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Sulde Stress Cracking Susceptibility of Welded X-60 and X-65 Pipeline Steels
C. Natividad,* M. Salazar,** A. Contreras,** A. Albiter,** R. Prez,** and J.G. Gonzalez-Rodriguez,***

ABSTRACT
The susceptibility of API X-60 and X-65 longitudinal weld beads to sulde stress cracking (SSC) has been evaluated using slow strain rate tests (SSRT) in the NACE solution saturated with hydrogen sulde (H2S). The tests were supplemented by potentiodynamic polarization curves and hydrogen permeation measurements. The weld beads were produced using the submerged arc welding (SAW) process. Three different temperatures were used: room temperature (25C), 37C, and 50C. The corrosion rate, taken as the corrosion current density, Icorr, the amount of hydrogen uptake for the weldments, C0, and the SSC susceptibility increased with an increase in the temperature from 25C to 50C. Although anodic dissolution seems to play an important role in the cracking mechanism, the most likely mechanism for the cracking susceptibility of X-60 and X-65 weldments in H2S solutions seems to be hydrogen embrittlement. KEY WORDS: hydrogen embrittlement, sulde stress corrosion cracking, X-60 and X-65 steel weldments

INTRODUCTION
The oil industry contains a wide variety of corrosive environments. Mexican crude oil and gas commonly contain entrained water, carbon dioxide (CO2), and
Submitted for publication December 2004; in revised form, August 2005. Corresponding author. E-mail: ggonzalez@uaem.mx. * UNAM, Facultad de Qumica Circuito Interior, C.U., Edicio B, C.P. 04510, Mxico, D.F. Mexico. ** Instituto Mexicano del Petrleo, Programa de Investigacin y Desarrollo de Ductos, Eje Central Lzaro Crdenas #152, San Bartolo Atepehuacan, 07730, Mxico, D.F. Mexico. *** UAEM-CIICAP, Av. Universidad 1001, Col. Chamilpa, 6225Cuernavaca, Mor., Mexico.

hydrogen sulde (H2S). The transport of these types of products always induces failures in the pipeline systems, and not less frequently in the weld beads. The welding industry has recognized that weldinduced stresses play an important role in certain localized corrosion phenomena. Each year, tens of million of dollars are expended to replace or repair pipes and vessels that suffer excessive localized metal loss, stress corrosion cracking (SCC), or hydrogen embrittlement (HE). When sulde is present, this type of brittle failure is known as sulde stress cracking (SSC), and it has been established as a particular case of HE. Weld metal corrosion is normally attributed to the differences in composition and to differences in electrochemical potentials between the parent metal, heat-affected zone (HAZ), and weld metal. A lower electrochemical potential of the weld bead is commonly related to the composition, microstructure, and distribution of inclusions.1 The suitable sour service materials are listed in NACE MR0175,2 whereas the TM01773 lists Method A as one of the tests to be performed to determine the inclusion of a material in MR0175. Many highstrength, low-alloy steels are precluded from undergoing this test, especially in the as-welded condition, due to either high parent material hardness or the formation of high-localized stressed weld regions in the weld HAZ. Specications for welded sample testing are not addressed in the NACE standard primarily because this test is geared toward wrought samples. Welded samples differ from homogeneous samples because of their local variations in microstructure and

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TABLE 1 Chemical Compositions of X-60 and X-65 Steels (wt%)

Steel X-60 X-65 C 0.025 0.04 Mn 1.57 1.48 Si 0.14 0.25 P 0.012 0.012 S 0.002 0.002 Al 0.044 0.041 Nb 0.097 0.047 Cu 0.31 0.09 Cr 0.29 0.02 Ni 0.17 0.5 Mo 0.03 V 0.002 0.069 Ti 0.014 0.017

TABLE 2 Welding Parameters

Parameter Current Voltage Travel speed Argon ow rate Preheating temperature Heat input Stick out Value 320 A 20 V 3.6 mm/s 22 L/min 250C 17.11 KJ/cm 12 mm

compositions. The development of multi-phase microstructures is important for the attainment of certain mechanical properties, but it can be detrimental for resistance to SSC. Carbon-rich phases such as pearlite, bainite, or martensite can be particularly susceptible to this mode of HE.4-7 The goal of this study was to evaluate the susceptibility to SCC in H2S-containing environments of weld beads obtained from API X-60 and X-65 pipeline steels produced by the submerged arc welding (SAW) techniques using the slow strain rate testing (SSRT) technique, although the Method A test in TM0177 is not an SSRT test but a constant load tensile test.

