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CORROSION
PRINCIPLES

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Table of Contents

Page No.

1.0 Introduction 1

2.0 References and Definitions 1

2.1 References 1
2.2 Definitions 1

3.0 Why Metals Corrode 2

3.1 Corrosion Defined 2
3.2 Metal Ores 2
3.3 Chemical Free Energy 2

4.0 Nature of Corrosion Reaction 3

4.1 Corrosion by Water 3
4.2 Voltage Source 3
4.3 Electrical Circuits 3
4.4 Polarization 4

5.0 Nature of Metals 6

5.1 Inhomogeneities in Metal Surfaces 6

6.0 Effect of Electrolyte Composition 7

6.1 Conductivity 7
6.2 Hydrogen Ion Concentration (pH) 7
6.3 Dissolved Gases 8
6.3.1 Oxygen 8
6.3.2 Carbon Dioxide 9
6.3.3 Hydrogen sulphide 9
6.4 Chloride Ions 10

7.0 Physical Variables 10

7.1 Temperature 10
7.2 Pressure 11
7.3 Velocity 11
7.3.1 Erosion/Velocity (API RP 14E) 11

8.0 Forms of Corrosion 12

8.1 Uniform Corrosion 12
8.2 Pitting Corrosion 12
8.3 Bimetallic Corrosion 14
8.4 Flow Enhanced Corrosion (Erosion Corrosion) 15
8.5 Cavitation Corrosion 15

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Table of Contents

Page No.

8.6 Intergranular Corrosion 15

8.7 Hydrogen Induced Failures 16
8.8 Sulphide Stress Cracking 16
8.9 Stress Corrosion Cracking 17
8.10 Corrosion Fatigue 18
8.11 Microbiologically Influenced Corrosion (MIC) 19
8.12 Oxygen Corrosion 19
8.13 Sweet Corrosion (CO2) 20
8.14 Sour Corrosion (H2S) 21

Attachments:
1. Free Energies of Metal Oxides 22
2. Galvanic Series in Sea Water 23
3. Galvanic Corrosion Material Selection Guide 24
4a. Corrosion Cell 29
4b. Zinc-Copper Corrosion Cell 29
5. Electromotive Force Series 30
6a. Polarization Curve 31
6b. Corrosion Rate of Steel vs. pH 31
7. Corrosion Rate of Steel vs. O2 32
8. H2S Service Induced Cracking of Steels 33
9. Qualitative Categorization of Coupon Corrosion Rates for 34
Oil Production Systems
10. Corrosion Rate of Steel vs CO2 35

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1.0 INTRODUCTION

This document is intended to provide operations personnel with an overview of

the upstream oil and gas industry corrosion principles. The reader is
encouraged to read about the subjects covered in this overview in more detail
as required.

2.0 REFERENCES AND DEFINITIONS

2.1 References

Corrosion and Water Technology for Petroleum Producers, L. W. Jones, 1988

Corrosion Engineering, M. G. Fontana and N. D. Greene,1978
Recommendations for Preventing Hydrogen-Induced Cracking (HIC) in
Upstream Operations, EPR EPR.23PS.89
Corrosion Basics - An Introduction, NACE 1984
Corrosion Control in Petroleum Production, TPC 5, NACE 1979
Biologically Induced Corrosion, NACE 1985
Preparation and Installation of Corrosion Coupons and Interpretation of Test
Data in Oilfield Operations, NACE RP0775
Petroleum Engineering, “Treating and Monitoring 45,000 B/D Injection Water”,
D. Wheeler, Burmah Oil and Gas Co., 1975
Society of Petroleum Engineers, SPE No. 4064, “Efficient Removal of Oxygen in
a Water Flood by Vacuum Deaeration”, W. J. Frank, Humble Oil and Refining
Co., 1972

2.1 Definitions

ρm - fluid/gas mix density (lb/ft3)

C - empirical constant, where
C = 100, per API RP 14E for carbon steels or,
C = 160+ for corrosion resistant alloys
d - pipe ID (inches)
E - potential (volts)
HIC - Hydrogen Induced Cracking
HRC - Rockwell “C” Hardness number
I - current (amps)
medium - in this text, a medium is the fluid to which a component is
exposed and with which it may react (plural: media)
MIC - Microbiologically Influenced Corrosion

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P - pressure
QG - gas flow rate (mmscfd)
QL - liquid flow rate (BPD)
S - specific gas gravity (Air = 1.0)
S.G. - specific gravity of the liquid mix relative to water
SOHIC - Stress Oriented Hydrogen Induced Cracking
SRB - Sulphate Reducing Bacteria
SSC - Sulphide Induced Cracking
SWC - Stepwise Cracking
T - temperature
Ve - erosional flow velocity (ft/sec)
VG - gas velocity (ft/sec)
VL - fluid velocity (ft/sec)
Z - gas compressibility factor

3.0 WHY METALS CORRODE

3.1 Corrosion Defined

In its broadest sense, corrosion can be defined as the deterioration of a

substance or its properties because of a reaction with its environment.
Primarily in the oilfield, it is more specific to say the concern is with the
destruction of metal by a chemical reaction with a given environment, caused
by existence of an electrochemical mechanism. This overview specifically
addresses metallic corrosion. Deterioration of non-metallic materials is beyond
the scope of this document.

3.2 Metal Ores

Most metals are found in nature as ores which are typically metallic oxides or
sulphides. Metals are refined from ores by reduction, a forcing of the metal
ions to give up their charges and become metallic atoms in a regular lattice
array. For this to take place, energy in the form of heat or electricity must be
supplied. It is the energy stored in the metal during the refining process that
provides the driving force for corrosion.

3.3 Chemical Free Energy

It can be shown by chemical thermodynamics that the driving force for any
chemical reaction is the chemical free energy. For any spontaneously occurring
reaction, the free energy change is negative. If the calculation shows the free
energy to be positive, the reaction cannot take place without an external

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source of energy. Attachment 1 shows the calculated free energy change for
the formation of a number of metal oxides. What these numbers mean is that,
from a free energy standpoint, aluminium will tend to form its oxide very
easily, iron almost as easily, copper only to minor extent, and gold only with an
input of energy. Since steel (iron) is our basic structural metal and its free
energy is so negative, we are continually faced with the tendency of the metal
to return to its oxide. It should be noted that the magnitude of ∆G does not
alone determine the rate at which a metal returns to its oxide.

4.0 NATURE OF CORROSION REACTIONS

4.1 Corrosion By Water

Nearly all corrosion problems which occur in oilfield production operations are
due to the presence of water. In order to corrode, the metal surface must be
in contact with a water phase. For example, if a well produces at a high oil-to-
water ratio, very little corrosion is likely to occur because the water is mixed
with oil as an oil-external emulsion. On the other hand, in low oil-to-water
ratio wells, corrosion occurs because free water contacts the metal surface.
Corrosion in the presence of water depends on electrochemical processes.
Electric current flows and there must be a driving force and a complete
electrical circuit.

4.2 Voltage Source

The source of voltage (driving force) in the corrosion process is the energy
stored during the refining process. Due to the difference of free energy values
of various metals, these voltages are different for each metal. Potential values
are a function of both the metal and the chemical and physical characteristics
of the water. Attachment 2, the Galvanic Series, is a practical table where
common metals and alloys are arranged based on their respective potentials in
sea water. Attachment 3 is a guide that shows the probable effect of coupling
two dissimilar metals in sea water.

