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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

Carbon Dioxide Corrosion in Oil and Gas


ProductionA Compendium

M.B. Kermani,* and A. Morshed**

ABSTRACT INTRODUCTION
The present mechanistic understanding and practical impli- In the search for new sources of oil and gas, opera-
cations of carbon dioxide (CO2) corrosion of carbon and low- tional activities have moved to harsher environments
alloy steels in hydrocarbon production have been reviewed. in deeper high-pressure/high-temperature wells and
This is based on the fact that CO2 corrosion is by far the deep water. These have created increased challenges
most prevalent form of attack encountered in upstream op-
to the economy of project development and subse-
erations. The intent of the review was to provide information
quent operations wherein facilities integrity and
on the mechanisms, highlight key parameters affecting its
occurrence, and draw attention to areas requiring further accurate prediction of materials performance are be-
research. The primary focus was placed on two key param- coming paramount. In addition, the economic move
eters affecting CO2 corrosion that had received little system- toward multi-phase transportation through subsea
atic attention, including the morphology, nature, and completions and long infield flowlines has a tendency
characteristics of the surface film and steel composition, for increased risk of corrosion.
microstructure, and finishing conditions. In addition, the role Corrosion, therefore, remains a major opera-
of environmental and hydrodynamic variables is briefly pre- tional obstacle to successful hydrocarbon produc-
sented. The review has highlighted key areas of progress tion, and its optimum control and management is
both mechanistically and industrially and has led to a num-
regarded necessary for the cost-effective design
ber of key messages recommending areas for additional
of facilities and their safe operations. It has wide-
research to further the understanding of CO2 corrosion
ranging implications on the integrity of many materi-
mechanisms to enable improved predictive capabilities for
the effective use and deployment of carbon and low-alloy als used in the petroleum industry.
steels in oil and gas production. The impact of corrosion on the oil and gas indus-
try can be viewed in terms of its effect on capital and
KEY WORDS: acetic acid, carbon steel, carbon dioxide corro- operational expenditures (CAPEX and OPEX) and
sion, corrosion layer, flow dynamics, iron carbonate, low-alloy health, safety, and the environment (HSE).1 Corro-
steels, metallurgy, mesa attack, oil and gas production
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

Corresponding author. capital expenditure, 5% of lost/deferred production,
* KeyTech Limited, PO Box 275, Camberley, Surrey GU15 2FH,
United Kingdom. and 11.5% increase to the lifting costs.1-3 These are
** University College London, Torrington Place, United Kingdom. estimated figures and operator dependent, obtained
0010-9312/03/000131/$5.00+$0.50/0
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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

from a number of publications.1-4 The spread of surface film and steel composition. In addition, the
these figures are highly dependent on the manner role of environmental and physical variables affecting
to which a corrosion control philosophy is planned its occurrence is presented. Another key issue is the
and implemented as they vary according to opera- performance and characteristics of welds, although
tions and operators. One operator puts the cost of this subject was not covered in the present review as
corrosion as 30 cents for the production of each it requires detailed and focused attention. The review
barrel of oil equivalent (0.3 $/boe) or 1.5% of the highlights key areas of progress and draws attention
turnover.4 to the future direction of research and development
The industry continues to lean heavily on the to enable improved and economical design of facili-
extended use of carbon and low-alloy steels, which ties for oil and a gas production.
are readily available in the volumes required and
are able to meet many of the mechanical, structural, CO2 CORROSION
fabrication, and cost requirements. Their technol-
ogy is well developed and they represent an economi- CO2 corrosion, or sweet corrosion, of carbon
cal materials choice for many applications. However, and low-alloy steels is not a new problem. It was first
a key issue for their effective use is their poor recorded in the U.S. oil and gas industry in the
general and CO2 corrosion performance. Given the 1940s, followed by several studies since then.6-9 Dry
conditions associated with oil and gas production CO2 gas by itself is not corrosive at the temperatures
and transportation, corrosion must always be seen encountered within oil and gas production. It needs
as a potential risk. The risk becomes real once an to be dissolved in an aqueous phase to promote an
aqueous phase is present and is able to contact the electrochemical reaction between steel and the con-
steel, providing a ready electrolyte for the corrosion tacting aqueous phase. CO2 is soluble in water and
reaction to occur. brines. However, it should be noted that it has a
similar solubility in both the gaseous and liquid
Oilfield Corrosion hydrocarbon phases. Thus, for a mixed-phase
Oilfield corrosion manifests itself in several system, the presence of hydrocarbon phase may
forms, among which CO2 corrosion (sweet corrosion) provide a ready reservoir of CO2 to partition into the
and hydrogen sulfide (H2S) corrosion (sour corrosion) aqueous phase.
in the produced fluids and oxygen corrosion in water CO2 is usually present in produced fluids. Al-
injection systems are by far the most prevalent forms though it does not in itself cause the catastrophic
of attack encountered in oil and gas production. H2S failure mode of cracking associated with H2S,2 its
corrosion and materials optimization is covered else- presence in contact with an aqueous phase neverthe-
where,3 and corrosion in water injection systems is less can result in very high corrosion rates where
outside the present review. The majority of oilfield the mode of attack is often highly localized (mesa
failures result from CO2 corrosion of carbon and low- corrosion).
alloy steels primarily due to inadequate knowledge/
predictive capability and the poor resistance of car- CO2 Corrosion Mechanism
bon and low-alloy steels to this type of attack.1-4 Its Corrosion of carbon steel in CO2-containing envi-
understanding, prediction, and control are key chal- ronments is a very complex phenomenon and still
lenges to sound facilities design, operation, and sub- requires further elucidation. Various mechanisms
sequent integrity assurance. have been proposed for the process. However, these
Recent studies clearly have demonstrated that, either apply to very specific conditions or have not
despite extensive research over the past four de- received widespread recognition and acceptance.9-19
cades, the mechanistic understanding of CO2 corro- In general, CO2 dissolves in water to give car-
sion remains incomplete. Existing quantitative bonic acid (H2CO3), a weak acid compared to mineral
models are unreliable in predicting the actual long- acids since it does not fully dissociate:
term CO2 corrosion rate of carbon and low-alloy
steels, which invariably results in over-specification CO2 + H2O CO2 H2O H2CO3 H + + HCO3 (1)
of materials and impacts adversely on the cost of
production of oil and gas.1-9 As a consequence of the equilibrium described in
The intent of this review article was to capture Equation (1), much debate continues in the literature
the current understanding of CO2 corrosion of carbon as to the rate-determining step (RDS) in the reaction
and low-alloy steels in hydrocarbon production. It of the dissolved CO2 with a steel surface. Schwenk10
provides information on the mechanisms, highlights proposed that H2CO3 simply provides a source of H+
key parameters affecting its occurrence, and draws ions leading to the normal cathodic hydrogen evolu-
attention to areas requiring further research. The pri- tion reaction. de Waard and Milliams11 proposed that
mary focus was placed on two key parameters affect- H2CO3 is directly reduced at the steel surface,
ing CO2 corrosion, including the morphology of the whereas Ogundele and White12 point to the HCO3 ion

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TABLE 1
Mechanisms of the Anodic Dissolution of Iron in CO2-Containing Media19-20

Reaction No. Reaction or Equilibrium pH < 4 4<pH<5 pH> 5

1a HCO3 (HCO3)ads 1a 1a 1b
1b CO2+(OH )ads (HCO3)ads
2 (HCO3)ads (HCO3)ads+e RDS
3 (HCO3)ads (HCO3+)ads+e RDS(A)
4 (HCO3+)ads+OH (CO3)ads +H 2O RDS
5 Fe (CO3)ads + H2O Fe+++HCO 3+OH

15 Tafel slope (mV/log) 60/2 = 30 60/1.5=40 60/0.5= 120
15 H+ reaction order 2 1 0
15 CO2 reaction order 1 1 1
(A)
RDS = rate-determining step.

being reduced directly. The possible RDS in cathodic Types of CO2 Corrosion Damage
reactions, therefore, are summarized as follows: CO2 corrosion occurs primarily in the form of
general corrosion and three variants of localized
Schwenk corrosion (pitting, mesa attack, and flow-induced
localized corrosion).9 In studying CO2 corrosion, a
(HCO3 ): H + + e H, 2H H2 (2) clear distinction should be made between pure CO2
corrosion and a combined interaction of erosion/CO2
de Waard and Milliams corrosion, which may be exacerbated by CO2 corro-
sion. The latter characterizes itself in the form of
H2CO3 + e H + HCO3 RDS (3) ripple marks, horseshoes, comet tails, and dinosaur
foot prints,8,18 whereas the former is described in
this paper.
HCO3 + H + H2CO3 and 2H H2 (4)
Pitting Pitting occurs at low velocities and
around the dew-point temperatures in gas-producing
Ogundele and White
wells. In the field, only occasional pits have been ob-
served, which were either accidental adjacent to non-
HCO3 + e H + CO23 RDS (5) metallic inclusions or incipient mesa attack.7-8,18 The
pitting susceptibility increases with temperature and
HCO3 + H + e H2 + CO23 (6) CO2 partial pressure. In several related works on pit-
ting, Schmitt and coworkers15-17 discussed the effects
While the Ogundele mechanism only deals with alka- of temperature, Cl concentration, nature of anions
line pH conditions and the Schwenk and deWaard and cations, as well as corrosion inhibitors on the pit
mechanisms are only a possible hypothesis, recent initiation during the first stages of CO2 corrosion of
reactions put forward by Crolet, et al.,19 are the most pure iron and low-alloy steels at 5 bar CO2. They also
likely mechanism encountered. Based on the reaction reported that literally all alloys of technical interest
proposed by Crolet, the anodic dissolution of iron in might undergo pitting corrosion in CO2 environments
CO2-containing media is summarized in Table 1 with at the right conditions. Finally, they showed that Pb
respective RDS at different pH conditions.19-20 This additions inhibited localized corrosion (including pit-
table goes beyond summarizing the anodic dissolu- ting) through deposition at local anodes. On the
tion reactions and includes the respective Tafel other hand, Videm and coworkers23-24 concluded that
slopes derived from each pH condition. the pitting of carbon steel in CO2-containing environ-
Whichever is strictly mechanistically correct, it is ments was almost independent of the chloride con-
evident that the concentrations of dissolved CO2 spe- tent. Therefore, it was different from many other
cies in solution and the mass transport of dissolved metal environment combinations. However, the
CO2 to the steel surface have a critical influence on harmful ion, if any, responsible for the pitting of
the reaction and subsequent corrosion rate13 and carbon steels in CO2 solutions was not identified.
that every dissolved species present in the media can The discussion on pitting of carbon steels in
contribute to the cathodic reaction (Ref. 9 and Pots21 sweet environments has not reached a convincing
and Nesic, et al.22). Hence, there is a clear need to be conclusion. Various authors attribute the pitting ini-
able to characterize solution chemistry with respect tiation and its propagation to different factors and
to CO2 dissolution where the resulting acidification there is no generally applicable rule for its prediction.
will depend also on water composition and its buffer- Mesa-Type Attack Mesa attack is a type of lo-
ing capacity.14 calized corrosion and occurs in low to medium flow

