CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
Carbon Dioxide Corrosion in Oil and Gas
ProductionA Compendium
M.B. Kermani,* and A. Morshed**
ABSTRACT
The present mechanistic understanding and practical impli-
cations of carbon dioxide (CO2) corrosion of carbon and low-
alloy steels in hydrocarbon production have been reviewed.
This is based on the fact that CO2 corrosion is by far the
most prevalent form of attack encountered in upstream op-
erations. The intent of the review was to provide information
on the mechanisms, highlight key parameters affecting its
occurrence, and draw attention to areas requiring further
research. The primary focus was placed on two key param-
eters affecting CO2 corrosion that had received little system-
atic attention, including the morphology, nature, and
characteristics of the surface film and steel composition,
microstructure, and finishing conditions. In addition, the role
of environmental and hydrodynamic variables is briefly pre-
sented. The review has highlighted key areas of progress
both mechanistically and industrially and has led to a num-
ber of key messages recommending areas for additional
research to further the understanding of CO2 corrosion
mechanisms to enable improved predictive capabilities for
the effective use and deployment of carbon and low-alloy
steels in oil and gas production.
KEY WORDS: acetic acid, carbon steel, carbon dioxide corro-
sion, corrosion layer, flow dynamics, iron carbonate, low-alloy
steels, metallurgy, mesa attack, oil and gas production
Corresponding author.
* KeyTech Limited, PO Box 275, Camberley, Surrey GU15 2FH,
United Kingdom.
** University College London, Torrington Place, United Kingdom.
0010-9312/03/000131/$5.00+$0.50/0
CORROSIONVol. 59, No. 8 2003, NACE International
INTRODUCTION
In the search for new sources of oil and gas, opera-
tional activities have moved to harsher environments
in deeper high-pressure/high-temperature wells and
deep water. These have created increased challenges
to the economy of project development and subse-
quent operations wherein facilities integrity and
accurate prediction of materials performance are be-
coming paramount. In addition, the economic move
toward multi-phase transportation through subsea
completions and long infield flowlines has a tendency
for increased risk of corrosion.
Corrosion, therefore, remains a major opera-
tional obstacle to successful hydrocarbon produc-
tion, and its optimum control and management is
regarded necessary for the cost-effective design
of facilities and their safe operations. It has wide-
ranging implications on the integrity of many materi-
als used in the petroleum industry.
The impact of corrosion on the oil and gas indus-
try can be viewed in terms of its effect on capital and
operational expenditures (CAPEX and OPEX) and
health, safety, and the environment (HSE).1 Corro-
sion failures, the majority of which are related to
carbon dioxide (CO2) corrosion,1-5 have been reported
to account for some 25% of all safety incidents,
2.8% turnover, 2.2% tangible asset, 8.5% increase on
capital expenditure, 5% of lost/deferred production,
and 11.5% increase to the lifting costs.1-3 These are
estimated figures and operator dependent, obtained
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
from a number of publications.1-4 The spread of
these figures are highly dependent on the manner
to which a corrosion control philosophy is planned
and implemented as they vary according to opera-
tions and operators. One operator puts the cost of
corrosion as 30 cents for the production of each
barrel of oil equivalent (0.3 $/boe) or 1.5% of the
turnover.4
The industry continues to lean heavily on the
extended use of carbon and low-alloy steels, which
are readily available in the volumes required and
are able to meet many of the mechanical, structural,
fabrication, and cost requirements. Their technol-
ogy is well developed and they represent an economi-
cal materials choice for many applications. However,
a key issue for their effective use is their poor
general and CO2 corrosion performance. Given the
conditions associated with oil and gas production
and transportation, corrosion must always be seen
as a potential risk. The risk becomes real once an
aqueous phase is present and is able to contact the
steel, providing a ready electrolyte for the corrosion
reaction to occur.
Oilfield Corrosion
Oilfield corrosion manifests itself in several
forms, among which CO2 corrosion (sweet corrosion)
and hydrogen sulfide (H2S) corrosion (sour corrosion)
in the produced fluids and oxygen corrosion in water
injection systems are by far the most prevalent forms
of attack encountered in oil and gas production. H2S
corrosion and materials optimization is covered else-
where,3 and corrosion in water injection systems is
outside the present review. The majority of oilfield
failures result from CO2 corrosion of carbon and low-
alloy steels primarily due to inadequate knowledge/
predictive capability and the poor resistance of car-
bon and low-alloy steels to this type of attack.1-4 Its
understanding, prediction, and control are key chal-
lenges to sound facilities design, operation, and sub-
sequent integrity assurance.
Recent studies clearly have demonstrated that,
despite extensive research over the past four de-
cades, the mechanistic understanding of CO2 corro-
sion remains incomplete. Existing quantitative
models are unreliable in predicting the actual long-
term CO2 corrosion rate of carbon and low-alloy
steels, which invariably results in over-specification
of materials and impacts adversely on the cost of
production of oil and gas.1-9
The intent of this review article was to capture
the current understanding of CO2 corrosion of carbon
and low-alloy steels in hydrocarbon production. It
provides information on the mechanisms, highlights
key parameters affecting its occurrence, and draws
attention to areas requiring further research. The pri-
mary focus was placed on two key parameters affect-
ing CO2 corrosion, including the morphology of the
660
surface film and steel composition. In addition, the
role of environmental and physical variables affecting
its occurrence is presented. Another key issue is the
performance and characteristics of welds, although
this subject was not covered in the present review as
it requires detailed and focused attention. The review
highlights key areas of progress and draws attention
to the future direction of research and development
to enable improved and economical design of facili-
ties for oil and a gas production.
CO2 CORROSION
CO2 corrosion, or sweet corrosion, of carbon
and low-alloy steels is not a new problem. It was first
recorded in the U.S. oil and gas industry in the
1940s, followed by several studies since then.6-9 Dry
CO2 gas by itself is not corrosive at the temperatures
encountered within oil and gas production. It needs
to be dissolved in an aqueous phase to promote an
electrochemical reaction between steel and the con-
tacting aqueous phase. CO2 is soluble in water and
brines. However, it should be noted that it has a
similar solubility in both the gaseous and liquid
hydrocarbon phases. Thus, for a mixed-phase
system, the presence of hydrocarbon phase may
provide a ready reservoir of CO2 to partition into the
aqueous phase.
CO2 is usually present in produced fluids. Al-
though it does not in itself cause the catastrophic
failure mode of cracking associated with H2S,2 its
presence in contact with an aqueous phase neverthe-
less can result in very high corrosion rates where
the mode of attack is often highly localized (mesa
corrosion).
CO2 Corrosion Mechanism
Corrosion of carbon steel in CO2-containing envi-
ronments is a very complex phenomenon and still
requires further elucidation. Various mechanisms
have been proposed for the process. However, these
either apply to very specific conditions or have not
received widespread recognition and acceptance.9-19
In general, CO2 dissolves in water to give car-
bonic acid (H2CO3), a weak acid compared to mineral
acids since it does not fully dissociate:
CO2 + H2O CO2 H2O H2CO3 H + + HCO3 (1)
As a consequence of the equilibrium described in
Equation (1), much debate continues in the literature
as to the rate-determining step (RDS) in the reaction
of the dissolved CO2 with a steel surface. Schwenk10
proposed that H2CO3 simply provides a source of H+
ions leading to the normal cathodic hydrogen evolu-
tion reaction. de Waard and Milliams11 proposed that
H2CO3 is directly reduced at the steel surface,
whereas Ogundele and White12 point to the HCO3 ion
CORROSIONAUGUST 2003

Mechanisms of the Anodic Dissolution of Iron in CO2-Containing Media19-20
Reaction No. Reaction or Equilibrium
1a HCO3 (HCO3)ads
1b CO2+(OH )ads (HCO3)ads
2 (HCO3)ads (HCO3)ads+e
3 (HCO3)ads (HCO3+)ads+e
4 (HCO3+)ads+OH (CO3)ads +H 2O
5 Fe (CO3)ads + H2O Fe+++HCO 3+OH
15 Tafel slope (mV/log)
15 H+ reaction order
15 CO2 reaction order
(A)
RDS = rate-determining step.
being reduced directly. The possible RDS in cathodic
reactions, therefore, are summarized as follows:
Schwenk
(HCO3 ): H + + e H, 2H H2
de Waard and Milliams
H2CO3 + e H + HCO3 RDS
HCO3 + H + H2CO3 and 2H H2
Ogundele and White
HCO3 + e H + CO23 RDS
HCO3 + H + e H2 + CO23
While the Ogundele mechanism only deals with alka-
line pH conditions and the Schwenk and deWaard
mechanisms are only a possible hypothesis, recent
reactions put forward by Crolet, et al.,19 are the most
likely mechanism encountered. Based on the reaction
proposed by Crolet, the anodic dissolution of iron in
CO2-containing media is summarized in Table 1 with
respective RDS at different pH conditions.19-20 This
table goes beyond summarizing the anodic dissolu-
tion reactions and includes the respective Tafel
slopes derived from each pH condition.
Whichever is strictly mechanistically correct, it is
evident that the concentrations of dissolved CO2 spe-
cies in solution and the mass transport of dissolved
CO2 to the steel surface have a critical influence on
the reaction and subsequent corrosion rate13 and
that every dissolved species present in the media can
contribute to the cathodic reaction (Ref. 9 and Pots21
and Nesic, et al.22). Hence, there is a clear need to be
able to characterize solution chemistry with respect
to CO2 dissolution where the resulting acidification
will depend also on water composition and its buffer-
ing capacity.14
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
TABLE 1
pH < 4 4<pH<5 pH> 5
1a 1a 1b
RDS
RDS(A)
RDS
60/2 = 30 60/1.5=40 60/0.5= 120
2 1 0
1 1 1
Types of CO2 Corrosion Damage
CO2 corrosion occurs primarily in the form of
general corrosion and three variants of localized
corrosion (pitting, mesa attack, and flow-induced
localized corrosion).9 In studying CO2 corrosion, a
(2) clear distinction should be made between pure CO2
corrosion and a combined interaction of erosion/CO2
corrosion, which may be exacerbated by CO2 corro-
sion. The latter characterizes itself in the form of
(3) ripple marks, horseshoes, comet tails, and dinosaur
foot prints,8,18 whereas the former is described in
this paper.
(4)
Pitting Pitting occurs at low velocities and
around the dew-point temperatures in gas-producing
wells. In the field, only occasional pits have been ob-
served, which were either accidental adjacent to non-
(5) metallic inclusions or incipient mesa attack.7-8,18 The
pitting susceptibility increases with temperature and
(6) CO2 partial pressure. In several related works on pit-
ting, Schmitt and coworkers15-17 discussed the effects
of temperature, Cl concentration, nature of anions
and cations, as well as corrosion inhibitors on the pit
initiation during the first stages of CO2 corrosion of
pure iron and low-alloy steels at 5 bar CO2. They also
reported that literally all alloys of technical interest
might undergo pitting corrosion in CO2 environments
at the right conditions. Finally, they showed that Pb
additions inhibited localized corrosion (including pit-
ting) through deposition at local anodes. On the
other hand, Videm and coworkers23-24 concluded that
the pitting of carbon steel in CO2-containing environ-
ments was almost independent of the chloride con-
tent. Therefore, it was different from many other
metal environment combinations. However, the
harmful ion, if any, responsible for the pitting of
carbon steels in CO2 solutions was not identified.
The discussion on pitting of carbon steels in
sweet environments has not reached a convincing
conclusion. Various authors attribute the pitting ini-
tiation and its propagation to different factors and
there is no generally applicable rule for its prediction.
Mesa-Type Attack Mesa attack is a type of lo-
calized corrosion and occurs in low to medium flow
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 1. A typical example of severe mesa attack experienced on
internal surfaces of pipelines transporting CO 2 -containing
hydrocarbon fluids (courtesy of Institute for Energy Technology, IFE).
conditions where the protective iron carbonate film
forms but it is unstable to withstand the operating
regime. It manifests itself in large flat-bottom steps
with sharp edges. Corrosion damage in these loca-
tions is well in excess of the surrounding areas.9
Figure 1 is an example of mesa attack experienced
on an internal surface of pipelines exposed to CO2-
containing environments.
Crolet, et al.,25 proposed that the microstruc-
turally formed galvanic coupling between steel (its
ferrite phase) and the cementite (Fe3C) layer was one
possible cause to promote mesa attack in sweet envi-
ronments. According to the same author,18 mesa at-
tack was observed in mature oil wells or, conversely,
in young gas wells under high pressure of acid gases.
Even in the presence of high fluid flow rates, its
characteristics were totally different from the typical
features of erosion corrosion. Mesa attack appeared
to be a little sensitive to the velocity of water in the
pipe, but extremely dependent on fluid composition.18
Ikeda, et al.,26 attributed the initiation of mesa
attack to the competitive film formation reactions
between ferrous carbonate (FeCO3) and magnetite
(Fe3O4). Although, in actual field conditions, Fe3O4
has not been detected.18,27 The codeposition of both
compounds could initiate the mesa corrosion by dis-
turbing the protective film formation. They concluded
that the initiation mechanism of mesa corrosion was
closely related with the formation of a poorly protec-
tive FeCO3 film or the localized destruction of a
protective film.
Videm and coworkers28-30 showed that flow-
induced mesa attack could occur in water saturated
with FeCO3 under turbulent flow conditions where
film formation is prevented locally. In similar work,
Dugstad and coworkers30-31 demonstrated that the
662
initiation of mesa attack was a result of the marginal
film stability of FeCO3. However, as indicated earlier,
chemical instability of the film has a more pro-
nounced influence on the formation of mesa attack
than any mechanically driven effect by fluid dynam-
ics.27 Dugstad then discussed the relation between
Fe2+ content of the environment and the initiation of
mesa attack for sweet environments.31 According to
him, when mesa attack has initiated, a galvanic cell
would probably establish where the film-covered sur-
face was cathodic and the mesa-attacked areas were
anodic.31 As described later, trace concentrations of
Cr alloying element when added to carbon steel re-
duced mesa attack to a great extent.32-33
Again, the exact conditions under which mesa
attack forms are poorly understood and further sys-
tematic studies are necessary to prevent its occur-
rence in the field.
Flow-Induced Localized Corrosion This form of
corrosion starts from pits and/or sites of mesa attack
above critical flow intensities. It then propagates by
local turbulence created by the pits or steps at the
mesa attack or by protruding geometry. The local
turbulence combined with the stresses produced
during scale growth may destroy existing scales.15-17
Once the scale is damaged or destroyed, the flow
conditions then may prevent reformation of protec-
tive scale on the exposed metal.9,16-17 Flow-induced
localized corrosion attack is principally observed in
laboratory experiments in the absence of complete
control of fluid chemistry.
KEY FACTORS
INFLUENCING CO2 CORROSION
CO2 corrosion is influenced by a number of pa-
rameters, including environmental, physical, and
metallurgical variables as illustrated in Figure 2.
The majority of these have been covered extensively
by a number of authors and captured elsewhere.6,8-9
Notable parameters affecting CO2 corrosion include:
fluid makeup as affected by water chemistry,
pH, water wetting, hydrocarbon characteris-
tics, and phase ratios9,34-36
CO2 and H2S content9,37-40
temperature9,34-35,41
steel surface, including corrosion film mor-
phology, presence of wax, and ashphaltene9
fluid dynamics9,29,39-41
steel chemistry32-33,38,42-45
All parameters are interdependent and can inter-
act in many ways to influence CO2 corrosion. In the
present article, emphasis has been placed on two key
issues relating to metallurgical variables and surface
film as key parameters not covered systematically
elsewhere. Other influential parameters are covered
extensively by others8-9,34 and have been given only a
brief mention here.
CORROSIONAUGUST 2003

