CORROSION ENGINEERING SECTION
Effect of Microstructure on Corrosion of Steels
in Aqueous Solutions Containing Carbon Dioxide
S. Al-Hassan,* B. Mishra, D.L. Olson,** and M.M. Salama***
ABSTRACT
The influence of microstructure on the corrosion rate of steels
in a carbon dioxide (CO2)-containing aqueous solution was
measured experimentally as a function of pH, temperature,
and partial pressure of CO2 . An attempt was made to quan-
tify and relate the microstructure to the corrosion rate. The
effect of alloy microstructure was increasingly evident at
temperatures up to 60C but diminished above 60C. The
corrosion rate increased with temperature in the activation-
controlled regime, where a nonprotective iron carbonate
(FeCO3) scale formed. Diffusion-controlled corrosion through
a stable scale of iron hydroxycarbonate (Fe2[OH]2CO3) was
responsible for lowering the corrosion rate above 60C.
Under a diffusion-controlled corrosion mechanism, micro-
structure of the steel had no effect on corrosion rate.
KEY WORDS: activation, activation energy, carbon steel,
carbon dioxide corrosion, diffusion, iron carbonate, iron
hydroxycarbonate, microstructure, steel, temperature
INTRODUCTION
The role of various environmental and metallurgical
factors on corrosion of iron in carbon dioxide (CO2)-
bearing aqueous solutions has been the subject of
several comprehensive reviews.1-2 DeWaard and
Submitted for publication April 1997; in revised form, September
1997.
* Institute of Paper Science and Technology, 500 10th St., NW,
Atlanta, GA 30318.
** Center for Welding, Joining, and Coatings Research, Department
of Metallurgical and Materials Engineering, Colorado School of
Mines, Golden, CO 80401.
*** Product Research and Development, Conoco, Inc., Ponca City. OK
74603.
0010-9312/98/000107/$5.00+$0.50/0
480 1998, NACE International
Milliams3 suggested a mechanism where corrosion in
this environment proceeds in a catalytic way by di-
rect reduction of carbonic acid (H2CO3) and in which
the charge-transfer reaction is the rate-determining
step. Another study has shown that the corrosion
rate increases with an increase in bicarbonate ion
concentration.4-5 Several equations have been devel-
oped empirically to relate the corrosion rate to the
partial pressure of CO2 (PCO2), temperature, and pH of
the solution.6-9 These studies are helpful in the oil
and natural gas industry in estimating corrosion
behavior if the applied material properties and the
environmental parameters are identical to those in
the study.
For an activation-controlled mechanism of
corrosion, which is applicable below 60C in a CO2-
saturated solution at atmospheric pressure, a
corrosion rate equation has been developed for iron
alloys using the fundamental reaction rate theory.10
Equation (1) is expressed in terms of only three pro-
cess variables: pH, temperature, and PCO2:
Corrosionrate = C pH PCO e Q/kT
1.33 0.67
(1)
2
where k is the Boltzmann constant, T is the absolute
temperature, and Q is the activation energy for the
corrosion reaction.
Equation (1) compares very well with most of the
empirical relationships developed within a restricted
range of T, pH, and PCO2 values.10 The equation allows
the inclusion of other variables, such as flow, impuri-
ties, inhibitors, and steel microstructure through the
CORROSIONJUNE 1998

