CHAPTER-9

CORROSION

Corrosion can be defined as the destructive attack of a metal by a

chemical or electrochemical reaction with its environment. The air oxidation of
hot steel forming an iron oxide coating is an example of chemical attack.
Corrosion of this type seldom occurs in the oil field. The second type,
electrochemical corrosion, occurs at a solid-liquid interface. This occurs in
nearly every instance where oil field waters contact steel equipment. The
corrosion commonly occurring in water handling systems consists mainly of acid
gas attack. Acid gas corrosion is caused, for the most part, by H2S. No doubt
CO2 causes some corrosion, especially when aided by dissolved oxygen. However,
the comparative effect of CO2 has been grossly over-emphasized.
In order to have electrochemical corrosion, the following four factors are
necessary:
-anode
-cathode
-electrolyte
-external connection.
Remove any of these and corrosion will cease. This is the principle of corrosion
mitigation; to remove one of the four components necessary for the corrosion

reaction. The anode and cathode are called electrodes. The anode is the
electrode at which oxidation occurs or where electricity leaves the metal and
enters the electrolyte. For iron, the anode reaction is shown in equation (1),
where iron is oxidized to the ferrous ion.
Fe = Fe++ + 2eH+ = H2 eReduction occurs at the cathode. An example is the reduction of hydrogen ion,
shown in equation (2).
The electrolyte of interest here is water. Its function is not only to carry
corrosive materials to the surface but also to provide a medium of electron
transfer utilizing ions. Any connection, excluding the electrolyte, between the
anode and the cathode is an external connection. Anodes and cathodes both
exist on steel surfaces. The body of the steel serves as an external connection.
The severity of corrosion depends upon the potential generated between the
anode and cathode.
A good example of corrosion is a dry cell. The center carbon electrode is
the cathode. A zinc case serves as anode. These electrodes are separated by an
electrolyte that is essentially ammonium chloride solution. When an external
connection in the form of a flashlight bulb is attached, corrosion occurs as zinc
goes into solution, and the bulb glows. The greater the flow of electricity
through the cell, the greater is the amount of zinc that corrodes. The

relationship between the amount of zinc corroding and the flow of current is
quantitative.

Forms of corrosion damage

Uniform or thinning corrosion
In this form of corrosion attack, the entire surface of the metal is
corroded, and the metal thickness reduced by a uniform amount. This would
occur with a homogenous metal when no difference in potential existed between
any points on the surface. The anode in galvanic corrosion could undergo
thinning.
Pitting corrosion
This is the most common type of attack that occurs with heterogeneous
metals such as steels and other alloys. It is a localized attack, where the rate of
corrosion is greater at some areas than at others. This is caused by differences
in potential between different points on the metal surface. A brake in an oxide
film protecting a metal surface can cause pitting attack.
Intergranular Corrosion
This form of corrosion occurs with alloys when a difference in potential
exists between the grain boundary and the grain. The smaller grain boundary
acts as the anode. This type of corrosion is particularly serious with aluminum
alloys containing copper and austenitic stainless steels containing carbon.

Galvanic corrosion
Galvanic corrosion occurs where two different metals or alloys come in
contact. The severity of galvanic corrosion depends upon the difference in
potential between the two metals, and the relative size of the cathode and
anode areas. The galvanic series for metals and alloys in seawater in table (1).
Active metals are at the top of the series. Coupling a metal near the top with
one near the bottom will cause galvanic corrosion of the more active metal.
If the area of the active metal is very large compared with the area of
less active metal, corrosion will not be so severe. Polarization will also modify the
amount of current flowing during the corrosion reaction.
Water in the Corrosion Process
The presence of water is essential to the low temperature corrosion
process. However, pure water containing no dissolved substances is only very
mildly corrosive to iron. Since iron is anodic to hydrogen in pure water, the iron
corrodes to produce hydrogen gas and ferrous hydroxide, which raises the pH of
the water. The attack proceeds until the solubility of ferrous hydroxide is
exceeded and the ferrous hydroxide deposits on the metal surface in the form
of a film, smothering the corrosion reaction.
Water containing impurities or dissolved substances can be corrosive or
non-corrosive, depending on the nature of the dissolved substances. Chromates
and phosphates are dissolved in water to inhibit or reduce corrosion. Other