4.3 Electrical Circuits

The electrical circuit of the corrosion process consists of an anode, cathode,

electrolyte and metallic return path (see Attachment 4a).

• The anode is that portion of the metal surface that is corroded. It is the
point at which metal dissolves, or goes into solution. When metal
dissolves, the metal atom loses electrons and is oxidised. The reaction for
iron is:

Fe → Fe++ + 2e- (1)

The iron ion goes into solution and two electrons are left behind in the
metal.

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• The cathode is that portion of the metal surface where reduction takes
place and does not dissolve. The electrons left behind by the oxidation
reaction at the anode travel through the metallic path to the cathodic
surface where they are consumed by reaction with an oxidising agent that
must be present in the electrolyte. This consumption of electrons is called
a reduction reaction. Three typical reactions are:

2H+ + 2e- → H2 (Acidic Solutions) (2)

With oxygen present:

O2 + 4H+ + 4e- → 2H2O (Acidic Solutions) (3)

OR
O2 + 2H2O + 4e- → 4OH- (Neutral or Alkaline Solutions) (4)

H+ and O2 are examples of the oxidising agents referred to above.

• A metallic return path is necessary for the electrons generated at the

anode to travel to the cathode where they are consumed. Electrical current
flow is actually this passage of electrons through the metallic path. In
corrosion terminology, the conventional or positive current is usually used
to indicate the direction of current flow. Therefore, corrosion currents flow
from the anode to the cathode in the electrolyte and from cathode to anode
in the metallic circuit. Corrosion of the metal occurs where positive current
leaves the metal to the electrolyte. (See Attachment 4a.)

• In order to support the reduction and oxidation reactions and to complete

the electrical circuit, both the anode and cathode must be covered by the
same electrolyte. Electrolytes conduct electricity because they contain ions.
In oil and gas production, the most commonly encountered electrolytes are
water solutions of salts and acids.

4.4 Polarization

Attachment 4a shows a typical corrosion cell on the surface of a metal. As was

explained in the previous Section, an electrical circuit is formed between the
cathode and anode, thus allowing a potential difference to be established
between them. It is this shift in potential as the corrosion current flows that is
termed polarization.

The effects of polarization are also important in galvanic (bimetallic) corrosion,

which is more fully discussed in Section 8.3. To illustrate this, consider the
experimental copper-zinc cell shown in Attachment 4b. If the circuit is open
and no current is flowing, then the electrodes each have a characteristic
potential as shown in Attachment 5. Attachment 6a shows a plot of those
potentials at zero current on a potential versus current graph.

When a small amount of current is allowed to flow through the external circuit,

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the potential of the electrodes changes slightly, the copper electrode becomes
more anodic, and the zinc electrode more cathodic (as shown in Attachment
6a). As more current is allowed to flow, the potentials continue to change
(polarize) and the potential difference between the two decreases to a value
limited primarily by the resistance of the electrolyte solution (Re).

If polarization is not taking place, then there is no corrosion.

The magnitude of strength of a corrosion cell is determined by the difference in

electrical potential between the anode and the cathode. This voltage difference
is greatly influenced by the level of polarisation which may be achieved in the
corrosion circuit. Several factors may reduce the polarisability of the corrosion
circuit, such as:

• a film of corrosion product on the metal

• build-up of a hydrogen gas layer
• presence of corrosion inhibitors
• presence of sulphate reducing bacteria
• increased pressure
• increased temperature
• increased electrolyte turbulence or velocity
• low resistivity of the electrolyte

The result of a reduction in polarisability is a decrease in polarization. The

passage of an impressed direct current will also have an effect on the level of
polarization. The corrosion rate may rise or fall, depending upon the direction
of the current.

In the absence of oxygen, hydrogen deposited on cathodes as the result of cell

action (refer back to Attachment 4a) tends to remain as a polarizing film that
resists additional hydrogen ions. The additional ions must seek points of entry
more remote from the anode until the voltage (V) equals the current (I) times
the resistance (R) according to Ohm’s law. Resistance is due to the metallic
path, the electrolyte path and the polarization of the anode and the cathode.
This relationship for multiple cell action is described by Kirchoff’s second law
as:

∑ emf = ∑ IR (5)
OR
E c - Ea = IRe + IRm (6)

Where:
Re = resistance of electrolyte
Rm = resistance of metal
Ec = effective polarized potential of the cathode
Ea = effective polarized potential of the anode
I = current flowing in circuit

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Corrosion will continue, but the rate will only change if the polarisability is
altered hence producing a change in polarisation. This occurs when hydrogen
is removed from the cathode. Once an E = IR steady state is reached, further
cell action depends upon the rate of hydrogen removal from the cathode. That
rate is largely controlled by the rate at which oxygen reaches the cathode. In
oilfield operations, hydrogen removal from the cathode is usually accomplished
by one of the mechanisms discussed in paragraph 4.3 above.

5.0 NATURE OF METALS

5.1 Inhomogeneities in Metal Surfaces

Metal atoms do not necessarily dissolve at a single point on a metal surface,

nor are cathode areas restricted to one area on the surface. The reason certain
areas of the metal surface act as anodes centers on the inhomogeneities in the
metal surface, in the electrolyte or both. Potential differences on the metal
surface are a natural result and are a primary cause of the initiation of localized
corrosion cells. The type of corrosion that occurs usually gives a clue as to the
major cause.

Commercial metals are not homogeneous but contain inclusions, precipitates

and several different phases. Steel is an alloy of iron and carbon. Where pure
iron is a relatively weak, ductile material, the alloy, steel, is a much stronger
material. As a result of combining part of the iron with carbon, the resultant
metal contains dissolved carbon and precipitated iron carbide (Fe3C). The iron
carbide that has a lower tendency to corrode than pure iron is distributed
within the iron as tiny microscopic islands. The Fe3C and pure iron are in
electrical contact so when the steel is placed in an electrolyte, an electrical
circuit is completed and current flows through thousands of microcells on the
steel surface. The locations of the anodic and cathodic areas of the microcells
may change as corrosion products accumulate shifting the anodic areas.

In solid solution alloys, such as 304 or 316 stainless steel, or Monel 400, there
may be potential differences arising from concentration differences from point
to point. This concentration difference can be evident when metals are formed
or reformed such as in castings or weldment of metals. Here is where an area
relationship can be very harmful. If the anode is small compared to a large
cathode, the corrosion may occur at a rapid rate due to the high current
density on the anode.

Local heating, such as welding, can result in changes of the nature of phases
and their compositions or changes in grain size and grain boundaries creating
differences in potentials. Intergranular attack may be accelerated by the
potential differences between the grains and grain boundaries.

Stress such as that applied during cold working or cold forming of the metal
can set up potential differences along the surface of the metal. The stressed
areas will be anodic to the unstressed areas. Scratches or abrasions on the
metal surface will act in the same manner.

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6.0 EFFECT OF ELECTROLYTE COMPOSITION

There are two aspects to the effects of electrolyte composition on the corrosion
circuit. The first is the conductivity of the electrolyte and the effect of
electrolyte on the base corrosion potential of the system. The second has to do
with the presence or absence of oxidizing agents which are necessary for the
cathodic portion of the corrosion cell. The anodic reaction cannot occur in the
absence of a corresponding reaction at the cathode, regardless of the
conductivity of the cathode.

