Corrosion Basics

Engineering Encyclopedia
Saudi Aramco DeskTop Standards
Corrosion Principles
Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramco’s
employees. Any material contained in this document which is not
already in the public domain may not be copied, reproduced, sold, given,
or disclosed to third parties, or otherwise used in whole, or in part,
without the written permission of the Vice President, Engineering
Services, Saudi Aramco.
Chapter : Materials And Corrosion Control For additional information on this subject, contact
File Reference: COE10101 O.S. Abdul Hamid on 874-2532 or A.M. Al-Ghamdi on 873-1290
Engineering Encyclopedia Materials And Corrosion Control
CONTENTS PAGES
DEFINITION OF CORROSION 1
THE EFFECTS OF CRYSTALLINE STRUCTURE ON THE
MECHANICAL PROPERTIES OF METALS AND ALLOYS 2
Crystalline Structure of Perfect Solids 3
Crystalline Structure of Imperfect Solids 5
Alloys 6
Mechanical Properties of Metals and Alloys 8
Stress-Strain Relationship 11
Stress-Strain Under Uniaxial Loading 12
WHY METALS CORRODE 15
Electromotive Force Series 16
The Electrochemical Corrosion Cell 18
FACTORS THAT AFFECT THE CORROSION RATE OF METALS 24
Electrolyte Conductivity 24
Electrolyte pH 24
Dissolved Gases 27
Oxygen 27
Carbon Dioxide 34
Hydrogen Sulfide 39
Dissolved Salts 40
Oil Content 42
Velocity 42
Erosion Corrosion 42
Impingement 43
TYPES OF MICROBIOLOGICAL ORGANISMS 44
Terminology and Classifications 44
MIC Process 45
Anaerobic Bacteria 48

Slime-Forming Bacteria 48
Iron-Oxidizing Bacteria 49
Sulfur-Oxidizing Bacteria 49
GLOSSARY 50

DEFINITION OF CORROSION
A general definition of corrosion is the deterioration of a substance, or its properties, because

of a reaction with its environment. Most materials corrode when they are exposed to certain
environments. For example, wood rots, iron rusts, and even stone is worn away by water.
Corrosion is inevitable, but it can be slowed or temporarily stopped. However, you must
thoroughly understand the corrosion process in order to control corrosion.
This module will discuss only the corrosion of metals because most of the structures and
systems in the petroleum industry are made from metal. A better definition of corrosion for
the petroleum industry is the destruction of metals by electrochemical reactions.
Saudi Aramco DeskTop Standards 1

THE EFFECTS OF CRYSTALLINE STRUCTURE ON THE MECHANICAL

PROPERTIES OF METALS AND ALLOYS
All solid materials are classified by the arrangement of their atoms. The two basic structures
of solid materials are amorphous and crystalline. The atoms of amorphous materials are not
arranged in an overall pattern (Figure 1). Glass is an example of an amorphous material. The
atoms of crystalline solids are arranged in a pattern like bricks in a building (Figure 2). The
atom arrangement is the same throughout the solid. Metals are examples of crystalline solids.
Atom Arrangement in an Atom Arrangement in a

Amorphous Solid Crystalline Solid
Figure 1 Figure 2

Crystalline Structure of Perfect Solids
The basic building block of a crystalline solid is called a unit cell. The unit cell consists of
metal atoms arranged in a repeating three-dimensional pattern similar to bricks in a wall. Each
atom in a unit cell is surrounded by an identical arrangement of atoms. There are 14 different
unit cell arrangements. Figure 3 shows the three most common unit cells that are found in
metals and alloys. The three unit cells are called “close-packed structures” because their
arrangement minimizes the open spaces, or interstices, between the atoms.
Unit Cells for Body-Centered Cubic, Face-Centered Cubic,

and Hexagonal Close-Packed Structures
Figure 3
Most metals are manufactured from natural compounds called ores. These ores usually
contain metals that are combined with oxygen or sulfur. Useful metals are produced when the
ores are processed or refined to remove oxygen and sulfur. Solid metal crystals, or grains,
form by the processes of nucleation and growth as liquid metal cools from the molten state.
The liquid-to-solid transformation begins with the nucleation of grains in the liquid phase
(Figure 4-A). The grains continue to grow by addition of unit cells until they begin to
impinge on each other (Figures 4-B and 4-C). A single grain contains thousands of unit cells
in a three-dimensional array. When two grains with different orientations impinge on one
another, they form a 3-dimensional interface called a grain boundary. Figure 4-D shows
grains and grain boundaries of a metal sample that has been cut, polished, and etched to show
the grain structure. The difference in contrast between the grains is due to the different
orientations of the unit cells in the grains.

Crystalline Structure of Perfect Solids, Cont’d
A B
G r a i n G r a i n b o u n d a r y
C
D
Nucleation and Grain Growth in a Polycrystalline Solid

Figure 4
Atoms at the grain boundaries are not in their usual places because the recurring structures of
the unit cells are disrupted. This condition gives the grain boundaries a higher energy level
than the rest of the grain and allows the metal to be attacked more rapidly at the grain
boundaries in corrosive environments.
The size of the grains depends on both the rate of nucleation and the rate of grain growth.
When the nucleation rate is low and the grain growth rate is high, the grains will usually be
large. When the nucleation rate is high and the grain growth rate is low, the grains will be
small. Grain sizes vary considerably, but they usually range from 0.025 mm to 0.25 mm.
The cooling rate is also an important factor in determining the size of the grains. A slow,
continuous cooling rate produces a larger grain size and a “coarser” microstructure. A fast,
continuous cooling rate produces a smaller grain size and a “finer” microstructure. The
strength of a polycrystalline solid can be increased by treating the material to achieve a fine
grain size. These strengthening mechanisms can be induced without changing the
composition of the metal.

Crystalline Structure of Imperfect Solids
Real crystalline solids do not have perfect structures. Although real solids are not perfect,
their imperfections, or defects, are limited. Consequently, real crystalline solids can be
represented as perfect solids that contain small defects (Figure 5). A defect at an atomic site
or interstice in a unit cell is called a point defect. A point defect can be a vacant site (void), a
matrix atom in the wrong place, or a foreign atom. A foreign atom is called an impurity atom.
An impurity atom that takes the place of a matrix atom is called a substitutional impurity
atom. An impurity atom in an interstice is called an interstitial impurity atom. A matrix atom
in an interstice is called a self-interstitial atom.
S e l f - i n t e r s t i t i a l
i m p u r i t y a t o m
M a t r i x a t o m
S u b s t i t u t i o n a l
I n t e r s t i t i a l
V a c a n c y
( V o i d )
Point Defects in a Crystalline Structure

Figure 5

Alloys
Pure metals do not provide the strength or other mechanical properties that are necessary for
engineering applications. Most useful metals are mixtures of several elements. These types
of metals are called alloys or solid solutions. The element that makes up most of an alloy is
the base metal or solvent. Other elements that are present in smaller amounts are called
alloying elements or solutes.
The mixture of the solvent and solute atoms can occur in one of two ways. If the solute atoms
are large, they may substitute themselves in the solvent atoms sites. This type of solid is
called a substitutional solid solution. For example, large atoms such as chromium, nickel, or
manganese in an iron matrix would represent a substitutional solid solution.
Alternatively, if solute atoms are much smaller than the solvent atoms, the solute atoms can
locate in an interstice between the solvent atoms. This type of solid is called an interstitial
solid solution. Basically, interstitial solid solutions provide a higher degree of strengthening
than substitutional solid solutions.
An example of an interstitial solid solution is steel, which is the most common alloy that is
used in oil field production equipment. Steel is an alloy of carbon in iron, with iron as the
base metal. Carbon atoms are much smaller than iron atoms. Thus, carbon forms an
interstitial solid solution in iron.
A few alloys are homogeneous mixtures. A homogeneous mixture is called a solid solution or
a single phase because the alloying elements are completely dissolved within the base metal.
For example, copper and nickel both have face-centered cubic structures. If nickel is added to
copper, the unit cell crystalline structure of copper does not change.
Other alloys contain more than one phase. These alloys are called inhomogeneous alloys. In
an inhomogeneous alloy, the alloying elements may be concentrated at certain areas such as
grain boundaries. Carbon steel is an example of an inhomogeneous alloy. Carbon steels are
formed by adding up to 1% carbon to iron. Some of the carbon reacts chemically with the
iron to form iron carbide (Fe3C, also called cementite). Iron carbide makes the carbon steel
much stronger than plain iron. Figure 6 shows a photomicrograph of a carbon steel surface.
The dark lines in the figure are small particles of iron carbide. The white background is
relatively pure iron, or ferrite.

