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480 1998, NACE International CORROSIONJUNE 1998
CORROSION ENGINEERING SECTION
TABLE 1
Chemical Composition of Tested Plain Carbon and Alloyed Steels
Alloy C Mn Si S P Others
reaction constant (C). To study the effect of any one Chromium oxide (Cr2O3) is said to form on
variable on corrosion rate, all other parameters must duplex and martensitic stainless steels (SS) at high
be held constant. The limit of application for this temperature, and CO2 has little effect on the film
equation extends up to the point where corrosion structure. It has been reported that chromium in
becomes controlled by diffusion as a result of the steels dissolves to form a complex ion (CrO42) and
formation of stable corrosion products on the steel that the thickness of the chromium-containing oxide
surface. is independent of pH.18 For general corrosion pur-
The present work describes experimental work poses, the addition of chromium in iron steadily
conducted with the steel microstructure as the pro- decreases corrosion rate by forming the passive film
cess variable. The influence of microstructure on C and lowering the anodic dissolution rate in active
in Equation (1) was measured quantitatively. Micro- state. This decreased corrosion rate is strongly de-
structure is a controllable variable that can be pendent upon chromium content up to 20 wt%.19-20
modified to improve corrosion resistance of steels. It is commonly known that a tempered martensi-
Microstructure also can be described in terms of its tic structure etches faster than an annealed
chemical composition and heat treatment. structure. As the tempering temperature of marten-
site increases, the corrosion rate decreases, in the
Corrosion Product temperature range where Fe3C starts to precipitate
Earlier work has shown that different phases in and coarsen.21 However, another study showed that
a steel microstructure provide sites for anodic and the corrosion rate of tempered eutectoid steel pro-
cathodic reactions.11 Thus, it is reasonable to expect duced three peaks at 260C, 340C, and 440C
that the shape, size, and distribution of these phases where hardness showed inflexions.22 Carbon and
affect the corrosion rate. It has been reported that low-hardenable steels are most resistant when
iron carbide (i.e., cementite [Fe3C]) was the only con- quenched and tempered or double-tempered to form
stituent of the corrosion product found in a failed martensite in the (Rockwell) hardness range of HRC
steel check valve, and a corrosion mechanism was 22 maximum.23
suggested accordingly.12 It later was confirmed that
Fe3C was not the corrosion product but merely ex- EXPERIMENTAL
isted in the scale as a result of its presence in the
steel as the cathodic site. The main end product of API(1) X-52 line pipe steel (UNS G10220),(2) type
corrosion of iron in this environment has been deter- 1080 eutectoid steel (UNS G10800), 2.25% Cr-1% Mo
mined as iron carbonate (FeCO3), the solubility of alloy steel (UNS J22090), and pure iron (99.99%
which decreases with temperature and increases [UNS K00095]) were used for corrosion tests under
with CO2 pressure.13 FeCO3 has been reported to be atmospheric pressure in CO2-saturated synthetic
nonprotective below 60C,2 containing voids and brine solution as a function of temperature. Nominal
grain boundaries.14 Above 60C, protectiveness has chemical compositions for the three steels are given
been said to increase with temperature.15 Another in Table 1. Table 2 lists the heat treatments applied
study placed this transition temperature at 90C, and the test temperatures used. A wide range of
below which the corrosion rate increased steadily,6 microstructures were obtained as a result of the dif-
even with FeCO3 precipitation. Above 100C, iron ferent heat treatments and chemical compositions.
oxides (Fe3O4 and then Fe2O3) have been said to Corrosion test coupons of 38 mm by 38 mm by
form. FeCO3 codeposition with Fe3O4 is considered 6.4 mm (1.5 in. by 1.5 in. by 0.125 in., surface area
hazardous.16 Iron bicarbonate (Fe[HCO3]2) was in the range of 3,500 mm2 to 4,000 mm2 [5.4 in.2 to
identified in one study as the primary corrosion 6.2 in.2]) were machined from each material and pol-
product.17 ished to 400-grit finish. The samples were cleaned in
acetone and subsequently dried and weighed with an
(1)
American Petroleum Institute, 1220 L. St., NW, Washington, DC accuracy of 104 g. The solution volume-to-surface
20005. area ratio was held constant at 4.4 mL/mm2.