6.1 Conductivity

The electrical resistance of typical electrolytes is usually much higher than that
of metal, therefore the resistance of the electrolyte will normally predominate
in the corrosion cell reaction. The more conductive the electrolyte, the easier
current can flow and the faster corrosion will occur. The amount of metal that
dissolves is directly proportional to the amount of current flow between anode
and cathode. For iron, one amp of current flowing for one year will result in
the loss of 20 pounds (9.1 kg) of metal. It is important to remember that
other factors will also have an impact on the corrosivity of the electrolyte, the
conductivity only determining the ease at which corrosion currents are able to
flow from anode to cathode.

6.2 Hydrogen Ion Concentration (pH)

The pH of water is the negative logarithm of the hydrogen ion concentration:

pH = -log (H+) (7)

The greater the concentration of hydrogen ions, the more acid the solution and
the lower the pH value. Hydrogen ions (H+) make a solution acidic and,
therefore, force the pH towards zero. Hydroxyl ions (OH-) make a solution
basic or alkaline and force the pH towards 14. The following lists the pH
ranges for acidic, neutral, and alkaline conditions:

pH Range Classification
< 7.0 Acidic
7.0 Neutral
> 7.0 Basic or Alkaline

The corrosion rate of steel usually increases as the pH of the water decreases,

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although extremely high pH solutions can also be corrosive (see Attachment

6b). The actual variation of corrosion rate with pH is dependent on the
composition of the electrolyte. Since pH is a negative logarithmic function, a
10-fold reduction or increase in the hydrogen ion concentration is required to
effect a pH change of one.

6.3 Dissolved Gases

Oxygen, carbon dioxide, or hydrogen sulphide gases, when dissolved in water,

increase its corrosivity. Dissolved gases are the primary cause of most
corrosion problems in oil and gas production. The following paragraphs discuss
each gas independently, but it is important to note that corrosion rates are also
greatly influenced by physical variables such as temperature, pressure and
velocity. Similarly, the Figures referred in these paragraphs are for specific
conditions and are only intended to reflect the relative corrosion tendencies of
each.

6.3.1 Oxygen

Dissolved oxygen can cause severe corrosion at very low concentrations (less
than 100 ppb or 0.1 ppm) and if either or both CO2 and/or H2S are present, it
further increases their corrosivity. Attachment 7 is a composite graph from
results of three different studies showing corrosion rates as a function of
oxygen concentration:

The solubility of oxygen in water is a function of pressure, temperature, and

chloride content. Although it is not usually present in produced water, it is
often introduced into oilfield water handling systems through failures to
maintain oxygen free gas blankets on water handling vessels, vacuums created
by positive displacement pumps or separator dump valves and/or exposure to
the atmosphere. Water from lakes, streams, fresh water aquifers, rain or
oceans usually will be oxygen saturated. Oxygen is more soluble at high
pressures and lower temperatures and is less soluble in salt water than in fresh
water.

Oxygen accelerates corrosion under most circumstances because it is a strong

and rapid oxidising agent in cathodic reactions. It will easily combine with
electrons at the cathode and allow the corrosion reactions to proceed at a rate
limited by the rate at which oxygen can diffuse to the cathode as discussed in
Section 4.3:

O2 + 4H+ + 4e- → 2H2O (Acidic Solutions) (3)

OR
O2 + 2H2O + 4e- → 4OH- (Neutral or Alkaline Solutions)
(4)

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6.3.2 Carbon Dioxide

When carbon dioxide dissolves in water, it forms carbonic acid, decreases the
pH of the water, and increases its corrosivity. Corrosion in the presence of
dissolved CO2 is referred to as sweet corrosion. There are numerous
intermediate reactions which may be summarised as:

CO2 + H2O → H2CO3 (Carbonic acid) (8)

Fe + H2CO3 → FeCO3 + H2 (Iron Carbonate)

(9)

Factors governing the solubility of carbon dioxide are pressure, temperature,

and composition of the water. Increased pressure, reduced temperature, or
reduced water salinity each increase CO2 solubility which lowers pH. Many
dissolved minerals buffer the water, thus minimising the effects of the above
changes on pH reduction.

Partial pressure of carbon dioxide can be used as a yardstick to predict the

corrosiveness of a system. The partial pressure of carbon dioxide can be
determined by the formula:

CO2 partial pressure (psia pp) = Total pressure of gas (psia) x

Mole fraction of CO2 in gas (10)

In general, field experience indicates that, in the presence of an electrolyte, a

partial pressure above about 30 psia may cause severe corrosion rates;
between 7 psia and 30 psia may cause high corrosion rates and, less than 7
psia can still cause low to moderate corrosion rates.

6.3.3 Hydrogen Sulphide

Hydrogen sulphide is soluble in water at pressures and temperatures common

in oilfield operations and, when dissolved, behaves as a weak acid and usually
causes pitting. Attack due to the presence of dissolved hydrogen sulphides is
referred to as sour corrosion.

The general corrosion reaction of steel is:

H2O
H2S + Fe → FeS + H2 (11)

The iron sulphide produced generally adheres to the surface as a black scale
and is cathodic to the steel that, in the presence of water, causes local severe
corrosion in the form of deep pitting. However, in some instances, a thin iron
sulphide scale may be relatively impermeable and actually slow down the
corrosion reaction if erosion or some other mechanism does not remove the

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scale.

Hydrogen sulphide can be generated by sulphate reducing bacteria (SRB).

These bacteria contribute to corrosion by their ability to flourish in the absence
of oxygen and their ability to change sulphate ions into hydrogen sulphide.
The anaerobic conditions under a colony constitute a differential aeration cell
with the bulk of the electrolyte, whereas their ability to produce hydrogen
sulphide can cause severe localized corrosion. Refer to Section 8.11.

Under certain pressure conditions, the hydrogen produced by the corrosion

reaction can diffuse into the metallic lattice to cause embrittlement and
subsequent cracking of susceptible metals. Refer to Section 8.7 and
Attachment 8 for further discussion of this phenomenon.

6.4 Chloride Ions

The most common electrolyte in oil production is water, and one of the most
common ions in solution is the chloride ion. The chloride ion and its
concentration has a major effect on the corrosion reactions as noted below:

• An increase in concentration of chlorides increases the conductivity of the

solution and, therefore, allows corrosion currents to occur more rapidly.
• Chloride anions (negatively charged ions) tend to react very easily with
cations (e.g. Fe+2) going into solution at the corrosion cell anode. These
reactions, therefore, reduce polarization by allowing more cations to come
into solution that increases the conductivity of the electrolyte.
• Although not a weight loss type corrosion, increased concentration of
chloride ions increases the susceptibility of austenitic stainless steels to pit
and crack. See Section 8.9 and also refer to the CIMS Metallurgy and
Metallic Material Selection Guidelines.

7.0 PHYSICAL VARIABLES

The variables of temperature, pressure, and velocity need to be accounted for

when designing and implementing a corrosion control program. Correct
application inhibitors and cathodic protection as corrosion control methods are
very dependent on these variables. Temperature and pressure are interrelated,
and the corrosivity of a system is further influenced by velocity.