FIGURE 2. CO2 corrosion, the influential parameters.
Environmental Parameters
Environmental factors that affect the inherent
corrosivity of the aqueous phase therefore will affect
CO2 corrosion. These include solution chemistry,
CO2 partial pressure, temperature, the in-situ pH,
H2S, and the effect of organic acids.
Solution Chemistry and Supersaturation While
there are still limited debates about the mechanism
of CO2 corrosion in terms of which dissolved species
are involved in the corrosion reaction, it is evident
that the resulting cathodic corrosion rate is depen-
dent on the partial pressure of CO2 gas and tempera-
ture. Partial pressure of CO2 gas thus will determine
solution pH and the concentration of dissolved spe-
cies for a given temperature.
Supersaturation plays a vital role in the forma-
tion and stability of a protective corrosion layer.
Supersaturation is defined as log [A+][B]/Ksp for an
insoluble salt (AB) having an equilibrium reaction of
AB = A+ + B, where A+ and B are ionic species and
Ksp is the solubility product. In any sweet environ-
ment, a particularly insoluble salt can play an impor-
tant role in reducing the corrosion rate. High
supersaturation of A+ and B leads to precipitation of
a corrosion layer/film that therefore would reduce
the corrosion rate through several kinds of effects,
including:18
provision of a diffusion barrier (extended dif-
fusion length between the metal substrate and
the corrosive medium);
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
formation of a low-porosity protective layer
(lowering the exposed surfaces compared with
the steel surface and hence less areas to be
corroded);
creation of concentration gradients of the prin-
cipal chemical species (Fe++ and HCO3). This is
potentially the most influential and particu-
larly difficult to model. Ingress of solution to
soak the porosity leads to steep concentration
gradients, which may induce a significant shift
of the local pH and water chemistry from the
bulk conditions, and therefore, a genuine ef-
fect of liquid surface state.
Altogether, the precipitation rate and protective
characteristics of any scale depend heavily on the
supersaturation of the bulk solution. Hence, any
variations in this level of supersaturation could affect
the severity of the corrosion. For iron carbonate sys-
tems, this can be portrayed as a reaction similar to
Fe(HCO3)2 FeCO3 + H2CO3.46 The interdependency
of supersaturation with the respective rates of iron
dissolution and reprecipitation is shown in Figure 3
as a function of temperature. Figure 3 illustrates that
while iron carbonate solubility to achieve saturation
remains a little dependent on temperature, the limit
of supersaturation is achieved at lower Fe2+ concen-
trations with increasing temperature and hence
facilitates the formation of FeCO3.31
CO2 Partial Pressure CO2 partial pressure has
been used in pH calculations and corrosion rate
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 3. Fe++ solubility in pure water as a function of temperature
at 0.1 MPa CO2 partial pressure. Open squares represent results
obtained with corroding steel present, where the water volume to
steel surface area ratio is 4 cm 3/cm 2. Filled triangles are Fe++
concentrations calculated from pH. Filled squares are results
obtained with solid iron carbonate. The dashed line is iron carbonate
solubility calculated from IUPAC data.31
measurements by many authors.6,9,11,36,37,47-49 In most
cases, a relationship has been developed between the
CO2 partial pressure and corrosion rate. However,
with some exception,36,48 the majority of pH calcula-
tions in these relationships do not take on board
that produced water cannot stay supersaturated in
CaCO3. It also should be noted that for gas wells
with increasing pressure, the non-ideality of the
natural gas will play an increasing role. Instead of
the CO2 partial pressure, the CO2 fugacity (fco2)
should be used.50 The difficulty is that for the pur-
pose of homogeneity between nonideal phases, when
fugacity is used for the gas phase, an activity coeffi-
cient (co2) should also be introduced for the water
phase. Unfortunately, fco2 is often available from
PVT data, but rarely co2,36,48 and this may be the
reason for the simplistic use of fco2 in the prediction
of corrosion rates.
Operating Temperature The operating tempera-
ture strongly affects the nature, characteristics, and
morphology of surface film, which, in turn, influ-
ences the CO2 corrosion process. At temperatures
in excess of ca. 80C, the solubility of FeCO3 in the
solution is decreased and high supersaturation leads
to FeCO3 precipitation.41 At low temperature ranges
(< ca. 70C), corrosion rate progressively increases
with temperatures up to an intermediate tempera-
ture range (between 70C to 90C), after which the
corrosion rate then diminishes. However, at sites
where breakdown in the formation of FeCO3 occurs,
664
corrosion process proceeds unhindered, which may
lead to severe localized attack. This is an important
design consideration.9 It is thought that the increase
of corrosion rate in the low-temperature range is due
to an increase of mass-transfer rate as a result of
flow effect and slow FeCO3 formation rate.27 Conse-
quently, after the formation of the protective scale, a
diffusion process may become the RDS in the corro-
sion process.19 However, as described in the Solution
Chemistry and Supersaturation Section, this does
not rule out the potential for the occurrence of local-
ized corrosion or the formation of nonprotective cor-
rosion scales (i.e., when the aspects of solid surface
states [diffusion barrier and porous layers] are su-
perseded by those of liquid surface states [membrane
effect and local water chemistry]27), as described in
the section on surface film.
In Situ pH Solution pH plays an important role
in the corrosion of carbon steels by influencing both
the electrochemical reactions that lead to iron disso-
lution and the precipitation of protective scales that
governs the various transport phenomena associated
with the former. Under certain conditions, solution
constituents of the aqueous phase will buffer the pH,
which can lead to precipitation of a corrosion scale
and the possible lowering of corrosion rates. It
should be noted that, as described in the section on
film formation, in certain circumstances the corro-
sion layer can even be corrosive and increase the
severity of attack.8-9,19,27
As an example, by increasing pH from 4 to 5, the
solubility of Fe++ is reduced five times; for an increase
from pH 5 to 6, this reduction is around 100 times.8
A low solubility can correspond to higher supersatu-
ration, which therefore accelerates the precipitation
process of FeCO3 film. For pH values >5, the prob-
ability of film formation is thus increased and that
can contribute to the lower corrosion rates observed.
It must be noted that the solubility of the FeCO3
should not be confused with that of the iron ion.8-9,18
Effect of H2S Ignoring the cracking aspects of
corrosion problems associated with sour service, low
levels of H2S can affect CO2 corrosion in different
ways. H2S can either increase CO2 corrosion by
acting as a promoter of anodic dissolution through
sulfide adsorption and affecting the pH or it can de-
crease sweet corrosion by forming a protective sulfide
scale. The exact interaction of H2S on the anodic dis-
solution reactions (Table 1) is not clear.
For similar conditions, oil and gas installations
could experience lower corrosion rates in sour condi-
tions compared to completely sweet systems. This is
attributable to the fact that the acid created by the
dissolution of H2S is about three times weaker than
that of carbonic acids, but H2S gas is about three
times more soluble than CO2 gas. As a result, the
effect of both CO2 and H2S gases on lowering the
solution pH and potentially increasing corrosion rate
CORROSIONAUGUST 2003

