Solutions, stress corrosion cracking

Brasses are susceptible to dezincification in aqueous solutions when they contain >15 wt% zinc. Stress corrosion cracking susceptibiUty is also significant above 15 wt % zinc. Over the years, other elements have been added to the Cu—Zn base alloys to improve corrosion resistance. For example, a small addition of arsenic or phosphoms helps prevent dezincification to make brasses more usefiil in tubing appHcations. 

Standard Test Methods for Use ofMattsson s Solution of pH 7.2 to Evaluate the Stress Corrosion Cracking Susceptibility of Copper—Zinc Alloys, ASTM G 37-85, American Society for Testing and Materials, Philadelphia, Pa., 1992. 

Conditions that favor dezincification include stagnant solutions, especially acidic ones, high temperatures, and porous scale formation (2). Additions of small amounts of arsenic, antimony, or phosphoms can increase the resistance to dezincification. These elements are, however, not entirely effective in preventing the dezincification of the two-phase (cc—P) brasses because dezincification of the P-phase is not prevented (31). Another area of corrosion concern involves appHed or residual stresses from fabrication that can lead to EIC of brasses in the form of stress-corrosion cracking. 

Virtuallv evety alloy system has its specific environment conditions which will prodiice stress-corrosion cracking, and the time of exposure required to produce failure will vary from minutes to years. Typical examples include cracking of cold-formed brass in ammonia environments, cracking of austenitic stainless steels in the presence of chlorides, cracking of Monel in hydrofluosihcic acid, and caustic embrittlement cracking of steel in caustic solutions. 

Fig. 2-17 Relation between the time to failure by intergranular stress corrosion cracking and potential for tensile specimens of soft iron (a) boiling 55% Ca(N03)2 solution, 5 = 0.65 R a = 0.90 R (b) 33% NaOH, a = 300 N mm, at various temperatures.

In water solutions containing hydrogen sulfide, austenitic steels fail by stress corrosion cracking when they are quenched and tempered to high strength and hardness (above about Rockwell C24). 

If, after fabrication, heat treatment is not possible, materials and fabrication methods must have optimum corrosion resistance in their as-fabricated form. Materials that are susceptible to stress corrosion cracking should not be employed in environments conducive to failure. Stress relieving alone does not always provide a reliable solution. 

Caustic Embrittlement—a form of stress corrosion cracking that occurs in steel exposed to alkaline solutions. 

Alloy 400 has good mechanical properties and is easy to fabricate in all wrought forms and castings. K-500 is a modified version of this alloy and can be thermally treated and is suitable for items requiring strength, as well as corrosion resistance. Alloy 400 has immunity to stress corrosion cracking and pitting in chlorides and caustic alkali solutions. 

Eliminate unfavorable environments. The presence of oxygen and other oxidizers is a critical factor in stress corrosion cracking. For example, the cracking of austenitic stainless steel in chloride solutions can be reduced or completely eliminated if oxygen is removed. 

Heterogeneities associated with a metal have been classified in Table 1.1 as atomic see Fig. 1.1), microscopic (visible under an optical microscope), and macroscopic, and their effects are considered in various sections of the present work. It is relevant to observe, however, that the detailed mechanism of all aspects of corrosion, e.g. the passage of a metallic cation from the lattice to the solution, specific effects of ions and species in solution in accelerating or inhibiting corrosion or causing stress-corrosion cracking, etc. must involve a consideration of the detailed atomic structure of the metal or alloy. 

Sandoz, G., Fujii, C. T. and Brown, B. F., Solution Chemistry Within Stress-corrosion Cracks in Alloy Steels , Corros. Sci., 10, 839 (1970)... 

Wilde, B. E. and Kim, C. D., The R61e of Hydrogen in the Mechanism of Stress-corrosion Cracking of Austenitic Stainless Steel in Hot Chloride Media , Corrosion, 28, 350 (1972) Lin, F. and Hochman, R. F., Electrochemical Study of Stress-corrosion Cracking of Ti 8-1-1 Alloy and NaCl Solutions , Corrosion, 28, 182 (1972)... 

Nitrogen compounds These also arise from both natural and synthetic sources. Thus ammonia is formed in the atmosphere during electrical storms, but increases in the ammonium ion concentration in rainfall over Europe in recent years are attributed to increased use of artiflcial fertilisers. Ammonium compounds in solution may increase the wettability of a metaland the action of ammonia and its compounds in causing season cracking , a type of stress-corrosion cracking of cold-worked brass, is well documented. 

In tests lasting for 14 days, Copson found that the susceptibility of steel to stress-corrosion cracking in hot caustic soda solutions increased with increase in nickel content up to at least 8-5%. Alloys containing 28% and more of nickel did not fail in this period. In boiling 42% magnesium chloride the 9% nickel-iron alloy was the most susceptible of those tested to cracking (Table 3.38). Alloys containing 28 and 42% nickel did not fail within 7 days. 

Fig. 8.3 Schematic representation of the stress corrosion cracking mechanism of the pit (after Pickering and Swann ). (a) Tubular pits initiated at solute-rich slip step. The pits may, but need not necessarily, follow the slip plane once they are initiated, (b) Ductile tearing along a plane containing the tubular pits. The stress is increased across the plane because of the reduced cross section and the stress raising effect...

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