7.1 Temperature

Like most chemical reactions, corrosion rates generally increase with

temperature. For example, in a system open to the atmosphere, the corrosion
rate generally increases with increasing temperature until the concentration of
dissolved gases decreases. In a closed system, this is not necessarily the case.
In addition, many metallic alloys have minimum temperature limitations to

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prevent H2S service related cracking or other toughness problems.

7.2 Pressure

Pressure also affects the rates of corrosion reactions. More gas goes into
solution as the pressure increases, which may, depending on the dissolved gas,
increase the corrosivity of the solution. The partial pressure of CO2 or H2S in a
system is calculated as follows (refer to Section 6.3.2):

partial pressure (psia pp) = Total absolute pressure (psia) x

mol % CO2 or H2S (12)

7.3 Velocity

Velocity has a significant effect on corrosion rates. Stagnant or low velocity

fluids usually give low general corrosion rates, but pitting rates may be high.
Corrosion rates generally increase with increasing velocity due to the
depolarising effect on the cathode. High velocities and the presence of
suspended solids or gas bubbles can lead to erosion corrosion, impingement, or
cavitation. On the other extreme, oil, gas, or multi-phase pipelines operating
at low velocities can result in corrosion along the bottom of a pipeline. The low
flow condition is referred to as stratified or laminar flow which can be modelled
using commercially available computer programs.

7.3.1 Erosion/Velocity (API RP 14E)

Any fluid, gas, or multiphase pipeline or piping system should be operated

below its calculated erosional velocity to prevent flow enhanced corrosion
(erosion corrosion). API RP 14E, “Design and Installation of Offshore
Production Platform Piping Systems,” provides the following equation to
calculate the erosional velocity limit for any oil or gas piping:
C
Ve = 1
(13)
(ρm ) 2

where:
Ve = erosional flow velocity (ft/sec)
ρm = fluid/gas mix density (lb/ft3)
C = empirical constant, where
C = 100, per API RP 14E for carbon steels or,
C = 160+ for corrosion resistant alloys

To calculate the density of two phase flow systems use:

ρm =
(12,409)( S. G.) P + ( 2.7) SRP
(14)
(198.7) P + ZRT

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where:
S.G. = specific gravity of the liquid mix relative to water.
S = specific gas gravity (Air = 1.0)
R = gas/liquid ratio, ft3/bbl
T = operating temperature, oR (same as oF + 460)
Z = gas compressibility factor
P = absolute pressure, psia (psig + 14.7)

The actual velocity for oil or water piping/pipeline systems is:

QL
VL = 0.012 (15)
d2
where:
VL = fluid velocity (ft/sec)
QL = liquid flow rate (BPD)
d = pipe ID (inches)

The actual velocity of gas piping/pipeline systems is:

Q G TZ
VG = 60 (16)
d2P
where:
QG = gas flow rate (mmscfd)
VG = gas velocity (ft/sec)
T = operating temperature
Z = gas compressibility factor
P = pressure (psig)

8.0 FORMS OF CORROSION

8.1 Uniform Corrosion

Uniform corrosion is a weight loss corrosion where the area of metal loss is
spread over a relatively large area so that the surface is attacked uniformly.
This type of corrosion can be common in atmospheric corrosion of industrial or
marine locations. Strong uninhibited acids will uniformly corrode steel very
rapidly. In general, however, uniform corrosion occurs gradually thus failures
take longer to occur.

Uniform corrosion can be addressed in original design criteria by adding a

corrosion allowance to design metal thickness. It is very important to
recognize that this is not a corrosion control measure. The extra metal
thickness simply allows more time for detection and mitigation before
equipment capability or operations safety is jeopardized. Refer to Attachment
9 which lists the relative severity of average (uniform) corrosion rates.

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8.2 Pitting Corrosion

Pitting is the most common cause of corrosion failures occurring in oil and gas
industry production equipment. It occurs when the metal undergoing corrosion
suffers metal loss at localized areas rather than over a large area or the entire
surface area. The entire driving force of the corrosion reaction is concentrated
at these localized areas. The corrosion rate at these areas will be many times
greater than the average corrosion rate over the entire surface. Pitting is much
more dangerous than uniform corrosion because the pitted area can become
penetrated in a short time. Refer to Attachment 9 which lists the relative
severity of corrosion pitting rates.

8.2.1 There are many causes of pitting in metals and alloys but, generally, they are
caused by localized differences in the metal or in the electrolyte. Localized
differences in electrolyte composition are referred to as concentration cells as
discussed below:

• Crevices promote formation of concentration cells. In oxygenated systems,

oxygen in the crevice may be consumed more rapidly than fresh oxygen
can diffuse into the crevice. This difference in oxygen concentration at
crevices and open areas creates a potential difference and results in
corrosion of metal in oxygen-deficient areas. In addition, the pH in a
crevice decreases compared to the bulk solution which may result in a
more acidic environment thus accelerating corrosion. This is particularly
the case with 300 (austenitic) and 400 (martensitic) series stainless steels.
• When metal surfaces are uniform and the electrolyte contains varying
amounts of dissolved oxygen, oxygen concentration cells occur. An
example is a bare or poorly coated pipeline buried under a paved or
compacted road. Under the road, the soil is not well aerated, but on either
side of the road the soil is well aerated. Locally, severe attack can occur on
the pipe at the edge of the road in the transitions from the compacted
nonaerated soil to the loose, aerated soil.
• The deposition of a solid on a metal surface can cause increased corrosion
under the deposit due to differential oxygen concentration. In addition,
sulphate reducing bacteria may thrive under these deposits magnifying the
corrosion process by creating hydrogen sulphide.

8.2.2 A common cause of pitting in carbon steel is the formation of local cells due to
the partial breakdown or destruction of protective scales. When a corroding
metal becomes covered with a corrosion product that is dense, impermeable
and adherent, the product protects the metal from its environment. Localized
removal of this protective scale may precipitate the onset of preferential
corrosion of the exposed metal surfaces. If the scale is a conducting scale
(e.g. FeS), then damage to it could result in intense attack of the area that lost
its protective scale layer. This is the classic pit scenario. In the case of
detachment of a conducting scale, or removal of a non-conduction scale (e.g.
calcium carbonate), then there should be little attack at the damage scale area,
although the attack may be greater beneath a detached scale.

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8.2.3 Stainless steels are the most susceptible ferrous alloys to pitting, primarily
because of the very properties that make them stainless. Stainless steels
derive their corrosion resistance from the formation of a thin iron chromium
oxide film and the ability to maintain that film. If the film becomes destroyed
at local areas, those areas become anodic and pitting results.

8.3 Bimetallic Corrosion

When two dissimilar metals are placed in electrical contact in electrolyte

containing an oxidizing agent, the more reactive one will corrode and the other
may either not corrode at all, or will corrode at reduced rate, depending upon
the extent of polarization of the cathode (see Attachments 3 and 4). This
coupling of dissimilar metals is referred to as a bimetallic couple or a galvanic
cell. It can be destructive, accelerating the corrosion rate of the more reactive
of the two metals.

8.3.1 The galvanic cell is used in a practical way in cathodic protection. When steel
is connected to a more reactive metal, such as magnesium, the steel is the
cathode and is protected; and the magnesium is the anode and corrodes.

