B. Kermani, M. Dougan, J.C. Gonzalez, C. Linne, R.

Cochrane, "Development of Low

Carbon Cr-Mo Steels with Exceptional Corrosion Resistance for Oilfield
Applications," CORROSION 2001NACE International, 2001).

Lowering C and hence improving the inherent corrosion performance and weldability. Maximising
the effect of a given addition of cr by ensuring that it remained in ss in the matrix rather than
forming carbide

Ahieving the desired properties by microalloying additions and mechanical and heat tretments. 15

The conclusion drawn is that, as expected, Cr is detrimental to the anodic reaction on bare steel
below a certain level of |Cr addition.

Loosely

The outcome has demonstrates that low-alloyed steels with approximely 3% Cr are able to form
chromium rich protective corrosion films.

The films form at conditions in which iron carbonate films are barely stable, and they grow at least
down to PH5. The films lower the corrosion rate and the low alloyed steels corrode at considerably
lower rates , 3-10 time less, than non-alloyed reference steels.

Incombination with microalloing 3wt%Cr is necessary to give the required increase in corrosion
resistance- 1.5wt% \Cr is insufficient. Electrochemical measurements indicate that Cr is detrimental
to the anodic reaction at the lowest concentration and thus can lead to inconsistency in the
corrosion performance of low Cr containing steels. At 3% CR or more protective films form at
conditions in which iron carbonate films are barely stable. These films grow at least down to
pH5.#The carbide forming microalloying elements facilitate the formation of Cr rich protective films
not present on conventional steels.

A number of low carbon steels cointaining microalloying addition have shown improved resistance
to CO2 corroiosn by a factor of 3-10 whilst maintining a cost penalty no grater 1.5 times that of
conventional grades of carbon steels.

M.B. KERMANI, A. MORSHED, CORROSION 59, 8 (2003): P. 659-683. 4444444444

All parameters are interdependent and can interact in many ways to influence CO 2 corrosion. In the
present article, emphasis has been placed on two key issues relating to metallurgical variables and
surface
film as key parameters not covered systematically
ELSEWHERE.

Corrosion Film Characteristics Characteristics of corrosion product significantly affect the CO 2

corrosion process. Formation of surface film can provide subsequent protection, enhanced
corrosion, or uncontrolled reaction, all subject to the nature, morphology, and growth habit of the
corrosion product. Due to the importance of this subject, it is described in a separate section on
film formation.

High supersaturation of A+ and B leads to precipitation of a corrosion layer/film that therefore

would reduce the corrosion rate through several kinds of effects, including: 18
provision of a diffusion barrier (extended diffusion length between the metal substrate and
the corrosive medium);
formation of a low-porosity protective layer (lowering the exposed surfaces compared with the
steel surface and hence less areas to be corroded);
creation of concentration gradients of the principal chemical species (Fe ++ and HCO3). This is
potentially the most influential and particularly difficult to model. Ingress of solution to soak the
porosity leads to steep concentration gradients, which may induce a significant shift of the local pH
and water chemistry from the bulk conditions, and therefore, a genuine effect of liquid
surface state.

At temperatures in excess of ca. 80C, the solubility of FeCO3 in the solution is decreased and high
supersaturation leads to FeCO3 precipitation
At low temperature ranges (< ca. 70C), corrosion rate progressively increases with temperatures
up to an intermediate temperature range (between 70C to 90C), after which the corrosion rate
then diminishes. However, at sites where breakdown in the formation of FeCO 3 occurs, corrosion
process proceeds unhindered, which may lead to severe localized attack.

