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Award Abstract #1041803

SCIART: Collaborative Research: Protection of Silver Objects from Corrosion using Atomic Layer Deposited Barrier Coatings

Division Of Materials Research
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Initial Amendment Date: September 8, 2010
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Latest Amendment Date: September 8, 2010
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Award Number: 1041803
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Award Instrument: Standard Grant
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Program Manager: Lynnette D. Madsen
DMR Division Of Materials Research
MPS Direct For Mathematical & Physical Scien
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Start Date: September 15, 2010
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End Date: August 31, 2014 (Estimated)
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Awarded Amount to Date: $79,170.00
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Investigator(s): Glenn Gates ggates@thewalters.org (Principal Investigator)
Terry Drayman-Weisser (Co-Principal Investigator)
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Sponsor: Walters Art Museum
600 North Charles Street
Baltimore, MD 21201-5185 (410)547-9000
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Program Reference Code(s): 0000, 8011
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Program Element Code(s): 1253, 1774


NON-TECHNICAL DESCRIPTION: The corrosion of silver artifacts, especially polished silver surfaces, is a monumental problem for art collections throughout the world. As objects in major museums are typically one of a kind, conservation methods and techniques require overwhelming evidence of treatment effectiveness, improvement over existing methods, and reversibility. This research will develop a novel multilayer, multifunctional transparent barrier coating for silver using a very powerful technique known as "atomic layer deposition" (ALD), which allows for the creation of nanometer thick layers of metal oxides with an exquisite level of control, literally at the atomic level. The resulting multilayer films will be optimized to reduce the rate of silver corrosion, while complying with the rigorous standards of art conservation practice. This museum and university partnership will result in an effective, low-cost strategy to reduce silver artifact corrosion, which also preserves artifact appearance and composition without precluding future conservation-treatment strategies. These benefits will be shared with the global museum conservation community through publications and presentations. In addition, the Walters Art Museum will educate the public about the project and the connection between art and science through specially prepared, on-going outreach activities in their galleries.

TECHNICAL DETAILS: In this work multilayer-structured, multifunctional atomic layer deposition (ALD) films for conservation of silver art objects are fabricated, characterized and optimized. Tarnishing of silver is a critical problem, presently producing irreparable damage to priceless art objects in museum collections throughout the world. The approach is based upon ALD: an innovative, thermally activated gas phase process for synthesizing nanometer-thick solid films by sequential exposure to 2 or more gas reactants to induce self-limited chemisorbed surface reactions, which reduces the rate of oxidant arrival at the underlying surface by orders of magnitude. Multiple compositions and layer structures are explored to optimize barrier performance and optical clarity. Tarnishing is evaluated via reflectance spectroscopy, and using x-ray photoelectrons spectroscopy (XPS) to measure the amount of sulfur on the surface subsequent to stripping the oxide after a series of exposures. Accelerated transport of oxidants through the film and reaction at the silver surface, using both exposure to atmospheres with controlled, elevated concentrations of H2S, and increasing the temperature of ALD coated samples are employed to establish the characteristic time scales, likely decades or longer. The reversibility of ALD metal oxide coatings is evaluated to determine if either the deposition or the removal of thin layers of metal oxides on silver changes the physical characteristics or chemical composition of the silver surface. The direct impingement of oxidant molecules through pinholes in barrier coatings is prevented by depositing multiple layers of alternating oxides of aluminum and titanium. Novel oxidant gettering functionality is introduced via deposition of buried layers of platinum into the films. Patterning of silver substrates is used to quantify the effect coatings have on the optical properties of micro and macro features and evaluation of the role of the starting topography on the topographical and compositional stability of the surfaces of art objects during ALD oxide deposition, removal, and on the local rate of tarnishing. Students at both the graduate and undergraduate level are trained in cutting-edge ALD film fabrication and characterization techniques, and in museum conservation practices in this collaboration between the Walters Art Museum and the University of Maryland.


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K. Larsen. "Researchers develop ultrathin coating to protect silver artifacts from corrosion," Materials Performance, v.50, 2011, p. 16.

A. E. Marquardt, E. M. Breitung, T. Drayman-Weisser, G. Gates, G. W. Rubloff, and R. J. Phaneuf. "Characterization of Atomic Layer Deposited Films as Diffusion Barriers for Silver Art Objects," ECS Transactions, v.58, 2013, p. 277. 


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