8.3.2 The area principle implies that in galvanic corrosion, the cathode to anode ratio
is of great significance in a galvanic cell with a large anode and a small
cathode, corrosion is spread over a large area and very little corrosion damage
will occur. However, in a cell with a small anode and a large cathode, corrosion
is concentrated at the anode and severe corrosion damage will occur. Refer to
Attachment 3.

8.3.3 It is important to know that coupling dissimilar metals together in a neutral pH,
nonaerated fluid may not cause corrosion. The fluid has to be corrosive to at
least one member of the dissimilar metal couple for bimetallic corrosion to
occur.

8.3.4 Weld line corrosion in piping/pipelines and ring worm corrosion in downhole
tubing are types of galvanic cells that are caused by the manufacturing process
of the steel as discussed below:

• When a metal is welded, the welding process results in localised heat,

creating a microstructure near the weld which differs from the
microstructure of the parent metal. This difference in microstructure can
create a potential difference and set up a corrosion cell. A similar problem
can result from an improper choice of welding rods. In this case, the
potential differences are due to the differences in the composition of the
weld and parent metals.
• Ring worm corrosion is due to the upsetting process in the manufacture of

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downhole tubing and usually occurs as sweet corrosion (See Section 8.13).
The heat required in upsetting causes the transition zone in the heated end,
or upset, to have a different grain structure from the rest of the pipe body.
A transition zone in grain structure near the upset runout, typically within
18” of the pin end, can cause a potential difference and set up a local
corrosion cell. Fully normalizing the tubing after the upset process will
return uniformity to the grain structure which will eliminate this corrosion
potential.

8.4 Flow Enhanced Corrosion (Erosion Corrosion)

Most metals depend on the formation and maintenance of a protective scale for
corrosion resistance. Removal of this scale at local areas can lead to
accelerated attack. High velocity flow or turbulence can erode away the
protective scale to expose fresh metal to corrosive attack. The combination of
the erosion of the scale and corrosion of the underlying metal is termed flow
enhanced corrosion (erosion corrosion). Carbon steel piping systems and
downhole tubing must be designed to maintain velocities below the API RP 14E
critical velocity discussed in Section 7.3.1.

8.4.1 A phenomenon similar to erosion-corrosion, but more localized, is know as

impingement. This occurs when a stream impinges upon a metal surface and
breaks down protective films at very small areas. The resulting attack is
characteristically in the form of pits elongated and undercut on the downstream
end. Impingement often results from turbulence surrounding small particles
adhering to a metal surface.

8.5 Cavitation Corrosion

Although corrosion normally plays a minor role in the rate of cavitation

damage, it is important to recognize its effect. Cavitation is the formation and
collapse of vapour bubbles in fluids because of rapid changes in pressure. It
can occur whenever the absolute pressure at a point in the liquid stream is
reduced to the vapor pressure of the fluid so that bubbles form, and this is
followed by a rapid rise in pressure resulting in bubble collapse. Cavitation
damage is the wearing away of metal from repeated impact blows from
collapse of bubbles within a fluid, such as that caused when a pump’s suction is
starved.

8.6 Intergranular Corrosion

Intergranular corrosion is preferential attack of a metal’s grain boundaries.

Intergranular corrosion can occur in the absence of stress. It is caused by
precipitation of impurities at grain boundaries, or changes in the alloying
elements at the grain boundary areas. For example, depletion of chromium in
the grain boundary of stainless steel can be lead to intergranular corrosion.

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Proper heat treatment or control of chemistry of the steel can reduce the
susceptible grain boundary constituent and render the alloy more resistant to
intergranular attack.

8.7 Hydrogen Induced Failures

Hydrogen atoms may be produced on a metal surface in an aqueous

environment by a corrosion reaction, cathodic protection, electroplating or acid
pickling. Some of the hydrogen atoms combine to form gaseous molecular
hydrogen (H2) on the metal surface and are released to the environment. A
portion of the atoms are absorbed by the metal and this entry of hydrogen
atoms into the metal may have some very undesirable effects. Hydrogen-
induced cracking (HIC) and hydrogen embrittlement are two types of
phenomena that can occur.

8.7.1 Hydrogen entry into low strength steel can result in HIC if there is a
microscopic defect in the steel such as a lamination or inclusion. HIC is
typically manifested as blisters, stepwise cracking (SWC), and/or stress
oriented HIC (SOHIC). A lamination or void in the steel provides a place for
hydrogen atoms to combine, form hydrogen gas, and result in sufficient
pressure to cause blistering. Blisters are visible on a surface when the voids
responsible for the HIC are near the surface. SWC is initiated at inclusions on
different planes through the metal wall. The initial crack propagation occurs
along the axis of the inclusion and then interconnects with cracks on other
planes to form the SWC. The term SOHIC is used to indicate that the
characteristics of HIC have been influenced by applied or residual stresses,
usually from welding. These stresses will cause cracks to initiate and
propagate perpendicular to existing HIC. This can result in cracks that
eventually propagate through the steel wall (see Attachment 8).

Solutions to HIC include controlling the metal chemistry to minimise the affects
of inclusions or laminations, and controlling corrosion with coating or inhibitors
to minimise the generation of hydrogen.

8.7.2 Hydrogen entry into high strength steels or steels with a hardness above 22
HRC can result in hydrogen embrittlement. A material can fail in a brittle
manner at stresses well below its nominal yield strength. Hydrogen
embrittlement is normally limited to high strength materials due to the fact
that these materials reach tensile strengths high enough to initiate the failure
mechanism. It is often very difficult to distinguish between failures caused by
hydrogen embrittlement or stress corrosion cracking. The susceptibility to
hydrogen embrittlement increases with increasing strength and hardness.
Even though a steel contains hydrogen, no permanent damage occurs unless
sufficient stress is applied to cause the steel to crack. Therefore, in many
cases, the hydrogen can be baked out by heat treatments, restoring the
original properties of the metal.

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8.8 Sulphide Stress Cracking (SSC)

Sulphide stress cracking is a spontaneous brittle failure that occurs in steels

and high strength alloys when exposed to moist hydrogen sulphide. This
phenomenon is also referred to as sulphide cracking, sulphide corrosion
cracking, and sulphide stress corrosion cracking. All the names refer to the
same corrosion phenomenon, hydrogen embrittlement (see Section 8.7.2),
which requires that hydrogen sulphide be present, water (even in minute
quantities) a high strength material, and tensile stress (either applied or
residual). Sulphide stress cracking (SSC) may occur very rapidly after
exposure to a sour environment, or it may take place after considerable time
has passed. Refer to NACE MR0175 (latest revision) for guidelines on selecting
materials resistant to SSC. Also, refer to Attachment 8. Materials are
susceptible to SSC when the following conditions are met :

• Plain carbon steels with maximum yield strengths above 90,000 psi and
hardness above HRC22 are susceptible to sulphide stress cracking at
temperatures below 190oF (88oC). The higher the steel strength, the
shorter the time to failure. A hardness of HRC22 is not an absolute value;
alloying with other materials can cause failures below this level, and for
certain heat treatments, the permissible hardness level can be increased.
• The time to failure decreases as the stress level increases. The stresses
can be applied or residual.
• The time to failure decreases as the hydrogen sulphide concentration
increases. Failure can occur at H2S partial pressures as low as 0.05 psia
pp, and even lower if the steel hardness greatly exceeds HRC22.
• Cracking tendency increases as the pH decreases. The tendency to failure
can be drastically reduced if the pH of a solution is maintained above 9.0.
This is why high pH drilling fluids are used to drill sour wells.
• Cracking susceptibility decreased rapidly above a temperature of 150oF
(65oC).

