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CORROSION ENGINEERING SECTION

Effect of Chromium on the Pitting Resistance of Oil Tube Steel in a Carbon Dioxide Corrosion System
C.F. Chen,‡,* M.X. Lu,** D.B. Sun,** Z.H. Zhang,*** and W. Chang****

ABSTRACT
Pitting corrosion and structure characteristics of carbon dioxide (CO2) corrosion products on N80, 1Cr, and 4Cr steel were studied. The results indicated that Cr-containing steels can suppress pitting corrosion effectively. While the Cr content in the matrix reached 4%, no pitting corrosion appeared on 4Cr steel. Cr existed mainly as amorphous compound Cr(OH)3 in corrosion products. With the improvement of Cr content in the steel matrix, the content of Cr(OH)3 in corrosion products increased remarkably, which could not only reduce the electrical conductivity of corrosion products but could also improve the cation selectivity of corrosion products. These two factors could improve the pitting resistance of Cr-containing steels. KEY WORDS: carbon dioxide corrosion, chromium-containing steel, corrosion product, ion selectivity, pitting

INTRODUCTION
It has been well known that carbon dioxide (CO2) corrosion resulted in the failures of tubing and casing, in which pitting was one of the main failure degradation modes. There are several mechanisms of pits forma-

* ** *** ****

Submitted for publication June 2003; in revised form, September 2004. Corresponding author. E-mail: changfeng_chen@hotmail.com. Department of Materials Science and Engineering, University of Petroleum, Changping, Beijing, China 102249. Corrosion and Protection Center, University of Science and Technology of Beijing, Xueyuan Rd., Beijing, China 100083. Technology Center, Baoshan Iron and Steel Co., Ltd., Baoshan, Shanghai, China 201900. Research Center, China National Offshore Oil Corporation Jingxin Building, Dongsanhuan Bei Rd., Chaoyang District, Beijing, China 100027.

tion.1-3 Ikeda, et al.,1 considered that, at a middle temperature, ranging from 60°C to 100°C, the corrosion products that formed on a carbon steel (CS) surface were porous and readily led to pitting. Xia, et al.,2 concluded that a porous layer of corrosion products could screen some sites on a metal surface from aggressive anions, while exposing other sites. Furthermore, the galvanic couples produced in this fashion could induce pitting.2 Moreover, flow-induced localized corrosion (FILC) was also suggested as one of the important causes of pit formation.4-9 But in some conditions, for example, such as in static CO2 environments, pits can be found under compact corrosion products. In order to control the CO2 corrosion of CS, considering both applications and economics, low Crcontaining steels were developed.10-16 These kinds of steel cannot only reduce the uniform corrosion, but they can also prevent pitting. Previously, Cr enrichment in the corrosion products formed on low-Cr steels in CO2 environments was considered the reason why low-Cr steels have shown good corrosion resistance.10 In addition, this kind of protective corrosion film can reform more easily, making localized attack less serious on Cr-containing steels than on unalloyed CS.16 Previous work has suggested that the ion selectivity of Cr-enriched corrosion products should be one of the important reasons to prevent localized corrosion.17 The objective of this study was to analyze the microstructure of CO2 corrosion products on CS (N80 steel), 1%Cr, and 4%Cr steel, and discuss the influence of the different structures of corrosion products on pitting.

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0010-9312/05/000125/$5.00+$0.50/0 © 2005, NACE International

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TABLE 1 Chemical Compositions (%) and Microstructure of N80, 1Cr, and 4Cr Steels
Steel N80 1Cr 4Cr C 0.24 0.15 0.18 Si 0.22 0.31 0.32 Mn 1.19 0.96 1.07 P 0.013 0.01 0.01 S 0.004 0.004 0.005 Cr — 1.12 4.08 Microstructure Tempered martensite Tempered martensite Tempered martensite

TABLE 2 Concentration of Various Ions of Extraction Brine from an Oil Field
Cl– g/L 19
2– SO4 – HCO3