Iron Carbide
(Fe3C)
Iron
Photomicrograph of a Carbon Steel Surface

Figure 6

Mechanical Properties of Metals and Alloys
Mechanical properties of metals and alloys (i.e., strength, ductility, and toughness ) are
important for the design of oil field production equipment. Strength is a measure of the level
of stress that is required to make a material fail. Ductility identifies the amount of permanent
strain before a material fractures. Toughness refers to a material’s resistance to fracture. For
metals and alloys, these mechanical properties can be changed through the use of
microstructural control (alloy composition and heat treatment). Strength and ductility tend to
be incompatible because higher strength materials generally do not have higher fracture
resistance. The only way to gain strength, ductility, and fracture resistance is to make the
metal’s grains smaller.
The practical methods of microstructural control are subject to certain constraints that are
imposed by the fabrication process. Many low-strength parts (e.g., engine blocks) and
complicated parts (e.g., turbine blades) are made by casting. The microstructures of materials
that are cast tend to be coarse (large grain size) and inhomogeneous (contain large dispersed
particles). Consequently, as-cast materials have relatively low strength. High strength
requires a fine microstructure. A fine microstructure can best be obtained in wrought
materials where a large ingot is worked into shape by rolling, extruding, or drawing, as shown
in Figure 7. Because of the large strains involved during forming, metallic materials need to
be relatively soft during fabrication. Thus, fabrication is often carried out at high
temperatures when the metal is more plastic (soft).
A . R o l l i n g
Die Cold drawing die

Die holder
Hot rolled tube Reduced diameter
Container
and wall reduction
Ram
Stationery
mandrel
Extruded Dummy
T ube gripped at end
metal block
and pulled through die
B . E x t r u s i o n C . D r a w i n g
Illustration of Working Operations Used to Form Metal Parts

Figure 7

Mechanical Properties of Metals and Alloys, Cont’d
The most widely used mechanical property for a metal is its yield strength. The tensile
strength of a metal is a measure of the amount of stress it can support before it breaks or
fractures. Stress, σ, is the force per unit area that acts on a material. In Figure 8, the tensile
stress on the metal sample is the force divided by the cross-sectional area of the metal sample
or P/A.
S t r e s s = σ = P / A
Uniaxial Loading
Figure 8

Stresses that are applied to a metal will cause it to change shape or deform. Two types of
deformation can occur. They are elastic and plastic deformation. Small stresses cause elastic
deformation. Elastic deformation is reversible and time independent, which means that the
metal will return to its original shape after small stresses are removed. Larger stresses cause
plastic deformation. Plastic deformation is not reversible. In plastic deformation, the metal
does not return to its original shape after the forces are removed.
Some metals fracture with very little plastic deformation. Metals that fracture with little
plastic deformation are called brittle materials. Cast iron and high-strength steel are examples
of brittle materials. Other metals can undergo considerable plastic deformation before they
fracture.
Stress-Strain Relationship
All metals can be elastically deformed; however, metals behave differently when they are
elastically deformed. Stress and strain characterize the behavior of metals under mechanical
loading. Strain is the percent change in the initial dimensions of a solid under a mechanical
load. Figure 9 shows the simplest way to visualize strain. It shows a material under uniaxial
tension, σ. The material has an original length lo. The uniaxial tension stretches the material
by a distance ∆l. Strain is the percentage increase in the length of the material or ∆l/lo x100.
∆l
Strain in a Structure Under Uniaxial Tension

Figure 9

The relationship between stress and strain during elastic deformation is known as Hooke's
law. Hooke's law states that
stress/strain = constant
where the constant is called the elastic modulus. Hooke's law is limited to strains less than
1%. The elastic modulus is slightly influenced by defects and small amounts of alloying
elements. The elastic modulus is also called Young’s Modulus, which has a value of 206.8 x
105 MPa (30 x 106 psi) for steels.
Stress-Strain Under Uniaxial Loading
The mechanical properties of a metal depend on its microstructure and environment. The
mechanical properties of metals can be tested by subjecting them to uniaxial loading. The
most common test is the tensile test (Figure 10). In the tensile test, a material sample is placed
into a machine and stretched at a constant rate. The sample is deformed in the smaller cross-
sectional area called the gauge length. The test results are plotted as stress-strain curves.
Constant rate of elongation
Moveable grip
Sample
Gauge length
Grip in fixed
position
Schematic of a Specimen in a Tensile Test

Figure 10

Under small stresses, most materials exhibit the elastic behavior described by Hooke's law.
Brittle materials fracture with little plastic deformation. Figure 11 shows a very brittle metal
that fractures with no apparent plastic deformation. Cast iron and high-strength steel exhibit
this type of stress-strain behavior.
x Fracture
Strain ∆l x 100
lo
Stress-Strain Relationship for a Brittle Material

Figure 11

Figure 12, below, shows stress-strain curves for metals that exhibit both elastic and plastic
deformation. Notice the sharp yield point at the transformation between elastic and plastic
deformation for mild steel. The tensile stress required to cause plastic behavior at the yield
point is called the yield stress. The maximum stress the material can support before it
fractures is called the ultimate tensile strength (UTS). Almost all body-centered cubic
structures exhibit this type of stress-strain behavior; however, the yield point is often not well
defined. The lower stress-strain curve in Figure 12 is for aluminum. Metals with face-
centered cubic and hexagonal close-packed structures exhibit this type of behavior.
UTS
Yield
point
Steel
(BCC)
Aluminum
(FCC and HCP)
Strain ∆l x 100 Plastic region

lo
Elastic region
Stress-Strain Relationship for Mild Steel and Aluminum

Figure 12

WHY METALS CORRODE
As mentioned earlier, most metals are produced from natural compounds called ores. These
ores contain metals that are combined with oxygen or sulfur. Metals are formed when ores
are heated to remove oxygen and sulfur. Metals store this heat as chemical potential energy
during the refining process. Metals corrode when they release stored energy through
electrochemical reactions.
Figure 13 shows the refining and corrosion cycle for a common iron ore called hematite,
Fe2O3. Hematite changes to iron when energy is added during the refining process. Steel
mills add carbon during the alloying process to change the iron to steel. The steel releases the
stored energy when it changes to rust, Fe2O3, during the corrosion process. Notice that
hematite and rust have the same composition.
The refining and corrosion cycle in Figure 13 is similar to rolling a ball up a hill (Figure 14-
A) and then letting the ball roll down the hill (Figure 14-B). The ball gains potential energy
as it is rolled up the hill. The ball releases this potential energy as it rolls down the hill. If
obstacles are
S t e e l
Refined A
metals gain
F e + C
( S i , e t c . )
potential
l l o y i n g
C o r r o s i o n
P r o c e s s
P r o c e s s
energy
similar to a
H O
ball that is
CO ,
O , 2+
F e [ F e ]
rolled up a
2
etc.
hill.
E n e r g y
Corrosion
E n e r g y
B
A d d e d
R e l e a s e d
( H e a t )
releases F e
2
O
potential
( H e m a t i t e )
I r o n O r e
energy
similar to
Refining-Corrosion Cycle
the ball as it
Figure 13
rolls down
placed in the path of the ball, it can be stopped the hill.
or slowed down (Figure 14-C). Similarly, C
corrosion can be slowed or temporarily Corrosion

controlled if the proper methods are used. control is
like placing
an obstacle
in the path
of the ball.
Figure 14

