11/7/24, 7:45 PM Cp101: Corrosion Mechanics

Corrosion and Cathodic Protection

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Corrosion Mechanisms
Corrosion Mechanisms
Uniform Corrosion

Uniform attack is the most common form of boiler corrosion, uniformly reducing the metal thickness by
converting metal into an oxide. The oxide layer can be protective or nonprotective. When the layer is protective,
as is a layer of magnetite (Fe 3 O 4 ), the corrosion rate typically decreases with time and eventually approaches
a low constant rate. If nonprotective scales develop, corrosion rates are significantly higher and are typically
linear with time. Boiler water treatments are designed to stabilize the protective oxide films so corrosion
decreases with time. Because the metal losses associated with protective oxide films are uniform and occur at a
predictable rate, a corrosion allowance can be included in the system design.

Pitting Attack
Figure 1 Pitting Attack and Uniform Corrosion Comparison

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Pitting occurs when the protective oxide film breaks down locally. A schematic of pitting attack compared to
uniform corrosion is shown in figure 1. Once the protective film is disrupted, an active corrosion site (anode) is
created, and it corrodes rapidly. The oxide or metal directly adjacent to the pit is a reduction site (cathode) for the
corrosion reaction, and it is not corroded. Numerous pits typically form over the exposed material surface. The
distribution, size and number of pits vary with local water conditions as well as material condition.

Wastage is localized corrosion of the tubes near the tubesheet; this results from enrichment of sludge deposits
with phosphate from the treatment chemicals originally used in recirculating steam generators.

Galvanic Attack
When two dissimilar metals are joined and exposed to an aqueous solution, a galvanic cell is formed. The
difference in electrical potential between the two dissimilar metals creates a galvanic cell (see Figure 2). Electric
current flows through the metal as a result of the electric potential; this causes causes corrosion of one of the
metals and protection of the other. The degree to which corrosion occurs depends upon a number of factors
including the difference in electric potential, the surface area of each metal and the conductivity of the aqueous
solution.

Note that the two dissimilar metals may be two different elements, such as the copper and steel (i.e. iron) tubes
shown in figure 2. They may also actually be the same metal (i.e. steel) containing localized regions that are
different due to slight variations in thickness, roughness or contaminant compositions.

Figure 2 Galvanic Corrosion

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Unfavorable Area Effect

An unfavorable area effect is created when a small anode and a relatively large cathode are formed. This effect
results in a faster corrosion rate and usually pitting of the metal. With a relatively large cathode surface area
available to speed the reduction reaction along, electrons are very quickly consumed at the cathode. The anode in
turn will produce more electrons through oxidation (corrosion) to supply the cathode reaction. In addition, with a
small anode, the corrosion is confined to a small area and any loss of metal is quickly apparent.

An example of this is where a cathodic protective film begins to break down, the exposed metal forms an anode.
The size of the anode is small relative to the rest of the metal still covered by the protective film, which is the
cathode. The small anode area is what results in the pitting corrosion typical of protective film breakdown.

Electrochemical Cell (Galvanic Cell)

Corrosion reactions are carried out by means of an electrochemical cell. An electrochemical cell consists of four
basic components: the anode, the cathode, the electrolyte and a metal path or circuit completer. In a corrosion
reaction, the corrosion occurs at the anode.

Anode

The anode is a key basic component of an electrochemical cell. An anode is an area of metal that is higher in
energy than the surrounding or adjoining metal, which becomes the cathode. An anode may form for several
reasons; if the anode and cathode have the same metal composition, local impurities or deficiencies may set up
an energy difference; the manufacturing or fabricating process may transfer energy to some atoms and not
others, or a cathodic scale covering the metal surface may have gaps of exposed metal thereby creating an anode.
If the metals are of different composition, different amounts of energy were required in the production of the
metal and so the atoms of the metal have different energy levels. Contact between metals of different
composition can result in galvanic corrosion, provided that an electrolyte is contacting both metals.

The metal of the anode is the metal that corrodes and this is where the oxidation half-reaction occurs. At the
anode, the metal corrodes due to the metal atoms losing electrons and forming metal ions, which travel into the
electrolyte. The loss of electrons is the oxidation half-reaction. For example, an iron atom can lose two electrons
and form an iron ion, as indicated by the following reaction.

Fe (solid) → Fe +2 + 2 electrons

The process of the atoms of the solid metal forming metal ions, which travel into the electrolyte, results in a loss
of solid metal that may be visible as corrosion. The texture of the metal may be changed from smooth to rough
or porous, and holes or pits may appear in a once solid surface.

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The Fe+2 ions that are released at the anode continue to react with O2 and H2O to form hydrated rust molecules
(Fe2O3.H2O).

