Fundamentals of Corrosion

METALLURGY TRAINING MODULE 4
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Fundamentals of Corrosion
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Introduction
Corrosion is the degradation of a metal due to chemical or electrochemical interaction
with its environment. It may or may not involve actual loss of material. In the Oil Patch
we deal with some of the most hostile environments in the world. It is vital that the
engineers who design and specify materials for ARGUS Subsea equipment have a
good understanding of the fundamentals of corrosion. Corrosion can shorten the
lifetime of our equipment. It may interfere with the functioning of the equipment. It may
be very slow and insidious, or sudden and catastrophic. Once equipment is installed,
its too late: corrosion must be accounted for in the design stages. There are many
mechanisms for corrosion. It is important that you become familiar with each in order to
be able to mitigate or prevent their occurrence through proper design and material
selection. In this training module well introduce the basics of corrosion. Well build upon
this in the next module by examining wellhead and trim selection.
The Chemistry of Corrosion

We are not going to dive too deeply into the electrochemistry of corrosion. It is a very
complex subject that would require a great deal more time than we have available in
this course. Instead some basic principles of chemistry will first be presented that will
allow you to reason through most corrosion mechanisms and to draw the right
conclusions. Lets go back to high school chemistry class and do some reviewing!
The Dalton model of the atom (see Figure 1) consists of three types of particles:
protons, electrons, and neutrons. Protons have a positive charge; electrons have a
negative charge, and neutrons of course have no charge. Protons and neutrons are
clumped together in the nucleus in the center of the atom, while electrons orbit around
the nucleus a considerable distance away. For every proton in the nucleus, there is an
electron orbiting around the nucleus so the atom has no net charge. Modern atomic
theory states that the electrons can only occupy certain, discrete energy bands called
shells. Each shell can only accommodate a limited number of electrons before it
becomes filled. Any additional electrons must then go into the next available shell. The
electrons in the outer most, unfilled shell are known as valence electrons. These are
the electrons that are available for forming chemical bonds with other atoms.
When an atom is involved in a chemical reaction it will either transfer valence electrons
to or share valence electrons with another atom in order to completely fill its outer shell
and become stable. An atom (or a group of atoms acting together as a unit) will typically
gain or lose an electron in a chemical reaction thus will have a net charge. An atom that
has a net charge is called an ion. A positive ion is known as a cation, and a negative ion
is known as an anion. If an atom loses one or more electrons in a chemical reaction it is
said to have been oxidized. If one or more electrons are gained, it is said to have been

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reduced. An easy way to remember the difference is the Spanish word Ole! (Oxidation
Loses Electrons). Note that oxidation may or may not involve oxygen.
Figure 1: The Dalton Model of the Atom

Now we are going to shift gears and talk about a French chemist named Henry Louise
Le Chatelier (1850-1936). Le Chatelier studied chemical equilibrium and developed a
fundamental principle that describes how a system in equilibrium reacts to an external
stimulus. Le Chateliers principle states that a system in chemical equilibrium always
acts to oppose changes in equilibrium. To restore equilibrium; the system will favor a
chemical reaction to reduce or eliminate the disturbance in order to restabilize at
thermodynamic equilibrium. In other words, if a system in equilibrium is subjected to a
change in concentration, temperature, or total pressure, the equilibrium will shift in order
to minimize that change. A good grasp of Le Chateliers principle will stand you in good
stead when it comes to working through some of the corrosion processes that well be
talking about without having to tread the dangerous waters of thermodynamics,
electrochemistry, or the Nernst equation!
Lets start out be defining what we mean by equilibrium. Well use a hypothetical
example of a solution of A and B reacting to form C and D. When we first pour the
solution of A into a beaker with a solution of B in it, the A will immediately start to react
with B to form C and D. The amount of A and B will decrease as the amount of C and D
increases, but only until a certain concentration of C and D is reached. At this point, the

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equilibrium point, some of the C and D dissociate to A and B at the same rate that A
and B are reacting to form C and D. At equilibrium, the amounts of reactants and
products remain the same. Note that there are still lots of reactions occurring, but there
is no net gain or loss of the reactants or products. In chemical shorthand we can write
our chemical equation at equilibrium as A + B C + D.
Well use Le Chateliers principle to find out what happens to the equilibrium point in the
reaction A + B C + D when we change the concentration of one of the substances. I
call Le Chateliers principle the teeter totter principle (or see saw principle depending on
what part of the country youre from) for reasons that will become self evident. Figure 2
illustrates our hypothetical chemical reaction in equilibrium.
Figure 2: A System in Equilibrium
If we now add a little more B, what will happen to our system? It goes out of kilter
(Figure 3). Applying Le Chateliers principle, more A and B will have to react in order to
form more C and D to get things back in balance. The new equilibrium point shifts to the
right (see Figure 4).
D
C
B
A
+
Figure 3: Adding More B Results in Non-Equilibrium

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Figure 4: Back in Equilibrium

Suppose now that instead of adding some B, we remove some B. What will happen to
our system? Again it goes out of whack (see Figure 5). Applying le Chateliers principle
we see that some C and D must dissociate into A and B to restore the balance. The
new equilibrium point will shift to the left and favor the formation of more A and B at the
expense of C and D (see Figure 6).
Figure 5: Remove Some B and the System is in Non-Equilibrium

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Figure 6: Back in Equilibrium

From our time well spent on the playground with the teeter totters, we can see that if we
add reactants to one side of a chemical reaction in equilibrium, the equilibrium point will
shift in favor of the formation of additional products on the other side. If we remove
some products from one side of a chemical reaction in equilibrium, more of the products
on the other side will react to make up the loss and establish a new equilibrium point.
So much for Le Chatelier and his teeter totters. Now we need to discuss water the
liquid phase of H2O. There can be no corrosion of our equipment unless there is water
present. An understanding of the chemistry water is essential to understanding Oil
Patch corrosion. If we look at a glass full of water there doesnt appear to be much
going on, but looks can be deceiving! At any given moment of time there are water
molecules dissociating into H+ (hydrogen) and OH- (hydroxyl) ions; and an equal
number of both H+ and OH- ions recombining to form water molecules. We can show
this using chemical shorthand as:
H2OLiquid H+ + OHThe amount of H+ ions in solution at room temperature is approximately 10 -7 mole/liter

of water. A mole as you may recall from your high school chemistry class is the
number of atoms in 12 grams of carbon 12 which is equal to Avagadros number of
6.023 X 1023.
The amount of H+ ions although relatively small in comparison to the amount of water
molecules present in our glass of water, plays a very important role in the corrosion of
metals. It gets rather awkward talking about the concentration of H + ions in terms of 10
to some negative exponent so well refer to the concentration in terms of pH. The pH of
an aqueous solution is defined as follows:
pH = log 1/ [H+] = - log [H+]

+
Where [H ] is the concentration of the H+ in moles/liter.

The pH of the water in our glass at room temperature will be log [10-7] which equals 7.
By definition, a solution with a pH of 7 is said to be neutral. Note from our formula that
the more H+ ions we have, the lower the value of pH will be. A solution with a pH below
7 (thus with more H+ ions than water at room temperature) is by definition an acid
solution. A solution with a pH over 7 (thus with fewer H+ ions than water at room
temperature) is by definition a base (or alkaline) solution.
If we immerse a carbon steel part into water it will corrode. We can summarize the
overall reaction as:
4Fe + 3O2 + 6H2O 4Fe(OH)3 or rust

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Note that I said summarize because there are a lot of different reactions going on at
various times as the iron is corroded. These individual reactions are important because
often they are the rate controlling step for the overall reaction. Rust is actually a
hydrated form of iron hydroxide, but the rust formula of Fe(OH) 3 is detailed enough for
our purposes. Looking at the above reaction shows that the corrosion of iron requires
that both water and oxygen must be present in order for rust to form.
Lets start by first looking at what happens when pure iron is immersed in water that has
been deaerated (all the oxygen removed). Some iron atoms will be oxidized and go into
solution as either a ferrous or ferric ion as shown by the following reactions:
Fe Fe+2 + 2e-
(Ferrous ion)
Fe Fe+3 + 3e-
(Ferric ion)
As the iron atoms are oxidized and form positive ions (cations), negative electrons are
released. The iron will continue to into solution until the surrounding water becomes
saturated.
Were almost done with the high school chemistry refresher course. We still need to
review the concept of ideal gases and partial pressures before we move on to the
college level stuff! Gases play a very important role in many corrosion processes
common to the Oil Patch. An ideal gas is defined as one in which all collisions between
atoms or molecules are perfectly elastic and in which there are no attractive forces
between atoms or molecules. Obviously there is no such thing as an ideal gas, but it
serves as a useful model for explaining how gases behave. It is often referred to as the
billiard ball model because the gas atoms or molecules interact with each just as billiard
balls do.
Consider a box with ideal gas molecules in it. The pressure in the box is a result of the
molecules colliding with the walls of the box. If we put more molecules in the box, the
number of collisions at any point in time will go up and so will the pressure. If we
expand the volume of the box, but keep the number of molecules the same, the number
of collisions occurring at any point in time will decrease and so will the pressure. This is
quantified by the ideal gas law which can be stated as follows:
PV = nRT
Where P = absolute pressure
V = volume
n = number of gas molecules in moles
R = universal gas constant

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T = absolute temperature
Looking at the ideal gas law shows that for a given volume and temperature, there is a
direct correlation between the pressure and the number of molecules. Double the
number of molecules and pressure is then doubled. All other things being constant,
there is also a direct correlation between pressure and temperature, pressure and the
number of molecules, volume and temperature, and volume and the number of
molecules. This is fortuitous as it will make our gas calculations easy!
Partial pressure may be defined as that portion of the total pressure of a system made
up of two or more different ideal gases that is contributed by any one of the gases by
itself. Lets assume we have a box containing nothing but molecules of gas #1. The
pressure gage on our box reads 100psi absolute. If we replace half of the gas #1
molecules in our box with an equal number of gas #2 molecules, the overall pressure in
our box will remain the same because the total number of gas molecules hasnt
changed. Now the gas #1 molecules are only contributing half of the collisions and so
are responsible for just half of the total pressure. If the total pressure in the box is 100
psi, then the partial pressure of either gas#1 or gas #2 would be 50 psi. With an ideal
gas, the partial pressure of a specific gas in a mixed gas system can be found by
multiplying either the volume percent or mole percent of that specific gas (the values
are the same for an ideal gas) times the total system pressure.
Corrosion Electrochemistry
The weight loss type of corrosion that steel experiences in Oil Patch environments is
electrochemical in nature. Electrochemistry deals with the chemical changes produced
by electricity and the production of electricity by chemical changes. Most of our study of
electrochemistry will focus on the various types of galvanic cells that can form in metals.
Galvanic cells are named in honor of the Italian scientist Luigi Aloisio Galvani (17371798) who was among the first studied them. Well define a galvanic cell for the
moment as two dissimilar electrodes connected via an external circuit that are
immersed in an electrolyte. An electrolyte is an aqueous solution of ions that are
capable of carrying a current. The potential difference between the electrodes will
create a current until equilibrium is reached in the system.
The iron that went into solution in our deaerated water produced positive ions and
negative electrons. This creates an electrical potential whose magnitude is proportional
to the number of atoms going into solution. If we could measure this potential we could
quantify the tendency of the iron to go into solution or corrode. Potential; however,
cannot be measured directly: voltage, or the difference between two potentials, can. We
will measure the potential difference between an electrode made out of a metal of
interest and a reference electrode in a galvanic cell using an arrangement as shown in
Figure 7. The reference electrode is often a platinum tube (essentially inert) with

