iron oxide pigments in the history of painting. Appl. Clay Sci. 22, 223–236. Jovanović, V., 2001. Five painters: Stojan Aralica, Jefto Perić, Milo Milunović, Petar Lubarda, Sava Šumanović: Memories and Letters. Tiski svet, Novi Sad. Korolija-Crkvenjakov, D. , Andrić, V., Marić-Stojanović, M., Gajić-Kvaščev, M.,
Gulan, J., Marković, N. 2012. The Iconostasis of the Krušedol Monastery Church, The Gallery of Matica srpska, Novi Sad and University of Belgrade Vinča, Institute of Nuclear Sciences Belgrade. La Russa, M.F., Ruffolo, S.A., Belifore, C.M., Comite, V., Casoli, A., Berzoli, M., Nava, G., 2014. A scientific approach to the characterization of the painting technique of an author: the case of Raffaele Rinaldi. Appl. Phys. A 144, 733–740. Meilunas, R.J., Bentsen, J.G., Steinberg, A., 1990. Stud. Conserv. 35, 33–51. Miliani, C., Rosi, F., Brunetti, B.G., Sgamellotti, A., 2010. In situ noninvasive study of artworks: the molab multitechnique approach. Acc. Chem. Res 43, 728–738. Oriola, M., Možir, A., Garside, P., Campo, G., Nualart-Torroja, A., Civil, I., Odlyha, M., Cassar, M., Strlič, M., 2014. Looking beneath Dali's paint: non-destructive canvas analysis. Anal. Methods 6, 86–96. Ortega-Avilés, M., Vandenabeele, P., Tenorio, D., Murillo, G., Jiménez-Reyes, M., Gutérrez, N., 2005. Spectroscopic investigation of a ‘Virgin of Sorrows’ canvas painting: a multi-method approach. Anal. Chim. Acta 550, 164–172. Rosi, F., Burnstock, A., Van den Berg, K.J., Miliani, C., Brunetti, B.G., Sgamellotti, A., 2009. A non-invasive XRF study supported by multivariate statistical analysis and reflectance FTIR to assess the composition of modern painting materials. Spectrochim. Acta Part A 71, 1655–1662. Trifunović, L., 1973. Serbian paintings: 1900–1950. Nolit, Belgrade. Van de Voorde, L., Van Pevenage, J., De Langhe, K., De Wolf, R., Vekemans, B., Vincze, L., Vandenabeele, P., Martens, M.P.J., 2014. Non-destructive in situ study of “Mad Meg” by Pieter Bruegel the elder using mobile X-ray fluorescence, X-ray diffraction and Raman spectrometers. Spectrochim. Acta Part B 97, 1–6. Van der Snickt, G., Janssens, K., Schalm, O., Aibéo, C., Kloust, H., Alfeld, M., 2010. James Ensor's pigment use: artistic and material evolution studied by means of portable X-ray fluorescence spectrometry. X-Ray Spectrom. 39, 103–111.
Contents lists available at ScienceDirect
Radiation Physics and Chemistry journal homepage: www.elsevier.com/locate/radphyschem
Radiation Physics (Bergstrom)
The characterization of canvas painting by the Serbian artist Milo Milunović using X-ray fluorescence, micro-Raman and FTIR spectroscopy Lj. Damjanović a,n, M. Gajić-Kvaščev b, J. Đurđević a, V. Andrić b, M. Marić-Stojanović c, T. Lazić d, S. Nikolić d a
University of Belgrade-Faculty of Physical Chemistry, Studentski trg 12-16, 11000 Belgrade, Serbia University of Belgrade-Vinča Institute of Nuclear Sciences, P.O. Box 522, 11000 Belgrade, Serbia c National Museum Belgrade, Trg Republike 1a, 11000 Belgrade, Serbia d University of Arts in Belgrade-Faculty of Applied Arts, Kralja Petra 4, 11000 Belgrade, Serbia b
H I G H L I G H T S
In situ EDXRF, micro-Raman and FTIR spectroscopy were employed. Pallete of painting “The Inspiration of the poet” by Milunović has been determined. Obtained results allowed evaluation of the painter’s technique. Milo Milunović worked on the clay ground imitating Nicoals Poussin’s technique.