(2)
UNS numbers are listed in Metals and Alloys in the Unified
Numbering System, published by the Society of Automotive Specimens were immersed in the solution for 100 h,
Engineers (SAE) and cosponsored by ASTM. 200 h, 400 h, and 800 h of exposure. Temperature
TABLE 2
Heat Treatments and Corrosion Test Temperatures for Steel Specimens(A)
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 200 h). At a fixed temperature, weight losses of steels
was used to clean the scale following the exposure heat-treated differently showed a general trend in
test, and the sample weight losses were recorded. that the annealed specimen corroded the least, and
Synthetic brine solution for each experiment was the as-received material (thermomechanically pro-
prepared by dissolving commercial sodium chloride cessed) corroded the most, while the quenched and
(noniodized NaCl) with tap water to make 3 wt% tempered group of steel coupons showed corrosion
solution. CO2 gas was allowed to bubble in the solu- rates in between the two extremes. Results also
tion at least 24 h to ensure total saturation prior to showed that the higher the tempering temperature,
the tests. The pH of the solution was 5.0 at the start the lower was the weight loss. Normalized specimens
of the experiments but gradually stabilized at 5.4 corroded at a rate closer to the as-received specimen
over the 800-h duration. (Figures 1[b] and [c]).
Weight loss experiments were conducted in a At higher periods of exposure (i.e., 400 h), weight
polytetrafluoroethylene-lined cabinet (0.43-m3 loss increased, showing stronger influence of the
[15-gal] volume) equipped with a water jacket to microstructure, even with the detection of scale pre-
control the solution temperature up to 70C. The cipitation of FeCO3 at 51C. This observation implied
experimental solution was isolated from the outside that FeCO3 precipitated under these conditions was
environment by water sealing the cabinet cover. The not protective. This situation continued up to 800 h
pressure inside the cabinet could not exceed the of exposure (Figure 1[b]). However, at 58C and 65C,
atmospheric pressure. CO2 gas was allowed to bubble the corrosion rate started to decrease. The compara-
in the solution at a slow flow rate to ensure total tive decrease in corrosion rate was significant at 65C,
saturation through the entire experiment. where a parabolic rate of corrosion was evident, as
opposed to the linear rate at lower temperatures. The
RESULTS decrease in the corrosion rate at 65C along with a
parabolic rate of corrosion coincided with the detec-
The weight loss of X-52 steel in all the heat- tion of iron hydroxycarbonate (Fe2[OH]2CO3) at 800 h
treated conditions increased with increasing of exposure time. Figure 2 shows the x-ray diffraction
temperature (Figures 1[a] through [d]), which indi- (XRD) analysis, which suggested that, as a result of
cated dissolution of iron was the primary process, the formation of Fe2(OH)2CO3, or the conversion of
particularly in the initial periods of exposure (i.e., FeCO3 to Fe2(OH)2CO3, the scale started to become
(a) (b)
(c) (d)
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 25C to 51C. This effect started to diminish at 58C
scale incorporated the Fe3C phase into it from the and above, as Fe2(OH)2CO3 started to form and
steel after the dissolution of iron from the ferrite thicken. This observation suggested Fe2(OH)2CO3 was
phase. Also, as the tempering temperature of the more adherent, protective, and therefore, more effec-
quenched samples increased, higher incorporation of tive in reducing the corrosion rate than FeCO3.
Fe3C was expected. The 2.25% Cr-1% Mo steel was tested at two
The effect of heat treatment or microstructure for temperatures (25C and 51C). Weight-loss measure-
X-52 grade steel increased with temperature from ments are shown in Figures 3(a) and (b), respectively.
