Effect of Microstructure on the Stress Corrosion Cracking of X-80 Pipeline Steel in Diluted Sodium Bicarbonate Solutions

J. G. Gonzalez-Rodriguez, * M. Casales, ** VM. Salinas-Bravo, *** J. L. Albarran, **** and L. Martinez

ABSTRACT

TranSgmUlar

develop

stress corrosion cracking (TGSCC) can in pipelines under normal operating condi-

tions when a coating breaks down and groundwater comes into contact with the outside surface. Since the first TGSCC observed in the pipelines ofTransCanada Pipe Lines, Ltd. in 1985, many other cmmtries such as Italy. Mexico, and Russia have experienced such failures. Intergranular stress corrosion cracking (ICSCC) of pipelines can also occur in highly concentrated bicarbonate-carbonate [HCO;/COzl solution with high pH I-9 to 11). This type of stress corrosion cracking (SCCl occurs in a very restricted range of electrochemical potentials I-550 mV vs a saturated calomel electrode [SCE] to -650 mV,,J. Dominated by film rupture and dissolution, this is so-called classical SCC..3 For instance. Might and Duquette, using a high-purity carbon steel (0.019 wt%) in 170 g/L ammonium carbonate I[NH,],COJ solutions at 70C found that, in this case. SCC occurs by dissolution processes (not necessarily stress related] and not by hydrogen embrittlement since the pH inside the cracks was 8.7, at which hydrogen evolution is thermodynamically impossible. However, several instances of TGSCC were detected recently at coating disbandment areas of Canadian pipelines. Many researchers are focusing more attention on this new SCC phenomenon because it is associated with much lower HCO;/CO;concentrations and pH values (5.5 to 7.5) than those at which classical SCC occurs. Many efforts have been made to understand the mechanism of this SCC in this nonclassical envimnment.6. The studies have focused mainly on the effect of electrochemical potential and solution composition. However. since different manufacturers supply pipeline steels with different thermochemical heat

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0010-9312/021000131/$5.00+$0.50/0 f3 2002. NACE International

CORROSION-IULY

2002

TABLE

Chemical c hln MO P

Composition Nb s

ofXt30

Pipeline
Si

Steel (wt%)
Al Ti Ni cr

treatments, very little information is available on this matter. Lopez. et al., carried out SCC tests on API X-80 steel in a NACE solution sing modffied wedgeopening-loaded (MWOL) specimens in a water-sprayed heat treatment. They explained that the relative SCC susceptihlllty of the steel in this heat treatment was attributable to its microstructure, which consisted of a extremely fine pearlite in a ferrite matrix. Under these conditions. numerous hydrogen-induced microcracks apparently formed at the crack tip plastic region, some of which were able to join the main crack to promote crack gwvth. These cracks developed preferentially at inclusions and hard spots induced by the heat treatment. such as fme carbides in grain boundaries and fine pearlite regions. It was suggested that the improved SCC resistance was related to the energy needed for microcrack propagation and brldging through the ferritic matrix. However, this condition was still considered more susceptible. as indicated by the elongations to failure, than that for the as-received condition. The objective of this work was to study the effect of different heat treatments and, therefore, microstructure on the SCC resistance of a pipeline steel in diluted sodium bicarbonate INaHCO$ solutions using the slow strain rate testing (SSRIJ technique.

TABLE

Heat Treafmenfs Heat Treatment

Water-quenched Water-sprayed Quenched and tempered

Given to X-80 Pipeline Sfeel

Conditions 850C. 30 min. quenched in static water 85OC, 30 min. cooled with sprayed water Water-quenched + 350C fw 30 min. air-cooled

grade chemicals. The fracture surfaces were then examined using scanning electron microscopy @EM). Potentiodynamic polarization curves were measured in 0.1, 0.05. 0.01. and 0.005 M NaHCO, at a sweep rate of 1.0 mV/s (slow scan1 using a fully automated potentiostat controlled with a desktop computer. Some additional polarization cwves were obtained in 0.01 M NaHCO, at 10 mV/s (fast scan) to evaluate the SCC susceptibility of the steel by film rupture.

