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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 (CO 2 )-containing aqueous solution was measured experimentally as a function of pH, temperature, and partial pressure of CO 2 . 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 60°C but diminished above 60°C. The corrosion rate increased with temperature in the activation- controlled regime, where a nonprotective iron carbonate (FeCO 3 ) scale formed. Diffusion-controlled corrosion through a stable scale of iron hydroxycarbonate (Fe 2 [OH] 2 CO 3 ) was responsible for lowering the corrosion rate above 60°C. 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 (CO 2 )- 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.

Milliams 3 suggested a mechanism where corrosion in this environment proceeds in a catalytic way by di- rect reduction of carbonic acid (H 2 CO 3 ) 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 CO 2 (P CO 2 ), 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 60°C in a CO 2 - 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 P CO 2 :

Corrosionrate = C × pH 1.33 × P CO 2

0.67 × e – Q/kT

(1)

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 P CO 2 values. 10 The equation allows the inclusion of other variables, such as flow, impuri- ties, inhibitors, and steel microstructure through the

480

0010-9312/98/000107/$5.00+$0.50/0

© 1998, NACE International

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

TABLE 1

Chemical Composition of Tested Plain Carbon and Alloyed Steels

Alloy

C

Mn

Si

S

P

Others

X-52

0.14

1.26

0.22

0.002

0.018

Nb 0.022 Cr 2.3, Mo 1.37

2.25% Cr-1% Mo Type 1080

0.08

0.83

0.52

0.006

0.022

0.78

1.26

0.22

0.020

0.03

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 [Fe 3 C]) 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 Fe 3 C 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 (FeCO 3 ), the solubility of which decreases with temperature and increases with CO 2 pressure. 13 FeCO 3 has been reported to be nonprotective below 60°C, 2 containing voids and grain boundaries. 14 Above 60°C, protectiveness has been said to increase with temperature. 15 Another study placed this transition temperature at 90°C, below which the corrosion rate increased steadily, 6 even with FeCO 3 precipitation. Above 100°C, iron oxides (Fe 3 O 4 and then Fe 2 O 3 ) have been said to form. FeCO 3 codeposition with Fe 3 O 4 is considered hazardous. 16 Iron bicarbonate (Fe[HCO 3 ] 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.

Chromium oxide (Cr 2 O 3 ) is said to form on duplex and martensitic stainless steels (SS) at high temperature, and CO 2 has little effect on the film structure. It has been reported that chromium in steels dissolves to form a complex ion (CrO 4 2 ) 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 Fe 3 C starts to precipitate and coarsen. 21 However, another study showed that the corrosion rate of tempered eutectoid steel pro- duced three peaks at 260°C, 340°C, and 440°C 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 CO 2 -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 mm 2 to 4,000 mm 2 [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 ± 10 4 g. The solution volume-to-surface area ratio was held constant at 4.4 mL/mm 2 . Specimens were immersed in the solution for 100 h, 200 h, 400 h, and 800 h of exposure. Temperature

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 760°C/1 h; OQ

Normalized 920°C/1 h; AC

Normalized 950°C/2 h; AC

Normalized 950°C/2 h; AC

Normalized 760°C/1 h; AC

Normalized 960°C/1 h; AC

Annealed 875°C/2 h; FC

Annealed 875°C/2 h; FC

Normalized 760°C/1 h; FC

 

50°C/h

Quenched and tempered 950°C/1 h, WQ 350°C temper; AC

Quenched and tempered 950°C/1 h, WQ 350°C temper; AC

Annealed 760°C/1 h; FC

15°C/h

Quenched and tempered 950°C/1 h, WQ 400°C temper; AC

Quenched and tempered 950°C/1 h, WQ 400°C temper; AC

Quenched and tempered 950°C/1 h, WQ 475°C temper; AC

Quenched and tempered 950°C/1 h, WQ 475°C temper; AC

Test temperatures

Test temperatures

Test temperatures

Test temperatures

25°C, 38°C, 51°C, 58°C, and 65°C

25°C, 51°C, and 65°C

25°C and 51°C

25°C and 51°C

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

was controlled to within ± 2°C. 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. CO 2 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-m 3 [15-gal] volume) equipped with a water jacket to control the solution temperature up to 70°C. 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. CO 2 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.,

482

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 FeCO 3 at 51°C. This observation implied that FeCO 3 precipitated under these conditions was not protective. This situation continued up to 800 h of exposure (Figure 1[b]). However, at 58°C and 65°C, the corrosion rate started to decrease. The compara- tive decrease in corrosion rate was significant at 65°C, where a parabolic rate of corrosion was evident, as opposed to the linear rate at lower temperatures. The decrease in the corrosion rate at 65°C along with a parabolic rate of corrosion coincided with the detec- tion of iron hydroxycarbonate (Fe 2 [OH] 2 CO 3 ) 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 Fe 2 (OH) 2 CO 3 , or the conversion of FeCO 3 to Fe 2 (OH) 2 CO 3 , the scale started to become