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hydrogen gas bubbling through it. It is connected to the electrode made from the metal
of interest via an external circuit. A voltmeter will be used to measure the potential
difference. The voltage obtained is called the electrode potential of the metal of interest.
This type of galvanic cell is known as a standard hydrogen reference electrode cell.
Figure 7: Standard Hydrogen Reference Electrode Cell

Hydrogen oxidizes as H2 2H+ + 2e-. When we connect up our cell as shown in Figure
7 and measure the voltage, a negative voltage means that the metal of interest is easier
to oxidize than hydrogen while a positive voltage means its harder to oxidize. We can
take a series of measurements for different metals and then tabulate them in order of
the magnitude of their electrode potentials. Such a table is known as the Electromotive
Force Series (see Table 1). Note that Table 1 is arranged so that the higher up a metal
is in the table, the more negative the electrode potential, and the easier it is to oxidize.
The metals at the bottom of the table are harder to oxidize than hydrogen and are thus
considered more noble (or less active) than metals higher up in the table.There are
other types of reference electrodes besides the hydrogen electrode. The silver/silver
chloride reference electrode is often used in the field to make electrode potential
measurements of offshore structures and subsea equipment.

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Table 1
Standard Electromotive Force (EMF) Series
Electrode Reaction
Li Li+ + eK K+ + eCa Ca+2 + 2eNa Na+ + eMg Mg+2 + 2eBe Be+2 + 2eAl Al+3 + 3eTi Ti+2 + 2eZr Zr+4 + 4eMn Mn+2 + 2eCb Cb+3 + 3eZn Zn+2 + 2eCr Cr+3 + 3eFe Fe+2 + 2eCd Cd+2 + 2eCo Co+2 + 2eNi Ni+2 + 2eMo Mo+3 + 3eSn Sn+2 + 2ePb Pb+2 + 2eFe Fe+3 + 3eH2 2H+ + 2eCu Cu+2 + 2eCu Cu+ + eAg Ag+ + ePd Pd+2 + 2ePt Pt+2 + 2eAu Au+3 + 3e-
Electrode Potential Eo (V), 25oC

-3.05
-2.93
-2.87
-2.71
-.2.37
-1.85
-1.66
-1.63
-1.53
-1.18
-1.1
-0.763
-0.74
-0.440
-0.403
-0.277
-0.250
-0.2
-0.136
-0.126
-0.045
0
+ 0.337
+0.521
+0.800
+0.987
+ 1.2
+1.50

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In a galvanic cell consisting of two dissimilar metal electrodes connected via an external
circuit and immersed in an electrolyte, the electrode where oxidation takes place is
called the anode. The other electrode where reduction takes place is called the
cathode. The anode is where most of the corrosion will occur. Lets look at example
galvanic cell that has an iron electrode and a gold electrode (see Figure 8) and where
we have deaerated the electrolyte (removed all the oxygen). Intuition tells us the iron
will corrode and the gold probably will not. How can we be sure? We can use the EMF
table and Le Chateliers principle to help us find the answer.
Figure 8: Galvanic Cell with Dissimilar Electrodes
There are four possible outcomes in Fe-Au galvanic cell. They are:
The iron electrode could corrode.

The gold electrode could corrode.
Both electrodes could corrode.
Neither electrode could corrode.
Whats it going to be? Lets start by looking at the oxidation reactions in the EMF table
for both iron and gold. Iron can go into solution as either Fe +2 or Fe+3. Both of these

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reactions Fe Fe+2 + 2e- and Fe Fe+3 + 3e- have more negative electrode potentials
than Au Au+3 + 3e- and thus oxidize easier. The iron will go into solution as the
ferrous and ferric ions while producing an abundance of free electrons at the surface of
the iron electrode. These free electrons will go from the iron electrode around the
exterior circuit and end up at the gold electrode. Gold has a large, positive electrode
potential and is thus not easily oxidized. Will the gold electrode in our cell corrode
(oxidize) ever so slightly? The answer is no. Corrosion at the gold electrode will be
totally suppressed by the electrons being fed to it by the corroding iron electrode. To
understand why, we need to employ Le Chateliers teeter totter principle again.
If we disconnect the external wire between the two electrodes, a miniscule amount of
gold may dissolve in the electrolyte in the reaction Au Au+3 + 3e-. The reaction will
continue until equilibrium is reached. This is shown in Figure 9.
Figure 9: Equilibrium (External Wire Detached)

Now lets look at what happens when the external wire is reconnected to the iron
electrode. The free electrons produced by the oxidation of the iron electrode will travel
around the external circuit and be dumped at the gold electrode upsetting our
equilibrium teeter totter (see Figure 10). If we apply Le Chateliers principle to Figure
10, well see that the reaction must shift to the left to restore balance or equilibrium in
our upset system. There is very little Au+3 in solution to begin with because gold is so
noble. What little there is will be quickly inundated by a continuous flow of electrons and
be reduced back to solid gold deposited on the gold electrode. Bottom line is that the
oxidation of the iron supplies electrons to the gold electrode that will completely
suppress the gold being oxidized. In our cell the iron electrode corrodes (is oxidized)
while the gold electrode does not.
If there is only a miniscule amount of gold going into solution, it should only take a small
number of iron atoms to go into solution to totally suppress the corrosion of the gold.
Yet when the iron electrode is connected to the gold electrode, corrosion at the iron
electrode is accelerated. Whats going on here? Theres something very ugly going on

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in the electrolyte surrounding the gold electrode (the cathode of our cell). Our gold
electrode is covered with bubbles: hydrogen gas. Remember our Chemistry 101 lesson
when we talked about how a small quantity of water dissociates at room temperature in
the reaction H2O H+ + OH-. Some of the hydrogen ions that are produced will react
with the extra electrons being dumped on the surface of the gold cathode to form
hydrogen gas. This is a two-step process as shown by the following:
1. H+ + e- H (atomic hydrogen)
2. H + H H2 (hydrogen gas)
The second step is the rate controlling step for hydrogen gas formation. Hydrogen is
bad news for a lot of different reasons, but for now well focus just on its effect on the
corrosion that takes place at iron anode.
Figure 10: Non-Equilibrium - Equilibrium is out of whack when the external wire is
connected and electrons flow to the cathode from the external circuit.
Iron may go into solution as either a ferrous or ferric ion. From Table 1 the electrode
potential for Fe Fe+2 + 2e- is -0.440 volt and for Fe Fe+3 + 3e- is -0.045 volt. The
majority of the iron will thus go into solution as the ferric ion (Fe+ 3) because of its more
negative electrode potential. Lets disconnect the external wire from our Fe electrode for
a moment. Some of the iron will dissolve and go into solution until the surrounding
electrolyte because saturated and equilibrium is reached as shown in Figure 11. Now if
we reattach the wire, the free electrons produced when the Fe goes into solution will
travel through the outside circuit to the gold electrode where they will be consumed in
the reaction H+ + e- H (atomic hydrogen). Our system is out of whack again (see
Figure 12).

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Figure 11: Equilibrium (Wire Disconnected)
Figure 12: Out of Whack (Wire Connected)

Again if we apply Le Chateliers principle, then it becomes apparent that more iron must
corrode in order to make up the loss of electrons at the cathode and restore equilibrium.
The number of Au+3 ions being reduced at the cathode is inconsequential. The
reduction of the H+ ions at the cathode is the greatest sink for the free electrons being
produced by the corroding iron and is the reason why the corrosion of the iron
accelerates when connected to the gold electrode. Some of the H+ ions are charged
electrostatically into the cathode. Others will be reduced to form monoatomic hydrogen.
The individual hydrogen atoms that form may then agglomerate and form H 2 gas in the
form of bubbles on the cathode surface. This is a rather slow reaction involving the
diffusion of hydrogen atoms. The hydrogen gas bubbles at the cathode will eventually
break free from the surface and be lost to the atmosphere. Le Chateliers principle tells
us that more water must dissociate in the reaction H2O H+ + OH- to make up the loss

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of the H+ ions at the cathode. Note that this also increases the OH- concentration
surrounding the cathode thus raising the pH.
Theres plenty going on at the anode of our cell! The OH - ions will combine with Fe+2
and Fe+3 ions to form Fe(OH)2 and Fe(OH)3. The formation of these compounds
effectively removes the OH-, Fe+2, and Fe+3 ions from our solution. Our good friend Le
Chatelier says more iron must corrode to make up the loss of the ferrous and ferric
ions, and that more water must dissociate to make up the loss of the OH- .
By connecting our iron electrode to a gold electrode via an external circuit in a
deaerated electrolyte, we increased the corrosion rate of the iron. But because the
formation of hydrogen gas from monoatomic hydrogen is slow, the corrosion rate of our
iron electrode is still not very fast. There are a chain of reactions that must occur for the
iron electrode to corrode and the overall corrosion rate can only go as fast as the
slowest reaction in that chain. We have already described the corrosion of iron to form
rust as:
4Fe + 3O2 + 6H2O 4Fe(OH)3 or rust

Weve talked about two of the three things necessary for rust to form: iron and water.
Its time to talk about the third necessary ingredient - oxygen. We examined the
simplified case of an iron and gold electrode in a deaerated (oxygen free) electrolyte
solution. Now lets add oxygen to our cell and see what transpires. One of the new
reactions that will occur near the cathode is O 2 + 4H+ + 4e- 2H2O. Here oxygen
combines with the hydrogen ions and free electrons from the corroding iron to form
water. This very rapid reaction is much more efficient in removing hydrogen and
electrons than the two-step cathodic reactions that produce hydrogen gas. As a
consequence corrosion at the iron anode is greatly accelerated as more iron must go
into solution to make up the loss of electrons at the cathode. The slow, hydrogen gas
formation reaction in the deaerated electrolyte was the rate controlling step for
corrosion. By adding oxygen to our cell, we have by passed it and allowed corrosion to
take off!
Another new cathodic reaction is O2 + 2H2O + 4e- 4OH-. Again more free electrons
are lost so that more iron must go into solution to replace them. The hydroxyl ions (OH-)
will be attracted to the anode where they will combine with Fe +2 ions to form Fe(OH)2.
The Fe(OH)2 , in turn, may react with water and oxygen to form Fe(OH)3.These
reactions effectively remove the iron ions from our system. Le Chateliers principle now
requires that more iron must corrode to make up their loss. Things are starting to
snowball! Clearly oxygen is bad news when it comes to the corrosion of iron. The major
reactions occurring in our aerated (containing oxygen) cell is summarized below.