Electromotive Force Series
The driving force for electrochemical corrosion is related to the energy that is stored by
metals during the refining process. Metals corrode at different rates because they store
different amounts of energy. Magnesium, aluminum, and iron are metals that require and
store a lot of energy during the refining process. Other metals require and store lower
amounts of energy. Copper and silver are examples of these types of metals.
The corrosion potential of a metal can be measured with a reference half-cell and a voltmeter.
A piece of metal and a reference half-cell are placed in a solution such as water or brine
(Figure 15). Then, they are connected to the terminals of the voltmeter. The voltage reading
from the voltmeter is called the half-cell potential. The half-cell potential is the difference in
potential between the metal and the reference half-cell.
0 . 7 6
V o l t m e t e r
R e f e r e n c e
h a l f - c e l l
M e t a l
E l e c t r o l y t e
(
w a t e r o r b r i n e )
Half-Cell Potential Measurement

Figure 15

Electromotive Force Series, Cont’d
In all cells, the measured voltage arises from two sources—an electric potential at the anode
and an electric potential at the cathode. It is impossible to measure the electrode potential of
one electrode because a complete circuit requires two electrodes. The conventional procedure
is to select one electrode as a reference electrode and to assign it a zero value of electric
potential. Then, the other electrode's potential is referenced to this zero value. By
international convention, the standard hydrogen electrode has been assigned a zero value at
25°C, 1 atm H2 pressure, and 1 Molar H+ concentration. When the voltage of a metal is
measured with respect to a standard hydrogen electrode, the entire voltage is attributed to the
metal.
The potentials of various metals have been measured with respect to a standard hydrogen
electrode, and they are arranged in the table shown in Figure 16. This table, the
Electromotive Force Series for Metals, ranks metals according to their tendency to corrode.
The metals with the most negative potentials appear at the top of the series. Metals near the
top of the series will corrode easily in many environments. These metals require more energy
to be refined from their ores. Metals near the bottom of the list will not corrode as easily.
They require less energy to be refined from their ores.
Metal Volts*
Most energy Magnesium -2.36 Most eager to corrode
required to refine Aluminum -1.66
Zinc -0.76
Iron -0.44
Tin -0.14
Lead -0.13
Hydrogen Electrode 0.00
Copper 0.34
Silver 0.80
Least energy Platinum 1.20
required to refine Gold 1.50 Least eager to corrode
*Voltage measured against the standard hydrogen electrode for each metal immersed in a 1.0 Molar
solution of the metal ions at 25°C.
Electromotive Force Series for Metals

Figure 16

The Electrochemical Corrosion Cell
Electrochemical reactions cause most of the corrosion in the petroleum industry.

Electrochemical reactions involve the transfer of electrons. Electrons and ions produced
during the corrosion process migrate freely throughout the system. The transfer of electrons
is directly associated with the creation of an electrical circuit. This electrical circuit and its
associated chemical reactions are called an electrochemical corrosion cell. For a corrosion
cell to exist, it must contain all of the following four components:
• an anode where corrosion (metal loss) occurs

• a cathode where electrons are consumed
• a metal path through which electrons move from the anode to the cathode
• an electrolyte in which oxidation and reduction reactions occur
An electrochemical corrosion cell can occur between two metals or on the surface of one
metal. Figure 17 shows an electrochemical corrosion cell between two dissimilar metals
(magnesium and steel). The cell is called a galvanic corrosion cell. The two dissimilar metals
are connected with a copper wire (metal path) and placed in salt water. The magnesium has a
more negative potential so it acts as an anode. The steel has a less negative (more positive)
potential than magnesium; therefore, the steel acts as a cathode.
M e t a l P a t h
C u r r e n t
M g S t e e l
Cathode
Anode
Corrosion Cell Between Dissimilar Metals

Figure 17

Anodic Half-Cell Reactions
The chemical reaction at the magnesium anode is called an anodic half-cell reaction. Figure
18 is a magnified view of the anodic half-cell reaction. When the metal corrodes, metal atoms
lose electrons and go into the electrolyte as positively charged metal ions. This reaction is
shown in the following equation:
Mg ⇒ Mg2+ + 2e-
Magnesium Magnesium Electrons
Ions
A n o d i c H a l f - C e l l
2+
M g
2+
M g
A n o d e E l e c t r o l y t e
Anodic Half-Cell Reaction

Figure 18
The reaction above is an example of oxidation. Oxidation is a chemical reaction where

electrons are lost. Two electrons are left behind in the metal when each magnesium ion goes
into the electrolyte. The loss of metal into the electrolyte is characteristic of the
electrochemical processes that occur at the anode.

Cathodic Half-Cell Reactions
Electrons that are produced in the anodic half-cell reaction flow through the metal path to the
cathode. At the cathode, the electrons are used in a chemical reaction. The chemical reaction
at the cathode is called a cathodic half-cell reaction.
Figure 19 shows reactions that occur at the cathode in acid solutions. Hydrogen ions from the
acid solution use electrons from the cathode to form hydrogen atoms. Two hydrogen atoms
usually combine to form a molecule of hydrogen gas as follows:
2H+ + 2e- ⇒ H2 ⇑
Hydrogen Electrons Hydrogen
Ions Gas
C a t h o d i c H a l f - C e l l
+ e
H
H
H
2
+ e
H
H
+ e
H
H
H
2
+ e
H
+ H
E l e c t r o l y t e C a t h o d e
Cathodic Half-Cell Reaction

Figure 19
The cathodic half-cell reaction is an example of reduction. Reduction is a chemical reaction

where electrons are consumed. No metal is lost at the cathode. All corrosion occurs at the
anode.

Combined Anodic and Cathodic Reactions
Previously, two metals were used to represent an electrochemical corrosion cell; however,
anodic and cathodic areas also occur on the surface of one metal. For example, Figure 20 is a
magnified view of a metal surface that is corroding in an acid solution. The oxidation
reactions at the anodic area generate electrons and release iron cations (Fe2+) into the acid.
The electrons travel through the metal to the cathode. At the cathode, the electrons reduce
hydrogen ions from the acid solution to hydrogen atoms. Some of these hydrogen atoms
combine to form molecular hydrogen gas. These oxidation and reduction reactions are
characteristic of electrochemical corrosion reactions.
A c i d
+
S o l u t i o n
2+
Fe
C a t h o d e
H
H
A n o d e
2+
Fe
+ +
+ +
H H
H H
e e
M e t a l
Corrosion Cell on a Metal Surface

Figure 20

Anodic and cathodic areas can occur at many places on a metal surface. General corrosion
occurs when thousands of these tiny corrosion cells occur over the entire surface of the metal.
An example is when carbon steel is placed in an acidic salt solution. As shown previously,
exposed areas of iron and iron carbide create areas with different potentials on the steel
surface. The iron carbide has a lower potential than pure iron, so iron carbide acts as a
cathode. The corrosion cell created by iron and iron carbide is shown in Figure 21. Pitting
occurs when anodes are concentrated in small areas on the surface of the metal.
F e C
F e
( C a t h o d e )
( A n o d e )
M i l d S t e e l
Representation of a Microscopic Corrosion Cell on a Carbon Steel Surface

Figure 21

In nature, the flow of electrons creates electric current. The transfer of electrons between
anodic and cathodic areas creates an electric current in a corrosion cell. Electrons flow from
the anode to the cathode through the metal path, as was shown in Figure 20. Figure 22 shows
the conventional current flow in a typical corrosion cell for iron. By custom, electric current
flows in the opposite direction from electrons in the metal path. The current then flows from
the anode, into the electrolyte, and toward the cathode. Notice that current flows through both
the electrolyte and metal path. Electrons flow only through the metal path.
ELECTROLYTE
ANODE CATHODE
METAL
Conventional Current Flow in a Typical Corrosion Cell

Figure 22
Polarization
Often, electrochemical reactions decrease with time. This decrease occurs because the
potential of the anode becomes more cathodic and the potential of the cathode becomes more
anodic. The potential difference between the anode and cathode decreases. The change in
the potential of the anode and cathode is called polarization. Polarization is caused by current
flow.