Mg2+ 1.05

Ca2+ 0.39

Na+ 11.99

2– CO3

1.14

0.6

0.12

EXPERIMENTAL PROCEDURES
The materials used for testing were API(1) N80 grade steel, 1%Cr- and 4% Cr-containing steels. Chemical compositions and microstructure of the steels are shown in Table 1. The coupons were quenched from 900°C and tempered at 700°C, which resulted in a tempered martensite microstructure. Coupon specimens, 15 mm in width, 40 mm in length, and 2 mm in thickness, were used for hightemperature and high-pressure static CO2 corrosion testing. The coupons’ exposed surfaces were ground and polished with 320#, 600#, and 1,000# grit paper, washed with water, degreased, cleaned, and dried with acetone. The concentration values of various ions in the electrolyte are shown in Table 2. The testing was carried out in a high-temperature and high-pressure autoclave. Before testing, the solution was purged with purified N2 to deoxidize for 2 h, and then the coupons were installed into an autoclave and the solution was deoxidized for 2 h. After purging with N2, the CO2 was put through in the autoclave, and the temperature and pressure were raised to and maintained at the required level. The testing temperature was 78°C, the pressure was 1 MPa, and the testing time was 240 h. The corrosion products and pits formed on the steel surface were examined using scanning electron microscopy (SEM) and an x-ray diffraction (XRD) analyzer. A quantitative analysis of elements in the corrosion products was carried out using energy-dispersive x-ray (EDX) analysis. The chemical state of the elements was analyzed using x-ray photoelectron spectroscopy (XPS).

RESULTS AND DISCUSSION Structure Characteristics of Corrosion Products
The morphologies of the corrosion products are shown in Figure 1. It is evident that the morphology of
(1)

American Petroleum Institute (API), 1220 L St. NW, Washington, DC 20005.

the corrosion products on N80 steel is different from those on 1Cr and 4Cr steels. The crystals piled up more compactly on the N80 steel, as shown in Figure 1(a), which was found to be ferrous carbonate (FeCO3) by XRD (Figure 2[a]). In Figures 1(c) and (e), the corrosion products on 1Cr and 4Cr steels have the same morphology and show no crystal characteristics. The clear amorphous pattern from the XRD spectra shown in Figure 2(c) demonstrates that the corrosion products of 4Cr steel are composed mainly of an amorphous compound with a small quantity of chromium carbide (Cr7C3), chromium oxide (Cr2O3), and FeCO3. Although the corrosion products on 1Cr steel have the same morphology as 4Cr steel, XRD spectra shown in Figure 2(b) indicate that the products are composed mainly of FeCO3. Only a small Cr2O3 XRD peak can be seen in the spectra. From the EDX data of the corrosion products on 1Cr steel listed in Table 3, the Cr enriched the corrosion products as much as 10% in mass; however, there is no corresponding diffraction intensity for the chromic compound in the XRD spectra. It means that Cr exists in the corrosion products on 1Cr steel mainly as an amorphous compound as well, which has a weak diffraction ability to x-ray. When more FeCO3 crystals were present in corrosion products, FeCO3 diffraction peaks would cover up the diffraction intensity of the Cr compound. From the results in Table 4, the EDX data of Fe, Cr, and O content distribution in the corrosion products on 4Cr steel, it can be seen that Cr was further enriched in the corrosion products, and especially in the surface of the corrosion products, the Cr content was approximately 30% in mass. XPS was used to analyze the elements’ chemical state in the corrosion products on Cr-containing steels. Compared with standard binding energies, the chemical state of a chromic amorphous compound could be identified. Spectra results of the corrosion products on 1Cr steel are shown in Figure 3 and binding energies of Fe, Cr, O, and C are listed in Table 5. As shown, Cr mainly exists in the form of Cr(OH)3, which is an amorphous compound. This observation is consistent with Ikeda and Ueda’s results.10

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FIGURE 1. Surface morphologies of CO2 corrosion products of (a) N80, (c) 1Cr, and (e) 4Cr, and pitting morphologies under the corrosion products of (b) N80, (d) 1Cr, and (f) 4Cr.