art ic l e i nf o Article history: Received 23 April 2015 Received in revised form 15 June 2015 Accepted 17 June 2015 Available online 25 June 2015 Keywords: Canvas painting Milo Milunović EDXRF spectroscopy Micro-Raman spectroscopy FTIR spectroscopy
a b s t r a c t A canvas painting by Milo Milunović “The Inspiration of the poet” was studied by energy dispersive X-Ray fluorescence (EDXRF), micro-Raman and Fourier transform infrared (FTIR) spectroscopy in order to identify materials used by the artist and his painting technique. Study is perfomed combining in situ nondestructive method with the preparation and study of cross-section samples and raw fragments of the samples. Milo Milunović, an eminent painter from Balkan region, made a copy of the Nicolas Poussin's original painting in Louvre in 1926/27. Obtained results revealed following pigments on the investigated canvas painting: vermilion, minium, cobalt blue, ultramarine, lead white, zinc white, cadmium yellow, chrome-based green pigment and several earth pigments – red and yellow ocher, green earth and umber. Ground layer was made of lead white mixed with calcium carbonate. & 2015 Elsevier Ltd. All rights reserved.
1. Introduction Canvas paintings are among the most heterogeneous works of art and their characterization is a demanding analytical task (Oriola et al., 2014).Traditionally, characterization of canvas painting has been mainly carried out by art-historians and restorers by naked eye and by microscopic analysis. Information obtained in this way, combined with consistent evidence of the art materials obtained by physico-chemical techniques can help conservators and restorers to select the most appropriate procedures for the purposes of restoration. The scientists always have to balance the possible risks of damage against the benefits that are gained from the investigation of n
Corresponding author. Fax: þ 381 2187 133. E-mail address: [email protected] (Lj. Damjanović).
http://dx.doi.org/10.1016/j.radphyschem.2015.06.017 0969-806X/& 2015 Elsevier Ltd. All rights reserved.
the art-work. Hence, the risk of damage/information ratio should be considered and optimized carefully for each investigation (Dredge et al., 2003; Ortega-Avilés et al., 2005). Significant progress in this area is made by continuous advances in non-invasive experimental techniques (Adriaens, 2005; Miliani et al., 2010; Alfeld and Broekaert, 2013). In the cases where samples are available, amounts of obtained material are usually in micro or submicro range containing different analytes. These complex mixtures most often include organic and inorganic compounds, thus use of different analytical techniques is required for a complete characterization of the investigated samples (Doménech-Carbó et al., 2001). In this work we present multianalytical study of canvas painting “The inspiration of the poet” made by Milo Milunović (1897– 1967), a distinguished painter from Balkan region. He studied art in Florence under the apprenticeship of Antonio Augusto Giacometti (1912–1914), and later in Paris (1919–22; 1926–32). During
136
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
his stay in Paris, he developed friendships with many artists such as Chaim Soutine, Massimo Campigli, AntoineBourdelle (who bought several Milunović's paintings, which are now in the Bourdelle Museum in Paris – two paintings are included in the permanent exhibition). With two colleagues, Milo Milunović founded the Academy of Fine Arts in Belgrade, Serbia in 1937, where he worked as a professor. He was also cofounder of School of Fine Arts in Cetinje, Montenegro in 1947. Milo Milunović's artistic importance and regional influence is manifested through domestic and international exibitions: 45 independent (e.g. Paris, Cardot Gallery, 1928– 29, 1932) and over 320 group (e.g. Salon des Tuileries, 1927 and Galerie Bernheim Jeune, 1931) exhibitions. His creative work is described in monographies, prefaces of catalogs, books and encyclopedias (Trifunović, 1973; Ćelić-Simeonović and Milunović, 1997; Jovanović, 2001). Almost consistently following the beliefs of Cezanne, who was his great inspiration, that “The Louvre is a book from which we learn to read” and that “One should do Poussin all over from Nature” Milunović copied the Nicolas Poussin's painting “The inspiration of the poet” in the Louvre in 1926/27. “The Inspiration of the poet” painted by Milunović is 2.18 m 1.80 m large. The painting was firstly in the possession of Milunović's brother at Cetinje, Montenegro till 1931, when it was sent to Belgrade to his friend Kosta Hakman. The painting was sold to the French Club in Belgrade in 1935 where it stayed till the beginning of the World War II. It is not known where the painting was till 1967 when it was displayed again in the hall of the Craftsman Workhouse building in Belgrade. Since 1990 it has been permanently exhibited in the hall of the Faculty of Fine Arts in Belgrade. This painting was brought to the Faculty of Applied Arts in Belgrade for restoration, which provided a unique opportunity for a scientific investigation. This is the