FACTORS THAT AFFECT THE CORROSION RATE OF METALS
Many factors affect the corrosion rate of metals. Some of these factors are characteristics of
the electrolyte such as conductivity, pH, dissolved gases, dissolved salts, oil content, and
velocity.
Electrolyte Conductivity
The conductivity of an electrolyte determines how easily positive current flows from the
anode to the cathode in a corrosion cell. An electrolyte becomes more conductive when it has
more ions dissolved in it. For example, salt water is more conductive than distilled water
because of the positive sodium ions and negative chloride ions dissolved in the salt water. In
general, the corrosion rate of a metal will increase as the conductivity of the electrolyte
increases because corrosion current flows more easily between the anode and cathode in the
electrolyte. The conductivity of water produced with hydrocarbons is primarily determined
by the amount of sodium chloride that is dissolved in the water. Other dissolved salts and the
dissolved acid gases, carbon dioxide and hydrogen sulfide also contribute to the conductivity
of produced waters.
The theoretical weight loss of a metal due to corrosion can be calculated by using the
following formula.
W= I x t x e
where:
I = current in amperes
t = time in seconds
e = electrochemical equivalent*
* See Table 14.9 in Corrosion Basics—An Introduction, p. 332.
Electrolyte pH
The degree of acidity or alkalinity of the electrolyte may also affect the corrosion rate of steel.
pH measures the acidity or alkalinity of a water solution. A solution becomes more acidic as
the concentration of hydrogen ions increases. pH is defined as the negative logarithm of the
hydrogen ion concentration.
pH = -log[H+]

Electrolyte pH, Cont’d
The pH scale is usually expressed as a number between 0 and 14, as shown in Figure 23. A
solution with a pH of 7 is neutral. The acidity of a solution increases as the pH decreases
from 7 to 0. The alkalinity of a solution increases as the pH increases from 7 to 14. The pH
value is a logarithmic function; so, a pH of 4 is 100 times more acidic than a pH of 6.
NEUTRAL
INCREASINGLY ACIDIC INCREASINGLY ALKALINE
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH SCALE
pH Scale
Figure 23

Figure 24 shows how the corrosion rate of steel varies with a change in pH when oxygen is
present. Normally, the corrosion rate of steel increases as the solution becomes more acidic.
However, some metals such as aluminum, zinc and lead show increased corrosion rates in
both low pH and high pH solutions.
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
General Effect of pH on Corrosion Rate of Steel

Figure 24
Although the corrosion rate changes with pH, the rate also depends on the composition of the
electrolyte. In brines, protective scales such as carbonate and hydroxides can form. These
scales may slow down or prevent the corrosion of steel.
The pH of the electrolyte and the presence of dissolved gases often affect the corrosion rate
more than conductivity affects it. Common corrosive gases are oxygen, carbon dioxide, and
hydrogen sulfide. Most natural waters will not be corrosive if these gases are taken out of
solution and the pH is kept at a neutral or alkaline level. For example, sea water is corrosive
to steel in most situations; however, seawater can become non-corrosive if dissolved oxygen
is removed and if the pH is kept at 7.0 or above. Saudi Aramco uses this technique to control
corrosion at the Qurayyah seawater treatment plant, which is the largest seawater injection
system in the world.

Dissolved Gases
Oxygen
Oxygen corrosion is characterized by pitting attack. Dissolved oxygen corrodes steel more
rapidly than does an equivalent amount of carbon dioxide or hydrogen sulfide. Oxygen can
cause corrosion at concentrations as low as 50 parts per billion (ppb). Also, a small amount
of dissolved oxygen can drastically increase the corrosivity of water that contains carbon
dioxide or hydrogen sulfide.
Oxygen is usually not present in subsurface waters. Oxygen can enter petroleum production
systems in many places. It is important to keep oxygen out of production systems. For
example, a gas blanket (2 - 4 oz.) may be needed on tanks to prevent oxygen from being
sucked into a tank when the liquid level is lowered. Pumps, especially centrifugal pumps, can
suck in oxygen. Oxygen can even enter when the pump’s mechanical seals appear to be
satisfactory. Oxygen can also be sucked into a line under pressure through small leaks if the
fluid velocity is high. Oxygen may also enter through loose mechanical couplings such as
Victaulic or threaded couplings.
Water from lakes, oceans, or streams is saturated with oxygen. Water pumped from shallow
wells may also contain oxygen. Sometimes, these types of water are used for water injection.
All dissolved oxygen should be removed from these waters to prevent corrosion.
Dissolved oxygen speeds up corrosion in two ways: (1) it depolarizes the cathode, and (2) it
forms iron precipitates that prevent anodic polarization. One possible cathodic reaction for
the corrosion process is as follows:
2H+ + 2e- ⇒ H2 ⇑
Hydrogen Electrons Hydrogen
Ions Gas
When oxygen is present in the electrolyte, two other cathodic reactions are possible. The
cathodic reaction that occurs depends on the pH of the solution. In solutions with an acidic
pH, the cathodic reaction is as follows:
O2 + 4H+ + 4e- ⇒ 2H2O

Oxygen Hydrogen Electrons Water
Ions
In solutions with a neutral or alkaline pH, the cathodic reaction is as follows:
O2 + 2H2O + 4e- ⇒ 4OH-

Oxygen Water Electrons Hydroxyl
Ions

The rate of these reactions is determined by the availability of oxygen at the cathode. The
availability of oxygen at the cathode is limited by the diffusion rate of oxygen through the
solution.
To understand the effect of oxygen, consider a reaction without oxygen (Figure 25).
Hydrogen ions accept electrons at the cathode and form hydrogen gas on the metal surface.
On the right side of the figure, the hydrogen gas bubbles build up over the cathode. These
hydrogen gas bubbles prevent other hydrogen ions from accepting electrons at the cathode;
therefore, the corrosion process slows down. This process is called cathodic polarization.
2 +
F e
2 +
F e
2 +
2 +
F e
H H H
H F e H H H
2 2 2
2 2 2 2
C a t h o d e
-
e
-
e
C a t h o d e
A n o d e
I r o n M e t a l
Cathodic Polarization
Figure 25
In Figure 26, oxygen is present in the system. When oxygen is present, it easily accepts
electrons at the cathode. The corrosion rate is limited mostly by the rate at which oxygen can
diffuse to the cathode. Thus, oxygen acts as a cathodic depolarizer. Dissolved oxygen acts as
a cathodic depolarizer at as little as 50 ppb.
2 +
+ F e
H +
2 +
F e
H + 1 / 4 O
1 / 2 H O
2 +
2 +
F e
F e
H H
H H H
2 2
2 2 2
- -
e e
e -
-
e
e
e
C a t h o d e
C a t h o d e
A n o d e
I r o n M e t a l
Cathodic Depolarization
Figure 26

Oxygen also accelerates corrosion by preventing polarization of the anode. Oxygen reacts
with iron ions at the anode to form iron precipitates that prevent anodic polarization.
Corrosion increases because more iron goes into solution to keep the ferrous ion
concentration in chemical equilibrium with iron. The following equations show how oxygen
reacts with iron ions to form iron precipitates.
Iron is oxidized at the anode. The iron atom loses two electrons and goes into solution as a
ferrous ion. The corrosion reaction at the anode is as follows:
Fe ⇒ Fe2+ + 2e-
Iron Ferrous
Atoms Ions
Oxygen chemically reacts with ferrous ions in solution and oxidizes the ferrous ions to ferric
ions. This reaction is shown as follows:
Fe2+ ⇒ Fe3+ + e-
Ferrous Ferric
Ions Ions
If the pH of the solution is above 4, the ferric ions react with hydroxyl ions in the electrolyte
to form ferric hydroxide. Ferric hydroxide is insoluble and precipitates from solution as
follows:
Fe3+ + 3OH- ⇒ Fe(OH)3⇓

Ferric Hydroxyl Ferric
Ions Ions Hydroxide
Ferric hydroxide can increase or decrease the corrosion rate. If solid ferric hydroxide is
carried away from the steel surface, the corrosion rate will increase. If ferric hydroxide is
deposited on the metal surface, the corrosion rate will be reduced. Deposits on the surface
slow down the cathodic reactions by forming a barrier between the steel and the water.
Although the corrosion rate usually decreases when ferric hydroxide is deposited, some pits
may continue to form because the deposits do not totally protect the steel.