Cathode

The cathode is another key basic component of an electrochemical cell and it is the place where the reduction
half-reaction occurs. At the cathode, electrons released from the atoms at the anode combine with positive ions
(cations) in the electrolyte. The reaction at the cathode happens on the surface of the cathode. This is the
reduction half-reaction.

Typical Cathode Reactions

There are many different reactions that can occur at the cathode but there are four common reactions.

In a strongly acidic environment, hydrogen ions and electrons can react to form hydrogen gas.

2H + + 2 electrons → H 2 (gas)

The formation of hydrogen gas can lead to several severe forms of corrosion.

In a slightly acidic environment and in the presence of dissolved oxygen, hydrogen ions, oxygen and electrons
can react to form water.

4H + + O 2 (gas) + 4 electrons → 2H 2 O

In a neutral or slightly alkaline environment, dissolved oxygen, water and electrons can react to form hydroxide
ions.

O 2 + 2H 2 O + 4 electrons → 4OH -

As a result of this reaction, an initially neutral environment will become increasing alkaline over time. This may
shorten the lifespan of any nearby coatings.

If metal ions are present they may react with electrons to deposit metal or plate out. For example, copper ions in
the electrolyte may react with electrons to produce copper metal that would plate out on the cathode.

Cu +2 + 2 electrons → Cu (solid)

Of all the reactions listed this is the least common.

Electrolyte

The electrolyte carries the current (as a flow of positive ions) between the anode and cathode. It is the source of
reactants (ions) for the cathode reaction. The more ions that are present in the electrolyte, the more effective it is
at promoting corrosion. The electrolyte is frequently water, e.g. boiler feedwater, moisture in soil, etc. More
correctly, it should be stated that the electrolyte is an aqueous solution, since something has to be dissolved in
the water to provide the necessary ions.

Metal Path

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The metal path or circuit completer is required to provide a path for electrons to travel from the anode to the
cathode. It can be a wire such as in a cathodic protection system or it can be the metallic structure itself. Anodes
and cathodes can be on the same piece of metal only atoms apart from each other or they can be miles apart
(long line corrosion). As long as the electrons have a metallic path along which they can flow easily and the
other three components of the cell are present, distance is not a factor in corrosion.

All four components of the cell must be present for a corrosion reaction to occur. If any one component is
removed or altered, the corrosion will not happen or will be reduced. For instance, if an insulator is placed in the
metal path between the anode and cathode, preventing the flow of electrons from the anode to the cathode, the
corrosion will stop. If a coating is placed between the cathode and the electrolyte, the corrosion will be reduced
because a reaction cannot easily occur between the electrons on the surface of the cathode and ions in the
electrolyte.

Oxygen Concentration Cell

An oxygen concentration cell or differential aeration cell is formed when metal is exposed to two different
concentrations of oxygen. The difference in the amount of oxygen will cause the metal exposed to the higher
oxygen concentration to become the cathode, and the metal exposed to the lower oxygen concentration will be
the anode. This happens frequently in areas under sludge or other deposit, or in underground structures.

The metal under sludge or a deposit is exposed to a lower oxygen in the electrolyte and so becomes the anode.
The rest of the metal, which is in contact with a higher oxygen concentration in the electrolyte, becomes the
cathode. For localized deposits it is important to remove all or part of the deposit and inspect underneath for pits.
Pits can form rapidly in this situation as an unfavorable area effect consisting of a small anode and a large
cathode is created. Corrosion control can be achieved by using scale inhibitors or removing sludge as soon as it
is formed.

For buried structures, the soil underneath the structure can have a different concentration of oxygen than the soil
above the structure. As the soil is removed, the structure placed in the hole and the soil replaced, oxygen from
the air is introduced to the soil. The undisturbed soil underneath the buried structure has relatively small amounts
of oxygen. The region of low oxygen becomes the anode and so corrosion (pitting) is most likely to occur on the
bottom or underneath side of the buried structure.

Effective control can be achieved in several ways; by monitoring the cathodic protection system, by repairing
any damage to the coating, by putting down a layer of aerated soil or gravel beneath the structure or surrounding
the structure with soil of more uniform aeration.

An oxygen concentration cell is also the mechanism by which pits propagate. Fluid or electrolyte can become
stagnant within a pit. The metal at the top of the pit is exposed to oxygen in the electrolyte and the metal at the
bottom is exposed to a lower concentration of oxygen. The metal at the bottom of the pit thus becomes the anode
and the rest of the metal becomes the cathode. Over time, the pit becomes deeper and deeper until it either
completely penetrates the metal and forms a hole, or depending on direction, may form a crack that elongates
along the length of the metal.