are fundamentally the same. In addition, H2S might
play a significant role on the type and properties
of the corrosion films, improving or undermining
them.8-9
Videm, et al.,38 and Mishra, et al.,37 have re-
ported two opposing results concerning H2S. While
the former has reported that very small amounts of
H2S in CO2-containing water augmented the corro-
sion rate, the latter has argued that small amounts
of H2S had some inhibitive effect on CO2 corrosion of
steels. They attributed this to the formation of an
iron sulfide film that apparently was more protective
than FeCO3.
Many papers have been published on the inter-
action of H2S with low-carbon steels.6,8-9,39-40,51-52 How-
ever, literature data on the interaction of H2S and
CO2 is still limited since the nature of the interaction
with carbon steel is complex. The majority of open
literature does indicate that CO2 corrosion rate is re-
duced in the presence of H2S at ambient tempera-
tures. Nevertheless, it must be emphasized that H2S
also might form a nonprotective layer and that it
might catalyze the anodic dissolution of bare steel.
Steels may experience some form of localized corro-
sion in the presence of H2S, although very little infor-
mation is available. Published laboratory work has
not been conclusive, indicating that there is a need
to carry out further studies to clarify the mechanism.
A recent failure showed how the corrosion rate in the
presence of a high concentration of H2S might be
higher than predicted using CO2 corrosion prediction
models. However, in spite of the work on H2S corro-
sion of steels, no equations or models are available
to predict corrosion, as is the case for CO2 corrosion
of steels.9
Effect of Acetic Acid Organic acids present in
production fluids has long been considered to signifi-
cantly influence and complement CO2 corrosion. The
influence has been shown to occur systematically in
all field conditions where CO2 corrosion was ob-
served.18,27,53 Addition of acetic acid (HAc) to the test
environment reduces the protectiveness of the films
and increases the sensitivity to mesa attack. This
attributes to a lower Fe2+ supersaturation in the
corrosion film and at the steel surface. Significant
reduction in film stability was observed when the
concentration of undissociated HAc in the solution
was increased from 0.05 mmol to 0.2 mmol, but the
results are too few to give more accurate threshold
values.19,53-56
Crolet and Bonis14,55 make the point that CO2-
induced acidification also can cause partial re-asso-
ciation of anions, such as acetates and propionates,
to form organic acids. Such weak acids then will in-
crease the oxidizing power of H+ by raising the limit-
ing diffusion current for cathodic reduction (cf.
Reaction [2]). The presence of such acids also will
tend to solubilize the dissolving iron ions and sup-
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
press FeCO3, or oxide film formation, which can
otherwise passivate the steel surface.25,35,55
It is also often observed, at least in laboratory
tests, that water or brine acidified with CO2 to a given
pH produces a more corrosive solution than acidify-
ing to the same pH with mineral acid. This is gener-
ally attributed to the fact that because carbonic acid
(H2CO3) is not fully dissociated in solution, it pro-
vides a reservoir of H+ ions over and above that deter-
mined by the solution pH (log[H+]). In essence, this
is the same effect as that once cited by Crolet and
Bonis14 in the presence of organic acids (weak acids)
(i.e., increasing the oxidizing power of H+). For low
concentrations of HAc (very few mM), however, the
effect cannot but remain negligible with respect to
the tens or hundreds of mM of dissolved CO2.19 In
addition, the presence of HAc may change the
mechanism of the anodic dissolution of iron through
competitive adsorption of acetate ions, CH3COO
(or Ac) and HCO3, although this was shown to have
only a slight inhibiting effect.19,55
Generally, the presence of HAc caused a signifi-
cant increase in the corrosion rates in CO2 environ-
ments.53,56 HAc (along with other organic acids) could
jeopardize the protective corrosion product scales
formed in top-of-the-line corrosion.57
At low CO2 partial pressure, CO2 corrosion disap-
pears, but in certain fields, it can be replaced by a
genuine HAc corrosion. It has been shown that this
was not caused by any influence of the HAc, either
on the cathodic reaction of H+ or on the anodic disso-
lution of iron, but rather by its effect on the protec-
tiveness of the corrosion layer. In the presence of
traces of free HAc, the majority of corrosion layers on
bare metal was no longer FeCO3, but iron acetate,
which had a much greater solubility.19
In a similar work,25 it has been reported that
at a given pH, any replacement of a concentration
or a flux of bicarbonate by an equivalent quantity
of acetate would considerably increase the local
solubility of iron. This decreases the protectiveness
of the corrosion layer in proportion, by increasing
iron concentration gradients, and therefore allowing
and subsequently raising the fluxes of corrosion
products, which potentially can be removed through
the layer. An overview of the concentration gradient
of acetate ions close to the metal surface is shown
in Figure 4.23
The presence of HAc is a key issue in CO2 corro-
sion, which requires further extensive studies.
Physical Parameters
Along with environmental and metallurgical pa-
rameters, physical parameters play an important role
in CO2 corrosion of carbon and low-alloy steels by
influencing hydrodynamics of the system and the in-
terface between the environment and the steel sub-
strate. These include water wetting, wax effect,
665
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 4. Illustration of possible HAc enrichment in a corrosion
layer as a result of internal acidification and galvanic coupling
between steel and cementite.25
surface films, crude oil, and fluid dynamics and are
mostly covered by others.8-9 Their interactive and
complementary influences affect the onset of film for-
mation and removal. These effects have been high-
lighted briefly here.
Water Wetting CO2 corrosion occurs when
water is present in the system and it wets the steel
surface. The intensity of CO2 corrosion attack in-
creases with the time during which the water phase
is in contact with the steel surface. Therefore, the
water content (water cut) and the notion of water
wetting are important variables. There are at least
three different notions of water wetting as follows:58
Hydrodynamic concept focuses on modeling a
continuous water phase at the fluid/wall in-
terface, which is primarily over the corrosion
layer. However, it is evident that corrosion
does not occur over the corrosion layer, but
beneath it. This concept therefore cannot be
directly relevant to corrosion modeling as
influenced by water wetting.
Electrochemistry and surface physics concept
relates to liquid in direct contact with the
metallic phase. This can be, in part, highly in-
fluential in the modeling of water wetting.
CO2 corrosion-related concept in which liquid-
soaked porous film continues to hold water,
even if the bulk phase in contact with the wall
is temporarily either pure oil (in oil lines) or
just a thin, wet film (in a pure gas line without
any ongoing water condensation). This pro-
vides a favorable boosting for the sealing of
cementite or hydrated mill scales during the
corrosion process and, as a consequence,
facilitates the onset of protectiveness in an
originally nonprotective film.27 Such circum-
stances can occur during shutdown periods
or in slug flow conditions.
666
Therefore, the influence of water cut on corro-
sion rate should be considered in association with
the flow velocity and the flow regime effects in the
context of the above notions of water wetting, par-
ticularly using a combination of the second and
third notions.27
It is known that emulsions can form in oil/water
systems. If a water-in-oil emulsion is formed and the
water is held in the emulsion, then the water wetting
of steel is prevented or greatly reduced, causing the
corrosion rate to decrease. If, on the contrary, an
oil-in-water emulsion is formed, then water wetting
of steel will happen. The transition from a water-in-
oil emulsion to oil-in-water occurs at around 30% to
40% water in many oil lines and, in a straight pipe
with emulsified liquids, an obvious increase in the
corrosion rate can be observed.59 So, as a rule of
thumb, for water cuts <30 wt%, the corrosion rate is
often significantly reduced,9,59 although there are
many exceptions to this.60 The water cut threshold
depends primarily on the maturity of hydrocarbon
(immature oils still contain natural surfactants) and
the nature of its kerogen (I, II, III)27 as explained in a
later section.
Corrosion Film Characteristics Characteristics
of corrosion product significantly affect the CO2 cor-
rosion process. Formation of surface film can provide
subsequent protection, enhanced corrosion, or un-
controlled reaction, all subject to the nature, mor-
phology, and growth habit of the corrosion product.
Due to the importance of this subject, it is described
in a separate section on film formation.
Effect of Wax The presence of wax in oil pipe-
lines can influence CO2 corrosion damage in two
ways, either exacerbating the damage or retarding
the process. These are dependent on the nature of
wax layer and subject to flow dynamics, temperature,
and other physical parameters. Based on data gath-
ered in sweet oil lines in the U.S., a layer of wax (par-
affin) deposited on a carbon steel substrate caused
heavy pitting in anaerobic sweet environments. The
proposed corrosion mechanism is the diffusion of
CO2 through the wax layer, which can provide a large
cathodic area that promotes anodic dissolution of
steel at discontinuities of the wax layer.9 However,
generally, wax can provide a degree of protection,
albeit its protection is not reliable.
Effect of Crude Oil Corrosion tests conducted
on steel in brine environments in the absence of
crude oil do not give an accurate representation of
the behavior of the steel corrosion in a crude oil/
brine production environment. This can lead to gross
errors when using the test results to estimate poten-
tial corrosion problems.61-63
Although there has not been any specific investi-
gation on the effect of crude oil type on protective-
ness of FeCO3 scale, it has been determined that
crude oils modify the morphology, composition, and
CORROSIONAUGUST 2003

compaction of corrosion products for the different
oil/water ratios evaluated.64 Hydrocarbon appears to
destabilize the formation of a passive FeCO3 film, ac-
celerating the localized corrosion.27,61-62 Competitive
wetting of steel surfaces by water and then by oil has
been reported to play an important role.65-66
A combination of water cut and hydrocarbon
type play a key role in affecting CO2 corrosion. In
this, the maturity of hydrocarbon (immature oils still
contain natural surfactants) and the nature of its
kerogen (I, II, III)27 are main issues. While this infor-
mation is extremely important, it is rarely recorded
or reported. It should be noted that some crude oils
also release natural corrosion inhibitors, which aid in
lowering the corrosion rate.27
Crude oil plays an important and differing role
on CO2 corrosion and has not received due attention.
Flow and Erosion The effect of flow on CO2
corrosion still remains a contentious area in the pre-
dictive processes. This effect should be discarded in
predictive modeling unless it is fully defined and con-
trolled by the production process throughout the
production life. However, it is not only fluid content
that needs to be determinedthe flow regime is of
equal importance, which, for multi- or mixed phase
fluids, will determine whether water wetting of the
steel surface will occur. Clearly, if continuous hydro-
carbon wetting occurs, then the corrosion risk will
be extremely low.59 Key factors here are oil/water
ratio and emulsion tendency/stability. For many
crude oils, the presence of a water cut > 30% will
lead to water becoming the continuous phase for a
fully mixed oil/water system, such that corrosion
then becomes a continuous potential risk.59,62 Simi-
larly, if the gas/oil ratio (GOR) is >5,000, then con-
tinuous water wetting by the condensed water can
be expected.8-9
The flow parameter currently favored for deter-
mining the effect of velocity on corrosion rate and
scale and inhibitor film formation/stability is liquid
shear stress at the pipe wall. Although there is lim-
ited reported data on upper limits regarding shear
stress, a figure of 100 Pa for C-steel above which dis-
ruption to surface films becomes a concern is consid-
ered by some as appropriate.67 However, it must be
recognized that for specific situations it may be nec-
essary to conduct laboratory tests under simulated
flow conditions.
Laboratory testing becomes particularly critical
where erosion, as a result of the presence of particu-
lates, is a concern. There are no industry guidelines
that adequately cover this situation. The commonly
cited API RP-14E68 recommended practice strictly
refers to pure gas-in-liquid-induced erosion (i.e., no
particulates present) and applies the basic formula:
( )
Ve = C / m (7)
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
where Ve, mixed velocity (ft/s or m/s), m, mixed fluid
density (lb/ft3 or kg/m3), and C are constants.
The relationship is essentially empirical as is the
value of the constant (C) used for a given material.
This is more often than not based on the individual
operator experience.
Metallurgical Parameters
Chemical composition, heat treatment, and
microstructural features play important roles on
corrosion of carbon steels in CO2 environments.
While most authors have reported the beneficial
effects of chromium additions,26,29,42-45,68-79 there is not
yet a consensus on the optimum amount of Cr in the
steel structure. Apart from Cr, molybdenum has been
found to improve the corrosion resistance of carbon
steels.42 In a related work, Videm and Dugstad23
showed that small amounts of Cu, Ni, Cr (and possi-
bly Mo) increases the corrosion potential of carbon
steels, making it more noble. However, Cu additions
may have a side effect on inhibitor efficiency as re-
ported by Gulbrandsen and Nyborg.43
A laboratory study has shown that the sulfur
content of carbon steels appears to influence the CO2
corrosion rate as well. Certain high-S carbon steels
were more corrosion resistant than low-S carbon
steels in low-shear-stirred CO2 corrosion tests,74
although the steel samples used in this work were
not representatives of oil industry grades and the
practical implication of the work is uncertain.
Work by Kermani and coworkers44,80 has paved
the way to developing an optimum metallurgy of
carbon and low-alloy steels for both downhole and
transportation facilities through addition of microal-
loying elements like V, Ti, Mo, Cu, and Cr.
ALLOYING ELEMENTS
It is now well established that small quantities of
chromium (0.5 wt% to 3 wt%) can offer improved cor-
rosion resistance of low-alloy steels in CO2-contain-
ing media by promoting the formation of a stable,
protective chromium oxide film.8-9,33,72,77 It also has
been appreciated recently that for carbon and low-
alloy steels, there may be a correlation between pro-
tectiveness of the corrosion layer in the active state
and a possible passivation by a super protective
layer.8,72 The development of novel carbon and low-
alloy steels with superior resistance to CO2 corrosion
using metallurgical conditioning recently has been
made in the laboratory and subsequently by indus-
trial casts covering a wide range of parameters in-
cluding microalloying constituents, heat treatment
processing, and steel production scenarios. Corro-
sion performance and properties of optimum steels
developed in this project have been verified through
evaluation of the industrial casts,80 offering superior
CO2 corrosion while tolerating H2S corrosion for ap-
667
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 5. Schematic presentation of relative effect of additional
microalloying elements on corrosion rate.44,80
FIGURE 6. Schematic overview illustration of different categories of
steel ranked according to their Cr level.44,80
plication in Region 2 of ISO-15156.81 The philosophy
underlying the work of Kermani and coworkers44,80
was based on a combination of two principles:
lowering C and adding carbide-forming alloy-
ing elements to maximize the effect of a given
addition of chromium and molybdenum, by
ensuring that they remain in solid solution;
achieving the desired properties by
microalloying additions and mechanical and
heat treatments.
Steel compositions were designed with low-
carbon contents and contain microalloying additions
of stronger carbide-forming elements (V, Ti, and Nb).
The intention was that these microalloying elements
should preferentially combine with the carbon in a
given steel, leaving Cr and Mo uncombined in the
ferrite to provide enhanced corrosion resistance. In
addition, the presence of Si can lead to bainite for-
mation under normalized conditions. Thus, this ele-
ment, together with Ni, was used to bring back the
strength caused by the loss of carbon. The transfor-
668
mation characteristics of the steel and the heat treat-
ment following initial cooling was studied to allow
measures to prevent heat-affected zone (HAZ) crack-
ing during welding. The strength and toughness re-
quirements were met through grain size refinement,
the promotion of bainitic microstructure, and the
precipitation strengthening effect of the alloy carbides.
Extensive metallurgical and corrosion character-
ization of laboratory heats44 and industrial casts,80
produced with new but economically realistic ranges
of alloy contents, has led to the development of novel
categories of low C, Cr-containing steels with supe-
rior resistance to CO2 corrosion. The work utilized
the existing metallurgical knowledge of modern steel
properties and extensive knowledge of steel corrosion
behavior to identify the role of alloying elements to
define optimum steel compositions likely to meet the
strength, properties, weldability, and corrosion resis-
tance targets required by the oil industry.
Based on the outcome of this extensive study,
certain compositional trends were confirmed. The re-
sults are summarized in terms of individual alloying
elements in Figure 5, as follows:
Cr An optimum Cr content had a significant
beneficial role on the CO2 corrosion performance
of the steels. They categorized the effect of Cr as
follows:
5% Cr category: the lowest corrosion rate
3% Cr category
1.5% Cr category
1% Cr category
0.02% Cr category: the highest corrosion rate
An overview of these categories are presented
schematically in Figure 6, illustrating a progressive
reduction in corrosion rate with increasing Cr con-
tent, the extent of which is subject to other alloying
constituents and heat treatment.
While 3% Cr proved to offer a 10-times reduction
in corrosion rate, 1.5% Cr was not sufficient to en-
sure this level of resistance. The optimum level of Cr
addition was not determined, albeit a level between
2% to 3% Cr was considered essential to achieve the
expected improvement in corrosion performance sub-
ject to additional microalloying constituents.
V V had a major beneficial effect on reducing
corrosion rate.45,80
Ti Ti had some beneficial effects on the corro-
sion rate, although inconsistent, and some unsatis-
factory effects on mechanical properties. Control of
properties in the Ti steels proved difficult, although
Ti additions could help to reduce HAZ hardness.
Mo Mo had no effect on the corrosion rate in
the active state at low pH, but helped to get a genu-
ine passivation in case of upward pH shifts beneath
an already protective corrosion scale.
Si and Cu These microalloying elements
showed beneficial effects on CO2 corrosion comple-
mentary to the effect of Cr, albeit subject to the
CORROSIONAUGUST 2003