substances such as salts, acids, hydrogen sulphite, carbon dioxide, and oxygen
can increase corrosivity of the water. Generally, the water encountered in oil
field operations contains one or more of these substances, which increase its
corrosivity.
In addition to the impurities, which are commonly found in water,
temperature and velocity also influence the corrosivity of water. Seldom is a
corrosion problem encountered where only one of these contributing factors is
present. Generally, the problem is complex because of these various influences
and the manner in which they may interact with each other.
Influence of Dissolved Oxygen
Oxygen dissolved in water is probably the most troublesome corrosion
producing substance. The product of corrosion of iron by oxygen containing
water is a mixture of iron oxides, usually hydrated, and generally referred to as
rust. The following equations illustrate this in the simplest form and in water
containing only dissolved oxygen.
Fe + 2 H
2H

2 Fe

= Fe

++

+ 2 H0

+ O 2 = H 2O

++

+ O2 + H 2 O = 2 Fe+++ + 2 OH

The action of the oxygen is twofold, it depolarizes the cathode, and it oxidizes
the ferrous ions to ferric ions, which form the insoluble (above pH = 3) ferric
hydroxide. If the formation of ferric hydroxide occurs out of contact with the

metal, there is no stifling of the reaction by this corrosion product. In a closed

system, this reaction will continue until the dissolved oxygen is used up and the
ferrous hydroxide smothers the reaction. However, in system in contact with
the air, the oxygen supply is continually replenished. The rate of corrosion, in
this case, is generally restricted by the transport of oxygen from the air
through the water to the metal. While the rate of corrosion may not be as high
as that produced by the attack of acids, the inexhaustible supply of air assures
that the reaction may continue for a long period of time. The corrosion rate of
steel in water has been found to be approximately proportional to oxygen
content up to 5.5 cc/litre. The corrosion rate is lower at higher oxygen
concentrations. This may be explained by the fact that at low oxygen
concentrations, the corrosion product formed is not as impermeable to oxygen
diffusion as that formed at higher oxygen concentrations. Hydrated ferrous
hydroxide

is

formed

first

in

both

cases.

However,

at

high

oxygen

concentrations, the ferrous compounds are oxidized at a rate sufficiently rapid

to precipitate the hydrated ferric hydroxide next to the metal as a protective
film.
In waters containing high salt concentrations, corrosion is proportional to
the amount of oxygen dissolved in the water. As the salt concentration in the
water increases, the solubility of oxygen decreases and, consequently, the

corrosion rate is reduced. In waters containing low salt concentrations, the

corrosion is governed by the conductivity of the water.
Corrosion can also be caused by differential aeration cells, which are
concentration cells caused by differences in oxygen concentration between two
parts of the system. This results in a difference in potential between the
portion of high oxygen concentration and that of low oxygen concentration.
Corrosion occurs in differential aeration cells at the area of low oxygen
concentration.
Corrosion of iron, which occurs at a water-air interface, can be attributed
to differential aeration. Oxygen from the air is available to the meniscus area
formed at the water line. As oxygen is depleted at levels beneath the water line,
the meniscus area becomes cathodic to the immersed iron. In hard waters, the
alkaline

cathodic

reaction

products

precipitate

calcium

and

magnesium

compounds, which deposit on the iron and shield a part of it from the aerated
solution. Since this shielded area is deprived of oxygen, corrosion occurs here at
the water line.

Influence of Dissolved Carbon Dioxide

Carbon dioxide dissolved in water can contribute to the corrosion of
steel. Corrosion caused by water containing dissolved carbon dioxide is
characterized by clean, uniform thinned surfaces below the water line. The rate
and amount of corrosion is dependent upon the salts dissolved in the water, the
carbon dioxide content, the oxygen content, the temperature, and the
composition of the steel. Carbon dioxide in water is present as:
-the carbon dioxide in carbonate ions;
-the carbon dioxide necessary to convert the carbonates to bicarbonates;
-the amount of carbon dioxide necessary to keep the bicarbonates in solution;
and
-any excess carbon dioxides.
This excess carbon dioxides is referred to as aggressive carbon dioxides, and
is the most corrosive form.
For equal concentrations, carbon dioxide dissolved in water is not as
corrosive as oxygen dissolved in water. At 600C, a solution containing 4 ml. of
dissolved oxygen is seven times as corrosive as one containing the same volume
of dissolved carbon dioxide. In distilled water with only oxygen present, the
corrosion rate of mild steel 0.15 percent carbon increases two-fold between
600C and 900C: whereas the corrosion rate increases by 2.6 fold in the same
temperature range with only carbon dioxide dissolved in distilled water. The