The solubility of oxygen in water is a function of temperature, pressure and dissolved salt
content. Figure 27 shows the solubility of oxygen as a function of dissolved salt content at
20°C and 30°C. Notice that, at either temperature, oxygen becomes less soluble as the salt
concentration increases. For a given salt concentration, Figure 27 also shows that the
solubility of oxygen is lower at higher temperatures.
10
8 20°C
6
30°C
0
0 5 10 15 20 25 30 35
NaCl Concentration (ppm x 1000)

Effect of NaCl Concentration on Oxygen Solubility
Figure 27

Figure 28 compares the corrosion rates for iron in oxygenated water in closed and open
systems at different temperatures. In a closed system with a fixed amount of oxygen, the
corrosion rate of steel increases as the temperature increases. An example of a closed system
is a steam boiler. In the figure, the corrosion rate of steel in an open system begins to
decrease above 80°C. The corrosion rate decreases because oxygen is less soluble at higher
temperatures. The decrease in corrosion rate due to lower oxygen solubility is greater than
the increase in corrosion rate that is caused by a rise in temperature.
30
Closed System
20
10
Open System
0
0 20 40 60 80 100 120 140 160 180
Temperature, °C
Effect of Temperature on Corrosion of Iron in Oxygenated Water

Figure 28

Figure 29 shows that the corrosion weight loss of steel is nearly proportional to the oxygen
concentration for low levels of oxygen that is dissolved in water; however, the overall weight
loss begins to level off with further increases in dissolved oxygen concentration because a
layer of iron oxide forms on the metal surface. These corrosion deposits reduce the speed at
which anodic and cathodic reactions occur, and they reduce the general weight loss over the
metal surface, as shown in Figure 29. Pitting attack usually continues to occur under the iron
oxide corrosion deposits.
Corrosion as a Function of Oxygen Concentration

Figure 29

A difference in oxygen concentration of the electrolyte in two areas of a system causes

pitting. This type of corrosion cell is called an oxygen concentration cell. Corrosion occurs
in the area with the lowest oxygen content. Roads are a common cause of oxygen
concentration cells in buried pipelines (Figure 30). Roads and traffic pack soil down so that it
is less permeable to oxygen. Also, asphalt prevents oxygen from reaching the soil
underneath.
Paved Open
road desert
Electric Electric
current current
Packed
Aerated Soil Non-Aerated Soil Aerated Soil
Oxygen Concentration Cell Created by Paved Roads

Figure 30
Saudi Aramco has experienced some evidence of dissolved oxygen corrosion attack in utility
lines that supply raw water. In these cases, the interiors of 24-inch and 36-inch pipelines have
been protected with in situ cement lining.

Carbon Dioxide
Carbon dioxide is a corrosive gas that is very soluble in water. It is usually present in
petroleum or natural gas production. Carbon dioxide corrosion often takes the form of pitting
attack. The corrosion pits are usually deep with steep sides and sharp edges.
The following chemical reactions show how carbon dioxide increases the corrosivity of water.
Carbon dioxide dissolves in water to form carbonic acid as follows:
CO2 + H2O ⇔ H2CO3

Carbon Water Carbonic
Dioxide Acid
Carbonic acid ionizes to form hydrogen and bicarbonate ions.
H2CO3 ⇔ H+ + HCO3-
Carbonic Hydrogen Bicarbonate
Acid Ion Ion
The bicarbonate ion ionizes further to form hydrogen and carbonate ions.
HCO3- ⇔ H+ + CO32-
Bicarbonate Hydrogen Carbonate
Ion Ion Ion
The chemical reactions above show that carbon dioxide may be found in water as free carbon
dioxide, disassociated carbonic acid, bicarbonate ions, or carbonate ions. The pH of the water
decreases as carbonic acid ionizes to form hydrogen and bicarbonate ions. The pH decreases
because water becomes more acidic as the hydrogen ion concentration increases. This
reduction in pH is responsible for carbon dioxide corrosion. Carbon dioxide corrosion is
sometimes called “sweet” corrosion. Saudi Aramco has seen evidence of sweet corrosion in
the Wasia brine handling system. Large diameter pipe has suffered severe general corrosion.
This severe corrosion causes aggressive thinning of the pipe wall. Corrosion has been
prevented with cement-lined pipe or with pipe that is internally coated with fusion bonded
epoxy (FBE).
The solubility of carbon dioxide in water is affected by the pressure, temperature and
composition of the water. The solubility of carbon dioxide increases as pressure increases.
The partial pressure of carbon dioxide can be calculated to estimate the corrosivity of sweet
gas condensate wells as follows:

PCO2 = (XCO2) (p)
where-
PCO2 = the partial pressure of carbon dioxide
XCO2 = the mole fraction of carbon dioxide in the gas stream
p = the total system pressure
The mole fraction of a gas, X, is equal to its mole percent divided by 100. In gas analysis, gas
composition is usually reported in volume percent. Volume percent is equivalent to mole
percent; therefore, the mole fraction of CO2 is equal to the volume percent divided by 100.
For example, the partial pressure of CO2 in a gas system that operates at 1000 psig and
contains 10 percent CO2 can be calculated as follows:
XCO2 = 10%/100 = 0.1
PCO2 = (0.1)(1000) = 100 psi
The guidelines in Figure 31 have been used to predict the corrosivity of sweet gas condensate
wells.
Carbon Dioxide
Partial Pressure Corrosivity Rating
>0.207 Mpa (>30 psi) Usually indicates corrosion

0.048 - 0.207 Mpa (7 - 30 psi) May indicate corrosion
< 0.048 Mpa (<7 psi) Non-corrosive
Corrosivity Prediction for Sweet Gas Condensate Wells

Figure 31
NOTE: The effect of temperature is not included in these general guidelines. These
guidelines do not apply when produced water has a high mineral content. The guidelines also
do not apply when the gas stream contains oxygen and/or hydrogen sulfide.

If it is necessary to consider temperature, use the following equation developed by DeWaard

and Milliams. The maximum corrosion rate for a “sweet” system can be calculated at any
temperature and partial pressure of carbon dioxide. The equation describes corrosion
conditions in systems without protective corrosion deposits. The equation is as follows:
2,320
Logr = 8.73 − − 5.55x10−3 T + 0.67LogPCO2
(T + 273)
where -
r = corrosion rate in mils per year
T = temperature in degrees Celsius
PCO2 = partial pressure of CO2 in pounds per square inch

The nomograph in Figure 32 is used to calculate carbon dioxide corrosion rates using the
DeWaard and Milliams equation. For example, At 7°C and 1.5 psi CO2 partial pressure, the
corrosion rate is 4 mpy. Notice that even low partial pressures of carbon dioxide can produce
high corrosion rates as the temperature increases.
200
70
65 100
80
60
400 60
55
40
300
50 20
100
45 80 10
60 8
40 6
40
4
35
20
2
30
10
8 1.0
25 0.8
6
0.6
20 4
0.4
2
15 0.2
1
10 0.1
Corrosion Rate, mpy CO2 Partial
5 pressure, psi
0
Temperature, °C
Nomograph for Calculation of Corrosion Rates as a Function of

CO2 Partial Pressure and Temperature (DeWaard and Milliams)
Figure 32

Carbon dioxide solubility is also affected by the composition of water. Iron reacts with
carbonate ions in water to form iron carbonate. When no more iron carbonate can dissolve in
solution, it precipitates as a corrosion product, as shown by the chemical reaction below.
Fe + 2H+ + CO32- ⇒ FeCO3⇓ + H2

