Stress corrosion cracking

• Certain austenitic stainless steels and aluminium alloys crack in the presence of chlorides. This limits the usefulness of austenitic stainless steel for containing water with higher than a few parts per million content of chlorides at temperatures above 50 °C (122 °F);
• mild steel cracks in the presence of alkali (e.g. boiler cracking and caustic stress corrosion cracking) and nitrates;
• copper alloys crack in ammoniacal solutions (season cracking);
• high-tensile steels have been known to crack in an unexpectedly brittle manner in a whole variety of aqueous environments, especially when chlorides are present.

With the possible exception of the latter, which is a special example of hydrogen cracking, all the others display the phenomenon of subcritical crack growth, i.e. small surface flaws propagate (usually smoothly) under conditions where fracture mechanics predicts that failure should not occur. That is, in the presence of a corrodent, cracks develop and propagate well below critical stress intensity factor (${\displaystyle K_{\mathrm {Ic} }}$). The subcritical value of the stress intensity, designated as ${\displaystyle K_{\mathrm {Iscc} }}$, may be less than 1% of ${\displaystyle K_{\mathrm {Ic} }}$.

A similar process (environmental stress cracking) occurs in polymers, when products are exposed to specific solvents or aggressive chemicals such as acids and alkalis. As with metals, attack is confined to specific polymers and particular chemicals. Thus polycarbonate is sensitive to attack by alkalis, but not by acids. On the other hand, polyesters are readily degraded by acids, and SCC is a likely failure mechanism. Polymers are susceptible to environmental stress cracking where attacking agents do not necessarily degrade the materials chemically. Nylon is sensitive to degradation by acids, a process known as hydrolysis, and nylon mouldings will crack when attacked by strong acids.

Close-up of broken nylon fuel pipe connector caused by SCC

For example, the fracture surface of a fuel connector showed the progressive growth of the crack from acid attack (Ch) to the final cusp (C) of polymer. In this case the failure was caused by hydrolysis of the polymer by contact with sulfuric acid leaking from a car battery. The degradation reaction is the reverse of the synthesis reaction of the polymer:

Ozone cracking in natural rubber tubing

Cracks can be formed in many different elastomers by ozone attack, another form of SCC in polymers. Tiny traces of the gas in the air will attack double bonds in rubber chains, with natural rubber, styrene-butadiene rubber, and nitrile butadiene rubber being most sensitive to degradation. Ozone cracks form in products under tension, but the critical strain is very small. The cracks are always oriented at right angles to the strain axis, so will form around the circumference in a rubber tube bent over. Such cracks are dangerous when they occur in fuel pipes because the cracks will grow from the outside exposed surfaces into the bore of the pipe, so fuel leakage and fire may follow. Ozone cracking can be prevented by adding anti-ozonants to the rubber before vulcanization. Ozone cracks were commonly seen in automobile tire sidewalls, but are now seen rarely thanks to the use of these additives. On the other hand, the problem does recur in unprotected products such as rubber tubing and seals.

This effect is significantly less common in ceramics which are typically more resilient to chemical attack. Although phase changes are common in ceramics under stress these usually result in toughening rather than failure (see Zirconium dioxide). Recent studies have shown that the same driving force for this toughening mechanism can also enhance oxidation of reduced cerium oxide, resulting in slow crack growth and spontaneous failure of dense ceramic bodies.[2]

Illustrated are regions of different crack propagation under stress corrosion cracking. In region I, crack propagation is dominated by chemical attack of strained bonds in the crack. In region II, propagation is controlled by diffusion of chemical into the crack. In region III, the stress intensity reaches its critical value and propagates independent of its environment.

Subcritical crack propagation in glasses falls into three regions. In region I, the velocity of crack propagation increases with ambient humidity due to stress-enhanced chemical reaction between the glass and water. In region II, crack propagation velocity is diffusion controlled and dependent on the rate at which chemical reactants can be transported to the tip of the crack. In region III, crack propagation is independent of its environment, having reached a critical stress intensity. Chemicals other than water, like ammonia, can induce subcritical crack propagation in silica glass, but they must have an electron donor site and a proton donor site.[3]