TABLE 1
Chemical Composition of Tested Plain Carbon and Alloyed Steels
Alloy C Mn
X-52 0.14 1.26
2.25% Cr-1% Mo 0.08 0.83
Type 1080 0.78 1.26
reaction constant (C). To study the effect of any one
variable on corrosion rate, all other parameters must
be held constant. The limit of application for this
equation extends up to the point where corrosion
becomes controlled by diffusion as a result of the
formation of stable corrosion products on the steel
surface.
The present work describes experimental work
conducted with the steel microstructure as the pro-
cess variable. The influence of microstructure on C
in Equation (1) was measured quantitatively. Micro-
structure is a controllable variable that can be
modified to improve corrosion resistance of steels.
Microstructure also can be described in terms of its
chemical composition and heat treatment.
Corrosion Product
Earlier work has shown that different phases in
a steel microstructure provide sites for anodic and
cathodic reactions.11 Thus, it is reasonable to expect
that the shape, size, and distribution of these phases
affect the corrosion rate. It has been reported that
iron carbide (i.e., cementite [Fe3C]) was the only con-
stituent of the corrosion product found in a failed
steel check valve, and a corrosion mechanism was
suggested accordingly.12 It later was confirmed that
Fe3C was not the corrosion product but merely ex-
isted in the scale as a result of its presence in the
steel as the cathodic site. The main end product of
corrosion of iron in this environment has been deter-
mined as iron carbonate (FeCO3), the solubility of
which decreases with temperature and increases
with CO2 pressure.13 FeCO3 has been reported to be
nonprotective below 60C,2 containing voids and
grain boundaries.14 Above 60C, protectiveness has
been said to increase with temperature.15 Another
study placed this transition temperature at 90C,
below which the corrosion rate increased steadily,6
even with FeCO3 precipitation. Above 100C, iron
oxides (Fe3O4 and then Fe2O3) have been said to
form. FeCO3 codeposition with Fe3O4 is considered
hazardous.16 Iron bicarbonate (Fe[HCO3]2) was
identified in one study as the primary corrosion
product.17
(1)
American Petroleum Institute, 1220 L. St., NW, Washington, DC
20005.
(2)
UNS numbers are listed in Metals and Alloys in the Unified
Numbering System, published by the Society of Automotive
Engineers (SAE) and cosponsored by ASTM.
CORROSIONVol. 54, No. 6
CORROSION ENGINEERING SECTION
Si S P Others
0.22 0.002 0.018 Nb 0.022
0.52 0.006 0.022 Cr 2.3, Mo 1.37
0.22 0.020 0.03
Chromium oxide (Cr2O3) is said to form on
duplex and martensitic stainless steels (SS) at high
temperature, and CO2 has little effect on the film
structure. It has been reported that chromium in
steels dissolves to form a complex ion (CrO42) and
that the thickness of the chromium-containing oxide
is independent of pH.18 For general corrosion pur-
poses, the addition of chromium in iron steadily
decreases corrosion rate by forming the passive film
and lowering the anodic dissolution rate in active
state. This decreased corrosion rate is strongly de-
pendent upon chromium content up to 20 wt%.19-20
It is commonly known that a tempered martensi-
tic structure etches faster than an annealed
structure. As the tempering temperature of marten-
site increases, the corrosion rate decreases, in the
temperature range where Fe3C starts to precipitate
and coarsen.21 However, another study showed that
the corrosion rate of tempered eutectoid steel pro-
duced three peaks at 260C, 340C, and 440C
where hardness showed inflexions.22 Carbon and
low-hardenable steels are most resistant when
quenched and tempered or double-tempered to form
martensite in the (Rockwell) hardness range of HRC
22 maximum.23
EXPERIMENTAL
API(1) X-52 line pipe steel (UNS G10220),(2) type
1080 eutectoid steel (UNS G10800), 2.25% Cr-1% Mo
alloy steel (UNS J22090), and pure iron (99.99%
[UNS K00095]) were used for corrosion tests under
atmospheric pressure in CO2-saturated synthetic
brine solution as a function of temperature. Nominal
chemical compositions for the three steels are given
in Table 1. Table 2 lists the heat treatments applied
and the test temperatures used. A wide range of
microstructures were obtained as a result of the dif-
ferent heat treatments and chemical compositions.
Corrosion test coupons of 38 mm by 38 mm by
6.4 mm (1.5 in. by 1.5 in. by 0.125 in., surface area
in the range of 3,500 mm2 to 4,000 mm2 [5.4 in.2 to
6.2 in.2]) were machined from each material and pol-
ished to 400-grit finish. The samples were cleaned in
acetone and subsequently dried and weighed with an
accuracy of 104 g. The solution volume-to-surface
area ratio was held constant at 4.4 mL/mm2.
Specimens were immersed in the solution for 100 h,
200 h, 400 h, and 800 h of exposure. Temperature
481
CORROSION ENGINEERING SECTION

TABLE 2
Heat Treatments and Corrosion Test Temperatures for Steel Specimens(A)