Iron Hydrogen Carbonate Iron Hydrogen
Ions Ions Carbonate
Iron carbonate corrosion products that form on the steel surface greatly reduce the corrosion
rate. Here is an example. The top curve in Figure 33 shows the maximum corrosion rate as a
function of CO2 partial pressure at room temperature. The lower curve in the figure shows
the corrosion rate of a steel surface that is covered with a layer of iron carbonate and that is
under similar conditions.
Assume that iron carbonate is not present. At a carbon dioxide partial pressure of 20 psi, steel
will corrode at a rate of about 48 mils/year. With an iron carbonate layer on the steel surface,
the corrosion rate for the same carbon dioxide partial pressure is about 17 mils/year.
1000
800
a W d e r D aa
n a 600 W d De aar
x Abramyan (6)
400 Ovodov (%)
x Greco and W
right (8)
Rhodes and Clark (7)
x
x
200
x
100
x
80
60
~48 mils
x
40 x
x
x
20 x
~17 mils
x
10
1 2 4 6 8 10 20 40 60 80 100 200 400 600 1000
CO2 Partial Pressure (psi)

Uniform Corrosion Rate of Steel as a Function of CO2 Partial Pressure at Room Temperature
Figure 33

It is difficult to predict whether protective iron carbonate films will form in aqueous carbon
dioxide environments. Sometimes, a protective iron carbonate film never forms, and
corrosion continues at the rate that is shown by the upper curve in Figure 33. If the iron
carbonate film forms, severe pitting can occur in breaks or defects in the film.
Hydrogen Sulfide
Hydrogen sulfide (H2S) is a corrosive gas that is often present in petroleum and natural gas
production. Except for a few offshore fields, most of Saudi Aramco's production contains
CO2 and H2S. Hydrogen sulfide is usually produced along with CO2. Hydrogen sulfide is
more soluble in water than is CO2. However, CO2 makes the H2S more corrosive. A very
small amount of oxygen can also increase the corrosion rate.
Hydrogen sulfide dissolves in water to form a weak acid. The weak acid dissociates to
hydrogen ions. The hydrogen ions are responsible for the corrosive nature of H2S. Hydrogen
sulfide usually causes pitting in steel. Hydrogen sulfide also causes blistering of steel, sulfide
stress cracking, hydrogen embrittlement, and hydrogen-induced cracking. Hydrogen sulfide
corrosion is sometimes called "sour" corrosion. The corrosion reactions of H2S, water and
iron are complex; however, the general corrosion reaction can be shown as follows:
Fe2+ + H2S ⇒ FeS⇓ + 2H+

Ferrous Ions Hydrogen Sulfide Iron Sulfide Hydrogen
Insoluble iron sulfide (FeS) corrosion products deposit quickly on steel surfaces in aqueous
H2S environments. This rapid deposit occurs because of the low solubility of iron sulfide in
water. The iron sulfide deposits protect steel surfaces under many conditions. Pitting occurs
at areas where protective iron sulfide deposits do not cover steel surfaces. Pitting may be
quite severe in these areas because iron sulfide is cathodic to steel. Any exposed steel
becomes the anode of a galvanic corrosion cell.
The composition of iron sulfide corrosion deposits varies although the composition is often
shown as FeS. Six different crystalline structures of iron sulfide have been identified in oil
field systems. Some iron sulfide deposits are rich in iron. Other iron sulfide deposits are rich
in sulfur. The ratio of iron to sulfur in the deposits depends upon both the environmental
conditions of the system and the composition of the electrolyte.
Temperature and pressure affect the solubility of oxygen, carbon dioxide, and hydrogen
sulfide in the same way. An increase in temperature reduces the solubility of dissolved H2S
in an open system. Temperature also affects sulfide stress cracking, hydrogen embrittlement,
and hydrogen-induced cracking of steels in H2S service. Sulfide stress cracking and
hydrogen embrittlement are most likely to occur at temperatures up to 65°C (150°F).

An increase in pressure will increase the solubility of H2S in water; however, an increase in
dissolved H2S may not greatly increase the corrosion rate. Protective iron sulfide corrosion
deposits can form with dissolved H2S concentrations as low as 10 to 50 ppm. An increase in
H2S concentration does not greatly increase the overall corrosion rate after iron sulfide
deposits cover the steel surface.
Dissolved Salts
Dissolved salts, pH, and dissolved gases have a major effect on the corrosivity of an
electrolyte. Dissolved salts simultaneously change the conductivity and solubility of
dissolved gases in the electrolyte. The conductivity of water increases as its dissolved salt
content increases; however, gases become less soluble in water as the dissolved salt content
increases. Figure 34 shows how increasing the dissolved sodium chloride concentration
changes the corrosion rate of steel that is immersed in aerated water. At first, the water
becomes more corrosive to steel due to the increase in conductivity. Then, the reduced
solubility of oxygen affects the corrosion rate more than the increased conductivity affects the
corrosion rate. The result is that the corrosion rate begins to decline with added salt content.
Similar curves can be drawn for waters that are saturated with carbon dioxide and hydrogen
sulfide at different salt concentrations.
0
0 3 5 10 15 20
NaCl Concentration, Wt %
Effect of Sodium Chloride Concentration on the Corrosion of Steel in Aerated Solutions

Figure 34

Dissolved Salts. Cont’d
The kinds of salts dissolved in water also affect the corrosion rate. Research shows that
chloride ions aid corrosion more than do sulfate, bicarbonate, or carbonate ions. Chloride
ions prevent uniform corrosion deposits from forming a protective film on many corroding
metal surfaces. As a result, pitting corrosion can occur in many environments. Chloride ions
may also cause crevice corrosion and stress corrosion cracking of stainless steels.
The type of cations that are dissolved in water also influence corrosion rates. Laboratory tests
show that some cations are more corrosive than are other cations. Figure 35 lists some of
these cations. The cations at the top of the list increase corrosion rates more than do the
cations at the bottom of the list.
Cations
1. Ferric More influence
2. Potassium on corrosion rate
3. Sodium
4. Barium
5. Calcium
6. Manganese Less influence
7. Magnesium on corrosion rate
Cations in the Order of Their Corrosivity

Figure 35

Oil Content
Mixtures of oil and brine occur often in petroleum operations. Oil does not conduct
electricity; therefore, corrosion is not possible when oil wets the metal surface. Even highly
conductive brine that is emulsified (mixed in small droplets) in oil may not be corrosive. In
this case, the oil prevents contact between the electrolyte and the metal. The same salt water
may be very corrosive if it wets the metal surface of a tank or flowline. Oil that is emulsified
in water does not protect the metal from corrosion if water wets the surface.
Because of their ability to oil wet steel surfaces, some crude oils show natural corrosion
inhibition tendencies. Saudi Aramco has studied the natural corrosion-inhibiting properties of
various crude oils. The results indicate that in 15% crude oil/65% brine mixtures that contain
CO2 and H2S, natural corrosion-inhibiting properties are rated as follows:
Greatest inhibition properties Abu-Safa Medium

Arabian Extra Light
Arabian Light
Zulu/Marjan Medium
Least inhibition properties Safaniya Heavy
The inhibition properties of crude oils probably explains why flowlines that carry very high
water content raw crude have not experienced significant corrosion problems. Selected
problems occurred on lines where water displaced oil on the bottom in order to wet the metal
surface.
Velocity
A difference in velocities between two areas can create oxygen concentration cells in water
that contains dissolved oxygen. Less oxygen reaches the metal surface in stagnant areas than
in areas with higher velocity. Corrosion occurs in the areas with the lowest oxygen content.
Erosion Corrosion
Usually, the rate of corrosion increases as velocity increases. The rate increases because
corrosive agents such as oxygen, carbon dioxide, or hydrogen sulfide get to the metal surface
quicker due to the increase in velocity. At high velocities, protective corrosion deposits or
inhibitor films may be torn from the metal and thereby expose the unprotected metal surface.
The unprotected metal surface will suffer higher corrosion rates.

Impingement
Moving waters that contain solids are often more corrosive than similar waters without solids.
Solids strike protective corrosion deposits and break them off. Thus, the metal surface is
constantly exposed to the corrosive environment. Corrosion that is related to velocity and
solids in the water is most severe at bends in piping.
The effect of velocity on corrosion rates is not always predictable. Stagnant or low velocity
areas in a system may also have high corrosion rates. One reason is that sulfate-reducing
bacteria can grow under these conditions and lead to severe localized corrosion. Saudi
Aramco's program for the treatment of hydrotest water as well as its mothballing procedures
(Saudi Aramco Engineering Standard 007 and Saudi Aramco Engineering Report 2365) are
applications of current technology to control corrosion in stagnant and low velocity areas.

