Pitting Corrosion

Pitting corrosion is a localized form of corrosion by which cavities or "holes" are produced in the material. Pitting is considered to be more dangerous than uniform corrosion damage because it is more difficult to detect, predict and design against. Corrosion products often cover the pits. A small, narrow pit with minimal overall metal loss can lead to the failure of an entire engineering system. Pitting corrosion, which, for example, is almost a common denominator of all types of localized corrosion attack, may assume different shapes.

Suppose . . . that a small cavity exists in the surface of the metal into which oxygen cannot diffuse quickly. A current will be produced between the unaerated area within the cavity, which will become anodic, and the aerated part of the surface outside, which will be the cathode; soluble salt will be formed at the anodic surface within the cavity, but this will not, of course, interfere with further anodic attack. At the mouth of the cavity where the soluble metallic salt from the interior mixes with the alkali from the cathodic part outside, hydroxide may be precipitated, but it will not put a stop to the anodic attack proceeding within. Since the rate of attack is determined by the supply of oxygen to the whole surface outside the pit, and since it is all concentrated on the small area within the pit, the rate at which the corrosion bores into the metal will be very great; . . . U.R. Evans, 1924 Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a semipermeable membrane of corrosion products. Pits can be either hemispherical or cup-shaped Pitting is initiated by: a. Localized chemical or mechanical damage to the protective oxide film; water chemistry factors which can cause breakdown of a passive film are acidity, low dissolved oxygen concentrations (which tend to render a protective oxide film less stable) and high concentrations of chloride (as in seawater) b. Localized damage to, or poor application of, a protective coating c. The presence of non-uniformities in the metal structure of the component, e.g. nonmetallic inclusions. Theoretically, a local cell that leads to the initiation of a pit can be caused by an abnormal anodic site surrounded by normal surface which acts as a cathode, or by the presence of an abnormal cathodic site surrounded by a normal surface in which a pit will have disappeared due to corrosion.

In the second case, post-examination should reveal the local cathode, since it will remain impervious to the corrosion attack as in the picture of an aluminum specimen shown on the right. Most cases of pitting are believed to be caused by local cathodic sites in an otherwise normal surface. Apart from the localized loss of thickness, corrosion pits can also be harmful by acting as stress risers. Fatigue and stress corrosion cracking (SCC) may initiate at the base of corrosion pits. One pit in a large system can be enough to produce the catastrophic failure of that system. An extreme example of such catastrophic failure happened recently in Mexico, where a single pit in a gasoline line running over a sewer line was enough to create great havoc to a city, killing 215 people in Guadalajara.

Corrosion Pit Shapes

Pitting corrosion can produce pits with their mouth open (uncovered) or covered with a semipermeable membrane of corrosion products. In this micrograph of an aluminum specimen exposed to a 3,5% NaCl solution for seven days one can clearly (?) see different types of attack on the same surface. The width of the picture is approximately 1 mm.
Can you see at least three regions of attack in this picture? ('click here' if you want to see our answer)

Localized Corrosion of Aluminum

The corrosion attack of aluminum of the 2000 family is mixed. While most of the surface is uniformly pitted (yellow arrow), as A92024 would do in similar conditions, we can see the formation of deeper pits (red arrow) that are surrounded by unattacked regions (blue arrow).

Pits can be either hemispherical or cup-shaped.In some cases they are flat-walled, revealing the crystal structure of the metal, or they may have a completely irregular shape. Pitting corrosion occurs when discrete areas of a material undergo rapid attack while most of the adjacent surface remains virtually unaffected. The following are common pit shapes divided in two groups:

Trough Pits
Narrow, deep Shallow, wide Elliptical Vertical grain attack

Sideway Pits
Subsurface Undercutting Horizontal grain attack

Pit Depth Measurement

Pit depth measurement has been a requirement of corrosion inspectors for many years. Many different tools for the measurement of corrosion damage have been developed. The most successful of the pit depth tools was a lever type pit gauge used by Mr. William R. Thorpe, a former Chevron inspector in the Tulsa area. Mr. Thorpe had company craftsmen fashion a variety of configurations during his tenure there. As a retirement present, his coworkers presented him with a new copy of his latest configuration. (adapted from Pit Gauges History and Development by: Mark Palynchuk, General Manager Western Instruments Inc.) Unfortunately Mr. Thorpe passed on soon after his retirement, but his pit gauge lived on, through an accounting firm. Any further development ceased, but this incredibly simple product became an industry standard for 40 years. As a result, of corrosion inspectors complaining about the limitations of the Thorpe, the development of Western Instruments bridging pit gauge resulted.