microstructure, heat treatment, their interaction,
and corrosion conditions.
It is concluded that V-microalloyed steel contain-
ing Cr, Si, Mo, V, and Cu is the most promising com-
position in terms of corrosion resistance and
mechanical properties.44-45,80 This steel offered good
levels of strength and toughness and good hot ductil-
ity, making it suitable for continuous casting.
Weldability is an issue for this composition, making
it only readily suitable at this time for downhole ap-
plications (e.g., threaded connections).80 Further
studies are underway to improve the weldability by
reducing C, V, and Mo contents, without compromis-
ing corrosion resistance. A very small addition of Ti
(below stoichiometry with nitrogen) could be used to
reduce HAZ hardness.78
While corrosion rates of reference steels (X70,
X65, or L80) increased with time, the new composi-
tion steels exhibited progressively reduced corrosion
rates with time, stabilizing after the initial expo-
surea clear indication of the progressively protec-
tive nature of the corrosion film that formed on the
experimental steels and the necessity to carry out
long-term corrosion experiments (in excess of 7 days)
to allow steady-state conditions. The conclusion
drawn is that, as expected, Cr is effective above a
certain level, below which it is detrimental to the an-
odic reaction on bare steel. Inconsistency in the cor-
rosion performance of low-Cr-containing steels has
been experienced by a number of operators.8-9,73,76
The data demonstrated that the calculated value
of free Cr and V, generally, proved to be good indi-
cators of CO2 corrosion performancenevertheless,
microalloying constituents and resultant microstruc-
ture have influential and complementary roles.44,80
SURFACE FILMS; CORROSION LAYERS
CO2 corrosion of carbon and low-alloy steels is
strongly dependent on the surface films formed dur-
ing the corrosion processes. The protectiveness, rate
of formation/precipitation, and the stability of the
film control the corrosion rate and its nature (general
corrosion or localized corrosion, especially mesa at-
tack). Precipitation kinetics of FeCO3 film is affected
by the iron and carbonate concentrations, and its
subsequent formation and growth are extremely tem-
perature sensitive.46 It is not the thickness of the film
but the structure and its morphology that leads to
low corrosion and protectiveness.9,19 It is interesting
to note that a corrosion layer containing the same
solid components can be either extremely protective82
or not very protective, or can even be corrosive.19,25 It
has not been very clear why under some conditions
these scales form and mitigate further corrosion and
sometimes, in spite of favorable thermodynamic con-
ditions for their formation, they do not precipitate at
all and the corrosion continues unhindered.
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
In general, the protective characteristics of a cor-
rosion film/layer depend on both the carbon steel
characteristics (microstructure, heat treatment his-
tory, alloying elements) and environmental variables
(solution pH, temperature, solution composition, flow
rate, etc.). The former has been covered earlier
through influencing and modification of steel chemis-
try and treatment processes.8-9,41-44,47,70-79 This section
focuses on the latter and discusses how film/scale
properties are influenced by the environmental fac-
tors, bearing in mind:
their properties and effects on corrosion rate
effects of various variables on the properties of
the film/layer
modification of the surface films and its growth
habits
Further studies that are necessary for the im-
provement of the corrosion of carbon and low-alloy
steels in CO2-containing environments through
enhancing the properties of the surface film are
proposed.
Film Formation
Based on extensive observations made by many
workers, corrosion films in the 5C to 150C tem-
perature range in water containing CO2 can generally
be divided into four main classes:
transparent films
iron carbide (Fe3C) films
iron carbonate (FeCO3) films
iron carbonate plus iron carbide (Fe3C +
FeCO3) films
These are reviewed in this section and their over-
all characteristics are summarized in Table 2.
Transparent Films Transparent films are
rarely cited in the literature. They are <1 m thick
and only observed at around room temperature. The
film appears to form faster by reducing the tempera-
ture below ambient. This class of film is not thermo-
dynamically the most stable solid corrosion product
and can form in CO2-containing water with a very low
ferrous ion concentration. Increasing the ferrous ion
concentration makes this film more protective, slow-
ing down the corrosion rate by about an order of
magnitude and possibly more after long expo-
sures.25,35,55,77,83 Carbon steels protected by this trans-
parent film can be susceptible to crevice and chloride
pitting corrosion in a similar manner to passivated
stainless steels.44,56,72,83 Auger electron spectroscopy
showed that this film did not contain carbonate, but
rather iron and oxygen ions roughly in the proportion
of 1:2. Etching indicated a constant ratio between
iron and oxygen in the full thickness of the film.83 It
is important to examine this film in view of the con-
troversy on the existence of metastable solid FeCO356
and the well-known dehydration of FeOOH in the
steps leading to the classical passivation of iron.84 As
these observations were not repeated, it is now ques-
669
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

TABLE 2
Characteristics of Corrosion Films

Corrosion Temperature Range Characteristics/ Growth Habit

Film Class of Formation (C) Nature and Composition

Transparent Forms at room <1 m thick, transparent Forming fast as temperature

temperature and once formed, it is very reduces to < room temperature
below protective mainly consisting of Fe and oxygen

Iron carbide No range <100 m thick, metallic, Spongy and brittle, consisting
conductive, and nonadherent of Fe and C

Iron carbonate Min. required in laboratory Adherent, protective, and Cubic morphology, consisting
conditions 50C to 70C nonconductive of Fe, C, and O

Iron carbonate Maximum 150C All depends on how FeCO3 is Consisting of ferrous carbide
+ iron carbide (higher temperatures blended with Fe3C and ferrous carbonate
not studied)

firm or otherwise invalidate its formation and its ef-

FIGURE 7. A pure iron carbide layer formed at 60C and 1 to
3 times supersaturation.72
FIGURE 8. An overview of corrosion layers seen on a tubular showing
a tough, empty cementite layer adjacent to gouges caused by wire
line runs (courtesy of J.L. Crolet).
tionable whether this O/Fe ratio of 2:1 actually cor-
responded to FeII or FeIII.58
Transparent films have been ignored by many
researchers and a systematic study is needed to con-
fect on FeCO3 formation.
Iron CarbideCementite (Fe3C) Films Anodic
dissolution of carbon steel leads to the formation of
dissolved ferrous ions. This process leaves behind
some uncorroded Fe3C film (cementite) that accumu-
lates at the surface. Unlike FeCO3 scale, the Fe3C
film can be fragile and porous and therefore suscep-
tible to flow conditions,6 or it can be a tough cement-
ite network similar to graphitization of pig iron
in acidic waters.58 A tough cementite layer adjacent
to gouges caused by wire line runs is shown in
Figure 7.27 At fast flow rates in unbuffered CO2-
containing water, the corrosion film consists mainly
of Fe3C plus constituents of some alloying elements
from the substrate. A reduction of the flow rate may
increase the amount of Fe3C, but it also leads to the
presence of FeCO3 in the film.28-29,31,35 Figure 8 shows
an overview of a pure Fe3C film referred to as empty
cementite.72
An empty cementite network forms a conductive
porous sponge layer on which the cathodic reaction
can take place. It is very adherent, with a metallic to
black appearance. Its thickness is up to 100 m
when formed under laboratory conditions19 and milli-
meters in the field.27 The morphology shown in Fig-
ure 9 was thus observed at the region of an unlifted
water slug at the bottom of a gas well in Nigeria in
very agitated fluid conditions.27 This shows nonpro-
tective tubercules of profuse FeCO3 deposits above a
thick base of empty cementite.
Fe3C film significantly affects the corrosion pro-
cess and increases the corrosion rate by a factor of
3 to 10 by playing a number of roles, including:
Galvanic coupling: Fe3C has a much lower
overpotential for the cathodic reactions than
iron and thus galvanic contact between the two
can accelerate the dissolution of iron by accel-
erating the cathodic reaction in the presence of
<<1 ppm Fe2+ in water.25,72,77

