Corrosion Control and Tactics: by Gerald O. Davis, P.E. Davis Materials & Mechanical Engineering, Inc

Corrosion Control and Tactics
A SunCam online continuing education course

By
Gerald O. Davis, P.E.
Davis Materials & Mechanical Engineering, Inc.

Introduction
Corrosion in its several forms is a well-known problem that occurs in many applications.
The associated costs are many and widespread in scope. These corrosion-induced costs
may include customer dissatisfaction with deteriorated appearance or function of
consumer products, serious personnel injury due to material failures, large financial
losses from litigation that may follow personnel injuries or fatalities or extended
shutdowns of continuous operating manufacturing plants due to corrosion. In the latter
case the cost of repair or replacement of the specific corroded equipment often is minor
compared to the cost of lost production caused by the shutdown. It has been estimated
that the direct cost of corrosion across all U.S. industries in 1998 was $276 billion, or
more than 3% of the countrys gross domestic product in that year. Reference 1.
Many research and development efforts have been and are in progress in universities and
industries to combat corrosion by various approaches. This work includes gaining more
complete basic understanding of the several specific mechanisms of corrosion through
their electrochemical and metallurgical aspects; developing and adequately testing new
metallic alloys that combine good resistance and other needed characteristics; applying
nanotechnology to anticorrosion coatings, developing fundamentally different and
reliable corrosion sensors; etc. All these efforts are justified and potentially can provide
big payoffs.
While R&D concerning new approaches to control corrosion is proceeding there are
many methods and tactics that are well established and effective that, unfortunately, are
not always used. Often this may be because the probability of corrosion was overlooked
or misunderstood by the responsible individual or engineering team during the design of
the product or system. Corrosion and its control are not topics given much attention in
most engineering curriculums. It may also be that management mandates the decision to
omit some method of corrosion control based on the rationale that it will not be effective
in the given application or, more frequently, the initial cost is prohibitive.
The objective of this course is to show that there can be many ways to lessen and control
corrosion in a given application. Some of these can be relatively easy and inexpensive to
apply especially when compared to the human and financial costs that may be incurred
by omitting them. The main point is simply to be aware of what parameters cause or
accelerate corrosion and what actions, if taken early in the planning phases of
engineering, can be helpful in avoiding major corrosion effects.
Before discussing the classic corrosion control methods and specific tactics that may be
used in different applications, some fundamental information may be useful. This will
include certain aspects of electrochemistry, brief descriptions of the various forms of
attack and a discussion of some important environmental and application parameters that
affect corrosion rates.
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Copyright 2011 Gerald O. Davis
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Some Electrochemical Aspects of Corrosion
Aqueous corrosion of metals has both electrical and chemical aspects. Therefore some
basic ideas from electrochemistry are essential in understanding and in seeking to control
those processes. Non-metals such as polymers (plastics), ceramics (e.g., glasses and
refractories) and composite materials (combinations of two or more classes of materials)
also can deteriorate and fail due to exposure to specific environmental or mechanical
conditions but, in general, those failure mechanisms are not electrochemical.
When metals corrode two types of simultaneous, electrochemical reactions always occur.
These reactions are oxidation and reduction (redox reactions). Oxidation reactions
produce electrons while reduction reactions consume electrons. The areas of the metal
surface where the oxidation reaction occurs are known as anodes and the areas where
reduction occurs are known as cathodes. Oxidation is the conversion of stable,
electrically neutral metal atoms into electrically charged ions of that metal (or into a
insoluble compound with nonmetallic elements) as electrons are released. These electrons
from the anodic reaction sites flow through and below the surface of the exposed metal to
the cathodic reduction sites. Ions generated at the anodic sites conduct electrical current
through the corrosive medium known as the electrolyte - away from the exposed
surface in an opposite direction to that of the electron flow. Oxidation at the anodic sites
results in chemical dissolution and penetration of the metal. At the same time, at the
cathodic reduction sites, the electrons generated by the oxidation reaction are consumed
in the process of producing other chemical species that are released into the electrolyte.
In general corrosion the anodic and cathodic regions on the metal continually change and
switch locations so that the attack and penetration is approximately uniform at most areas
across the exposed surface. In the many forms of localized corrosion, e.g., pitting or
stress-corrosion cracking, the anodic oxidation reaction is concentrated and remains at a
specific location. The attack is essentially confined in a specific area, e.g., at the bottom
of pits or at the tip of a growing crack. Thus the rates and effects of localized forms of
corrosion are typically more detrimental than general corrosion.
There is only one possible type of anodic, oxidation reaction and that is the conversion of
the uncharged atomic form of the given metal into charged ions of that metal while
releasing electrons into the metal. These ions then may either go directly into the
electrolyte or they may react further to generate insoluble compounds. By comparison
there are several possible cathodic or reduction reactions possible dependent on the
corrosive medium present. One very common cathodic reaction is the reduction of
molecular oxygen dissolved in water to produce hydroxide ions while consuming
electrons. Another common cathodic reaction is the reduction of hydrogen ions in an acid
to produce molecular hydrogen gas while consuming electrons. Multiple cathodic
reduction reactions can be active simultaneously. If an acid that contains air (oxygen) or
chemical species that are readily reduced, e.g., ferric or cupric ions, is exposed to a
susceptible metal, both hydrogen ion reduction to generate hydrogen gas and oxygen
reduction (or reduction of other oxidizing species) can occur at the cathodic sites on the
metal.
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A fundamental concept in the electrochemistry of corrosion is that oxidation and
reduction reactions occur simultaneously and each must occur at the same rate. This has
significant practical importance. For example, if the oxygen reduction cathodic reaction
applies in a given situation then the rate of the overall corrosion that occurs can be
retarded or accelerated depending largely on how efficiently dissolved oxygen in the
water reaches the exposed metal surface. Specific application parameters determine the
availability of the oxygen as will be discussed later. Another example applies to chemical
corrosion inhibitors. When these are added to electrolytes they can limit the rate of
corrosion by slowing the oxidation reaction or the reduction reaction or, in many cases,
both reactions.
Not all liquids are electrolytes and thus not all liquids support corrosion. An electrolyte
must be able to permit the efficient transport of electrically charges ions. This
characteristic is the electrical conductivity of the liquid medium. Electrolytes may include
a great variety of substances, for example - normal fresh and saltwater or acid solutions
with or without added chemical species. Specific additional constituents can result in the
electrolyte becoming either more or less corrosive. Certain pure liquids such as
demineralized water and hydrocarbons like gasoline, lubrication oils and alcohols cannot
support corrosion because they do not ionize or only ionize slightly and thus their
conductivity is very poor.
Both thermodynamic and kinetic relationships govern the incidence of corrosion. Energy
relationships from thermodynamics determine which combinations of metals or alloys
and specific environmental conditions may or may not result in corrosion. For those
combinations in which corrosion may occur, the practical issue then becomes how fast
the reactions will take place. Thats when kinetic relationships take over. Most practical
engineering alloys are thermodynamically unstable, i.e., they are subject to corrosion,
when exposed to a variety of electrolytes. Even so corrosion scientists make valuable use
of thermodynamic relationships in their studies. However, for this course normally used
engineering alloys will be assumed and thus corrosion can and will occur with them in
practical usage. The important question then becomes what can be done to affect the
kinetics and decrease the rate of attack.
Any given metal exposed to a specific electrolyte has a unique potential measured in
volts known as its electrode potential. These potentials are not measured independently
but, instead, must be measured with respect to another very stable metallic electrode
known as a reference electrode. There are different types of reference electrodes for
laboratory and for field usage.
When corrosion of a metal electrode begins there is a net flow of electric current and a
change in electrode potential from its thermodynamic equilibrium state. As the corrosion
rate increases the metal changes its potential and becomes more positive. This change is
anodic polarization. The magnitude of the anodic potential is directly related to the
propensity for oxidation to occur on the metal for the given application conditions. The
terms anodic potential and oxidizing power are often used interchangeably. Every
electrode potential value has an associated level of current flow. This current value is
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directly proportional to the rate of corrosion occurring. The corrosion current can be
measured in laboratory tests and in many field applications.
The magnitude of the flowing anodic current, and therefore the corrosion rate, is
measured in amps (or microamps). A small change in potential often has a much larger
change in current and, therefore, in the resulting corrosion rate. Typically corrosion
current is represented on laboratory data plots as a current density. This derived value is
the ratio of the corrosion current at a given potential to the exposed area of the metallic
sample being evaluated. A high value of current density indicates a high rate of corrosion
for a given sample size.
In addition to anodic polarization, cathodic polarization of a laboratory sample electrode
or a metallic surface in field service applications can be accomplished. This causes the
potential of the metal to become more negative as the rate of anodic oxidation (corrosion)
is reduced. The resulting anodic corrosion current and thus the rate of corrosion is greatly
reduced (but not stopped completely) as the potential is made more negative. This is the
basis for the widely used method of corrosion control cathodic protection.
During corrosion the rate of reduction that occurs during polarization is controlled by one
of two possible mechanisms. Sometimes polarization occurs by a combination of the two.
These mechanisms are activation and concentration polarization. Each includes a ratecontrolling step or aspect of their mechanism that governs how fast the reduction reaction
can occur and, therefore, what the overall corrosion rate can be. In contrast to the
reduction reaction, the anodic oxidation portion of the corrosion process generally occurs
readily and does not present a restraint on the overall corrosion rate. These two reduction
polarization mechanisms are important because common application variables such as
temperature, pH, concentration and velocity have different effects on corrosion rates
according to which mechanism is active. These variables are discussed later.
Activation polarization is predominant in certain corrosive media. It involves the multiple
steps that occur at the interface of the exposed metal and the electrolyte to accomplish the
reduction reaction. Hydrogen reduction with generation of hydrogen gas bubbles in an
acid is a typical example. Here the activation steps include first an adsorption of
hydrogen ions from the acid onto the metal surface; these ions then must join with
electrons that came through the metal from the anodic sites to form single hydrogen
atoms at the metal surface; these atoms must then join together on the metal surface to
form hydrogen molecules and finally these molecules must join together to form bubbles
of hydrogen gas that leave the surface. One of these steps will be the slowest in the series
and it will govern the rate of reduction that can occur.
Concentration polarization predominates in certain corrosive applications when there is a
limited quantity of specific chemical species in the bulk electrolyte that is needed to
support the reduction reaction on the metal surface. An example of this situation might
include a dilute, relatively high pH acid, e.g., pH of about 5.5, without any oxygen or
other oxidizing species present so that there would be few hydrogen ions available in the
bulk solution to be reduced. (Note - Remember from basic chemistry that the
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concentration of hydrogen ions in an acid is inversely proportional to its pH and that
oxygen and other oxidizing chemical species are reduced while reducing species are
oxidized.) Another example where concentration polarization applies is water that
contains little dissolved oxygen or other oxidizing species (such as ferric, cupric or
chromate ions) so that the available oxidizing species at the metal surface are severely
limited. The possible rate of reduction often is restrained in each of these examples.
The critical, rate-controlling factor in concentration polarization is the rate of diffusion
possible in the given situation. That is the ability of limited quantities of reducible agents,
i.e., oxidizing species, present to move from the bulk electrolyte through the diffusion
layer on the metal surface, contact the metal surface and react. This diffusion layer
contains less reducible species than the bulk electrolyte. Rates of diffusion through the
diffusion layer depend on several of the application variables mentioned earlier.