As an example, by increasing pH from 4 to 5, the

solubility of Fe++ is reduced five times; for an increase
from pH 5 to 6, this reduction is around 100 times. 8
A low solubility can correspond to higher supersaturation,
which therefore accelerates the precipitation
process of FeCO3 film. For pH values >5, the probability
of film formation is thus increased and that
can contribute to the lower corrosion rates observed.
It must be noted that the solubility of the FeCO3
should not be confused with that of the iron ion. 8-

Metallurgical Parameters

While most authors have reported the beneficial

effects of chromium additions,26,29,42-45,68-79 there is not
yet a consensus on the optimum amount of Cr in the
steel structure. Apart from Cr, molybdenum has been
found to improve the corrosion resistance of carbon
steels.42 In a related work, Videm and Dugstad23

It is now well established that small quantities of

chromium (0.5 wt% to 3 wt%) can offer improved corrosion
resistance of low-alloy steels in CO2-containing
media by promoting the formation of a stable,
protective chromium oxide film

While 3% Cr proved to offer a 10-times reduction

in corrosion rate, 1.5% Cr was not sufficient to ensure
this level of resistance. The optimum level of Cr
addition was not determined, albeit a level between
2% to 3% Cr was considered essential to achieve the
expected improvement in corrosion performance subject
to additional microalloying constituents.

The conclusion drawn is that, as expected, Cr is effective above a certain level, below which it is
detrimental to the anodic reaction on bare steel. Inconsistency in the corrosion performance of low-
Cr-containing steels has
been experienced by a number of operators.8-9,73,76

CO2 corrosion of carbon and low-alloy steels is strongly dependent on the surface films formed
during the corrosion processes. The protectiveness, rate of formation/precipitation, and the stability
of the film control the corrosion rate and its nature (general corrosion or localized corrosion,
especially mesa attack).
Precipitation kinetics of FeCO3 film is affected by the iron and carbonate concentrations, and its
subsequent formation and growth are extremely temperature sensitive. 46 It is not the thickness of
the film but the structure and its morphology that leads to low corrosion and protectiveness. 9,19 It is
interesting to note that a corrosion layer containing the same solid components can be either
extremely protective82 or not very protective, or can even be corrosive.19,25 It has not been very
clear why under some conditions these scales form and mitigate further corrosion and sometimes,
in spite of favorable thermodynamic conditions for their formation, they do not precipitate at all
and the corrosion continues unhindered.

FeCO3 reduces the corrosion rate by reducing and virtually sealing film porosity. With altering
neither the local phase compositions nor the concentration gradient, this restricts the diffusion
fluxes of the species involved in the electrochemical reactions. Moreover, even prior to sealing
cementite, its precipitation can lead to coverage and, therefore, can limit its electrochemical
activity. This is explained further in the section on operating temperatures. All authors agree that
increasing the temperature would improve the protectiveness of the FeCO 3 scale as well as its
adhesion and hardness35 and that the higher the temperature, the more improved the
protectiveness.
However, there is little agreement on a practical threshold temperature. Some have reported
that the maximum corrosion rate observed for carbon steel in sweet environments was from 60C
to 70C and then it started to decline due to growth of protective FeCO 3 films.86-87 In another work,35
it has been suggested that the lowest temperature necessary to obtain FeCO 3 films that would
reduce the corrosion rate significantly was 50C and the protectiveness was increased also by
increasing the pH. It has been argued that the protective films formed at higher temperatures and
pressures provided better protection than those formed at low temperatures and pressures. The
level of protection increased with exposure time,88 which is the time dependency of the process.
Some key environmental parameters that influence
the iron carbonate film formation/precipitation
are described here.

The pH increase also improves the protective properties of the FeCO 3. Videm and Dugstad35
reported that at pH
6.00 good protection could be obtained by FeCO3 films even at room temperature. In a related
work, they demonstrated that an increase in pH also made film formation more likely as a result of
a reduction in the solubility of Fe2+.83 Similarly, de Moraes, et al.,92 reported that protective layers
could be observed only for pH values >5very protective layers were present only at high
temperatures (93C) and high pH values (pH 5.5), although these results are now disputed.1

C. Morales, T. Perez, G. Echaniz, G.L. Turconi, "Development of Low Alloyed Carbon Steel Octg
Products for Corrosive Environments," ND.

666666666666666
CO2 corrosion of low alloy steels is very dependent on water chemistry and flow conditions, and may vary in a
large degree from conditions leading to protective film formation and "worst case corrosion" where no
protective films are formed; local breakdown of corrosion films may
result in rapid local attack or mesa corrosion attack14.