670 CORROSIONAUGUST 2003


Local acidification: Cathodic reactions can take
place preferentially at Fe3C sites, thus physi-
cally separating the anodic and cathodic corro-
sion reactions. This leads to changes in the
water composition with the aqueous phase at
cathodic regions becoming more alkaline and
that at the anodic sites more acidic.18-19,25,27,72,77
This can cause internal localized acidification
and promote corrosion on the metal surface.
Fe2+ Enrichment: Having left behind the car-
bide layer, ferrous ions dissolving at the metal
surface diffuses over a larger distance, so that
the continuous concentration gradient neces-
sary for this diffusion ends in a larger Fe++ en-
richment at the metal surface. This increases
local supersaturation of ferrous ions and facili-
tates the formation of FeCO3.
Film Anchoring: In certain conditions, corro-
sion film consists of a combination of Fe3C and
FeCO3. In these films, Fe3C acts as a frame-
work anchoring the precipitated FeCO3 on the
surface-enhancing film properties with im-
proved tolerance to mechanical shear at high
flow rates. In these situations, localized corro-
sion is greatly reduced.38,79,83
Despite a high concentration of ferrous ions,
local acidification at the surface may lead to unfavor-
able conditions for the precipitation of FeCO3.19,25,56,77,82
This may lead to FeCO3 precipitating within or on the
top of the cementite layer. This type of film forms ei-
ther a corrosion layer with poor contact and bonding
to the metal surface or with unfilled regions between
metal surface and the corrosion film. This corrosion
film provides little protection, so corrosion rates can
be high. A local high corrosion rate tends to increase
the local pH difference between adjacent anodic and
cathodic regions, which subsequently favors further
development of the nonprotective film.19,25,72,79,82
In general, the accumulation of Fe3C has a con-
trasting role on corrosion behavior, depending on its
manner of formation and its dominance within the
film structure and process. On one hand, by prevent-
ing the diffusion of ferrous ions from the surface, it
promotes the formation of FeCO3 film to offer a de-
gree of protection. By blending uniformly into FeCO3
film, it will enhance its properties and protectiveness,
as described in the following section. On the other
hand, Fe3C could provide local acidification and
facilitate galvanic corrosion and hence increased rate
of attack. Invariably, steel microstructure governs
carbide distribution, which thus affects film stability
or instability. This has been postulated to govern
corrosion behavior as described elsewhere in the pa-
per (Alloying Elements Section44,80).
Iron CarbonateSiderite (FeCO3) Films In
terms of corrosion mitigation, FeCO3 or siderite is the
most important film that can grow on carbon steels
in sweet environments. Film formation is strongly
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 9. Iron carbide layer forming on the metal surface followed
by partial siderite sealing leading to a nonprotective film.56
dependent on the thermodynamics and kinetics of
FeCO3 precipitation. Supersaturation plays the most
important role in FeCO3 film growth and its morphol-
ogy. A high supersaturation of FeCO3 is necessary to
form a protective film, particularly at low tempera-
tures.41,72 In principle, the precipitation process com-
prises two steps, nucleation and particle growth. The
morphology of the film therefore depends on the
dominating step.72,77 Once the film is formed, how-
ever, it will remain protective at a much lower super-
saturation.41 Protective film formation is accelerated
by measures that restrict the transport of reaction
products from the surface.72
The adherence and thickness of the FeCO3 scale
depend on the metal microstructure.8-9 The scale
grown on normalized steels with a pearlitic/ferritic
microstructure was more adherent, having larger
crystals more densely packed and thicker than those
formed on quenched and tempered steels.85 This is
explained further in the following section.
FeCO3 reduces the corrosion rate by reducing
and virtually sealing film porosity. With altering nei-
ther the local phase compositions nor the concentra-
tion gradient, this restricts the diffusion fluxes of the
species involved in the electrochemical reactions.
Moreover, even prior to sealing cementite, its precipi-
tation can lead to coverage and, therefore, can limit
its electrochemical activity. This is explained further
in the section on operating temperatures. All authors
agree that increasing the temperature would improve
the protectiveness of the FeCO3 scale as well as its
adhesion and hardness35 and that the higher the
temperature, the more improved the protectiveness.
However, there is little agreement on a practical
threshold temperature. Some have reported that
the maximum corrosion rate observed for carbon
steel in sweet environments was from 60C to 70C
and then it started to decline due to growth of protec-
tive FeCO3 films.86-87 In another work,35 it has been
suggested that the lowest temperature necessary to
obtain FeCO3 films that would reduce the corrosion
671
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
rate significantly was 50C and the protectiveness
was increased also by increasing the pH.
It has been argued that the protective films
formed at higher temperatures and pressures pro-
vided better protection than those formed at low tem-
peratures and pressures. The level of protection
increased with exposure time,88 which is the time
dependency of the process.
Some key environmental parameters that influ-
ence the iron carbonate film formation/precipitation
are described here.
Temperature Effect: As mentioned earlier,
growth of FeCO3 scale is a slow temperature-depen-
dent process.41,46 It has been reported that FeCO3
scale was more protective at higher temperatures
(60C to 100C) with little protection at lower tem-
peratures6,33,89 (<60C) with Fe3C predominating the
film. Above 100C, a tight and adherent film was
formed with suggestions6 that magnetite was the
stable scale above 121C and the dominant scale at
250C,90 although magnetite has not been detected in
field conditions. An increased precipitation rate at
high temperatures (>60C) could explain why the
corrosion rate went through a maximum in the tem-
perature range from 60C to 90C.
pH Effect: pH is the most important factor in
FeCO3 scale formation. It influences the solubility of
FeCO3, and, under suitable conditions, increasing
pH decreases the FeCO3 solubility and promotes its
precipitation in the environment, resulting in lower
corrosion rates. In CO2-saturated environments, for-
mation of FeCO3 would decrease the corrosion rate
by diminishing the diffusion of reactive species
through the precipitated FeCO3 film.33,41,91 The pH in-
crease also improves the protective properties of the
FeCO3. Videm and Dugstad35 reported that at pH
6.00 good protection could be obtained by FeCO3
films even at room temperature. In a related work,
they demonstrated that an increase in pH also made
film formation more likely as a result of a reduction
in the solubility of Fe2+.83 Similarly, de Moraes, et
al.,92 reported that protective layers could be ob-
served only for pH values >5very protective layers
were present only at high temperatures (93C) and
high pH values (pH 5.5), although these results are
now disputed.18
Fe2+ Concentration Effect: Siderite formation
occurs in conditions where the concentration of Fe2+
ions in the aqueous phase exceeds the solubility
range of FeCO3, bearing in mind that other species
also influence this process. It is also noteworthy that
there are indeed two corrosion products, namely Fe++,
resulting from the anodic reaction and HCO3, from
the cathodic reaction.27 In uniform corrosion, they
are released consistently so that different concentra-
tions of released ferrous ions also correspond to dif-
ferent concentrations of released bicarbonate, which
will lead to local changes in pH.27,29 A ferrous ion
672
concentration well below the solubility limit of FeCO3
not only prevented the formation of FeCO3-containing
films, but also dissolved the existing films.35,81 Videm
and Dugstad28 concluded that a change of 30 ppm
Fe2+ can sometimes affect the corrosion rate to the
same degree as a change in CO2 concentration of
1,000 ppm (2 bar) at 90C.
H2S Effect: In the presence of both H2S and
CO2, simplified calculations indicate that iron sulfide
may constitute the corrosion product layer when the
H2S/CO2 ratio exceeds about 1/5,000sour systems
considerations then would be expected to apply.93
Occasionally, it has been reported94 that the corro-
sion product film formed under these conditions
(containing FeS or Fe2S depending upon the H2S par-
tial pressure) was apparently more protective than
FeCO3. The opposite also has been reported, espe-
cially at very low H2S concentrations, wherein a mix-
ture of layers forms comprising inner carbonate and
outer sulfide.95-96
Iron Carbonate (FeCO3) Plus Iron Carbide (Fe3C)
Films This type of film is the most common film
found on carbon and low-alloy steel surfaces in CO2-
containing environments. During CO2 corrosion of
carbon steels, the Fe3C phase is cathodic (corrosion
resistant) and may embed within the FeCO3 film. The
structure of the film then will depend on where and
when the FeCO3 precipitation takes place. On one
hand, if it occurs directly and integrates within the
carbide phase, then a protective and stable film will
form that often can stand high fluid flow conditions.
On the other hand, initial formation of a cementite
layer on the surface followed by partial FeCO3 sealing
close to or beyond the external limit of cementite can
lead to a nonprotective film. An example of this is
shown in Figure 10.25,27,72 In contrast, if cementite
phase effectively sealed the siderite layer formed in
contact with the metal surface, an incomplete sealing
or a partial redissolution of FeCO3 anywhere else is
not detrimental and the corrosion film remains pro-
tective, as shown in Figure 11.25,27,72
Crolet, et al.,25 have categorized the morphologies
of corrosion film formation as affecting protective-
ness. This is shown in a simplified diagram in Figure
12. The diagram is based on an analysis of the diffu-
sion/precipitation issues and the resulting pH shifts,
and is backed by observations of the actual mor-
phologies of protective and nonprotective corrosion
layers.
As mentioned earlier, the structure of the mixed
film plays an important role on the formation and
breakdown of protective carbonate films. This is in-
fluenced by the carbon content and the size and dis-
tribution of carbides, which therefore is dependent of
the microstructure of steel.85 The ferritic-pearlitic
steels have a carbide structure, which gives a good
framework for the buildup of protective carbonate
films.79 Quenched and tempered steels and ferritic
CORROSIONAUGUST 2003
 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 10. An empty, thick, and porous cementite network formed
on tubing recovered from the field, which was covered by a porous
but hard and mechanically resisting siderite tubercule (courtesy of
J.L. Crolet27).
steels with low carbon content have a finely distrib-
uted carbide structure that does not give an inte-
grated framework to anchor and enhance the
formation of protective carbonate films.32,38,77,79 Ex-
CORROSIONVol. 59, No. 8
FIGURE 11. A cementite layer sealed by siderite forming a protective
film.25,72
FIGURE 12. Different morphologies observed for protective and
nonprotective corrosion layers (after Crolet, et al.25).
periments with the plain carbon steel after different
heat treatments showed that both corrosion rate and
the ability to form protective films decreases with in-
creasing tempering temperature, indicating that the
carbide structure of the steel plays an important role
for the formation of protective corrosion films.77
As mentioned earlier, it is likely that Fe3C lamel-
lae at the metal/corrosion film interface can anchor
the film and contribute to corrosion protection.27,35,79
This anchoring effect of the carbide phase is believed
to be the main factor influencing the adhesion of the
FeCO3 film to the surface and has been reported by
many workers.9,33,55,77,79
Film Breakdown and Localized Corrosion
A sensitive balance between the formation and
destruction of the protective film governs the subse-
quent corrosion progress and determines whether
uniform or localized attack will take place.30
Mesa attack can be initiated by local breakdown
of the protective film or by the growth of pits beneath
673
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
the porous corrosion film by a local cell mechanism.
The remaining corrosion film on top is removed
stepwise by the turbulent flow before the pit can con-
tinue to grow into a larger mesa attack. When the
film has been torn away in one area, the corrosion
attack continues further beneath the film close to the
edge until another piece of the film is removed. It is
assumed that a galvanic cell is set up between the
anodic, film-free metal in the bottom of the mesa at-
tack and the cathodic, film-covered metal outside the
mesa attack, leading to a high corrosion rate in the
base of the mesa-attacked area.33,43,97
Enhancement in the formation of protective films
affects the corrosion rate in the base of the mesa by
enabling the formation of carbonate films, which can
then stop further growth of the mesa attack. Shallow
mesa attack covered with corrosion films have been
found in experiments on precorroded samples, and
linear polarization resistance (LPR) measurements
have shown that the growth of this mesa attack
slows down gradually during the experiment and
eventually stops. This shows that reformation of pro-
tective films in mesa-attacked areas is possible when
the growth rate of the mesa attack is not too
high.31,41,72 With a better quality of the initial protec-
tive films, the effect of galvanic coupling between the
mesa-attacked area and the surrounding area with
intact corrosion films can be smaller, resulting in a
slower and less catastrophic mesa attack. Rate of
growth at mesa-attacked areas has been shown to be
excessively higher than the adjacent unattacked ar-
eas, reaching some 20 mm/y to 30 mm/y in water
with around 2 bar CO2, pH 5.5 to 5.8, and 3% NaCl
at 80C.31,41,72,97 In laboratory tests, mesa attack oc-
curred under these conditions at a flow rate of 7 m/s
but not below 2.5 m/s. Low-chromium-containing
steels (0.5% to 1% Cr) did not suffer deep mesa at-
tack under these conditions.97
Fluid Flow Effects The effect of flow rate on the
corrosion rate originates primarily from localized
flow-induced changes introduced by the corrosion
film. Fe3C particles remaining on the surface, the
FeCO3 buildup, and the accumulation of alloying ele-
ments in the corrosion film are flow-dependent phe-
nomena.30 As mentioned earlier, a clear distinction
should be made between pure CO2 corrosion and a
combined interaction of erosion-CO2 corrosion.
Flow rate of water containing CO2 has two princi-
pal effects on film formation and corrosion rate and
form. First, it prevents the formation and slows down
its growth by reducing the local supersaturation.
Second, flow can damage film locally to cause local-
ized corrosion, especially mesa attack. When the sur-
face corrosion film is poorly adherent to the surface,
the effect of flow rate on localized corrosion is most
serious.47,69
In low-temperature conditions from 30C to
60C, films might not form or might not become pro-
674
tective for a long period in continuous flow loop ex-
periments. This therefore could lead to fast uniform
corrosion, although protective films can form at these
temperatures when water stagnation on steel is
prevalent.70,83
In the presence of solids (sand), erosion-corro-
sion can produce higher wall penetration rates than
erosion or corrosion alone. Three typical behaviors
have been found. At low velocities, a protective FeCO3
scale formed over all surfaces of an elbow, and corro-
sion rates were very low. At high velocities, impinge-
ment on elbow surfaces by sand particles entrained
in the flow prevented protective layers forming in the
elbow. Corrosion rates were high and uniform over
the entire surface. At intermediate velocities, protec-
tive layers formed over the entire elbow surface, ex-
cept at very localized points where impinging sand
particles prevented scale formation. Deep pits formed
at these locations and wall penetration rates were
extremely high. These conditions are damaging but
can be avoided by reducing or increasing flow veloci-
ties. A computational model for the prediction of
sand erosion in piping systems was used to simulate
experiments to explain the three observed behaviors
and predict conditions defining boundaries between
them.98
Siderite (FeCO3) formed only in low-velocity,
single-phase flows where pH increased above 5.0.
Corrosion rates after scale formation decreased by
almost 1 order of magnitude. No FeCO3 scale formed
in tests involving high-velocity, low-pH, single-phase
flows or two-phase flows.85
In fact, at medium or high pH conditions, protec-
tive films always form unless the following param-
eters are met conjointly in laboratory testing:58
initial bare surface
room temperature
uninterrupted high flow rate from the start of
the test
In the absence of each, films do form and be-
come protective and their protectiveness remains un-
affected by flow. This basic irreversibility of corrosion
layers82 explains the reported temperature effect,
which essentially appears as a laboratory artifact and
most unexplained good performance of the film expe-
rienced in real field conditions, which can be the re-
sult of inevitable shutdown periods.58
The influence of solid particles (sand) and their
interactions with flow-induced corrosion is not fully
understood, and predictive models do not include
corrosion-enhanced erosion by solids.
Iron Carbonate/Siderite (FeCO3) Scale:
Recent Progress
The significance of steel characteristics and envi-
ronmental variables on the protective nature of
FeCO3 (siderite) corrosion films was emphasized ear-
lier. A recent study has demonstrated the intricacy of
CORROSIONAUGUST 2003