Several metals and their alloys are known as active-passive metals. These materials
experience distinctly different rates of corrosion at different potentials, i.e., from higher
to very small rates as potentials increase. The idealized anodic polarization plot in Figure
1 illustrates this behavior. The figure shows a range of corrosion potential values versus
the logarithm of corresponding values of current density. The plot shows polarization
above the equilibrium potential, i.e., Eq, the minimum potential represented. Increasing
corrosion potentials on the vertical axis are said to become more noble or anodic (both
terms are used). By comparison, decreasing values of potential on the vertical axis are
said to become more active.
As indicated in Figure 1, three separate regions exist for active-passive materials. The
active anodic corrosion region involves a steady increase in corrosion current and thus
increasing corrosion rates as the potential becomes more noble. At the top end of the
active region, there are two important values - the primary passive potential, Epp, and the
corresponding critical anodic current density for passivity, Ip. The corrosion current
drastically decreases and the passive state initiates when these values are attained. Then
corrosion rates in the fully passive region are stable and remain very low for a range of
increasing anodic potentials. Finally, when the potential exceeds a specific noble value,
i.e., Eloc, the current again increases as potential increases. This region is known as the
transpassive area. Localized attack occurs above Eloc.
Active-passive materials include iron, chromium, nickel, titanium and alloys of these
metals. This is fortunate because alloys that contain these elements also often have
mechanical properties that allow them to be practical engineering materials in many
applications. The classic example is the group of austenitic stainless steels. These and
other active-passive materials often provide reduced corrosion rates when passive that are
less than their rates in the active range by factors of 10,000 to 1,000,000.
It should be clearly understood that active-passive behavior for a given alloy can occur in
one electrolyte but not in another. This also applies to other variable service conditions.
The effects of variable service conditions are discussed later.
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Figure 1. Active-Passive Polarization (from Ref. 2, page 321)

As mentioned above, localized forms of corrosion, e.g., pitting, crevice corrosion and
stress-corrosion cracking, are not seen in the passive region but begin and accelerate
whenever the potential at the start of the transpassive region, i.e., shown in Figure 1 as
Eloc, is exceeded. This minimum potential value is more commonly known as the
protection potential or breakdown potential. When all other conditions are equivalent,
crevice corrosion will typically initiate on a given alloy at a less noble breakdown
potential than the potential at which pitting starts on that same alloy without a crevice
being present.
The specific mechanisms by which various active-passive alloys form the passive
condition are not well understood. However, it is clear that a film forms on the metal
surface typically an oxide layer - and this provides a barrier between the electrolyte and
the metal below. These films are extremely thin on the order of 30 angstroms or less in
thickness - and they can be fragile. General corrosion can initiate when there is overall
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breakdown of an entire passive film but frequently there is only localized rupture of the
film at specific spots on a metal surface. One of the localized forms of corrosion may
then begin at that failure site in the film.
The relative sizes of the active and the passive regions plus the values of the Epp
potential, the Eloc protection (or breakdown) potential and the ability of an alloy to
quickly repair its passive film when local film rupture occurs are all important to its
corrosion resistance. These results depend on a combination of the specific electrolyte,
the chemical composition of the given alloy and several service factors.
Types of Corrosion
General (or uniform) corrosion occurs when there is attack in a fairly consistent pattern
at all wetted areas on a metal. This happens because anodic and cathodic microscopic
areas continually switch with time and no one area suffers extra, localized penetration.
Typically this form of attack occurs on plain carbon steel (mild steel) that does not form a
robust passive film like alloyed active-passive materials such as stainless steels.
In most applications its easier to control general corrosion compared to the many types
of localized attack. Traditional control methods such as using a coating can be effective.
It is much easier to detect and monitor general corrosion and so effective inspection
intervals can be planned. Added thickness above the metal thickness needed for
mechanical strength alone can be used as a corrosion allowance as a means of
preventing failure. In addition much information is available on general corrosion rates of
several metals for a variety of corrosive media so that the metal thickness necessary for a
given service life often can be effectively estimated.
Atmospheric corrosion has characteristics in common with traditional general corrosion.
It accounts for a major category of corrosion cost across many applications. Typically
carbon steel is the material affected. Low-alloy steels offer better resistance than
plain carbon steels. The nature of the attack from atmospheric corrosion depends on
whether or not the moisture is retained or drained from the metal surface, the presence
and concentration of certain chemical species that exist in the atmospheric air and the
availability of oxygen. The latter is necessary for the very common oxygen reduction
cathodic reaction. Sulfur dioxide and chloride ions in the air are the critical chemical
species most important to the level of attack that occurs. Both accelerate corrosion.
Galvanic corrosion is well known as the result of electrical contact between dissimilar
metals when both are wetted by an electrolyte. The metal in the couple that is the most
active, i.e., most likely to corrode in the given corrosive medium, will suffer accelerated
corrosion whereas the other metal will experience decreased corrosion rates. These are
the anodic and the cathodic metals, respectively, in the galvanic couple. The anodic metal
corrodes and sacrifices itself and in the process provides protection against corrosion of
the more cathodic (noble) metal. This process is the basis for the sacrificial anode type of
cathodic protection.
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Combating galvanic corrosion is often addressed by avoiding galvanic couples of
dissimilar metals or alloys that are far apart in a standard galvanic series. The materials in
such a series are listed according to their unique electrode potentials in seawater at room
temperature. These electrode potentials are thermodynamic parameters and thus the
standard series does not consider kinetic effects. Its use is not always reliable for
predicting attack. For example, whether a stainless steel is in its active or its passive state
for the actual application conditions needs to be established before using a traditional
galvanic series to make predictions on the rate of galvanic attack that is likely.
The area ratio of anodic to cathodic metals in a galvanic couple is very important.
Maximum rates occur with a small anode area and a large cathode area. Thus a large
anodic metal area relative to the area of the cathodic metal is most desirable.
Pitting corrosion is a localized form of attack in which there is a breakdown of the
passive protective film at very specific spots on the metal surface followed by
concentrated metal dissolution and penetration into the surface at those spots. The anodic
oxidation reaction occurs in the pits while the cathodic reduction reaction occurs on the
area surrounding each pit. Like many forms of corrosion there is an initiation phase and,
once started, a propagation phase in which the pit penetration increases rapidly. The
initiation phase generally lasts a long period in comparison to the propagation phase.
Pitting is a much more difficult problem to deal with than general corrosion. This is
because its initiation can be triggered by a range of very local conditions that may not be
obvious. These might include a scratch on the metal surface, a metallurgical irregularity
at the surface, e.g., a sulfide inclusion in the alloy, or a high local concentration of
aggressive ions that breakdown the passive film at a small area. Because of its localized
nature, inspection for corrosion damage due to pitting is much more problematic than
general corrosion and thus pitting can be much more of a threat.
Pitting is most common on active-passive alloys such as stainless steels and nickel alloys
plus aluminum alloys when severe application conditions exist. Pitting can also occur on
carbon steel but it is less common. That is because a passive film that forms on plain
carbon steel is more susceptible to being damaged due to conditions compared to alloys
with more robust films. Carbon steel is more likely to experience general corrosion.
Crevice corrosion is a form of localized attack that occurs in the wetted portions of
several types of closely confined, but not completely closed-off areas on a metal. Such
areas could include the gasket surfaces of a pipe flange, overlapping plates or plates that
butt up to one another but are not sealed at the interface, the free space between the
threads on a bolt and the threads inside the nut it is fastened to, under countersunk screw
heads, etc. The creviced or partially closed region does not require that two metals be in
close contact. Attack can and often does start under sand, dirt or debris collected on a
wetted metal surface.
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Similar to pitting, in crevice corrosion the anodic oxidation reaction occurs inside the
creviced area while the necessary cathodic reaction occurs just outside on the nearby
freely exposed area. There is an initiation phase in which the passive film on the metal
breaks down inside the creviced area and accelerated corrosion begins and propagates
while the reduction reaction occurs outside. The time necessary for the process to begin is
dependent on all the various factors that can accelerate or retard all corrosion
mechanisms but there is another factor unique to crevice attack. That is the geometry and
dimension of the crevice opening. If it is open enough to let the electrolyte freely move in
and out or if it is completely closed off (as with a properly sealed crevice) then no attack
will occur. However, crevice attack occurs when the interface opening is very small but
still open enough for the electrolyte to get in but too small for it to freely circulate. Once
started crevice attack is often rapid like pitting.
In general, crevice corrosion presents a greater practical problem than pitting. When all
other conditions are equivalent, a given alloy in a given corrosive medium will have
crevice corrosion initiate in any susceptible crevices present before pitting will start on a
freely exposed area of that metal surface. As stated earlier the protection (breakdown)
potential for pitting is more noble than that for crevice corrosion when all other
conditions are equal. Another practical issue is created by the fact that it is often very
difficult to design and/or fabricate a variety of equipment and omit all potential creviced
areas. The more creviced areas that exist in a given application the greater is the
probability of crevice attack.
Stress-corrosion cracking (SCC) is a one of the localized forms of attack that combines
a corrosion process and a mechanical cracking process to make the result worse than
either mechanism acting alone. SCC requires a specific corrosive medium and alloy
combination, tensile stress and varying time periods (depending on specific levels of
aggressiveness of the causative factors) for synergistic interaction of these factors. Even
though there are several susceptible combinations see Table 1 SCC is unique in that
particular alloys crack in particular corrosive media but not in others. For example,
carbon steel is subject to SCC in certain sodium hydroxide (caustic) solutions but not in
seawater whereas austenitic stainless steels will not crack in caustic but may crack in
many chloride-containing media such as seawater if other conditions permit.
The stress that causes SCC is constant or static unlike the stress in corrosion fatigue. It
must be tensile stress and not compressive. The application direction of tensile stress acts
to further open a crack and to expose fresh metal to the corrosive medium. This twostep, mechanical and corrosion process continues as the crack advances. Propagation is
most rapid when the primary stress component acts perpendicular to the primary crack
path. The tensile stress can be applied stress or, very frequently, it is residual stress.
Residual tensile stresses can be caused by a variety of manufacturing processes such as
welding, cold working or heat treatment. These residual stresses can be most dangerous
in causing SCC because they are often overlooked.
Time of interaction of the causative factors is an important parameter in the incidence of
SCC. If the given combination of alloy and corrosive medium are susceptible, other
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Table 1. Known Combinations of Alloys and Corrosive Media

Subject to SCC [or HE] (from Ref. 3, page 831)
Carbon steels Nitrate, hydroxide, carbonate/bicarbonate, acidified cyanide and
amine aqueous solutions; anhydrous ammonia; gaseous hydrogen at
high temperature and pressure
Low alloy steels Aqueous solutions with hydrogen sulfide and/or halide ions;
gaseous chlorine, hydrochloric & hydrobromic acids; gaseous
hydrogen or gaseous hydrogen sulfide (each at ambient temperature);
sulfide impurities in aqueous solutions; arsenic, antimony or bismuth
ions in aqueous solutions at ambient temperature. HE is most common.
Austenitic stainless steels Hot solutions with chloride and other halide ions; fluoride
ions in aqueous solutions at ambient temperature if steel is sensitized;
oxygen dissolved in liquid water at temperatures above 570 F if steel
is sensitized; hydroxide solutions if temperature is above 210 F;
polythionic acids at ambient temperature if steel is sensitized.