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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-
FIGURE 1. A typical example of severe mesa attack experienced on rence in the field.
internal surfaces of pipelines transporting CO 2 -containing Flow-Induced Localized Corrosion This form of
hydrocarbon fluids (courtesy of Institute for Energy Technology, IFE). 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
conditions where the protective iron carbonate film mesa attack or by protruding geometry. The local
forms but it is unstable to withstand the operating turbulence combined with the stresses produced
regime. It manifests itself in large flat-bottom steps during scale growth may destroy existing scales.15-17
with sharp edges. Corrosion damage in these loca- Once the scale is damaged or destroyed, the flow
tions is well in excess of the surrounding areas.9 conditions then may prevent reformation of protec-
Figure 1 is an example of mesa attack experienced tive scale on the exposed metal.9,16-17 Flow-induced
on an internal surface of pipelines exposed to CO2- localized corrosion attack is principally observed in
containing environments. laboratory experiments in the absence of complete
Crolet, et al.,25 proposed that the microstruc- control of fluid chemistry.
turally formed galvanic coupling between steel (its
ferrite phase) and the cementite (Fe3C) layer was one KEY FACTORS
possible cause to promote mesa attack in sweet envi- INFLUENCING CO2 CORROSION
ronments. According to the same author,18 mesa at-
tack was observed in mature oil wells or, conversely, CO2 corrosion is influenced by a number of pa-
in young gas wells under high pressure of acid gases. rameters, including environmental, physical, and
Even in the presence of high fluid flow rates, its metallurgical variables as illustrated in Figure 2.
characteristics were totally different from the typical The majority of these have been covered extensively
features of erosion corrosion. Mesa attack appeared by a number of authors and captured elsewhere.6,8-9
to be a little sensitive to the velocity of water in the Notable parameters affecting CO2 corrosion include:
pipe, but extremely dependent on fluid composition.18 fluid makeup as affected by water chemistry,
Ikeda, et al.,26 attributed the initiation of mesa pH, water wetting, hydrocarbon characteris-
attack to the competitive film formation reactions tics, and phase ratios9,34-36
between ferrous carbonate (FeCO3) and magnetite CO2 and H2S content9,37-40
(Fe3O4). Although, in actual field conditions, Fe3O4 temperature9,34-35,41
has not been detected.18,27 The codeposition of both steel surface, including corrosion film mor-
compounds could initiate the mesa corrosion by dis- phology, presence of wax, and ashphaltene9
turbing the protective film formation. They concluded fluid dynamics9,29,39-41
that the initiation mechanism of mesa corrosion was steel chemistry32-33,38,42-45
closely related with the formation of a poorly protec- All parameters are interdependent and can inter-
tive FeCO3 film or the localized destruction of a act in many ways to influence CO2 corrosion. In the
protective film. present article, emphasis has been placed on two key
Videm and coworkers28-30 showed that flow- issues relating to metallurgical variables and surface
induced mesa attack could occur in water saturated film as key parameters not covered systematically
with FeCO3 under turbulent flow conditions where elsewhere. Other influential parameters are covered
film formation is prevented locally. In similar work, extensively by others8-9,34 and have been given only a
Dugstad and coworkers30-31 demonstrated that the brief mention here.

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CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

FIGURE 2. CO2 corrosion, the influential parameters.

Environmental Parameters formation of a low-porosity protective layer


Environmental factors that affect the inherent (lowering the exposed surfaces compared with
corrosivity of the aqueous phase therefore will affect the steel surface and hence less areas to be
CO2 corrosion. These include solution chemistry, corroded);
CO2 partial pressure, temperature, the in-situ pH, creation of concentration gradients of the prin-
H2S, and the effect of organic acids. cipal chemical species (Fe++ and HCO3). This is
Solution Chemistry and Supersaturation While potentially the most influential and particu-
there are still limited debates about the mechanism larly difficult to model. Ingress of solution to
of CO2 corrosion in terms of which dissolved species soak the porosity leads to steep concentration
are involved in the corrosion reaction, it is evident gradients, which may induce a significant shift
that the resulting cathodic corrosion rate is depen- of the local pH and water chemistry from the
dent on the partial pressure of CO2 gas and tempera- bulk conditions, and therefore, a genuine ef-
ture. Partial pressure of CO2 gas thus will determine fect of liquid surface state.
solution pH and the concentration of dissolved spe- Altogether, the precipitation rate and protective
cies for a given temperature. characteristics of any scale depend heavily on the
Supersaturation plays a vital role in the forma- supersaturation of the bulk solution. Hence, any
tion and stability of a protective corrosion layer. variations in this level of supersaturation could affect
Supersaturation is defined as log [A+][B]/Ksp for an the severity of the corrosion. For iron carbonate sys-
insoluble salt (AB) having an equilibrium reaction of tems, this can be portrayed as a reaction similar to
AB = A+ + B, where A+ and B are ionic species and Fe(HCO3)2 FeCO3 + H2CO3.46 The interdependency
Ksp is the solubility product. In any sweet environ- of supersaturation with the respective rates of iron
ment, a particularly insoluble salt can play an impor- dissolution and reprecipitation is shown in Figure 3
tant role in reducing the corrosion rate. High as a function of temperature. Figure 3 illustrates that
supersaturation of A+ and B leads to precipitation of while iron carbonate solubility to achieve saturation
a corrosion layer/film that therefore would reduce remains a little dependent on temperature, the limit
the corrosion rate through several kinds of effects, of supersaturation is achieved at lower Fe2+ concen-
including:18 trations with increasing temperature and hence
provision of a diffusion barrier (extended dif- facilitates the formation of FeCO3.31
fusion length between the metal substrate and CO2 Partial Pressure CO2 partial pressure has
the corrosive medium); been used in pH calculations and corrosion rate

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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
FIGURE 3. Fe++ solubility in pure water as a function of temperature the electrochemical reactions that lead to iron disso-
at 0.1 MPa CO2 partial pressure. Open squares represent results lution and the precipitation of protective scales that
obtained with corroding steel present, where the water volume to governs the various transport phenomena associated
steel surface area ratio is 4 cm 3/cm 2. Filled triangles are Fe++ with the former. Under certain conditions, solution
concentrations calculated from pH. Filled squares are results constituents of the aqueous phase will buffer the pH,
obtained with solid iron carbonate. The dashed line is iron carbonate which can lead to precipitation of a corrosion scale
solubility calculated from IUPAC data.31 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-
measurements by many authors.6,9,11,36,37,47-49 In most sion layer can even be corrosive and increase the
cases, a relationship has been developed between the severity of attack.8-9,19,27
CO2 partial pressure and corrosion rate. However, As an example, by increasing pH from 4 to 5, the
with some exception,36,48 the majority of pH calcula- solubility of Fe++ is reduced five times; for an increase
tions in these relationships do not take on board from pH 5 to 6, this reduction is around 100 times.8
that produced water cannot stay supersaturated in A low solubility can correspond to higher supersatu-
CaCO3. It also should be noted that for gas wells ration, which therefore accelerates the precipitation
with increasing pressure, the non-ideality of the process of FeCO3 film. For pH values >5, the prob-
natural gas will play an increasing role. Instead of ability of film formation is thus increased and that
the CO2 partial pressure, the CO2 fugacity (fco2) can contribute to the lower corrosion rates observed.
should be used.50 The difficulty is that for the pur- It must be noted that the solubility of the FeCO3
pose of homogeneity between nonideal phases, when should not be confused with that of the iron ion.8-9,18
fugacity is used for the gas phase, an activity coeffi- Effect of H2S Ignoring the cracking aspects of
cient (co2) should also be introduced for the water corrosion problems associated with sour service, low
phase. Unfortunately, fco2 is often available from levels of H2S can affect CO2 corrosion in different
PVT data, but rarely co2,36,48 and this may be the ways. H2S can either increase CO2 corrosion by
reason for the simplistic use of fco2 in the prediction acting as a promoter of anodic dissolution through
of corrosion rates. sulfide adsorption and affecting the pH or it can de-
Operating Temperature The operating tempera- crease sweet corrosion by forming a protective sulfide
ture strongly affects the nature, characteristics, and scale. The exact interaction of H2S on the anodic dis-
morphology of surface film, which, in turn, influ- solution reactions (Table 1) is not clear.
ences the CO2 corrosion process. At temperatures For similar conditions, oil and gas installations
in excess of ca. 80C, the solubility of FeCO3 in the could experience lower corrosion rates in sour condi-
solution is decreased and high supersaturation leads tions compared to completely sweet systems. This is
to FeCO3 precipitation.41 At low temperature ranges attributable to the fact that the acid created by the
(< ca. 70C), corrosion rate progressively increases dissolution of H2S is about three times weaker than
with temperatures up to an intermediate tempera- that of carbonic acids, but H2S gas is about three
ture range (between 70C to 90C), after which the times more soluble than CO2 gas. As a result, the
corrosion rate then diminishes. However, at sites effect of both CO2 and H2S gases on lowering the
where breakdown in the formation of FeCO3 occurs, solution pH and potentially increasing corrosion rate

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are fundamentally the same. In addition, H2S might press FeCO3, or oxide film formation, which can
play a significant role on the type and properties otherwise passivate the steel surface.25,35,55
of the corrosion films, improving or undermining It is also often observed, at least in laboratory
them.8-9 tests, that water or brine acidified with CO2 to a given
Videm, et al.,38 and Mishra, et al.,37 have re- pH produces a more corrosive solution than acidify-
ported two opposing results concerning H2S. While ing to the same pH with mineral acid. This is gener-
the former has reported that very small amounts of ally attributed to the fact that because carbonic acid
H2S in CO2-containing water augmented the corro- (H2CO3) is not fully dissociated in solution, it pro-
sion rate, the latter has argued that small amounts vides a reservoir of H+ ions over and above that deter-
of H2S had some inhibitive effect on CO2 corrosion of mined by the solution pH (log[H+]). In essence, this
steels. They attributed this to the formation of an is the same effect as that once cited by Crolet and
iron sulfide film that apparently was more protective Bonis14 in the presence of organic acids (weak acids)
than FeCO3. (i.e., increasing the oxidizing power of H+). For low
Many papers have been published on the inter- concentrations of HAc (very few mM), however, the
action of H2S with low-carbon steels.6,8-9,39-40,51-52 How- effect cannot but remain negligible with respect to
ever, literature data on the interaction of H2S and the tens or hundreds of mM of dissolved CO2.19 In
CO2 is still limited since the nature of the interaction addition, the presence of HAc may change the
with carbon steel is complex. The majority of open mechanism of the anodic dissolution of iron through
literature does indicate that CO2 corrosion rate is re- competitive adsorption of acetate ions, CH3COO
duced in the presence of H2S at ambient tempera- (or Ac) and HCO3, although this was shown to have
tures. Nevertheless, it must be emphasized that H2S only a slight inhibiting effect.19,55
also might form a nonprotective layer and that it Generally, the presence of HAc caused a signifi-
might catalyze the anodic dissolution of bare steel. cant increase in the corrosion rates in CO2 environ-
Steels may experience some form of localized corro- ments.53,56 HAc (along with other organic acids) could
sion in the presence of H2S, although very little infor- jeopardize the protective corrosion product scales
mation is available. Published laboratory work has formed in top-of-the-line corrosion.57
not been conclusive, indicating that there is a need At low CO2 partial pressure, CO2 corrosion disap-
to carry out further studies to clarify the mechanism. pears, but in certain fields, it can be replaced by a
A recent failure showed how the corrosion rate in the genuine HAc corrosion. It has been shown that this
presence of a high concentration of H2S might be was not caused by any influence of the HAc, either
higher than predicted using CO2 corrosion prediction on the cathodic reaction of H+ or on the anodic disso-
models. However, in spite of the work on H2S corro- lution of iron, but rather by its effect on the protec-
sion of steels, no equations or models are available tiveness of the corrosion layer. In the presence of
to predict corrosion, as is the case for CO2 corrosion traces of free HAc, the majority of corrosion layers on
of steels.9 bare metal was no longer FeCO3, but iron acetate,
Effect of Acetic Acid Organic acids present in which had a much greater solubility.19
production fluids has long been considered to signifi- In a similar work,25 it has been reported that
cantly influence and complement CO2 corrosion. The at a given pH, any replacement of a concentration
influence has been shown to occur systematically in or a flux of bicarbonate by an equivalent quantity
all field conditions where CO2 corrosion was ob- of acetate would considerably increase the local
served.18,27,53 Addition of acetic acid (HAc) to the test solubility of iron. This decreases the protectiveness
environment reduces the protectiveness of the films of the corrosion layer in proportion, by increasing
and increases the sensitivity to mesa attack. This iron concentration gradients, and therefore allowing
attributes to a lower Fe2+ supersaturation in the and subsequently raising the fluxes of corrosion
corrosion film and at the steel surface. Significant products, which potentially can be removed through
reduction in film stability was observed when the the layer. An overview of the concentration gradient
concentration of undissociated HAc in the solution of acetate ions close to the metal surface is shown
was increased from 0.05 mmol to 0.2 mmol, but the in Figure 4.23
results are too few to give more accurate threshold The presence of HAc is a key issue in CO2 corro-
values.19,53-56 sion, which requires further extensive studies.
Crolet and Bonis14,55 make the point that CO2-
induced acidification also can cause partial re-asso- Physical Parameters
ciation of anions, such as acetates and propionates, Along with environmental and metallurgical pa-
to form organic acids. Such weak acids then will in- rameters, physical parameters play an important role
crease the oxidizing power of H+ by raising the limit- in CO2 corrosion of carbon and low-alloy steels by
ing diffusion current for cathodic reduction (cf. influencing hydrodynamics of the system and the in-
Reaction [2]). The presence of such acids also will terface between the environment and the steel sub-
tend to solubilize the dissolving iron ions and sup- strate. These include water wetting, wax effect,