FIGURE 13. Iron carbonate scale precipitated on carbon steel
samples at 75C exposed to a solution at pH 6.30 at 1 bar CO2
showing a somewhat cubic appearance (magnification: X6,000).99
how corrosion protection offered by a precipitated
FeCO3 scale on carbon steel substrate can be im-
proved through varying or adjusting some of the en-
vironmental parameters such as pH, temperature,
solution composition, and periodic exposure to air.99
Among these, pH was shown to be the most influen-
tial variable in affecting the precipitation of FeCO3.
The key factor preventing the growth of a protec-
tive siderite scale was that the nucleation and growth
of crystals of this compound were extremely tempera-
ture sensitive and slow with a rather high activation
energy, confirming an earlier indication by others.46
In this respect, for siderite as well as calcite and
other forms of calcium carbonates, the limits of the
domain of precipitation are not driven by saturation
(thermodynamic stability) but by supersaturation
(kinetics). Also, it is worth noting that scaling inhibi-
tion is crystal specific and there was an indication
that some scale inhibitors could prevent the forma-
tion of calcium carbonate but not siderite.99
Key points of observation emerging from this
work on corrosion films/layers formed under sider-
ite-forming conditions (pH range from 5.60 to 6.30,
75C, and 1 bar CO2 pressure) are highlighted:90
The film consisted primarily of FeCO3 and re-
sembled a perfect cubic morphology (bearing
in mind that siderite is a rhombohedric crys-
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
FIGURE 14. Iron carbonate scale formed after 260 h of immersion
in a solution (at pH 6.30, 75C, and 1 bar CO2) showing a compact
appearance.99
tal) as shown in Figure 13 as also previously
seen by others.41
The film was a few micrometers thick and
formed just after 24 h immersion. Scale thick-
ness, as measured by a scanning electron mi-
croscope (SEM), increased progressively with
time, becoming more compact (Figure 14). Sid-
erite cube dimensions play an important role
here, as suggested by others,8,18,27 in affording
further protection by hindering the ingress of
corrosive species toward the metal substrate. It
should be noted that the key issue of the liquid
surface state has not been observed by SEM.
Periodic exposure to the atmosphere, or more
precisely to oxygen (through removal and re-
exposure of samples), improved significantly
the scale adhesion to the substrate.
The work reiterated that FeCO3 precipitation
coincided with a sudden drop in weight change
and its associated corrosion rate.
Similar immersion tests conducted with pure
iron (99.5%) samples produced a patchy,
cracked, and loosely adherent FeCO3 scale.
This was attributed to the absence of a carbide
network in pure iron.
Solution chemistry played an important role in
altering the protective characteristics of the
675
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
TABLE 3
Effect of Various Parameters on Scale Protectiveness 99
Surface
Parameter Coverage Stability Adhesion
Oxygen * *
Magnesium * *
Temperature * *
pH * *
Carbide phase * *
* Improvement in certain characteristics of the scale.
No improvement was observed.
Note: Stability should not be confused with adhesion. Stability means
the endurance of the scale toward environmental variables like solution
pH and flow velocity.
precipitating FeCO3 scale. In these series of
tests, scales developed in distilled water were
less adherent to the substrate than those de-
veloped in a solution containing trace Mg2+
ions simulating produced fluid chemistry, and
Mg2+ ions improved siderite scale protection
and adhesion. However, magnesium-related
trends have not been observed in field evalua-
tions.14,36
The nucleation and growth of FeCO3 crystals
was a slow, temperature-dependent process;
consequently, any environmental changes that
retarded the precipitation process therefore led
to progressively increased corrosion.
The work highlighted that the terms protective-
ness or corrosion-resistant properties of a scale
were loosely defined definitions. Therefore, the pro-
tective characteristics of FeCO3 scale were translated
through the following specific properties allowing
better characterization:
scale density (or, in other words, pore distribu-
tion in the scale)
adhesion
stability
surface coverage
Based on this, the effect of various environmen-
tal parameters affecting scale characterization and
protectiveness have been tabulated. These are sum-
marized in Table 3, demonstrating that solution pH
is the most influential parameter in the precipitation
of FeCO3 scale and seemingly the only parameter
that affects scale density.99 The work of Nesic, et al.,
has led to modeling of the possibility of predicting the
influence of FeCO3 film.20
CORROSIVITY
As a general statement, the corrosivity of the
aqueous phase will be dependent on CO2 partial
pressure, temperature, solution chemistry, and in-
situ pH. On one hand, at a given partial pressure of
CO2, condensed waters (associated with gas produc-
676
tion) are in general more corrosive than formation
waters since they do not contain any buffering or
scale-forming species and inherently have a lower in-
Density situ pH. On the other hand, at a given pH, the simple
chemistry of condensed water at low CO2 partial
pressures may be less corrosive than some complex
chemistries of reservoir water under higher CO2
partial pressures.27
*
Software and spreadsheet-based programs now
exist for characterizing water chemistry such that
concentrations of dissolved species and solution pH
can be readily calculated.36,100-104 Nevertheless, the oil
and gas industry has grown up assessing the pres-
ence of dissolved CO2 in water in terms of CO2 partial
pressure. This simply derives from the application of
Henrys Law for a gas in equilibrium with a liquid
and the approximation of ideality, where the thermo-
dynamic activity of CO2 in water is assessed through
its partial pressure in the gas. This remains valid
up to high CO2 partial pressures, particularly on a
logarithmic pressure scale, which is that related to
pH variations.
Viewing it starting from reservoir conditioning,
Crolet and Bonis14,36,55,105 consider variations in CO2
concentration resulting simply from differences in
the solubilities and activity coefficients in the phases
present. Thus, for example, in three-phase produc-
tion, which is generally highly turbulent, even
though the CO2 equilibrium is never perfect, any
deviations remain relatively insignificant. Conse-
quently, it is more reasonable, and certainly much
easier, to express the amount of CO2, not in terms of
its concentration in each phase, but as its chemical
potential (or thermodynamic activity or fugacity).
Provided conditions are not close to the gas liquefac-
tion point, this is simply equivalent to the partial
pressure of CO2 in the gas phase. By extrapolation,
reference then can be made to CO2 partial pressure
even in systems where there is no free gas phase
present. Experimentally, this virtual partial pres-
sure corresponds to the real partial pressure of CO2,
which would appear in the nascent gas phase if the
system were to be depressurized. At the bottom of an
oil well, this virtual partial pressure will be the very
first bubble at the bubble pressure of the reservoir
fluid; in a gas free line downstream of the gas sepa-
rator, this will be the partial pressure at the last gas
in the separator.18
Variations of dissolved CO2 along the flow line
will affect the solubility of potential scaling com-
pounds, particularly CaCO3, which can interfere with
the corrosion process and possibly its inhibition, if
precipitated. The in-situ pH level can also affect the
solubility of ferrous oxides and hydroxides, increas-
ing their solubility with decreasing pH. However, of
particular importance are conditions that favor depo-
sition of FeCO3 (siderite). Formation of FeCO3 serves
to complicate the picture further, as it can, under
CORROSIONAUGUST 2003