RESULTS Microstructures
The microstructures produced by the different heat treatments, including those of specimens in the as-received condition, are shown in Figure 1. The microstructure of the as-received sample shows bands of ferrite alternated with bands of pearlite [Figure l[al), and a fine dispersion of precipitates was also found. The quenched and tempered sample shows partially recrystallized grains with the presence of icipient acicular ferrite and isolated pearlite grains,

EXPERIMENTAL

PROCEDURES

The material used was a modern X-80 pipeline steel, with niobium and high manganese contents to gain high strength, with cornposluon and heat treatments as specified in Tables 1 and 2. respectively. The water-sprayed heat treatment simulated a improper welding procedure. Cylindrical tensile specimens with a 25.00.mm gauge length and 2.50-n,, gauge diameter were machined from an unused plpeline perpendicular to the rolling direction. Before testing, the specimens were abraded longitudinally with 600.grade emery paper, degreased. and masked (except for the gauge length). Specimens were subjected to conventional, monotonic SSRT in air as an inert environment and in 0.05 M and 0.01 M NaHCO, soluUon at a strain rate of 1.36 x lob /s at room temperature. Most of the tests were performed at the open-circuit potential, but a few were performed under potentiostatic control. All potentials are vs SCE. The test solutions were prepared from analytical-

as well as a fine dispersionof precipitates(Figure

lIbl1. Figure l(c) presents the microstructure of the samples cooled in water spray, and it shows a incomplete transfmmation of pearlite in a recrystallized ferrite matrix with fewer precipitates. The samples quenched in water (Figure l[dll present a typical structure of martensite with massive segregation at the martensitic lath boundaries: a fine dispersion of precipitates is also apparent.

Effect ofNaHC0, Concentration on the Polarization Curves

Figure 2 illustrates the polarization curves of the steel in the as-received condition in NaHCO, at different concentrations. The shape of the polarization crves changed with HCO; concentration in terms of the presence of a passive region. The most diluted solution showed no evidence of a passive region. probably attributable to a pH effect, whereas all the 585

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(b)

Cd)

other solutions did. A white-gray ftim formed on the surface in the 0.01-M solution, whereas a yellowbrown surface film formed in the 0.01-M and 0.05-M solutions. The potential at which the passive region (Ed started increased with the solution concentration, but the passive current density Ii& increased as the solution concentration was lowered. All the curves had, however, a ccmnnon featurethe appearance of a second anodic peak just before establishing the passive region. This second anodic peak appeared at potentials of - -700 mV for the 0.01-M solution, - -500 mV for the 0.05-M solution, and - -650 mV for the 0.01-M solution. The lower solution concentrations resulted in a narrower passive region. The effect of the heat treatment (including the as-received condition) on the polarization curves in 0.05 M and 0.01 M NaHCO, is shown in Figures 3 and 4. respectively. In all cases, the presence of the second anodic peak is evident although, in the 0.01-M solution at which it appeared, it is virtually the same (- -700 mVl. and in all cases the steel presented a

passive region. In both solutions, the lowest i,, value was exhibited by the steel in the as-received condition followed by the quenched steel. In the 0.05-M solution, the water-sprayed pipeline steel had the highest $-, value. but in 0.01 M this and the tempered steel had virtually the same a.. value. In all the heat treatments, all the solutions produced pitting corrosion, except the most concentrated one. The pit density and size increased with decreasing solution concentration despite the microstructure. The tendency of the steel to fail by SCC caused by f%m rupture was evaluated on the basis that there was at least one order of magnitude difference in i,, between the slow and fast sweep~~~~ and that the iP.. in the fast sweep was >l mA/cn? The results of the $=a values in the active-passive region for the different heat treatments using slow and fast sweeps are given in Table 3. Using these criteria. Table 3 shows that the heat treatments of the quenched and the quenched and tempered samples made the steel more susceptible to SCC, whereas the water-sprayed

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1E-3
Current

0.01
Density (mAfcm2)

0.1
on the polarization cuwe for

FIGURE 3. Effect of heat treatment X-80 steel in 0.05 M NaHCO,.

and the as-received tible.