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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
FIGURE 4. Illustration of possible HAc enrichment in a corrosion with emulsified liquids, an obvious increase in the
layer as a result of internal acidification and galvanic coupling corrosion rate can be observed.59 So, as a rule of
between steel and cementite.25 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
surface films, crude oil, and fluid dynamics and are depends primarily on the maturity of hydrocarbon
mostly covered by others.8-9 Their interactive and (immature oils still contain natural surfactants) and
complementary influences affect the onset of film for- the nature of its kerogen (I, II, III)27 as explained in a
mation and removal. These effects have been high- later section.
lighted briefly here. Corrosion Film Characteristics Characteristics
Water Wetting CO2 corrosion occurs when of corrosion product significantly affect the CO2 cor-
water is present in the system and it wets the steel rosion process. Formation of surface film can provide
surface. The intensity of CO2 corrosion attack in- subsequent protection, enhanced corrosion, or un-
creases with the time during which the water phase controlled reaction, all subject to the nature, mor-
is in contact with the steel surface. Therefore, the phology, and growth habit of the corrosion product.
water content (water cut) and the notion of water Due to the importance of this subject, it is described
wetting are important variables. There are at least in a separate section on film formation.
three different notions of water wetting as follows:58 Effect of Wax The presence of wax in oil pipe-
Hydrodynamic concept focuses on modeling a lines can influence CO2 corrosion damage in two
continuous water phase at the fluid/wall in- ways, either exacerbating the damage or retarding
terface, which is primarily over the corrosion the process. These are dependent on the nature of
layer. However, it is evident that corrosion wax layer and subject to flow dynamics, temperature,
does not occur over the corrosion layer, but and other physical parameters. Based on data gath-
beneath it. This concept therefore cannot be ered in sweet oil lines in the U.S., a layer of wax (par-
directly relevant to corrosion modeling as affin) deposited on a carbon steel substrate caused
influenced by water wetting. heavy pitting in anaerobic sweet environments. The
Electrochemistry and surface physics concept proposed corrosion mechanism is the diffusion of
relates to liquid in direct contact with the CO2 through the wax layer, which can provide a large
metallic phase. This can be, in part, highly in- cathodic area that promotes anodic dissolution of
fluential in the modeling of water wetting. steel at discontinuities of the wax layer.9 However,
CO2 corrosion-related concept in which liquid- generally, wax can provide a degree of protection,
soaked porous film continues to hold water, albeit its protection is not reliable.
even if the bulk phase in contact with the wall Effect of Crude Oil Corrosion tests conducted
is temporarily either pure oil (in oil lines) or on steel in brine environments in the absence of
just a thin, wet film (in a pure gas line without crude oil do not give an accurate representation of
any ongoing water condensation). This pro- the behavior of the steel corrosion in a crude oil/
vides a favorable boosting for the sealing of brine production environment. This can lead to gross
cementite or hydrated mill scales during the errors when using the test results to estimate poten-
corrosion process and, as a consequence, tial corrosion problems.61-63
facilitates the onset of protectiveness in an Although there has not been any specific investi-
originally nonprotective film.27 Such circum- gation on the effect of crude oil type on protective-
stances can occur during shutdown periods ness of FeCO3 scale, it has been determined that
or in slug flow conditions. crude oils modify the morphology, composition, and

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compaction of corrosion products for the different where Ve, mixed velocity (ft/s or m/s), m, mixed fluid
oil/water ratios evaluated.64 Hydrocarbon appears to density (lb/ft3 or kg/m3), and C are constants.
destabilize the formation of a passive FeCO3 film, ac- The relationship is essentially empirical as is the
celerating the localized corrosion.27,61-62 Competitive value of the constant (C) used for a given material.
wetting of steel surfaces by water and then by oil has This is more often than not based on the individual
been reported to play an important role.65-66 operator experience.
A combination of water cut and hydrocarbon
type play a key role in affecting CO2 corrosion. In Metallurgical Parameters
this, the maturity of hydrocarbon (immature oils still Chemical composition, heat treatment, and
contain natural surfactants) and the nature of its microstructural features play important roles on
kerogen (I, II, III)27 are main issues. While this infor- corrosion of carbon steels in CO2 environments.
mation is extremely important, it is rarely recorded While most authors have reported the beneficial
or reported. It should be noted that some crude oils effects of chromium additions,26,29,42-45,68-79 there is not
also release natural corrosion inhibitors, which aid in yet a consensus on the optimum amount of Cr in the
lowering the corrosion rate.27 steel structure. Apart from Cr, molybdenum has been
Crude oil plays an important and differing role found to improve the corrosion resistance of carbon
on CO2 corrosion and has not received due attention. steels.42 In a related work, Videm and Dugstad23
Flow and Erosion The effect of flow on CO2 showed that small amounts of Cu, Ni, Cr (and possi-
corrosion still remains a contentious area in the pre- bly Mo) increases the corrosion potential of carbon
dictive processes. This effect should be discarded in steels, making it more noble. However, Cu additions
predictive modeling unless it is fully defined and con- may have a side effect on inhibitor efficiency as re-
trolled by the production process throughout the ported by Gulbrandsen and Nyborg.43
production life. However, it is not only fluid content A laboratory study has shown that the sulfur
that needs to be determinedthe flow regime is of content of carbon steels appears to influence the CO2
equal importance, which, for multi- or mixed phase corrosion rate as well. Certain high-S carbon steels
fluids, will determine whether water wetting of the were more corrosion resistant than low-S carbon
steel surface will occur. Clearly, if continuous hydro- steels in low-shear-stirred CO2 corrosion tests,74
carbon wetting occurs, then the corrosion risk will although the steel samples used in this work were
be extremely low.59 Key factors here are oil/water not representatives of oil industry grades and the
ratio and emulsion tendency/stability. For many practical implication of the work is uncertain.
crude oils, the presence of a water cut > 30% will Work by Kermani and coworkers44,80 has paved
lead to water becoming the continuous phase for a the way to developing an optimum metallurgy of
fully mixed oil/water system, such that corrosion carbon and low-alloy steels for both downhole and
then becomes a continuous potential risk.59,62 Simi- transportation facilities through addition of microal-
larly, if the gas/oil ratio (GOR) is >5,000, then con- loying elements like V, Ti, Mo, Cu, and Cr.
tinuous water wetting by the condensed water can
be expected.8-9 ALLOYING ELEMENTS
The flow parameter currently favored for deter-
mining the effect of velocity on corrosion rate and It is now well established that small quantities of
scale and inhibitor film formation/stability is liquid chromium (0.5 wt% to 3 wt%) can offer improved cor-
shear stress at the pipe wall. Although there is lim- rosion resistance of low-alloy steels in CO2-contain-
ited reported data on upper limits regarding shear ing media by promoting the formation of a stable,
stress, a figure of 100 Pa for C-steel above which dis- protective chromium oxide film.8-9,33,72,77 It also has
ruption to surface films becomes a concern is consid- been appreciated recently that for carbon and low-
ered by some as appropriate.67 However, it must be alloy steels, there may be a correlation between pro-
recognized that for specific situations it may be nec- tectiveness of the corrosion layer in the active state
essary to conduct laboratory tests under simulated and a possible passivation by a super protective
flow conditions. layer.8,72 The development of novel carbon and low-
Laboratory testing becomes particularly critical alloy steels with superior resistance to CO2 corrosion
where erosion, as a result of the presence of particu- using metallurgical conditioning recently has been
lates, is a concern. There are no industry guidelines made in the laboratory and subsequently by indus-
that adequately cover this situation. The commonly trial casts covering a wide range of parameters in-
cited API RP-14E68 recommended practice strictly cluding microalloying constituents, heat treatment
refers to pure gas-in-liquid-induced erosion (i.e., no processing, and steel production scenarios. Corro-
particulates present) and applies the basic formula: sion performance and properties of optimum steels
developed in this project have been verified through

( )
evaluation of the industrial casts,80 offering superior
Ve = C / m (7) CO2 corrosion while tolerating H2S corrosion for ap-

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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
FIGURE 5. Schematic presentation of relative effect of additional properties and extensive knowledge of steel corrosion
microalloying elements on corrosion rate.44,80 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
FIGURE 6. Schematic overview illustration of different categories of schematically in Figure 6, illustrating a progressive
steel ranked according to their Cr level.44,80 reduction in corrosion rate with increasing Cr con-
tent, the extent of which is subject to other alloying
constituents and heat treatment.
plication in Region 2 of ISO-15156.81 The philosophy While 3% Cr proved to offer a 10-times reduction
underlying the work of Kermani and coworkers44,80 in corrosion rate, 1.5% Cr was not sufficient to en-
was based on a combination of two principles: sure this level of resistance. The optimum level of Cr
lowering C and adding carbide-forming alloy- addition was not determined, albeit a level between
ing elements to maximize the effect of a given 2% to 3% Cr was considered essential to achieve the
addition of chromium and molybdenum, by expected improvement in corrosion performance sub-
ensuring that they remain in solid solution; ject to additional microalloying constituents.
achieving the desired properties by V V had a major beneficial effect on reducing
microalloying additions and mechanical and corrosion rate.45,80
heat treatments. Ti Ti had some beneficial effects on the corro-
Steel compositions were designed with low- sion rate, although inconsistent, and some unsatis-
carbon contents and contain microalloying additions factory effects on mechanical properties. Control of
of stronger carbide-forming elements (V, Ti, and Nb). properties in the Ti steels proved difficult, although
The intention was that these microalloying elements Ti additions could help to reduce HAZ hardness.
should preferentially combine with the carbon in a Mo Mo had no effect on the corrosion rate in
given steel, leaving Cr and Mo uncombined in the the active state at low pH, but helped to get a genu-
ferrite to provide enhanced corrosion resistance. In ine passivation in case of upward pH shifts beneath
addition, the presence of Si can lead to bainite for- an already protective corrosion scale.
mation under normalized conditions. Thus, this ele- Si and Cu These microalloying elements
ment, together with Ni, was used to bring back the showed beneficial effects on CO2 corrosion comple-
strength caused by the loss of carbon. The transfor- mentary to the effect of Cr, albeit subject to the

