The Material World of Color: Chemical Characterization of

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“The Material World of Color: Chemical Characterization of Pigments in Art”

Barbara Berrie Head of Scientific Research, National Gallery of Art

Eric Breitung Senior Research Scientist, Metropolitan Museum of Art

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The Material World of Color: Chemical Characterization of Pigments in Art

Barbara Berrie, Head of Scientific Research National Gallery of Art, Washington D.C. 12

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We’ll start with a few thoughts about what is color Instrumental methods used to identify and characterize colorants and some examples Unexpected discoveries about artists’ innovation and experimentation with colorants

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What is color? Color is the visual perceptual property corresponding in humans to the categories called red, green, blue, and others. Color derives from the spectrum of light (distribution of light power versus wavelength) interacting in the eye with the spectral sensitivities of the light receptors. Color categories and physical specification of color are also associated with objects, materials, lights sources, etc., based on their physical properties such as light absorption, reflection, or emission spectra. By defining a color space, colors can be identified numerically be their coordinates.

wikipedia 15

http://www.oneonta.edu/faculty/baumanpr/geosat2/RS-Introduction/RS-Introduction.html

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http://www.srh.noaa.gov/jetstream/clouds/color.htm

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Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

What is the red pigment known as “Dragon Blood” made from? • • • • •

Insect Vegetable Mineral Dragon Synthetic organic

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Answer: vegetable The pigment is made from the resin from trees, most often Croton, Daemonorps or Draecaena trees

https://phytognosisblog.files.wordpress.com/2013/02/dragons-bloodtree.jpg

https://dragondreaming.wordpress.com/dra gons-blood/

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Subtractive Primaries mixing paint

Additive Primaries mixing light

Livingstone, Margaret S. Vision and Art (Updated and Expanded Edition) : The Biology of Seeing. New York, NY: Abrams, 2013. 22

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Some Sources of Color Physical • • • • •

scattering Interference diffraction dispersion refraction

Chemical • ligand (crystal) field transitions • charge transfer -- ligand to metal -- metal to ligand -- intervalence -- band gap transitions -- lattice defects

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Electronic Transitions in Organic Molecules

http://www.chemguide.co.uk/analysis/uvvisible/theory.html#top

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Cr3+

Mn+ Sn4+

Cu2+ Al3+

carminic acid

Many fun facts about red pigments at https://storify.com/ngadc/seeingredchat

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Absorbance Spectra

Morales, Kathryn M. and Barbara H. Berrie. "A Note on Characterization of the Cochineal Dyestuff on Wool Using Microspectrophotometry." e-PreservationScience 12, (2015): 8-14.

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Some of the Analytical Methods Used to Identify Colorants in Works of Art Sample Required • • • •

chromatographic methods mass spectrometry optical microscopy (PLM) scanning electron microscopy with energy dispersive (or WDS) analysis • infrared/Raman spectroscopy • X-ray powder diffraction

No Sample Required • X-ray fluorescence analysis • Raman spectroscopy • multispectral imaging – VIS-NIR-SWIR – XRF mapping

For more information on any of the techniques go to: http://cameo.mfa.org/wiki/About_CAMEO

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Art Object Analyzer US Patent 4178513, Dec 11, 1979

Handheld XRF 2014

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X Ray Fluorescence (and Energy Dispersive) X Ray Analysis

e-1 or X ray Characteristic X ray

Energy levels of atomic orbitals

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Seaurat, Seascape, 1890

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Texture is Given to the Surface using Calcareous Sand

Frédéric Bazille, The Ramparts at Aigues-Mortes, 1867 31

Vibrational Spectroscopy

Licensed under Public Domain via Commons https://commons.wikimedia.org/wiki/File:Asymmetrical_stretching.gif#/media/File:Asymmetrical_stretching.gif

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Fourier transform infrared spectroscopy Near-infrared imaging Raman spectroscopy

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Micro-Raman spectrum reveals artist’s use of bismuth metal

Jean Bourdichon, Katherine Hours, 1480-1485 Trentelman, Karen.; Turner, Nancy.: J. Raman Spectr. 2009, 40, 577-584.

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NIR Reflectance Spectroscopy

Number 1, 1950 (Lavender Mist), 1950, Jackson Pollock. National Gallery of Art, Washington, D.C. Ailsa Mellon Bruce Fund.

Fiber Optic Reflectance Spectroscopy

Maestà (Madonna and Child with Four Angels), c.1290, Master of Città di Castello. National Gallery of Art, Washington, D.C. Samuel H. Kress Collection.

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Scanning electron microscopy/ energy dispersive X ray analysis

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Orazio Gentileschi The Lute Player, 1608

Roy, A., B. H. Berrie. 1998. A new lead-based yellow in the seventeenth century. In: Roy A., Smith P., editors. Painting Techniques: History, Materials and Studio Practice Contributions to the Dublin Congress 7-11 September 1998. Dublin: IIC, London. p 160-165.