Hydrogen Damage
When corrosion occurs in aqueous systems hydrogen, which is generated as a byproduct, can diffuse into the
tube metal. In carbon steels the hydrogen may react with carbon to form methane gas. This reaction causes the
metal to be locally decarburized, because the carbon in the steel is being consumed. This decarburization causes
the steel to become weakened. The generated methane gas typically collects at grain boundaries and
discontinuities within the metal; as the gas pressure builds, small fissures are formed. Eventually these fissures
can link and cause a through-wall tube failure. Figure 3 is a schematic of hydrogen attack showing the steps that
occur and the final result. Hydrogen attack can occur in both carbon and low alloy steels.
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Figure 3 Hydrogen Attack

Hydrogen damage is more likely to occur when corrosion is rapid. Tubes have been known to fail within hours
of the onset of corrosion. The failures are usually, though not necessarily, associated with a heavy scale on the
tube surface. Often, heavy scale is blown off during the failure. The failures are typically described as window
openings because a small rectangular section is often blown out of the tubing. The prevention of scale on the
water side of the tubing as well as close control of the water chemistry can prevent hydrogen attack.

Other Forms of Corrosion

Erosion Corrosion

When protective scales are removed by flowing water or particles, the corrosion rates increase. There is usually a
pattern of corrosion associated with the flow of fluids or particles. The angle of impingement, velocity, nature of
fluids or particles, and other factors determine the severity of erosion-corrosion. A special form of this corrosion
that occurs in fluids is cavitation, which causes the protective surface scales to be removed because of the
formation and implosion of gas bubbles in a fluid. Cavitation occurs in flowing fluid systems when the pressure
drop causes the local fluid pressure to fall below its vapour pressure at the local temperature. In water systems,
erosion corrosion appears in the form of gullies, grooves or pits, usually with some directional orientation. This
type of attack occurs at restrictions and bends in tube circuits where fluid velocity changes.

Stress Corrosion Cracking

Stress corrosion cracking (SCC) occurs below the material yield strength and is the result of environmental
influences. Figure 4 shows the process of stress corrosion cracking and some typical features. This type of
cracking occurs only under specific combinations of materials, environments and stress levels. Stress cracking is
time dependent, it may proceed rapidly, or many years of trouble free service may be realized before the crack
extends to failure. Cracks may be intergranular or transgranular. Stress corrosion cracks are typically branched,
and usually there are numerous small secondary cracks associated with the main fracture area. These cracks are
mainly seen in austenitic stainless steels.

Figure 4 Stress Corrosion Cracking

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Subcritical Crack Growth

Subcritical crack growth refers to crack propagation due to cyclic fatigue, stress corrosion cracking, creep crack
growth or a combination of the three. Stress corrosion cracking and creep crack growth are time based while
fatigue crack growth is based on the number of stress cycles.

Fatigue Crack Growth

Metal fatigue, although studied for more than 100 years, continues to plague structures subjected to cyclic
stresses. The traditional approach to prevent fatigue failures is to base the allowable fatigue stresses on test
results of carefully made laboratory specimens or representative structural components.

The significant events of metal fatigue are crack initiation and subsequent growth until the net section yields or
until the stress intensity factor of the structure exceeds the material's resistance to fracture. Traditional analysis
assumes that a structure is initially crack free. However, a structure can have cracks that originate during
fabrication or during operation; therefore, fatigue crack growth calculations are required to predict the service
life of a structure.

Fatigue crack growth calculations can:

1. Determine the service life of a flawed structure that (during its lifetime) undergoes significant in-service
cyclic loading, or
2. Determine the initial flaw size that can be tolerated prior to or during a specified operating period of the
structure. The most useful way of presenting fatigue crack growth rates is to consider them as a function of
the stress intensity difference, AK, which is the difference between the maximum and minimum stress
intensity factors.

To calculate fatigue crack growth, an experimentally determined curve is used. ASME Code, Section XI contains
growth rate curves for pressure vessel steels.

Figure 5 Types of Cracks

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Creep Crack Growth

Predicting the remaining life of fossil power plant components from creep rupture data alone is not reliable.
Cracks can develop at critical locations and these cracks can then propagate by creep crack growth.

At temperatures above 427°C (800°F), creep crack growth can cause structural components to fail. Operating
temperatures for selected fossil power plant components range from 482 to 593°C (900 to 1100°F); at these
temperatures, creep deformation and crack growth become dependent on strain rate and time exposure.
Macroscopic crack growth in a creeping material occurs by nucleation and joining of microcavities in the highly
strained region ahead of the crack tip.