Nickel alloys Inconel 600 alloys in polythionic acids at ambient temperature
if sensitized and in hot NaOH; Inconel 600 alloys in the very high
temperature, dilute chloride conditions in nuclear reactors; Alloys 400
and B-3 in hydrofluoric acid.
Copper alloys Aerated aqueous ammonia solutions; amines in aqueous solutions;
nitrogen oxides with moisture; sulfur dioxide gas with moisture.
Aluminum alloys Halide ions in aqueous solutions at ambient temperature for high
strength alloys; fuming nitric acid (that is acid at concentrations
above about 85%) at temperatures above 210 F for high strength
alloys.
Titanium alloys (For industrial alloys Grades 1,2,9,12 & 28) Nitrogen tetroxide,
fuming nitric acid; anhydrous methanol. (Higher strength, aerospace
alloy grades may also be susceptible to these same media plus
aqueous halide solutions and certain organic compounds with halide
ions.)
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overall conditions for producing corrosion are severe and the tensile stress level is high,
then initiation and propagation of SCC can be very rapid. However, if the susceptible
combination of alloy and corrosive still exists but one or more of the other factors is
greatly reduced in intensity then the cracking process can take an extended period.
SCC can be minimized by several means that influence one or more of the factors that act
together to cause the process or by other control measures to be reviewed later.
Hydrogen embrittlement (HE) should not be confused with SCC. HE is a metallurgical
and mechanical process without a corrosion component. HE is caused by the entry of
atomic hydrogen into susceptible metals. This hydrogen charging greatly lowers the
ductility of the affected alloy and can make it fracture with little or no prior plastic
deformation. HE is not reduced or controlled by the several ways employed to control
corrosion. This mechanism often causes lowered ductility without fracture in lower
strength plain carbon steel but it can cause complete brittle fracture in high strength
steels. The strength of a steel is indicated by its metallurgical hardness. It has been found
that ASTM A-193, Grade B-7 bolts dont crack due to HE if their hardness on the
Rockwell C scale is 22 (HRC 22) or less (Reference 8, page 140). There have been many
proposals that atomic hydrogen effects can combine with and accelerate SCC that is
occurring. This is most likely to occur in high strength steels when atomic hydrogen can
be changed into the material and conditions for the occurrence of SCC also exist.
Corrosion Fatigue is a widespread form of localized attack that, like SCC, results from
the combined effects of a corrosion process and tensile mechanical stress. Unlike SCC
the stress in corrosion fatigue is cyclic and often fluctuates irregularly with time. This
form of attack is so widespread because fatigue itself - without the added effect of
corrosion - is a (if not the) major factor in producing failures in a variety of dynamic
mechanical equipment and in other situations where cyclic tensile stresses act. A
corrosive environment adds to the incidence of failure by lowering the level of tensile
stress or the number of stress cycles necessary for failure. Failure is typically initiated on
the surface of the exposed metal and propagates as a growing crack through the crosssection until too little material remains to withstand the load.
Very aggressive corrosive applications are not required for corrosion fatigue. It has been
shown for some alloys that this form of attack occurs sooner when exposed to plain
water as compared to the same alloys exposed to pure mechanical fatigue (without the
water) for identical fatigue parameters. The probability of pitting on a particular alloy in a
given electrolyte is often a prime indicator of its susceptibility to corrosion fatigue in that
same medium. This is because pits concentrate whatever level of tensile stress is acting
and thus initiation of fatigue cracking is accelerated.
Most of the classic corrosion control measures apply to corrosion fatigue and these are
the first line of defense against this form of attack. In the mechanical area the best
preventative measures are to minimize all tensile stresses at or near the surface of the
metal. Just as in SCC this applies to both applied and residual tensile stresses. Some
applications that induce cyclic tensile stresses include rotating shafting, reciprocating
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components, temperature changes that produce thermal stresses and flow-induced

vibrations. The effect of the frequency of the acting cyclic stresses is different in
corrosion fatigue versus fatigue without a significant corrosive component. In the latter
the frequency of the stresses has little or no effect on how soon failure occurs. However,
in corrosion fatigue a lower frequency of the cycles is more detrimental and causes
quicker failure. This is because the advancing crack remains open and exposed to the
corrosive medium for longer periods when the frequency of the cyclic stresses is low.
Erosion-corrosion (E-C) is a combination of flow-induced abrasive wear and corrosion.
It produces more metal damage than either process acting alone. Often the normally
protective passive film on the metal surface is damaged by high velocity or turbulent flow
of the process steam and this permits accelerated corrosion.
E-C frequently is found in very localized areas on a metal surface where velocities and/or
turbulence are the highest. The abrasive degradation portion of E-C is enhanced if there
are hard solid particles, e.g. as a slurry, in the flowing fluid. While the metals abrasion
resistance plays a role in its resistance to E-C, it has been found that a more important
factor in overall resistance is the metals corrosion resistance in the specific electrolyte.
Most metals and alloys have a critical velocity. Above this value, E-C begins and
significantly increases in the given electrolyte. If the critical value must be exceeded for a
specific application, it is necessary to use either a more corrosion resistant alloy or to use
a suitable coating on the less resistant alloy.
The occurrence of E-C is directly affected from an electrochemical perspective dependent
on whether the rate of corrosion is controlled by a concentration or by activation
polarization mechanism. This is discussed later.
Intergranular attack (IGA) is preferential corrosion in the regions surrounding the
metallurgical grain boundaries of susceptible alloys with little or no attack of the grains.
Susceptibility occurs when certain alloys are exposed to specific temperatures for
sufficient time periods and precipitation of a portion of the normal constituents in the
alloys move to grain boundary areas. This critical temperature range often occurs
during cooling after welding the material or during incorrect heat treatment. The critical
temperature exposure may also occur in service. The distinct segregation and
heterogeneous condition caused by the precipitation process makes the affected alloys
much more susceptible to accelerated corrosion near the grain boundaries. Attack around
the entire circumference of some grains can cause whole grains to fall completely out of
the alloys matrix. Corrosion rates determined by post-exposure weight loss
measurements then indicate rapidly increasing rates with time of exposure to the
electrolyte.
An alloy that has become subject to IGA through temperature and time exposure is said
to have become sensitized. Stainless steels and nickel-based alloys plus aluminum alloys
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are subject to this form of corrosion. If tensile stresses are acting in a sensitized alloy,
frequently intergranular SCC will occur in which the advancing crack travels between the
grains of the material. Generally the crack is perpendicular to the direction of the primary
tensile stress. Many types of electrolytes can cause IGA in sensitized alloys, e.g.,
austenitic stainless steels can experience IGA in several types of inorganic and organic
acids and in seawater.
The most common example of IGA occurs in the frequently used wrought austenitic
stainless steels, i.e., Types 304 and 316. When these alloys are exposed to temperatures
in the range of approximately 900 to 1500 degrees F they can be sensitized. The carbon
present in these alloys has a high affinity for joining with chromium and in this
temperature range it combines with chrome to form chromium carbides that precipitate to
grain boundary areas. The result is that the percentage of chromium in the alloys adjacent
to the grain boundaries is significantly reduced below its pre-sensitized level. Chromium
is the major element in stainless steels (and to a lesser extent in nickel alloys) that allows
them to develop a passive, corrosion-resistant state. The minimum chromium
concentration in stainless alloys to achieve this passive state is about 12%. After
significant chromium carbide precipitation has occurred the chromium content
immediately adjacent to grains can be far less than 12%.
IGA can also be a problem in cast stainless steel alloys due to the same mechanism as in
the wrought alloys. These cast alloys are often used for pump casings and valves in the
chemical and petrochemical industries and IGA often is a problem.
Chromium carbide precipitation and, specifically, the percentage of carbon present in an
alloy are directly connected to IGA of nickel-based alloys just as in stainless steels.
However, in nickel alloys the mechanism is more complicated and the temperature ranges
necessary for sensitization differ somewhat from those that apply to stainless steels.
Inconel 600 is one nickel-base alloy that has been widely used in nuclear reactors that has
experienced failures due to IGA and/or intergranular SCC. These failures occur in high
temperature reactor water containing low concentrations of chloride ions.
IGA failures can occur in certain high strength aluminum alloys that contain copper,
magnesium, zinc or manganese. Unlike stainless steels and nickel alloys, here carbon
does not play a role but instead copper, magnesium, zinc or manganese compounds
precipitate to grain boundaries and create electrochemical differences with the nearby
grains. These potential differences promote IGA. Susceptible aluminum alloys are those
in the 2XXX, 7XXX and 5XXX classes.
The possible solutions to IGA include either making specific material selections initially
to avoid the problem or, where possible, using a post-sensitization heat treatment to
regain the original homogeneous metallurgical composition that can resist attack.
Alternative material choices are discussed later.
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Dealloying (or selective leaching) corrosion occurs when one element in an alloy is
preferentially attacked. The remaining material is generally left with essentially the same
original shape and dimensions but the mechanical properties of the alloy are severely
diminished. Currently there is no general agreement on the specific causes.
The two most common examples of dealloying are preferential attack of zinc in certain
brass alloys (dezincification) and the preferential attack of the iron in gray cast iron
(graphitic corrosion). The amount of zinc and/or certain other elements present in brass
alloys determine whether or not they suffer dezincification. Graphitic corrosion often
occurs only after many years of service and is most often seen in older underground
utility piping.
Alternative material selections are generally the most practical approach to controlling
these forms of attack.
Microbiological influenced corrosion (MIC) is a form of corrosion produced by the
results of the life processes of certain microorganisms or simply by their presence on a
metallic surface. Different microorganisms can produce a variety of effects that lead to
accelerated corrosion. These include formation of black iron sulfide deposits that create
corrosion cells on carbon steel; production of either mineral or organic acids and the
resulting lowered pH; formation of hydrogen sulfide and the associated corrosive
condition in oil and natural gas applications; driving the electrode potential of stainless
steels more anodic and out of their passive state into the pitting range plus generating
hydrogen so that high strength steels are made more susceptible to HE or SCC.
Microorganisms often form a slime deposit on metallic surfaces called biofilms. The
presence of these films alone without the added other effects of different
microorganisms can often cause crevice corrosion.
Most all alloys are subject to MIC although titanium alloys offer resistance. Carbon steels
and cast irons are the materials where MIC is most often encountered. These materials
most often suffer general corrosion while stainless steels and aluminum alloys experience
pitting and crevice attack due to MIC.
The microbes involved with MIC require three essentials. These are water, some type of
nutrient, e.g., a source of hydrocarbons, nitrogen or phosphorus, and some source of
energy. The latter can be supplied by sunlight or by the redox (oxidation and reduction)
chemical reactions that occur in all corrosion. Some microbes are anaerobic such as the
very common sulfate reducing bacteria (SRB) and need an oxygen-free environment to
live and grow while others require oxygen to do the same. Many types of microbes can
survive over a wide range of temperatures from subzero levels up to maximum of about
200 degrees F. They cannot live at very high temperatures. Submerged colonies of
microbes attach to metal surfaces and grow quickest when exposed to stagnant or low
velocity liquids. They can survive over a wide range of pH.
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MIC may occur in several types of applications. Industrial water-handling systems are
probably the most common. Others include the exterior of underground pipelines, in fire
sprinkler systems and on marine piers and other structures exposed to seawater. MIC has
also been a significant problem on aluminum in the lower sections of commercial
aircraft below galleys and restrooms when adequate constraints on liquid spills are
missing. Stainless steels are particularly susceptible to MIC at welds.