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microstructure, heat treatment, their interaction, In general, the protective characteristics of a cor-
and corrosion conditions. rosion film/layer depend on both the carbon steel
It is concluded that V-microalloyed steel contain- characteristics (microstructure, heat treatment his-
ing Cr, Si, Mo, V, and Cu is the most promising com- tory, alloying elements) and environmental variables
position in terms of corrosion resistance and (solution pH, temperature, solution composition, flow
mechanical properties.44-45,80 This steel offered good rate, etc.). The former has been covered earlier
levels of strength and toughness and good hot ductil- through influencing and modification of steel chemis-
ity, making it suitable for continuous casting. try and treatment processes.8-9,41-44,47,70-79 This section
Weldability is an issue for this composition, making focuses on the latter and discusses how film/scale
it only readily suitable at this time for downhole ap- properties are influenced by the environmental fac-
plications (e.g., threaded connections).80 Further tors, bearing in mind:
studies are underway to improve the weldability by their properties and effects on corrosion rate
reducing C, V, and Mo contents, without compromis- effects of various variables on the properties of
ing corrosion resistance. A very small addition of Ti the film/layer
(below stoichiometry with nitrogen) could be used to modification of the surface films and its growth
reduce HAZ hardness.78 habits
While corrosion rates of reference steels (X70, Further studies that are necessary for the im-
X65, or L80) increased with time, the new composi- provement of the corrosion of carbon and low-alloy
tion steels exhibited progressively reduced corrosion steels in CO2-containing environments through
rates with time, stabilizing after the initial expo- enhancing the properties of the surface film are
surea clear indication of the progressively protec- proposed.
tive nature of the corrosion film that formed on the
experimental steels and the necessity to carry out Film Formation
long-term corrosion experiments (in excess of 7 days) Based on extensive observations made by many
to allow steady-state conditions. The conclusion workers, corrosion films in the 5C to 150C tem-
drawn is that, as expected, Cr is effective above a perature range in water containing CO2 can generally
certain level, below which it is detrimental to the an- be divided into four main classes:
odic reaction on bare steel. Inconsistency in the cor- transparent films
rosion performance of low-Cr-containing steels has iron carbide (Fe3C) films
been experienced by a number of operators.8-9,73,76 iron carbonate (FeCO3) films
The data demonstrated that the calculated value iron carbonate plus iron carbide (Fe3C +
of free Cr and V, generally, proved to be good indi- FeCO3) films
cators of CO2 corrosion performancenevertheless, These are reviewed in this section and their over-
microalloying constituents and resultant microstruc- all characteristics are summarized in Table 2.
ture have influential and complementary roles.44,80 Transparent Films Transparent films are
rarely cited in the literature. They are <1 m thick
SURFACE FILMS; CORROSION LAYERS and only observed at around room temperature. The
film appears to form faster by reducing the tempera-
CO2 corrosion of carbon and low-alloy steels is ture below ambient. This class of film is not thermo-
strongly dependent on the surface films formed dur- dynamically the most stable solid corrosion product
ing the corrosion processes. The protectiveness, rate and can form in CO2-containing water with a very low
of formation/precipitation, and the stability of the ferrous ion concentration. Increasing the ferrous ion
film control the corrosion rate and its nature (general concentration makes this film more protective, slow-
corrosion or localized corrosion, especially mesa at- ing down the corrosion rate by about an order of
tack). Precipitation kinetics of FeCO3 film is affected magnitude and possibly more after long expo-
by the iron and carbonate concentrations, and its sures.25,35,55,77,83 Carbon steels protected by this trans-
subsequent formation and growth are extremely tem- parent film can be susceptible to crevice and chloride
perature sensitive.46 It is not the thickness of the film pitting corrosion in a similar manner to passivated
but the structure and its morphology that leads to stainless steels.44,56,72,83 Auger electron spectroscopy
low corrosion and protectiveness.9,19 It is interesting showed that this film did not contain carbonate, but
to note that a corrosion layer containing the same rather iron and oxygen ions roughly in the proportion
solid components can be either extremely protective82 of 1:2. Etching indicated a constant ratio between
or not very protective, or can even be corrosive.19,25 It iron and oxygen in the full thickness of the film.83 It
has not been very clear why under some conditions is important to examine this film in view of the con-
these scales form and mitigate further corrosion and troversy on the existence of metastable solid FeCO356
sometimes, in spite of favorable thermodynamic con- and the well-known dehydration of FeOOH in the
ditions for their formation, they do not precipitate at steps leading to the classical passivation of iron.84 As
all and the corrosion continues unhindered. these observations were not repeated, it is now ques-

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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-


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
FIGURE 7. A pure iron carbide layer formed at 60C and 1 to
increase the amount of Fe3C, but it also leads to the
3 times supersaturation.72
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-
FIGURE 8. An overview of corrosion layers seen on a tubular showing
cess and increases the corrosion rate by a factor of
a tough, empty cementite layer adjacent to gouges caused by wire
line runs (courtesy of J.L. Crolet). 3 to 10 by playing a number of roles, including:
Galvanic coupling: Fe3C has a much lower
overpotential for the cathodic reactions than
tionable whether this O/Fe ratio of 2:1 actually cor- iron and thus galvanic contact between the two
responded to FeII or FeIII.58 can accelerate the dissolution of iron by accel-
Transparent films have been ignored by many erating the cathodic reaction in the presence of
researchers and a systematic study is needed to con- <<1 ppm Fe2+ in water.25,72,77

670 CORROSIONAUGUST 2003


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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- FIGURE 9. Iron carbide layer forming on the metal surface followed
richment at the metal surface. This increases by partial siderite sealing leading to a nonprotective film.56
local supersaturation of ferrous ions and facili-
tates the formation of FeCO3.
Film Anchoring: In certain conditions, corro- dependent on the thermodynamics and kinetics of
sion film consists of a combination of Fe3C and FeCO3 precipitation. Supersaturation plays the most
FeCO3. In these films, Fe3C acts as a frame- important role in FeCO3 film growth and its morphol-
work anchoring the precipitated FeCO3 on the ogy. A high supersaturation of FeCO3 is necessary to
surface-enhancing film properties with im- form a protective film, particularly at low tempera-
proved tolerance to mechanical shear at high tures.41,72 In principle, the precipitation process com-
flow rates. In these situations, localized corro- prises two steps, nucleation and particle growth. The
sion is greatly reduced.38,79,83 morphology of the film therefore depends on the
Despite a high concentration of ferrous ions, dominating step.72,77 Once the film is formed, how-
local acidification at the surface may lead to unfavor- ever, it will remain protective at a much lower super-
able conditions for the precipitation of FeCO3.19,25,56,77,82 saturation.41 Protective film formation is accelerated
This may lead to FeCO3 precipitating within or on the by measures that restrict the transport of reaction
top of the cementite layer. This type of film forms ei- products from the surface.72
ther a corrosion layer with poor contact and bonding The adherence and thickness of the FeCO3 scale
to the metal surface or with unfilled regions between depend on the metal microstructure.8-9 The scale
metal surface and the corrosion film. This corrosion grown on normalized steels with a pearlitic/ferritic
film provides little protection, so corrosion rates can microstructure was more adherent, having larger
be high. A local high corrosion rate tends to increase crystals more densely packed and thicker than those
the local pH difference between adjacent anodic and formed on quenched and tempered steels.85 This is
cathodic regions, which subsequently favors further explained further in the following section.
development of the nonprotective film.19,25,72,79,82 FeCO3 reduces the corrosion rate by reducing
In general, the accumulation of Fe3C has a con- and virtually sealing film porosity. With altering nei-
trasting role on corrosion behavior, depending on its ther the local phase compositions nor the concentra-
manner of formation and its dominance within the tion gradient, this restricts the diffusion fluxes of the
film structure and process. On one hand, by prevent- species involved in the electrochemical reactions.
ing the diffusion of ferrous ions from the surface, it Moreover, even prior to sealing cementite, its precipi-
promotes the formation of FeCO3 film to offer a de- tation can lead to coverage and, therefore, can limit
gree of protection. By blending uniformly into FeCO3 its electrochemical activity. This is explained further
film, it will enhance its properties and protectiveness, in the section on operating temperatures. All authors
as described in the following section. On the other agree that increasing the temperature would improve
hand, Fe3C could provide local acidification and the protectiveness of the FeCO3 scale as well as its
facilitate galvanic corrosion and hence increased rate adhesion and hardness35 and that the higher the
of attack. Invariably, steel microstructure governs temperature, the more improved the protectiveness.
carbide distribution, which thus affects film stability However, there is little agreement on a practical
or instability. This has been postulated to govern threshold temperature. Some have reported that
corrosion behavior as described elsewhere in the pa- the maximum corrosion rate observed for carbon
per (Alloying Elements Section44,80). steel in sweet environments was from 60C to 70C
Iron CarbonateSiderite (FeCO3) Films In and then it started to decline due to growth of protec-
terms of corrosion mitigation, FeCO3 or siderite is the tive FeCO3 films.86-87 In another work,35 it has been
most important film that can grow on carbon steels suggested that the lowest temperature necessary to
in sweet environments. Film formation is strongly obtain FeCO3 films that would reduce the corrosion

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rate significantly was 50C and the protectiveness concentration well below the solubility limit of FeCO3
was increased also by increasing the pH. not only prevented the formation of FeCO3-containing
It has been argued that the protective films films, but also dissolved the existing films.35,81 Videm
formed at higher temperatures and pressures pro- and Dugstad28 concluded that a change of 30 ppm
vided better protection than those formed at low tem- Fe2+ can sometimes affect the corrosion rate to the
peratures and pressures. The level of protection same degree as a change in CO2 concentration of
increased with exposure time,88 which is the time 1,000 ppm (2 bar) at 90C.
dependency of the process. H2S Effect: In the presence of both H2S and
Some key environmental parameters that influ- CO2, simplified calculations indicate that iron sulfide
ence the iron carbonate film formation/precipitation may constitute the corrosion product layer when the
are described here. H2S/CO2 ratio exceeds about 1/5,000sour systems
Temperature Effect: As mentioned earlier, considerations then would be expected to apply.93
growth of FeCO3 scale is a slow temperature-depen- Occasionally, it has been reported94 that the corro-
dent process.41,46 It has been reported that FeCO3 sion product film formed under these conditions
scale was more protective at higher temperatures (containing FeS or Fe2S depending upon the H2S par-
(60C to 100C) with little protection at lower tem- tial pressure) was apparently more protective than
peratures6,33,89 (<60C) with Fe3C predominating the FeCO3. The opposite also has been reported, espe-
film. Above 100C, a tight and adherent film was cially at very low H2S concentrations, wherein a mix-
formed with suggestions6 that magnetite was the ture of layers forms comprising inner carbonate and
stable scale above 121C and the dominant scale at outer sulfide.95-96
250C,90 although magnetite has not been detected in Iron Carbonate (FeCO3) Plus Iron Carbide (Fe3C)
field conditions. An increased precipitation rate at Films This type of film is the most common film
high temperatures (>60C) could explain why the found on carbon and low-alloy steel surfaces in CO2-
corrosion rate went through a maximum in the tem- containing environments. During CO2 corrosion of
perature range from 60C to 90C. carbon steels, the Fe3C phase is cathodic (corrosion
pH Effect: pH is the most important factor in resistant) and may embed within the FeCO3 film. The
FeCO3 scale formation. It influences the solubility of structure of the film then will depend on where and
FeCO3, and, under suitable conditions, increasing when the FeCO3 precipitation takes place. On one
pH decreases the FeCO3 solubility and promotes its hand, if it occurs directly and integrates within the
precipitation in the environment, resulting in lower carbide phase, then a protective and stable film will
corrosion rates. In CO2-saturated environments, for- form that often can stand high fluid flow conditions.
mation of FeCO3 would decrease the corrosion rate On the other hand, initial formation of a cementite
by diminishing the diffusion of reactive species layer on the surface followed by partial FeCO3 sealing
through the precipitated FeCO3 film.33,41,91 The pH in- close to or beyond the external limit of cementite can
crease also improves the protective properties of the lead to a nonprotective film. An example of this is
FeCO3. Videm and Dugstad35 reported that at pH shown in Figure 10.25,27,72 In contrast, if cementite
6.00 good protection could be obtained by FeCO3 phase effectively sealed the siderite layer formed in
films even at room temperature. In a related work, contact with the metal surface, an incomplete sealing
they demonstrated that an increase in pH also made or a partial redissolution of FeCO3 anywhere else is
film formation more likely as a result of a reduction not detrimental and the corrosion film remains pro-
in the solubility of Fe2+.83 Similarly, de Moraes, et tective, as shown in Figure 11.25,27,72
al.,92 reported that protective layers could be ob- Crolet, et al.,25 have categorized the morphologies
served only for pH values >5very protective layers of corrosion film formation as affecting protective-
were present only at high temperatures (93C) and ness. This is shown in a simplified diagram in Figure
high pH values (pH 5.5), although these results are 12. The diagram is based on an analysis of the diffu-
now disputed.18 sion/precipitation issues and the resulting pH shifts,
Fe2+ Concentration Effect: Siderite formation and is backed by observations of the actual mor-
occurs in conditions where the concentration of Fe2+ phologies of protective and nonprotective corrosion
ions in the aqueous phase exceeds the solubility layers.
range of FeCO3, bearing in mind that other species As mentioned earlier, the structure of the mixed
also influence this process. It is also noteworthy that film plays an important role on the formation and
there are indeed two corrosion products, namely Fe++, breakdown of protective carbonate films. This is in-
resulting from the anodic reaction and HCO3, from fluenced by the carbon content and the size and dis-
the cathodic reaction.27 In uniform corrosion, they tribution of carbides, which therefore is dependent of
are released consistently so that different concentra- the microstructure of steel.85 The ferritic-pearlitic
tions of released ferrous ions also correspond to dif- steels have a carbide structure, which gives a good
ferent concentrations of released bicarbonate, which framework for the buildup of protective carbonate
will lead to local changes in pH.27,29 A ferrous ion films.79 Quenched and tempered steels and ferritic

