Hostname: page-component-cd9895bd7-7cvxr Total loading time: 0 Render date: 2024-12-23T19:35:22.482Z Has data issue: false hasContentIssue false

In situ high-temperature X-ray diffraction characterization of silver sulfide, Ag2S

Published online by Cambridge University Press:  05 March 2012

Thomas Blanton*
Affiliation:
Eastman Kodak Company, Rochester, New York 14650-2106
Scott Misture
Affiliation:
Alfred University, Alfred, New York 14802
Narasimharao Dontula
Affiliation:
Eastman Kodak Company, Rochester, New York 14650-2106
Swavek Zdzieszynski
Affiliation:
Alfred University, Alfred, New York 14802
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]

Abstract

Silver sulfide, Ag2S, is most commonly known as the tarnish that forms on silver surfaces due to the exposure of silver to hydrogen sulfide. The mineral acanthite is a monoclinic crystalline form of Ag2S that is stable to 176°C. Upon heating above 176°C, there is a phase conversion to a body-centered cubic (bcc) form referred to as argentite. Further heating above 586°C results in conversion of the bcc phase to a face-centered cubic (fcc) phase polymorph. Both high-temperature cubic phases are solid-state silver ion conductors. In situ high-temperature X-ray diffraction was used to better understand the polymorphs of Ag2S on heating. The existing powder diffraction file (PDF) entries for the high-temperature fcc polymorph are of questionable reliability, prompting a full Rietveld structure refinement of the bcc and fcc polymorphs. Rietveld analysis was useful to show that the silver atoms are largely disordered and can only be described by unreasonably large isotropic displacement parameters or split site models.

Type
Technical Articles
Copyright
Copyright © Cambridge University Press 2011

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

Bruker-AXS (2009). TOPAS v. 4.0, Bruker-AXS, Madison, WI.Google Scholar
Cava, R. J., Reidinger, F., and Wuensch, B. J. (1980). “Single-crystal neutron diffraction study of the fast-ion conducting β-silver sulfide between 186 and 325°C,” J. Solid State Chem. JSSCBI 31, 6980. 10.1016/0022-4596(80)90009-2CrossRefGoogle Scholar
Djurle, S. (1958). “An x-ray study on the system Ag–Cu–S,” Acta Chem. Scand. ACHSE7 12, 14271436. 10.3891/acta.chem.scand.12-1427CrossRefGoogle Scholar
Eckold, G., Funke, K., Klaus, J., and Lechner, R. E. (1976). “The diffusive motion of silver ions in α -silver iodide. Results from quasielastic neutron scattering,” J. Phys. Chem. Solids JPCSAW 37, 10971103. 10.1016/0022-3697(76)90137-2Google Scholar
Frueh, A. J. (1961). “The use of zone theory in problems of sulfide mineralogy, Part III: Polymorphism of Ag2Te and Ag2S,” Am. Mineral. AMMIAY 46, 654660.Google Scholar
Hoshino, S. (1957). “Crystal structure and phase transition of some metallic halides. IV,” J. Phys. Soc. Jpn. JUPSAU 12, 315326. 10.1143/JPSJ.12.315CrossRefGoogle Scholar
Hull, S., Keen, D. A., Sivia, D. S., Madden, P., and Wilson, M. (2002). “The high-temperature superionic behaviour of Ag2S,” J. Phys.: Condens. Matter JCOMEL 14, L9L17. 10.1088/0953-8984/14/1/102Google Scholar
ICDD (2010). “Powder Diffraction File,” edited by Dr. Soorya Kabekkodu, International Centre for Diffraction Data, Newtown Square, Pennsylivania.Google Scholar
Misture, S. T. (2003). “Large-volume atmosphere-controlled diffraction furnace,” Meas. Sci. Technol. MSTCEP 14, 10911098. 10.1088/0957-0233/14/7/326CrossRefGoogle Scholar
Miyatani, S. (1981). “Ionic conductivity in silver chalcogenides,” J. Phys. Soc. Jpn. JUPSAU 50, 34153418. 10.1143/JPSJ.50.3415Google Scholar
Okazaki, H. (1967). “Deviation from the Einstein relation in average crystals self-diffusion of Ag+ions in α-Ag2S and α-Ag2Se,” J. Phys. Soc. Jpn. JUPSAU 23, 355360. 10.1143/JPSJ.23.355Google Scholar
Rickert, H. (1978). “Solid ionic conductors: Principles and applications,” Angew. Chem., Int. Ed. Engl. ACIEAY 17, 3746. 10.1002/anie.197800371CrossRefGoogle Scholar
Sadanaga, S., and Sueno, S. (1967). “X-ray study on the αβ transition of Ag2S,” Mineral. J. MJTOAS 5, 124143.Google Scholar
Strock, L. W. (1936). “Crystal structure of high-temperature silver iodide, α-AgI,” Z. Phys. Chem. ZPCFAX B25, 441459.Google Scholar
Takahashi, T. (1973). “Solid silver ion conductors,” J. Appl. Electrochem. JAELBJ 3, 7990. 10.1007/BF00613497CrossRefGoogle Scholar
Takahashi, T. (1978). “Silver and copper ion conductors in the solid state,” Pure Appl. Chem. PACHAS 50, 10911098. 10.1351/pac197850091091CrossRefGoogle Scholar
Tsuchiya, Y., Tamaki, S., Waseda, Y., and Toguri, J. M. (1978). “The structure of α-Ag2S,” J. Phys. C JPSOAW 11, 651659. 10.1088/0022-3719/11/4/008Google Scholar
Wikipedia (2010). “Silver sulfide,” http://en/wikipedia.org/wiki/Silver_sulfide.Google Scholar