Control methods for MIC include using biocides to kill the microbes and adding chemical
corrosion inhibitors to retard corrosion. Coatings as well as design changes may be
useful. Specific knowledge is needed to effectively analyze and control MIC problems.
Effects of Environmental and Application Variables
This section will discuss the primary in-service variables, besides the many different
electrolytes, that affect corrosion rates. These factors include the following:
Temperature
pH
Concentration of certain chemical species in the electrolyte
Flow velocity (or the static condition)
Heterogeneous conditions
Temperature of the Electrolyte Corrosion is, in part, a chemical reaction process and thus the rate of the reaction is
generally increased as the temperature of the electrolyte increases. In acidic conditions
the rate or kinetics of the corrosion reaction will typically double for every 18 degrees F
increase. In these situations the rate-controlling cathodic reaction is the reduction of
hydrogen ions to produce the evolution of molecular hydrogen gas. In near neutral or in
alkaline pH electrolytes the governing cathodic reaction very often is the reduction of
oxygen in water to form hydroxide ions. In this case the rate of corrosion generally
doubles for about every 55 degrees F increase in temperature.
Corrosion rates do not always increase as temperature increases. The classic example of
this occurs in a comparison of a recirculating, closed, steel water piping system and a
recirculating, open-to-the-atmosphere steel water system. In both types of water systems
the typical rate-controlling corrosion reaction is the reduction of dissolved oxygen. This
assumes no other oxidizing species or acids are present in the water to support another
type of reduction reaction. In this closed system the overall rate of corrosion continually
increases as the temperature increases. This is because the oxygen in the air required for
the reduction reaction cannot escape the system.
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In the open system the same relationship applies initially. However, at about 176 degrees
F the solubility of oxygen begins to decrease significantly and since the system is open it
can escape. The rate of corrosion then begins to decrease because the cathodic reduction
reaction is being restrained. By the time the boiling point of the water is reached the
corrosion reaction is essentially shutdown because the necessary oxygen is no longer
available. The difference in corrosion rates of the two systems is shown in Figure 2.
This relationship between water temperature, solubility of oxygen in the water and the
resulting corrosion rate is important because it occurs so frequently. Higher corrosion
rates are not always associated with higher temperatures but they often are. This serves to
make the point that there are very few general rules that always apply in analyzing
corrosion rates.
Another effect of temperature occurs with certain metals in galvanic contact. At normal
ambient temperature, in a galvanic couple between zinc and carbon steel the zinc is the
anode and it is preferentially corroded while the steel is the cathode that is protected by
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the zinc. The corrosion rate of the steel is then greatly diminished compared to its rate
when uncoupled in the same electrolyte. However, starting at about 140 degrees F and at
higher temperature the roles are reversed and the steel becomes the anode that is
preferentially attacked while the zinc is protected.
Temperature, along with certain other environmental variables, has important effects on
anodic polarization, i.e., the plot shown schematically in Figure 1, of active-passive
alloys. These changes affect the potential and associated current at which there is a
switch from active to passive behavior and the potential range over which passivity is
maintained.
pH of the Electrolyte The corrosion rates of many alloys are generally independent of pH over mid-range
values of approximately 5 to 9 when assessing this variable alone. Changes in rates
either higher or lower occur outside of this range depending on the specific alloy as
well as other conditions. The other conditions are very important because applicable
variables all work together synergistically to generate a specific result for the given alloy.
Besides pH the other conditions can include temperature, availability of dissolved oxygen
(commonly affected by electrolyte velocity), the presence or absence of tensile stresses in
the metal, other chemical species in the electrolyte, etc.
First consider the effects of pH changes on iron, plain carbon steels and low-alloyed
steels. These materials all experience very similar corrosion rates in aerated, soft water at
ambient temperature as a function of pH. Figure 3 plots the results of a series of tests of
iron completed in ambient, soft water at different pH values. To generate these data
sodium hydroxide or hydrochloric acid was added to the water to produce higher or lower
pH values, respectively.
Corrosion rates (CR) for pH values over the range of 10 down to 4 are stable for the
stated conditions. Corrosion in that range is controlled by the rate of oxygen reduction
where oxygen is readily available in the aerated water. Over that range a protective
barrier of hydrated ferrous oxide forms and is maintained on the metal surface. At higher,
more alkaline pH values the corrosion rates decrease because the metal is shifted into its
passive range for the stated conditions. At the other extreme of pH values, lower than 4,
the hydrated ferrous oxide barrier is dissolved; corrosion rates increase significantly and
are controlled by the reduction of the readily available hydrogen ions.
It should be emphasized that the results in Figure 3 apply only for the stated conditions of
ambient temperature, soft water, readily available oxygen, and (although not stated) it is
implied that there are no significant tensile stresses in the metal tested. Variations from
these conditions would likely produce different results.
The general role of temperature in its affect on corrosion has already been discussed. The
use of soft water is important because unlike hard water it has little or no minerals that
can precipitate out of solution and form protective scales (if uniformly distributed) made
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up of compounds such as carbonates on the metal surface. Thus this soft water would be
expected to show a smaller range of pH values with stable, non-increasing corrosion rates
compared to the use of hard water. The use of aerated water for the tests is important
because it confirms that sufficient oxygen was available for cathodic oxygen reduction
not to be limited and thus the overall corrosion rate was not limited in the mid-pH range
as would be the case if there had been a deficit of oxygen. Also, while not stated,
it is implied that other oxidizing agents such as ferric or cupric ions were not added to the
water to add possible cathodic reduction reactions. It is also implied that effective
chemical corrosion inhibitors were not present in the soft water.
It is indicated in Table 1 that SCC can occur in carbon steels in sodium hydroxide
solutions if tensile stresses are present and if the temperature is sufficiently high. Sodium
hydroxide was added to the soft water to create the very alkaline pH values
seen in Figure 3. Neither high temperature nor tensile stresses in the metal were factors in
producing the data shown.
As mentioned in the previous section on temperature, the value of pH of an electrolyte
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along with its temperature and the concentration of certain aggressive ions present all
have significant influences on the electrochemical behavior of active-passive alloys.
Figure 4 illustrates these effects. This shows generic effects of these three variables as a
family of anodic polarization curves for a typical active-passive alloy.
As pH decreases, i.e., as the concentration of hydrogen ions increase, the nose of the
polarization moves to the right and becomes slightly more noble. At the same time the
protection or breakdown potential becomes more active. These effects also occur due to
increasing temperature of the electrolyte. In addition, the same effects are particularly
seen with stainless steels as the concentration of chloride ions in the electrolyte increase.
There are consequences of the effects seen in Figure 4. First the extent of the active
corrosion zone for this typical active-passive alloy increases as the nose moves to the
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right. Thus the maximum current density, i.e., the critical current density for passivity, Ip,
increases and the switch from high active rates to the drastically lower rates in the passive
region is delayed. Secondly the potential range over which the alloy is passive is
decreased as the primary potential for passivity, Epp, becomes more noble as the
breakdown potential, Eloc, decreases. The alloys susceptibilities to either active corrosion
or one of the forms of localized attack is then increased. If just one of these changes
occurs lower pH, increasing temperature or increasing chloride concentration - the
effect on corrosion rates is negative and when more than one occurs simultaneously the
synergistic negative effects are intensified.
The resistance of stainless steels to general corrosion is typically good for high pH values
even at raised temperatures up to about 200 degrees F. Their resistance to acidic pH
values also depends on several factors including temperature, the composition of the
alloy, the specific acid and its concentration, the degree of aeration and the presence and
concentration of chloride ions. Choosing stainless steel alloys will be discussed further in
the Material Selection section on control methods.
For a given set of conditions, specific types of alloys respond to pH as a variable in
different ways. Nickel alloys are noted for being very resistant to high pH values (except
when caused by ammonia or its compounds or when oxidizing conditions also exist in the
electrolyte) and, depending on their specific alloyed composition, they can be useful in
low pH conditions. Copper and copper-based alloys are generally resistant to all acidic
pH conditions as long as no oxidizing agents, i.e., oxygen itself; oxidizing acids such as
nitric or very concentrated sulfuric or chromic acids; or oxidizing ions such as ferric or
cupric ions are also present. Copper and copper alloys are typically resistant to mildly
alkaline conditions other than those caused by ammonia and ammonia-like compounds. It
is well known that copper and its alloys are susceptible to SCC in ammonia. Zinc and
lead experience a sharp increase in corrosion rates at high pH values. Aluminum alloys
are generally useful in a mid-pH range of about 7 to 9 but they can experience significant
corrosion rates in both more acidic and more alkaline pH ranges. Aluminum can provide
excellent general corrosion resistance but depending on the specific alloy and other
conditions may be subject to one of the localized forms of attack.
Concentration of Specific Chemical Species in the Electrolyte
As discussed, the concentration of oxygen in the electrolyte is frequently a factor in the
rate of corrosion that occurs. This is also true due to the presence of one of the oxidizing
ions or an oxidizing acid. A common example of the effect of an oxidizing agent is the
rate of corrosion on bare steel in a marine environment when part of the metal is above
and part is below the water level. The portion of the metal at and just above the high tide
water level called the splash zone corrodes much quicker that the metal that is well
below the low tide water level. This is partly because oxygen is readily available at and
above the splash zone to support corrosion but its concentration is likely much more
limited well below the low tide level. Alternate wetting and drying in the splash zone also
accelerates attack. Still another example of this is that most corrosion typically occurs on
a buried steel or iron object that projects up out of the soil at and just below the ground
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level. There is usually less attack well below the ground level because it is more difficult
for oxygen to diffuse through the soil and reach the buried metal.
As shown in Figure 4, the concentration of chloride ions in an electrolyte often is
important in the degree of corrosion that occurs on metals that have an active-passive
behavior. The corrosion of carbon steel in aerated water is directly proportional to the
concentration of chloride ions present up to about 6,000 ppm (0.6 %). Above this level
the solubility of oxygen starts decreasing and then that factor becomes rate controlling,
Reference 6, page 187. The effect of one variable on corrosion cannot be evaluated in
isolation.
Typically the initiation and propagation of pitting, crevice attack plus SCC or corrosion
fatigue (if sufficient stresses are present in the latter two cases) will increase for stainless
steels as the concentration of chloride ions increase. This occurs when the chloride ions
cause local breakdown in the normal passive film at spots where their concentrations are
the highest. The effect is strongest when the electrolyte has an acidic pH. The effect is
less pronounced when the electrolyte has a neutral pH and oxygen is present.
Unless a given active-passive material is able to resist the concentration of chlorides
present or quickly repair its passive film at a break in the film local corrosion can begin.
Nickel alloys have similar behavior to stainless steels but usually, depending on their
composition, have greater resistance to the effects of chlorides. Although they do not
have an active-passive behavior, aluminum alloys behave similar to stainless steels. As
mentioned, chlorides have a deleterious effect on carbon steels but their passive films are
much inferior and less robust than higher alloyed materials. On carbon steels when their
relatively weak passive films are broken much of the entire surface is affected, film repair
does not occur and general rather than a localized form of corrosion typically starts.