In the LEEDS program, steels compositions were designed with low carbon content and microalloying addition
of strong carbide-forming elements (V, Ti, Mo, Nb), varying Cr content. The intention was that these
microalloying elements should preferentially combine with C, leaving Cr uncombined to provide corrosion
resistance (through the formation of stable and protective corrosion deposits). Considering the program results,
SIDERCA and CINI are working in the design, production and testing of a 3% Cr steel. In this work some
aspects of the production and evaluation of
this material are presented. at the different test temperatures. 3% Cr steel corrosion rates are lower than those of
the reference steels, in all conditions. For 3% Cr steel, the presence of corrosion products formed during "pre-
corrosion" process reduces corrosion rates; corrosion mitigation increase as severity of the process increase

Electrochemical tests showed that the difference between 3% Cr and reference materials performance
remarkably increased when corrosion products film is formed. Differences in appearance between 3% Cr and
reference steels tested samples can be observed by simple visual examination. After corrosion tests, all samples
were covered by dark grey corrosion films but presenting different characteristics depending on the type of
steel: 3% Cr steel tested surfaces were smooth and rather brilliant; reference steels presented the typical aspect
of CO2 corroded carbon steel, opaque and uneven

Optical and SEM observations revealed also differences between 3% Cr steel and reference steels. Figure 13
shows surface appearance of 3% and 1% Cr steels tested at 60C; 3% Cr film is more regular, numerous cracks
formed upon drying. Film formed on 3% Cr steel is more adherent than formed in reference steels; evaluation of
0% and 1% Cr steels using SEM revealed areas where corrosion products are not present or corrosion films are
thinner.

To study corrosion products, tested samples were sectioned and analysed using SEM/EDX. Films on 3% Cr
steel were rather dense and even corrosion attack of metal was observed. Reference steels films are thicker than
the ones observed on 3%Cr steel; for these materials (1% and 0% Cr) there were some pores in the corrosion
films. Analysis of Cr and Fe content of the films was performed using EDX. The corrosion films consisted
mainly of Cr (almost negligible in the case of 0% Cr steel) and Fe compounds (C and O were detected). EDX
results indicates that films formed on 3% Cr steel are Cr rich, presenting a relation wt%Cr:wt%Fe higher than 1
(this ratio is 0.035 in the steel).
The ratio Cr:Fe increase near to the surface of the film, reaching values close to 10. For 1% Cr steel films Fe
concentration is higher than Cr concentration, presenting values of Fe:Cr lower than 1.

Electrochemical tests showed that 3% Cr steel presents a better corrosion performance than reference steels.
The difference between 3% Cr and reference materials performance remarkably increased when test samples
were "pre-corroded". For the 3% Cr steel the tendency was for its corrosion rates to reduce as the "precorrosion"
severity increases; this behaviour was not observed for reference steels. This an indication of
progressively protective nature of the corrosion film formed on 3% Cr steel and the differential behaviour is,
then, considered to be related to the characteristics of formed corrosion products.
Differences in appearance between 3% Cr and reference steels tested samples can be observed. Film formed
on 3% Cr steel is more brilliant, adherent and dense than formed in reference steels. The difference in
appearance
and protectivity between 3%Cr steel and reference steels is related to the Cr content in the corrosion film.
Essential criterion for evaluating the corrosion resistance of 3Cr
steel
in CO2 environments: Prepassivation
Jinyang Zhu a, Lining Xu a,, Minxu Lu a, Lei Zhang a, Wei Chang b, Lihua Hu b 40 40 40

The low corrosion rate of 3Cr steel is caused by prepassivation, which is believed to be related to the formation of a Cr(OH) 3
layer on the surface of the steel, thus modifying the anodic reaction. The open-circuit
voltage (OCP) of 3Cr steel exhibited a tendency to increase over time from _0.67 to _0.48 V. Simultaneously,
the solution pH near the substrate decreased, which affected the cathodic reaction with the possible
participation of the direct reduction of H+. Modifying both anodic and cathodic reactions maintains
the OCP in the desired potential range, causing spontaneous prepassivation to occur.