From Figure 4 and Table 5, Cr mainly exists in the form of Cr2O3 and Cr(OH)3 on the surface of corrosion products on 4Cr steel, but in the inner position it exists mainly in the form of Cr(OH)3. The Cr7C3 is a

residual product after the metal matrix was dissolved, so it could be estimated that the Cr7C3 distributes evenly in the corrosion products. In the CO2 corrosion products on 4Cr steel, Fe existed mainly in the form

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TABLE 3 Content of Typical Elements in CO2 Corrosion Products on 1Cr Steel (wt%)
Cr Inner layer Middle layer Surface layer 4.63 10.56 12.88 Fe 71.81 24.53 10.01 O 9.76 34.60 41.78

TABLE 4 Content of Typical Elements in CO2 Corrosion Products on 4Cr Steel (wt%)
Cr Fe 38.72 6.43 4.85 O 43.77 68.91 44.71 Inner layer Middle layer Surface layer 5.49 13.83 29.22

(a)

(b)

(c)
FIGURE 2. XRD spectra of corrosion products on (a) N80 steel, (b) 1Cr, and (c) 4Cr.

2– of FeCO3. The characteristic peak of C4+ of CO3 in the inner position is much more obvious than on the surface, as shown in Figure 4(a), i.e., the content of FeCO3 in the surface of corrosion products is smaller than within the inner position; this finding is consistent with the EDX data in Table 4. Based on the analysis described above, the schematic structure diagram of corrosion on the three types of steel is shown in Figure 5.

Since all the tests were carried out in static conditions, the corrosion products on the three kinds of steel were intact. However, under the corrosion products of N80 and 1Cr steel, some pits were found, but 4Cr steel had no pitting and appeared as uniform corrosion, as shown in Figures 1(b), (d), and (f). Comparing Figures 1(b) through (d), the pit size on N80 steel appears bigger than that on 1Cr steel. The same experimental results can be found in Takabe and Ueda’s work.14 As we know, while examining the surface morphologies of a coupon using SEM, it should be conductive. Otherwise, electric charges generated by an electron gun will accumulate on the coupon’s surface and cannot be conducted away immediately. This practice will lead to some bright white areas in the SEM image. According to this experimental phenomenon, the conductivity of corrosion products can be estimated approximately. Observing the corrosion products on N80 steel by SEM, electric charges did not accumulate on its surface. This result indicated that the corrosion products on N80 steel were conductive. However, electric changes could accumulate on 4Cr steel’s surface easily, leading to some bright white areas in the SEM image, which means that the corrosion products on 4Cr steel were not conductive. In addition, electric changes accumulated on 1Cr steel’s surface, but the bright white areas in the 1Cr steel’s SEM image were less than those in the 4Cr steel. It could be concluded that the conductivity of corrosion products on 1Cr steel was between that of N80 and 4Cr steel.

Formation of Corrosion Products
For CS, there are three main anodic reactions in the CO2 corrosion process shown in Reactions (1) through (3);18-19 if the matrix contains some Cr, another anodic reaction could occur, as described in Reaction (4).10

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(a)

(b)

(c)
FIGURE 3. XPS spectra (a) C , (b) Cr, (c) Fe, and (d) O in the corrosion products on 1Cr steel.

(d)

TABLE 5 Comparison of the Standard and Experimental Bonding Energies of the Compounds Constituting Corrosion Products on 1Cr and 4Cr Steel (eV)
Experimental Value of 1Cr Surface Middle Layer Layer 710.39 577.20 531.31 284.60 289.40 710.38 577.20 531.58 284.60 289.40 Experimental Value of 4Cr Surface Middle Layer Layer 710.13 577.08 530.92 284.60 710.30 577.26 531.23 284.60 289.20

Valence State Fe2p3/2 Cr2p3/2 O1s C1s

FeCO3 710.20 — 531.90 289.40

Standard Value Cr2O3 Cr(OH)3 — 576.80 531.00 — — 577.30 531.20 —

Cr7C3

282.8

Fe → Fe 2+ + 2e
– Fe + HCO3 → FeCO3 + 2e + H +

(1) (2) (3) (4)

Fe + CO2 – → FeCO3 + 2e 3 Cr + 3OH – → Cr( OH)3 + 3e

The standard electrode potential of Reaction (4) is lower than in Reactions (1) through (3). Consequently,

Cr(OH)3 can precipitate on the matrix surface. Cr(OH)3 has the character of cation selectivity.17 These kinds of corrosion products can block anions such as Cl–, 2– – CO3 , and HCO3 penetrating the corrosion products and reduce the anionic concentration at the interface between the corrosion products and matrix. As a result, the anodic Reactions (1) through (3) can be suppressed and the corrosion rate can be reduced. In this way, the content of FeCO3 in corrosion products can also be reduced.