certain conditions, passivate the corrosion reaction
making it even more difficult to accurately predict
corrosion rates.58
CO2 CORROSION PREDICTION
Over the years much effort has been expended in
studying factors controlling the performance of mate-
rials in production environments in an attempt to
define the safe operating limits of candidate materials
in terms of the environmental and mechanical condi-
tions. This knowledge is gained, in part, from some
comprehensive, empirical-based field statistics, such
as those by API,7,68,106 laboratory-based information
translated by quantitative regression to predictive a
corrosion rate,9,91,100-104 and comprehensive well sta-
tistics based upon the actual field values of relevant
scientific quantities.36,105
The laboratory-based equations have been con-
ventionally based using the de Waard and Milliams
nomogram.9,96-97,100 Nonetheless, in the past, it was
imperative that candidate materials were assessed
in the laboratory prior to their application in the field
so that costly and potentially hazardous failures are
avoided. However, the relevance of some of these
short-term tests to long-term performance was ex-
ceedingly difficult to establish other than by long-
term experience or evaluation.
The inherent corrosivity of acidic gases has long
been recognized and has prompted extensive studies
of the subject.6-9,100 These have led to the develop-
ment of predictive models or criteria that attempt to
correlate corrosion to acidic gas partial pressure.
However, in merely using these predictive models,
there is a danger of working with a too simplistic or
clear-cut picture of the situation. Any predictions
that are made are not only influenced by the validity
of the model, but also the quality and reliability of
the supplied production and operational data used to
calculate the corrosion risk.
The engineer ideally wants a predictive tool that
can be readily applied and is suitable for application
at all stages of project development and subsequent
operation. This may seem a tall order but it may
nevertheless be argued that the fundamentals of the
CO2 corrosion process will be common to all situa-
tions; it is the overlying effects of such factors as
flow regime, film formation/deposition, hydrocarbon
phase, realistic and representative testing, steel
chemistry, and corrosion inhibitor that cloud or com-
plicate the picture.
A true industry standard approach to predicting
CO2 corrosion does not exist, although there are
aspects of commonality between the various ap-
proaches/models in use by the industry. There is no
professional body or agency such as NACE Interna-
tional providing standard basic guidelines to work
fromunlike the situation for H2S.81,107-108 While it
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
may be argued that such guidelines, because of the
complexity of the problem, would either be too gener-
alized and/or too conservative for certain situations,
their presence nevertheless would have a unifying
influence to a degree and at least provide a common
reference point from which to work.
Having determined the water chemistry, this
then needs to be translated into a corrosion risk,
preferably expressed quantitatively as a rate and type
of attack. The easiest parameter to relate to (and in
general, measure) experimentally and in the field is
the partial pressure of CO2. Thus, over the years, a
number of empirical relationships have evolved with
varying levels of complexity and theoretical sub-
stance. In the simplest form, API7 in the late 1950s
provided a Rule of Thumb criteria for carbon and
low-alloy steels. After a first period of high popular-
ity, this rule endured several exceptions and fell into
oblivion with just periodic quotes, such as that by
Mudge and Levesque,109 who cite the following Rule
of Thumb criteria for carbon and low-alloy steels, or
the complementary note from Crolet:18
PCO2 < 0.5 bar (7 psi)
Corrosion Unlikely: implying that corrosion is
uniform and the rate is <0.1 mm/y
0.5 bar (7 psi) < PCO2 < 2 bar (30 psi)
Corrosion Possible: implying that corrosion rate
might be between 0.1 mm/y to 1 mm/y and
design consideration is based on life expectancy
PCO2 > 2 bar (30 psi)
Corrosion likely: implying that corrosion rate
may exceed 1 mm/y, which is unacceptable
where partial pressure of CO2 is denoted as PCO2
These are based on field experience, principally
in the U.S. No subsequent standard guidelines exist
as to the courses of action necessary for each condi-
tion, although experience will trigger the corrosion
engineer to look initially toward certain possible op-
tions (e.g., use of a corrosion inhibitor or more corro-
sion-resistant alloys). However, designing on such a
basis is not a very satisfactory way to operate.
Rules of thumb may be viewed as:
an aid to first-pass materials selection
offering qualitative and generalized assessment
More specific questions on service life, risk
analysis, corrosion allowance, and inhibited corro-
sion rates require the ability to conduct a quantita-
tive assessment (i.e., the ability to predict corrosion
rates for a given set of conditions). In addition, con-
sequence of corrosion is a key issue when corrosivity
assessment is carried out. Nevertheless, the relation-
ship between corrosion rate and CO2 partial pressure
has formed the basis of a number of predictive mod-
els/equations for carbon steels, even though claims
have been made that PCO2 bears little relation to the
decision by the field operator.110
Experimental work has lead to a number of
equations or models being developed relating corro-
677
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
sion rate of carbon and low-alloy steels to CO2 partial
pressure,11,36,91,94,100-104,111 from which individual op-
erators have each developed their own approach or
philosophy.
Most equations or models have been derived
from a range of experimental conditions. For ex-
ample, the de Waard and Milliams equation or nomo-
gram11 was originally derived for a 0.1% NaCl
solution test medium at a flow velocity of ca. 1 m/s,
temperatures up to 80C, and PCO2 up to 1 bar for
X52 C-steel. Greco and Wright94 used 0.04% NaCl
solution at 86F and PCO2 up to 4.5 bar; Videm and
Dugstad28 used distilled water, up to 120C, 6.5 bar
PCO2, and 20 m/s flow velocity. The models developed
by Fang, et al.,102 and Liu and Erbar104 are based on
theoretical analysis together with the use of data
taken from the literatureboth of these models were
specifically developed for gas well corrosion.
While the use of simple NaCl brine might eventu-
ally mimic water in gas systems, when considering
brines co-produced with crude oil, their water chem-
istries are far more complex and their influence (buff-
ering) thus needs to be corrected when using these
equations. Many parameters, such as temperature,
pH, partial pressures of CO2 and H2S, gas/oil ratio
(GOR) and water production (water/oil ratioWOR),
water composition, together with flow rate and re-
gime, have a greater or lesser effect on the corrosion
rate. Furthermore, not all of these parameters are
independent of each other, pH being a good example.8-9
Finally, direct field validation of the predicted
corrosion rates often is difficult to unequivocally sub-
stantiate. This is particularly true when a model
needs detailed data, which are seldom gathered in
the field. Furthermore, these data are not totally de-
fined throughout the service life of equipment.18
Several prediction models for CO2 corrosion of oil
and gas pipelines are available. These models have
very different approaches in accounting for oil wet-
ting and the effect of protective corrosion films, and
this accounts for much of the differences in behavior
between the models. All the models are capable of
predicting the high corrosion rates found in systems
with low pH and moderate temperature, while the
models can predict quite different results for situa-
tions at high temperature and high pH, where protec-
tive corrosion films may form. An overview of
capabilities and shortfalls of the available models has
been provided by Nyborg100 and is also summarized
in EFC Publication 23.9
An intermediate approach that places direct em-
phasis on knowledge of the water chemistry is the
prediction tool developed by Crolet and Bonis.36,105
This tool is an advanced field database that calcu-
lates the factual input data, especially pH, free HAc,
and potential corrosivity, in terms of corrosion risk
for the occurrence of failure within the life of the
well. It defines the severity of CO2 corrosion in wells
678
in terms of low and high risk as a function of
workover statistics, plus a medium category for
borderline or undocumented conditions. Crolet and
Bonis compared these with all the basic information
available at the time, combining both field experi-
ences and laboratory data. Key parameters included
in this multiple correlation were the potential corro-
sivity (what is observed in the laboratory on bare
surfaces but just taken as an index of electrochemi-
cal reactivity and in no way a corrosion rate predic-
tion) and the field features (in-situ pH, Ca2+/HCO3
ratio, concentration of dissolved organic acids
[mainly HAc], and, to a lesser extent, flow velocity).
This tool expresses two distinctive tables indicating
corrosion risks, one for oil-producing wells and one
for the gas-producing wells. It complements the API
rules7 and explains their exceptions; notably that
CO2 corrosion is indeed ubiquitous at high PCO2 and
it progressively disappears at low PCO2, unless H2CO3
is supplemented by free organic acids and the CO2
corrosion by HAc corrosion.19,27,81 This, to a great
deal, concludes the original debates launched in
19447-8,19,106 on the concept of damaging mechanisms
caused by either CO2 or organic acids when the first
decision was made in 1958 in favor of a CO2-only
mechanism7 followed by the origin of the great many
exceptions to the API rules.7,106
Industry Practice
While an industry standard approach to predict
CO2 corrosion damage does not exist per se, the work
of Shell8-9,11,91,101 in this area has provided a strong
reference statement from or against which to work.
The de Waard and Milliams equation or nomogram
has been developed as an engineering tool. It pre-
sents in a simple form the relationship between po-
tential corrosivity (worst case) of aqueous media for
a given level of dissolved CO2, defined by its partial
pressure at a given temperature.
The current form of the basic Shell equation is
as follows:8-9,91,101,112
1 / Vcor = 1 / Vr + 1 / Vm (8)
log( Vr ) = 5.07 1,119 / ( t + 273) + 0.58 log(PCO2 )
(9)
0.34( pHactual pHCO2 )
Vm = 2.7( Vliq 08 / diam 0.2 ) PCO2 (10)
where Vcor is the corrosion rate (mm/y); Vr and Vm
represent the maximum kinetic reaction and mass-
transfer rates, respectively; t is temperature (C),
PCO2 is partial pressure of CO2; pHactual is the actual
pH; pHCO2 is pH resulting from CO2 only; Vliq is liquid
velocity (m/s); and diam is the hydraulic diameter
(m). The important influence of temperature on CO2
corrosion is depicted in Figure 15.8,112
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 CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

There are appropriate correction factors for gas

fugacity, corrosion scales/surface films (i.e., Fe3O4
and/or FeCO3), the influence of flow (mass-transfer
effects), and steel composition. Correlation with field
experience suggests that the de Waard approach gen-
erally predicts the worst-case corrosion rate. The cor-
rection factors for pH and scale (scale factor applied
at temperatures > 60C) are simplified versions, but
they nevertheless appear suitable for many applica-
tions, especially for formation waters.
The relative simplicity of the de Waard and
Milliams approach and its ease of use have undoubt-
edly been positive factors in its broad acceptance,
although its complexity has grown over the years as
better appreciation of the CO2 corrosion process and
influence of water chemistry have evolved together
with correlation with field experience.36,100,103,111
There would appear to be a trade-off between a
models relative ease of use vs availability, detail, and
reliability/accuracy of necessary input data/condi-
tions vs degree of accuracy/absoluteness required of
FIGURE 15. Effect of temperature on CO2 corrosion.8,112
the assessment of the corrosion risk. The latter will
also be influenced by the ease and sensitivity of sub-
sequent corrosion monitoring and inspection. EFC Publication 239 sets out a process for deter-
On the other hand, the well database of Crolet mining CO2 corrosion risk/rate. In achieving this,
and Bonis36,105 also requires some tedious calcula- a key element is the interaction between the corro-
tions for the figures used as input in the correlation, sion engineer and the petroleum engineer to ensure
and this is also made through a spreadsheet called that the service conditions are correctly defined and
CORMED. This may have given the false impression relevant.
that CORMED is just a model like others, whereas its
goal is to translate the analytical sheets of the raw CO2 CORROSION CONTROL
field data into the requested factual inputs (pH, free
HAc, etc.) and automatically compare them to their The wide-ranging environmental conditions pre-
respective critical values in the published tables. vailing in the oil and gas industry necessitates the
CORMED places direct emphasis on knowledge of the appropriate and cost-effective materials choice and
water chemistry and defines severity in terms of low, corrosion control measures. Corrosion can impose a
medium, or high risk. If early workovers in the first significant cost penalty on the choice of material at
10-year period have been reported in similar condi- the design stage, and its possible occurrence also
tions, it is concluded that the corrosion risk is re- has serious safety and environmental implications.
spectively high or otherwise low. Considering that a Furthermore, as production conditions tend to be-
tubing is ~10 mm thick, this means that the average come more corrosive, they require a more stringent
corrosion rate will be respectively above or below corrosion management strategy.
0.1 mm/y, which is precisely the information given Corrosion control may be affected in a number
by conventional corrosion tables. of ways, either singularly or in combination. In the
Both the de Waard and Milliams nomogram and case of oil and gas production, the corrosion control
CORMED approach have been developed from a methods include:
basic consideration of the CO2 corrosion reactions change/modify operational parameters (e.g.,
the former is more empirical in origin and the latter flow, temperature, remove water) or system
is more theoretical. Both have attempted to account design (e.g., remove sharp bends, deadlegs,
for the overlying effects either by applying correction crevices)
factors (de Waard and Milliams) or through field cor- change/modify chemistry of the environment
relation (CORMED). (e.g., remove O2 from any liquid reinjected in
Finally, it is worth restating that all available the production flow, lower CO2 partial pres-
models/equations only apply to carbon and low-alloy sure, scavenge H2S, add corrosion inhibitor,
steels and are not strictly valid in the presence of H2S increase pH)
due to formation of protective sulfide films, which change/modify interfacial conditions of metal
may nevertheless be susceptible to localized break- (surface modifications or possible implementa-
down under long-term exposure. tion of cathodic protection)