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Anodic Reactions Occurring at the Iron Electrode:
Fe Fe+2 + 2eFe+2 + 2(0H-) Fe(OH)2

4Fe(OH)2 + 2H2O + O2 4Fe(OH)3
Cathodic Reactions Occurring at the Gold Electrode
2H+ +2e- H2
4H+ +O2 +4e- 2H20
O2 + 2H2O + 4e- 4OHWell we have beat Le Chateliers principle to a pulp in this section, but you can see how
useful it is in explaining whats going on in a galvanic cell. Its relatively easy to apply
the teeter totter principle to the above reactions and explain why corrosion of the iron
sky rockets when oxygen is introduced into our cell. We examined a cell with iron and
gold electrodes, but the principles are the same for other combinations of metals. The
metal with the more negative potential in the EMF table is more easily oxidized and will
become the anode. Oxidation (corrosion) takes place at the anode. The metal with the
more positive potential in the EMF table is more noble (less easily oxidized) and will
become the cathode of our galvanic cell. Reduction takes place at the cathode. The
greater the difference in electrode potentials between the anode and cathode, the
greater the driving force for corrosion at the anode. Conversely, the smaller the
difference, the lower the driving force. If the driving force is insignificant in a given
environment, then that combination of metals is said to be compatible in that
environment.
Other Types of Galvanic Cells

The Fe-Au dissimilar metal cell we just talked about is an example of composition
galvanic cell. A composition galvanic cell consists of two different types of metals in
electrical contact and immersed in an electrolyte. Composition galvanic cells may
become established on the surface of a metal part if there is enough variation in the
local composition. For example duplex stainless steels have a microstructure consisting
of roughly equal amount of ferrite and austenite. The austenite and ferrite phases have
significantly different compositions. In some environments, the ferrite phase will
become the anode of a galvanic cell and preferentially corrode.
Another type of galvanic cell is called the stress cell. If you have ever visited a pipe yard
you may have noticed that the pipe threads tend to corrode faster than the non-

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machined pipe surfaces. This is because the threads contain residual stresses from the
threading operation. They will have a higher electrode potential than an unstressed
areas of the pipe. The cold work imparted during the cutting of the threads raises the
internal energy of the atoms in the metals crystal structure at that location. It thus takes
less additional energy to overcome the cohesive forces bonding them together and to
remove them from the surface of the metal.
Concentration cells are another important type of galvanic cell. The electrode potential
of a metal will vary with the concentration of the electrolyte (the corrosive medium).
When the surface of a metal part is exposed to different concentrations of the same
electrolyte, the areas exposed to the weaker or dilute solution will become anodic to
those exposed to the more concentrated solution. The areas exposed to the weaker
solution will thus corrode. This seems counterintuitive, but can easily be explained by
our old friend (you guessed it!) Le Chateliers principle and by examining the workings
of a copper/copper sulfate concentration cell (see Figure 13).
Figure 13: The Copper/Copper Sulfate Cell
A copper/copper sulfate concentration cell consists of two identical copper electrodes

that are connected via an external circuit and are immersed in copper sulfate (CuSO4)

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solutions of different strengths. The copper sulfate salt dissociates into Cu+2 and SO4-2
ions forming the electrolyte. The cell itself is divided in two by a semi-permeable
membrane that allows the flow of current. One side of the cell has a dilute solution of
copper sulfate while the other is concentrated. The copper will corrode or go into
solution until equilibrium is reached according to Cu Cu+2 + 2e-. The dearth of copper
ions in the dilute side will shift the equilibrium point of this reaction to the right. The
abundance of copper ions in the concentrated side will shift it to the left. The copper
electrode in the dilute solution will have to corrode to provide more Cu+2 ions and thus
become the anode. The electrons freed up by oxidation taking place at the anode travel
via the external circuit to the copper electrode in the concentrated solution. Here they
combine (reduce) some of the Cu+2 ions which then plate out on the electrode as
metallic copper.
A very special type of concentration cell of paramount importance to Oil Patch
engineers is the oxygen concentration cell. This is illustrated in Figure 14 where two
identical iron electrodes are immersed in an electrolyte in a galvanic cell. The cell is
divided in two by a semi-permeable membrane. Oxygen is bubbled under one of the
electrodes creating an oxygen rich environment in that side of the cell. Which electrode
will become the anode?
Figure 14: Oxygen Concentration Cell

After our discussion of how the presence of oxygen speeds up the corrosion of iron,
youd probably guess the oxygen rich side, but youd guess wrong! The electrode in the

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oxygen poor side will become the anode. This seems counterintuitive, but Le Chateliers
principle will once again come to our rescue and help us solve this conundrum. One of
the cathodic reactions that we examined was O2 + 2H2O + 4e- 4OH-. By adding more
oxygen to the electrode where this reaction is occurring (the cathode), we move the
equilibrium point in favor of the OH-. As we produce more hydroxyl ions, we use up
some of the free electrons supplied by the anode. The anode must make up this loss by
corroding faster and producing more electrons. The electrode in the high oxygen
electrolyte is thus the cathode and the electrode in the low oxygen electrolyte is the
anode. Oxygen concentration cells are responsible for a great deal of corrosion damage
on our type of equipment. They can form wherever there is a crevice, a pit, overlapping
surfaces, etc. where oxygen can be depleted through corrosion reactions, but cannot
easily be replenished. Lets look at some examples.
Consider a threaded steel pipe connection subsea. Water will seep in between the
threads and cause some corrosion. This depletes the water of oxygen. Seawater
cannot easily flow into the joint and replenish the oxygen. The pipe surfaces just
outside the joint will constantly be swept by seawater that is well oxygenated. The
threaded area will become the anode of an oxygen concentration cell while the
surrounding surfaces of the pipe will be the cathode. Because the exposed surface of
the pipe is so much greater than the threaded area, corrosion of the threads will be very
rapid.
An open storage tank partially filled with water will corrode just below the water line. The
area immediately adjacent to the water line will be rich in oxygen while the area just
below will be poor in oxygen. Corrosion will result in a ring of lost metal just below the
surface.
Mill scale or any type of partial surface deposit on a steel pipe may result in the creation
of an oxygen concentration cell. The bare surface of the pipe will be well oxygenated
while the area underneath the scale or deposit will be oxygen poor and become the
anode. If the scale or deposit is relatively isolated, then the cathode-to-anode surface
area ratio may be quite large. This may result in the formation of a pit underneath the
scale or deposit that may rapidly perforate the pipe.
The final type of galvanic cell is known as a differential temperature cell. Here the
anode and cathode consist of the same type of metal, but are exposed to different
temperatures. They may be on the same part or on different parts that are immersed in
the same electrolyte. Not all metals behave the same way in a differential temperature
cell. Copper and lead, for example, will corrode at the lower temperature while the area
at the higher temperature will be the cathode. The copper or lead will dissolve at the low
temperature and then deposit on the surfaces at the higher temperature. For silver, the
situation is reversed: the area exposed to the high temperature is the anode and to the
low temperature the cathode. Steels in dilute, oxygenated chloride solutions will
generally have the anode in the warmer temperature electrolyte and the cathode at the

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lower, but the polarity may reverse as the reaction progresses depending on a number
of other factors including the amount of oxygen available, the velocity of the electrolyte,
etc.
Differential temperature cells are generally not a problem for our type of equipment
because a substantial difference in temperature must exist between the inlet and outlet
surfaces of the equipment exposed to the same electrolyte for differential temperature
cell corrosion to be significant. It is most often encountered in heat exchangers, boilers,
etc.
This completes our survey of galvanic cells. The corrosion that actually takes place on a
part is often the result of a combination of different types of galvanic cells. For example,
suppose a stainless steel part is set on a pallet and a carbon steel shaving gets
embedded in its surface. When the part is placed in service and is exposed to seawater, the carbon steel will become the anode of a dissimilar metal (composition) cell. It
will rapidly corrode leaving a pit at the surface. This in turn may create the conditions
ripe for an oxygen concentration cell. As the pit grows, the composition of the
electrolyte within the pit may change from the surrounding seawater and create
additional concentration cells within the pit. Corrosion is a complex business!
Corrosion Kinetics
The information presented in the EMF table was very useful in determining the ease
with which a metal can be oxidized. It allowed us to predict which metal in a dissimilar
metal cell would become the anode. Looking at gold, platinum, palladium, and silver in
the table we see theyre all at the bottom (have the highest positive electrode potential)
and therefore are very noble (not likely to corrode). This fits well with our common
experience with these metals. Now look at aluminum. At -1.66 volt for its standard
electrode potential its relatively high up the table so its easily oxidized, yet we use
aluminum for pots and pans for cooking, for boats, etc. because of its good corrosion
resistance! Whats going on here? Well it turns out that easily oxidized doesnt
necessarily equate to a high corrosion rate. Kinetics is the study of the rate of chemical
reactions. In the case of aluminum, the surface of the aluminum is very easily oxidized
by reacting with oxygen, but the oxide forms a tenacious, continuous, impervious film
on the surface of the part. This is aluminums armor: it isolates the rest of the aluminum
for the corrosive environment. Yes, the aluminum was easily oxidized as predicted by
the EMF table, but the EMF table couldnt predict that the rate of corrosion would be
very low because of the protective oxide layer that formed. The EMF table has limited
use in predicting the actual amount of corrosion that will occur in a given environment
because it doesnt consider the kinetics of corrosion. In this section well examine some
of the important factors that do determine the nature of the corrosion and how fast it
may occur.