Pilas 15Z

One previous study reported that 3Cr steel can

improve CO2 corrosion resistance by a factor of 310 and maintain
a cost less than 1.5 times higher than that of conventional grades of
carbon steel [3]. In recent studies, the majority of scholars have
hypothesized that the addition of Cr can increase the density and
protectiveness of the corrosion film, thus creating effective CO 2
corrosion resistance

In this study, we discovered that prepassivation occurs in 3Cr

steel. Prepassivation was a criterion for both 3Cr steel and all other
Cr-containing low alloy steels, and provided a fast evaluation
method for corrosion resistance. Moreover, this study provided a
detailed mechanism by which chromium addition considerably
improved the corrosion resistance by simultaneously affecting
anodic and cathodic processes.

Fig. 3
shows that the anode polarization curves for the anode reaction
of the 3Cr steel exhibit a decrease in current between E1
(_520 mV vs. Ag/AgCl) and E2 (_430 mV vs. Ag/AgCl), which is
not present in that of the X65 steel without Cr. This phenomenon
is identified as prepassivation [8].

The corrosion
rate of the X65 steel was measured for comparison. Fig. 2 illustrates
that after 292 h of immersion, the average corrosion rate
of the 3Cr steel is less than a quarter of that of the X65 steel.

shows the micro morphologies of

these two polarized samples; in Fig. 4a, the scratches caused by
grinding are clearly visible on the sample. When polarized to Ea,
the 3Cr steel sample exhibited little corrosion and the sample
was in a passive state. However, the sample polarized to Eb was
severely corroded, and many corrosion products accumulated on
the substrate surface (Fig. 4b) because that Eb was above E2 and
the sample was in a transpassive state. Therefore, the sample
polarized to Eb was severely corroded when the polarization potential
was high.
The Cr(OH)3 was prepared
from ammonia and Cr(NO3)3. As shown in Fig. 5, regarding
the layer on the 3Cr steel surface, two sets of peaks located at
578 cm_1 and 701 cm_1 were observed and were consistent with
the peaks (555 cm_1, 713 cm_1) in the Cr(OH)3. Therefore, the layer
on the 3Cr steel surface mainly consisted of Cr(OH) 3. As the polarization
progressed, the chromic hydroxides continually formed on
the 3Cr steel surface, thereby causing the prepassivation observed
in the anode polarization curves.

Raman spectroscopy (/rmn/; named after Sir C. V. Raman) is a spectroscopic technique

used to observe vibrational, rotational, and other low-frequency modes in a system. [1] Raman
spectroscopy is commonly used in chemistry to provide a fingerprint by which molecules can be
identified.

This pattern indicates that the OCP entered the potential

range of prepassivation after the initial increase, meaning that prepassivation
occurred spontaneously

In CO2 environments, 3Cr steel demonstrates short prepassivation

with a range of approximately _520 to _430 mV (vs. Ag/AgCl).
The prepassivation is caused by a Cr(OH)3 layer that forms on the
steel surface.
Spontaneous prepassivation is the main cause of the favorable
CO2 corrosion resistance of 3Cr steel. The key factors of spontaneous
prepassivation are the decrease in pH near the steel surface
and the change in cathodic reaction.

MECHANISM OF PROTECTIVE FILM FORMATION

DURING CO2 CORROSION OF CARBON STEEL 777777777
The precipitation rate is slow, and a high degree of supersaturation of iron carbonate in the water is
necessary in order to get sufficient amount of carbonate depositing on the steel surface.

The precipitation of FeCO, is facilitated by increased pH, increased temperature and by all measures which
can reduce the transport of reactants and corrosion products to and from the steel surface.

These films can be very thick as shown in Figure 1. The development of thick, non-protective porous films
is not only a laboratory effect, as similar films can be seen on steel exposed in the field, see Figure 2. The
films can grow for months without giving protection unless the steel is exposed at stagnant or wet
conditions. After a stagnant or wet period of a few days, corrosion rates are usually reduced 5-100 times, as
shown by the results in

That means that iron carbonate can precipitate and deposit on the surface if it is not removed successively
by the flow. Whether it deposits or not depends amongst other factors on the kinetics of precipitation and
on how it is anchored to the surface.

