Surface chemical reactions in Paintings

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Dustin Osborne
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1 Surface chemical reactions in Paintings Katrien Keune Rijksmuseum Amsterdam and University of Amsterdam, The Netherlands

2 #Umeet #uva #wvdw 2

3 #Umeet #uva #wvdw 3

4 #Umeet #uva #wvdw 4

5 Preferred appearance? 5

6 2 3 1 Vincent van Gogh s Bedroom (1888; canvas 72 x 90 cm), Van Gogh Museum, Amsterdam Research: E. Hendricks et al.; Van Gogh Museum, Cultural Heritage Agency of the Netherlands (RCE) and Netherlands Organization for Scientific Research (NWO) in cooperation with Prof. R. S. Berns, Munsell Color Science Laboratory.

; Van Gogh Museum, Cultural Heritage Agency of the Netherlands (RCE) and

7 Paint sample research paint cross-sections 20 μm Macroscopic detail of De Dorser, Van Gogh (1889), Van Gogh museum Paint cross-section Image: L.Carlyle Light microscopic image under UV Sample from De Dorser, Van Gogh (1889), Van Gogh museum

9 Realgar (AsS) and Orpiment (As 2 S 3 ) Still life with five apricots, Adriaen de Coorte, 1704, Royal Picture Gallery Mauritshuis, The Hague

10 Realgar (AsS) and Orpiment (As 2 S 3 ) - photodegradation paint layer 2? 1 paint layer paint layer 1? AsS As 2 O 3 Ground layer FeAsO + Ca 3 (AsO 4 ) 2 As-XANES at SSRL Image segmentation based on PCA Arsenic Phases Photodegradation products: AsO 3, AsO 5

12 Zinc Oxide (ZnO) Couple with Clouds in their Heads, Salvador DalÍ, 1936, Museum Boijmans van Beuningen

13 Zinc Oxide (ZnO)

14 Zinc Oxide (ZnO) intact paint degraded paint ZnO + 2RCOOH Zn(RCOO) 2 + H 2 O (R = C 15 H 31 /C 17 H 33 )

15 Zinc Oxide (ZnO) Photo shoot of Dalí and Gala taken by Cecil Beaton (1936)

16 After treatment: visually acceptable

17 Lead white pigments Still life with Asparagus, Adriaen Coorte, 17 e C, oil on paper on panel, Rijksmuseum PbO + 2RCOOH Pb(RCOO) 2 + H 2 O (R = C 15 H 31 /C 17 H 33 )

18 Lead pigments + fatty acids --> lead soaps PbO + 2RCOOH Pb(RCOO) 2 + H 2 O (R = C 15 H 31 /C 17 H 33 )

20 Ultramarine disease Restoration by Annetje Boersma, Rotterdam Van Eyck, The Three Marys at the Tomb, c , oil on oak panel, Museum Boijmans Van Beuningen, Rotterdam

21 Macroscopic imaging X-ray fluorescence Macro-XRF scanner prof. J. Dik, TUDelft and profs. G. Van der Snickt en K. Janssens, University Antwerp

22 Macroscopic imaging X-ray fluorescence Lead (L-line) Copper (K-line) Potassium (K-line) XRF elemental macro maps

23 Correlating macro- and microscopic imaging Potassium Copper Lead

Containing the mineral Lazurite; (Na,Ca) 8 [(S,Cl,SO 4,OH) 2

24 Ultramarine traditional separation method Lapis lazuli power Resin Beeswax Linseed oil Precious stone: Lapis Lazuli Containing the mineral Lazurite; (Na,Ca) 8 [(S,Cl,SO 4,OH) 2 (Al 6 Si 6 O 24 )] S 3 - chromophore Kneeded in water or lye solution

25 Intensity, arb. units Intensity, arb. units Intensity, arb. units Intensity, arb. units Preliminary results S-XANES No heat 415 C 600 C 750 C = S 3 radical contributions Energy, kev Energy, kev Energy, kev Energy, kev

27 Sunflowers by Van Gogh Sunflowers, (January 1889), Vincent van Gogh ( ) Oil on canvas, 95 cm x 73 cm, Van Gogh Museum, Amsterdam

28 Sunflowers by Van Gogh Primrose Chrome (PbCr 1-x S x O 4, 0.45 x 0.55, orthorhombic) Lemon Chrome (PbCr 1-x S x O 4, 0.2 x 0.4) Middle Chrome (mainly pure PbCrO 4, monoclinic). Paint is: - Crumbly - Sensitive to solvents Internal porosity? Microscopic image, normal Microscopic image, UV Backscatter electron image

29 3-D Backscatter image: in-situ microtoming Beam Stage Zeiss Sigma with Gatan 3View system Centre for Microscopy and Microanalysis, University of Queensland, Australia

30 Example of 3D Backscatter image of paint cross-section In situ microtoming Sections of 60 nm BSE images at 2 kev 500 slices 50 x 50 μm Contrast inverted! Paint sample from Winding the skein by Leighton (1878) Queensland Art Gallery, Australia

31 3-D Backscatter image of paint cross-section Sections of 50 nm BSE images at 1.3 kev 200 slices 38.8 x 38.8 μm Voxel size: 9.7 x 9.7 x 50 nm

32 Image Segmentation PbCrO 4 Porous Binding medium Unknown 7.8 µm 38.8 µm 9 µm 38.8 µm Data processing and image segmentation (Avizo/Matlab): Florian Meirer

33 Image Segmentation - Quantification Total analyzed volume: µm 3 PbCrO 4 Porous Binding medium Unknown Volume fractions % 0.34 % % 0.24 % 78 %wt 22 %wt According to literature %wt %wt According to analyses of tube paints from 19 th C (Berthaut) 2 72 %wt 28 %wt 1. H. Kühn, M. Curran, Artists Pigments, vol. 1, Cambridge University Press, London 1986, p J. Salvant, Doctoral Thesis, Pierre-and-Marie-Curie University, 2012, p. 130

34 Porosity Porosity: at the macro/meso-pore scale diffusion is not possible 38.8 µm 38.8 µm 3% 11% 9% 9 µm 77%

35 NICAS

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