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Consider the copper/copper sulfate concentration cell that we talked about earlier (refer
back to Figure 13). This consisted of two identical copper electrodes immersed in
electrolytes of different concentrations of copper sulfate. We used Le Chateliers rule to
show that the electrode in the weak solution became the anode and corroded, while the
electrode in the concentrated solution became the cathode and had additional copper
plate out on it. The initial driving force for this reaction may be quite strong, but what
happens over a period of time? In our closed system, the weak solution is becoming
richer and richer in Cu+2 ions as the anode corrodes. The concentrated solution, on the
other hand, is getting weaker and weaker as copper ions are reduced and plate out on
the cathode. You can see where this is going. The difference in electrode potential
(voltage) between the two copper electrodes becomes less and less as the
concentration of the copper ions in the electrolytes begin to approach each other.
Eventually the corrosion will stop and equilibrium will be reached. The cell has become
polarized.
Polarization is the voltage drop in an electrochemical cell caused by the continuous
operation of the cell. It is a measure of how the rates of reactions at the anode and
cathode are slowed down by various environmental factors such as changes in metal
ion concentration, oxygen content, etc. or by surface process factors such as
absorption, film formation, etc. Concentration polarization typically occurs at the
cathode because of a lack of reactants immediately adjacent to the surface where there
is a gradient in the ion concentration in the electrolyte. As the ions are used up in
chemical reactions at the cathode, they must be made up by additional ions diffusing
through the depleted layer. This diffusion becomes the rate controlling step for
corrosion. Activation polarization typically occurs when a surface film is formed on the
anode or cathode. This makes it more difficult for ions in the electrolyte to reach the
electrodes surface effectively isolating it from the environment. The film formation may
involve a series of reactions; the slowest of which will be the rate controlling step.
Hydrogen formation at the cathode of our Fe-Au dissimilar metal cell is an example of
activation polarization. As previously mentioned it is a two-step process with hydrogen
ions first being reduced and then combining to form hydrogen gas. As the hydrogen
atoms are formed they blanket the surface of the cathode making it more difficult for
ions to reach the surface. The rate controlling step is the formation of H 2 gas. This is a
relatively slow process: If it were rapid the adsorbed hydrogen atoms on the surface
would quickly form hydrogen gas bubbles and be lost to the atmosphere. They would
not accumulate and form a protective shield. Another important example of activation
polarization is the calcareous deposit that forms when we cathodically protect a steel
structure in seawater. Well discuss this in detail in the training module on Marine
Corrosion.
We introduced this section by describing how a protective oxide layer forms on
aluminum in many environments. Aluminum has a strong tendency to oxidize as

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evidence by its position in the EMF table, but this does not necessarily equate to a high
corrosion rate. Metals that have the ability to form corrosion products that tightly adhere
to their surface and form a permanent, impervious barrier to the surrounding
environment are said to have been passivated. While this protective layer may not
entirely prevent further corrosion, it will greatly retard its rate. We use many corrosion
resistant alloys or CRAs in the Oil Patch the majority of which are in the passive
condition because of a protective surface layer of corrosion products (typically an
oxide). These include stainless steels, titanium alloys, aluminum alloys, and nickel base
alloys. In environments where the protective surface layer cannot form, the metal may
be in the active state or condition and freely corrode.
Clearly there are some shortcomings in trying to use the EMF table to predict if
significant corrosion will occur. It does not take into account passivity. Depending on the
environment (the corrosive media), electrode potentials will change and the relative
positions of the metals within the table may change. The galvanic series was developed
to overcome these shortcomings. A galvanic series is a list of metals in order of their
tendency to oxidize in comparison to a standard calomel electrode (SCE) in a specific
environment at a given set of conditions (temperature, etc.). Table 2 shows the galvanic
series for seawater at ambient temperatures. Metals high in the table are anodic to
those below them. If a metal A is coupled to a different metal B that is lower in the table
and immersed in seawater, metal A will become the anode and may corrode. The
farther apart the metals are in the table, the greater the driving force for corrosion. If the
difference is in hundreds of millivolts, galvanic corrosion may be severe. If the
difference is in tens of millivolts, corrosion will probably not be an issue and the metals
are compatible.
You will note in Table 2 that some metals are listed twice: once in the active condition
and then again in the passive. It can make a big difference! The metal may switch from
active to passive or passive to active depending on changing environmental conditions.
It is important to know what types of environments are conducive to promoting the
passive condition and which environments may attack and breach the protective
surface layer and lead to active corrosion. Many of the alloys we use depend upon a
protective oxide surface film. The film is attacked by halide ions with chlorides being the
worst offenders because they are so common in Oil Patch environments. Many CRAs
are carefully alloyed to strengthen this film and make it more resistant to halide attack.
Increased chromium, nitrogen, and especially molybdenum are often used for this
purpose.
Just because a metal is high up in Table 2 does not mean it will corrode rapidly in
seawater. It must be coupled to another metal lower in the table for a galvanic corrosion
to occur. Aluminum, for example is used in making Navy ship boat hulls that are quite
resistant to corrosion in seawater. The relative sizes (surface areas) of the anode and
cathode play a significant role in the anodes corrosion rate. The greater the cathode-toanode size ratio, the more accelerated anode corrosion becomes. The larger cathode

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area acts as a bigger sink for the free electrons given up from the anode as it corrodes.
Our teeter totter can only be balanced if the anode corrodes faster in order to supply
more electrons. If the anode is much greater in surface area than the cathode, the
amount of corrosion that occurs per unit area is greatly reduced.
Table 2
Galvanic Series in Seawater
At Ambient Temperatures
Anodic
Cathodic
Magnesium
Magnesium Alloys
Zinc
Beryllium
Aluminum
Cadmium
Carbon Steel
Cast Iron
12 14% Chromium Stainless Steel (Active)
Ni Resist
8% Nickel, 18% Chromium Stainless Steel (Active)
Lead
Tin
Naval Brass
Nickel (Active)
Inconel (Active)
Silicon Bronze
Nickel (Passive)
Inconel (Passive)
Monel
12 14% Chromium Stainless Steel (Passive)
8% Nickel, 18% Chromium Stainless Steel (Passive)
Silver
Titanium
Platinum
Graphite

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In an electrochemical cell, current flows from the anode to the cathode via the external
circuit and then back to the anode through the electrolyte. There is a voltage drop
associated with the current flow through the electrolyte. Ohms law states that the
current through a conductor between two points is directly proportional to the potential
difference across the two points or V=IR where V is volts, I is the current in amperes,
and R is the resistance in ohms. The resistance of the electrolyte to our corrosion
current is dependent on several factors. It is of course strongly dependent on the
concentration of the ions that make it conductive. The resistance of the electrolyte is
also a function of the distance between the anode and the cathode the farther apart
they are, the greater the resistance. The larger the subsequent voltage drop, or IR drop
as it is typically called, between the anode and cathode, the lower driving force for
corrosion. The bottom line for all this is that an anode/cathode combination in a given
electrolyte will undergo less corrosion if they are farther apart than if they are closer
together.
Temperature plays a critical role in establishing corrosion rates. For most corrosive
processes that affect our equipment, the higher the temperature, the greater the rate of
corrosion, but there are some exceptions. You may remember the old rule of thumb
from Chemistry 101 that the rate of a chemical reaction approximately doubles for every
10oC rise in temperature. This certainly will speed up corrosion reactions at the anode
and cathode, but there are some mitigating effects that may occur. The solubility of
gases that impact corrosion (such as oxygen) becomes less in water as temperature
increases. Protective scales may form on a metals surface as the temperature is raised
that will greatly reduce the rate of corrosion.
In the electrochemical cells weve examined so far the electrolyte is stationary. In real
life the electrolyte can flow relative to a metals surface. Does this impact the corrosion
rate? You bet it does! But its effect is a mixed bag. Sometimes it will increase corrosion;
sometimes it will reduce corrosion depending on circumstances and the metals
involved.
Concentration cells that form pits on steel in seawater, for example, will grow more
rapidly in stagnant water than in flowing seawater. Flowing seawater tends to flush out
the pits and prevent a concentration gradient from getting established thus reducing the
rate of corrosion. On the other hand, a flowing electrolyte may increase corrosion
through several different mechanisms. It may erode off protective scale or adherent
corrosion products thus exposing fresh metal to corrode. It will reduce concentration
polarization by reducing the thickness of the depleted boundary layer through which
ions must diffuse to reach the surface of the metal. And finally a flowing electrolyte with
a low concentration of a corrodent (a corrosive substance) may actually deliver more of
that corrodent to the surface of a metal than a stagnant electrolyte rich in that
corrodent. There are other important velocity effects as well that well discuss in the
training module on Wellhead Corrosion.

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Types of Corrosion Damage

In this section well do a survey of the different forms or types of corrosion damage that
may occur on our type of equipment. There may be several forms of corrosion going on
simultaneously on a metal part. Not all forms of corrosion will result in a physical loss of
metal (or weight loss corrosion). In certain environments, some metals may become
embrittled and crack at tensile loads well under their yield strength with no weight loss
whatsoever.
1. Uniform Attack
As the name suggests, uniform attack is general weight loss type of corrosion where
the metal weight loss occurs evenly over the corroding surface (see Figure 15). There
are many tables available that give the uniform corrosion rates of different metals in
different environments. The information is generally presented in terms of either mils of
metal lost per year or weight loss per unit area per year. Use these numbers with
caution! The corrosion rates are generally highest in the first couple of years then taper
down. The information presented may be an average rate for a period of years.
Localized corrosion (see the sections on pitting and crevice corrosion below) may occur
far faster than an average general corrosion rate.
Figure 15: Uniform Corrosion

2. Pitting
Stainless steels and other alloys that rely on a passive oxide film to impart corrosion
resistance are especially prone to a type of corrosion in the presence of a halide

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solutions (such as seawater) known as pitting. Pitting is a very localized form of

corrosion that initiates where the passive film is damaged chemically, electrochemically,
or mechanically thus exposing the underlying metal. Pits may start where dislocations
reach the surface, where second phases (non-metallic inclusions, embedded metallic
particles, microsegregration, etc.) emerge on the surface, or where there are scratches
or other type of damage leaving a low spot on the surface. These initiation points are
anodic to the remaining portions of the surface. Lets look at pit growth in a stainless
steel immersed in seawater (see Figure 16).
Figure 16: Pitting
Assume the protective oxide layer in our stainless steel is breached by the chloride ions
in the seawater at a given point exposing the underlying base metal. The base metal
exposed at this point is now no longer in the passive, but in the active condition and
starts to corrode. Dissolved oxygen in the seawater will try to repassivate or repair the
breach, but the high corrosion current density may prevent the healing of the wound.
The current density is high because of the very large cathode-to-anode surface area
ratio (the area of the pit is a very small fraction of the total surface area).

