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Wednesday, May 31 • 3:30pm - 4:00pm
065. (Research and Technical Studies) Elucidating Daguerreotype Degradation Through Surface Species Formation Using Localized Surface Plasmon Resonance Spectroscopy

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The nanostructured silver-mercury or silver-mercury-gold daguerreotype image is particularly reactive and prone to degradation by tarnishing, oxidation, and photodamage.(1–3) Treatment protocols to reverse existing signs of degradation have all but halted, as many historical efforts to clean daguerreotypes have been shown to promote further damage.(3,4) Conservation efforts are complicated by a lack of understanding of the composition and reactivity of the nanostructured surface that forms the daguerreotype image. Numerous studies over the past few decades have identified various surface species and have partially elucidated the mechanisms by which they react;(4,5) however, many questions remain unanswered. Using angle-dependent scattering spectroscopy, we have developed a protocol to measure nanoscale changes of the daguerreotype surface using the localized surface plasmon resonance (LSPR) of the Ag/Hg image particles, which are extremely sensitive to changes in their composition and dielectric environment. Studying spectral shifts in the LSPR of the image particles upon controlled exposure to environmental elements such as humidity, oxygen, chlorine, and sulfur provides further insight into image deterioration occurring from surface reactions. This method has been combined with other spectroscopic methods, such as Fourier-transform infrared spectroscopy (FTIR) and surface-enhanced Raman spectroscopy (SERS) to offer a more complete view of daguerreotype degradation at the nanoscale level. Until we have a comprehensive understanding of how daguerreotypes interact with their environment, these images remain in peril of irreversible damage. References 1. Marquis, E. A., Chen, Y., Kohanek, J., Dong, Y. & Centeno, S. A. Exposing the sub-surface of historical daguerreotypes and the effects of sulfur-induced corrosion. Corros. Sci. 94, 438–444 (2015). 2. Centeno, S. A., Schulte, F., Kennedy, N. W. & Schrott, A. G. The formation of chlorine-induced alterations in daguerreotype image particles: a high resolution SEM-EDS study. Appl. Phys. A 105, 55–63 (2011). 3. Ravines, P., Wiegandt, R. & Wichern, C. M. Surface characterisation of daguerreotypes with the optical metrological technique of confocal microscopy. Surf. Eng. 24, 138–146 (2008). 4. Da Silva, E., Robinson, M., Evans, C., Pejović-Milić, A. & Heyd, D. V. Monitoring the photographic process, degradation and restoration of 21st century Daguerreotypes by wavelength-dispersive X-ray fluorescence spectrometry. J. Anal. At. Spectrom. 25, 654 (2010). 5. Centeno, S. A., Meller, T., Kennedy, N. & Wypyski, M. The daguerreotype surface as a SERS substrate: characterization of image deterioration in plates from the 19th century studio of Southworth & Hawes. J. Raman Spectrosc. 39, 914–921 (2008).

Author order: J. Catalano, A. Murphy, Y. Yao, N. Zumbulyadis, S.A. Centeno, C. Dybowski. 

avatar for Andrea E. Schlather

Andrea E. Schlather

Postdoctoral Fellow, Metropolitan Museum of Art
Andrea E. Schlather is currently an Annette de la Renta Junior Fellow at The Metropolitan Museum of Art, where she is working to understand the optical response of daguerreotype surfaces. In 2015, she received her Ph.D. in Chemistry from the Laboratory for Nanophotonics at Rice University... Read More →

avatar for Silvia Centeno

Silvia Centeno

Research Scientist, Metropolitan Museum of Art, Department of Scientific Research
Silvia A. Centeno is currently a Research Scientist in Department of Scientific Research (DSR) at The Metropolitan Museum of Art (The Met), in New York, where her main responsibilities include the investigation of the material aspects of works of art, with a focus on paintings, works... Read More →

Wednesday May 31, 2017 3:30pm - 4:00pm CDT
Riverside West Exhibit Hall Exhibit Level, East Tower