first scientific study of Milo Milunović's artwork and it was perfomed combining in situ non-destructive energy dispersive X-Ray fluorescence (EDXRF) spectroscopy, which has been proven to be efficient in the study of canvas painting materials (Rosi et al., 2009; Campos et al., 2014; Van de Voorde et al., 2014), with the preparation and study of cross-section samples as well as raw fragments of the samples. In-house developed portable EDXRF spectrometer was used for investigation of well-preserved regions of the painting, while paint chips taken from the edges of the damaged regions were investigated by optical microscopy, microRaman and FTIR spectroscopy. The aim of this study was to gather information about materials (pigments and ground layer) and painting technique used by the artist, combining data obtained by different analytical techniques.
2. Experimental Portable in-house developed EDXRF spectrometer was used for the non-invasive and non-destructive analysis of the painting. The excitation X-ray tube (Oxford, Rh anode, max voltage 50 kV, max current 1 mA, air cooled) is mounted on a motorized platform which allows easy movement along all three axes. The construction allows precise movement of 1 mm in each direction. The detection of the characteristic X-rays was made by compact X-ray spectrometer (X123, Amptek Inc.) with Si-PIN detector (6 mm2/500 μm, Be window 12.5 μm thickness and 1.5 in. detector extension) which is mounted on the excitation X-ray protection box together with two laser pointers which enable alignment of the measuring system at the desired point to be analyzed. The energy resolution of used detector was 160 eV at 5.89 keV. The excitation X-ray beam has been collimated passing through especially designed collimator mounted at the end of the tube. The
Fig. 1. Photographs of Milo Milunović's canvas painting “The Inspiration of the poet”: (a) front side-EDXRF spectra were collected at the points labeled 1–39, samples were taken from the areas labeled MM-1 to MM-6; (b) backside-EDXRF spectra were collected at the points labeled 40–45. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
measurements were performed without additional filtering of the excitation beam. Measuring system is mounted on the cantilever which enables portability, sufficient stability, easy movement and handling, even during analysis of large scale paintings like the one analyzed in this study. Geometry of the experimental setup for all measurements was the same: distance between surface of the painting and the end point of the collimator was 16 mm, distance between analyzed surface and detector window was 21 mm and angle between detector and X-ray tube axes was 45°. The X-ray tube voltage was altered to give excitation of 40 keV. In this experimental setup, with detection path in the air, only elements heavier than Si can be detected. For all the measurements filament current was set at 300 μA and acquisition time was 40 s since only qualitative analysis was performed. For the spectra acquisition and processing ADMCA software was used (Amptek Inc.). Total of 45 points (see Fig. 1) were analyzed. Analyzed points were selected to represent particular colors on the surface layer of the painting. Few points on the backside of the painting were also analyzed for the characterization of preparation layer. Investigated canvas painting was well-preserved. Hence it was
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
possible to take only small number of samples. In total 6 samples of paint chips were taken from the edges of existing damaged regions of the painting: 3 samples were taken from painted canvas which was folded under the frame and 3 samples from the front of the painting (see Fig. 1a, samples denoted “MM”). Samples of approximately 1 mm2 or even smaller were removed by sharp and clean scalpel. Cross sections of 6 samples were recorded by optical Olympus BX51M microscope equipped with UV lamp Olympus U-RFL-T and U-MWUS3 and U-MWBS3 filters. Micro-Raman spectra were recorded in situ from cross-sections of 6 samples on a DXR Raman Microscope (Termo Scientific). The 532 nm line of a diode-pumped solid state high brightness laser was used as the exciting radiation and the power of illumination at the sample surface ranged between 3 and 10 mW. Collection of the scattered light was made through an Olympus microscope with infinity-corrected confocal optics, 25 mm pinhole aperture, standard working distance objective 50 , gratings of 900 lines/mm and 1800 lines/mm, and resolution of 2 cm 1. Acquisition time was 2 s with 15 scans. The laser spot diameter on the sample was 1 mm. Thermo Scientific OMNIC software was used for spectra collection and manipulation. The identification of pigments was performed by comparison of recorded spectra with spectra of
137
pigments from homemade database or from literature (Bell et al., 1993; Bikiaris et al., 2000). The FTIR spectra of 6 samples of paint chips, which were grounded to a powder, were recorded on a FTIR Nicolet 6700 spectrometer using KBr pellets technique, in the wavenumber range from 4000 to 400 cm 1.