Pb Sn/Sb

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Vincent van Gogh Self-Portrait, 1889 August, 1889 St. Rémy F 626

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http://www.nga.gov/content/ngaweb/Collection/artist -info.1349.html?artobj_artistId=1349&pageNumber=1

Detail of the area of paint which was protected from light by the edge of the frame. The original violet color remains visible.

it is dark purple-blue…” Letter 604 /800

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Audience Survey Question ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

This is a scan of a color film transparency of the painting. Why does the background appear purple instead of blue in this image? • • • • •

The picture was taken in 1910 The picture was photoshop-ed He used magic paint The IR response of color film None of the above

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Why is the picture of van Gogh’s Self Portrait purple? Do you remember that I told you that we perceive color based on our reception of wavelengths of light in the so-called visible region of the electromagnetic spectrum? In comparison, the sensitivity of the chemical in color film that registers reds goes lower in energy than our eyes do. So, if there something that reflects in the close infrared spectrum the dye responds to it and creates a chemical we see as red. Cobalt blue, CoAl2O4, the major pigment van Gogh used in the paint in the background of this painting does in fact reflect this near infrared radiation, sometimes called the photographic region; the dye in the film undergoes a chemical reaction and makes the red color. In combination with the chemical that makes blue, we see purple! 43

Spectral Dye Density Curves of Kodak Elite Film

Fiber–Optic Reflectance Spectra of Cobalt Blue in Various Binders

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Br. 1990: 801 | CL: 604 From: Vincent van Gogh To: Theo van Gogh Date: Saint-Rémy-de-Provence, Thursday, 5 and Friday, 6 September 1889 letter 800 dated early September 1889://www.vangoghletters.org/vg/letters/let800/letter.html

• • • • • • • • •

Van Gogh Letter Example https://commons.wikimedia.org/wiki/File:Vincent_van_Gogh__Letter_VGM_491_-_The_Yellow_House_F1453_JH_1590.jpg

10 mètres toile Grands tubes 6 tubes blanc de zinc ,, ,, 2 ,, vert d’emeraude 2 ,, cobalt Petits tubes 2 Carmin 1 vermillon 1 Grand tube laque ordinaire 6 pinceaux Putois [fitch], 25 poil noir

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1.

5% eosine A ppt by lead acetate

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5% eosine A on blanc fixe

3.

5% eosine A on clay

4.

5% eosine A on barytes and kiesselguhr

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5. 10% eosine barium lake of brilliant orange R on blanc fixe

Jennison, 1900 The Manufacture of Lake Pigments

6. 10% eosine barium lake of brilliant orange R ppt on a clay and alumina lake, simultaneous with the production of blanc-fixe 46

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eosin

Geldorf M, de Keijzer M, van Bommel M, Pilz K, Salvant J, van Keulen H et al. Van Gogh's Geranium Lake. In: Vellekoop M, Geldorf M, Hendricks E, Jansen L, De Tagle A, editors. Van Gogh's Studio Practice. Amsterdam: Van Gogh Museum; 2013. p. 268-89.

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zinc white, chrome yellow, organic reds, emerald green, chalk, red lead?

ultramarine, chrome yellow, emerald green, zinc white

lead white, barium sulfate, yellow iron oxide, chalk

lead white, chalk, barium sulfate

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lead salt of eosin?

BSE image of a scraping of the pink paint on the palette

phloxine?

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Pb

Al

Geldorf M, de Keijzer M, van Bommel M, Pilz K, Salvant J, van Keulen H et al. Van Gogh's Geranium Lake. In: Vellekoop M, Geldorf M, Hendricks E, Jansen L, De Tagle A, editors. Van Gogh's Studio Practice. Amsterdam: Van Gogh Museum; 2013. p. 268-89.

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Microspectrophotometry

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λ ex 433nm λ cutoff 476nm

565

581

*

512

*

* acidified cochineal

*

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anthraquinones Madder alizarin Carmine

carminic acid

xanthenes Rose Bengal

Geranium lake

erythrosine

phloxine 56

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Additional Resources •

http://www.nga.gov/content/ngaweb/conservation/publications/publicationlist.html

•

Sgamellotti A, Brunetti BG, Miliani C. Science and Art: The Painted Surface. Royal Society Of Chemistry; 2014.

•

Berrie BH. Rethinking the History of Artists' Pigments Through Chemical Analysis. Annual Review of Analytical Chemistry. 2012; 5: 441-59. http://www.annualreviews.org/doi/abs/10.1146/annurev-anchem-062011-143039

•

http://www.eu-artech.org/files/Ext_ab/Casadio.pdf

•

Shugar AN, Mass JL. Handheld XRF for art and archaeology. Leuven University Press; 2012.

•

Serrano A, van den Doel A, van Bommel M, Hallett J, Joosten I, van den Berg KJ. Investigation of crimson-dyed fibres for a new approach on the characterization of cochineal and kermes dyes in historical textiles. Analytica Chimica Acta. doi:http://dx.doi.org/10.1016/j.aca.2015.09.046.

•

http://www.metmuseum.org/exhibitions/listings/2015/van-gogh/color-fading 57

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Surprising Results • Glasses and frits of various colors including an orange-yellow which was designed for enamelling glass and painting ceramics • Metal flakes, including elemental bismuth, were used for dark colors. • Van Gogh used the brilliant eosin (with erythrosine and phloxine) from the time was available as an artist’s pigment.

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Conclusion Artists love to experiment with new materials to get interesting and innovative color effects

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“As a high school teacher, [Chemistry and the Art Detective], provides more info to show students how chemistry is used in real jobs. This webinar was a great connection to the artists/art lovers in the classroom.

Victoria Hornik-Rosinski, Science Department, Cabrini Highs School

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The Material World of Color: Chemical Characterization of

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