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Copper Corrosion Mechanisms of Polysulfides

Published online by Cambridge University Press:  10 February 2011

Anne M. Chaka ,
John Harris  and
X. P. Li
Anne M. Chaka
Affiliation:
The Lubrizol Corporation, 29400 Lakeland Boulevard, Wickliffe, OH 44092–2298, chaka@lubrizol.com
John Harris
Affiliation:
Molecular Simulations, Inc., 9685 Scranton Road, San Diego, CA 92121–9990
X. P. Li
Affiliation:
Molecular Simulations, Inc., 9685 Scranton Road, San Diego, CA 92121–9990
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Abstract

Corrosive behavior of commercial organopolysulfides of the type R-(S)n-R is known to increase dramatically towards copper-based alloys when n ≥ 4, whereas di- and trisulfides are essentially inert. Three possible reasons for this behavior are examined using local and nonlocal density-functional theory as well as post-Hartree-Fock theory at the MP2 level. The hypotheses are: the shorter chains are protected from the surface by steric hindrance of the terminal organic groups, longer polysulfides can chelate copper atoms and remove them from the surface, and S-S bonds become weaker and more reactive as the polysulfide chains become longer. We find the predominant reason for the increase in corrosive behavior to be a dramatic decrease in S-S bond dissociation energy when n ≥ 4 due to stabilization of the unpaired electron via delocalization in RSS• thiyl radicals. The thiyl radicals are thus the species which is capable of attacking and corroding the copper surface. Chelation is eliminated as a possible mechanism, and steric protection and oil solubility afforded by the organic terminal groups are found to play a minor role.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 492: Symposium S – Microscopic Simulation of Interfacial Phenomena in Solids… , 1997 , 219
Copyright
Copyright © Materials Research Society 1998

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