EXPERIMENTAL PROCEDURES
In this work, longitudinal weld beads of API X-60 and X-65 pipelines steels were analyzed. These pipes

are typically used in the Mexican pipeline systems. They have an outside diameter of 42 in. (1,066 mm) (X-60) and 24 in. (609.6 mm) (X-65), with a wall thickness of 0.5 in. (12.7 mm) (X-60) and 0.562 in. (14.27 mm) (X-65). The chemical composition of these steels is shown in Table 1. Table 2 shows the welding parameters used to join the pipeline steels. A ller wire electrode with a chemical composition consisting of 0.08% C, 1.1% Mn, and 0.6% Si was used. Cylindrical tensile specimens with a 25.00-mm gauge length and a 2.50-mm gauge diameter were machined from an unused pipeline perpendicular to the rolling direction, as shown in Figure 1, which shows a schematic illustration of the orientation and location of the sample with respect to the longitudinal seam weld. Before testing, the specimens were abraded longitudinally with 600-grade emery paper, degreased, and masked, with the exception of the gauge length. The masking agent used was an inert resin and it has been observed that it does not induce crevice-type corrosion at the end of the test. Specimens were subjected to conventional, monotonic, SSRT testing in air, as an inert environment, and the standard NACE solution (5% sodium chloride [NaCl], 0.5% acetic acid [CH3COOH], and saturated with hydrogen sulde [H2S]) at a strain rate of 1.00 106 s1 at room temperature, (25C), 37C, and 50C. All the tests were performed at the open-circuit potential. According to the authors experience, stress/strain curves give some conicting results; instead of this,

(a)

(b)

FIGURE 1. Schematic illustration of the orientation and location of the sample with respect to the longitudinal seam weld.

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the loss in ductility was assessed in terms of the percentage reduction in area (%RA) using: % RA = Ai Af 100 Ai (1)

where Ai and Af are the initial and nal areas, respectively. A susceptibility index to SCC (ISCC) was calculated as follows: ISCC = % RA AIR % RA NACE % RA AIR (2)

where %RAAIR and %RANACE are the percentage reduction in area values in air and in the H2S-saturated NACE solution, respectively, previously deaerated with nitrogen gas. The fracture surfaces were then examined using scanning electron microscopy (SEM). Potentiodynamic polarization curves were performed at a sweep rate of 1.0 mV/s using a fully automated potentiostat controlled with a desktop computer. These tests were done in duplicate. Hydrogen permeation tests were carried out using the two-component Devanathan-Stachurski8 cell. The specimen, which was fabricated from the same pipe sample as the tensile specimens, was mounted between the two compartments, giving an effective area of 3.14 cm2 exposed to the H2S-containing solution, under open-circuit conditions to generate hydrogen. The hydrogen collection compartment contained an electrolyte of 0.5 M sodium hydroxide (NaOH) solution purged with nitrogen (N2) gas. The Pd-plated specimen surface exposed to this solution was potentiostatically passivated at a constant potential of 300 mV vs. a saturated calomel electrode (SCE), which was used as reference electrode in the polarization curves also. In both cases, a graphite rod was used as an auxiliary electrode. Potentiodynamic polarization curves were performed once the free corrosion potential value (Ecorr) was stable, i.e., it did not change more than 2 mV/min. The scanning started at 500 mV, with respect to Ecorr, and nished at 300 mV more positive than Ecorr, at a scanning rate of 1 mV/s. Corrosion current values (Icorr) were calculated using Tafel extrapolation. When the passive current reached a constant value, then the H2S-containing solution was poured into the other compartment to start the hydrogen permeation experiments. Polarization curves were repeated at least three times when there was no more than 10 mV to 15 mV in the Ecorr values and the difference in current densities was within an error of 5%. Temperatures were kept constant by using a heating tape. The hydrogen coefcient diffusion (D) was calculated using: D= L2 6t lag (3)

(a)

(b)
FIGURE 2. Micrographs obtained by optical microscopy of the weldments: (a) X-65 and (b) X-60 steel.

where L is the specimen thickness (0.7 mm) and tlag, the lag time, is the time elapsed when 63% of the steady-state permeation current, Jss, has been reached. The number of Pd-coated hydrogen atoms at the entrance surface, C0, was calculated using: J ss = DC0 L (4)

RESULTS AND DISCUSSION

Figure 2 shows micrographs of the X-60 and X-65 steels weldments. These gures clearly show the different microstructures found in a weldment, which itself consists mainly of polygonal and coarse acicular ferrite. This microstructure optimizes the strength and the toughness of the weld beads.9-12 The results of the hardness measurements obtained from the different zones of the weld bead are presented in Figure 3.