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Inside the pit the iron will go into solution as Fe Fe+2 + 2e-. The free electrons that
are produced travel to the passivated surface of the part where they react with oxygen
and water in the cathodic reaction O2 + 2H2O + 4e- 4OH-. The surface of the part
will become increasing more negative. The environment within the pit becomes
increasingly more positive as positive ferrous ions are produced as iron atoms go into
solution. Negatively charged chloride ions in the seawater are attracted to the positively
charged iron ions in the pit. The two ions will meet and react with water in the reaction
FeCl2 + 2H2O Fe(OH)2 + 2HCl. The Fe(OH)2 deposits on the surface of the passive
area surrounding the mouth of the pit and begins to cap it off. It will eventually be
oxidized to Fe(OH)3. This deposit restricts the flow of the external seawater into the pit.
Note that HCl, a strong acid, is produced by this reaction. This accumulates in the pit
lowering the pH. The now acidified environment in the pit greatly increases the
corrosion rate. Oxygen is depleted in the pit during the corrosion process and the
restricted opening at the mouth of the pit prevents seawater from replenishing it so an
oxygen concentration cell is set up. Now we have the perfect storm!
Pitting is very insidious form of corrosion. A pit grows very rapidly. Most metal loss will
occur at the bottom of the pit. The rate of corrosion in a pit cannot be predicted from a
table giving general corrosion rates. A pit may initiate and grow and eventually perforate
a part long before any significant general corrosion occurs. Whether or not a given alloy
with a passivated surface will pit in a chloride solution is very dependent on the
concentration of the chlorides and the temperature. In a given environment, these
alloys may have a critical pitting temperature (or CPT) below which the passivated layer
will remain intact and pitting will not occur. ASTM G48 prescribes standardized test
methods for determining the CPT of alloys in a ferric chloride solution.
3. Crevice Corrosion
Crevice corrosion is corrosion that occurs in a confined space (or crevice) in a single
part or between two parts that is exposed to an electrolyte, but with restricted access.
Faying surfaces, inside cracks or seams, underneath gaskets or seals, between bolt
and nut threads, under the heads of rivets; areas where the gap is broad enough to
allow corrodent in, but narrow enough to make it stagnant are all prone to crevice
corrosion. The mechanism for crevice corrosion is very similar to that of pitting. The
stagnant electrolyte within the crevice becomes more positive as metal ions corrode. In
seawater this attracts and concentrates negative ions (such as Cl - in seawater) from the
surrounding electrolyte. This allows the formation of hydrochloric acid within the crevice
lowering the pH to as low as 1-3. Oxygen is depleted within the crevice and not easily
replaced so an oxygen concentration is established. The inside of the crevice is anodic
to the much larger surface are outside the crevice so corrosion becomes very rapid.
Dissimilar metal galvanic corrosion may play a role in crevice corrosion when the
crevice is between two different types of metal. Crevice corrosion may occur between a
metal and a non-metal part (for example, between a pump shaft and a plastic packing).

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Like pitting, crevice corrosion is very insidious. There may be severe crevice corrosion
occurring on a part or assembly with little evidence of general weight loss (uniform)
corrosion. The rate of corrosion in a crevice cannot be predicted from a table giving
general corrosion rates. Whether or not crevice corrosion will occur on a part or in
between parts in an assembly is very much dependent on geometric factors. A small
gap of only a few microns is ideal to initiate crevice corrosion, but wider gaps can also
be problematic if the starting crevice is deep thus restricting the flow of electrolyte into
the gap. Flowing electrolyte can reduce the tendency for both pitting and crevice
corrosion by constantly sweeping out the electrolyte in these confined spaces so
concentration gradients cannot form. Metals in a particular environment may have a
critical crevice temperature (or CCT) below which crevice corrosion will not occur.
ASTM G48 also prescribes standardized test methods for determining the CCT (in
addition to the CPT) of alloys in a ferric chloride solution.
Designers can do much to prevent crevice corrosion from occurring. Eliminate gaps
altogether between mating parts by welding rather than bolting together. Seal weld gaps
to prevent the electrolyte from entering. Go to higher alloyed metals that have a more
stable film (a higher CCT) in a given environment. Coat the parts so that the coating
material fills or seals off the gaps and blocks the entry of the electrolyte altogether.
Cathodic protection (C/P) can effectively prevent both pitting and crevice corrosion of
parts subsea, but careful attention to the C/P design parameters is required. It requires
a higher current density to prevent pitting and crevice corrosion in a CRA than it does to
prevent general weight loss corrosion.
4. Intergranular Attack (IGA)

Intergranular attack is corrosion that preferentially occurs at a metals grain boundaries
(see Figure 17). It may severely decrease a metals strength and ductility. Grain
boundaries are anodic to the surrounding metal and preferentially corrode for several
possible reasons. First is that grain boundaries have inherently higher internal energy
associated with them. This may allow a stress cell to become established. Another
possible reason is the metal immediately adjacent to a grain boundary may have a
different composition than the bulk of the metal thus allowing a composition cell to
become established. The volume of grain boundaries is very small in comparison to the
bulk of the metal. The cathode-to-anode ratio is thus very large and rapid corrosion may
take place.
Many corrosion resistant alloys (CRAs) rely on a passive chromium oxide layer to
isolate them from the corrosive environment. Chromium has a strong affinity for carbon
within a certain temperature range (about 800-1600F) where it will combine with the
carbon and form a chromium carbide (often a M23C6 type carbide). Thus a single
carbon atom can tie up almost four chromium atoms. These carbides typically

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precipitate along grain boundaries denuding the areas adjacent to the grain boundaries
of their chromium. When this has occurred, the metal is said to have been sensitized
(see Figure 18). If a sensitized CRA is exposed to an electrolyte, rapid IGA may occur
because the denuded areas along the grain boundaries are anodic to the bulk of the
metal.
Figure 17: Intergranular Attack or IGA

(From Wikipedia - http://en.wikipedia.org/wiki/Intergranular_corrosion)
The precipitation of carbides is time-temperature dependent. Sensitization is only a
problem if the cumulative time within the offending temperature range from all thermal
cycles is sufficient to precipitate enough carbides to significantly alter the electrode
potential of the chromium denuded areas. It is impossible to avoid going through the
precipitating temperature range during heat treatment, but the damage can be
minimized by passing through the range as quickly as possible. This is why CRAs are
typically water quenched after solution annealing. Sensitization effects are cumulative.
The total time within the precipitation range must be considered including cool down
from solution annealing, welding, stress relieving, etc.
Curves that show when sensitization reaches an unacceptable degree as a function of
time and temperature are available for a variety of CRAs. Figure 19 is one for austenitic
stainless steels such as 316. Note that there are several curves shown in the figure
based upon the carbon content of the steel. All steels, including stainless steels, have
some amount of carbon in them. As can be seen in Figure 19, the lower the amount of
carbon, the longer the metal must remain within the carbide precipitation temperature
range before sensitization becomes a problem. 316 stainless steel may have up to
0.08% carbon. At this carbon content, we have less than a minute to cool through the

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sensitizing range making all but the thinnest 316 part impossible to heat treat or weld
without getting some sensitization. If we reduce the carbon level to 0.03% maximum,
we have increased our time allowed time before sensitization becomes a problem to
about 10 hours. This gives us plenty of time to cool parts down from solution annealing
temperatures or to weld them without worrying about sensitization.
Figure 18: Sensitized Metal

(From Wikipedia:http://en.wikipedia.org/wiki/Intergranular_corrosion)

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Figure 19: Time-Temperature Sensitization Curves for Austenitic Stainless Steels

The L grades of stainless steels (e.g. 316L, 304L, 317L) restrict carbon to 0.03%
maximum to allow for greater processing time within the sensitizing temperature range.
The down side of restricting carbon is that the lower carbon content of the L grades
typically results in a slightly lower yield strength especially in large parts.
Another way to prevent sensitization is by tying up the carbon with another element that
forms a high temperature carbide that is stable so that the carbon is no longer free to
combine with the chromium within the sensitizing temperature zone. This is the basis
for the stabilized grades, such as 321 (stabilized with titanium) and 347 (stabilized with
columbium and tantalum). Even stabilized grades may undergo a localized form of IGA
called knife line attack when welded. Metal immediately adjacent to the weld pool will
be heated up well above the dissolution temperature of the titanium, columbium, or
tantalum carbides putting them all back into solution. This area cools very rapidly after
the weld torch has passed by and carbides of any sort may not have time to precipitate
out. As a consequence, at room temperature there will be a lot of free carbon available.
When the welding torch passes by again for the second bead, the carbon rich area gets
reheated. If this narrow area gets heated into the temperature range of about 10001450F, chromium carbides can precipitate out faster than the titanium, columbium, or
tantalum carbides. Corrosion may then occur intergranularly in along a narrow plane
adjacent to the weld. This is known as knife line attack. It can be minimized or
prevented by the selection proper welding parameters. Alternatively the entire welded

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structure can be resolution annealed to put any chromium carbides back into solution
and allow the stabilized carbides to form during subsequent cooling.
5. Selective Leaching (Dealloying)

Selective leaching, or dealloying as it is sometimes called, is the preferential removal of
one or more of the alloying elements in a metal alloy through corrosion. The
dezincification of brass (a copper-zinc alloy) in seawater is the most widely known
example. Apparently the mechanism causing it is not just dissimilar metal galvanic
corrosion on a microscale because both the copper and zinc corrode and go into
solution. The zinc stays in solution, but the copper, the more noble metal, precipitates
out at the surface. This results in a spongy, porous mass of copper with some copper
oxides that may maintain the original shape of the part (which may appear to be
undamaged), but has greatly reduced strength and ductility. Dont be fooled by the
name naval brass. This copper-zinc alloy, used for centuries for top side equipment on
ships will rapidly undergo dealloying if immersed in seawater. Selective leaching may
occur uniformly on the surface of a part, or in a localized area. The latter is often called
plug selective leaching.
Certain bronze alloys are notorious for dealloying in seawater. There are many types of
bronzes and some are relatively immune to dealloying, while others dealloy rapidly.
Know which ones youre dealing with! Sometimes certain bronze alloys can be made
much less susceptible to dealloying through stabilizing heat treatments. Here are some
families of bronzes that may be subject to selective leaching:
Aluminum bronzes loss of aluminum (dealuminification)

Tin bronzes loss of tin (destannification)
Silicon bronzes loss of silicon (desiliconification)
Nickel aluminum bronzes have good resistance to dealloying if properly heat treated.
The element that is preferentially removed in dealloying may change depending on the
environment. The Monels for example, are alloys of about 60% nickel, 30%, and a
few other elements depending on the specific alloy. In some acid solutions the copper
will be selectively removed; and in other its the nickel that is removed.
6. Corrosion-Erosion
Corrosion-erosion (or erosion-corrosion if you prefer) is the removal of material through
the combined effects of erosion and corrosion. The removal rate is much higher than
would be expected from the simple addition of the effects of corrosion or erosion acting