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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
FIGURE 10. An empty, thick, and porous cementite network formed
many workers.9,33,55,77,79
on tubing recovered from the field, which was covered by a porous
but hard and mechanically resisting siderite tubercule (courtesy of
J.L. Crolet27).
Film Breakdown and Localized Corrosion
A sensitive balance between the formation and
destruction of the protective film governs the subse-
steels with low carbon content have a finely distrib- quent corrosion progress and determines whether
uted carbide structure that does not give an inte- uniform or localized attack will take place.30
grated framework to anchor and enhance the Mesa attack can be initiated by local breakdown
formation of protective carbonate films.32,38,77,79 Ex- of the protective film or by the growth of pits beneath

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the porous corrosion film by a local cell mechanism. tective for a long period in continuous flow loop ex-
The remaining corrosion film on top is removed periments. This therefore could lead to fast uniform
stepwise by the turbulent flow before the pit can con- corrosion, although protective films can form at these
tinue to grow into a larger mesa attack. When the temperatures when water stagnation on steel is
film has been torn away in one area, the corrosion prevalent.70,83
attack continues further beneath the film close to the In the presence of solids (sand), erosion-corro-
edge until another piece of the film is removed. It is sion can produce higher wall penetration rates than
assumed that a galvanic cell is set up between the erosion or corrosion alone. Three typical behaviors
anodic, film-free metal in the bottom of the mesa at- have been found. At low velocities, a protective FeCO3
tack and the cathodic, film-covered metal outside the scale formed over all surfaces of an elbow, and corro-
mesa attack, leading to a high corrosion rate in the sion rates were very low. At high velocities, impinge-
base of the mesa-attacked area.33,43,97 ment on elbow surfaces by sand particles entrained
Enhancement in the formation of protective films in the flow prevented protective layers forming in the
affects the corrosion rate in the base of the mesa by elbow. Corrosion rates were high and uniform over
enabling the formation of carbonate films, which can the entire surface. At intermediate velocities, protec-
then stop further growth of the mesa attack. Shallow tive layers formed over the entire elbow surface, ex-
mesa attack covered with corrosion films have been cept at very localized points where impinging sand
found in experiments on precorroded samples, and particles prevented scale formation. Deep pits formed
linear polarization resistance (LPR) measurements at these locations and wall penetration rates were
have shown that the growth of this mesa attack extremely high. These conditions are damaging but
slows down gradually during the experiment and can be avoided by reducing or increasing flow veloci-
eventually stops. This shows that reformation of pro- ties. A computational model for the prediction of
tective films in mesa-attacked areas is possible when sand erosion in piping systems was used to simulate
the growth rate of the mesa attack is not too experiments to explain the three observed behaviors
high.31,41,72 With a better quality of the initial protec- and predict conditions defining boundaries between
tive films, the effect of galvanic coupling between the them.98
mesa-attacked area and the surrounding area with Siderite (FeCO3) formed only in low-velocity,
intact corrosion films can be smaller, resulting in a single-phase flows where pH increased above 5.0.
slower and less catastrophic mesa attack. Rate of Corrosion rates after scale formation decreased by
growth at mesa-attacked areas has been shown to be almost 1 order of magnitude. No FeCO3 scale formed
excessively higher than the adjacent unattacked ar- in tests involving high-velocity, low-pH, single-phase
eas, reaching some 20 mm/y to 30 mm/y in water flows or two-phase flows.85
with around 2 bar CO2, pH 5.5 to 5.8, and 3% NaCl In fact, at medium or high pH conditions, protec-
at 80C.31,41,72,97 In laboratory tests, mesa attack oc- tive films always form unless the following param-
curred under these conditions at a flow rate of 7 m/s eters are met conjointly in laboratory testing:58
but not below 2.5 m/s. Low-chromium-containing initial bare surface
steels (0.5% to 1% Cr) did not suffer deep mesa at- room temperature
tack under these conditions.97 uninterrupted high flow rate from the start of
Fluid Flow Effects The effect of flow rate on the the test
corrosion rate originates primarily from localized In the absence of each, films do form and be-
flow-induced changes introduced by the corrosion come protective and their protectiveness remains un-
film. Fe3C particles remaining on the surface, the affected by flow. This basic irreversibility of corrosion
FeCO3 buildup, and the accumulation of alloying ele- layers82 explains the reported temperature effect,
ments in the corrosion film are flow-dependent phe- which essentially appears as a laboratory artifact and
nomena.30 As mentioned earlier, a clear distinction most unexplained good performance of the film expe-
should be made between pure CO2 corrosion and a rienced in real field conditions, which can be the re-
combined interaction of erosion-CO2 corrosion. sult of inevitable shutdown periods.58
Flow rate of water containing CO2 has two princi- The influence of solid particles (sand) and their
pal effects on film formation and corrosion rate and interactions with flow-induced corrosion is not fully
form. First, it prevents the formation and slows down understood, and predictive models do not include
its growth by reducing the local supersaturation. corrosion-enhanced erosion by solids.
Second, flow can damage film locally to cause local-
ized corrosion, especially mesa attack. When the sur- Iron Carbonate/Siderite (FeCO3) Scale:
face corrosion film is poorly adherent to the surface, Recent Progress
the effect of flow rate on localized corrosion is most The significance of steel characteristics and envi-
serious.47,69 ronmental variables on the protective nature of
In low-temperature conditions from 30C to FeCO3 (siderite) corrosion films was emphasized ear-
60C, films might not form or might not become pro- lier. A recent study has demonstrated the intricacy of

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FIGURE 13. Iron carbonate scale precipitated on carbon steel FIGURE 14. Iron carbonate scale formed after 260 h of immersion
samples at 75C exposed to a solution at pH 6.30 at 1 bar CO2 in a solution (at pH 6.30, 75C, and 1 bar CO2) showing a compact
showing a somewhat cubic appearance (magnification: X6,000).99 appearance.99

how corrosion protection offered by a precipitated tal) as shown in Figure 13 as also previously
FeCO3 scale on carbon steel substrate can be im- seen by others.41
proved through varying or adjusting some of the en- The film was a few micrometers thick and
vironmental parameters such as pH, temperature, formed just after 24 h immersion. Scale thick-
solution composition, and periodic exposure to air.99 ness, as measured by a scanning electron mi-
Among these, pH was shown to be the most influen- croscope (SEM), increased progressively with
tial variable in affecting the precipitation of FeCO3. time, becoming more compact (Figure 14). Sid-
The key factor preventing the growth of a protec- erite cube dimensions play an important role
tive siderite scale was that the nucleation and growth here, as suggested by others,8,18,27 in affording
of crystals of this compound were extremely tempera- further protection by hindering the ingress of
ture sensitive and slow with a rather high activation corrosive species toward the metal substrate. It
energy, confirming an earlier indication by others.46 should be noted that the key issue of the liquid
In this respect, for siderite as well as calcite and surface state has not been observed by SEM.
other forms of calcium carbonates, the limits of the Periodic exposure to the atmosphere, or more
domain of precipitation are not driven by saturation precisely to oxygen (through removal and re-
(thermodynamic stability) but by supersaturation exposure of samples), improved significantly
(kinetics). Also, it is worth noting that scaling inhibi- the scale adhesion to the substrate.
tion is crystal specific and there was an indication The work reiterated that FeCO3 precipitation
that some scale inhibitors could prevent the forma- coincided with a sudden drop in weight change
tion of calcium carbonate but not siderite.99 and its associated corrosion rate.
Key points of observation emerging from this Similar immersion tests conducted with pure
work on corrosion films/layers formed under sider- iron (99.5%) samples produced a patchy,
ite-forming conditions (pH range from 5.60 to 6.30, cracked, and loosely adherent FeCO3 scale.
75C, and 1 bar CO2 pressure) are highlighted:90 This was attributed to the absence of a carbide
The film consisted primarily of FeCO3 and re- network in pure iron.
sembled a perfect cubic morphology (bearing Solution chemistry played an important role in
in mind that siderite is a rhombohedric crys- altering the protective characteristics of the

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TABLE 3 tion) are in general more corrosive than formation


