Hostname: page-component-78c5997874-xbtfd Total loading time: 0 Render date: 2024-11-02T21:24:06.183Z Has data issue: false hasContentIssue false

Analysis of Lead Carboxylates and Lead-Containing Pigments in Oil Paintings by Solid- State Nuclear Magnetic Resonance

Published online by Cambridge University Press:  18 July 2014

Jaclyn Catalano
Affiliation:
Department of Scientific Research, The Metropolitan Museum of Art, New York, NY 10028, U.S.A. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, U.S.A.
Yao Yao
Affiliation:
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, U.S.A.
Anna Murphy
Affiliation:
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, U.S.A.
Nicholas Zumbulyadis
Affiliation:
Independent Researcher
Silvia A. Centeno
Affiliation:
Department of Scientific Research, The Metropolitan Museum of Art, New York, NY 10028, U.S.A.
Cecil Dybowski
Affiliation:
Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, U.S.A.
Get access

Abstract

Soap formation in traditional oil paintings occurs when heavy-metal-containing pigments, such as lead white, 2Pb(CO3)2·Pb(OH)2, and lead-tin yellow type I, Pb2SnO4, react with fatty acids in the binding medium. These soaps may form aggregates that can be 100-200 μm in diameter, which swell and protrude through the paint surface, resulting in the degradation of the paint film and damage to the integrity of the artwork. In addition, soap formation has been reported to play a role in the increased transparency of paint films that allows the painting support, the preparatory drawing, and the artists’ alterations to become visible to the naked eye. The factors that trigger soap formation and the mechanism(s) of the process are not yet well understood. To elucidate these issues, chemical and structural information is necessary which can be obtained by solid-state 207Pb, 119Sn, and 13C nuclear magnetic resonance (NMR). In the present study, a combination of 207Pb NMR pulse sequences was used to determine accurately the NMR parameters of lead-containing pigments and lead carboxylates known to be involved in soap formation, such as lead palmitate, lead stearate, and lead azelate. These results show that the local coordination environment of lead azelate is different from lead palmitate or lead stearate and therefore it is unlikely that lead azelate would be incorporated into an ordered structure containing lead palmitate and lead stearate. In addition, the chemical shifts of the pigments obtained are different from those of the soaps, demonstrating that 207Pb NMR is useful in characterizing the components when present in a mixture, such as a paint film. The NMR methods discussed can also be applied to other Pb-containing cultural heritage materials, electronic and optoelectronic materials, superconducting materials, and environmentally contaminated materials.

Type
Articles
Copyright
Copyright © Materials Research Society 2014 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Noble, P., Boon, J. J. and Wadum, J., ArtMatters 1, 4661 (2003).Google Scholar
Keune, K., PhD Thesis, University of Amsterdam, 2005.Google Scholar
Spring, M., Ricci, C., Peggie, D. and Kazarian, S., Analytical and Bioanalytical Chemistry 392(1), 3745 (2008).10.1007/s00216-008-2092-yCrossRefGoogle Scholar
Higgitt, C., Spring, M. and Saunders, D., National Gallery Technical Bulletin 24, 7595 (2003).Google Scholar
Centeno, S. A. and Mahon, D., The Metropolitan Museum of Art Bulletin 67(1), 1219 (2009).Google Scholar
Hale, C., Arslanoglu, J. and Centeno, S. A., in Studying Old Master Paintings. Technology and Practice, edited by Spring, M. (Archetype Publications and The National Gallery, London, 2011), pp. 5964.Google Scholar
Van der Weerd, J., PhD Thesis, University of Amsterdam, 2002.Google Scholar
Boon, J. J., van der Weerd, J., Keune, K., Noble, P. and Wadum, J., in ICOM-CC 13th Triennial Meeting (Rio de Janeiro, 2002), Vol. 1, pp. 410–406.Google Scholar
Eibner, A., Malmaterialienkunde als Grundlage der Maltechnik. (Verlag von Julius Springer, Berlin, 1909), pp. 121.Google Scholar
Noble, P., van Loon, A. and Boon, J. J., in ICOM Committee for Conservation 14th Triennnial Meeting (James and James, The Hague, 2005), Vol. 1, pp. 496503.Google Scholar
van Loon, A, PhD Thesis, University of Amsterdam, 2008.Google Scholar
Fayon, F., Farnan, I., Bessada, C., Coutures, J., Massiot, D. and Coutures, J. P., Journal of the American Chemical Society 119(29), 68376843 (1997).10.1021/ja963593fCrossRefGoogle Scholar
Dybowski, C. and Neue, G., Progress in Nuclear Magnetic Resonance Spectroscopy 41 (3-4), 153170 (2002).10.1016/S0079-6565(02)00005-5CrossRefGoogle Scholar
Dmitrenko, O., Bai, S., Beckmann, P. A., van Bramer, S., Vega, A. J. and Dybowski, C., Journal of Physical Chemistry A 112(14), 30463052 (2008).10.1021/jp711182zCrossRefGoogle Scholar
Catalano, J., Yao, Y., Murphy, A., Zumbulyadis, N., Centeno, S. A. and Dybowski, C., Applied Spectroscopy 68(3), 280286 (2014).10.1366/13-07209CrossRefGoogle Scholar
Neue, G., Dybowski, C., Smith, M. L., Hepp, M. A. and Perry, D. L., Solid State Nuclear Magnetic Resonance 6(3), 241250 (1996).10.1016/0926-2040(95)01225-7CrossRefGoogle Scholar
MacGregor, A. W., O'Dell, L. A. and Schurko, R. W., Journal of Magnetic Resonance 208(1), 103113 (2011).10.1016/j.jmr.2010.10.011CrossRefGoogle Scholar
Eichele, K., HBA 3.1 and WSOLIDS, University of Tubingen, 2013.Google Scholar
Keune, K. and Boon, J. J., Stud. Conserv. 52(3), 161176 (2007).10.1179/sic.2007.52.3.161CrossRefGoogle Scholar
Plater, M. J., De Silva, B., Gelbrich, T., Hursthouse, M. B., Higgitt, C. L. and Saunders, D. R., Polyhedron 22(24), 31713179 (2003).10.1016/S0277-5387(03)00461-3CrossRefGoogle Scholar
Martinetto, P., Anne, M., Dooryhée, E., Walter, P. and Tsoucaris, G., Acta Crystallographica Section C 58(6), i82i84 (2002).Google Scholar
Verhoeven, M. A., Carlyle, L., Reedijk, J., Haasnoot, J.G., in Reporting Higlights of the De mayerne Programme., edited by J. J. a. F. Boon, E.S.B.(The Hague: Netherlands Organisation for Scientific Reserach (NWO). 2006), pp. 3342.Google Scholar
Keisch, B., in Studies in the History of Art (1971-1972), Vol. 4, pp. 121133.Google Scholar
Gavarri, J. R., Vigouroux, J. P., Calvarin, G. and Hewat, A. W., Journal of Solid State Chemistry 36(1), 8190 (1981).10.1016/0022-4596(81)90194-8CrossRefGoogle Scholar
Gabuda, S. P., Kozlova, S. G., Terskikh, V. V., Dybowski, C., Neue, G. and Perry, D. L., Solid State Nuclear Magnetic Resonance 15(2), 103107 (1999).10.1016/S0926-2040(99)00038-7CrossRefGoogle Scholar
, R. Clark, J. H., Cridland, L., Kariuki, B. M., Harris, K. D. M. and Withnall, R., Journal of the Chemical Society. Dalton Transactions. (16), 2577-2582 (1995).10.1039/dt9950002577CrossRefGoogle Scholar