8.9 Stress Corrosion Cracking (SCC)

Stress corrosion cracking is caused by the synergistic action of a corrosive

medium and applied tensile stress; that is, the combined effect of the two is
greater than the sum of the single effects. In absence of the corrodent, the
alloy could easily support the stress. The stress is always a tensile stress and
can be either applied or residual. When a metal suffers stress corrosion
cracking, metal loss from corrosion is generally very low, although most likely,
pits will occur and the cracks will develop in the base of the pits. All alloys are
subject to stress corrosion cracking. Stress corrosion cracking results from
exposure of a particular alloy to a particular corrosive medium. No one
corrosive medium causes stress corrosion in all alloys, and most alloys are
subject to attack in only a few specific corrosive media. Because stress
corrosion cracking tendency increases with increasing stress, one approach to
prevent failure is to minimise stress. In some cases, shot peening to induce

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compressive stresses is used to reduce stress corrosion cracking tendencies.

Increasing solution concentration increases stress corrosion cracking

tendencies and, therefore, in environments with no electrolyte (i.e., dry gases),
stress cracking will not occur.

8.9.1 The most common corrosive which cause stress corrosion cracking in carbon
and low alloy steels are sodium hydroxide and nitrate solutions. Chemical
inhibition and proper stress relieving are widely used to control cracking in
these environments.

8.9.2 Stress Corrosion Cracking (SCC) of high strength steels occurs in salt solutions,
moist atmospheres, and even in tap water if the steel is ultra high strength
steel. Cracking tendency increases with the strength of the steel. Experience
or testing is necessary to determine the corrosive and conditions which will
cause cracking of high strength steels.

8.9.3 The hardenable stainless steels, which include martensitic stainless steel and
precipitation hardening stainless steels, when treated to high hardness levels
have tendencies to stress corrosion crack. To reduce this tendency, the
strength of the steels can be reduced by heat treating the alloys.

8.9.4 Austenitic stainless steels are susceptible to both transgranular and

intergranular cracking. These steels are most susceptible in electrolytes
containing chloride ions. Therefore, austenitic stainless steels are not
recommended for use in chloride containing environments at temperatures
above about 150oF (65oC). Hot caustic solutions are also a source of cracking
for austenitic stainless steels; however, these steels will resist attack by caustic
at low temperatures and concentrations. Refer to CIMS-MS-1.0, Metallurgy
and Metallic Material Selection Guidelines.

8.10 Corrosion Fatigue

When metals are repeatedly stressed in a cyclic manner, they will fail in a
brittle manner at stresses far below the yield or tensile strength of the
material. There exists a limiting stress below which steel may be cyclically
stressed indefinitely without failure. This stress is called the endurance limit
and is always lower than the yield and tensile strengths. The fatigue life of
metal is substantially reduced when the metal is cyclically stressed in a
corrosive environment. The simultaneous occurrence of cyclic stress and
corrosion is called corrosion fatigue, and the steel no longer exhibits an
endurance limit.

8.10.1 In corrosion fatigue, the corrosivity of the environment is extremely important.

The presence of dissolved gases especially oxygen carbon dioxide or

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The presence of dissolved gases, especially oxygen, carbon dioxide or

hydrogen sulphide, results in a pronounced reduction in fatigue life. Pitting or
localized attack is most damaging to fatigue life, but even slight general
corrosion will substantially reduce time to failure.

8.10.2 The corrosion fatigue performance of carbon and low alloy steels is
independent of strength. Therefore, heat treating and alloying are used to
increase corrosion resistance rather than enhance physical properties of the
metal to increase fatigue life.

8.10.3 Surface conditions and stress history have a large bearing on fatigue life.
Notches imposed in manufacturing or installation can decrease fatigue life.
Also, the time available for corrosion damage to occur is extremely important
in the corrosion fatigue behaviour of materials. Cycle frequency must also be
considered as a major variable in corrosion fatigue performance.

8.11 Microbiologically Influenced Corrosion (MIC)

Microbiologically influenced corrosion is pitting type corrosion. Microorganisms

can exert considerable influence on the corrosion rate. The type of bacteria
most commonly associated with corrosion in oilfield operations is the sulphate
reducing bacteria (SRB). The metabolic process of the SRB reduces sulphates
to sulphides and consume large quantities of hydrogen in the process to
produce H2S. The polarization film in the cathode areas provide the hydrogen;
therefore, the SRB act as strong depolarizes which causes accelerated
corrosion rates. Bacteria can be controlled with bactericides. The following
describes the SRB depolarization process:

SO4-2 + 8H+ → (SRB) → S-2 + 4H2O (Depolarization) (17)

In addition to the depolarizing effect, the production of hydrogen sulphide

(H2S) will accelerate the corrosion process as shown below:

Fe+2 + S-2 → FeS (Corrosion product) (18)

or simplified
H2O
H2S + Fe → FeS + 2H
(11)

In the presence of an oxidizing agent, the iron sulphide (FeS) deposited is

cathodic to the steel and a galvanic cell can be set up. This may result in
pitting of areas where the iron sulphide film has bee partially detached from
the surface of the steel. An iron sulphide film that is adherent and undamaged
can actually provide protection to the steel.

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8.12 Oxygen Corrosion

8.12.1 Water produced with oil seldom contains dissolved oxygen; however, oxygen
corrosion can be found in downhole and surface facility equipment. It is
usually caused by careless operating techniques, faulty equipment or by
oxygen rich wash water used for desalting. The presence of CO2 or H2S
drastically increases the rate of oxygen corrosion. Attachment 7 shows the
relation of dissolved oxygen content to the corrosion rate of steel in brine.
Note that oxygen can be highly corrosive above 20 parts per billion. As
discussed in Section 6.3.1, the cathodic corrosion reaction of steel in an oxygen
environment is as follows:

O2 + 2H2O + 4e- → 4OH- (Acidic Solutions) (3)

OR
O2 + 4H+ + 4e- → 2H2O (Neutral or Alkaline Solutions) (4)

8.12.2 Oxygen corrosion is generally an external problem in primary production

equipment. In areas of high relative humidity, such as offshore structures,
serious atmospheric pitting and overall corrosion can occur. The presence of
accumulated solids can absorb water from the air, thus increasing the rate of
corrosion by keeping the surface wet.

8.12.3 Oxygen in oilfield brine or flood water is a major cause of corrosion in

waterflood injection equipment. Rapid perforation of the metal, obstruction of
flow, and formation plugging by the corrosion products can occur. Oxygen can
also cause injection well plugging if the injected water contains dissolved iron
or manganese that react with the oxygen to form insoluble compounds.

8.12.4 Corrosion of offshore structures is divided into four areas of attack and is due
to oxygen corrosion in each zone. The mud zone, that portion below the mud
line, may suffer the least attack because of the high resistivity of the mud and
little dissolved oxygen. This, of course, will not be the case where
microbiologically assisted corrosion can take place. The submerged zone is
always covered by water and the corrosion tends to be uniform, generally
shallow pits. The splash zone, that area which is alternatively wetted by wave
action, tends to be the most corrosive zone. The atmospheric zone may
appear dry but, especially near the water surface and on the underside of
members, the humidity is always close to 100% so the surfaces remain moist.

