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In situ XRPD study of the ambient-pressure synthesis of nonstoichiometric Ag3O from Ag–Ag2O thin films: Phase abundance, unit-cell parameters, and c/a as a function of temperature and time

Published online by Cambridge University Press:  28 October 2020

Paul J. Schields Open the ORCID record for Paul J. Schields [Opens in a new window] ,
Nicholas Dunwoody ,
David Field  and
Zachary Wilson
Paul J. Schields*
Affiliation:
Albany Molecular Research Inc., West Lafayette, IN47906, USA
Nicholas Dunwoody
Affiliation:
Tetraphase Pharmaceuticals, Inc., Watertown, MA02472, USA
David Field
Affiliation:
Calgary, AB, CanadaT2M 0E
Zachary Wilson
Affiliation:
Groton, MA01450, USA
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]
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Abstract

Ag3O was synthesized by jet-milling magnetron-sputtered Ag–Ag2O thin films. Heating the jet-milled powders in air and N2 from 40 to 148 °C at ambient pressure produced Ag3O-rich powders. The phase composition and unit-cell parameters of the jet-milled powders were measured as a function of temperature with in situ X-ray powder diffraction experiments from −186 to 293 °C. Ag3O was also produced by ball milling and sonicating jet-milled films at ambient conditions. The phase composition, unit-cell parameters, and thermal-reaction rates indicate nonstoichiometric Ag3O was produced from the reaction of metastable, nonstoichiometric Ag2O (cuprite structure) and ccp Ag. The thermal expansion of Ag3O is anisotropic; below 25 °C, the a-axis expansion is about twice the c-axis expansion resulting in a negative slope of c/a(T). The reversal of the sign of c/a(T) near 25 °C is dramatic. The thermal reaction is arrested when the temperature is rapidly increased from ambient to 130 °C. Ag3O is metastable and decreases its unit-cell volume during kinetic decomposition to Ag when heated above ambient temperature in air and nitrogen. The relative volume expansion of Ag3O is about 80% less than Ag at room temperature and below. The suite of nonstoichiometric Ag3O produced by heating displays a linear relation between c/a and unit-cell volume at room temperature. The c/a and unit-cell volume of a hydrothermally grown Ag3O single crystal reported in a published structure determination was the Ag-rich, low-volume end member of the linear series. The c/a and unit-cell volume are sensitive indicators of the oxygen content and state of disorder.

Keywords

Ag3OAg2OAgin situ thermal reactionthermal expansionnonstoichiometryXRPD
Type
Technical Article
Information
Powder Diffraction , Volume 35 , Issue 4 , December 2020 , pp. 247 - 261
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Copyright
Copyright © 2020 International Centre for Diffraction Data

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