increase in corrosion rate can be attributed to increased diffusion rates of

dissolved gases with increased temperature. The greater increase corrosion rate
in the carbon dioxide solution with increased temperature is caused by a
decrease in acidity required at the metal surface for hydrogen evolution. This
makes the carbon dioxide more effective.
In corrosion caused by carbon dioxide dissolved in water, the following
reaction applies where carbon dioxide reacts with water to form bicarbonate
but not carbonate:
2CO2 + 2H2O + 2e- = 2HCO3- + H2
The depolarizing reaction of oxygen at the cathode is:
2O2 + 4H2O + 8e- = 8OHComparison of these reactions indicates that, on the basis of electrons, oxygen
dissolved in water should be roughly 4 times as corrosive as an equal molar
amount of carbon dioxide. When dissolved in water, carbon dioxide acts as an
acid, so that increasing the partial pressure of the carbon dioxide increases the
acidity of the solution and the corrosion rate. Corrosion resulting in hydrogen
gas evolution may occur at pH 6 with carbon dioxide, whereas pH 4 is required
with highly ionized hydrochloric acid. This can be explained by the fact that
carbonic acid is a slightly ionized acid and therefore would require a greater
amount of carbonic acid, or more total acidity, to obtain pH 6 than the amount

of hydrochloric acid necessary to obtain pH 4. The rate of corrosion is

influenced by the partial pressure of carbon dioxide.
Water that contains both dissolved oxygen and carbon dioxide is more
corrosive to steel than water, which contains only an equal total concentration of
one of these gases. For example, in a solution containing 10 cc of carbon dioxide
per litre, the corrosion rate is 8 mils per year (mpy); in a solution containing
0.67 cc of dissolved oxygen per litre, the corrosion rate is 4 mpy. A solution
containing the above amounts of each these dissolved gases has a corrosion rate
of 17 mpy, which is greater than the sum of the corrosion rates of the individual
gases. This effect occurs at low oxygen concentrations and may be related to
the nature of the corrosion products. At high oxygen concentrations, the
adherent film formed by corrosion on the surface of the metal is essentially
unaffected by the carbon dioxide, whereas at low oxygen concentrations, the
carbon dioxide interferes with the formation of the corrosion film, resulting in
an increased corrosion rate.
Dissolved carbon dioxide influences the solubility of magnesium and
calcium carbonates. These salts sometimes precipitate on the surface of metal
pipe and form a protective coating. Water containing aggressive carbon dioxide
will not deposit this protective coating. Salts dissolved in water may act as
buffers, thereby preventing the pH from reaching a low enough value to produce
serious corrosion.

In waters containing high ratios of carbon dioxide to oxygen, corrosion is

accompanied by the evolution of hydrogen; the corrosion rate is governed by the
acidity and by the composition of and physical structure of the steel. At low
ratios, oxygen depolarization controls the reaction and all low-alloy composition
steels corrode the same. Different investigators have found a difference in
corrosion rates of different low-alloy steels in aqueous systems containing only
dissolved carbon dioxide.
Influence of dissolved H2S
H2S, like carbon dioxide, are not corrosive in the absence of moisture.
Water containing dissolved hydrogen sulfide is corrosive. Hydrogen sulfide is
very soluble in water and, when dissolved behaves as a very weak dibasic acid,
yielding an acid solution in distilled water. Generally, when H2S exists at the
bottom of an oil or gas well dissolved in a brine, there is no oxygen or other
oxidizing agent with it. Under these conditions, the dissolved H2S will attack
iron and nonacid-resistant alloys. When the brine is pumped to the surface,
oxygen from the air dissolves in the brine giving a water, which may even be
corrosive to acid resistant alloys. Dissolved oxygen will slowly oxidize the h2s to
give water and free sulfur according to the equation.
H2S + O2 = H2O + S
The rate of corrosion of mild steel in distilled water containing dissolved
hydrogen sulfide varies with the concentration of dissolved gas. This variation