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (c) (b) (d) FIGURE 1. Weight loss in CO 2 -containing aqueous

(a)

CORROSION ENGINEERING SECTION (a) (c) (b) (d) FIGURE 1. Weight loss in CO 2 -containing aqueous

(c)

CORROSION ENGINEERING SECTION (a) (c) (b) (d) FIGURE 1. Weight loss in CO 2 -containing aqueous

(b)

CORROSION ENGINEERING SECTION (a) (c) (b) (d) FIGURE 1. Weight loss in CO 2 -containing aqueous

(d)

FIGURE 1. Weight loss in CO 2 -containing aqueous solutions for X-52 steel as a function of time at: (a) 38°C, (b) 51°C, (c) 58°C, and (d) 65°C.

more protective. Furthermore, it was evident that the scale incorporated the Fe 3 C 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 Fe 3 C was expected. The effect of heat treatment or microstructure for X-52 grade steel increased with temperature from

25°C to 51°C. This effect started to diminish at 58°C and above, as Fe 2 (OH) 2 CO 3 started to form and thicken. This observation suggested Fe 2 (OH) 2 CO 3 was more adherent, protective, and therefore, more effec- tive in reducing the corrosion rate than FeCO 3 . The 2.25% Cr-1% Mo steel was tested at two temperatures (25°C and 51°C). Weight-loss measure- ments are shown in Figures 3(a) and (b), respectively.

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION FIGURE 2. XRD analysis of corrosion scale formed on X-52 steel in normalized

FIGURE 2. XRD analysis of corrosion scale formed on X-52 steel in normalized condition after 400 h of exposure at 65°C and 51°C 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 51°C. 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 51°C (Figure 3[b]). The weight loss in pure -iron and type 1080 eutectoid steel at 25°C and 51°C is shown in Figures 4(a) and (b). Both alloys corroded at a higher rate at 51°C than at 25°C, 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 25°C and up to 200 h at 51°C), while specimens normalized in air and normalized in a furnace corroded at the lowest rates (up to 400 h at 25°C and up to 200 h at 51°C). The onset of the diffusion-controlled parabolic rate of corrosion in eutectoid steel occurred at the relatively lower temperature of 51°C when compared with the X-52 steel, where a clear shift in the corrosion mode was observed only above 60°C. This observation implied that microstructural features in the eutectoid steel enhanced adherence of the scale and made it somewhat protective even at lower temperatures. Microstructures in eutectoid steel at 25°C showed a similar effect as in the X-52 steel at 51°C, with quenched samples corroding at lower rates. This effect resulted from the role of the microstructure in improving FeCO 3 protectiveness. Normalized-in-air and normalized-in-furnace samples corroded at similar rates at both temperatures, with the differ- ence in weight loss increasing with prolonged exposure. For eutectoid steel at 25°C, as with the

484

For eutectoid steel at 25 ° C, as with the 4 8 4 (a) (b) FIGURE

(a)

For eutectoid steel at 25 ° C, as with the 4 8 4 (a) (b) FIGURE

(b)

FIGURE 3. Weight loss in CO 2 -containing aqueous solutions for 2.25% Cr-1% Mo steel as a function of time at: (a) 25°C and (b) 51°C.

X-52 steel, FeCO 3 was not protective. At 51°C, FeCO 3 clearly precipitated. Pure iron at both 25°C and 51°C and in both heat-treated conditions corroded at far lower rates than any alloy steel, which showed the effect of

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (b) FIGURE 4. Weight loss in CO 2 -containing aqueous solutions for

(a)

CORROSION ENGINEERING SECTION (a) (b) FIGURE 4. Weight loss in CO 2 -containing aqueous solutions for

(b)

FIGURE 4. Weight loss in CO 2 -containing aqueous solutions for type 1080 and pure -iron samples as a function of time at: (a) 25°C and (b) 51°C.

carbon content on corrosion of ferrite. However, the weight loss of iron heat-treated at 920°C was slightly higher than at 960°C. 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 P CO 2 , 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-

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 Fe 3 C is more cathodic than ferrite and has a lower overpotential for hydro- gen evolution. 21 This leads to microgalvanic cells to be formed between Fe 3 C 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/Fe 3 C 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

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(a)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(c)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(e)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(b)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(d)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 5. Optical photomicrograph of X-52 steel

(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 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 350°C to 475°C, 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

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 Fe 3 C 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-

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(a)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(c)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(e)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(b)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(d)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 6. Optical photomicrograph of 2.25% Cr-1%