(a) (b)
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 lar microstructure on corrosion. A relationship, thus,
weight loss of iron heat-treated at 920C was slightly could be established if the microstructure was quan-
higher than at 960C. This effect, again, increased tified in terms of the phases present.
with prolonged exposure and with higher tempera- Annealed samples of X-52 steel showed the low-
ture. For pure iron, there was no scale on specimens est effect, while the as-received thermomechanically
at any exposure time at either testing temperature. control-processed (TMCP) samples showed the largest
Figures 5 through 7 show the optical photomicro- effect. Microstructures of the alloy steels showed a
graphs of differently heat-treated samples of X-52 significantly higher influence on corrosion rate, as
line pipe steel, 2.25% Cr-1% Mo low-alloy steel, compared with the pure iron (Table 4).
and type 1080 eutectoid steel and pure iron,
respectively. DISCUSSION
Application of Corrosion Rate Model It is well established that Fe3C is more cathodic
Plotting Arrhenius curves for the corrosion rate than ferrite and has a lower overpotential for hydro-
in mm/y as a function of the temperature of the test gen evolution.21 This leads to microgalvanic cells to
solution for different heat treatments in alloys al- be formed between Fe3C and ferrite, resulting in
lowed the determination of the activation free energy selective attacks at and around pearlite bands.24
(G*) for the corrosion reaction. These plots for X-52 However, it has been observed that, under certain
steel under different heat-treatment conditions are conditions, segregation results in more efficient
shown in Figures 8(a) and (b). Average values of G* cathodic sites along the ferrite/Fe3C interfaces. Thus,
calculated from the slope of the lines are given in it was understandable that the pearlite distribution
Table 3. in the normalized specimen increased the area of
Using the process variables of solution tempera- contact between the pearlite and ferrite grains,
ture, pH, and PCO2, the calculated values of G*, and since the proeutectoid ferrite is more refined in an
the measured corrosion rate, the values of C in annealed specimen than in a normalized one.25 The
Equation (1) were calculated (Table 4). These values normalized specimen had reduced amounts of
were an average over the range of temperatures proeutectoid ferrite, which consequently increased
tested. It was clear that C was a strong function of the pearlite phase. These factors contributed to the
the steel microstructure. The magnitude of these higher corrosion rate in the normalized specimen
constants was a measure of the effect of any particu- than the annealed sample (Figure 1). The higher rate
(a) (b)
(c) (d)
(e) (f)
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 corrosion rate was virtually constant over the test
of the fact that hot-working induced mechanical duration. Samples with ferrite/pearlite microstruc-
deformation in the steel which deformed and crushed tures in the as-received and normalized heat
the pearlite phase into the softer ferrite matrix as treatment conditions showed a faster rate of corro-
bainite. sion at later periods of exposure. This phenomenon
In quenched and tempered specimens, as car- in pearlite/ferrite microstructures was attributed to
bide coarsens in the temperature range of 350C to the fact that the more the samples (ferrite) corroded,
475C, coarser particles have smaller surface area the higher was the exposure of Fe3C to the solution,
than fine particles for any given surface area-solution leading to larger cathodic sites in the microcells.
interface and for a given carbon content of the alloy. Annealed samples, with their banded structure of
Figure 1 suggests that, although quenched and tem- pearlite/ferrite, however, deviated from this trend
pered samples initially corroded at a higher rate, the and corroded at the lowest rate. This behavior sug-
(a) (b)
(c) (d)
(e) (f)
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 austenite to decompose to ferrite and/or a ferrite-
and ferrite (i.e., pearlite distribution heat- Fe3C mixture, and, therefore, made it possible for the
treatment) was more important in determining the martensite or bainite to form at lower cooling rates.26
alloy corrosion rate than the contact area between In the quenched and tempered samples, chromium
pearlite and the solution (i.e., pearlite proturbance and molybdenum delayed and retarded the decompo-
into solution time of exposure). sition of martensite into ferrite and carbides upon
The quenched and tempered samples corroded tempering, since these atoms have to diffuse to form
at the lowest rate in 2.25% Cr-1% Mo steel, while the carbides, which is a very sluggish process. The nor-
annealed specimen showed the highest rate of corro- malized specimen corroded at a rate lower than the
sion. This observation was sharper at 51C compared annealed steel because the former contained a lower
to the lower temperatures. Metallurgically, the alloy- percentage of Fe3C. In addition, the time allowed to
ing elements in steel increased the time required for form carbides of alloying elements in annealed speci-
(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 etc.) on the corrosion of ferrite. However, the weight
protective elements. loss in iron heat-treated at 920C was slightly higher
For the type 1080 eutectoid steel, the samples than the sample heat-treated at 960C. This effect
normalized in air and in the furnace corroded at increased with time and temperature of exposure.