with hydrogen sulfide concentrations ranging from 2 to 2600 ppm at a constant

temperature. The corrosion rate increases rapidly up to a hydrogen sulfide
content of 150 ppm, remains nearly constant in the range 150 to 400 ppm, and
diminishes rapidly as the concentration of hydrogen sulfide approaches 1600
ppm. From 1600 ppm to 2640 ppm, the corrosion rate remains fairly constant,
indicating that high concentrations of hydrogen sulfide may act to inhibit the
corrosion reaction. The use of polysulfides in aqueous systems to prevent
blistering and fissuring has been disclosed. Polysulfides are not recommended
for use in acid solutions.
The corrosion rate in water containing dissolved hydrogen sulfide is also
influenced by the presence of dissolved salts and dissolved carbon dioxide. The
corrosion rates in the brine solutions are higher than those in distilled water,
and the brine containing hydrogen sulfide gives the highest corrosion rate. The
differences in corrosion rates are attributed to the corrosion products formed
in the different solutions. In the distilled water system, kansite (Fe9S8) formed
only a moderately protective tarnish until more protective pyrrhotite(Fe0.875S)
and pyrite (FeS2) scales formed. Since only kansite scale formed in the brine
systems, the corrosion rate continued to increase.
The corrosion rate is also influenced by the composition of the steel
exposed to water-containing hydrogen sulfide. This difference is pronounced
between different alloys but may also be evident between different

compositions of essentially the same alloy. A 10 mpy difference has been found
in the corrosion rates of two copper-bearing mild steel samples exposed to
water saturated with the same mixture of oxygen, carbon dioxide, and hydrogen
sulfide. This indicates the possibility of incurring an error in comparing the
corrosivity of two environments on the basis of corrosion of steel tubing or flow
lines without considering the compositions of the steels.
Influence of dissolved salts
Salts dissolved in water have a marked influence on the corrosivity of
water. At extremely low concentrations of dissolved salts, different anions and
cations show varying degrees of influence on the corrosivity of the water. The
anions most commonly found in water are chloride, sulphate and bicarbonate. The
effect on the corrosivity of distilled water to steel resulting from the addition
of these ions is shown in figure (1). In the concentration range shown in this
graph, the sulphate ion has a greater effect on the corrosivity of the water
than the chloride ion, and the bicarbonate ion shows inhibitive tendencies. In
solutions containing bicarbonate ion along with either chloride or sulphate ion at
concentrations up to 100 ppm, the bicarbonate ion showed increasing inhibition
with increasing concentration but did not entirely prevent corrosion.
The influence of the anion on corrosivity also depends upon the metal in
question. Waters containing sulphate ion would not seriously corrode lead
because of the formation of lead sulphate on the surface of the lead. The

corrosion rate of stainless steel is greater in 0.1 mole potassium chloride than in
0.1 mole potassium sulphate because of greater penetration of the protective
oxygen or oxide coating by the chloride ion. The order of decreasing penetrating
power of anions has been given as :
chloride > bromide > iodide > fluoride > sulphate > nitrate > monohydrogen
phosphate.
Water solutions containing equal concentrations of salts of the same anion
but different cations show different degrees of corrosivity of mild steel. With
alkali metal chlorides, the corrosion rate is the greatest in potassium chloride
solutions, less in sodium chloride solutions, and lowest in lithium chloride
solutions. The order of decreasing corrosiveness of cations has been given as:
ferric > chromic > ammonium > aluminium > potassium > sodium > lithium > barium >
strontium > calcium > manganese > cadmium > magnesium.
Generally, the corrosivity of waters containing dissolved salts increases
with increasing salt concentration until a maximum is reached,

and then the

corrosivity decreases. This may be attributed to increased electro-conductivity

because of the increased salt content, until the salt concentration is great
enough to cause an appreciable decrease in the oxygen solubility, resulting in a
decreased rate of depolarization. The dissolved salts may also decrease the
protectivity of any corrosion products, which form, and thus increase corrosion.
Influence of pH