3. Results and discussion Milo Milunović's canvas painting “The Inspiration of the poet” investigated in this work is shown in Fig. 1. The surface of the painted layer was covered with a thin layer of dust and dirt, which notably changed its color. Parts of the painting were cleaned before this study and investigated points in cleaned areas are: 10, 12, 13, 15, 16, 17, 24, 29, 30, 31, 32, and 34 (see Fig. 1a). The excess canvas is folded and fixed with metal nails to the slats of the blind frame. The surface of the excess canvas is covered with a uniform layer of preparation, indicating that the canvas was prepared before stretching. According to restorers, this feature together with the fact that the format of the painting is large with a uniformly applied preparation suggests that the canvas was
Fig. 2. The EDXRF spectra recorded at: (a) red sections of paint layer-points 14, 19 and 38; (b) white sections of paint layer-points 17, 32 and 34; (c) brown sections of paint layer-points 8, 23 and 36; (d) backside of painting – points 40–43. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
138
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
industrially prepared. 3.1. EDXRF spectroscopy Qualitative EDXRF spectroscopy analysis of paint layer of investigated canvas painting was performed at 39 points shown at Fig. 1a. The detected elemental composition at the measuring points allowed identification of following pigments used by the artist. 3.1.1. Red pigments The EDXRF spectra recorded at red sections of paint layer, at points 14, 19 and 38, are shown at Fig. 2a. Three different red pigments were identified: vermilion (HgS), red ochre (Fe2O3 þclayþsilica) and minium (Pb3O4). According to the tone and hue of the color it can be assumed that minium is probably used in mixture with red ochre (Van der Snickt et al., 2010). 3.1.2. Green pigments In all EDXRF spectra recorded at green sections of paint layer (points 1, 24–28) intensive Fe peak has been detected indicating presence of green earth (hydrous aluminosilicate of iron, magnesium and potassium). Characteristic trace elements for green earth, K, Ti, and Mn, were also detected confirming use of this pigment (Bevilacqua et al., 2010). Lighter hues of green color have been obtained by mixing with lead white (basic lead carbonate, 2PbCO3 Pb(OH)2) and zinc white (ZnO). Particular hues (points 24, 27 and 28) have been the most probably obtained by addition of cadmium yellow (CdS). Several EDXRF spectra recorded at green sections of paint layer show presence of Cr. Precise distinction between use of chrome green, Cr2O3, and viridian, Cr2O3 2H2O, at these points is not possible by used analytical technique. Based on the art historians' knowledge, the most likely artist has used viridian for intense dark hues of green color (point 26). Another possibility is that chrome green has been used for olive green tone or that viridian has been mixed with cadmium yellow to achieve such tone (points 24 and 28). 3.1.3. Blue pigments Blue sections of paint layer (points 6, 10 and 13) were made by cobalt blue pigment (CoO Al2O3). Blue tones at points 2, 20 and 21 were obtained by mixtures of iron based pigments: Prussian blue, Fe4[Fe(CN)6]3, or green earth with ultramarine, (Na8–10[Al6Si6O24]S2–4). Neither Prussian blue nor ultramarine can be unambiguously determined by this analytical technique (Korolija-Crkvenjakov et al., 2012). 3.1.4. White pigments The most intense hue of white color (point 32) has been obtained with lead white. Zinc white was added for particular tone (points 34 and 35) (Brostoff et al., 2009). Green earth was used in the mixture with lead white and zinc white for gray tones (points 12, 15, 17 and 18). Representative EDXRF spectra recorded at white sections of paint layer are shown at Fig. 2b. 3.1.5. Yellow pigments Yellow sections from the dress (points 3–5, 29–31) were made of iron-based pigment-yellow ochre (Fe2O3 H2O or FeOOH þclayþ silica). Different hues were obtained by addition of zinc white, although presence of lead white in this mixture cannot be excluded. 3.1.6. Other pigments The precise determination of pigments used for flesh tones (points 9, 11, 16, 22 and 39) was difficult because the surface of paint layer was covered with dirt. The most probably lead white