Sometimes a feature of the application can increase the concentration of chloride ions at
specific areas on the metals surface that is well above the level that exists in the absence
of that factor. For example, if a susceptible alloy is exposed to a marine atmospheric
corrosion environment with high levels of airborne chlorides and typically high
humidity it is important where the metal is located. Its nearness to the sea is important
because close proximity will generate more attack. However, another feature is whether
or not it is sheltered from rain. If it is in the open and exposed to rain then the chlorides
from the sea air will be washed off the surface periodically and corrosion may be less
severe. If it is exposed to the salt air but protected from the rain the chloride
concentration can build with time and corrosion rates are likely to be high. Crevices on
the metal make matters worse because they can collect and concentrate chlorides inside
that cannot be easily washed away by rain.
Other chemical species besides oxygen or oxidizing species and chlorides can be
important to the incidence and rate of corrosion. For example, fluoride ions in aqueous
solutions and as fluorine gas cause high corrosion rates in titanium alloys whereas these
alloys have a high resistance to chlorides in seawater. Sulfur compounds and sulfides
often cause accelerated attack on copper and silver. These two elements are commonly
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used in electrical and electronic contacts because of their normal, low electrical
resistance.
Atmospheric exposure of copper or silver to sulfides as from hydrogen sulfide gas
produces a copper or silver tarnish that is very thin but sufficient to increase the electrical
contact resistance so that many low-voltage electrical or electronic devices may not
function reliably. Another example is sulfur dioxide produced by many industrial
processes. This often causes accelerated atmospheric corrosion of carbon steel.
High concentrations of dissolved metal in an electrolyte when that metal or alloy is the
material of construction can serve as indicators of accelerated, on-going corrosion.
Chemical analyses of the electrolyte after different periods of exposure can be used to
indicate approximate rates of corrosion. Specific inspections or maintenance can then be
planned when the particular part or section of the system cannot be assessed by other
means. For example, high concentrations of iron or zinc in a process liquid likely would
indicate high rates of corrosion of carbon steel or galvanized components, respectively.
This is true especially for general rather than localized corrosion with the associated
greater corroding area and larger quantities of corroded metal dissolving in the
electrolyte. It would also apply to localized forms of attack but the quantities of dissolved
metal likely would be smaller for equivalent exposure periods.
Flow Velocity
The influence of electrolyte velocity, or agitation, e.g., as in an agitated chemical reaction
vessel, on corrosion rates can be complex. The effect of this parameter depends on the
specific alloy, the electrolyte, whether the corrosion polarization is under activation or
concentration control and the level of velocity acting. The form of corrosion can also be
important. In many incidences increased velocities can be negative, in others velocity can
have little or no effect and in some cases increased velocities can be beneficial.
Four of the common situations are illustrated by the schematic curves shown in Figure 5,
Cases A - D. This information and illustrations were adopted from information in
Reference 2, page 20. In the figure relative velocity (V) values are shown on the vertical
axis and relative corrosion rates (CR) are on the horizontal axis for each case.
Case A in Figure 5 applies to carbon steel and low alloy carbon steels as well as copper
exposed to water having limited quantities of dissolved oxygen. Corrosion rates are
controlled by the speed of oxygen diffusion from the bulk electrolyte to the metal surface
in order to supply the oxygen reduction reaction. The CRs are therefore under
concentration polarization control. When the velocity increases the available bulk oxygen
can more readily move through the diffusion layer next to the metal surface and reach the
surface where it can be reduced. Therefore velocity and corrosion rates are directly
proportional.
Unlike Case A., the alloys in Case B readily passivate. Initially the stainless steels and
titanium in Case B behave like Case A but then they passivate, CRs drop significantly
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and remain essentially constant. While in the passive region these alloys are unaffected
by velocity increases. Like Case A, the CRs are under concentration control but the
reducible species are now the oxidizing ions ferric or cupric. Initially greater velocities
bring more of these ions to the metal surface but because of their oxidizing power (ability
to shift to more noble potentials) the alloys passivate. In addition, the inherent properties
of both stainless steels and titanium allow them to make the transition from the active
to the passive state where this is not possible for the plain carbon steels and copper in
Case A.
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Case C involves alloys that corrode at relatively high rates in specific acids. Plain carbon
steels and low alloy steels experience very high CRs in hydrochloric acid and stainless
steels show relatively high rates in sulfuric acid. In these situations the CRs are under
activation polarization control because these strong acids can readily ionize and supply
all the hydrogen ions needed for the cathodic reduction reactions. Increased velocity is
not needed to bring more of the hydrogen ions to the metal surface to support corrosion
and, therefore, CRs are independent of changes in velocity.
Case D in Figure 5 illustrates two types of materials lead in dilute sulfuric acid and
plain carbon or low alloy steels that form thick, insoluble sulfate films that provide
barriers to corrosion as long as the films are intact. These films are relatively unstable
compared to the very thin, tightly adherent passive films that form on stainless steels and
other corrosion resistant active-passive alloys. There is generally little initial effect of
increasing velocities in Case D. Then a critical high velocity is attained (unique to the
given alloy) in which the sulfate film is removed by the mechanical shearing action of the
increasing velocities. After exceeding the specific critical velocity, corrosion rates
increase greatly. This last stage marks the beginning of erosion-corrosion.
The value of the critical velocity shown in Case D depends largely on which class of
materials is being considered. Plain carbon steels and gray cast irons typically have the
lowest values. Copper-based alloys offer some improvement, i.e., somewhat higher
critical values. Typically the higher alloyed stainless steels as well as the nickel-based
alloys and titanium alloys permit the highest allowable critical velocities before erosioncorrosion begins. Many alloys offer good resistance to a given corrosive medium when
the electrolyte is static or has a very low velocity. However, they experience erosioncorrosion in that same medium when their critical velocity is exceeded. For this reason it
is necessary when choosing a material to consider if it will ever be exposed to high
velocities. If it will then information must be obtained on its corrosion rate at expected
velocities and not just for its rate based on static immersion in the given electrolyte.
Increased velocities can often have beneficial effects as long as the increase is not enough
to cause erosion-corrosion. Case B in Figure 5 is an example of this. There the electrode
potentials of easily passivated active-passive alloys are switched from the active
corrosion region to the passive region by the action of the increased velocity that
transports more of the oxidizing ferric and cupric ions to the metal surfaces.
Increased velocities are also helpful in minimizing the initiation of certain localized
forms of corrosion. Pitting, crevice attack and MIC are each less likely in electrolytes that
are not stagnant. Moving electrolytes tend to wash away sand, dirt and general debris that
otherwise might collect on a metal surface and create crevice corrosion. Increased
velocities can be helpful when using chemical corrosion inhibitors. The specified
concentration of an inhibitor is critical in its effectiveness. Some minimum level of
velocity helps to maintain the desired inhibitor concentration by continually bringing
fresh treated solution to metal surfaces.
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Heterogeneous Conditions in Applications
Several circumstances may occur in applications in which dissimilar, nonuniform conditions increase the rate of corrosion. Very often this is because these
conditions produce either macro or micro-scale electrochemical cells, i.e., anodes
and cathodes, which do not generally exist in more homogeneous situations.
One of the most obvious of these circumstances occurs in the galvanic coupling of
dissimilar metals. This macro-scale example results in accelerated corrosion of the more
anodic member of the galvanic couple. Of course in most applications this result is
undesirable. However, corrosion control by cathodic protection with a sacrificial anode
material is a beneficial application of this idea. Accelerated corrosion of the zinc coating
on galvanized steel that serves to protect the steel substrate is an example.
Crevices on a metal surface are another macro-scale example of the creation of
heterogeneous conditions. Different chemical conditions are promoted inside versus
outside crevices so that crevice attack is initiated and eventually propagated inside the
partially closed-off areas. The anodic reaction occurs inside crevices while the cathodic
reduction reaction occurs on the surrounding, freely exposed area. As stated previously,
crevices can also concentrate aggressive ions inside and create a heterogeneous condition
versus the much lower ion concentration on freely-exposed areas.
Typically metals that are commercially pure are more corrosion resistant than alloys of
that metal. However, the pure, homogeneous metal usually does not have the necessary
mechanical properties to be a practical engineering material. One solution is to use a
cladding of commercially pure metal on an alloyed substrate of the metal. The cladding
provides corrosion resistance while the substrate provides strength.
This is the basis for many Alclad-plus-another alloy combinations that have been used for
years in aircraft and aerospace applications. Alclad cladding exposed to the corrosive is
commercially pure aluminum, e.g., Alloy 1100, and has low strength while the thicker
substrate is a heat treatable aluminum alloy such as Alloy 2024. The latter alloy has
copper as its major alloying element. After heat treatment the copper in 2024
precipitates from the aluminum-copper, single phase solid solution to form a second
phase of copper particulates. This precipitation greatly increases the strength of the 2024
but the presence of the second (different) phase of copper particulates, i.e., a micro-scale
heterogeneous condition, also greatly lowers the alloys corrosion resistance.
For the Alclad combination described to function the electrode potentials of the cladding
and the substrate alloys must be approximately equal in the electrolyte. This value for the
non-heat treatable cladding is generally fixed. However, the several types of
heat treatments, i.e., tempers, are possible with the substrate alloy and these produce
different final potentials. There are other approaches to corrosion control in which it is
desired for the Alclad to act as a sacrificial anode and thus provide cathodic protection to
the substrate. In this case the Alclad and the substrate must have different potentials. This
is accomplished by using a heat treatment for the substrate that results in it having a
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potential that is cathodic relative to that of the cladding.
Welds and the areas immediately adjacent to them, i.e., the heat affected zones (HAZ),
often are particularly susceptible to corrosion but those same alloys without welds in the
same electrolytes may be resistant. The heat from welding creates non-uniform, microscale metallurgical conditions such as different grain sizes or segregation of alloyed
elements between the weld, HAZ and the unaffected portions of the parent metal. IGA is
the possible result of the latter depending on the time the alloy spends in its sensitization
range during cool down from welding temperature, its composition and whether or not it
is then exposed to a corrosive medium that can cause IGA. The alloy is made susceptible
to IGA because the area adjacent to grain boundaries has a different chemical
composition than nearby homogeneous grains.
Welding also introduces stresses in the metal that remain as residual stresses around the
weld area after the material cools. These areas are subject to greater corrosion than
surrounding parent metal that does not have these stresses. Residual weld stresses are
additive to applied stresses generated in service and are often overlooked. The total level
of tensile stress present residual plus applied contributes to the probability of SCC or
corrosion fatigue. It is important, often vital, in a variety of corrosive applications to
apply a post-weld heat treatment, i.e., a stress relief annealing treatment, suitable for the
given application to lessen the residual stress contribution to total stress.
Ambient-temperature, plastic deformation of an alloy during fabrication, i.e., cold
working, also introduces residual stresses. These stresses are confined to certain areas of
the material that has been cold worked such as at bends, at sheared edges or where the
metal has been drawn through a die. Such areas are susceptible to accelerated corrosion
where nearby areas that were not similarly worked are not. This effect is particularly
severe in acidic environments. If practical, cold worked areas should be stress relief
annealed after cold working and if this is not possible they should be viewed as
susceptible regions for careful, periodic inspections once service begins.
In applications where there is circulation of the electrolyte there can be significant local
differences in velocities and turbulence. The general effects of velocity can be complex
and depend on the several factors previously discussed. However, if the critical velocity
for the given situation is exceeded erosion-corrosion can start and corrosion rates will be
greatly increased versus areas that are below that critical value. This is also true in areas
where there is local turbulence such as at orifices, short radius piping elbows and across
pressure let down valves. Like cold worked areas, all these areas deserve special attention
during maintenance inspections.