Effect of Various Parameters on Scale Protectiveness 99 waters since they do not contain any buffering or
scale-forming species and inherently have a lower in-
Surface
Parameter Coverage Stability Adhesion Density situ pH. On the other hand, at a given pH, the simple
chemistry of condensed water at low CO2 partial
Oxygen * * pressures may be less corrosive than some complex
Magnesium * * chemistries of reservoir water under higher CO2
Temperature * *
partial pressures.27
pH * * *
Carbide phase * * Software and spreadsheet-based programs now
exist for characterizing water chemistry such that
* Improvement in certain characteristics of the scale. concentrations of dissolved species and solution pH
No improvement was observed.
can be readily calculated.36,100-104 Nevertheless, the oil
Note: Stability should not be confused with adhesion. Stability means
the endurance of the scale toward environmental variables like solution and gas industry has grown up assessing the pres-
pH and flow velocity. 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
precipitating FeCO3 scale. In these series of and the approximation of ideality, where the thermo-
tests, scales developed in distilled water were dynamic activity of CO2 in water is assessed through
less adherent to the substrate than those de- its partial pressure in the gas. This remains valid
veloped in a solution containing trace Mg2+ up to high CO2 partial pressures, particularly on a
ions simulating produced fluid chemistry, and logarithmic pressure scale, which is that related to
Mg2+ ions improved siderite scale protection pH variations.
and adhesion. However, magnesium-related Viewing it starting from reservoir conditioning,
trends have not been observed in field evalua- Crolet and Bonis14,36,55,105 consider variations in CO2
tions.14,36 concentration resulting simply from differences in
The nucleation and growth of FeCO3 crystals the solubilities and activity coefficients in the phases
was a slow, temperature-dependent process; present. Thus, for example, in three-phase produc-
consequently, any environmental changes that tion, which is generally highly turbulent, even
retarded the precipitation process therefore led though the CO2 equilibrium is never perfect, any
to progressively increased corrosion. deviations remain relatively insignificant. Conse-
The work highlighted that the terms protective- quently, it is more reasonable, and certainly much
ness or corrosion-resistant properties of a scale easier, to express the amount of CO2, not in terms of
were loosely defined definitions. Therefore, the pro- its concentration in each phase, but as its chemical
tective characteristics of FeCO3 scale were translated potential (or thermodynamic activity or fugacity).
through the following specific properties allowing Provided conditions are not close to the gas liquefac-
better characterization: tion point, this is simply equivalent to the partial
scale density (or, in other words, pore distribu- pressure of CO2 in the gas phase. By extrapolation,
tion in the scale) reference then can be made to CO2 partial pressure
adhesion even in systems where there is no free gas phase
stability present. Experimentally, this virtual partial pres-
surface coverage sure corresponds to the real partial pressure of CO2,
Based on this, the effect of various environmen- which would appear in the nascent gas phase if the
tal parameters affecting scale characterization and system were to be depressurized. At the bottom of an
protectiveness have been tabulated. These are sum- oil well, this virtual partial pressure will be the very
marized in Table 3, demonstrating that solution pH first bubble at the bubble pressure of the reservoir
is the most influential parameter in the precipitation fluid; in a gas free line downstream of the gas sepa-
of FeCO3 scale and seemingly the only parameter rator, this will be the partial pressure at the last gas
that affects scale density.99 The work of Nesic, et al., in the separator.18
has led to modeling of the possibility of predicting the Variations of dissolved CO2 along the flow line
influence of FeCO3 film.20 will affect the solubility of potential scaling com-
pounds, particularly CaCO3, which can interfere with
CORROSIVITY the corrosion process and possibly its inhibition, if
precipitated. The in-situ pH level can also affect the
As a general statement, the corrosivity of the solubility of ferrous oxides and hydroxides, increas-
aqueous phase will be dependent on CO2 partial ing their solubility with decreasing pH. However, of
pressure, temperature, solution chemistry, and in- particular importance are conditions that favor depo-
situ pH. On one hand, at a given partial pressure of sition of FeCO3 (siderite). Formation of FeCO3 serves
CO2, condensed waters (associated with gas produc- to complicate the picture further, as it can, under

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certain conditions, passivate the corrosion reaction may be argued that such guidelines, because of the
making it even more difficult to accurately predict complexity of the problem, would either be too gener-
corrosion rates.58 alized and/or too conservative for certain situations,
their presence nevertheless would have a unifying
CO2 CORROSION PREDICTION influence to a degree and at least provide a common
reference point from which to work.
Over the years much effort has been expended in Having determined the water chemistry, this
studying factors controlling the performance of mate- then needs to be translated into a corrosion risk,
rials in production environments in an attempt to preferably expressed quantitatively as a rate and type
define the safe operating limits of candidate materials of attack. The easiest parameter to relate to (and in
in terms of the environmental and mechanical condi- general, measure) experimentally and in the field is
tions. This knowledge is gained, in part, from some the partial pressure of CO2. Thus, over the years, a
comprehensive, empirical-based field statistics, such number of empirical relationships have evolved with
as those by API,7,68,106 laboratory-based information varying levels of complexity and theoretical sub-
translated by quantitative regression to predictive a stance. In the simplest form, API7 in the late 1950s
corrosion rate,9,91,100-104 and comprehensive well sta- provided a Rule of Thumb criteria for carbon and
tistics based upon the actual field values of relevant low-alloy steels. After a first period of high popular-
scientific quantities.36,105 ity, this rule endured several exceptions and fell into
The laboratory-based equations have been con- oblivion with just periodic quotes, such as that by
ventionally based using the de Waard and Milliams Mudge and Levesque,109 who cite the following Rule
nomogram.9,96-97,100 Nonetheless, in the past, it was of Thumb criteria for carbon and low-alloy steels, or
imperative that candidate materials were assessed the complementary note from Crolet:18
in the laboratory prior to their application in the field PCO2 < 0.5 bar (7 psi)
so that costly and potentially hazardous failures are Corrosion Unlikely: implying that corrosion is
avoided. However, the relevance of some of these uniform and the rate is <0.1 mm/y
short-term tests to long-term performance was ex- 0.5 bar (7 psi) < PCO2 < 2 bar (30 psi)
ceedingly difficult to establish other than by long- Corrosion Possible: implying that corrosion rate
term experience or evaluation. might be between 0.1 mm/y to 1 mm/y and
The inherent corrosivity of acidic gases has long design consideration is based on life expectancy
been recognized and has prompted extensive studies PCO2 > 2 bar (30 psi)
of the subject.6-9,100 These have led to the develop- Corrosion likely: implying that corrosion rate
ment of predictive models or criteria that attempt to may exceed 1 mm/y, which is unacceptable
correlate corrosion to acidic gas partial pressure. where partial pressure of CO2 is denoted as PCO2
However, in merely using these predictive models, These are based on field experience, principally
there is a danger of working with a too simplistic or in the U.S. No subsequent standard guidelines exist
clear-cut picture of the situation. Any predictions as to the courses of action necessary for each condi-
that are made are not only influenced by the validity tion, although experience will trigger the corrosion
of the model, but also the quality and reliability of engineer to look initially toward certain possible op-
the supplied production and operational data used to tions (e.g., use of a corrosion inhibitor or more corro-
calculate the corrosion risk. sion-resistant alloys). However, designing on such a
The engineer ideally wants a predictive tool that basis is not a very satisfactory way to operate.
can be readily applied and is suitable for application Rules of thumb may be viewed as:
at all stages of project development and subsequent an aid to first-pass materials selection
operation. This may seem a tall order but it may offering qualitative and generalized assessment
nevertheless be argued that the fundamentals of the More specific questions on service life, risk
CO2 corrosion process will be common to all situa- analysis, corrosion allowance, and inhibited corro-
tions; it is the overlying effects of such factors as sion rates require the ability to conduct a quantita-
flow regime, film formation/deposition, hydrocarbon tive assessment (i.e., the ability to predict corrosion
phase, realistic and representative testing, steel rates for a given set of conditions). In addition, con-
chemistry, and corrosion inhibitor that cloud or com- sequence of corrosion is a key issue when corrosivity
plicate the picture. assessment is carried out. Nevertheless, the relation-
A true industry standard approach to predicting ship between corrosion rate and CO2 partial pressure
CO2 corrosion does not exist, although there are has formed the basis of a number of predictive mod-
aspects of commonality between the various ap- els/equations for carbon steels, even though claims
proaches/models in use by the industry. There is no have been made that PCO2 bears little relation to the
professional body or agency such as NACE Interna- decision by the field operator.110
tional providing standard basic guidelines to work Experimental work has lead to a number of
fromunlike the situation for H2S.81,107-108 While it equations or models being developed relating corro-

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sion rate of carbon and low-alloy steels to CO2 partial in terms of low and high risk as a function of
pressure,11,36,91,94,100-104,111 from which individual op- workover statistics, plus a medium category for
erators have each developed their own approach or borderline or undocumented conditions. Crolet and
philosophy. Bonis compared these with all the basic information
Most equations or models have been derived available at the time, combining both field experi-
from a range of experimental conditions. For ex- ences and laboratory data. Key parameters included
ample, the de Waard and Milliams equation or nomo- in this multiple correlation were the potential corro-
gram11 was originally derived for a 0.1% NaCl sivity (what is observed in the laboratory on bare
solution test medium at a flow velocity of ca. 1 m/s, surfaces but just taken as an index of electrochemi-
temperatures up to 80C, and PCO2 up to 1 bar for cal reactivity and in no way a corrosion rate predic-
X52 C-steel. Greco and Wright94 used 0.04% NaCl tion) and the field features (in-situ pH, Ca2+/HCO3
solution at 86F and PCO2 up to 4.5 bar; Videm and ratio, concentration of dissolved organic acids
Dugstad28 used distilled water, up to 120C, 6.5 bar [mainly HAc], and, to a lesser extent, flow velocity).
PCO2, and 20 m/s flow velocity. The models developed This tool expresses two distinctive tables indicating
by Fang, et al.,102 and Liu and Erbar104 are based on corrosion risks, one for oil-producing wells and one
theoretical analysis together with the use of data for the gas-producing wells. It complements the API
taken from the literatureboth of these models were rules7 and explains their exceptions; notably that
specifically developed for gas well corrosion. CO2 corrosion is indeed ubiquitous at high PCO2 and
While the use of simple NaCl brine might eventu- it progressively disappears at low PCO2, unless H2CO3
ally mimic water in gas systems, when considering is supplemented by free organic acids and the CO2
brines co-produced with crude oil, their water chem- corrosion by HAc corrosion.19,27,81 This, to a great
istries are far more complex and their influence (buff- deal, concludes the original debates launched in
ering) thus needs to be corrected when using these 19447-8,19,106 on the concept of damaging mechanisms
equations. Many parameters, such as temperature, caused by either CO2 or organic acids when the first
pH, partial pressures of CO2 and H2S, gas/oil ratio decision was made in 1958 in favor of a CO2-only
(GOR) and water production (water/oil ratioWOR), mechanism7 followed by the origin of the great many
water composition, together with flow rate and re- exceptions to the API rules.7,106
gime, have a greater or lesser effect on the corrosion
rate. Furthermore, not all of these parameters are Industry Practice
independent of each other, pH being a good example.8-9 While an industry standard approach to predict
Finally, direct field validation of the predicted CO2 corrosion damage does not exist per se, the work
corrosion rates often is difficult to unequivocally sub- of Shell8-9,11,91,101 in this area has provided a strong
stantiate. This is particularly true when a model reference statement from or against which to work.
needs detailed data, which are seldom gathered in The de Waard and Milliams equation or nomogram
the field. Furthermore, these data are not totally de- has been developed as an engineering tool. It pre-
fined throughout the service life of equipment.18 sents in a simple form the relationship between po-
Several prediction models for CO2 corrosion of oil tential corrosivity (worst case) of aqueous media for
and gas pipelines are available. These models have a given level of dissolved CO2, defined by its partial
very different approaches in accounting for oil wet- pressure at a given temperature.
ting and the effect of protective corrosion films, and The current form of the basic Shell equation is
this accounts for much of the differences in behavior as follows:8-9,91,101,112
between the models. All the models are capable of
predicting the high corrosion rates found in systems 1 / Vcor = 1 / Vr + 1 / Vm (8)
with low pH and moderate temperature, while the
models can predict quite different results for situa- log( Vr ) = 5.07 1,119 / ( t + 273) + 0.58 log(PCO2 )
tions at high temperature and high pH, where protec- (9)
0.34( pHactual pHCO2 )
tive corrosion films may form. An overview of
capabilities and shortfalls of the available models has
been provided by Nyborg100 and is also summarized Vm = 2.7( Vliq 08 / diam 0.2 ) PCO2 (10)
in EFC Publication 23.9
An intermediate approach that places direct em- where Vcor is the corrosion rate (mm/y); Vr and Vm
phasis on knowledge of the water chemistry is the represent the maximum kinetic reaction and mass-
prediction tool developed by Crolet and Bonis.36,105 transfer rates, respectively; t is temperature (C),
This tool is an advanced field database that calcu- PCO2 is partial pressure of CO2; pHactual is the actual
lates the factual input data, especially pH, free HAc, pH; pHCO2 is pH resulting from CO2 only; Vliq is liquid
and potential corrosivity, in terms of corrosion risk velocity (m/s); and diam is the hydraulic diameter
for the occurrence of failure within the life of the (m). The important influence of temperature on CO2
well. It defines the severity of CO2 corrosion in wells corrosion is depicted in Figure 15.8,112

678 CORROSIONAUGUST 2003


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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)

