The Material World of Color: Chemical Characterization of Pigments

10/15/2015

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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

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

Barbara Berrie, Head of Scientific Research

National Gallery of Art, Washington D.C.

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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

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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 17

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Audience Survey Question

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

• Insect

• Vegetable

• Mineral

• Dragon

• Synthetic organic

ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT

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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-blood-tree.jpg

https://dragondreaming.wordpress.com/dragons-blood/

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Subtractive Primaries Additive Primaries

mixing paint mixing light

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

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Some Sources of Color

• scattering

• Interference

• diffraction

• dispersion

• refraction

• ligand (crystal) field transitions

• charge transfer

-- ligand to metal

-- metal to ligand

-- intervalence

-- band gap transitions

-- lattice defects

Physical Chemical

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

Electronic Transitions in Organic Molecules

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

Mn+

Sn4+

Al3+

Cu2+

Cr3+

carminic acid

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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. 26

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

• chromatographic methods • mass spectrometry • optical microscopy (PLM) • scanning electron

microscopy with energy dispersive (or WDS) analysis

• infrared/Raman spectroscopy

• X-ray powder diffraction

• X-ray fluorescence analysis

• Raman spectroscopy

• multispectral imaging

– VIS-NIR-SWIR

– XRF mapping

Sample Required No Sample Required

For more information on any of the techniques go to: http://cameo.mfa.org/wiki/About_CAMEO 27

Art Object Analyzer US Patent 4178513, Dec 11, 1979

Handheld XRF 2014

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Energy levels of atomic orbitals

e-1 or X ray

Characteristic X ray

X Ray Fluorescence (and Energy Dispersive) X Ray Analysis

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Seaurat, Seascape, 1890 30

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Frédéric Bazille, The Ramparts at Aigues-Mortes, 1867

Texture is Given to the Surface using Calcareous Sand

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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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https://commons.wikimedia.org/wiki/File:Asymmetrical_stretching.gif/media/File:Asymmetrical_stretching.gif

https://commons.wikimedia.org/wiki/File:Asymmetrical_stretching.gif/media/File:Asymmetrical_stretching.gif

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Fourier transform infrared spectroscopy

Raman spectroscopy

Near-infrared imaging

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Trentelman, Karen.; Turner, Nancy.: J. Raman Spectr. 2009, 40, 577-584.

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

Jean Bourdichon, Katherine Hours, 1480-1485

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

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.

Fiber Optic Reflectance Spectroscopy

NIR Reflectance Spectroscopy

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Scanning electron microscopy/ energy dispersive X ray analysis

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Orazio Gentileschi The Lute Player, 1608

Pb

Sn/Sb

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.

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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 41

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Audience Survey Question

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

ANSWER THE QUESTION ON BLUE SCREEN IN ONE MOMENT





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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!

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Fiber–Optic Reflectance Spectra of Cobalt Blue in Various Binders

Spectral Dye Density Curves of Kodak Elite Film

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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

• 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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Van Gogh Letter Example https://commons.wikimedia.org/wiki/File:Vincent_van_Gogh_-_Letter_VGM_491_-_The_Yellow_House_F1453_JH_1590.jpg

Jennison, 1900

The Manufacture of Lake Pigments

1. 5% eosine A ppt by lead acetate

2. 5% eosine A on blanc fixe

3. 5% eosine A on clay

4. 5% eosine A on barytes and kiesselguhr

5. 10% eosine barium lake of brilliant orange

R on blanc fixe

6. 10% eosine barium lake of brilliant orange

R ppt on a clay and alumina lake, simultaneous

with the production of blanc-fixe

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http://www.vangoghletters.org/vg/letters/let800/letter.html

http://www.vangoghletters.org/vg/letters/let800/letter.html

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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. 47

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lead white, chalk, barium sulfate

lead white, barium sulfate, yellow iron oxide, chalk

ultramarine, chrome yellow, emerald green, zinc white

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

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

phloxine?

lead salt of eosin?

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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. 52

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Microspectrophotometry

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581 565

512

*

*

* * acidified cochineal

λ ex 433nm λ cutoff 476nm

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Carmine Madder

Geranium lake

Rose Bengal

alizarin

carminic acid

erythrosine

phloxine

xanthenes

anthraquinones

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• http://www.nga.gov/content/ngaweb/conservation/publications/publication-list.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

Additional Resources

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http://www.nga.gov/content/ngaweb/conservation/publications/publication-list.html




http://www.annualreviews.org/doi/abs/10.1146/annurev-anchem-062011-143039









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





doi:http://dx.doi.org/10.1016/j.aca.2015.09.046.

doi:http://dx.doi.org/10.1016/j.aca.2015.09.046.

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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

66


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The Material World of Color: Chemical Characterization of Pigments