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in isolation. Erosion is the loss of metal due to abrasion or impingement of a moving

fluid. The fluid may or may not have entrained particulate matter in it. It can greatly
accelerate corrosion by stripping away or otherwise damaging protective adhesive films
(scale deposits for instance) or passive films (the oxide layer on stainless steel for
example) and thus continuously expose fresh metal to the electrolyte.
Sand is the biggest trouble maker in fluids coming out of wells. Sharp sand is very
effective in exposing fresh meat for the grinder as it strips away protective films and
removes the underlying metal through a cutting action. Alloys normally totally corrosion
resistant in a given environment may suffer severe weight loss corrosion in a short
period of time when their surfaces are scoured by sand moving in a high velocity fluid.
Corrosion-erosion may be fairly uniform along straight runs, but is typically much more
severe when the fluid is impinging directly onto a metals surface (at a tee or an elbow,
for instance). Particulate matter need not be present in the fluid, although it certainly will
make matters worse: high velocity liquids or gases by themselves can be very abrasive.
7. Corrosion Fatigue
Fatigue is the failure of a metal part under a cyclic load. The nominal load is lower than
the materials ultimate tensile strength and may be lower than its yield strength.
Corrosion fatigue is failure of a metal part through a combined action of fatigue and
corrosion in a specific environment. Metals that fail because of corrosion fatigue do so
at a lower number of cycles or at a lower stress per cycle than the same metal failing by
strictly mechanical fatigue in a benign environment such as air. Many metals are
subject to corrosion fatigue in seawater. Unprotected steel parts, for example, may
have a 50% or more reduction in fatigue life at a given load in seawater.
Cyclic loading in service may be due to vortex induced vibration, thermal cycles,
pressure pulses, etc. The number of cycles that a given part can withstand before
fracture is dependent on the amplitude of the applied stress (the difference between the
maximum and minimum stresses for each cycle) and the average stress. Higher
amplitude requires fewer cycles to failure. As the average or mean stress becomes
increasingly tensile, the smaller the amplitude has to be to maintain the same number
of cycles to failure.
Fatigue is a three stage process:

1. Crack Initiation - Localized strain in a metal is not completely reversible when a load
is reversed or removed. The stress around a microscopic imperfection may be

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considerably higher than the overall stress that the part sees and results in permanent
strain adjacent to the imperfection. As the part is repeatedly loaded, localized strains
around the imperfection will accumulate until a crack forms. Typically the crack initiation
stage takes up about 90% of a parts fatigue life. This is short circuited in corrosion
fatigue where pitting or other forms of corrosion facilitate crack initiation so that this
stage is only about 10% of the total fatigue life.
2. Crack Propagation The newly formed cracks grow larger in a direction normal to
the maximum tensile stress as the cyclic loading causes the material adjacent to the
crack tip to work harden. In corrosion fatigue, the corrosive media interacts with the
material at the crack tip allowing greater growth per cycle at a given load and hence
fewer cycles to failure. Similarly, the allowable load for a given fatigue life in a specific
environment is reduced in corrosion fatigue. Unlike fatigue in air, stage 2 (crack
propagation) in corrosion fatigue takes up about 90% of the fatigue life. This makes
fracture mechanics a powerful tool in evaluating fatigue life in corrosive environments.
3. Rapid Fracture The third stage begins when a crack has reached a critical size and
the effective cross section of the part can no longer support the applied load.
The behavior of a metal under a cyclic load is often represented in the form of a S/N
curves (see Figure 20). This is a plot of applied stress (S) versus the number of cycles
to failure (N). Ferrous materials fatigue tested in air or other benign environment have a
threshold stress below which failure will not occur regardless of the number of cycles.
This stress is known as the endurance or fatigue limit. Nonferrous alloys have no
fatigue limit and can only be subjected to a finite number of cycles however small the
applied stress. In a corrosive environment such as seawater, ferrous alloys (steels)
have no fatigue limit: they will eventually fail regardless of the applied stress once a
sufficient number of cycles has been reached. Great care must be exercised when
utilizing published S/N curves in determining the fatigue life of equipment - make sure
the curves are appropriate for your environment.

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Figure 20: S/N Curves for a Steel in Air and Seawater
Corrosion fatigue in steel parts immersed in seawater can often be greatly reduced with
a properly designed cathodic protection (C/P) system depending on a number of
different factors including the strength of the metal, the applied stress, and the C/P
potential. C/P is most effective with lower strength metals (below 100ksi YS) and at
lower applied stresses. The fatigue life in seawater may approach the fatigue life in air
under these conditions. The C/P extends the crack initiation stage by preventing pitting
and by providing a protective calcareous deposit. C/P may be problematic for higher
strength steels or for high applied loads. Hydrogen from cathodic protection may be
electrostatically charged into the steel at the crack tip and greatly increases the crack
growth rate in stage 2.
8. Stress Corrosion Cracking
Stress corrosion cracking (SCC), or environmentally assisted cracking (EAC) as it is
sometimes called, is an extremely important failure mode for Oil Patch equipment.
Every engineer must be thoroughly familiar with SCC so that it can be prevented in the
design stage of the equipment. SCC may cause a sudden, catastrophic, brittle failure
of a part at tensile loads that may be well below its yield strength. Three factors are
necessary for SCC to occur in a part:

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1. The part must be under a tensile stress. This may be an applied stress or a
residual stress. In general, the higher the tensile stress, the greater the
likelihood for SCC to occur. There may be a threshold stress below which SCC
does not occur in a particular environment.
2. The material must be in a susceptible condition. The tendency for a given
material to fail by SCC is dependent on many variables including,
microstructure, heat treat condition, hardness, and strength level. The risk of
SCC increases in most alloys as hardness and strength increase.
3. The part must be in a specific environment. Only certain combinations of
environments and alloys will lead to SCC. Environmental conditions affecting
SCC include the chemical species that are present and temperature. There
may be threshold levels of certain chemical species or a minimum temperature
below which SCC will not occur for a given material under a given tensile
stress.
Unfortunately many alloys that are used to make production equipment are subject to
SCC. Well examine steels, but realize that there are unique environments that may
result in SCC of other types of alloys. Product literature published by the companies
that develop new alloys for use in the Oil Patch always have information on corrosion
resistance in general and on the environments that may lead to SCC. Never, ever use a
new alloy without checking on its SCC resistance in your particular environment!
Ferritic steels (those having a BCC or BCT type structure such as carbon, low alloy, and
martensitic stainless steels) are subject to SCC when exposed to aqueous chlorides.
Chlorides are everywhere in oilfield environments. Produced water, completion fluids,
packer fluids, seawater, cutting fluids, sweat from an assemblymans hands all contain
enough chlorides to cause SCC in steels. The tendency for SCC to occur increases as
the chloride concentration increases, but only up to a certain point. Eventually a point is
reached where there are more than enough chloride ions present to cause SCC and
any additional ions cant make things any worse. At normal design loads, ferritic steels
can be safely used at a maximum hardness of 35HRC. This equates to a maximum
yield strength of about 135ksi. SCC may occur in steels with lower strength and
hardness if the tensile load approaches the yield strength of the material.
Austenitic stainless steels may stress corrosion crack in the presence of chloride ions,
but the tendency for SCC to occur in these alloys is very temperature dependent. They
are relatively immune to SCC at temperatures below 140F. API 6A revised the upper
temperature limit of temperature class S to 140F in order to permit the use of 316 and
other austenitic stainless steels. Cold working austenitic stainless steels may increase
their susceptibility to SCC. Cold working may produce fresh martensite in their
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stainless steels because of their continuous ferrite matrix have better SCC resistance
than the austenitics. Safe usage of these alloys is dependent on the particular alloy, the
chloride concentration, and the temperature.
Parts that fail by SCC often show no signs of weight loss corrosion. Depending on the
alloy and environment, cracking may be Intergranular or transgranular. Failure is always
brittle in nature with little associated plastic deformation except for the areas that failed
in ductile overload after the SCC cracks reduced the cross section of the part beyond
what could support the load. Cracks are typically branched (see Figure 21).
Figure 21: Branched Cracks Typical of SCC in an Austenitic Stainless Steel

Unlike a mechanical overload or fatigue cracking, SCC may occur at multiple initiation
points on the surface of a part as can be seen in Figure 21. They often begin at stress
risers such as scratches or corrosion pits. Time to failure is notoriously difficult to
predict. It may be measured in minutes to years depending on circumstances. Just
because a susceptible alloy has lasted a few years in the field does not mean it wont
fail the next day. The time dependency for an SCC is often predicated on the time it
takes for a different corrosion mechanism to create a stress riser such as a pit of a
certain depth.
There are three possible mechanisms for crack growth in SCC:

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Anodic Path (or Crack Tip) Dissolution - This mechanism involves accelerated
corrosion along a path of higher than normal corrosion susceptibility, such as a
grain boundary. The bulk of the metal surrounding the grain boundaries is
passive. Stresses tend to open up the crack tip disrupting any protective film and
allowing corrosion products to diffuse out and corrodents to move in to freshly
exposed metal. The crack tip becomes the anode of a electrochemical cell
having a very large cathode-to-anode surface area ratio.
Hydrogen Embrittlement Hydrogen is the smallest atom and can easily diffuse
into metal. It is attracted to areas under triaxial tension such as crack tips where
it will collect and cause a great deal of mischief. Through a mechanism not
clearly understood, it facilitates cleavage (brittle) fracture in the metal
surrounding the crack tip. The crack progresses into new ductile material,
becomes arrested, and then process repeats itself. Cracking may be very rapid.
We will discuss hydrogen embrittlement more when we look at Hydrogen
Damage.
Film Induced Cleavage A ductile material may be protected by a passive film

that is relatively brittle. A crack may easily propagate through this brittle layer
then become arrested as it enters the ductile material underneath. If the brittle
film forms through corrosion, then the area inside the crack will repassivate
forming a new brittle layer and the process repeat itself. This particular
mechanism of SCC is most often associated with the deposits that form on alloys
that have undergone selective leaching.
Depending upon the particular mechanism that is involved, cathodic protection may
mitigate or aggravate SCC. If the anodic path dissolution mechanism is the one in play,
C/P may prevent the SCC from occurring. If; however; hydrogen embrittlement is the
mechanism, then C/P may contribute to SCC failure. Hydrogen ions are
electrostactically charged into the metal at the cathode of an electrochemical cell.
Hydrogen will then collect at the crack tip.
Many engineers have succumbed to the sirens song that high strength is better. It may
allow you to minimize the size and weight of part. In the case of fasteners it may allow
you reduce the size or number of fasteners. It may allow for increased load capacity or
pressure rating. Designing a part using yield strength as the only criteria is fraught with
danger. The higher the yield strength, the lower the toughness and ductility, the harder
it will be to process the metal, the harder it will be to weld, but most importantly the
more susceptible it will become to SCC. Always use the lowest strength material you
can get away with because it will be the most forgiving material. Better a big, robust part
at low strength, than a compact, high strength part prone to cracking!