The chemical nature of the electrolyte is an important external factor

governing the rate of corrosion and the pH is an important characteristic of the
electrolyte. The influence of pH on the rate of corrosion of water solutions
containing oxygen from the air is dependent upon the metal corroded. Diagrams
illustrating the influence of pH on the rate of corrosion of some metals are
shown in figure (2) and (3).the Corrosion rates of the noble metals, gold and
platinum, are shown in figure (2) to be unaffected by the pH of the water. In
the same figure the characteristic curve showing effect of pH on the corrosion
of aluminum, zinc, and lead is shown. Here the metals show a large increase in
corrosion rate in both acidic and basic solutions.
The shape of this curve may be explained by the fact that aluminum, zinc,
and lead are amphoteric metals or ampholytes. That is, the metals from
hydroxide precipitates that are insoluble in water solutions approximating a
neutral pH, but they dissolve in solutions that are sufficiently alkaline or acidic.
In the neutral pH range where these metals form insoluble hydroxides, the
hydroxides will deposit on the surfaces of the metal, resulting in coatings, which
will retard corrosion. In highly acid water solutions, these metal ions form
soluble salts; consequently, the protective films are removed and corrosion
progresses. In highly alkaline water solutions, soluble complex compounds are
formed, such as sodium zincate (Na2ZnO2) and sodium aluminate

(NaAlO2) -

again destroying the protective films and permitting corrosion to proceed

unchecked.
A third type of pH corrosion rate diagram illustrating the effect of pH on
the corrosion rate of iron, nickel, cadmium, and magnesium is shown in figure (3).
This curve shows the formation of soluble compounds in a region of high acidity,
and the formation of less soluble and somewhat protective films in the neutral
region. In contrast to the amphoteric metals, these metals form hydroxides,
which are insoluble in highly alkaline environments and thus form protective
films at high pH values. The solubility curve of ferrous hydroxide as a function
of pH is similar in shape to the curve in figure (3).
In the pH range 4 to 9.5, the iron surface is in contact with an alkaline
saturated solution of hydrated ferrous oxide, and corrosion progresses as
oxygen diffuses through this barrier. The rate at which this layer of hydrated
ferrous oxide is formed depends upon the dissolved oxygen content. If the
acidity is due to a highly dissociated acid (such as hydrochloric), hydrogen
evolution will occur in the corrosion of iron at pH 4 or less. The hydrated
ferrous oxide will be dissolved at this low pH, resulting in direct contact
between acid and iron. Carbonic acid solutions react with iron at pH 6 or less,
resulting in hydrogen evolution. Since hydrogen evolution is probably the product
of direct attack on the iron by the acidity of the solution and since carbonic

acid is a weakly dissociated acid, it appears that total acidity is as important a

factor as pH.
A relatively dilute alkaline solution affords corrosion protection to iron,
but a highly alkaline solution does not. In a water solution of 4 percent sodium
hydroxide, the corrosion rate of iron is very low, and the potential of the iron on
the hydrogen scale is approximately 0.1 volt. At extremely high concentration of
sodium hydroxide, the potential drops to an active value, and iron corrodes,
forming soluble sodium ferrite (NaFeO2).
Influence of temperature
The effect of temperature changes on the corrosion rate in waters is more
complex than the simple chemical principle that an increase in temperature
increases the reaction rate. An increase in the temperature of a corroding
system has 4 main effects:
the rate of chemical reaction is increased
the solubility of gases in the water is decreased.
the solubility of some of the reaction products may change, resulting in
different corrosion reaction products.
viscosity is decreased and any thermal differences will result in increased
circulation.
Generally corrosion rate increases with increasing temperature. This is
particularly true when corrosion is due to the presence of mineral acids in water

, resulting in hydrogen evolution. However, in waters, which are corrosive due to

the presence of dissolved oxygen, the corrosion rate increases with increasing
temperature only until the temperature becomes high enough to cause an
appreciable decrease in the oxygen solubility. Further temperature increase
beyond this value results in a decrease in the corrosion rate for open systems,
where the oxygen is free to escape. In a closed system, the oxygen cannot
escape

and

the

corrosion rate

continues

to

increase

with

increasing

temperature. If the temperature increase is not uniform over the metal system,
the hotter areas
Influence of velocity
The flow of water over a metal surface influences the corrosion rate
chiefly through the effects of water movement on the other factors governing
corrosion. In stagnant waters or waters at zero velocity, the general corrosion
rate is usually low, but localized or pitting corrosion may occur. Generally, some
motion in a corrosive system causes greater uniformity and results in a thinning
type of corrosion rather pitting. Turbulence may occur at high velocities, and it
may result in non-uniform conditions that lead to pitting corrosion.
Corrosion Prevention Techniques
Water treatment
-de-aeration:

Oxygen can be removed from water by desecration. It is frequently applied to

boiler-feed water used for boilers operating at high temperature. At
temperatures existing in these boilers, even small amounts of oxygen present a
serious corrosion problem. Deaeration is also used on some water flood supply
waters in which the presence of oxygen presents a critical problem.
-degasification
It is a general term applied to the removal of dissolved gases such as carbon
dioxide and h2s. these dissolved gases are either removed entirely or their
concentrations reduced to such a value that they do not contribute significantly
to corrosion. In instances where sour water is the only available supply for
injection water, it is necessary to remove h2s. otherwise, corrosion may form
iron sulphite that will eventually plug the formation rock in the injection well.
-water softening
In addition to removing calcium and magnesium ions, the lime and soda ash
process for water softening removes dissolved carbondioxide. The pH of most
water softened by this method is increased. this may also contribute to reducing
corrosion.
Addition of inhibitors
Corrosion inhibitors are chemical substances that are added to the
corrosive environment to reduce or eliminate corrosion. By the addition of
corrosion inhibitors to water a simple and inexpensive solution to the corrosion

problem is often found. Otherwise, the solution to the corrosion problem may
require extensive modification and replacement of equipment or installation of
water treatment equipment.
Many commercially prepared corrosion inhibitors used in the oil field
contain surface active agents. When these are added to a system for the first
time, they remove loose deposits of corrosion products. Precautions should be
taken to prevent these deposits from accumulating in equipment or in injection
wells in order to prevent plugging.

Cathodic protection
Cathodic protection consists of applying an electrical current to the
surface of the metal to be protected in such a way that it will become a
cathodic area. The current is applied externally, so that a net positive current
enters all areas of the metal, including those that were previously anodic.
Cathodic protection is applied to protect steel, brass, lead, copper and aluminium
against corrosion when these metals are immersed in water.
Cathodic protection is particularly useful in protecting the submersed
areas of water tanks and filters. Since only the areas below the water line are
protected, other methods must be used to protect metal above the water line.

Cathodic protection has an advantage over coatings in protecting sand filters,

since coatings will not stand sand abrasion during backwashing operations.
Coatings
Removing or separating the corrosing environment from the metal can
prevent corrosion. This is the principle of coatings applied for corrosion
protection. Paint and galvanizing are examples of coatings that have been used
for many years.
Coatings can be divided into 3 general categories:
-metallic coatings
Most metal coatings are applied by dipping the article into a molten bath of the
metal or by electroplating the coating from aqueous solution. Some coatings are
also applied by metal spraying. Metal coatings can be classified as noble or
sacrificial. A noble metal coating such as chrome plating protects by its own
resistance to corrosion. Sacrificial coatings such as zinc and cadmium
cathodically protect the base metal.

Inorganic coatings
Vitreous enamels, cement lining, phosphate coatings and oxide coatings
represent inorganic coatings. Vitreous elements or glass coatings are very

corrosion-resisted but somewhat brittle. Cement coatings are very popular for
lining water flow lines.
Organic coatings
organic coatings are the most widely used means of protecting against
corrosion. These coatings represent a large variety of materials that can be
classified as paint, enamel, lacquer, and plastic linings. In recent years, plastic
linings have found frequent usage in protecting tubing, flowlines, and tanks from
corrosion. The surface preparation and application of these coatings is very
important in the success of the coating.
Use of plastics
Generally, plastics are used in applications where temperatures and
pressures are low. Plastic pipe is frequently used for flow lines with particularly
corrosive oilfield brines.
Metals
Metals resistant to corrosion are available for virtually all corrosive
environments encountered in the oil field. The limitation on the use of many of
these metals, such as platinum and gold, is their cost. There are many other
metals and alloys, whose cost is only slightly more than steel, that are resistant
to corrosion in specific applications.
The choice of a metal to resist corrosion in a specific application is
governed by the nature of the corrosive environment, use of the equipment, and

cost. In the oil field, the greatest use of corrosion resistant metals is for pumps
and meters. Here, the amount of metal required is not large and the ability to
resist corrosion necessary. Whenever a metal other than steel is used and is
joined to steel lines, it is important to take precautions to avoid galvanic
corrosion.