was used with addition of zinc white and iron based pigment (red or yellow ochre). Brown sections of paint layer (points 7, 8, 23, 36 and 37) were made of earth pigment umber (iron oxides with 6– 15% of MnO2) which was identified by the presence of strong peak of Fe and peak of Mn in the EDXRF spectra (Bevilacqua et al., 2010). Representative EDXRF spectra recorded at brown sections of paint layer are shown at Fig. 2c. Cadmium based pigment has also been determined. Since Cd was detected at sections of paint layer which are not yellow, it can be assumed that cadmium yellow was mixed with green, yellow and brown pigments. 3.1.7. Ground layer In order to obtain information about ground layer, EDXRF spectra of the painting's backside were recorded (Fig. 1b). EDXRF spectra obtained at points 40 to 43, shown in Fig. 2d, were identical. This finding indicates that the ground layer was homogeneously applied on the canvas which strongly supports assumptions of restorers that canvas was bought with already prepared ground layer. EDXRF spectrum recorded at the excess canvas with no paint layer folded under the frame, point 44, showed presence of only Pb and Ca, while Zn and Fe were not detected. This finding leads to the conclusion that lead white mixed with calcium carbonate (CaCO3) was used for the ground layer. However, this part of the canvas was exposed to external influences over time therefore it is difficult to eliminate with certainty presence of Zn in the ground layer.The possible interpretation of obtained results is that Zn and Fe originate from paint layer, but it cannot be distinguished precisely by EDXRF spectroscopy. The traces of tiny white splashes can be observed on the entire surface of the back of the canvas and the slats of the blindframe. EDXRF spectrum recorded at one of those white spots (point 45) showed presence of Pb, Zn, Ca, Fe, Ba and Sr. The chemical composition at this point differs from results obtained for ground layer indicating that these traces appeared at a later stage, due to improper storage. 3.2. Optical microscopy Optical microscopy provides information about the sequence and the thickness of the paint layer and it allows a preliminary characterization of the materials in the paint film and the ground layer. Optical micrographs and fluorescence photographs under UV light of 6 samples taken from the investigated painting are shown in Table 1. Ground layer appeared as a single, thick and consistent layer in all investigated samples. No fluorescence under UV light has been detected in ground layer of all 6 samples. This finding supports results obtained by EDXRF spectroscopy that zinc white was not used for ground layer. Optical micrographs of samples MM-1, MM-2, MM-3, MM-4 and MM-6 show three paint layers, while there are two layers of paint in the case of sample MM-5. Thin layer of red color applied on the ground layer is clearly visible in the cross sections of samples MM-2, MM-3 and MM-4 indicating that additional thick paint layers were painted over thin one. It is known that during 17th and 18th century painters were making several preparatory layers prior to beginning of painting. This was usually done with the combination of red, yellow and brown earths with lead white or minium. One of the examples is the painting the “The inspiration of the poet” by Nicolas Poussin made in Italy between 1627 and 1629, which has a brown ground layer with red grains (Duval, 1992). It appears that Milo Milunović was imitating this technique at the part of canvas with the darker colors in order to obtain similar effects as Poussin.