Caustic Attack

Caustic attack, also known as grooving or gouging, occurs in steam generating equipment on surfaces with
moderate to high heat flux (rate of heat transfer) under two distinctly different conditions:

1. In vertical tubes where deposits are present on the tube surfaces. In this situation, temperature gradients
exist through the boiling fluid film and the deposit on the heat transfer surface. The combined fluid film
and deposit locally increase the water temperature adjacent to the tube and result in increased boiling
within the deposit on the tube surface. This boiling is often described as wick boiling and causes dissolved
salts, such as sodium hydroxide (NaOH), to concentrate within the deposit. As a result, local areas of high
pH solutions can be formed causing accelerated corrosion.
2. In inclined tubes where the heat flux is directed through the upper half of the tube. In this case, the steam
generated tends to accumulate on the upper surface of the tube whether or not deposits are present. This
can potentially result in a steam blanket covering the top surface of the tube in the direction of flow. The
temperature gradient through the steam causes the top portion of the tube surface to highly concentrate
soluble salts in the boiler water. Because the tubes involved are generally not subject to high heat fluxes,
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the temperature gradient does not raise tube metal temperatures sufficiently high to cause overheating.
Again, local areas of high pH solutions can be formed and cause accelerated corrosion by continuously
dissolving and removing the protective magnetite layer. Characteristically, the resulting corrosion is in the
form of a wide smooth groove with the groove generally free of deposits and centered on the crown of the
tube. The corroded area can sometimes extend for 3 m (10 ft) or more along the length of the tube for as
long as the basic physical conditions causing it persist.

Acid Attack
Acid attack can occur similarly to the caustic attack in that impurities in the bulk water can become concentrated
at the heat transfer surface within deposits. Certain water treatments and impurities can allow a low pH solution
to develop under scales during the boiling process. The local areas of low pH solutions under the scale are also
prone to rapid corrosion. There also appears to be a means of concentrating sodium phosphate within deposits of
magnetite on high heat flux surfaces, at least where boiler pressures are in excess of 17.9 MPa gauge (2600
psig). Under these conditions and where sufficient bulk water phosphate concentrations exist to produce 0.02
molar phosphate concentrations within the boiling film on the deposit surface, the magnetite adsorbs substantial
quantities of sodium phosphate in a molar ratio of 2 to 1 (Na:P) or lower. At sufficiently high deposit
temperatures and loading of phosphate in the deposit, reactions apparently can take place within the deposit to
produce relatively insoluble sodium iron phosphates and rapid corrosion of the underlying metal surface.

Corrosion Fatigue
Corrosion fatigue is similar to stress corrosion cracking except that the loads are alternating instead of steady-
state. Fatigue in noncorrosive environments can occur at fluctuating loads well below the material yield strength.
The addition of a corrosive component speeds the failure.

Corrosion fatigue is the result of a certain combination of stress history, environment and materials. It is time
dependent, with a certain number of load cycles needed to initiate cracks. Corrosion fatigue may also occur as
the result of thermal cycling in a corrosive environment. In boiler tubing, corrosion fatigue is most common in
water-wetted surfaces where there is a mechanical constraint on the tubing. Corrosion fatigue can be found in
waterwall tubes adjacent to the windbox floor, buckstay or other welded attachments.

Creep and Creep-Rupture Test

It has long been known that certain nonmetallic materials, such as glass, undergo slow and continuous
deformation with time when subjected to stress. The concept of creep in metallic materials, however, did not
attract serious attention until the early 1920s. Results of several investigations at that time demonstrated that
rupture of a metallic material could occur when it is subjected to a stress at elevated temperatures for a
sufficiently long time, even though the load applied is considerably lower than that necessary to cause rupture in
the short time tensile test at the same temperature.

The earliest investigations of creep in the U.S. were sponsored by B&W in 1926. Many steels now used
successfully in power generating units and in the petroleum refining and chemical industries were tested and
proved in the course of these investigations, using the best equipment available at the time.

The creep-rupture test is used to determine both the rate of deformation and the time to rupture at a given
temperature. The test piece, maintained at constant temperature, is subjected to a fixed static tensile load. The
deformation of the test sample is measured during the test and the time to rupture is determined.

Microbial Induced Corrosion

Organisms in the water can contribute to corrosion; this is known as microbial-induced corrosion (MIC).
Bacteria that reduce sulphates can increase sulphide formation, with a corresponding increase in the corrosion
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rate. This type of attack is generally limited to exposed low temperature water [<93°C (200°F)] such as that used
in cooling towers .

Used with permisision of

Babcock & Wilcox (1992).
Steam, it's generation and use, 40th ed.
Barberton, OH.

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