X-52 2 .25% Cr-1% Mo Type 1080 Pure Iron

As-received; TMCP As-received; TMCP Quenched Normalized

760C/1 h; OQ 920C/1 h; AC

Normalized Normalized Normalized Normalized

950C/2 h; AC 950C/2 h; AC 760C/1 h; AC 960C/1 h; AC

Annealed Annealed Normalized

875C/2 h; FC 875C/2 h; FC 760C/1 h; FC
50C/h

Quenched and tempered Quenched and tempered Annealed

950C/1 h, WQ 950C/1 h, WQ 760C/1 h; FC
350C temper; AC 350C temper; AC 15C/h

Quenched and tempered Quenched and tempered

950C/1 h, WQ 950C/1 h, WQ
400C temper; AC 400C temper; AC

Quenched and tempered Quenched and tempered

950C/1 h, WQ 950C/1 h, WQ
475C temper; AC 475C temper; AC

Test temperatures Test temperatures Test temperatures Test temperatures

25C, 38C, 51C, 58C, and 65C 25C, 51C, and 65C 25C and 51C 25C and 51C

(A)
AC, air-cooled; FC, furnace-cooled; WQ, water-quenched; and OQ, oil-quenched.

was controlled to within 2C. Standard procedure
was used to clean the scale following the exposure
test, and the sample weight losses were recorded.
Synthetic brine solution for each experiment was
prepared by dissolving commercial sodium chloride
(noniodized NaCl) with tap water to make 3 wt%
solution. CO2 gas was allowed to bubble in the solu-
tion at least 24 h to ensure total saturation prior to
the tests. The pH of the solution was 5.0 at the start
of the experiments but gradually stabilized at 5.4
over the 800-h duration.
Weight loss experiments were conducted in a
polytetrafluoroethylene-lined cabinet (0.43-m3
[15-gal] volume) equipped with a water jacket to
control the solution temperature up to 70C. The
experimental solution was isolated from the outside
environment by water sealing the cabinet cover. The
pressure inside the cabinet could not exceed the
atmospheric pressure. CO2 gas was allowed to bubble
in the solution at a slow flow rate to ensure total
saturation through the entire experiment.
RESULTS
The weight loss of X-52 steel in all the heat-
treated conditions increased with increasing
temperature (Figures 1[a] through [d]), which indi-
cated dissolution of iron was the primary process,
particularly in the initial periods of exposure (i.e.,
200 h). At a fixed temperature, weight losses of steels
heat-treated differently showed a general trend in
that the annealed specimen corroded the least, and
the as-received material (thermomechanically pro-
cessed) corroded the most, while the quenched and
tempered group of steel coupons showed corrosion
rates in between the two extremes. Results also
showed that the higher the tempering temperature,
the lower was the weight loss. Normalized specimens
corroded at a rate closer to the as-received specimen
(Figures 1[b] and [c]).
At higher periods of exposure (i.e., 400 h), weight
loss increased, showing stronger influence of the
microstructure, even with the detection of scale pre-
cipitation of FeCO3 at 51C. This observation implied
that FeCO3 precipitated under these conditions was
not protective. This situation continued up to 800 h
of exposure (Figure 1[b]). However, at 58C and 65C,
the corrosion rate started to decrease. The compara-
tive decrease in corrosion rate was significant at 65C,
where a parabolic rate of corrosion was evident, as
opposed to the linear rate at lower temperatures. The
decrease in the corrosion rate at 65C along with a
parabolic rate of corrosion coincided with the detec-
tion of iron hydroxycarbonate (Fe2[OH]2CO3) at 800 h
of exposure time. Figure 2 shows the x-ray diffraction
(XRD) analysis, which suggested that, as a result of
the formation of Fe2(OH)2CO3, or the conversion of
FeCO3 to Fe2(OH)2CO3, the scale started to become

482 CORROSIONJUNE 1998


(a)
(c)
FIGURE 1. Weight loss in CO2-containing aqueous solutions for X-52 steel as a function of time at: (a) 38C, (b) 51C,
(c) 58C, and (d) 65C.
more protective. Furthermore, it was evident that the
scale incorporated the Fe3C phase into it from the
steel after the dissolution of iron from the ferrite
phase. Also, as the tempering temperature of the
quenched samples increased, higher incorporation of
Fe3C was expected.
The effect of heat treatment or microstructure for
X-52 grade steel increased with temperature from
CORROSIONVol. 54, No. 6
CORROSION ENGINEERING SECTION
(b)
(d)
25C to 51C. This effect started to diminish at 58C
and above, as Fe2(OH)2CO3 started to form and
thicken. This observation suggested Fe2(OH)2CO3 was
more adherent, protective, and therefore, more effec-
tive in reducing the corrosion rate than FeCO3.
The 2.25% Cr-1% Mo steel was tested at two
temperatures (25C and 51C). Weight-loss measure-
ments are shown in Figures 3(a) and (b), respectively.
483
CORROSION ENGINEERING SECTION

FIGURE 2. XRD analysis of corrosion scale formed on X-52 steel in

normalized condition after 400 h of exposure at 65C and 51C
temperatures.