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
139
Table 1 Optical micrographs and fluorescence photographs under UV light; magnification 100x. Sample Visible color of the sample before cleaning MM-1
Red with brown hue
MM-2
Blue
MM-3
Dark green
MM-4
Dark green
MM-5
Dark green
MM-6
Light blue
Optical micrographs
3.3. Micro-Raman spectroscopy Micro-Raman spectroscopy can yield detailed information about compounds present in different layers. In this study microRaman analysis is performed on the cross sections of samples taken from the investigated painting, thus it was possible to determine pigments used in specific layers. The red color in the top paint layer of sample MM-1 originates from hematite, the main colorant of red ochre, identified by
Fluorescence photographs under UV light
characteristic Raman shifts at 220, 240 and 290 cm 1, as shown in Fig. 3a (Bikiaris et al., 2000). Micro-Raman analysis of yellow pigment grains identified cadmium yellow, by characteristic peaks at 297 and 600 cm 1, in the top paint layer of sample MM-1, as shown in Fig. 3b (Bell et al., 1993). Raman spectra of thin red layer of paint applied over the ground layer (see optical micrographs in Table 1) were recorded for samples MM-3 and MM-4 and shown in Fig. 4. In the case of
140
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
Fig. 3. Raman spectra of pigments in a top paint layer of sample MM-1: (a) red (hematite-He) and (b) yellow (cadmium yellow-Cd-y).
sample MM-3 lead white was identified by characteristic Raman shift at 1050 cm 1, anatase by characteristic peak at 144 cm 1 and minium was identified by characteristic Raman shift at 550 cm 1 (Bell et al., 1993). Presence of goethite is confirmed by Raman shifts at 393 and 296 cm 1, Fig. 4a (Bikiaris et al., 2000). Red color in the case of sample MM-4originates from hematite identified by its characteristic Raman shifts at 220, 240, 290, 403 and 605 cm 1, Fig. 4b (Bikiaris et al., 2000). Peak at 144 cm 1 originates from anatase (Bell et al., 1993) which is usually present as a constituent of red ochre (Hradil et al., 2003). Presence of iron oxides and anatase in thin layer applied over ground layer indicate that it was made of ochres – red and yellow, with addition of lead white and minium for particular hue (Hradil et al., 2003). This finding is in accordance with EDXRF spectroscopy results obtained at the backside of the painting where Fe is detected homogenously distributed on the canvas. Moreover, it proves that Milo Milunović was imitating Poussin's technique in preparation of ground layer. Results obtained by EDXRF spectroscopy indicate presence of two blue pigments in the paint layer of the investigated canvas. Micro-Raman spectroscopy analysis identified ultramarine as blue
Fig. 4. Raman spectra of the thin red layer of paint applied over the ground layer of samples: (a) MM-3 and (b) MM-4; Abbreviations: Pb-w-lead white, Mi-minium, Go-goethite, An-Atanase, He-hematite.
pigment in a middle paint layer of sample MM-4, as shown in Fig. 5a. Blue pigment used in paint layer of the sample MM-6 is cobalt blue, as shown in Fig. 5b, which confirms EXDRF spectroscopy finding that cobalt blue was used at blue section of the paint layer. 3.4. FTIR spectroscopy FTIR analyses of 6 samples taken from the investigated canvas have been performed. These samples are mixtures of pigments, binders and extenders. Obtained FTIR spectra are shown in Fig. 6. IR absorption bands are relatively broad due to the overlapping of vibrational modes of different compounds in investigated samples. But it is possible to identify different materials by means of a few characteristic absorption bands. Characteristic bands for Si–O stretching vibrations appear as a broad signal between 1150 and 900 cm 1, indicating presence of earth pigments in all investigated samples (La Russa et al., 2014). Lead white is identified
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
141
Fig. 6. FTIR spectra of samples taken from the investigated canvas; vertical lines represent the positions of characteristic bands of lead white.