Primary Methods of Corrosion Control
It should be understood that the words control or mitigation are appropriate and
prevention is generally not when discussing corrosion. Thermodynamics dictates that
corrosion of practical engineering materials typically will occur. However, proper
application of known control methods and tactics (often coupled with adequate corrosion
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monitoring and inspection) can reduce the frequent incidence and rates of corrosion of
those materials to levels that will result in economic service.
The important roles of corrosion monitoring, inspection for corrosion and the value of
completing root-cause failure analyses will be discussed in the section on tactics.
There are four traditional classes or methods used to mitigate corrosion:
Use a coating or lining on the metal surface
Select an alloy that has good resistance to the electrolyte and service conditions
Apply cathodic protection
Add a suitable chemical corrosion inhibitor to the electrolyte
Coatings and Linings
This category of corrosion control is generally the most widely used method and can take
a wide range of forms. In most cases the coating or lining simply acts as a barrier
between the alloy and the corrosive medium. In addition certain metallic coatings have an
electrode potential that is anodic to the cathodic potential of the metal below it and thus
the coating also protects the substrate by acting as a sacrificial anode, i.e., providing
cathodic protection (CP).
The range of materials and applications in this category is extensive. It includes organic
coatings (e.g., paints), polymeric linings and coatings, conversion coatings for steel and
anodizing treatments for aluminum surfaces, galvanized and galvalume coatings on steel,
cladding, weld overlays, electroplating, thermal sprays, chemical setting ceramic linings
(e.g., acid bricks), porcelain enamels and glass linings. These many options mean that the
optimal selection of a coating, lining or cladding for a given application can be very
challenging. It is highly recommended that an objective, expert on coatings be consulted
when making a selection and to assure proper implementation of the selection.
Organic coatings as paints on structural carbon steel are likely the most common form of
corrosion control. Inorganic primers for steel that contain zinc to provide CP are often
used with different varieties of topcoats in immersion services. Inorganic zinc (IOZ) is
often used alone for atmospheric applications. Some common categories of organic
coatings include alkyds, acrylics, epoxies, phenolics and polyurethanes.
The one general rule that is most important in effective use of paint coatings (and also in
many other coating types) is the absolute need for good adhesion between the coating and
the metal surface. Without the proper adhesion the best, most corrosion-resistant coating
can disbond and fail to provide protection. This is primarily achieved by proper metal
surface preparation. This means using and enforcing a clear specification for the level of
surface preparation required in the given application. Some paint coatings are more
tolerant of less-than-perfect surface preparation than others. Alkyd coatings are known as
having a greater ability than other coating types to adhere to inferior surfaces.
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In the case of paint coatings, standardized surface preparation specifications are available
from the Structural Steel Painting Council (SSPC). The National Association of
Corrosion Engineers (NACE International) has similar standards. NACE also certifies
coating inspectors. These persons are often essential to obtaining a quality coating
system, i.e., the required surface preparation and specified coating characteristics.
Hot dipped galvanized steel is widely used. The thickness applied is directly proportional
to corrosion resistance. Galvalume is a combination of zinc and aluminum applied to
steel sheets. Its initial cost is more than galvanized steel but its corrosion resistance is
considerably greater in atmospheric applications. Galvalume is often used
as a roofing material for buildings.
Natural or synthetic elastomers (rubber) are often used as linings inside chemical storage
tanks. There are many material options in this category with various properties. Other
polymers (plastics), especially fluoropolymers, are often used as linings or as coatings in
steel pipe, in various piping components and on internal parts of pumps. They can
provide excellent corrosion resistance to a variety of electrolytes. Some commonly used
fluoropolymers are the oldest - polytetrafluorethylene (PTFE, Teflon), fluorinated
ethylene propylene (FEP), perfluoroalkoxy (PFA), ethylene tetrafluoro-ethylene (ETFE),
ethylene chlortrifluoroethylene (ECTFE) and polyvinylidene fluoride (PVDF). The
fluoropolymers generally have a maximum service temperature limit of about 500
degrees F. They also differ in mechanical properties and in their ability to be fabricated
into given configurations. Reference 5 provides a summary of these properties. Success
with polymers depends on proper selection for the given use and the abilities of the
application contractor.
Epoxy powder that is applied to metal surfaces by electrostatic spraying at high
temperature has been used in two common applications. The resulting coatings are fusion
bonded epoxy (FBE). One of these applications is for underground steel pipelines used in
for oil and natural gas transmission. This is another example where a high quality surface
preparation of the steel is essential in obtaining a good, long lasting coating.
Underground pipelines that transport hazardous materials must have both a coating and
cathodic protection (CP) by federal regulations. The initial costs of FBE coatings are
higher than other types of coatings for pipelines. However, the FBE has a significant
advantage in that it minimizes or prevents cathodic shielding for the CP system. This is
discussed in the CP section.
FBE is also frequently used to coat reinforcement bars (rebar) used in concrete. Bare
rebar in concrete is subject to corrosion, e.g., as used in bridge decks or in concrete piers
under marine-environment highways, due to moisture diffusion through the concrete and
the effects of road deicing salts or seawater exposure. There has been much controversy
about the effectiveness (and justification for the extra cost) of FBE rebar. Much of this
has been caused by damage to the coating due to handling during construction. FBE
coated rebar handled like bare rebar cannot be expected to remain free of defects.
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Another widely used category of coatings is claddings. This entails metallurgically
bonding a relatively thin layer of corrosion-resistant alloy to a thicker but corrosion-prone
substrate that often is carbon steel but other alloys also used. Thus corrosion resistance
and mechanical strength are attained in the economic composite. The top, thinner layer
may be a stainless steel, or a nickel, copper or aluminum metal or alloy. A related
category of coatings is weld overlays. Here a thinner layer (compared to normal cladding)
of the corrosion-resistant material over steel is attained by multiple welding passes using
a suitably alloyed weld material. The welding parameters have to be carefully controlled
to prevent the steel from diluting and thus diminishing the resistance of the overlay.
Material Selection
This class of corrosion control depends on choosing a given material that has the required
corrosion resistance as well as other needed properties for the given application. The
other properties might include strength, ductility, fracture toughness, strength-to-weight
ratio, high temperature resistance, thermal or electrical conductivity, etc. Clearly all
major classes of materials, i.e., metals, polymers, ceramics and composites, would be
considered for a completely thorough evaluation but here the emphasis will be on metals
and their alloys.
Before citing some potentially good corrosion-resistant material choices it is useful to
categorize and give some typical examples of the different types of corrosive media:
While other constituents often are important, it is helpful to classify waters according to
the approximate concentration of chloride ions they contain (Reference 6, page 189).
There are four general types. These are fresh water (less than 1,000 parts per million,
ppm); brackish water (1,000 to 10,000 ppm); seawater (25,000 to 35,000 ppm) and salt
brine (above 35,000 ppm). Like all electrolytes, chemical analysis is often necessary to
define the levels of these ions and others that can be important in a specific corrosion
evaluation. Potable waters in the fresh water category may be hard or soft depending on
whether or not they produce precipitated carbonate and magnesium scaling. In general
scaling from hard water is protective if the scaling occurs on exposed surfaces.
Alkalies (higher pH electrolytes) might include sodium or potassium hydroxides;
ammonia, amines (organic ammonia compounds); soda ash and hypochlorites (bleaches).
Acids can be either inorganic or organic. Generally the inorganic acids are more
corrosive. The inorganic acids are classified as either oxidizing, e.g., nitric, sulfuric (at
concentrations above 70%) and chromic or as reducing, e.g., sulfuric (at concentrations
less than 70% but especially if below 20%); hydrochloric; hydrofluoric; phosphoric and
carbonic. Two common organic acids are formic (the most aggressive of the organics)
and acetic. Each is a reducing acid. The corrosive nature of contamination-free sulfuric
acid in its reducing range can be altered significantly by the presence of contaminants
such as ferric or cupric ions, chromates, nitrates, nitrites, hydrogen sulfide and, as is
frequently true, chloride ions. See Reference 6.
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Soil often is an electrolyte for underground metallic structures. Its aggressiveness
depends on several factors including moisture content, electrical resistivity, and the
presence and concentrations of specific ions, e.g., chlorides and sulfides, plus pH, the
type of soil and the presence of microorganisms that can cause MIC. The American
Water Works Association provides a standard, AWWA C105, that includes criteria that
often are used to rank the relative corrosiveness of different soils. See also Reference 6,
pages 210 212.
Following are typically valid metallic material selections for several corrosive media and
applications. In some cases comments on poor options for the given situation are
provided. These are general recommendations. Often either mixtures of electrolytes or
trace contaminants occur such that general recommendations need to be modified. Also
the common application variables previously discussed, e.g., temperature, velocity or
heterogeneous conditions, have to be assessed to determine their effects in the specific
situation.
Coated carbon steel (usually with a quality painting system or galvanization) for exposure
to most atmospheric corrosion. Aluminum alloys are also widely used.
Bare weathering steel, e.g., A588, that contains about 0.30 % copper, to resist many
atmospheric exposures except for high chloride, sulfide and sulfate atmospheres.
Coated carbon steel for underground service (quality applied FBE is often used) along
with adequate cathodic protection specified for the particular local conditions.
Bare carbon steel for static storage of concentrated, i.e., 70% or more, sulfuric acid. Only
very low velocities (about 3 feet/second is a maximum) are permitted.
Bare carbon steel for storage of ammonia or ammonium hydroxide water solutions if a
small amount of iron contamination in the electrolyte is acceptable and certain provisions
can be met. A minimum of about 2000 ppm (0.2%) of water must be present and no air
should be present. Even so, post-weld stress relief of welds and low strength steels (not
hardened, higher strength steels) are recommended. Without these provisions SCC in
carbon steels is possible. If zero water is present, i.e., the electrolyte is anhydrous, SCC
of carbon steel is possible. In the latter case, 304 stainless steel (SS) is recommended for
temperatures up to approximately 212 degrees F.
If dissimilar metals or alloys must be used together in an application, select those that are
closest together in a traditional galvanic series in seawater. However, be aware of the
cautions mentioned in the galvanic corrosion section. Always use an insulator between
dissimilar metals when possible. If this is not possible, obtain a favorable anode-tocathode area ratio. That means avoid a small anode area galvanically coupled to a large
cathode area.
304 stainless steel (SS) for exposure to nitric and other strongly oxidizing acids. Use
304L if the SS must be welded to avoid IGA. Note: 316 SS (and 316L) provide inferior
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service to 304 and 304L. The molybdenum in 316 & 316L causes accelerated attack in
nitric and similar oxidizing acids compared to alloys without molybdenum.
SSs having high levels of molybdenum (Mo), chromium (Cr) and nitrogen (N) provide
the best resistance to pitting and/or crevice corrosion in waters and other media that
contain high levels of chlorides. The percentage of Mo present is particularly important.
This role of Mo also applies to nickel-based alloys that contain chromium.
High purity ferritic SSs, e.g., alloys 29-4 or 29-4-2; austenitic SSs with high nickel
contents, e.g., 20Cb-3; or nickel-based alloys, e.g., Alloy 200 or C-276, provide the best
resistance to SCC in electrolytes with high levels of chlorides. Nickel (Ni) content in
these alloys is the critical factor. Surprisingly, zero or a small percentage of Ni, as in 29-4
and 29-4-2, or Ni percentages of about 20% as in 20Cb-3 or more as in Ni-based alloys
provide the best resistance. The commonly used 300 series of austenitic SSs with 8 to
14% Ni are the most susceptible and they often experience SCC in chloride media.