The 2.25% Cr-1% Mo steel corroded, without excep-

tion, at rates lower than that of the X-52 steel. The
weight loss in 2.25% Cr-1% Mo samples increased as
temperature increased. The effect of microstructure
also was greater at the higher temperature of 51C. (a)
The sequence of heat-treated microstructures in
order of corrosion resistance in 2.25% Cr-1% Mo
steel differed from that of X-52 steel (compare
Figures 1 and 3). The quenched and tempered group
corroded at the lowest rate, while the annealed speci-
mens corroded at the highest rate. This observation
was sharper at 51C (Figure 3[b]).
The weight loss in pure -iron and type 1080
eutectoid steel at 25C and 51C is shown in Figures
4(a) and (b). Both alloys corroded at a higher rate at
51C than at 25C, which was similar in trend to the
X-52 steel. In eutectoid steel, quenched samples
corroded at higher rates at both temperatures during
early stages of exposure (up to 400 h at 25C and up
to 200 h at 51C), while specimens normalized in air
and normalized in a furnace corroded at the lowest
rates (up to 400 h at 25C and up to 200 h at 51C).
The onset of the diffusion-controlled parabolic rate of
corrosion in eutectoid steel occurred at the relatively
lower temperature of 51C when compared with the
X-52 steel, where a clear shift in the corrosion mode
was observed only above 60C. This observation
implied that microstructural features in the eutectoid
steel enhanced adherence of the scale and made it
somewhat protective even at lower temperatures. (b)
Microstructures in eutectoid steel at 25C FIGURE 3. Weight loss in CO2-containing aqueous solutions for
showed a similar effect as in the X-52 steel at 51C, 2.25% Cr-1% Mo steel as a function of time at: (a) 25C and (b) 51C.
with quenched samples corroding at lower rates. This
effect resulted from the role of the microstructure in
improving FeCO3 protectiveness. Normalized-in-air X-52 steel, FeCO3 was not protective. At 51C, FeCO3
and normalized-in-furnace samples corroded at clearly precipitated.
similar rates at both temperatures, with the differ- Pure iron at both 25C and 51C and in both
ence in weight loss increasing with prolonged heat-treated conditions corroded at far lower rates
exposure. For eutectoid steel at 25C, as with the than any alloy steel, which showed the effect of

