Near-Infrared Luminescence of Cadmium Pigments: In situ Identification and Mapping in Paintings

Abstract

A comprehensive study of the luminescence properties of cadmium pigments was undertaken to determine whether these properties could be used for in situ identification and mapping of the pigments in paintings. Cadmium pigments are semiconductors that show band edge luminescence in the visible range and deep trap luminescence in the red/infrared range. Emission maxima, quantum yields, and excitation spectra from the band edge and deep trap emissions were studied for sixty commercial cadmium pigments that span the color range from yellow to red (reflectance transition 470 to 660 nm). For paints containing cadmium pigments, luminescence from deep traps was more readily observable than that from the band edge, although the yield varied widely from zero to around 4.5%. Optimal excitation for emission is found to be in the visible for both pigments in powder form and mixed with a medium. The maxima of the deep trap emission shift with the band gap energy, providing a potentially useful way to assign pigment type even when used in pigment mixtures. The usefulness of the results of the study on mockups was demonstrated by the mapping of cadmium pigments of different hues with the aid of calibrated luminescence imaging spectroscopy in a painting by Edward Steichen, entitled Study for ‘Le Tournesol’ (1920). Analysis of the luminescence image cube reveals at least six unique spectral components, associated with emission from white pigments, paint binder, and cadmium red and yellow pigments. The results were compared with those from X-ray fluorescence spectrometry (XRF) and fiber-optic reflection spectroscopy (FORS) and the results obtained on paint samples containing cadmium pigments. These results show that, when present, the emission from traps can be used as an analytical tool to identify cadmium pigments, to distinguish among cadmium sulfide, cadmium zinc sulfide, and cadmium sulfoselenide, and to map cadmium pigments, even in mixtures.

Keywords

Luminescence Imaging spectroscopy Semiconductor luminescence Cadmium sulfoselenide Artists' pigments Art conservation Cultural heritage

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References

de la Rie

E. R.

, Studies Conserv. 27, 102 (1982).

de la Rie

E. R.

, Studies Conserv. 27, 1 (1982).

Delaney

J. K.

Zeibel

Thoury

Littleton

Palmer

Kathryn

de la Rie

E. R.

Hoenigswald

, Appl. Spectrosc. 64, 584 (2010).

Shionoya

Hen

W. H.

, Phosphor Handbook, Shionoya

Hen

W. H.

, Eds. (CRC Press, Boca Raton, FL, 1997).

Fiedler

Bayard

, Cadmium Yellows, Oranges and Reds in Artists' Pigments: A Handbook of Their History and Characteristics, Feller

R. L.

, Ed. (Cambridge University Press and National Gallery of Art, Cambridge, 1986).

Babentsov

Riegler

Schneider

Ehlert

Naan

Fiederle

, J. Cryst. Growth 280, 502 (2005).

Kitai

, Luminescent Materials and Applications (John Wiley & Sons, New York, 2008).

Chestnoy

Harris

T. D.

Hull

Brus

L. E.

, J. Phys. Chem. 90, 3393 (1986).

Babentsov

Sizov

, Opto-Electron. Rev. 16, 208 (2008).

10.

Lakowicz

J. R.

Gryczynski

Nowaczyk

Murphy

C. J.

, Anal. Biochem. 280, 128 (2000).

11.

Steckel

J. S.

Zimmer

J. P.

Coe-Sullivan

Stott

N. E.

Bulović

Bawendi

M. G.

, Angew. Chem. Int. Ed. 43, 2154 (2004).

12.

Murphy

C. J.

, Anal. Chem. 74, 520A (2002).

13.

Barnes

D. F.

, Geol. Survey Bull. 1052-C, 71 (1958).

14.

Bridgman

Gibson

H. L.

, Studies Conserv. 8, 77 (1963).

15.

Miyoshi

Ikeya

Shuichi

Takashi

, Jpn. J. Appl. Phys. 21, 1032 (1982).

16.

Casini

Lotti

Picollo

Stefani

Aldrovandi

, “Fourier Transform Interferometric Imaging Spectrometry: A New Tool for the Study of Reflectance and Fluorescence of Polychrome Surfaces”, in Conservation Science 2002, Townsend

J. H.

Eremin

Adriaens

, Eds. (Edinburgh, Scotland, 2003).

17.

Miliani

Sgamellotti

Kahrim

Brunetti

B. G.

Aldrovandi

van Bommel

M. R.

van den Berg

K. J.

Janssen

, “MOLAB. A mobile facility suitable for non-invasive in-situ investigations of early and contemporary paintings: Case study - Victory Boogie Woogie (1942–1944) by Piet Mondrian”, in IICOM Committee for Conservation 15th Triennial Meeting (New Dehli, 2008), p. 857.

18.

Pozza

Ajò

Giacomo

De Zuane

Favaro

, J. Cultural Heritage 1, 393 (2000).

19.

Comelli

Cosimo

Gianiuco

Cubeddu

Colombo

Toniolo

, Appl. Opt. 43, 2175 (2004).

20.

Fischer

Kakoulli

, Rev. Conserv. 7, 3 (2006).

21.

Geissbühler

, Ph.D. Thesis Université de Lausanne, Lausanne (2005).

22.

Bohren

C. F.

Huffman

D. R.

, Absorption and Scattering of Light by Small Particles (Wiley-Interscience, New York, 1998).

23.

Christie

R. M.

, Colour Chemistry (Royal Society of Chemistry, London, 2001).

24.

McKay

R. B.

, Technological Applications of Dispersions (Marcell Dekker, New York, 1994).

25.

Ermolovich

I. B.

Peka

G. P.

Shienkman

M. K.

, Surf. Sci. 24, 229 (1970).

26.

Smyntyna

Skobeeva

Malushin

, Radiation Measuremnts 42, 693 (2007).

27.

Verri

Vlementi

Comelli

Cather

Piqué

, Appl. Spectrosc. 62, 8 (2008).

28.

Krueger

, “Internal condition report on Study for Le Tournesol (The Sunflower) by Edward Steichen” (National Gallery of Art, Washington, D.C., 2009).

29.

Borgia

Fantoni

Flamini

Di Palma

T. M.

Guidoni

A. G.

Mele

, Appl. Surf. Sci. 127, 95 (1998).