8.13 Sweet Corrosion

Sweet corrosion results from the presence of water containing dissolved carbon
dioxide. Dissolved carbon dioxide (CO2) in water decreases the pH of the water
and increases its corrosivity. Refer to Attachment 10. The following shows

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how carbon dioxide results in the corrosion of steel:

CO2 + H2O → H2CO3 (Carbonic Acid)

Fe + H2CO3 →FeCO3 + H2 (Iron Carbonate)

It should be noted that the corrosion rates experienced in reality are higher
than indicated by these summary reactions.

8.13.1 Corrosion in the tubing of gas condensate wells usually takes the form of deep
pits with steep, undercut sides. This is sometimes referred to as “mesa”
corrosion due to the shape of the pitting profile, i.e. areas of unattacked metal
adjacent to pitted areas. The pits may penetrate the wall
completely in a relatively short period of time. This pitting is caused when the
carbon dioxide dissolves in water droplets that condense on the tubing wall.
The tubing below the point of condensation may relatively corrosion free.

8.13.2 The most serious sweet oil corrosion problem can usually be found in gas lift
wells. They are usually high water producers, and corrosion can be accelerated
if the injected gas lift gas contains carbon dioxide and/or small amounts of
oxygen.

8.14 Sour Corrosion

Corrosion caused by hydrogen sulphide dissolved in water is referred to as sour

corrosion. Refer to Section 8.11.

8.14.1 In oil well tubing, hydrogen sulphide can cause the development of scattered
pits with cone shape sides leading to a rounded bottom. Black iron sulphide
(FeS) scale will usually be present. The cathodic nature of the iron sulphide
scale results in the pitting of the underlying steel.

8.14.2 Equipment in high-pressure sour gas wells may fail due to sulphide stress
cracking, hydrogen embrittlement, or hydrogen induced cracking. Severe
pitting corrosion can also occur in sour gas wells.

8.14.3 Corrosion on the interior of oil or sour water storage tank roofs (fixed roof
design tanks) begins when condensed water droplets are saturated with
hydrogen sulphide. The extensive pitting which results can perforate the tank
deck. The interior bottoms of oil storage tanks are also subject to attack
because of the layer of water which usually forms at the bottom under the oil.
Additionally, corrosion scale falling from the top to the bottom of the tanks may
cause corrosion concentration cells. Corrosion of the shell of oil tanks is
normally negligible. However, sour saltwater tanks will be subject to roof, wall,
and floor internal corrosion.

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ATTACHMENT 1
(Section 3.3)

FREE ENERGIES (KINETICS) OF FORMATION OF METAL OXIDES

Symbol Metal Oxide Calories/Mole

(∆G)

Al2O3 Aluminium Oxide -376,700

Fe2O3 Ferric Oxide -177,100

MgO Magnesium Oxide -136,130

ZnO Zinc Oxide -76,080

CuO Cupric Oxide -30,400

Ag2O Silver Oxide +2,600

Au2O3 Auric (Gold) Oxide +18,810

Notes:
1. For example, aluminum will tend to form its oxide very easily, iron almost as easily,
copper only to a minor extent, and gold only with an input of energy.
2. The magnitude of ∆G does not alone determine the rate at which a metal returns to
its oxide.

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ATTACHMENT 2
(Section 4.2)
GALVANIC SERIES IN SEAWATER
VOLTS: SATURATED CALOMEL HALF-CELL REFERENCE ELECTRODE

+0.2 +0.1 0.0 -0.1 -0.2 -0.3 -0.4 -0.5 -0.6 -0.7 -0.8 -0.9 -1.0 -1.1 - 1.2 -1.3 -1.4 -1.5 -1.6 -1.7

Magnesium
Zinc
Beryllium
Aluminium Alloys
Cadmium
Mild Steel. Cast Iron
Low Alloy Steel
Austenitic Nickel Cast Iron
Aluminium Bronze
Naval Brass, Yellow Brass, Red Brass
Tin
Copper
Pb-Sn Solder (50/50)
Admiralty Brass, Aluminium Brass
Manganese Bronze
Silicon Bronze
Tin Bronzes (G & M)
Stainless Steel - Type 410, 416
Nickel Silver
90-10 Copper-Nickel
80-20 Copper-Nickel
Stainless Steel - Type 430
Lead
70-30 Copper - Nickel
Nickel - Aluminium Bronze
Nickel - Chromium Alloy 600
Silver Brazed Alloys
Nickel 200
Silver
Stainless Steel - Types 302, 304, 321, 347

Nickel - Copper Alloys 400, K-500

Stainless Steel - Types 316,
Alloy "20" Stainless Steels, cast and wrought
Nickel-Iron-Chromium Alloy 825
Ni-Cr-Mo-Cu-Si Alloy B
Titanium
Ni-Cr-Mo Alloy C
Platinum
Graphite

Alloys are listed in the order of the potential they exhibit in flowing sea water. Certain alloys indicated by the
symbol: in low-velocity or poorly aerated water, and at shielded areas may become active and exhibit a
potential near -0.5 volts.

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ATTACHMENT 3 (Page 1 of 5)
(Section 4.2 and 8.3.3)

CORROSION OF GALVANIC COUPLES IN SEA WATER AT 40- 80ºF (4-27ºC)

METAL CONSIDERED COUPLED Note: These Numbers correspond with the numbers and alloy designations listed in the left column.
WITH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
S
1 Magnesium Alloys E
L x x
S x
2 Zinc E x x x
L
S x
3 Beryllium E x x x
L x x x
S x
4 Aluminum Alloys E x x
L x x x x x x x x x x
S x x x
5 Cadmium E x x
L
S x
6 Mild Steel, Wrought Iron E x
L
S x x
7 Cast Iron, Flake or Ductile E x x
L x x x x x x x x x x x x x x x x x

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ATTACHMENT 3 (Page 2 of 5)
(Section 4.2 and 8.3.3)

METAL CONSIDERED COUPLED Note: These Numbers correspond with the numbers and alloy designations listed in the left column.
WITH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
S x
8 Low Alloy High Strength Steel E x x x
L x
S x x x
9 Austenitic Cast Iron, Types 1 & 2 E x x x x x
L x
10 Naval Br (CA464), Yel. Br (CA268), S x x
Al Br (CA687), Red Br(CA230), E x x x x x x x x x x x x x x x x
Adm'ty Br (CA443), Mn Bronze L x x x x x x x x x x x x x x x
S x x x x x
11 Tin E x x x x x x x x x x x x x x x x x
L x x x x x x x x x x x x x x x x
S x x x
12 Copper (CA102, 110), E x x x x x x x x x x x x x x x
Si Bronze (CA655) L x x x x x x x x x x x x x
S x x x x x x x x x x
13 Lead -Tin Solder E x x x x x x x x x x x
L x x x x x x x x x x x
S x x x x x x x x x x x x x x x x
14 Tin-Bronze (G&M) E x x x x x x x x x x x
L x x x x x x x x x x

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ATTACHMENT 3 (Page 3 of 5)
(Section 4.2 and 8.3.3)