Fig. 5. Raman spectra of: (a) blue pigment in a middle paint layer of sample MM-4 and pure ultramarine; (b) blue pigment in the paint layer of sample MM-6 and pure cobalt blue.
minium, cobalt blue, ultramarine, lead white, zinc white, cadmium yellow, chrome-based green pigment and several earth pigments – red and yellow ochre, green earth and umber. Lead white and calcite were used for ground layer. Milunović was imitating Poussin's technique in prepration of ground layer. The first scientific study of Milo Milunović's artwork revealed several important findings. (a) Pallete which artist used during his so called “French period” has been reconstructed; these data can be sucesfully used for investigation of other paintings which artist created in the same period but also for comparison with materials that Milunović used during his other phases. (b) Unambiguos determination of used materials allowed insight into artist's painting technique. This is particulary important to art historians for interpretation of Milunović's artwork, specially during his intesive interaction with French painters. (c) Applied analytical methodology provided substantial amount of data with minimal damage by sampling of precious artwork. (d) Last, but not least, the conclusions derived based on EDXRF spectra were confirmed by other applied analytical techniques, thus proving that EDXRF spectroscopy, as a qualitative method, is a viable tool in examinations of objects of art.
by bands at 3535, 1407 and 680 cm 1 originating from a hydroxyl stretching vibration, antisymmetric stretching vibrations and the rocking deformations of CO3 groups, respectively (Meilunas et al., 1990). In all FTIR spectra characteristic bands originating from the CH2 and CH3 stretching vibrations appear at 2925 cm 1 and 2850 cm 1 as well as carbonyl (C ¼O) stretching band at 1740 cm 1 (Derrick et al., 1999) revealing presence of organic matter probably used as a binder, but obtained results cannot be used for precise identification of compound from which these signals originate.
The authors gratefully acknowledge the financial support provided by Ministry of Education, Science and Technological Development, Republic of Serbia within the framework of projects OI177021, OI177012 and TR37021.The authors would also like to thank Prof. Ivanka Holclajtner-Antunović for help with micro-Raman spectroscopy experiments.
4. Conclusion
References
Spectroscopic study of Milo Milunović's canvas painting “The Inspiration of the poet” showed that painter has used a variety of pigments which, mixed in different combinations, produced a complex palette. Combining results obtained by different experimental techniques materials used by the artist were successfully determined. Following pigments were identified: vermilion,
Acknowledgments
Adriaens, A., 2005. Non-destructive analysis and testing of museum objects: an overview of 5 years of research. Spectrochim. Acta Part B 60, 1503–1516. Alfeld, M., Broekaert, J.A.C., 2013. Mobile depth profiling and sub-surface imaging techniques for historical paintings – a review. Spectrochim. Acta Part B 88, 211–230. Bell, I.M., Clark, R.J.H., Gibbs, P.J., 1993. Raman spectroscopy library of natural and synthetic pigments (pre 1850 AD). Spectrochim. Acta Part A 53, 2159–2179.
142
Lj. Damjanović et al. / Radiation Physics and Chemistry 115 (2015) 135–142