CORROSIONVol. 59, No. 8 679

CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
apply organic coating (e.g., fusion-bonded ep-
oxy, phenolic-modified epoxy) or use a liner
(e.g., polypropylene) to isolate metal from cor-
rosive environment
use more corrosion-resistant materials (e.g.,
13% Cr steel, duplex stainless steels) either in
the solid form or as cladding on carbon steel
use nonmetallics (e.g., fiber-reinforced plastics)
The relative merits of each approach must be
viewed in the context of the application, the required
service life, and the severity of the conditions. No
hard and fast rules exist in a general sense, and
many decisions are made based on past experience
and individual preference. Clearly, each action is as-
sociated with a cost that highlights the need for good
initial design together with a sound understanding of
the possible corrosion processes if cost-effective cor-
rosion management is to be achieved without com-
promising safety.
Finally, the value and importance of corrosion
monitoring and inspection should not be forgotten
and goes hand-in-hand with the above for the most
part and certainly where carbon and low-alloy steels
are used. In addition, the role of top-of-the-line cor-
rosion needs specific attention.
Corrosion inhibitors are used extensively
throughout the oil and gas industry offering, where
appropriate, a cost-effective means of corrosion con-
trol, particularly for flowlines, pipelines, and
trunklines. For the most part they are used to inhibit
the reactivity of carbon and low-alloy steels contact-
ing the aqueous phase co-produced with oil and gas.
TECHNOLOGY GAPS
This review has highlighted key areas of progress
both mechanistically and industrially based on which
a number of key messages recommending areas for
additional research has been drawn. These can lead
to further the understanding of CO2 corrosion
mechanisms to enable improved predictive capabili-
ties for the effective use and deployment of carbon
and low-alloy steel in oil and gas production. Notable
areas of technology gap requiring systematic studies
include:
CO2 corrosion testing: a complex procedure
and a topic of ongoing investigation. There is a
great need to develop a field reproducible and
consistent procedure to evaluate CO2 corrosion.
This should truly reproduce the known field
observation of corrosion damage from the worst
cases to those providing adequate protection
and incorporate all key parametric sensitivities.
Interaction of CO2 corrosion with H2S: the sig-
nificance of H2S promoting or retarding corro-
sion has received little due attention and is
a major source of concern in designing new
development.
680
Presence of hydrocarbon phase: hydrocarbon
plays a vital role in CO2 corrosion in terms of
its phase ratio, its partitioning capability for
CO2, water wetting, and its inhibiting effect on
CO2 corrosion. Further focused research to
characterize the nature of hydrocarbon phase
can lead to better predicative capabilities.
Steel chemistry: while major studies have led
to the development of carbon and low-alloy
steels with superior resistance to CO2 corrosion,
these require fine-tuning to produce steels
with inherent resistance to CO2 corrosion.
Flow modeling: further emphasis on flow mod-
eling to better quantify water wetting/shedding
can lead to improved predictive modeling,
bearing in mind flow regime and their changes
throughout the life of the field.
Welds: the performance of welds and preferen-
tial weld corrosion remain a major operational
obstacle, particularly in the absence of corro-
sion inhibition. This subject has not been re-
viewed in the present article and requires
focused attention.
HAc: while some recent work has discussed
the influential role of HAc, its role requires
further study to determine its complementary
effect on CO2 corrosion.
Siderite formation: siderite, when formed, of-
fers superior protection. Studies on early
nucleation and growth of siderite can be of
significant benefit in corrosion mitigation.
Erosion-corrosion: the presence of solids to in-
duce erosion and its interaction with corrosion
is poorly understood and the subject is in need
of clarification to develop a conjoint erosion-
corrosion model taking on board solid content.
CONCLUSIONS

This overview article has led to a number of key
conclusions emphasizing the importance of the sub-
ject in providing integrity management for oil and gas
production facilities.

Corrosion failures account for 25% of all safety
incidents, 2.8% turnover, 2.2% tangible asset, 8.5%
increase on capital expenditure, 5% of lost/deferred
production, 11.5% increase to the lifting costs or
more quantitatively ca. 0.30 $/boe. The majority of
these are associated with CO2 corrosion of carbon
and low-alloy steels with implications on capital and
operational expenditures (CAPEX and OPEX) and
health, safety, and the environment (HSE) and opera-
tor dependency.

The industry continues to lean heavily on the ex-
tended use of carbon and low-alloy steels, which are
readily available and are able to meet many of the
mechanical, structural, fabrication, and cost require-
ments. Their technology is well developed and they
CORROSIONAUGUST 2003

represent for many applications an economic materi-
als choice. However, a key obstacle for their effective
use is their limited corrosion performance.

CO2 corrosion of carbon and low-alloy steel re-
mains a complex phenomenon and, despite several
extensive studies over the past 4 decades, its mecha-
nism, realistic predication, and control are in need of
being addressed effectively. Its understanding, pre-
diction, and control remain key challenges to sound
facilities design, operation, and subsequent integrity
assurance.

CO2 corrosion is influenced by a large number of
parameters, including environmental, physical, and
metallurgical variables. All parameters are interde-
pendent and can interact in many ways to influence
CO2 corrosion.

Ignoring the corrosion problems associated with
sour service, low levels of H2S can affect CO2 corro-
sion in different ways, either complementing CO2 cor-
rosion by acting as a weak acid or have a positive
effect on sweet corrosion through the formation of a
protective sulfide scale.

Presence of HAc or, more generally, organic acids
reduces the protectiveness of the films and increases
the sensitivity to mesa attack. This is attributed to a
lower Fe2+ supersaturation in the corrosion film and
at the steel surface in the presence of organic acids.

Corrosion scales, when formed under certain con-
ditions, can afford superior protection. While their
formation and growth have been the subject of many
studies, favorable conditions for the development of a
truly protective film to provide subsequent effective
protection need further scrutiny.

Precipitation kinetics of FeCO3 is affected by the
iron and carbonate concentrations, and its subse-
quent formation and growth are extremely tempera-
ture sensitive. These can be categorized as follows:
At low temperature conditions (<75C), growth is
slow with consequent need for extremely long
testing to address it effectively
At intermediate temperatures (75C to 110C),
the precipitation reaction may influence corro-
sion reactions since there is no requirement for
supersaturation
At high temperatures (>110C), FeCO3 precipita-
tion is likely to be rapid and growth is diffusion-
controlled. Iron released by the corrosion
process therefore may re-precipitate immediately
at the surfaces, providing a complete adherent
protective layer.

Steel chemistry plays a significant role in provid-
ing protection against CO2 corrosion and can lead to
substantial economical gains.
ACKNOWLEDGMENTS
The authors acknowledge J.L. Crolet (formerly
with TotalFinaElf) for his significant input, help with
CORROSIONVol. 59, No. 8
CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING
correcting errors, and addition of pertinent informa-
tion. Helpful contributions of D. Harrop (BP), Y. Zhu
(Windsor Scientific Ltd), and D. Williams (University
College London) are also acknowledged.
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85. C.A. Palacios, J.R. Shadley, Corrosion 47, 2 (1991). 103. Y.M. Gunalton, Combining Research and Field Data for Cor-
86. J.K. Heuer, J.F. Stubbins, Corrosion 54, 7 (1998): p. 566-577. rosion Rate Prediction, CORROSION/94, paper no. 14 (Hous-
87. S. Rajappa, R. Zhang, M. Gopal, Modeling the Diffusion Ef- ton, TX: NACE, 1994).
fects through the Iron Carbonate Layer in the Carbon Dioxide 104. G. Liu, R.C. Erbar, Detailed Simulation of Gas Well Downhole
Corrosion of Carbon Steel, CORROSION/98, paper no. 16 Corrosion in Carbon Steel Tubulars, CORROSION/90, paper
(Houston, TX: NACE, 1998). no. 30 (Houston, TX: NACE, 1990).
88. Y.J.T. Kinsella, S. Bailey, Corrosion 54, 10 (1998): p. 835-842. 105. M.R. Bonis, J.L. Crolet, Basics of the Prediction of the Risks
89. J.R. Shadley, S.A. Shirazi, E. Dayalan, E.F. Rybicki, G. Vani, of CO2 Corrosion in Oil and Gas, CORROSION/89, paper no.
Modeling CO2 Corrosion of Carbon Steels in Pipe Flow, 466 (Houston, TX: NACE, 1989).
CORROSION/95, paper no. 118 (Houston, TX: NACE, 1995). 106. Condensate Well Corrosion, NGAA, Tulsa, OK, 1953.
90. D.W. Shannon, Role of Chemical Components in Geothermal 107. NACE MR0175, Sulfide Stress Cracking Resistant Metallic
Brine on Corrosion, CORROSION/78, paper no. 57 (Houston, Materials for Oilfield Equipment (Houston, TX: NACE, 2001).
TX: NACE, 1978). 108. Guidelines on Materials Requirements for Carbon and Low-
91. C. de Waard, U. Lotz, A. Dugstad, Influence of Liquid Flow Alloy Steels for H2S-Containing Environments in Oil and Gas
Velocity on CO2 Corrosion: A Semi-Empirical Model, CORRO- Production, Publication no. 16 (London, U.K.: The Institute of
SION/1995, paper no. 128 (Houston, TX: NACE, 1995). Materials, European Federation of Corrosion, 1995).
92. F.D. de Moraes, J.R. Shadley, J. Chen, E.F. Rybicki, Charac- 109. K. Mudge, C.J. Levesque, Oil Gas J. 27 (1982): p. 245.
terization of CO2 Corrosion Product Scales Related to Environ- 110. J.B. Bradburn, Water Production: An Index to Corrosion,
mental Conditions, CORROSION/2000, paper no. 30 NACE South Central Region Conf. (Houston, TX: NACE,
(Houston, TX: NACE, 2000). 1977).
93. Metals Handbook, Corrosion, 9th ed., vol. 13 (Materials 111. J. Kolt, E. Buck, D.D. Erickson, M. Achour, Corrosion Pre-
Park, OH: ASM International, 1987), p. 1,233. diction and Design Considerations for Internal Corrosion in
94. E.C. Greco, W.B. Wright, Corrosion 18 (1962): p. 119t. Continuously Inhibited Wet Gas Pipelines, U.K. Corrosion
95. P.R. Rhodes, Electrochemical Society Extended Abstracts, Conf. 1990, vol. 3 (London, U.K.: Institute of Materials, 1990),
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96. J.L. Crolet, Protectiveness of Corrosion Layers, in Modeling Steel, CORROSION/93, paper no. 69 (Houston, TX: NACE,
Aqueous Corrosion: From Individual Pits to System Manage- 1993).

CORROSION Contents
General ................................... 1
A n updated, free guide for the prospective
CORROSION author, with tips on manuscript
preparation, format, style, color artwork, and
Submission of Manuscripts ...... 1

Author's Acceptance Criteria ................. 1

Acceptable Forms of Articles .... 2

editorial policies.
Guide* Manuscript Format ................. 2

Publication Procedures ............ 2

Vol. 56, No. 1 January 2000

THE JOURNAL OF SCIENCE AND ENGINEERING

CORROSION General Style Requirements

for All NACE Publications ........ 3
THE JOURNAL OF SCIENCE AND ENGINEERING

CORROSION
Founded 1945
CORROSION SCIENCE

3 Path Dependence of the Potential-Current Density State for Cathodically

Polarized Steel in Seawater

12
W.H. Hartt and S. Chen
Influence of Overaging Treatment on Localized Corrosion of Al 6056
V. Guillaumin and G. Mankowski
Abbreviations, Acronyms,
24 Anticorrosion, Antiscale Coatings Obtained on the Surface of Titanium Alloys
by Microarc Oxidation Method and Used in Seawater
S.V. Gnedenkov, P.S. Gordienko, S.L. Sinebrukhov, O.A. Khrisanphova, and T.M. Skorobogatova
and Symbols ........................... 3
32 Prediction of Stress Corrosion Cracking Susceptibility of Stainless Steels
Based on Repassivation Kinetics
H.S. Kwon, E.A. Cho, and K.A. Yeom

41 In-Situ Imaging of Chloride Ions at the Metal/Solution Interface by Scanning

Combination Microelectrodes
C.-J. Lin, R.-G. Du, and T. Nguyen
Equations and Footnotes...... 4-5
48 Galvanostatic Pulse Measurements of Passive and Active Reinforcing Steel
in Concrete
D.W. Law, S.G. Millard, and J.H. Bungey

57 Variation of Slow Strain Rate Test Fracture Mode of Type 304L Stainless Steel
in 288C Water

Graphics ................................. 5
N. Saito, Y. Tsuchiya, F. Kano, and N. Tanaka

70 Corrosion Behavior of High-Purity Fe-Cr-Ni Alloys in the Transpassive Condition

M. Mayuzumi, J. Ohta, and K. Kako

CORROSION ENGINEERING

80 Effect of Biomineralized Manganese on the Corrosion Behavior of C1008

Mild Steel

90
B.H. Olesen, P.H. Nielsen, and Z. Lewandowski

An Electrochemical Approach to Predicting Long-Term Localized Corrosion

of Corrosion-Resistant High-Level Waste Container Materials
Metric Measurements .............. 6
D.S. Dunn, G.A. Cragnolino, and N. Sridhar

Numbers and Punctuation ... 6-7

References ............................... 7
*New Guidelines Effective Jan. 1, 2000.
Item # 32143 Trade Names
and Author Affiliations ............ 9

Index ..................................... 12

Author Checklist .................... 14 To order, contact: NACE Membership Services Department, 1440 South Creek Drive,
Houston, TX 77084-4906; Phone: 281/228-6223 or Fax: 281/228-6329; ask for Item no. 32143. For
immediate delivery by fax, call 1-800-327-3134. This information is also available on the NACE Web
page at www.nace.org.

CORROSIONVol. 59, No. 8 683