Use lower carbon grades of 304 or 316 SS, i.e., 304L or 316L, where IGA is likely in a
given service where 304 or 316 would otherwise be suitable. Post-sensitization heat
treatment often is impractical. Current steel mill practice is to automatically supply these
two standard grades of SSs in an extra low carbon or ELC version labeled as
304/304ELC or 316/316ELC. This practice permits limiting the carbon contents to a
maximum of 0.03 % as in the older low carbon versions as a standard procedure.
Copper tubing and brass fittings for handling potable water. Velocities must be limited to
prevent E-C.
Brasses with 15% or less zinc contents to prevent dealloying (dezincification) or, for
more commonly used brasses with more than 15% zinc, use those that also have about
1% tin plus about 0.2 % of arsenic, antimony or phosphorus. Tin has the major positive
effect in preventing dealloying but the minor elements enhance its role.
Commercially pure nickel (Alloy 200) for use in sodium hydroxide services. Nickel is
not resistant to ammonia or its derivatives in the presence of air. Reference 6, page 140.
Cathodic Protection (CP)
In this form of control DC electric current is supplied to the metal surface that is
corroding to counteract the DC current generated at the anodic areas there by the
corrosion process. By this action the electrode potential of the metal is polarized from an
anodic to a cathodic potential. Corrosion is not stopped completely but its rate is greatly
diminished so as to provide practical control.
The required level of applied CP current to achieve adequate protection depends
primarily on the bare metal surface area exposed to the electrolyte. For this reason CP is
commonly used with some type of coating on the metal to minimize the current required.
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However, no coating is perfect and different coatings will have various levels of small (or
not so small) defects, known as holidays, which allow exposure of the substrate metal.
The more current that is required for protection in a given application the lower, i.e.,
more negative or cathodic, the potential of the applied current source must be.
CP can be provided by two basic methods. The simplest is to use consumable current
sources, i.e., sacrificial anodes, which are galvanically coupled to the metal to be
protected. These anodes are more electrochemically active than the metal to which they
are electrically attached and thus they preferentially corrode while cathodically polarizing
the more noble metal and protecting it from corrosion. Typical sacrificial anode materials
are zinc, magnesium or aluminum and most frequently one of these is coupled to steel to
be protected. The other method of CP is impressed current CP (ICCP). Here a nonconsumable, anodic material in the electrolyte is electrically connected to the positive
terminal of an adjustable rectifier/transformer while the metal to be protected is
connected to the negative terminal. The rectifier consumes AC electrical power, converts
it to DC power and reduces the voltage (potential). This resulting DC current goes to the
non-consumable anodic material where it is discharged to travel through the electrolyte to
the metal to receive CP. Typical ICCP anode materials are graphite, cast iron or titanium
wire coated with platinum.
Sacrificial anode CP systems have the advantages of being simple with less initial and
operating costs. ICCP systems have higher initial and operating costs but they can be
adjusted to deliver more current and thus they can protect more square feet of bare metal
receiving CP compared to a sacrificial anode system. ICCP systems often cannot be used
in remote locations where AC power to supply the rectifier is unavailable or too costly to
bring to the area where the rectifier is located. It is essential in both types of systems to
complete regular monitoring and maintenance to assure an adequate CP potential, and
thus a proper level of current, is being delivered. Several matters can prevent successful
operation. Persons qualified to monitor and, especially to troubleshot and remedy
problems, are needed to make CP function as intended. It is not an option to install a
system, forget about required follow-up and expect good performance.
Cathodic shielding of CP current occurs when a coating on a buried pipeline receiving CP
separates from the metal - commonly at a holiday due to loss of adherence. This is
coating disbondment. At an affected holiday the electrolyte can enter the entire disbonded
area but applied CP current can penetrate only a short distance laterally there. The
remainder of the disbonded region receives little or no protective current and thus
corrosion is not mitigated. Shielded areas present problems because they cannot be
detected by the standard monitoring procedure of measuring CP potentials between the
pipe and a reference electrode placed in the soil at ground level at several spots along a
buried pipeline route.
Fusion bonded epoxy (FBE) coatings on pipe sections are installed in the applicators
shop. If proper procedures and quality control are used then and if the finished pipe
sections are handled carefully during transport and during setting in the ditch in the field,
these coatings are noted for having high adherence and resistance to cathodic shielding
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problems. Some type of coating still has to be applied in the field to cover the
circumferential field-completed welds that join the separate pipe sections. Shrinkable
plastic sleeves are often successfully used over these weld areas. Some other types of
pipeline coatings that are completely applied in the field, e.g., tapes, have been much less
successful in attaining good adherence and resistance to cathodic shielding.
CP is used in several types of applications. A simplest form is the role of zinc deposited
by hot dipping on structural steel or the use of certain Alcad on aluminum alloys as
previously discussed. Each provides CP by sacrificial corrosion of the more active metal
to protect the substrate. Attached sacrificial anodes have been used for many years to
protect the steel hulls of ships and the underwater steel portions of offshore drilling rigs.
Both sacrificial anode CP and ICCP are used for protection of buried pipelines, steel
gasoline storage tanks and for the outer bottom surfaces of aboveground storage tanks.
Often the inner surfaces of steel water tanks and steel tanks that hold corrosive chemicals
are coated and an ICCP system is installed. Rebar in concrete is also protected using CP
but, as is true all applications, regular monitoring is needed to attain long-term success.
Corrosion Inhibitors
Inhibitors are chemical species added to electrolytes in small concentrations to reduce
corrosion rates. They function either by adsorbing onto the metallic surfaces to be
protected, and thus providing thin barriers to attack, or by otherwise affecting the
electrochemistry of the given application to reduce rates. Most inhibitors are proprietary
products from specialized chemical treatment providers. Some products act alone but in
many applications two or more are specified to provide a greater beneficial effect due to
their synergistic interaction.
Choosing and applying an effective inhibitor (or combination) depends on the specifics of
the given application. This entails the metal to be protected, the electrolyte, service
temperature, the required inhibitor concentration for the specific conditions and
environmental regulations that may preclude a given type. The trade off between costs
versus effectiveness always is a prime consideration. Similar to the situation for MIC,
specialized expertise is needed to make the best technical recommendations.
There are many types of inhibitors and they may be classified in different ways. Some act
to control the anodic corrosion reaction, some to control cathodic corrosion reactions and
some affect both types. Some are effective when the primary cathodic reaction is oxygen
reduction and others when that reaction is hydrogen reduction to produce hydrogen gas.
Many exist as liquid additives for the electrolyte and some function because of their high
vapor pressures and thus abilities to release inhibiting gases to nearby metals to be
protected. The latter are used for equipment in closed storage and shipping containers.
Certain types of inhibitors must be used with great care. The specific concentration
employed is the key factor. These inhibitors are designed to shift (and help maintain) the
electrode potential of particular active-passive alloys from their active to their passive
ranges (as shown in Figure 1) in a given electrolyte where this would not otherwise
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occur. They are known as passivators or oxidizing inhibitors. If the inhibitor

concentration is too low for the specific service conditions the electrode potential of an
alloy might be moved further out on the active corrosion portion of its anodic polarization
curve but not far enough for it to shift back to its passive, low corrosion rate range. This
results in a faster rate of corrosion than would occur if no inhibitor of this type were used.
This problem may also occur in local areas of a metallic system, e.g., a lengthy or
complex piping system, if a sufficient concentration of the passivating inhibitor is not
delivered to all regions of the system. Corrosion rates likely will be much higher in these
deficient regions.
Some inhibitors cannot be used in certain applications because either they are chemically
toxic or, while they are beneficial in controlling corrosion, their presence in the process
stream interferes with desired chemical reactions. These results might be found in
manufacturing systems handling food-quality substances or in chemical manufacturing
plants.
Probably the most common applications of inhibitors are in recirculating cooling water
systems or to minimize corrosion in oil field production systems. In water systems
corrosion is just one of the considerations. The choice of inhibitor there must be
compatible with other potential problems such as scaling or the presence of biofouling
that may or may not affect corrosion but may influence effective heat transfer and cause
higher pumping costs due to flow constrictions. Multiple considerations may also exist in
oil field applications. As mentioned, vapor phase inhibitors are often effectively used
inside shipping and short-term storage containers for metallic equipment. In these
applications the selected inhibitor must not be harmful to any metals present or to any
non-metallic materials included in the shipped or stored equipment.
Inhibitors are sometimes added to the mix water for concrete to help protect the enclosed
rebar from corrosion in concrete structures such as bridge decks. One type commonly
used is calcium nitrite. However, like many practical engineering problems, there are
several interacting variables to be considered in choosing to use inhibitors. Some of these
factors include the quality of the installed concrete, the desired service life of the
reinforced structure, the depth of concrete cover over the top mat of rebar, the water-tocement ratio that is used in mixing the concrete, the use of CP or not and the use of
different rebar materials. Options in the latter area include bare carbon steel, epoxycoated carbon steel, stainless steel or a newer steel, i.e., ASTM A 1035, with apparently
excellent potential for these applications. Discounted, life-cycle costs of the various
alternatives need to be determined to make the most rational decisions. See Reference 7,
pages 559- 597 for discussions of the several interacting factors in this area of corrosion
control.
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Corrosion Control Tactics
The following are tactical recommendations and ideas to consider in seeking corrosion
control. Some will not be practical in particular situations. However, these items may
serve as a checklist for the engineer to use so as not to overlook some of the various,
possible approaches. The most promising ideas for the specific application should then be
investigated in depth.
Overall Questions and Factors to Consider:
Is it possible to favorably alter the corrosive environment or operating variables? This
might include the type or concentration of the electrolyte, the concentration of the
aggressive ions in it, the temperature, pH, degree of aeration, electrode potential, velocity
or stagnant conditions or various heterogeneous conditions.
Do application criteria permit the use of non-metals? Options might be solid polymeric
materials such as PVC tubing, polyethylene (regular or high density, HDPE) pipe or
polymeric coating and linings such as PTFE or rubber. Are any ceramics such as
corrosion-resistant acid brick and mortar or glass linings for chemical reaction vessels
possibilities? Are reinforced fiberglass piping, ducts or tanks potential options?
What design details can be changed to provide more inherent resistance? This should
always include providing geometry, sloping and/or outlet sizes to provide for consistent,
complete drainage of the electrolyte and to never allow a residue of it be retained in outof-service facilities. Others might be to eliminate all possible crevices including
providing for effective deposit or debris removal from metal surfaces; removing all
possible small radii and other surface features that create stress concentrators and are
difficult to effectively coat or specifying a quality surface finish on metals when
corrosion fatigue is a possibility. Reference 8 provides other beneficial approaches the
design engineer can use. Always configure the design for practical, regular inspections
and maintenance. When other options are impossible, design for partial, periodic
replacement of susceptible portions of the system without disturbing non-exposed
portions.
Consider using the failure modes and effects analysis (FMEA) procedure early during the
planning and design stages. This numerical procedure entails identifying all potential
failure modes (not just corrosive types but also mechanical, electrical, etc.), assigning a
probability and overall system consequence value to each and then using these values to
form a simple, weighted product. These results allow a rank ordering of the degree of
attention and justified funding for corrective actions according to the comparative
importance of identified, potential failure modes. Reference 9 provides more details.