Bevilacqua, N., Borgioli, L., AdroverGracia, I., 2010. Matteini, M. (Ed.), I Pigmentinell’arte. Dalla Preistoria Alla Rivoluzione Industrilae. Il Prato, Saonara, Italy. Bikiaris, D., Daniilia, S., Sotiropoulou, S., Katsimbiri, O., Pavlidou, E., Moutsatsou, A. P., 2000. Ochre-differentiation through micro-Raman and micro-FTIR spectroscopies: application on wall paintings at Meteora and Mount Athos, Greece. Spectrochim. Acta Part A 56, 3–18. Brostoff, L., Maynor, C., Speakman, R., 2009. Preliminary study of a Georgia O'Keeffe pastel drawing by XRF and mXRD. Powder Diffr. J. 24, 116–123. Campos, P.H.O.V., Kajiya, E.A.M., Rizzutto, M.A., Neiva, A.C., Pinto, H.P.F., Almeida, P. A.D., 2014. X-ray fluorescence and imaging analyses of paintings by the Brazilian artist Oscar Pereira Da Silva. Radiat. Phys. Chem. 95, 362–367. Ćelić-Simeonović, I., Milunović, Milo, 1997. Boundless Striving Towards the Essence of the Painter’s Matter and Colour. SANU, Belgrade. Derrick, M.R., Stulik, D., Landry, J.M., 1999. Infrared Spectroscopy in Conservation Science. The Getty Conservation Institute, USA. Doménech-Carbó, M.T., Casas-Catalán, M.J., Doménech-Carbó, A., Mateo-Castro, R., Gimeno-Adelantado, J.V., Bosch-Reig, F., 2001. Analytical study of canvas painting collection from the Basilica de la Virgen de los Desamparados using SEM/EDX, FT-IR, GC and electrochemical techniques. Fresenius' J. Anal. Chem. 369, 571–575. Dredge, P., Wuhrer, R., Phillips, M.R., 2003. Monet's painting under the microscope. Microsc. Microanal. 9, 139–143. Duval, A.R., 1992. Les préparations colorées des tableaux de l'Ecole Française des dix-septième et dix-huitième siècles. Stud. Conserv. 37, 239–258. Hradil, D., Grygar, T., Hradilova, J., Bezdička, P., 2003. Clay and iron oxide pigments in the history of painting. Appl. Clay Sci. 22, 223–236. Jovanović, V., 2001. Five painters: Stojan Aralica, Jefto Perić, Milo Milunović, Petar Lubarda, Sava Šumanović: Memories and Letters. Tiski svet, Novi Sad. Korolija-Crkvenjakov, D. , Andrić, V., Marić-Stojanović, M., Gajić-Kvaščev, M.,
Gulan, J., Marković, N. 2012. The Iconostasis of the Krušedol Monastery Church, The Gallery of Matica srpska, Novi Sad and University of Belgrade Vinča, Institute of Nuclear Sciences Belgrade. La Russa, M.F., Ruffolo, S.A., Belifore, C.M., Comite, V., Casoli, A., Berzoli, M., Nava, G., 2014. A scientific approach to the characterization of the painting technique of an author: the case of Raffaele Rinaldi. Appl. Phys. A 144, 733–740. Meilunas, R.J., Bentsen, J.G., Steinberg, A., 1990. Stud. Conserv. 35, 33–51. Miliani, C., Rosi, F., Brunetti, B.G., Sgamellotti, A., 2010. In situ noninvasive study of artworks: the molab multitechnique approach. Acc. Chem. Res 43, 728–738. Oriola, M., Možir, A., Garside, P., Campo, G., Nualart-Torroja, A., Civil, I., Odlyha, M., Cassar, M., Strlič, M., 2014. Looking beneath Dali's paint: non-destructive canvas analysis. Anal. Methods 6, 86–96. Ortega-Avilés, M., Vandenabeele, P., Tenorio, D., Murillo, G., Jiménez-Reyes, M., Gutérrez, N., 2005. Spectroscopic investigation of a ‘Virgin of Sorrows’ canvas painting: a multi-method approach. Anal. Chim. Acta 550, 164–172. Rosi, F., Burnstock, A., Van den Berg, K.J., Miliani, C., Brunetti, B.G., Sgamellotti, A., 2009. A non-invasive XRF study supported by multivariate statistical analysis and reflectance FTIR to assess the composition of modern painting materials. Spectrochim. Acta Part A 71, 1655–1662. Trifunović, L., 1973. Serbian paintings: 1900–1950. Nolit, Belgrade. Van de Voorde, L., Van Pevenage, J., De Langhe, K., De Wolf, R., Vekemans, B., Vincze, L., Vandenabeele, P., Martens, M.P.J., 2014. Non-destructive in situ study of “Mad Meg” by Pieter Bruegel the elder using mobile X-ray fluorescence, X-ray diffraction and Raman spectrometers. Spectrochim. Acta Part B 97, 1–6. Van der Snickt, G., Janssens, K., Schalm, O., Aibéo, C., Kloust, H., Alfeld, M., 2010. James Ensor's pigment use: artistic and material evolution studied by means of portable X-ray fluorescence spectrometry. X-Ray Spectrom. 39, 103–111.