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apply organic coating (e.g., fusion-bonded ep- Presence of hydrocarbon phase: hydrocarbon
oxy, phenolic-modified epoxy) or use a liner plays a vital role in CO2 corrosion in terms of
(e.g., polypropylene) to isolate metal from cor- its phase ratio, its partitioning capability for
rosive environment CO2, water wetting, and its inhibiting effect on
use more corrosion-resistant materials (e.g., CO2 corrosion. Further focused research to
13% Cr steel, duplex stainless steels) either in characterize the nature of hydrocarbon phase
the solid form or as cladding on carbon steel can lead to better predicative capabilities.
use nonmetallics (e.g., fiber-reinforced plastics) Steel chemistry: while major studies have led
The relative merits of each approach must be to the development of carbon and low-alloy
viewed in the context of the application, the required steels with superior resistance to CO2 corrosion,
service life, and the severity of the conditions. No these require fine-tuning to produce steels
hard and fast rules exist in a general sense, and with inherent resistance to CO2 corrosion.
many decisions are made based on past experience Flow modeling: further emphasis on flow mod-
and individual preference. Clearly, each action is as- eling to better quantify water wetting/shedding
sociated with a cost that highlights the need for good can lead to improved predictive modeling,
initial design together with a sound understanding of bearing in mind flow regime and their changes
the possible corrosion processes if cost-effective cor- throughout the life of the field.
rosion management is to be achieved without com- Welds: the performance of welds and preferen-
promising safety. tial weld corrosion remain a major operational
Finally, the value and importance of corrosion obstacle, particularly in the absence of corro-
monitoring and inspection should not be forgotten sion inhibition. This subject has not been re-
and goes hand-in-hand with the above for the most viewed in the present article and requires
part and certainly where carbon and low-alloy steels focused attention.
are used. In addition, the role of top-of-the-line cor- HAc: while some recent work has discussed
rosion needs specific attention. the influential role of HAc, its role requires
Corrosion inhibitors are used extensively further study to determine its complementary
throughout the oil and gas industry offering, where effect on CO2 corrosion.
appropriate, a cost-effective means of corrosion con- Siderite formation: siderite, when formed, of-
trol, particularly for flowlines, pipelines, and fers superior protection. Studies on early
trunklines. For the most part they are used to inhibit nucleation and growth of siderite can be of
the reactivity of carbon and low-alloy steels contact- significant benefit in corrosion mitigation.
ing the aqueous phase co-produced with oil and gas. Erosion-corrosion: the presence of solids to in-
duce erosion and its interaction with corrosion
TECHNOLOGY GAPS is poorly understood and the subject is in need
of clarification to develop a conjoint erosion-
This review has highlighted key areas of progress corrosion model taking on board solid content.
both mechanistically and industrially based on which
a number of key messages recommending areas for CONCLUSIONS
additional research has been drawn. These can lead
to further the understanding of CO2 corrosion  This overview article has led to a number of key
mechanisms to enable improved predictive capabili- conclusions emphasizing the importance of the sub-
ties for the effective use and deployment of carbon ject in providing integrity management for oil and gas
and low-alloy steel in oil and gas production. Notable production facilities.
areas of technology gap requiring systematic studies  Corrosion failures account for 25% of all safety
include: incidents, 2.8% turnover, 2.2% tangible asset, 8.5%
CO2 corrosion testing: a complex procedure increase on capital expenditure, 5% of lost/deferred
and a topic of ongoing investigation. There is a production, 11.5% increase to the lifting costs or
great need to develop a field reproducible and more quantitatively ca. 0.30 $/boe. The majority of
consistent procedure to evaluate CO2 corrosion. these are associated with CO2 corrosion of carbon
This should truly reproduce the known field and low-alloy steels with implications on capital and
observation of corrosion damage from the worst operational expenditures (CAPEX and OPEX) and
cases to those providing adequate protection health, safety, and the environment (HSE) and opera-
and incorporate all key parametric sensitivities. tor dependency.
Interaction of CO2 corrosion with H2S: the sig-  The industry continues to lean heavily on the ex-
nificance of H2S promoting or retarding corro- tended use of carbon and low-alloy steels, which are
sion has received little due attention and is readily available and are able to meet many of the
a major source of concern in designing new mechanical, structural, fabrication, and cost require-
development. ments. Their technology is well developed and they

680 CORROSIONAUGUST 2003


CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

represent for many applications an economic materi- correcting errors, and addition of pertinent informa-
als choice. However, a key obstacle for their effective tion. Helpful contributions of D. Harrop (BP), Y. Zhu
use is their limited corrosion performance. (Windsor Scientific Ltd), and D. Williams (University
 CO2 corrosion of carbon and low-alloy steel re- College London) are also acknowledged.
mains a complex phenomenon and, despite several
extensive studies over the past 4 decades, its mecha- REFERENCES
nism, realistic predication, and control are in need of 1. M.B. Kermani, D. Harrop, The Impact of Corrosion on the Oil
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diction, and control remain key challenges to sound 186-190.
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assurance. NACE International, 2000).
3. P. McIntyre, Corrosion Management 46, 3/4 (2002): p. 19.
 CO2 corrosion is influenced by a large number of 4. M. Bonis, P. Thiam, Measurement of Corrosion Costs within
parameters, including environmental, physical, and Elfs Exploration and Production, Eurocorr 2000, Conf. Euro-
metallurgical variables. All parameters are interde- pean Federation of Corrosion (London, U.K.: Institute of Mate-
rials, 2000).
pendent and can interact in many ways to influence 5. M.B. Kermani, D. Harrop, Materials Selection for Oil and Gas
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1993).
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sion in different ways, either complementing CO2 cor- vol. 1 (1985) and 2 (1986) (Houston, TX: NACE).
7. Corrosion of Oil and Gas Well Equipment (Dallas, TX: Ameri-
rosion by acting as a weak acid or have a positive can Petroleum Institute, 1958).
effect on sweet corrosion through the formation of a 8. M.B. Kermani, L.M. Smith, eds., Predicting CO2 Corrosion in
protective sulfide scale. the Oil and Gas Industry, European Federation of Corrosion
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eration of Corrosion Publication no. 23 (London, U.K.: Institue
the sensitivity to mesa attack. This is attributed to a
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ditions, can afford superior protection. While their Use of Synthetic Environments for Corrosion Testing
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14. J.L. Crolet, M.R. Bonis, Corrosion 39 (1983): p. 39.
studies, favorable conditions for the development of a 15. G. Schmitt, Fundamental Aspects of CO2 Corrosion, COR-
truly protective film to provide subsequent effective ROSION/83, paper no. 43 (Houston, TX: NACE, 1983).
16. G. Schmitt, S. Feinen, Effect of Anions and Cations on the
protection need further scrutiny. Pit Initiation in CO2 Corrosion of Iron and Steel, CORRO-
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iron and carbonate concentrations, and its subse- 17. G. Schmitt, D. Engels, SEM/EDX Analysis of Corrosion Prod-
ucts for Investigations on Metallurgy and Solution Effects in
quent formation and growth are extremely tempera- CO2 Corrosion, CORROSION/98, paper no. 149 (Houston,
ture sensitive. These can be categorized as follows: TX: NACE, 1988).
At low temperature conditions (<75C), growth is 18. J.L. Crolet, Which CO2 Corrosion, Hence Which Prediction?,
in Predicting CO2 Corrosion in the Oil and Gas Industry,
slow with consequent need for extremely long European Federation of Corrosion Publication no. 13 (London,
testing to address it effectively U.K.: Institute of Materials, 1994), p 1.
19. J.L. Crolet, N. Thevenot, A. Dugstad, Role of Free Acetic Acid
At intermediate temperatures (75C to 110C), on the CO2 Corrosion of Steels, CORROSION/99, paper no.
the precipitation reaction may influence corro- 24 (Houston, TX: NACE, 1999).
sion reactions since there is no requirement for 20. S. Nesic, J.L. Crolet, D.M. Drazic, Electrochemical Properties
of Iron Dissolution in the Presence of CO2Basic Revisited,
supersaturation CORROSION/96, paper no. 3 (Houston, TX: NACE, 1996).
At high temperatures (>110C), FeCO3 precipita- 21. B.F.M. Pots, Mechanistic Models for the Prediction of CO2
Corrosion Rates under Multi-Phase Flow Conditions, COR-
tion is likely to be rapid and growth is diffusion-
ROSION/95, paper no. 137 (Houston, TX: NACE, 1995).
controlled. Iron released by the corrosion 22. S. Nesic, R. Nyborg, A. Stangeland, Mechanistic Modeling
process therefore may re-precipitate immediately for CO2 Corrosion with Protective Iron Carbonate Films,
CORROSION/2001, paper no. 40 (Houston, TX: NACE,
at the surfaces, providing a complete adherent 2001).
protective layer. 23. K. Videm, A. Dugstad, Galvanic Influence of CO2 Corrosion,
 Steel chemistry plays a significant role in provid- CORROSION/89, paper no. 468 (Houston, TX: NACE, 1989).
24. K. Videm, A.M. Koren, Corrosion 49, 9 (1993): p. 746-754.
ing protection against CO2 corrosion and can lead to 25. J.L. Crolet, N. Thevenot, S. Nesic, Role of Conductive Corro-
substantial economical gains. sion Products on the Protectiveness of Corrosion Layers,
CORROSION/96, paper no. 4 (Houston, TX: NACE, 1996).
26. A. Ikeda, S. Mukai, M. Ueda, Prevention of CO2 Corrosion of
ACKNOWLEDGMENTS Line Pipe and Oil Country Tubular Goods, CORROSION/84,
paper no. 289 (Houston, TX: NACE, 1984).
27. J.L. Crolet, Corrosion in Oil and Gas Production, in Corro-
The authors acknowledge J.L. Crolet (formerly sion and Anticorrosion, eds. G. Beranger, H. Mazille (Paris,
with TotalFinaElf) for his significant input, help with France: Hermes Science, 2002).