METAL CONSIDERED COUPLED Note: These Numbers correspond with the numbers and alloy designations listed in the left column.
WITH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
S
15 Stainless Steel, 12-14% Cr E
(AISI Types 410,416) L
S x x x x x x x x x
16 Nickel Silver (CA 732, 735, 745, E x x x x x x x x x x x x x
752, 764, 770, 794) L x x x x x
S x x x x x x x x x
17 90/10 Copper-Nickel (CA706) E x x x x x x x x x x
L x x x x
S x x x x x x x x x
18 80/20 Copper-Nickel (CA710) E x x x x x x x x x x
L x x x x
S
19 Stainless Steel, 16-18% Cr E
(AISI Type 430) L
S x x x x x x x x x
20 Lead E x x x x x x x x x x x x
L x x x x x x x x x
S x x x x x x x
21 70/30 Copper-Nickel E x x x x x x x x x x x
(CA715) L x x x

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ATTACHMENT 3 (Page 4 of 5)
(Section 4.2 and 8.3.3)

METAL CONSIDERED COUPLED Note: These Numbers correspond with the numbers and alloy designations listed in the left column.
WITH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
S x x x x x x x
22 Nickel-Aluminium-Bronze E x x x x x x x x x x x x x
L x x x x x
S x x x x x x x x x x x
23 Nickel Alloy 600 E x x x x x x x x x x x x x x x x
L x x x x x x x
S x x x x x x x x x x x x x x x x x x
24 Silver Braze Alloys E x x x x x x x x x x x x x x x x
L x x x x x x x x x x x x
S x x x x x x x x x
25 Nickel E x x x x x x x x x x x x x x x x x x
L x x x x x x x x
S x x x x x x x x x x x x x x
26 Silver E x x x x x x x x x x x x x
L x x x x
27 Stainless Steel, 18 Cr, 8 Ni S x x
(AISI Types 302, 304, 321, 347) E x
L x
S x x x x x x
28 Nickel Alloys 400 E x x x x x x x x x x x x x x x
and K-500 L x x x x x

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ATTACHMENT 3 (Page 5 of 5)
(Section 4.2 and 8.3.3)

METAL CONSIDERED COUPLED Note: These Numbers correspond with the numbers and alloy designations listed in the left column.
WITH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
S x x x x x x x x x x x x
29 Stainless Steel, 18 Cr, 12 Ni-Mo E x x x x x x x x x x x x x x x x
(AISI Types 316, 317) L x x x x x x x
S x x x x x x x
30 Stainless Alloy 20, E x x x x x x x x x x x x x x x x
Nickel Alloy 825 L x x x x x x
S x x x x x x x
31 Titanium, Nickel Alloys C, E x x x x x x x x x x x x x x x x x x x x
C-276, 625 L x x x x x x x
S x x x
32 Graphite, Graphitized Cast Iron E x x
L x x

KEY:

● UNFAVORABLE - Normal deterioration of either material may be increased moderately or severely.

x UNCERTAIN - Direction and/or magnitude of effect on normal behavior may vary, depending on circumstances.
COMPATIBLE - Deterioration of either material is normally within tolerable limits.
S - Exposed are of the metal under consideration is small compared with the area of the metal with which it is coupled.
E - Exposed are of the metal under consideration is approximately equal to the area of the metal with which it is coupled.
L - Exposed are of the metal under consideration is large compared with the area of the metal with which it is coupled.

Source: Galvanic Corrosion Indicator, International Nickel Co. and NACE Corrosion Engineer's Reference Book, 1983 Edition.

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ATTACHMENT 4
(Sections 4.3 and 4.4)

4a : Corrosion Cell
(Section 4.3)

Electrolyte

Conventional Current Flow

Fe++ H+ OH-

e- e-
Electrons e-
Anode
(Corrosion area) Flow Cathode

4b : Zinc-Copper Corrosion Cell

(Section 4.4)

Zn Cu

Electrolyte

Anode Cathode

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ATTACHMENT 5
(Section 4.4)

ELECTROMOTIVE FORCE SERIES

Standard Reduction
Symbol Metal Potential Volts at 25oC
(vs Normal Hydrogen Electrode)

K Potassium -2.92 Greatest Tendency

Ca Calcium -2.87 to

Na Sodium -2.71 Corrode

Mg Magnesium -2.34

Be Beryllium -1.70

Al Aluminium -1.67

Mn Manganese -1.05

Zn Zinc -0.762

Cr Chromium -0.71

Fe Iron -0.44

Cd Cadmium -0.402

In Indium -0.346

Co Cobalt -0.277

Ni Nickel -0.250

Sn Tin -0.136

Pb Lead -0.126

H Hydrogen 0.00

Cu Copper 0.345

Hg Mercury 0.799

Ag Silver 0.800 Least Tendency

Pt Platinum 1.20 to

Au Gold 1.42 Corrode

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ATTACHMENT 6
(Sections 4.4 and 6.2)

6a : Polarisation Curve
(Section 4.4)

Potential

Cu

E corr I Re
corr

Re =
Electrolyte Resistance
Zn

Current corr

6b : Corrosion Rate of Steel vs pH

(Section 6.2)

Corrosion Rate

4 6 9 14

pH

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ATTACHMENT 7
(Sections 6.3.1 and 8.12)
Relation of Dissolved Oxygen to the
General Corrosion Rate of Steel

Corrosion Rate (mpy)

30

25

20

15

10

5
Note change of scale

0 20 50 75 125 1000 3000 4500 6000 8000

Oxygen Concentration (ppb)

Burma Oil Exxon Data O&G Consultant

Note: Variation in values are due to differences in CO2/H2S content and accuracy of O2 measurement.

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ATTACHMENT 8
(Sections 6.3.3, 8.7.1 and 8.8)
H2S Service Induced Cracking of Plate Steel and Welds

Vessel ID in Sour Environment

SSC

Laminations or
Blistering Inclusions

SWC

SOHIC

Plate Steel Weld Heat Affected Zone (HAZ)

LEGEND:
SOHIC - Stress Oriented Hydrogen Induced Cracking
SSC - Sulfide Stress Cracking
SWC - Stepwise Cracking

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ATTACHMENT 9
(Sections 8.1 and 8.2)

QUALITATIVE CATEGORIZATION OF COUPON CORROSION RATES FOR OIL PRODUCTION SYSTEMS

Average Corrosion Rates Pitting Rate

US Customary Metric (SI) US Customary Metric (SI)

(mpy(1)) (µm/a(2)) (mpy) (µm/a)

Low <1.0 <25 <5 <127

Moderate 1.0-4.9 25-126 5-7.9 127-201

High 5.0-10 127-254 8-15 202-381

Severe >10 >254 >15 >381

(1)
mpy = mils per year
(2)
µm/a = micrometer per annum

Note: This information is from NACE RP0775.

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ATTACHMENT 10
(Section 8.13)
CO2 General Corrosion Rate of Steel
Corrosion Rate (mpy)
1000

150oF (65oC) Flowing

77oF (25oC)

100

Non-Flowing 77oF (25oC)

10

1 10 100 1000

CO2 Partial Pressure (psia)

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Note: Graph is from a compilation of NACE data and is intended to show only the relationship of CO2 partial pressure to corrosion rate in flowing and non- flowing
conditions. Do not use this figure to predict CO2 corrosion rates.

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