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Fasteners are especially prone to SCC because they are highly loaded and have builtin stress risers in the form of thread roots. Cap screws are among the worst. Not only
are they threaded, but the juncture where the head joins the shank is very highly
stressed. Both are excellent stress risers for initiating SCC. Cap screws are often a
commercial part in an oil field equipment assembly. ASTM A574 is one of the most
common standards used for ordering steel cap screws. Never ever use them on
ARGUS Subsea equipment! Ill repeat that. Never, ever use them on ARGUS Subsea
equipment! They have a yield strength well over 150ksi and are guaranteed to
eventually fail by SCC in oil field environments. People use them because they are
commercially available. Its a big mistake. They can be used if they are tempered back
to 35HRC.
Wellhead equipment can be exposed to a myriad of fluids: environmental (such as
seawater), produced fluids, completion and packer fluids, and injected fluids. There are
hundreds of different chemicals that are routinely injected into wells for various reasons.
All must be carefully scrutinized for compatibility with the materials of construction to
insure that SCC does not occur.
9. Liquid and Solid Metal Embrittlement
Liquid metal embrittlement (LME) and solid metal embrittlement (SME) occur when a
normally ductile metal is exposed to a low melting temperature metal at an elevated
temperature for a period of time and becomes embrittled when the atoms of the low
melting temperature metal diffuse into the other metals grain boundaries thus lowering
the cohesive force between the grains. LME occurs at temperatures above the melting
point of the embrittling metal, while SME occurs below. A tensile stress is necessary for
cracking to occur. There are many combinations of metal couples that may undergo
LME and SME. The ones of most concern to us involve cadmium, zinc, and mercury as
the embrittling metals
Mercury is occasionally found in some gas wells. It can embrittle steels, nickel base
alloys, and aluminum alloys. It is generally not a problem for wellhead equipment
because the amount of mercury is typically very low and it is entrained in a production
fluid so not much contacts the surface of the wellhead equipment. It is a serious
problem for downstream heat exchangers that frequently use aluminum tubes. Here the
mercury may become concentrated and cause extensive cracking of the aluminum
tubes.
Cadmium and zinc may cause SME of steels exposed to temperatures above 350F
(API 6A temperature rating X). Both cadmium and zinc are often electroplated on steel
fasteners in order to provide corrosion resistance. They form a sacrificial coating that
cathodically protects the substrate. Zinc is also used in the form of galvanizing on many
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temperatures over 350F! At higher temperatures use black bolts (uncoated) or

phosphate coated fasteners.
Do not allow galvanized chains to come into contact with steel parts! The zinc that
makes up the galvanized coating is relatively soft that can easily be abraded onto the
surface of a harder, steel part. This may lead to LME or SME if the part later undergoes
a high temperature thermal cycle (heat treatment, welding, induction bending, stress
relieving, etc. Galvanized chains may not be found in your shop, but be careful of
truckers who use chains to secure their loads this is particularly a problem with pipes!
10. Hydrogen Damage
Hydrogen damage is an umbrella term used for a group of processes by which
hydrogen can degrade a metal. Well look only at those that may be encountered in the
Oil Patch where there is an external source of hydrogen. These include hydrogen
blistering, hydrogen attack, hydride formation, and hydrogen embrittlement. There are
many sources of hydrogen or hydrogen ions in the Oil Patch. Hydrogen is a byproduct
of the corrosion processes in aqueous solutions. It is present in acids used to acidize
wells. It is a byproduct of cathodic protection. Parts may be exposed to hydrogen during
manufacture if they are pickled, welded, or electroplated.
Hydrogen blistering may occur in low strength steels when hydrogen ions are reduced
and adsorbed onto the steels surface as monatomic hydrogen. These hydrogen atoms
then may diffuse into the steel where they will collect at microscopic voids or other
traps like the interface with nonmetallic inclusions. Here they will combine to hydrogen
gas. The gas molecule H2 is too big to diffuse out of a void so pressure begins to rise as
the amount of gas increases. If the void is just below the surface, the internal hydrogen
gas pressure in a void may cause a bulge or a blister in the surface.
Hydrogen attack of susceptible steels is most often seen in refineries and chemical
plants that use high pressure hydrogen in their processing. It occurs at temperatures
over 400F and is the result of hydrogen atoms diffusing into the steel and combining
with carbon to form methane gas in the reaction 4H + Fe3C CH4 + 3Fe This typically
occurs at voids, laminations, or other discontinuities Methane forming at the very
surface will be lost to the surrounding environment leaving a decarburized zone on the
surface of the part. Methane produced subsurface is too large to diffuse through the
steel and the pressure will build up as more and more methane forms. If this occurs
near the surface a blister may form. Cracking may occur in deeper locations. Carbon
steels are most susceptible to hydrogen attack. Alloying elements such as chromium
and molybdenum in low alloy steels form stable carbides that tie-up the carbon making
the carbon unavailable to react with hydrogen. As a consequence low alloy steels will
perform better than carbon steels. Nelson curves show the safe operating limits in
terms of temperature and hydrogen partial pressure for different steel alloys.

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Titanium, magnesium, tantalum, columbium, vanadium, and zirconium and some of

their alloys are subject to hydride embrittlement. These can combine with hydrogen to
form brittle hydrides. At low hydrogen concentrations (below the solubility limit) stress
assisted hydride formation causes embrittlement. Here hydrides form a brittle layer
along the length of the crack and at the crack tip. Local stresses at the crack tip fracture
this brittle layer exposing fresh metal and the process repeats itself. The process is
enhanced under conditions of slow strain. At hydrogen concentrations above the
solubility limit, severe embrittlement may occur as brittle hydrides precipitate out on slip
planes or other discontinuities. Increased strain rates, lower temperatures, and the
presence of stress risers in the material all lead to more severe embrittlement.
Well focus on titanium because the other metals are not often used in the Oil Patch.
Titanium is sometimes used especially for downhole applications because of its
excellent general weight loss corrosion resistance, its low modulus, and especially for
its light weight. Cases of hydride formation in titanium are rare in the Oil Patch, but they
can occur. The solubility of hydrogen in commercially pure titanium (alpha alloys) and in
alpha-beta alloys is low (50-300ppm). In beta alloys the solubility is about 4,000ppm.
Thus beta alloys can much tolerate more hydrogen before becoming embrittled:
hydrides will precipitate out once the hydrogen content exceeds the solubility limit. The
passive oxide layer that makes titanium corrosion resistant is an effective barrier to
hydrogen diffusion. It is important therefore to use titanium only where passivity is
maintained and to prevent mechanical damage to the protective film. Temperatures
above 80oC are generally necessary to cause significant hydrogen entry into the metal.
Diffusion is very sluggish at lower temperatures.
Hydride embrittlement of titanium may occur in seawater may occur under unusual
circumstances and is dependent on the specific alloy involved. Problems may occur if:
Titanium is coupled to a less noble metal

Cathodic protection system potential is < 0.85v SCE
Parts are actively strained
The pH is less than < 3 or > 12
The temperature is above 80oC
In general it is good practice to electrically isolate the titanium from less noble metals
and from the cathodic protection system when using it subsea.
Hydrogen embrittlement is the loss of ductility and toughness that occurs in a
susceptible metal when it interacts with hydrogen. Under a tensile load, it may lead to a
rapid and catastrophic failure. It may be considered a specialized case of stress
corrosion cracking where the cracking occurs in an environment containing hydrogen.
There are many theories about what causes hydrogen embrittlement and there may be
several different mechanisms involved. A few of the leading candidates are:

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Monatomic hydrogen diffuses into the metal and collects at discontinuities such
as voids, inclusions, porosity, etc. where the atoms combine to make hydrogen
gas. The hydrogen gas molecule is too big to diffuse out. Pressure then builds
up and leads to cracking.
Hydrogen entry into the metal at the crack tip is facilitated by triaxial tension.
Here it reduces the interatomic cohesive forces of the base metal.
Hydrogen at the crack tip interferes with the redistribution of stresses by plastic
deformation.
Regardless of what actually is going on at an atomic level, the effects of hydrogen
embrittlement are easily seen when a part fractures in two! Hydrogen is prevalent in Oil
Patch environments. It is a byproduct of corrosion processes; it is generated at the
surface of subsea equipment under cathodic protection, it is a byproduct of
electroplating processes and pickling operations. Hydrogen sulfide (H 2S) is gas often
found in oil and gas wells that can be a source of hydrogen. Recall that monatomic
hydrogen combines to form hydrogen gas on the surface of a cathode and that this gas
is then lost to the atmosphere. This reduces the amount of hydrogen diffusing into the
metal. Certain impurities present on the surface of the metal such as sulfur, arsenic,
phosphorous, or the cyanide ion (CN-), may interfere with the formation of the hydrogen
gas molecule thus permitting much more monatomic hydrogen to diffuse into the metal.
The presence of H2S increases the corrosion rate of steel thus increasing the amount of
hydrogen being generated. Like the sulfur, arsenic, and the other impurities just
mentioned, H2S poisons the formation of hydrogen gas thus allowing more hydrogen
atoms to diffuse into the metal and wreak havoc.
Many alloys commonly used in the Oil Patch are susceptible to hydrogen embrittlement
depending primarily on their heat treat condition, strength level, magnitude of tensile
stress, and the specific environment. The internal discontinuities, defects, strain fields,
precipitates, etc. that strengthen a metal provide the sites for hydrogen to interact with.
Thus the higher the strength of a metal, the more susceptible it becomes. A heat
treatment that provides a microstructure with rounded constituents is less susceptible
than one with sharp, angular constituents like martensite. Environmental factors are
important. Obviously the amount of hydrogen available is important, but other factors
such as the presence of chlorides, temperature, pH can also influence the tendency for
hydrogen embrittlement to occur. In general the higher the tensile load a susceptible
metal part is under, the more likely it will fail. Temperature has a mixed effect. In the
case of most steels, the worst case is at room temperature. The diffusion rate of
hydrogen is too slow at lower temperatures to allow much hydrogen to enter the steel.
At higher temperatures hydrogen will outgas from the part.