CORROSIONVol. 59, No. 8 681


CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

28. K. Videm, A. Dugstad, Effect of Flow Rate, pH, Fe2+ Concen- 54. J.D. Garber, K.A. Sangita, Factors Affecting Iron Carbonate
tration, and Steel Quality on the CO2 Corrosion of Carbon Scale in Gas Condensate Wells Containing CO2, CORRO-
Steels, CORROSION/87, paper no. 42 (Houston, TX: NACE, SION/98, paper no. 19 (Houston, TX: NACE, 1998).
1987). 55. J.L. Crolet, M.R. Bonis, The Role of Acetate Ions in CO2 Cor-
29. K. Videm, A. Dugstad, Mater. Perform. 3 (1989): p. 63-67. rosion, CORROSION/83, paper no. 160 (Houston, TX: NACE,
30. K. Videm, A. Dugstad, L. Lunde, Influence of Alloying Elements 1983).
upon the CO2 Corrosion Rate of Low-Alloyed Carbon Steels, 56. J.L. Crolet, S. Olsen, W. Wilhelmsen, Influence of a Layer of
CORROSION/91, paper no. 473 (Houston, TX: NACE, 1991). Indissolved Cementite on the Rate of the CO2 Corrosion of
31. A. Dugstad, The Importance of FeCO3 Supersaturation on the Carbon Steel, CORROSION/94, paper no. 4 (Houston, TX:
CO2 Corrosion of Carbon Steels, CORROSION/92, paper no. NACE, 1994).
14 (Houston, TX: NACE, 1992). 57. B.F.M. Pots, E.L.J.A. Hendriksen, CO2 Corrosion under Scal-
32. M. Ueda, A. Ikeda, Effect of Microstructure and Cr Content in ing ConditionsThe Special Case of Top-of-the-Line Corro-
Steel on CO2 Corrosion, CORROSION/96, paper no. 13 sion in Wet Gas Pipelines, CORROSION/2000, paper no. 31
(Houston, TX: NACE, 1996). (Houston, TX: NACE, 2000).
33. R. Nyborg, A. Dugstad, P. Dronen, Effect of Chromium on 58. J.L. Crolet, consultant, correspondence to M.B. Kermani (Au-
Mesa Corrosion Attack of Carbon Steel, Eurocorr 1997, gust through November 2002).
Conf. of European Federation of Corrosion, held Sept. 22-25 59. U. Lotz, L. van Bodengom, C. Ouwehand, Effect of Oil or Gas
(London, U.K.: Institute of Materials, 1997). Condensate on Carbonic Acid Corrosion, CORROSION/90,
34. B. Mishra, S. Al-Hassan, D.L. Olson, M.M. Salama, Corrosion paper no. 41 (Houston, TX: NACE, 1990).
53, 11 (1997): p. 852-859. 60. A.S. Green, B.V. Johnson, H.J. Choi, Flow-Related Corrosion
35. K. Videm, A. Dugstad, Mater. Perform. 4 (1989): p. 46-50. in Large Diameter Multiphase Flowlines, 65th SPE Annual
36. J.L. Crolet, M.R. Bonis, SPE Prod. Eng. 11 (1991): p. 449-453. Technical Conf. and Exhibition of the Society of Petroleum
37. B. Mishra, D.L. Olson, S. Al-Hassan, M.M. Salama, Physical Engineers, paper no. SPE 20685 (Richardson, TX: Society of
Characteristics of Iron Carbonate Scale Formation in Line Pipe Petroleum Engineers [SPE], 1990).
Steels, CORROSION/92, paper no. 13 (Houston, TX: NACE, 61. K.D. Efird, R.J. Jasinski, Corrosion 45, 2 (1989): p. 165-171.
1992). 62. U. Lotz, L. Van Bodegom, C. Ouwehand, Corrosion 47, 8
38. K. Videm, J. Kvarekvaal, T. Perez, G. Fitzsimons, Surface (1991): p. 635-645.
Effects on the Electrochemistry of Iron and Carbon Steel Elec- 63. H.J. Choi, T. Tonsuwannarat, Unique Roles of Hydrocarbons
trodes in Aqueous CO2 Solutions, CORROSION/98, paper no. in Flow-Induced Sweet Corrosion of X-52 Carbon Steel in Wet
1 (Houston, TX: NACE, 1998). Gas Condensate Producing Wells, CORROSION/2002, paper
39. B. Kaasa, T. Ostvold, Prediction of pH and Mineral Scaling in no. 02559 (Houston, TX: NACE, 2002).
Waters with Varying Ionic Strength Containing CO2 and H2S 64. M. Castillo, H. Rincon, S. Duplat, J. Vera, E. Baron, Protec-
for 0<T(C)<200 and 1<P(bar)<500, CORROSION/98, paper tive Properties of Crude Oils in CO2 and H2S Corrosion, COR-
no. 62 (Houston, TX: NACE, 1998). ROSION/2000, paper no. 5 (Houston, TX: NACE, 2000).
40. J.L. Crolet, M. Pourbaix, A. Pourbaix, The Role of Trace 65. C. de Waard, L. Smith, B. Craig, Influence of Crude Oil on
Amount of Oxygen on the Corrosivity of H2S Media, CORRO- Well Tubing Corrosion Rates, Eurocorr 2001, Conf. of Euro-
SION/91, paper no. 22 (Houston, TX: NACE, 1991). pean Federation of Corrosion (London, U.K.: Institute of Mate-
41. A. Dugstad, Formation of Protective Corrosion Films during rials, 2001).
CO2 Corrosion of Carbon Steel, Eurocorr 1997, Conf. of Euro- 66. J. Smart, WetabilityA Major Factor in Oil and Gas System
pean Federation of Corrosion, held Sept. 22-25 (London, U.K.: Corrosion, CORROSION/93, paper no. 70 (Houston, TX:
Institute of Materials, 1997). NACE, 1993).
42. S. Al Hassan, B. Mishra, D.L. Olson, M.M. Salama, Corrosion 67. B. Hedges, D. Paisley, R. Woollam, The Corrosion Inhibitor
54, 6 (1998). Availability Model, CORROSION/2000, paper no. 34 (Hous-
43. E. Gulbrandsen, R. Nyborg, Effect of Steel Microstructure and ton, TX: NACE, 2000).
Composition on Inhibition of CO2 Corrosion, CORROSION/ 68. American Petroleum Institute, Recommended Practice 14E
2000, paper no. 23 (Houston, TX: NACE, 2000). (API RP 14E), Recommended Practice for Design and Installa-
44. M.B. Kermani, J.C. Gonzales, C. Linne, M. Dougan, R. tion of Offshore Production Platform Piping Systems (Wash-
Cochrane, Development of Low-Carbon Cr-Mo Steels with ington DC: API, 1981).
Exceptional Corrosion Resistance for Oilfield Applications, 69. A. Dugstad, L. Lunde, K. Videm, Influence of Alloying Ele-
CORROSION/2001, paper no. 01065 (Houston, TX: NACE, ments upon the CO2 Corrosion Rate of Low-Alloyed Carbon
2001). Steels, CORROSION/91, paper no. 473 (Houston, TX: NACE,
45. R.M. Grau, Mechanisms for Improved Corrosion Resistance of 1991).
Steels in Carbonic Acid Environments (PhD thesis, University 70. E.W.J van Hunnik, B.F.M Pots, E.L.J.A. Hendriksen, The
of Leeds, 2000). Formation of Protective FeCO3 Corrosion Product Layers in
46. M.L. Johnson, M.B. Tomson, Ferrous Carbonate Precipitation CO2 Corrosion, CORROSION/96, paper no. 6 (Houston, TX:
Kinetics and its Impact on CO2 Corrosion, CORROSION/91, NACE, 1996).
paper no. 268 (Houston, TX: NACE, 1991). 71. T. Rogne, T.G. Eggen, U. Steinsmo, Corrosion of C-Mn-Steel
47. K. Videm, A. Dugstad, L. Lunde, Parametric Study of CO2 and 0.5% Cr Steel in Flowing CO2-Saturated Brines, CORRO-
Corrosion of Carbon Steel, CORROSION/94, paper no. 14 SION/96, paper no. 33 (Houston, TX: NACE, 1996).
(Houston, TX: NACE, 1994). 72. A. Dugstad, Mechanism of Protective Film Formation during
48. J.L. Crolet, M.R. Bonis, MP 24, 5 (1984): p. 35-42. CO2 Corrosion of Carbon Steel, CORROSION/98, paper no.
49. S. Nesic, J. Postlethwaite, Modeling of CO2 Corrosion Mecha- 31 (Houston, TX: NACE, 1998).
nisms, in Advanced Research Workshop on Modeling Aqueous 73. N. Blackburn, Downhole Materials Selection for Clyde Pro-
Corrosion: From Individual Pits to System Management, Proc. duction Wells: Theory and Practice, Society of Petroleum En-
of the NATO Advanced Research Workshop, eds. K.R. gineers, European Production Operations Conf. and
Threthewey, P.R. Roberge, held Sept. 6-8 (Kluwer Academic Exhibition, paper no. SPE 27604, held March 15-17
Publishers, 1994). (Richardson, TX: SPE, 1993).
50. J.R. Shadley, S.A. Shirazi, E. Dayalan, E.F. Rybicki, F.D. de 74. A.J. McMahon, Mater. Perform. 36, 12 (1997): p. 50-53.
Moraes, CO2 Corrosion Prediction in Pipe Flow under FeCO3 75. P.I. Nice, H. Takabe, M. Ueda, The Development and Imple-
Scale Forming Conditions, CORROSION/98, paper no. 51 mentation of a New Alloyed Steel for Oil and Gas Production
(Houston, TX: NACE, 1998). Wells, CORROSION/2000, paper no. 154 (Houston, TX:
51. K. Videm, J. Kvarekvaal, Corrosion 51, 4 (1995): p. 260-269. NACE, 2000).
52. A. Ikeda, M. Ueda, S. Mukai, Influence of Environmental Fac- 76. P.I. Nice, M. Ueda, The Effect of Microstructure and Chro-
tors on Corrosion, Advances in CO2 Corrosion, vol. 2, Proc. mium Alloying Content to the Corrosion Resistance of Low-
CORROSION/84 and CORROSION/85 Symp. on CO2 Corro- Alloy Steel Well Tubing in Seawater Injection Service,
sion in the Oil and Gas Industry (Houston, TX: NACE, 1985). CORROSION/98, paper no. 3 (Houston, TX: NACE, 1998).
53. Y. Garsany, D. Pletcher, B. Hedges,The Role of Acetate in CO2 77. A. Dugstad, H. Hemmer, M. Seiersten, Effect of Steel Micro-
Corrosion of Carbon Steel: Has the Chemistry Been Forgot- structure upon Corrosion Rate and Protective Iron Carbonate
ten?, CORROSION/2002, paper no. 02273 (Houston, TX: Film Formation, CORROSION/2000, paper no. 23 (Houston,
NACE, 2002). TX: NACE, 2000).

682 CORROSIONAUGUST 2003


CRITICAL REVIEW OF CORROSION SCIENCE AND ENGINEERING

78. R. Cochrane, Leeds University, work in progress. ment, eds. K.R. Trethewey, P.R. Roberge, NATO ASI Series,
79. D.E. Cross, Mesa-Type CO2 Corrosion and its Control, Series E: Applied Sciences, vol. 266 (Dordrecht NL, Kluwer
CORROSION/93, paper no. 118 (Houston, TX: NACE, 1993). Academic Publishers, 1994), p. 1-28.
80. M.B. Kermani, J.C. Gonzales, G.L. Turconi, D. Edmonds, 97. R. Nyborg, A. Dugstad, Mesa Corrosion Attack in Carbon
G. Dicken, L. Scoppio, Development of Superior Corrosion Steel and 0.5% Chromium Steel, CORROSION/1998, paper
Resistance 3%Cr Steels for Downhole Applications, CORRO- no. 29 (Houston, TX: NACE, 1998).
SION/2003, paper no. 03116 (Houston, TX: NACE, 2003). 98. J.R. Shadley, S.A. Shirazi, E. Dalayan, M. Ismail, E.F.
81. Petroleum and Natural Gas IndustriesMaterials for Use in Rybicki, Corrosion 52, 9 (1996).
H2S-Containing Environments in Oil and Gas Production 99. A. Morshed, Surface Modification for Corrosion Protection of
Part 1, ISO 15156 (Geneva, Switzerland, International Organi- Steel Pipes (PhD thesis, University College London, 2002).
zation for Standardization [ISO], 2002). 100. R. Nyborg, Overview of CO2 Corrosion Models for Wells and
82. J.L. Crolet, S. Olsen, W. Wilhelmsen, Observation of Multiple Pipelines, CORROSION/2002, paper no. 02233 (Houston,
Steady States in the CO2 Corrosion of Carbon Steel, CORRO- TX: NACE, 2002).
SION/95, paper no. 188 (Houston, TX: NACE, 1995). 101. C. de Waard, U. Lotz, D.E. Milliams, Corrosion 47, 12 (1991):
83. K. Videm, A. Dugstad, Film-Covered Corrosion, Film Break- p. 976-985.
down, and Pitting Attack of Carbon Steels in Aqueous CO2 102. C.S. Fang, J.D. Garber, R. Perkins, J.R. Reinhardt, Com-
Environments, CORROSION/90, paper no. 186 (Houston, puter Model of a Gas Condensate Well Containing Carbon
TX: NACE, 1990). Dioxide, CORROSION/89, paper no. 465 (Houston, TX:
84. S.H. Drissi, J.P. Mike, J.M. Genin, Corros. Sci. (1996): p. 623. NACE, 1989).
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),
vol. 76, no. 2 (Pennington, NJ: Electrochemical Society, p. 217.
1976), p. 300. 112. C. de Waard, U. Lotz, Prediction of CO2 Corrosion of Carbon
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