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(a)

(b)

(c)

(d)

FIGURE 4. XPS spectra of (a) C, (b) Cr, (c) Fe, and (d) O in the corrosion products on 4Cr steel. A: surface layer, B: inner layer.

On the other hand, Cr(OH)3 is a weak acidic substance, but FeCO3 can dissolve according to the following reactions in carbonic acid (H2CO3):20
– 2 FeCO3( s ) + HCO3 → Fe(CO3 )2 – + H +

(5)

the anodic reactions rate of Reactions (2) and (3) could be reduced effectively; thus, the content of FeCO3 in the corrosion products became lower. Cr2O3 is a product of the dehydration of Cr(OH)3. The reaction is presented in: 2Cr( OH )3 → Cr2O 3 + 3H 2O (7)

or FeCO3( s ) + H2CO3 → Fe(HCO3 )2 (6)

Influence of Corrosion Products on Pitting
In a previous work,17 the ion selectivity of corrosion products was used to explain the CO2 corrosion resistance of Cr-containing steel. The corrosion products composed of FeCO3 crystals are anion selective. Aggressive anions in corrosion electrolyte can penetrate it, resulting in a dissolved metal matrix. In particular, Cl– could be enriched and congregate at the interface between the corrosion products and the metal matrix, which leads to serious pitting. However, the corrosion products made of Cr(OH)3 have the character of cation selectivity. These kinds of corrosion products would minimize penetrating anions of

Then Cr(OH)3 would remain in the corrosion products after FeCO3 dissolved. This will lead to the enrichment of Cr content in corrosion products, especially in the surface of corrosion products, where the FeCO3 will be dissolved preferentially. Since the Cr content in the matrix of 1Cr steel was lower, it could not form enough Cr(OH)3 to suppress the anodic Reactions (2) and (3) effectively. So there was still more FeCO3 codeposited with Cr(OH)3. Improving Cr content in the steel matrix could provide more Cr(OH)3 formation in the corrosion products and

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FIGURE 5. Schematic structure diagrams of CO2 corrosion products formed on (a) N80, (b) 1Cr, and (c) 4Cr steel.

creases, as well as the ability of the corrosion products’ cation selectivity. This means that the material’s pitting resistance increases. This is probably one explanation for the pit morphology changes in Figures 1(b), (d), and (f). Crolet, et al.,3 considered that in CO2 corrosion conditions, the conductive corrosion products could cause galvanic coupling corrosion, resulting in acidification under the corrosion layer and facilitating the initiation of pitting corrosion. As mentioned above, the electrical conductivity of corrosion products decreases as the content of the nonconductor Cr(OH)3 among it increases. Thus, the necessary condition for forming galvanic coupling corrosion between the steel and conductive layers cannot be satisfied. (a)

CONCLUSIONS
❖ The improvement of Cr content in a steel matrix could cause the enrichment of Cr in corrosion products remarkably, yet the electrical conductivity of the corrosion products was decreased. Cr existed in corrosion products mainly in the form of amorphous compound Cr(OH)3. ❖ With the improvement of the Cr content in the steel matrix, the pitting resistance also improved. 4Cr steel even eliminated the pitting in a CO2 corrosion environment. ❖ The cation selectivity of the corrosion products on Cr-containing steel was one reason for the improved pitting resistance of the steel. ❖ With the decrease of electrical conductivity of corrosion products, the possibility of galvanic coupling corrosion between the steel and corrosion products was also reduced. Thus, the pitting resistance of the steel increased.

(b)
FIGURE 6. Ion-selectivity schematic diagrams of CO2 corrosion products formed on (a) N80 and (b) Cr-containing steel.

2– Cl–, CO3 , and HCO3. As a result, the anodic reactions could be suppressed and the corrosion rate reduced. Because Cl– could not be enriched nor congregate at the interface, pitting corrosion was suppressed. Figure 6 and Sato’s work21 illustrate the concept. While improving Cr content in the steel matrix, the content of Cr(OH)3 in the corrosion products in-

ACKNOWLEDGMENTS
This work was financially supported by the National Natural Science Foundation of China (no. 50231020) and the National Key Basic Research and Development Programme of China (no. G1999065004).

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