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The permeability of hydrogen in metals with a ferritic microstructure (body centered

cubic) is high, but these materials have a low capacity for absorbing hydrogen.
Conversely, hydrogen has poor diffusivity in austenitic materials (face centered cubic),
but these materials can absorb much more hydrogen in their microstructures than BCC.
Austenitic materials as a consequence tend to have better hydrogen embrittlement
resistance than those with BCC structures.
Hydrogen induced stress cracking or HISC is a very important type of hydrogen
embrittlement. It occurs on susceptible metal parts that are subsea and under cathodic
protection. The principle of cathodic protection is that the part to be protected is made
the cathode of an electrochemical cell. As the anode (typically aluminum) corrodes, it
provides free electrons that totally suppress corrosion at the cathode. The cathode
becomes negatively charged as a result of the influx of free electrons. Hydrogen ions in
the electrolyte (the seawater) are positively charged and thus are attracted to the
cathode. The cathode is thus electrostatically charged with hydrogen atoms its not
just a diffusion process. Hydrogen embrittlement may then occur. High strength carbon,
low, allow, and martensitic stainless steels are all subject to HISC if over 35HRC.
Duplex stainless steels are especially prone to HISC and require careful processing and
special design criteria when used under cathodic protection. Guidelines can be found in
DNV RP F112 Design of Duplex Stainless Steel Subsea Equipment Exposed to
Cathodic Protection. A thorough understanding of HISC is vitally important to every
subsea engineer. Material selection is an important aspect of HISC prevention, but
equally important is the design of the equipment. HISC is important enough that there
will be a separate training module just on this topic.
H2S embrittlement, also called sulfide stress cracking or SSC, is another very important
type of hydrogen embrittlement. As previously mentioned, H2S is very common in both
oil and gas wells. It acts as a poison that keeps monatomic hydrogen from combining to
form hydrogen gas thus frees up more atomic hydrogen for diffusion into the base
metal. The criteria for safe usage of materials are going to be more stringent or
restrictive than in other hydrogen environments because of this. For example 35HRC
maximum renders low alloy steels relatively immune to HISC, but 22HRC maximum is
required in H2S. Hydrogen sulfide is a very deadly gas to both people and metals.
NACE MR0175/ISO 15156 is the international standard most often imposed upon
metals used in production equipment for fields containing enough H2S to be a problem
in terms of embrittlement. This threshold limit of H2S is set by NACE at a partial
pressure of 0.05psi it doesnt take much H2S to cause problems. Oil and gas field
having 0.05 psi or more partial of H2S are said to be sour. Well look at this important
standard in detail in its own training module and in the training module on Wellhead
Corrosion.
In addition to the classical SSC already described, NACE MR 0175 recognizes several
other distinct forms of SSC based largely on the crack morphology or the location of
cracking. These include:

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Hydrogen Induced Cracking (HIC) This mode consists of cracks that occur
along certain planes in the microstructure in carbon and low alloy steels as
monatomic hydrogen diffuses into the metal and collects at discontinuities. Here
they combine to form hydrogen gas which is too large to diffuse out. Pressure
builds and eventually results in cracks. HIC is most often associated with rolled
products that have banded microstructures or laminations. No external stress is
necessary for HIC to occur.
Soft Zone Cracking (SZC) The heat affected zone (HAZ) of a weld has been
heated to a high temperature during welding and this may lower its yield
strength. It becomes a weak link in the load path in the part that may plastically
deform at loads under the specified minimum yield. This plasticity makes it more
susceptible to SSC than the parent metal away from the HAZ.
Stress Oriented Hydrogen Induced Cracking (SOHIC) This occurs mainly in

low strength ferritic pipe and pressure vessel materials. Staggered, small cracks
form perpendicular to the principle stress and link up with pre-existing HIC cracks
to form a ladder-like array of cracks.
Stepwise Cracking (SWC) This involves the linking of HIC cracks by cracks
growing perpendicular from one end of a HIC crack to the beginning of another
on a different plane producing a staircase-like appearance. It is most often
associated with low strength, rolled products such as plate.
Microbiologically Induced Corrosion (MIC)

The corrosion of ferrous alloys in water or soils that are poor in oxygen can be
accelerated by the presence of certain types of bacteria. Metal parts such as oil well
casings, water well pipe, buried pipelines, heat exchangers, cooling towers, etc. often
create the perfect environment for these types of bacteria to flourish. Anaerobic
bacteria are the most problematic. Anaerobic means that this group of bacteria can only
live in an environment with little or no oxygen present. Anaerobic bacteria that may
cause corrosion problems for steel components include sulfate reducing bacteria
(SRB), sulfur/sulfide-oxidizing bacteria, iron/manganese oxidizing bacteria, and
methane producing bacteria. SRB cause the most damage. The bacteria of course
dont attack the metal directly (they dont consume the metal as part of their diet!), but
the byproducts of their metabolism may accelerate corrosion of the underlying metal
through several different mechanisms. SRB, under some circumstances, can cause an
oil field with no H2S present initially to become sour later on its life through the following
proposed reactions:

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Anode:
4Fe 4Fe+2 + 8eCathode:
8H2O + 8e- 8H + 8OH8H + Na2SO4 4H2O + Na2S
Na2S + 2H2CO3 2NaHCO3 + H2S
Overall Reaction:
4Fe + 2H2O +Na2SO4 + 2H2CO3 3Fe (OH)2 + FeS + 2NaHCO3
SRB thus reduce inorganic sulfates to sulfides and in doing so consume large amounts
of hydrogen (depolarizing cathode areas). A large number of electrons are consumed at
the cathode so the anode must corrode more quickly to make up the difference. Note
that H2S is a by-product of one of the cathode reactions. SRB may cause a formation
with no H2S to become sour over a period of time particularly if water injection is used
to enhance production. Most customers always order equipment meeting NACE
requirements even if there is no starting H2S in the formation if water injection is
employed to maintain formation pressure. Injected water is a likely source for
introducing SRB into the formation, along with the nutrients they thrive on.
Other types of anaerobic bacteria can cause corrosion because the byproducts of their
metabolism are acidic. Aerobic bacteria (those that live in oxygen rich environments)
can indirectly cause corrosion by forming mats of slime that adhere to the surface of the
metal. This excludes the underlying metal from oxygen so an oxygen concentration cell
is set up.
Corrosion by Acid Gases

Acid gases, as the name suggests, are those gases that form acids when they are
dissolved in water. The two of most concern to the Oil Patch are carbon dioxide and
hydrogen sulfide. Weve already discussed how H2S can embrittle steel, but its
presence can also accelerate general weight loss corrosion and pitting. The acid gases
tend to form relatively weak acids. Any lowering of the pH, however, tends to depolarize
the cathode and increase the corrosion rate at the anode. The additional H + ions
provided by even a weak acid will consume electrons at the cathode that must be

BY
REV. A01
DATE
JDD
11/24/12
APPROVED
DATE
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replaced by the further corrosion of the anode. Over a period of time corrosion by even
a weak acid can become significant. H2S dissolved in water will form hydrosulfuric acid.
CO2 dissolved in water will form carbonic acid through the reaction:
CO2 + H2O H2CO3

Corrosion from CO2 without the presence of H2S is often called sweet corrosion. It is
characterized by broad, shallow pits on the surface of the metal that give the remaining
metal surface the appearance of mesas. Whether or not CO2 corrosion will be
significant is dependent on the partial pressure of the CO2. API 6A gives the following
guidelines:
Partial Pressure CO2
Relative Corrosivity
< 7 psi
Noncorrosive to carbon or low

alloy steels
7 to 30 psi
Slightly corrosive to carbon or

low alloy steels
> 30 psi
Moderately to highly corrosive to

carbon or low alloy steels
The amount of CO2 or H2S is typically given in a well analysis as a volume%, a mole (or
mol)%, or in parts per million ppm. Partial pressure calculations are always based upon
the shut-in pressure of the well do not use flowing pressure! Here are some sample
calculations.
Example #1
A well has a shut-in pressure of 5,000psi. The CO2 is reported as 4 vol% and the H2S
as 8ppm. What are the partial pressures of each?
For CO2
partial pressure = 0.04 X 5,000 psi = 200 psi
For H2S
partial pressure = (8 X 5,000 psi)/1,000,000 = 0.04 psi
Example #2

BY
JDD
APPROVED
REV. A01
DATE
11/24/12
DATE
Page 46 of 46
A well has a shut-in pressure of 10,000 psi. The CO2 is reported as 1.5 mol% and the
H2S as 5ppm. What is the partial pressure of each?
For CO2
partial pressure = 0.015 X 10,000 psi = 150 psi
For H2S
partial pressure = (5 X 10,000 psi)/1,000,000 = 0.05 psi
The API guidelines for CO2 corrosion are just that: guidelines and not gospel. There are
many other factors that mitigate or aggravate CO2 corrosion besides partial pressure.
Well examine the influence of these other factors in the training module on Wellhead
Corrosion. Dry CO2 and dry H2S wont cause corrosion or embrittlement: water must be
present for carrion to occur.

Fundamentals of Corrosion

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Fundamentals of Corrosion

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METALLURGY TRAINING MODULE 4

The Chemistry of Corrosion

METALLURGY TRAINING MODULE 4

Figure 1: The Dalton Model of the Atom

METALLURGY TRAINING MODULE 4

Figure 2: A System in Equilibrium

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Figure 4: Back in Equilibrium

Figure 5: Remove Some B and the System is in Non-Equilibrium

METALLURGY TRAINING MODULE 4

Figure 6: Back in Equilibrium

H2OLiquid H+ + OHThe amount of H+ ions in solution at room temperature is approximately 10 -7 mole/liter

pH = log 1/ [H+] = - log [H+]

Where [H ] is the concentration of the H+ in moles/liter.

4Fe + 3O2 + 6H2O 4Fe(OH)3 or rust

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

Figure 7: Standard Hydrogen Reference Electrode Cell

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Electrode Potential Eo (V), 25oC

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Figure 8: Galvanic Cell with Dissimilar Electrodes

The iron electrode could corrode.

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Figure 9: Equilibrium (External Wire Detached)

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METALLURGY TRAINING MODULE 4

Figure 11: Equilibrium (Wire Disconnected)

Figure 12: Out of Whack (Wire Connected)

METALLURGY TRAINING MODULE 4

4Fe + 3O2 + 6H2O 4Fe(OH)3 or rust

METALLURGY TRAINING MODULE 4

Anodic Reactions Occurring at the Iron Electrode:

Fe Fe+2 + 2eFe+2 + 2(0H-) Fe(OH)2

Other Types of Galvanic Cells

METALLURGY TRAINING MODULE 4

Figure 13: The Copper/Copper Sulfate Cell

A copper/copper sulfate concentration cell consists of two identical copper electrodes

METALLURGY TRAINING MODULE 4

Figure 14: Oxygen Concentration Cell

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METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

METALLURGY TRAINING MODULE 4

Types of Corrosion Damage

Figure 15: Uniform Corrosion

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solutions (such as seawater) known as pitting. Pitting is a very localized form of

Figure 16: Pitting

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METALLURGY TRAINING MODULE 4

4. Intergranular Attack (IGA)

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Figure 17: Intergranular Attack or IGA

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Figure 18: Sensitized Metal

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Figure 19: Time-Temperature Sensitization Curves for Austenitic Stainless Steels

METALLURGY TRAINING MODULE 4

5. Selective Leaching (Dealloying)