similar rates at 25C and 51C, showing the effect of This phenomenon was attributed to the decrease in
cooling rate on pearlite lamellae spacing, specially the grain-boundary area when iron was heat-treated
during the initial exposure and prior to the scale at the higher temperature of 960C. The grain
precipitation. For pure iron, heat-treated samples boundary was thought to be cathodic in pure iron to
corroded at rates far lower at 25C and 51C than the ferrite grains.
any of the alloy steel samples, showing the effect of The analyses conducted on corrosion scales by
carbon and other interstitials, as well as other alloy- XRD determined that FeCO3 was the end product
ing elements (e.g., chromium, molybdenum, nickel, when saturation requirements were met. However, it
(a) (b)
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 has been reported that high level of supersaturation
than the saturation requirement before a protective, is required for initial scale formation.
passive film could form. Thus, it was concluded that, The constant C in Equation (1) can be expressed
to precipitate FeCO3, the product of [Fe2+] x [CO32] in terms of the microstructure by quantifying the
must exceed the thermodynamic saturation limit volume fractions and distribution of the phases in
beyond the supersaturation condition.27-28 This ex- plain carbon steels. For alloyed steels, a chemical
plained why the FeCO3 precipitates formed at low composition term, similar to carbon equivalent,
temperature need a longer time to develop a protec- may be more appropriate. Measured corrosion rates
tive scale. This observation supported the result that supported this idea since the weight loss in X-52 was
FeCO3 was not seen to form at low temperatures. considerably lower than in type 1080 eutectoid steel
Also, it did not decrease the corrosion rate when it under identical test conditions. However, the pres-
formed at higher temperatures. Fe3C was left behind ence of chromium and molybdenum in 2.25% Cr-1%
after the ferrite dissolution in steels. The existence of Mo steel protected the bainitic structure from corrod-
Fe2(OH)2CO3 scale at 58C and 65C was protective, ing at a high rate.
which caused a decrease in the corrosion rate. G* for corrosion and the value of the constant
Fe2(OH)2CO3 may be considered a mixed transition C are shown in Tables 3 and 4. G* required for cor-
phase, if written as FeCO3Fe(OH)2, between nonpro- rosion in carbon and alloyed steels was significantly
tective FeCO3 and ferrous hydroxide (FeOH2). Ferrous higher than the pure iron material, which was con-
oxide (FeO) acts as a precursor for more protective sistent with the fact that corrosion in pure metals is
magnetite scales at even higher temperatures. very low. The effect of carbon could be shown quali-
Analysis of scales on 2.25% Cr-1% Mo steel tatively (Figure 9) by plotting the corrosion rates of
showed an amorphous nature on XRD. Films with X-52 and type 1080 steel grades in the quenched
vitreous structure are promoted by bond flexibility, condition as a function of carbon equivalent (Pcm).
and Cr is a good glass former since its oxides have Extrapolation of the lines on Figure 9 to a zero car-
good bond flexibility. It has been reported that gel-like bon level (i.e., ferrite phase) revealed corrosion rates
film is likely to form on iron-chromium alloys before similar to those measured on the pure iron samples
complete passivation by crystalline Cr2O3 oxide.29 (Figure 4). Figure 9 also shows that the slope of the
Scales on type 1080 steel were similar to those line at 51C was greater than that at 25C. Figure 9
on X-52 samples, while very thin scale formed on indicates that the effect of the principal elements,
pure iron, with no evidence of FeCO3 even at 51C. It especially C, increased with temperature.
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
TABLE 4
Corrosion Rate Constant C for Different Steels(A)
Steel Heat Treatment/Microstructure C
(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.