The influence of microstructure and chemical composition of

carbon and low alloy steels in CO2 corrosion.A state-of-the-art
appraisal 16 16 16

but different aspects are still uncertain and contradictory results can be found in the literature.
Approximately 60% of oilfield failures are related to CO2 corrosion mainly due to inadequate knowledgey
predictive capability and the poor resistance of carbon and low alloy steels to this type of corrosive attack
w1x.

From the materials cost point of view, the use of carbon and low alloy steel for tubbings and pipelines is
the most convenient option and, therefore, big efforts have been made in order to increase their corrosion
resistance.When the environment is too aggressive for bare carbon steels, the options to reduce corrosion
problems are the use of inhibitors or corrosion resistant alloys.

The corrosion rate will depend on the protectiveness of this scale. And the protectiveness of the surface
scale formed in CO2 saturated brines depend on the nature of the base alloy (composition, microstructure)
and on the properties of the environment (temperature, CO2 partial pressure, pH, etc.). The microstructure
is considered to have an important effect on how firmly the corrosion scale sticks to the surface.The
adherence of the corrosion product film, and hence its protectiveness, has often been related to
the presence of iron carbide and its morphology (laminar, globular, etc.).The idea is that the carbide phase
can strengthen the film and can anchor it to the steel substrate, then the size and distribution of these
carbides become very important w19,39,40x.However , the accumulation of carbides in the corrosion
product has been seen as the cause of increasing corrosion rate over time of exposure for ferritic perlitic
(FyP) steel
The authors describe two types of scales:
the primary scale, formed directly on the corroding
metal surface, which is non-compact, porous, with larger
crystals and well adhered, and a secondary scale which
can be formed on the top of the primary scale due to
the recrystallization of iron carbonate.The latter occurs
when the bulk solution reaches saturation in iron carbonate.
This secondary scale is compact, non-porous,
and detaches easily.

They showed that the combination of a Q and T martensitic microstructure with chromium content within
0.51 wt.% offered a better corrosion resistance than either this microstructural condition or the
combination of a Q and T bainitic and martensitic microstructure with little or no chromium
content (-0.1%).They stated that the role of the microstructure in improving the steel corrosion resistance
is not completely clear.

Ikeda et al. w50x showed that the addition of low concentrations of Cr to steels decreases the corrosion
rate (Fig.5 ).An analysis of the corrosion products was conducted and Cr enrichment was found.The
authors reported that the corrosion products were also adhesive, stiff and tough.

Cr content required to reduce corrosion rates was a function of the test temperature.At 60 8C, a beneficial
effect was obtained when the Cr content was above 1%, at 80 8C, a reduction in corrosion rate was
observed for Cr additions above 0.5% whilst 1% addition was required
to decrease the corrosion rate at 100 8C.

Using 3% Cr, 0.6% Si and Mo, V and Cu additions in a low carbon steel they obtained an improvement in
corrosion resistance of more than five times comparative to a standard X70 grade steel.

Effect of tempering temperature on microstructures and properties of

niobium and titanium microalloying low carbon bainite steel Defa Li 1,2,a ,
Feng Huang 3,b , Shisen Wang 1,c, Yuzhang Xiong 1,d, Shuqing Xing2,e,
Tao Xiong1,

Dugstad et al. w19x analysed the effect of the steel microstructure on corrosion rate and protective iron
carbonate film formation.They heat treated three lowalloyed carbon steels, St52, Cr0.87 and Cr0.53 (Table
1), and used a corrosion flow loop at 80 8C to conduct the tests.The experiments were performed in
chloride free solutions at 2 bar CO2 pressure and pH 5.8 during two weeks.In some cases, a 0.1% NaCl
solution was employed to improve conductivity.The corrosion rate was determined by means of weight
loss.
From the observed results, the authors concluded that the corrosion behavior of St52 steel was very
dependent on the heat treatment.The adherence of the corrosion product film was higher in the quenched
samples.The
austenited and quenched samples containing no carbides,
the as received samples (FyP) and the spheroidized
coupons that contained the largest carbides showed
corrosion rates lower than those of the Q and T samples.
However, an increase in the tempering temperature for
the quenched samples lead to a decrease in the corrosion
rate.No protective corrosion film was formed on the Fy
P (used-as-received steel) and the spherodized steel
coupons with the largest carbides. Corrosion films with protective properties were
formed on all the heat treated chromium containing steel