(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 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 51°C compared to the lower temperatures. Metallurgically, the alloy- ing elements in steel increased the time required for

austenite to decompose to ferrite and/or a ferrite- Fe 3 C 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 Fe 3 C. In addition, the time allowed to form carbides of alloying elements in annealed speci-

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(a)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(c)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(e)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(b)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(d)

CORROSION ENGINEERING SECTION (a) (c) (e) (b) (d) (f) FIGURE 7. Optical photomicrograph of type 1080

(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) 920°C normalized and (f) 960°C 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 25°C and 51°C, 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 25°C and 51°C 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,

488

etc.) on the corrosion of ferrite. However, the weight loss in iron heat-treated at 920°C was slightly higher than the sample heat-treated at 960°C. 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 960°C. 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 FeCO 3 was the end product when saturation requirements were met. However, it

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

CORROSION ENGINEERING SECTION (a) (b) FIGURE 8. Arnhenius plot to determine ∆ G* for corrosion of

(a)

CORROSION ENGINEERING SECTION (a) (b) FIGURE 8. Arnhenius plot to determine ∆ G* for corrosion of

(b)

FIGURE 8. Arnhenius plot to determine G* for corrosion of X-52 steel in CO 2 -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, passive film could form. Thus, it was concluded that,

is

required for initial scale formation. The constant C in Equation (1) can be expressed

to precipitate FeCO 3 , the product of [Fe 2+ ] x [CO 3 2 ]

in

terms of the microstructure by quantifying the

must exceed the thermodynamic saturation limit beyond the supersaturation condition. 27-28 This ex- plained why the FeCO 3 precipitates formed at low temperature need a longer time to develop a protec- tive scale. This observation supported the result that FeCO 3 was not seen to form at low temperatures. Also, it did not decrease the corrosion rate when it formed at higher temperatures. Fe 3 C was left behind

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%

after the ferrite dissolution in steels. The existence of Fe 2 (OH) 2 CO 3 scale at 58°C and 65°C was protective, which caused a decrease in the corrosion rate.

Mo steel protected the bainitic structure from corrod- ing at a high rate. G* for corrosion and the value of the constant

Fe 2 (OH) 2 CO 3 may be considered a mixed transition

C

are shown in Tables 3 and 4. G* required for cor-

phase, if written as FeCO 3 ·Fe(OH) 2 , between nonpro- tective FeCO 3 and ferrous hydroxide (FeOH 2 ). 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 Cr 2 O 3 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 FeCO 3 even at 51°C. It

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 (P cm ). 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 51°C was greater than that at 25°C. Figure 9 indicates that the effect of the principal elements, especially C, increased with temperature.

CORROSION ENGINEERING SECTION

TABLE 3

G* for Corrosion in CO 2 -Containing Aqueous Solutions

Material

Free Energy

(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 17 × %α + 8.7 × 10 18 × %p + 3.9 × 10 17 × %m

(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 CO 2 -containing solutions. However, 2.25% Cr-1% Mo steel indicated relative resistance.

2.25% Cr-1% Mo steel indicated relative resistance. FIGURE 9. Corrosion rate as a function of carbon

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 Normalized/8% P + 92% F Annealed/9% P + 91% F Q&T 350/tempered M Q&T 400/tempered M Q&T 475/tempered M

2.97 x 10 17 3.47 x 10 16 9.36 x 10 15 2.77 x 10 17 1.09 x 10 16 2.46 x 10 17

-Iron

Normalized 920°C/100% F Normalized 960°C/100% F

1.30 x 10 12 9.00 x 10 12

Type 1080

Normalized-Air/100% P Normalized-Furnace/100% P Annealed/100% P Quenched/100% M

1.14 x 10 17 7.00 x 10 18 8.70 x 10 18 3.90 x 10 17

2.25% Cr-1% Mo

As-received/100% B Normalized/50% B + 50% F Annealed/6% P + 94% F Q&T350/tempered B Q&T400/tempered B Q&T475/tempered B

1.90 x 10 16 3.20 x 10 16 5.10 x 10 16 1.10 x 10 16 3.20 x 10 16 1.20 x 10 16

(A) P CO 2 0.67 = 0.877; [H + ] 1.33 = 7.2 x 10 7 ; T = 25°C to 58°C; F, ferrite; P, pearlite; M, martensite; and B, bainite.

490

CORROSION–JUNE 1998

CORROSION ENGINEERING SECTION

CONCLUSIONS

The microstructure and chemical composition of

an alloy was shown to play a role in determining the corrosion rate in CO 2 -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 Fe 3 C, 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 Fe 3 C.

FeCO 3 precipitates by complex supersaturation

process within the adjacent solution. FeCO 3 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 Fe 2 (OH) 2 CO 3 at temperatures above 60°C.

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