484 CORROSIONJUNE 1998


(a)
FIGURE 4. Weight loss in CO2-containing aqueous solutions for type 1080 and pure -iron samples as a function of time
at: (a) 25C and (b) 51C.
carbon content on corrosion of ferrite. However, the
weight loss of iron heat-treated at 920C was slightly
higher than at 960C. This effect, again, increased
with prolonged exposure and with higher tempera-
ture. For pure iron, there was no scale on specimens
at any exposure time at either testing temperature.
Figures 5 through 7 show the optical photomicro-
graphs of differently heat-treated samples of X-52
line pipe steel, 2.25% Cr-1% Mo low-alloy steel,
and type 1080 eutectoid steel and pure iron,
respectively.
Application of Corrosion Rate Model
Plotting Arrhenius curves for the corrosion rate
in mm/y as a function of the temperature of the test
solution for different heat treatments in alloys al-
lowed the determination of the activation free energy
(G*) for the corrosion reaction. These plots for X-52
steel under different heat-treatment conditions are
shown in Figures 8(a) and (b). Average values of G*
calculated from the slope of the lines are given in
Table 3.
Using the process variables of solution tempera-
ture, pH, and PCO2, the calculated values of G*, and
the measured corrosion rate, the values of C in
Equation (1) were calculated (Table 4). These values
were an average over the range of temperatures
tested. It was clear that C was a strong function of
the steel microstructure. The magnitude of these
constants was a measure of the effect of any particu-
CORROSIONVol. 54, No. 6
CORROSION ENGINEERING SECTION
(b)
lar microstructure on corrosion. A relationship, thus,
could be established if the microstructure was quan-
tified in terms of the phases present.
Annealed samples of X-52 steel showed the low-
est effect, while the as-received thermomechanically
control-processed (TMCP) samples showed the largest
effect. Microstructures of the alloy steels showed a
significantly higher influence on corrosion rate, as
compared with the pure iron (Table 4).
DISCUSSION
It is well established that Fe3C is more cathodic
than ferrite and has a lower overpotential for hydro-
gen evolution.21 This leads to microgalvanic cells to
be formed between Fe3C and ferrite, resulting in
selective attacks at and around pearlite bands.24
However, it has been observed that, under certain
conditions, segregation results in more efficient
cathodic sites along the ferrite/Fe3C interfaces. Thus,
it was understandable that the pearlite distribution
in the normalized specimen increased the area of
contact between the pearlite and ferrite grains,
since the proeutectoid ferrite is more refined in an
annealed specimen than in a normalized one.25 The
normalized specimen had reduced amounts of
proeutectoid ferrite, which consequently increased
the pearlite phase. These factors contributed to the
higher corrosion rate in the normalized specimen
than the annealed sample (Figure 1). The higher rate
485
CORROSION ENGINEERING SECTION
(a)
(c)
(e)
FIGURE 5. Optical photomicrograph of X-52 steel in: (a) as-received, (b) normalized, (c) annealed, and (d) through
(f) quenched and tempered conditions.
of weight loss of as-received TMCP steel was a result
of the fact that hot-working induced mechanical
deformation in the steel which deformed and crushed
the pearlite phase into the softer ferrite matrix as
bainite.
In quenched and tempered specimens, as car-
bide coarsens in the temperature range of 350C to
475C, coarser particles have smaller surface area
than fine particles for any given surface area-solution
interface and for a given carbon content of the alloy.
Figure 1 suggests that, although quenched and tem-
pered samples initially corroded at a higher rate, the
486
(b)
(d)
(f)
corrosion rate was virtually constant over the test
duration. Samples with ferrite/pearlite microstruc-
tures in the as-received and normalized heat
treatment conditions showed a faster rate of corro-
sion at later periods of exposure. This phenomenon
in pearlite/ferrite microstructures was attributed to
the fact that the more the samples (ferrite) corroded,
the higher was the exposure of Fe3C to the solution,
leading to larger cathodic sites in the microcells.
Annealed samples, with their banded structure of
pearlite/ferrite, however, deviated from this trend
and corroded at the lowest rate. This behavior sug-
CORROSIONJUNE 1998

(a)
(c)
(e)
FIGURE 6. Optical photomicrograph of 2.25% Cr-1% Mo low-alloy steel in: (a) as-received, (b) normalized, (c) annealed,
and (d) through (f) quenched and tempered conditions.
gested the surface area of contact between pearlite
and ferrite (i.e., pearlite distribution heat-
treatment) was more important in determining the
alloy corrosion rate than the contact area between
pearlite and the solution (i.e., pearlite proturbance
into solution time of exposure).
The quenched and tempered samples corroded
at the lowest rate in 2.25% Cr-1% Mo steel, while the
annealed specimen showed the highest rate of corro-
sion. This observation was sharper at 51C compared
to the lower temperatures. Metallurgically, the alloy-
ing elements in steel increased the time required for
CORROSIONVol. 54, No. 6
CORROSION ENGINEERING SECTION
(b)
(d)
(f)
austenite to decompose to ferrite and/or a ferrite-
Fe3C mixture, and, therefore, made it possible for the
martensite or bainite to form at lower cooling rates.26
In the quenched and tempered samples, chromium
and molybdenum delayed and retarded the decompo-
sition of martensite into ferrite and carbides upon
tempering, since these atoms have to diffuse to form
carbides, which is a very sluggish process. The nor-
malized specimen corroded at a rate lower than the
annealed steel because the former contained a lower
percentage of Fe3C. In addition, the time allowed to
form carbides of alloying elements in annealed speci-
487
CORROSION ENGINEERING SECTION

(a) (b)

(c) (d)