TYPES OF MICROBIOLOGICAL ORGANISMS
Terminology and Classifications
Microscopic life forms, or microbes, are present in almost all water systems and soils.
Microbes can be either plants or animals. Plants are most common, and they are subdivided
under names such as bacteria, algae, fungi, etc. Plants get their energy from different sources.
Algae contain green chlorophyll, and they use photosynthesis to get their energy from
sunlight. All of the other plants can grow without sunlight. They get their energy by feeding
on other nutrients from the soil or water.
It is common in oil field operations to refer to all types of microbes as bacteria. Bacteria can
grow with or without oxygen. Bacteria that need oxygen to grow are called aerobes or
aerobic bacteria. Bacteria that need little or no oxygen to grow are called anaerobes or
anaerobic bacteria. Microbes that float or swim in water are called planktonic bacteria.
Microbes that attach to the metal surface are called sessile bacteria. Most of the bacteria
present in water systems are sessile.

MIC Process
Microbiologically-influenced corrosion (MIC) is corrosion as a result of the activity of

bacteria. Figure 36 shows the steps in biofilm formation. The biofilm begins when (1) small
organic materials attach to the metal surface and (2)microbes are adsorbed onto the organic
layer. A thick biofilm develops (3). The biofilm becomes thick enough to exclude oxygen
from the metal surface and form an anaerobic zone near the surface (4). Aerobic and
anaerobic bacteria species develop where conditions are most favorable for them (5). The
biofilm thickens until parts of it are torn away by flowing water. The process begins again
when the detached biofilm adsorbs onto another part of the metal surface. Studies of biofilms
show that bacteria populations climax in 10 to 14 days.
Anaerobic Aerobic WATER

Bacteria Bacteria
Organic
Material
4 5
3
Organic
2 Ae robic Biofilm
1 Layer Anaerobic Biofilm
Metal Surface
Steps in Biofilm Formation

Figure 36

MIC Process, Cont’d
MIC is mainly caused by the sessile bacteria in the biofilm. The biofilm can provide very
favorable conditions for both anaerobic and aerobic bacteria. The biofilm shelters many
microcolonies of various bacteria next to the metal surface. Figure 37 shows how anaerobic
bacteria develop microcolonies in the biofilm next to the metal surface. In the microcolony
on the left, protons and metal cations are transported or trapped to produce electrochemical
corrosion cells on the metal surface. Localized corrosion potentials can develop on the metal
surface and cause corrosion pitting.
Aerobic Biofilm
Anaerobic Biofilm
Microcolony Microcolony
Metal Surface
Anaerobic Bacteria Microcolonies Next to a Metal Surface
Figure 37

Figure 38 shows how the resulting electrochemical corrosion cell forms a corrosion pit. The
bacteria occupy the pit as it deepens. Corrosion may be related to differences in surface
potential, pH, or in chemical concentrations. Corrosion experts do not agree on the exact
mechanisms.
Aerobic Biofilm
Anaerobic Biofilm
Microcolony Microcolony
Corrosion
Potential
Anaerobic Bacteria Microcolonies Result in an Electrochemical Corrosion Cell

Figure 38

Anaerobic Bacteria
Sulfate-reducing bacteria (SRB) are the most important type of anaerobic bacteria. The
scientific name for the most common SRB is Desulfovibro desulfuricans. SRB generate H2S
which causes corrosion of buried steel structures and external surfaces of well casings. SRB
can live in environments with pH values from 5 to 9, temperatures from 4°C to 77°C, and
pressures up to 1,000 kg/cm2.
SRB consume sulfate ions to get their energy. They convert the sulfate ions to sulfide ions as
follows:
SO42- + 8H ⇒ S2- + 4H2O

Sulfate Atomic Sulfide Water
Ion hydrogen Ion
The hydrogen atoms come from the reduction reaction at the cathode. Hydrogen also comes
from cellulose, sugars, or other organic material present in soil, water, and oil field fluids.
The sulfide ion then reacts with iron ions from the anodic reaction to form iron sulfide as
follows:
Fe2+ + S2- ⇒ FeS

Iron Sulfide Iron
Ion Ion Sulfide
Iron sulfide will cause water to have a black appearance. Oil wet iron sulfide can create
problems because it helps to stabilize emulsions. Bacteria and their by-products can cause at
least two problems in waterflood systems. Iron sulfide and bacterial debris can plug injection
wells if they are carried over into the water injection system. Also, sulfate-reducing bacteria
in waterflood systems can make a reservoir become “sour.” Formation souring occurs when
bacteria produce H2S in reservoir rock. Hydrogen sulfide reduces the value of oil and gas and
increases the corrosion of production equipment. Formation souring has been observed in
North America, however, it has not been a problem in Saudi Aramco operations. Other
problems with iron sulfide were discussed earlier in the section on hydrogen sulfide.
Slime-Forming Bacteria
Many types of bacteria produce slime to protect themselves in adverse environments. Slime-
forming bacteria commonly occur in cooling towers and water injection systems. There are
several types of slime-forming bacteria (e.g., Pseudomonas, Enterobacteria, Micrococci, and
Bacillis). Generally, slime-forming bacteria are aerobic, but some slime-forming bacteria are
anaerobic. A high bacteria count, therefore, usually indicates the presence of slime-forming
bacteria. Most slime that is found in waterflood systems come from bacteria. The slime can
plug injection filters and formations.

Iron-Oxidizing Bacteria
Bacteria that oxidize iron are usually found in fresh water; however, they also occur in salt
water. These bacteria oxidize ferrous iron to ferric iron according to the following chemical
equation.
4FeCO3 + O2 + 6H2O ⇒ 4Fe(OH)3 + 4CO2

Iron Oxygen Water Ferric Carbon
Carbonate Hydroxide Dioxide
The ferric hydroxide precipitates as a coating on the bacteria cell wall. The carbon dioxide
can form carbonic acid and increase corrosivity.
Generally, iron-oxidizing bacteria are aerobic; however, they can grow in as little as 0.5 ppm
oxygen. These bacteria produce slime when they grow at low oxygen levels. Examples of
iron-oxidizing bacteria are Sideracapsa, Gallionella, and Spheratilus.
Sulfur-Oxidizing Bacteria
Aerobic and anaerobic bacteria oxidize sulfur and other sulfur compounds to produce sulfuric
acid. The best known aerobic, sulfur-oxidizing bacteria is Beggiatoa. They grow in open pits
and ponds or in waters that contain hydrogen sulfide. Beggiatoa appear as a gray slime. The
slime can plug injection filters and formations.

GLOSSARY
acidity An acid condition; the quality or state of being acid.
activation polarization The characteristics of the reaction control the corrosion rate.
Examples of characteristics are the type of metal, the hydrogen
ion concentration, and the temperature of the system.
adsorb To gather on a surface in a condensed layer.
aeration cell An oxygen concentration cell; an electrolytic cell resulting from

differences in dissolved oxygen at two points.
aerobes Bacteria that need oxygen to grow.
alkalinity An alkaline condition; the quality that constitutes an alkali.
alloying elements The elements in an alloy that are present in smaller amounts than
the base metal.
alloys Metals made from a mixture of two or more elements.
amorphous material Materials that usually exhibit short-range order in the position
and stacking sequence of their atoms or molecules.
anaerobes Bacteria that need little or no oxygen to grow.
anion An ion with a negative charge.
anode The electrode or area at which oxidation or corrosion occurs.
anodic half-cell reaction A chemical reaction that occurs at the anode.
anodic polarization The decrease in the initial anode potential that results from
current flow effects at or near the anode surface. The potential at
the anode becomes more noble (more positive) because of
anodic polarization.
aqueous Relating to water; an aqueous solution is a water solution.
base metal The metal that makes up most of an alloy; the principle metal
under a coating of another metal.
brine A heavily saturated salt solution.

brittle Descriptive of metals that allow little plastic deformation.
cathode The electrode or area where practically no corrosion occurs.

