Localized Corrosion

Localized corrosion is defined as the selective removal of metal by corrosion at small areas or zones on a metal surface in contact with a corrosive environment, usually a liquid. It usually takes place when small local sites are attacked at a much higher rate than the rest of the original surface. Localized corrosion takes place when corrosion works with other destructive processes such as stress, fatigue, erosion, and other forms of chemical attack. Localized corrosion mechanisms can cause more damage than any one of those destructive processes individually. There are many different types of localized corrosion. Pitting, stress corrosion cracking, chloride stress corrosion, caustic stress corrosion, primary side stress corrosion, heat exchanger tube denting, wastage, and intergranular attack corrosion are discussed in detail in the Chemistry Fundamentals Handbook.

Stress-Corrosion Cracking

One of the most serious metallurgical problems and one that is a major concern in the nuclear industry is stress-corrosion cracking (SCC). SCC is a type of intergranular attack corrosion that occurs at the grain boundaries under tensile stress. It tends to propagate as stress opens cracks that are subject to corrosion, which are then corroded further, weakening the metal by further cracking. The cracks can follow intergranular or transgranular paths, and there is often a tendency for crack branching.

The cracks form and propagate approximately at right angles to the direction of the tensile stresses at stress levels much lower than those required to fracture the material in the absence of the corrosive environment. As cracking penetrates further into the material, it eventually reduces the supporting cross section of the material to the point of structural failure from overload.

Stresses that cause cracking arise from residual cold work, welding, grinding, thermal treatment, or may be externally applied during service and, to be effective, must be tensile (as opposed to compressive).

SCC occurs in metals exposed to an environment where, if the stress was not present or was at much lower levels, there would be no damage. If the structure, subject to the same stresses, were in a different environment (noncorrosive for that material), there would be no failure. Examples of SCC in the nuclear industry are cracks in stainless steel piping systems and stainless steel valve stems. 

The most effective means of preventing SCC in reactor systems are: 1) designing properly; 2) reducing stress; 3) removing critical environmental species such as hydroxides, chlorides, and oxygen; 4) and avoiding stagnant areas and crevices in heat exchangers where chloride and hydroxide might become concentrated. Low alloy steels are less susceptible than high alloy steels, but they are subject to SCC in water containing chloride ions. Nickel-based alloys, however, are not effected by chloride or hydroxide ions.

An example of a nickel-based alloy that is resistant to stress-corrosion cracking is inconel. Inconel is composed of 72% nickel, 14-17% chromium, 6-10% iron, and small amounts of manganese, carbon, and copper.

Chloride Stress Corrosion

One of the most important forms of stress corrosion that concerns the nuclear industry is chloride stress corrosion. Chloride stress corrosion is a type of intergranular corrosion and occurs in austenitic stainless steel under tensile stress in the presence of oxygen, chloride ions, and high temperature.

It is thought to start with chromium carbide deposits along grain boundaries that leave the metal open to corrosion. This form of corrosion is controlled by maintaining low chloride ion and oxygen content in the environment and use of low carbon steels.

Caustic Stress Corrosion

Despite the extensive qualification of inconel for specific applications, a number of corrosion problems have arisen with inconel tubing. Improved resistance to caustic stress corrosion cracking can be given to inconel by heat treating it at 620°C to 705°C, depending upon prior solution treating temperature. Other problems that have been observed with inconel include wastage, tube denting, pitting, and intergranular attack.