Electrochemical Aspects of Stress Corrosion Cracking José R. Galvele Gerencia de Desarrollo, Comisi6n Nacional de Energia Arémica, 1429-Buenos Aires, Argentina IL INTRODUCTION Stress corrosion cracking, or environmentally induced cracking, is a challenging subject for very many reasons. It stands as an equal challenge to physicists, chemists, electrochemists, metallurgists, mechanical engi- neers, etc. It has been suffered by the human race since as long ago as the Bronze Age, but no convincing explanation has been found so far for this phenomenon. Many theories have been suggested, but, in spite of the optimistic claims of their authors, among which the present writer is included, Nature has inevitably condemned them to a poor, short life. The study of this subject involves such a wide spectrum of scientific disciplines that no scientist at present can cover it all with equal expertise. Since many of the cases of stress corrosion cracking take place in the presence of electrolytic environments, electrochemical reactions are in- volved in the process, The present chapter will concentrate on the electro- chemical aspects of stress corrosion cracking. The important contributions. made by electrochemistry to a better understanding of the problem will be reviewed. The limitations of electrochemistry in terms of providing a complete description of the problem will also be pointed out. 1. Definitions As the subject of this chapter is a fully interdisciplinary one, we will present here a series of definitions, which, while completely obvious to some readers, are unknown to or sometimes misused by others. Modern Aspects of Electrochemistry, Number 27, edited by Ralph E. White et al. Plenum Press, New York, 1995. 233234 José R, Galvele Figure 1. (a) Brass (64% Cu-26% Zn) alloy bar broken by overloading in air. Typical ductile failure. (Dashes = 10 zm.) (b) and (c) Samples of the same alloy as in (a), strained ina NaNO> solution at 0.2 V vs. NHE. Typical stress corrosion cracking fractures. (Dashes =100ym)Electrochemical Aspects of Stress Corrosion Cracking 235 Figure 1. (continued) (i) Environmentally Induced Cracking Our everyday experience with materials leads to the ideas of plastic- ity, ductility, fragility, and brittleness. The idea of plasticity is easily conveyed by the example of materials such as lead or plaster. Ductility is measured by the amount of plastic deformation a material shows before fracture. Ductile materials are exemplified by mild steel, aluminum, and lead. On the other hand, we get easily acquainted with the idea of fragility when we work with glass or ceramics. We say that a material is brittle when it breaks with almost no plastic deformation. For many practical applications, brittle materials are avoided. In the construction of the load-sustaining parts of innumerable devices, only ductile materials are used. This choice is made either for safety reasons or for the sake of durability of the structure. Over a century of experience in the use of many of these materials has shown that very often, as a result of exposure to the environment, ductile materials break unexpectedly in a brittle-like fashion (Fig. 1).