Reduction reactions take place at the cathode.
cathodic half-cell reaction A chemical reaction that occurs at the cathode.
cation An ion with a positive charge.
cementite A compound of iron and carbon, which is known chemically as

iron carbide. Cementite has the approximate chemical formula
Fe3C.
cracking The fracture of a metal in a brittle manner along a single or

branched path.
crystalline Materials that exhibit long-range order in the position and

stacking sequence of their atoms or molecules.
depolarize To eliminate or reduce polarization.
deposit A substance (produced by the environment) that forms on the

surface of a material.
differential aeration cell An oxygen concentration cell.
dislocation Defects that produce distortions centered about a line in a

crystalline solid.
ductility The ability of a metal to change form without breaking. A metal

is considered ductile if its cross sectional area can be reduced by
more than 50%.
electrical current A current caused by the flow of electrons. Electrical current

flows in a direction opposite to the flow of electrons.
electrochemical A corrosion cell that consists of an anode and a cathode in

corrosion cell electrical contact in an electrolyte.
electrochemical reaction A chemical reaction that involves the transfer of electrons and
electric current.
electrode A site where an electrical current enters the metal or leaves the
metal to enter the solution.

electrolyte An ionic conductor (usually an aqueous solution).
embrittlement Severe loss of ductility of a metal (or alloy).
film A thin surface layer that may or may not be visible.
galvanic cell A cell consisting of two different metals in contact with a

common electrolyte.
galvanic corrosion Corrosion that is increased because of the current that is caused
by a galvanic cell.
general corrosion Corrosion of a uniform manner.
grain A portion of a solid metal in which the atoms are arranged in an

orderly pattern.
grain boundary The irregular junction of two adjacent grains.
half-cell A pure metal that is in contact with a solution of known

concentration of its own ion. When two half-cells are coupled
together, the result is the development of an overall potential,
which is the sum of both half-cells.
homogeneous A condition where all elements in a chemical compound are

completely mixed.
hydrogen embrittlement A severe loss of ductility that is caused by hydrogen.
hydrogen-induced Hydrogen damage that is characterized by the brittle fracture of

cracking normally ductile alloys that are under sustained load in the
presence of hydrogen.
inhomogeneous A condition where all elements in a chemical compound are not

completely mixed.
interstitial atom An atom that is situated between the atomic components in a

crystalline solid.
interstitial solid solution A solid solution in which the solute atoms occupy positions that
do
not correspond to the lattice points of the solvent.
ion An electrically charged atom or group of atoms.

local cell A galvanic cell that is caused by small differences in the

composition of the metal or electrolyte.
metal path The contact between the anode and cathode that allows the flow
of electrons and electric current.
microbes Microscopic plant and animal life forms.
noble metal A metal that is not very reactive and that may be found naturally
in metallic form on earth. Silver, gold, and copper are examples
of noble metals.
nucleation The initiation of a phase transformation at discrete sites, the new

phase growing on nuclei (see nucleus).
nucleus The first structurally stable particle that is capable of initiating

recrystalization of a phase or the growth of a new phase.
oxidation A chemical reaction where electrons are lost. For example,

when a metal goes from the metallic state to the corroded state
(opposite of reduction).
oxygen concentration cell A galvanic cell that is caused by a difference in oxygen

concentration at two points on a metal surface.
pH A measure of the acidity or alkalinity of a solution. A value of

seven is neutral. pH numbers less than seven are acid. pH
numbers greater than 7 are alkaline. pH is the negative
logarithm of the hydrogen ion concentration.
pitting Highly localized corrosion that results in deep penetration at

only a few spots.
planktonic Bacteria that float or swim in the system.
point defect A defect at an atomic site or interstice in a unit cell.
polarization A change in potential that is caused by current flow.
reduction A chemical reaction that results in a gain of electrons (opposite

of oxidation).
rusting Corrosion of an iron or iron-based alloy to form a reddish-brown

product that is mostly hydrated ferric oxide.

sessile Bacteria that attach themselves to surfaces.
solid solution A homogeneous mixture where alloying elements are completely

dissolved in the base metal.
solubility The ability to be dissolved; relative capability of being dissolved.
standard electrode Potential of an electrode process. It is based on a scale that

potential uses the standard hydrogen half-cell as a reference.
strain A percentage change in the initial dimensions of a solid under

mechanical loading.
strength A measure of the level of stress that is required to make a

material fail.
stress Force per unit area.
stress corrosion cracking Cracking that results from a combination of corrosion and
tensile stress.
substitutional solid A solid solution in which the solute atoms are randomly located
at
solution some of the lattice points of the solvent.
sulfate-reducing bacteria Microorganisms that generate hydrogen sulfide by metabolizing

sulfates.
sulfide stress cracking Hydrogen-induced cracking of a metal in an environment that

contain hydrogen sulfide. SSC is associated with steels that have
yield strengths above 90,000 psi (23 Rockwell C).
toughness A measure of the work per unit volume that would be required in
order to cause fracture in a particular material; the measure of a
particular material’s resistance to fracture.
ultimate tensile strength The maximum load that a structure can support.
wrought material A material that is formed or fashioned by rolling, extruding, or

drawing (stamping) a large ingot.
yield point The point on a stress-strain curve of sudden plastic yield at the
start of plastic deformation (common only in low-carbon steels).

Corrosion Basics

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Corrosion Basics

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Engineering Encyclopedia

Saudi Aramco DeskTop Standards

Saudi Aramco DeskTop Standards

Saudi Aramco DeskTop Standards

A general definition of corrosion is the deterioration of a substance, or its properties, because

Saudi Aramco DeskTop Standards 1

THE EFFECTS OF CRYSTALLINE STRUCTURE ON THE MECHANICAL

Atom Arrangement in an Atom Arrangement in a

Saudi Aramco DeskTop Standards 2

Crystalline Structure of Perfect Solids

Unit Cells for Body-Centered Cubic, Face-Centered Cubic,

Saudi Aramco DeskTop Standards 3

Crystalline Structure of Perfect Solids, Cont’d

Nucleation and Grain Growth in a Polycrystalline Solid

Saudi Aramco DeskTop Standards 4

Crystalline Structure of Imperfect Solids

Point Defects in a Crystalline Structure

Saudi Aramco DeskTop Standards 5

Saudi Aramco DeskTop Standards 6

Photomicrograph of a Carbon Steel Surface

Saudi Aramco DeskTop Standards 7

Mechanical Properties of Metals and Alloys

Die Cold drawing die

Hot rolled tube Reduced diameter

and wall reduction

T ube gripped at end

and pulled through die

Illustration of Working Operations Used to Form Metal Parts

Saudi Aramco DeskTop Standards 8

Mechanical Properties of Metals and Alloys, Cont’d

Saudi Aramco DeskTop Standards 9

Strain in a Structure Under Uniaxial Tension

Saudi Aramco DeskTop Standards 10

Stress-Strain Under Uniaxial Loading

Constant rate of elongation

Schematic of a Specimen in a Tensile Test

Saudi Aramco DeskTop Standards 11

Stress-Strain Relationship for a Brittle Material

Saudi Aramco DeskTop Standards 12

Strain ∆l x 100 Plastic region

Stress-Strain Relationship for Mild Steel and Aluminum

Saudi Aramco DeskTop Standards 13

WHY METALS CORRODE

corrosion can be slowed or temporarily Corrosion

Saudi Aramco DeskTop Standards 14

Electromotive Force Series

Half-Cell Potential Measurement

Saudi Aramco DeskTop Standards 15

Electromotive Force Series, Cont’d

Electromotive Force Series for Metals

Saudi Aramco DeskTop Standards 16

The Electrochemical Corrosion Cell

Electrochemical reactions cause most of the corrosion in the petroleum industry.

• an anode where corrosion (metal loss) occurs

Corrosion Cell Between Dissimilar Metals

Saudi Aramco DeskTop Standards 17

Anodic Half-Cell Reactions

Anodic Half-Cell Reaction

The reaction above is an example of oxidation. Oxidation is a chemical reaction where

Saudi Aramco DeskTop Standards 18

Cathodic Half-Cell Reactions

Cathodic Half-Cell Reaction

The cathodic half-cell reaction is an example of reduction. Reduction is a chemical reaction