samples

were the least

suscep-

SSRT
The stress-elongation curves in air for the different heat treatments are given in Figure 5. It can be seen that the highest ductility was exhibited by the water-sprayed steel (-4 mm) and the lowest by the quenched and tempered steel, although the quenched steel had a total elongation very close to it (1.8 mm and 2.0 mm, respectively). The steel in the asreceived condition had an elongation-to-failure of 2.8 mm. As expected, the quenched steel had the highest ultimate tensile strength (UTS) value (-1,400 MPa). followed by the quenched and tempered steel (-1.200 MPa), whereas the sprayed steel and the steel in the as-received condition had the lowest UTS values (-650 MPa to 700 MPa). When tested in 0.05 M and 0.01 M NaHCO, solution, the pipeline steel in the as-received condition was barely affected since the total elongation-tofailure in air and in the two solutions was between 2.5 mm and 3.2 mm, a loss of 22% ductility. whereas the LIT3 lay between 620 MPa and 680 MPa [Figure 6). However, the situation was different for the quenched steel (Figure 7). In this case, the minimum elongation-to-failure obtained in 0.01 M NaHCO, solution Isimllar to the as-received condition) was 1.25 mm. compared with that in air (2.2 mm), a loss of 45% ductility. The UTS values in the three environments ranged between 1.200 MPa and 1,400 MPa, the lowest being recorded in 0.01 M NaHCO,. For the quenched and tempered pipeline steel. again. the lowest elongation-to-failure was obtained in 0.01 M NaHCO, solution (1.1 mm) compared with the value obtained in air (1.9 mm, a loss of 42% ductility), but the UTS values were very close in the three environments [Figure 8). Finally. for the watersprayed steel. once again, the lowest elongations r w

5ou 0 -500
-I,0001 0.01 0.1 Density (mAJcm2) curye for 1

Current
FIGURE 4. Effect X-80 steel in 0.01

of heat treatment M NaHCO,.

on the polarization

Effect of Heat Treatment Using Fast and Slow

TABLE 3 on the tw,. Values Obtained Sweeps in 0.01 M NaHCO, ivy (mAtem) at stow Scan 0.008 0.05 0.09 0.09 iv (mAtem) at Fast Scan 0.04

Heat
TW*tmet As-received Waterquenched Water-sprayed Quenched and tempered

2.00
0.4 1.05

to-failure value was obtained in 0.01 M NaHCO, (-3.00 mm) whereas the highest value was obtained in air Islightly longer than 4.00 mm, a loss of 25% ductility) (Figure 9). In this case. the lowest UTS value was obtained in 0.01 M NaHCO, also (-600 MPa) whereas the highest value was obtained in air I-700 MPal. These results are summarized inTable 4. To see the effect of the electrochemical potential on the SCC behavior of pipeline steels in diluted NaHCO, solutions, some tests were performed on the

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1.4wJ

,_. .... . . .._.

Air data

1,400 Pzoo. ~i,OOO-

As-received

0 1 Elongation 2 (mm) 3 4

Water-quenched 0 0 1 Elongation 2 (mm) 3 4

most susceptible material (i.e.. the water-quenched steel). and the results are shown in Figure IO. Marked reductions in the total elongation-to-failure were found for samples at anodic potentials with respect to E, whereas. at cathodic potentials, the ductility increased. Apical fracture surfaces in 0.01 M NaHCO, are presented in Figure 11. The quenched steel showed transgranular cracking whereas the water-sprayed steel exhibited quasicleavage features. Cross sections of the cracks in the quenched and sprayed steel are shown in Figure 12. which reveals evidence of corrosion products inside the cracks.

DISCUSSION
In highly concentrated bicarbonate-carbonate solutions with high pH l-9 to 11). the SCC of plpelines is intergranular and is dominated by tllm rupture and anodic dissolution (AD). The tendency for SCC to occur at any given specimen potential by film