(e) (f)
FIGURE 7. Optical photomicrograph of type 1080 steel in: (a) normalized-in-air, (b) normalized-in-furnace, (c) annealed,
and (d) quenched conditions and for pure iron in (e) 920C normalized and (f) 960C normalized conditions.

men was greater, which depleted the alloy from its
protective elements.
For the type 1080 eutectoid steel, the samples
normalized in air and in the furnace corroded at
similar rates at 25C and 51C, showing the effect of
cooling rate on pearlite lamellae spacing, specially
during the initial exposure and prior to the scale
precipitation. For pure iron, heat-treated samples
corroded at rates far lower at 25C and 51C than
any of the alloy steel samples, showing the effect of
carbon and other interstitials, as well as other alloy-
ing elements (e.g., chromium, molybdenum, nickel,
etc.) on the corrosion of ferrite. However, the weight
loss in iron heat-treated at 920C was slightly higher
than the sample heat-treated at 960C. This effect
increased with time and temperature of exposure.
This phenomenon was attributed to the decrease in
the grain-boundary area when iron was heat-treated
at the higher temperature of 960C. The grain
boundary was thought to be cathodic in pure iron to
the ferrite grains.
The analyses conducted on corrosion scales by
XRD determined that FeCO3 was the end product
when saturation requirements were met. However, it

488 CORROSIONJUNE 1998


(a)
FIGURE 8. Arnhenius plot to determine G* for corrosion of X-52 steel in CO2-containing aqueous solutions.
was clear that more ferrous ions had to be produced
than the saturation requirement before a protective,
passive film could form. Thus, it was concluded that,
to precipitate FeCO3, the product of [Fe2+] x [CO32]
must exceed the thermodynamic saturation limit
beyond the supersaturation condition.27-28 This ex-
plained why the FeCO3 precipitates formed at low
temperature need a longer time to develop a protec-
tive scale. This observation supported the result that
FeCO3 was not seen to form at low temperatures.
Also, it did not decrease the corrosion rate when it
formed at higher temperatures. Fe3C was left behind
after the ferrite dissolution in steels. The existence of
Fe2(OH)2CO3 scale at 58C and 65C was protective,
which caused a decrease in the corrosion rate.
Fe2(OH)2CO3 may be considered a mixed transition
phase, if written as FeCO3Fe(OH)2, between nonpro-
tective FeCO3 and ferrous hydroxide (FeOH2). Ferrous
oxide (FeO) acts as a precursor for more protective
magnetite scales at even higher temperatures.
Analysis of scales on 2.25% Cr-1% Mo steel
showed an amorphous nature on XRD. Films with
vitreous structure are promoted by bond flexibility,
and Cr is a good glass former since its oxides have
good bond flexibility. It has been reported that gel-like
film is likely to form on iron-chromium alloys before
complete passivation by crystalline Cr2O3 oxide.29
Scales on type 1080 steel were similar to those
on X-52 samples, while very thin scale formed on
pure iron, with no evidence of FeCO3 even at 51C. It
CORROSIONVol. 54, No. 6
CORROSION ENGINEERING SECTION
(b)
has been reported that high level of supersaturation
is required for initial scale formation.
The constant C in Equation (1) can be expressed
in terms of the microstructure by quantifying the
volume fractions and distribution of the phases in
plain carbon steels. For alloyed steels, a chemical
composition term, similar to carbon equivalent,
may be more appropriate. Measured corrosion rates
supported this idea since the weight loss in X-52 was
considerably lower than in type 1080 eutectoid steel
under identical test conditions. However, the pres-
ence of chromium and molybdenum in 2.25% Cr-1%
Mo steel protected the bainitic structure from corrod-
ing at a high rate.
G* for corrosion and the value of the constant
C are shown in Tables 3 and 4. G* required for cor-
rosion in carbon and alloyed steels was significantly
higher than the pure iron material, which was con-
sistent with the fact that corrosion in pure metals is
very low. The effect of carbon could be shown quali-
tatively (Figure 9) by plotting the corrosion rates of
X-52 and type 1080 steel grades in the quenched
condition as a function of carbon equivalent (Pcm).
Extrapolation of the lines on Figure 9 to a zero car-
bon level (i.e., ferrite phase) revealed corrosion rates
similar to those measured on the pure iron samples
(Figure 4). Figure 9 also shows that the slope of the
line at 51C was greater than that at 25C. Figure 9
indicates that the effect of the principal elements,
especially C, increased with temperature.
489
CORROSION ENGINEERING SECTION