Provide a rational financial basis for alternative corrosion control expenditures by
establishing the discounted, life-cycle cost of each option. Most engineering projects are
intended to function for multiple years. Comparing only the initial costs of alternatives
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does not consider the total costs that may occur in the future over expected, long service
lives. Several valid evaluation approaches for completing discounted, life-cycle cost
analyses are presented in the engineering economics course taken by most engineers.
These analyses often are completed in large organizations by cost engineering or
financial or accounting groups when assessing large capital projects. However, the
techniques are not difficult and may also deserve regular use by the individual engineer in
determining the economic viability of smaller expenditures. Most managers speak this
language and, hopefully, will welcome the input.
Factors Specific to the Types of Corrosion:
General attack use a corrosion allowance in material thickness above that needed for
mechanical strength; all four of the classic methods of corrosion control should be
considered for use, i.e. coatings, materials selection, CP and inhibitors.
Galvanic attack avoid dissimilar metals in contact if feasible; if this is not possible use
an electrical insulator to separate them; if an insulator is not feasible use materials that
are as close together as possible in a traditional galvanic series (but recognize the
discussed shortcomings of this) and obtain a favorable anode-to-cathode area ratio.
Another alternative is to coat, preferably, both metals but if thats not possible coat the
cathodic metal in the galvanic couple. No coating gives perfect coverage and if only the
anodic material is coated there will be a very unfavorable anode/cathode area ratio
created at each holiday in the coating on the anode while the large cathode is left bare.
Pitting and crevice attack in stainless steels be aware of the importance of the alloying
elements molybdenum (most important) plus chromium and nitrogen in selecting alloys
to provide resistance in the very common cases of electrolytes with chlorides; realize that
stagnant or very low velocity conditions promote attacks while moving liquids retard
attack; if crevices cannot be eliminated open the entrances to them as much as possible to
allow free exchange of the electrolyte in and out or use sealants to close them; all four of
the classic methods of corrosion control should be considered for use.
SCC recognize several situations that may induce or may help control SCC. These
include which unique alloy and corrosive media combinations are susceptible when
applied or residual tensile stresses also act. Identify residual stresses due to, for example,
shrinkage after welding, cold working or surface machining of metals and seek to
minimize them by stress relief heat treatment. Know the specific role of the alloyed
element nickel in stainless and nickel alloys susceptibility to SCC in chloride media.
Consider the possibility of control by compressive stresses imparted to a metal surface by
shot peening; recognize the possibility of attack on austenitic stainless steels under
certain thermal insulation and use sodium silicate inhibitors in the insulation as a control
measure. Know that carbon steel often provides more resistance to SCC than stainless
steels if the carbon steel does not experience prohibited rates of general corrosion in the
given medium. This idea can apply to the material used for the tubes in shell and tube
heat exchangers in open, recirculating cooling water systems where the cooling medium
is inhibited sea or brackish water. Reference 2, page 106.
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Corrosion fatigue eliminate all possible stress risers on the surfaces of dynamic
equipment or structures subject to cyclic stresses; use surface (case) hardening
techniques, e.g., nitriding or carburizing, to increase resistance; input helpful compressive
stresses to the metal surface by shot peening; when there is a choice, use butt welds rather
than fillet welds. Fillet welds are more susceptible, Reference 8 page 127. Recognize that
relatively benign corrosives environments can change pure mechanical fatigue to the
more dangerous corrosion fatigue form.
IGA (if possible) avoid the sensitizing temperature range (this is approximately 900 to
1400 degrees F for stainless steels) due to welding, any type of heat treatment or inservice exposure; if sensitizing exposure cannot be avoided typically use an extra low
carbon (ELC) grade of stainless steel; when an ELC stainless steel is welded also use
compatible ELC welding electrodes or filler metal; if the stainless alloy must be exposed
to the sensitizing temperature range for long periods (as in regular service) it may be
better to use a stabilized grade of stainless, i.e., 321 or 347 that contains titanium or
niobium, respectively, rather than a ELC grade. The titanium in 321 and the niobium in
347 have strong affinities for carbon and the carbides thus formed precipitate harmlessly
to grain boundary regions after critical temperature exposure leaving protective
chromium in place throughout the alloys matrix as desired. Note stainless grades 321
and 347 have no molybdenum so they offer inferior resistance to chloride pitting and
crevice attack compared to 316L. In critical applications where the main concern is IGA,
use the ASTM A 262, Practice C to confirm that a given stainless steel is resistant to
IGA.
E-C whenever possible minimize normal flow velocities and features that cause local
turbulence; recognize that providing for corrosion resistance to the given electrolyte will
provide more overall resistance to E-C than providing enhanced resistance to the abrasive
wear portion of the mechanism; provide filters in the flow stream to remove solid
particles that intensify attack; lessen turbulence by using a butterfly valve instead of a
globe or gate valve; take large pressure reductions in multiple steps rather than a single
one; seek to streamline flows rather than making abrupt direction changes in piping;
where E-C is unavoidable use local hard weld metal overlays or replaceable
impingement plates.
Dealloying recognize dezincification of brass as the most common type especially in
stagnant water with high temperature and higher concentrations of chlorides, i.e., more
than 500 ppm, and carbon dioxide; copper alloys with more than 15 % zinc are
susceptible; if these are needed use alloys with tin plus phosphorus, arsenic or antimony
in small amounts as inhibiting elements to resist attack. Recognize that loss of zinc in
brass alloys is a major cause of SCC in them. Besides inhibited brasses other resistant
alloys in order of increasing resistance are bronzes, aluminum bronzes, copper-nickel
alloys and Alloy 400 (Monel). Gray cast iron can suffer selective attack on the iron and
leave the graphite intact in soils especially those with sulfates or sulfate reducing bacteria
(SRB). Cast iron attack frequency takes many years to develop; this may also occur in
waters with low pH and in seawater; resistant alternatives to gray cast iron are ductile
iron, white cast iron and cast iron with 2- 3% nickel.
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MIC- recognize that all types of metals can be susceptible with the possible exception of
titanium alloys, i.e., switching from carbon steel to stainless is not an effective control
measure; stagnant water conditions and the presence of biofilms (slime) are well known
to promote attack and if there is an option always use the cleanest source of water in
cooling applications to minimize attack. Control measures include using coatings with CP
(often with more negative {cathodic} potentials than typically used when MIC is not
acting) for underground applications and chemical treatment with biocides in cooling
water systems. Once a given water treatment plan is in use there must be competent,
consistent long-term monitoring of the chemistry and corrosive action of the process
stream to assure harmful microbes and corrosion rates are being controlled by the specific
methods.
Along with the effective specific use of chemical corrosion inhibitors, analyzing and
effectively controlling MIC problems include some of the most difficult issues in the
corrosion field. It is recommended that specialized consultants or organizations that
concentrate on MIC (or inhibitors or both) be employed for such tasks rather than persons
or organizations that do not concentrate in these areas.
Maintenance, Monitoring/Inspection and Post-Mortem Activities
Note Many of the following ideas are especially applicable to continuous operating
facilities such as chemical plants, oil and petrochemical plants, pulp & paper processing
plants or electric power generation plants. However, there are many other types of
facilities and systems that may incur major costs or inconveniences for their owners or
clients if corrosion failures cause interruption of intended operations. Consider if any of
the following might have practical benefit in your specific application.
The most important potential costs of a corrosion failure relate to personnel or public
safety issues and/or environmental releases and the resulting legal liabilities from each.
Significant portions of the total life-cycle cost evaluation that (hopefully) is completed
for each alternative control measure investigated will be the future costs of necessary
maintenance and inspection activities as well as indicated replacements associated with
the given alternative. Very large future costs could exist for facilities that must function
on a 24/7 basis and, therefore, incur extremely high costs when there is an unplanned
shutdown. In these situations the cost of unavailability due to a corrosion failure often
will outweigh the initial cost of the most expensive corrosion control option. Thorough
economic analyses of all costs are justified for these cases.
Understand that effective corrosion control must be an on going and not a one-time
activity. Continually inspect for and monitor operational corrosion rates at susceptible
areas and in the most critical operating equipment to detect significant changes so that
timely corrections can be made. Suitable non-destructive evaluation (NDE) methods are
regularly used in many industries. In addition effective monitoring can be accomplished
by the use of weight-loss corrosion coupons to define average corrosion rates of alloys of
concern or by using electrical corrosion sensors to obtain approximate, instantaneous
corrosion rates. Another approach is to regularly take samples of the circulating
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electrolyte and chemically analyze them for changes in dissolved metal concentrations
(caused by corrosion) or for other detrimental chemical changes. These sample analyses
are mandatory when using corrosion inhibitors to confirm that the intended
concentrations are being maintained at all locations in a system.
Make and maintain detailed records of the results of all inspections, monitoring and
maintenance activities. Especially important to corrosion control are the magnitudes and
timing of chemical changes in the process stream or changes in other operating variables.
Electronic data storage and retrieval software make this activity much easier compared to
manual methods used in the past. Corrosion rates and deleterious changes that are well
documented can provide essential information for accomplishing planned, predictive
maintenance work. The alternative of taking unplanned, emergency shutdowns when a
failure occurs is always expensive. Being proactive in the future is usually easily justified
after the actual costs of an emergency shutdown are experienced.
Establish a policy of completing, documenting and maintaining records of thorough, rootcause failure analyses for significant material failures. Failures may be found to have
been produced by corrosion as well as other failure modes, e.g., pure mechanical
fatigue, fracture, wear, etc. The analyses should define the true root cause(s) of failures
such as a bad material selection, poor design details, unexpected changes in the service
environment, material defects, fabrication defects, improper or lack of required
maintenance, etc. The results of these analyses, if kept in an organized and readily
available form like the on-going monitoring and inspection records, can become very
valuable, locally applicable resources.
Continued implementation of the policies of making and keeping excellent records of all
monitoring, maintenance and root-cause failure analyses is becoming essential in current
industrial settings. In many industries a large percentage of experienced personnel are
reaching retirement age and leaving their responsibilities to much less experienced
persons. Access to thorough corrosion control maintenance and other lessons learned
records can be a great help to the newer workers in preventing repetition of past mistakes.
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References
1. Corrosion Costs and Preventative Strategies in the United States,FHWA-RD01-156, Federal Highway Administration, 2002
2. Fontana, M.G. and Greene, N.D., Corrosion Engineering, Second Edition,
McGraw-Hill Book Company, 1978
3. Failure Analysis and Prevention, Vol. 11, Metals Handbook, ASM International,
2002
4. Uhlig, H.H., Corrosion and Corrosion Control, Second Edition, John Wiley &
Sons, Inc., 1971
5. Stephans, L.C., Fluorpolymers as Chemical Process Vessel Linings, Materials
Performance, June 1999, pp. 42-47
6. Dillon, C.P., Corrosion Control in the Chemical Process Industries, Second
Edition, MTI Publication No. 45, Materials Technology Institute of the Chemical
Process Industries, Inc., 1994
7. Corrosion: Environments and Industries, Vol. 13C, Metals Handbook, ASM
International, 2006
8. Landrum, R.J., Fundamentals of Designing for Corrosion Control- A Corrosion
Aid for the Designer, National Association of Corrosion Engineers, 1989
9. Davis, G.O., Cost Effective Insurance: The FMEA Process, Maintenance
Technology, October 2009, pp.14-17 (available at www.MT-ONLINE.com)
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Page 41 of 41

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