rupture was evaluated on the basis that there was at least one order of magnitude difference in i-. between the slow and fast s~eeps,~~ and that the & in the fast sweep was >l mA/cn?. The difference of 1 mA/cm= between the slow and fast sweeps (Table 3) means that an intermediate passivation rate was ideal for a dissolution mechanism. A high passivation rate caused the crack tip to be protected continually while a low rate resulted in excessive dissolution at the crack tip. leading to blunting. Also, data in figure IO-where anodic potentials, which enhance the steel dissolution, also increased the SCC tendencysuggest that the cracking mechanism of pipelines In 0.01 M NaHCO, solutions is AD. It has been shown that, even under conditions that favor AD. the electrochemical conditions inside the pits are such that hydrogen discharge is possible. Parkins. working with X-65 pipeline steel in NS-4 solutions containing diluted carbon dioxide (COJ l=O.O05 M) at pH 6.5, considered that the results suggested dissolution and hydrogen ingress into the

steel. Similar results were found by Gu, et al., for X-80.type steel in the same solution. However, in the NS-4 solutions, the X-80 steel did not show any passive region whereas, in the present study, it did Figure 4). regardless of the microstructure. demonstrating the importance of the film rupture. Another difference is that. in the NS-4 solution. the SCC susceptibility increased as the applied potential was more cathodic, unlike the present case. in which cathodic potentials decreased the SCC susceptibility. These results confhm those of Parkis.15 that see of carbon steels in carbonate solutions occurred by the dissolution process of metal at the crack tips. The presence of corrosion products inside the cracks supports this idea. The dissolution rates at the crack tips were high enough to cause the crack walls to passivate. providing a large cathode inside the crack, coupled to a small anode at the crack tip where film rupture took place. The role of the applied potential was to maintain the alloy surface in the potential range where rapid rupture of the passive film led to a mzdmum dissolution rate at the crack tip, while at the same time fudng the potential of the crack walls in the passive regime. The quenched steel was most susceptible to SCC because the martensite was a highly stressed microstructure as a result of excess carbon trapped inter~titial1y.l~ Hence, it is assumed that grain boundruy carbon segregation coupled with severe internal stresses renders grain boundaries susceptible to stress corrosion crack propagation. So it is expected that, under these conditions. the crack propagation is mainly intergranular. In this work, the authors were not able to detect intergranular cracking. as evidented by Figures 11 and 12. However, as mentioned in the Introduction, in the nonclassical SCC found in lower concentrations of carbonate/bicarbonate solutions. the SCC propagation was transgranular, as opposed to the IGSCC found in highly concentrated carbonate/bicarbonate solutions. In the quenched condition, it is expected that carbon segregation at grain and interlath boundaries combined with an internally stressed martensite will give rise to an increasingly susceptible steel condition. Quenching followed by tempering, or normalizing and tempering, generallyjmproves the SCC resistance of steels. When crack growth occurs mainly by hydrogen embrittlement (HE). it is apparent that the distribution and type of hydrogen traps in the form of inclusions and second phases play a key role on the overall steel susceptibility. Among the microstructural features that can act as noxious traps of hydrogen are iclusions and segregation bands containing lower-temperature products (bainite and martensite). Therefore, the inherent SCC resistance is strongly affected by metallurgical variables responsible for the presence of inclusions, carbides, and segregation bands. CORROSION-W. 58, NO. 7

1,400t

TABLE
Effect

of Heat Treatment on the Elongation-to-Failure in Air and in NaHCO. Solutions Elongation-to-Failure (mm) 0.05 M NaHCO,

Heat Treatment

Air

0.01 M NaHCO,

I -200 -?@I 0
Overpotential

100
(mV)

200

300

CONCLUSIONS
9 SSRT results showed that X-80 steel is highly susceptible to SCC in 0.01 M NaHCO, solutions at room temperature. depending upon the heat treatment. and the SCC increased as the solution concentration was lowered. 0 Quenched steel and steel that was quenched followed by tempering were the most susceptible to SCC 589

CORROSION

SCIENCE

SECTION

(a)
FIGURE 11.

(b)

Micrographs ofX-80 specimens fractured in 0.01 M NaHCO, shown in: (a) Ihe quenched sfeel and (b) the water-sprayed steel.

(b)
quenched steel and (b, the waler-sprayed steel

in 0.01 M NaHCO,, whereas the as-received and water-sprayed steel samples were the least susceptible. 0 Tbe mechanism of SCC in X-80 pipeline steel in 0.01 M NaHCO, solutions was dominated by film rupture and AD.
REFERENCES

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2002