CO2 corrosion resistance of carbon steel in relation with

microstructure changes 434343
Nathalie Ochoa a, * , Carlos Vega a, Nadine P_eb_ere b, Jacques Lacaze b, Joaqun L.
Brito c
Electrochemical results revealed that corrosion resistance
increased in the following order: B < N < Q&T < A. From the polarization curves it was shown that
specifically, cathodic current densities were affected by microstructural changes. SEM images indicated
that ferrite dissolved earlier than cementite and a thin layer of corrosion products was deposited on the
steel surface. XPS analyses revealed that this layer was composed of a mixture of iron carbonate and nondissolved
cementite. It was also found that the quantity of FeCO 3 content on the steel surface was greater
for Q&T and A microstructures. These results, in agreement with the electrochemical data, indicate that
the deposition mechanism of iron carbonate is closely related to the morphology of the non-dissolved
cementite, determining the protective properties of the corrosion product layers.
Thus, some authors have found that the corrosion resistance of carbon steels with a ferritic/pearlitic
microstructure was higher
than that reached with martensitic steels, whereas other studies have reported the opposite [1e4]. However, as
pointed out by Lopez
et al. [1], results from these studies are not comparable because the experimental conditions were different.

Some authors [2,3,5,11e16] have found that the steel microstructure plays an important role on the adherence
of the corrosion
products which mainly consist of iron carbonate (FeCO3). Several authors have associated the protective
properties of the carbonate
films to the anchoring effect provided by iron carbide (Fe 3C) [1,2,11,12]; indeed, during the exposure time, the
ferritic phase
dissolves whereas iron carbide (contained in the pearlite) are highlighted. This effect is a consequence of the
galvanic coupling
that occurs between these micro-constituents: ferrite acts as anodic site whereas cementite acts as a cathode
[17,18]. However,
the role of these two components on the stability and on the protective properties of the corrosion product
layers is not well
understood. {Bhadeshia, 2015 #977}
Carbon Dioxide Corrosion in Oil and Gas
ProductionA Compendium
M.B. Kermani,* and A. Morshed** 2222222222222222

While most authors have reported the beneficial

effects of chromium additions,26,29,42-45,68-79 there is not
yet a consensus on the optimum amount of Cr in the
steel structure. Apart from Cr, molybdenum has been
found to improve the corrosion resistance of carbon
steels.42 In a related work, Videm and Dugstad23
showed that small amounts of Cu, Ni, Cr (and possibly
Mo) increases the corrosion potential of carbon
steels, making it more noble. However, Cu additions
may have a side effect on inhibitor efficiency as reported
by Gulbrandsen and Nyborg.43

Work by Kermani and coworkers44,80 has paved

the way to developing an optimum metallurgy of
carbon and low-alloy steels for both downhole and
transportation facilities through addition of microalloying
elements like V, Ti, Mo, Cu, and Cr.

The development of novel carbon and lowalloy

steels with superior resistance to CO2 corrosion
using metallurgical conditioning recently has been
made in the laboratory and subsequently by industrial
casts covering a wide range of parameters including
microalloying constituents, heat treatment
processing, and steel production scenarios.

An overview of these categories are presented

schematically in Figure 6, illustrating a progressive
reduction in corrosion rate with increasing Cr content,
the extent of which is subject to other alloying
constituents and heat treatment.
While 3% Cr proved to offer a 10-times reduction
in corrosion rate, 1.5% Cr was not sufficient to ensure
this level of resistance. The optimum level of Cr
addition was not determined, albeit a level between
2% to 3% Cr was considered essential to achieve the
expected improvement in corrosion performance subject
to additional microalloying constituents.

Cr is effective above a certain level, below which it is detrimental to the anodic reaction on bare
steel. Inconsistency in the corrosion
performance of low-Cr-containing steels has
been experienced by a number of operators.8-9,73,76
The data demonstrated that the calculated value
of free Cr and V, generally, proved to be good indicators
of CO2 corrosion performancenevertheless,
microalloying constituents and resultant microstructure
have influential and complementary roles