As the operational envelopes of pressure equipment (pipelines, boilers, vessels, piping, and storage tanks), oil country tubular goods (tubing/casing, drill pipe, bottom hole assemblies), bridges/structures, concrete, and aircraft components were pushed, so were their corrosion allowances. Unfortunately tools were slow to evolve, simply due to cost, but as the cost of equipment (and failures) increased, so did the perceived need of equipment to measure corrosion increased. Inspectors were constantly required to perform more accurate pit depth measurements even if their tools were inadequate. Other tools were adapted for pit measurement, such as machinists depth gauges. While the dial indicators (and micrometer barrels) used in depth

gauges were an improvement in accuracy, they were cumbersome to use for field inspection. Furthermore, dial indicators were expensive and any modification to them was cost prohibitive. With the advent of automatic machining, and computer aided designs, manufacturers of dial indicators were more readily able to perform short runs, with very specific modifications. This lead to the development of dial Indicator pit gauges. Today we see the use of highly specialized computer controlled coordinate measuring machines mapping entire areas of weight-loss corrosion. A modern ultimate pit gauge costing over $50,000. While such specialized tools fulfill a niche in industry, they require a skilled technician to operate, a specialist to interpret, and skilled maintenance and repair personnel. When an inspector is not familiar with specialized measurement tools, such as dial or digital indicators, a dial indicator pit gauge can be an intimidating piece of equipment. It was not recognized until recently that the greatest demand for pit gauges was not for these specialized tools but still for the the simple lever type pit gauge, a tool that had not changed in 40 years. Simple lever pit gauges have not evolved to meet modern industry requirements. For example, no gauge could be found with both metric and imperial scales. A development program was undertaken to test and identify the benefits and shortcomings, of lever type pit gauges, correct them, and manufacture them economically. The result of this program is a simple to use pit gauge, with a metric and two imperial scales, a unique pointer that aids the inspector to eliminate alignment errors. Since then the cost of the task specific dial indicators has been coming down. Furthermore, with an aging infrastructure the demand for corrosion measurement and monitoring has increased substantially. Over the last 20 years we have seen this industry evolve, with companies specializing in Corrosion Measurement and Monitoring. Specialized manufactures have evolved, such as ourselves, manufacturing industry specific tools. As Business 101 has taught us, when there is a demand, a supply will soon follow. Today we see digital indicators, and specialized fixtures, with their increased cost, being offered and used. This same gauge has applications for weld Inspection, with such capability as measuring; undercut depth, weld crown height, a porosity comparitor, with metric and imperial units.
Pit Propagation Mechanisms

The formulation of the mechanism of pitting corrosion of aluminium is very complex. Although, it is generally accepted that there are two steps to the mechanism:

Pit initiation
The initiation of pitting corrosion is often linked to the presence of local defects at the metal surface such as flaws in the oxide or segregates of alloy elements, and the presence of aggressive anions such as chlorides in the environment. The chlorides are believed to locally disrupt the oxide, preferably at pre-existing weak spots, resulting in microfissures of several nm in diameter.

Pit propagation
Amongst the many initiated pits only a few will propagate. The proposed mechanism shown here supports recent studies indicating that pitting corrosion of aluminium is a discontinuous process.

The overall reaction equation can be described as follows:

2Al + 3H2O + 3/2O2 2Al(OH)3

The pit propagation process is built up of different intermediate steps:

1. In the initiated pit, aluminium is dissolved : 2Al + 2Al3+ + 3e, and the Al3+ cations react with Cl anions to form a complex intermediate species AlCl4. Hydrolysis of this species results in acidification of the bottom of the pit to a pH < 3 (due to formation of H+). This highly aggressive environment results in autopropagation of the pit. 2. Al3+ cations concentrated at the bottom of the pit diffuse out of the pit, where they encounter a more alkaline environment due to the cathodic process of hydrogen gas evolution : 6H+ + 6e 3H2, or water reduction:
2

/3O2 + 3H2O + 6e 6OH

As a result aluminium hydroxide is formed and precipitates at the borders of the pit. This deposit of white corrosion product grows to eventually block off the entrance to the pit for further ionic exchange processes.