TABLE 3
G* for Corrosion in CO2-Containing Aqueous Solutions

Free Energy
Material (kcal/mol)

X-52 15.205
2.25% Cr-1% Mo 15.175
Iron 9.935
Type 1080 16.175

It is suggested that expressions such as

Equation (2) can be derived to measure the micro-
structural effect of steel on corrosion rate:

C = C* 1.0 10 % + 8.7 10 %p + 3.9 10 %m

17 18 17
(2)

where C* is a new constant incorporating factors

other than microstructure; and , p, and m are the
volume fractions of ferrite, pearlite, and martensite,
respectively. Equation (2) can be refined further to
show the effect of other phases, such as bainite, and
the effect of grain sizes and shapes, etc. Equation (2)
is suggested only as one possible way of quantifying
the microstructure and incorporating it into the cor-
rosion rate Equation (1). The limited volume fraction
data, shown in Table 4, have been used to develop
Equation (2). The value of the constants in Table 4
shows the relative susceptibility of type 1080 steel to
corrosion in CO2-containing solutions. However,
2.25% Cr-1% Mo steel indicated relative resistance.
FIGURE 9. Corrosion rate as a function of carbon content in steels.
Usually, the required mechanical properties in the
steel dictate the choice of heat treatment and not the
corrosion resistance. Furthermore, the improvement
in corrosion resistance derived by a change in heat
treatment must be significant to justify it. However,
this work provides a useful guide for the industry in
making such decisions.

TABLE 4
Corrosion Rate Constant C for Different Steels(A)
Steel Heat Treatment/Microstructure C

X-52 As-received/10% P + 90% F 2.97 x 1017

Normalized/8% P + 92% F 3.47 x 1016
Annealed/9% P + 91% F 9.36 x 1015
Q&T 350/tempered M 2.77 x 1017
Q&T 400/tempered M 1.09 x 1016
Q&T 475/tempered M 2.46 x 1017

-Iron Normalized 920C/100% F 1.30 x 1012

Normalized 960C/100% F 9.00 x 1012

Type 1080 Normalized-Air/100% P 1.14 x 1017

Normalized-Furnace/100% P 7.00 x 1018
Annealed/100% P 8.70 x 1018
Quenched/100% M 3.90 x 1017

2.25% Cr-1% Mo As-received/100% B 1.90 x 1016

Normalized/50% B + 50% F 3.20 x 1016
Annealed/6% P + 94% F 5.10 x 1016
Q&T350/tempered B 1.10 x 1016
Q&T400/tempered B 3.20 x 1016
Q&T475/tempered B 1.20 x 1016

(A)
PCO20.67 = 0.877; [H+]1.33 = 7.2 x 107; T = 25C to 58C; F, ferrite; P, pearlite; M, martensite; and B, bainite.

490 CORROSIONJUNE 1998

 CORROSION ENGINEERING SECTION

CONCLUSIONS 3. C. DeWaard, D.E. Milliams, Corrosion 31, 5 (1975): p. 177.

The microstructure and chemical composition of
an alloy was shown to play a role in determining the
corrosion rate in CO2-containing aqueous solutions.
Plain carbon steels corroded at a higher rate than a
chromium-molybdenum alloyed steel. Pure iron
showed the lowest rate of corrosion. Corrosion rate
also increased with an increase in carbon.
The corrosion rate of steels increased with tem-
perature in the region where corrosion was
activation-controlled. The microstructural effect on
corrosion also increased with temperature.
For plain carbon steels, the shape and distribution
of ferrite and Fe3C, resulting from different heat
treatments, influenced the corrosion rate. For chro-
mium-molybdenum steel, the alloying elements
greatly reduced the corrosion rate by directly protect-
ing the alloy and preventing the formation of Fe3C.
FeCO3 precipitates by complex supersaturation
process within the adjacent solution. FeCO3 reached
saturation in between pearlite lamellae, which helped
to anchor the corrosion scale to the specimen. The
corrosion rate started to decrease with the detection
of Fe2(OH)2CO3 at temperatures above 60C.
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