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(a)

(b)

(c)

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FIGURE 3. Hardness measurements in weld beads: (a) and (b) X-60 steel and (c) and (d) X-65 steel.

The hardness was measured at the middle of the weld bead (Figures 3[a] and [c]), known as the reheated zone. It was also measured at the middle of the upper weld bead. Remarkable differences can be observed between both measurements. A considerable decrease in hardness can be observed in the reheated zone. The hardness of ferritic-perlitic steels increases by increasing the perlite content. The obtained hardness values are within the recommended limits for avoiding cracking and fracture in the weld bead. Figures 4 and 5 show the effect of temperature on the polarization curves for X-60 and X-65 pipeline steels, respectively. As expected in these solutions, there is no passive region in any of the cases, only active dissolution. For both steels, the Ecorr decreases as the temperature is increased, with the most noble value at 25C and 600 mV, and the most active at 50C and around 800 mV. The Ecorr value for the X-60 steel at 37C was 650 mV whereas for the X-65 steel, it was 700 mV. For the X-60 steel, the anodic current density and the Icorr value increased as the temperature increased, but not for the X-65 steel.

Figure 6 shows two typical hydrogen permeation current transients obtained at 25C for both steels. It can be seen that the hydrogen permeation current is higher in the X-60-type steel than in the X-65 one by almost ve times, and the steady state is reached faster in the former than in the later. This gure shows some current-time transients, especially for the X-65 steel, which are consistent with diffusional processes. Figure 7 shows the effect of the temperature on the hydrogen uptake for both steels. It is clear that the amount of hydrogen uptake increases with temperature for both steels, being always higher in the X-60 than in the X-65-type steel. All these results are consistent with those found in the literature,12 as will be seen later. The susceptibility toward SSC was measured with the ISCC index, and the results are plotted in Figure 8. Values close to the unit mean that the steel is highly susceptible to SSC, whereas values close to zero mean that the steel is immune to SSC. Thus, Figure 8 clearly shows that, in all cases, regardless of the temperature, both steels are highly susceptible to SCC,

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FIGURE 4. Effect of temperature on the polarization curves in the saturated NACE solution with H2S for X-60 steel weldments.

FIGURE 5. Effect of temperature on the polarization curves in the saturated NACE solution with H2S for X-65 steel weldments.

FIGURE 6. Typical time variation of hydrogen permeation current in the saturated NACE solution with H2S for X-60 and X-65 steel weldments at 25C.

FIGURE 7. Effect of temperature on the C0 values for X-60 and X-65 steel weldments.

and the effect of the temperature is negligible, although the tendency is that this susceptibility increases with increasing temperature. X-60 pipeline steel was more susceptible toward SCC than the X-65 steel, although this difference seems to be negligible. An analysis of the fracture surfaces made by SEM revealed corroded surfaces in all the specimens, as shown in Figure 9, which show the fracture surface of the X-65 steel strained at 37C. However, even in conditions where the corrosion rate was the highest, i.e., at 50C, some quasi-cleavage features, arrowed, similar to those produced by HE, were found on the fracture surface of the X-60 steel (Figure 10). A surface-initiated crack propagated through a brittle fracture perpendicular to the applied stress until it reached a critical size where ductile rupture then occurred, usually at 45 to the tensile axis. This gen-

eral fracture morphology was exhibited regardless of whether the fracture initiated in the base metal, fusion zone, or HAZ. Post-fracture exposure of the fracture surface, in most cases, caused the formation of a corrosion product, making the determination of the fracture mode at times difcult or impossible in the SEM, even when the specimens were cleaned according to ASTM G 1.13 A chemical analysis of the inclusions found in the fracture surfaces of both steels was performed by energy-dispersion of x-rays and are given in Figure 11. The chemical composition of the inclusions found in the base metal were different for each steel, as can be seen from Figure 11, although they were similar in shape (globular) and size (7 m to 10 m). These inclusions are composed mainly of Fe, Mn, S, Ca, Si, Al, C, O, which can form (Fe, Mn)S, CaO, MnS-Al2O3 mixtures, Ca-Al-Si-Mg-O

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FIGURE 8. Effect of temperature on the ISCC values for X-60 and X-65 steel weldments.

FIGURE 9. SEM micrographs of X-65 steel weldment fractured by SSR tests in saturated NACE solution with H2S at 37C.

FIGURE 10. SEM micrographs of X-60 steel weldment fractured by SSR tests in saturated NACE solution with H2S at 50C.

globular inclusions, or Fe-Mn-S-O inclusions. These differences, mainly in chemical composition, can explain the differences observed in both hydrogen permeation current density (Figure 6) and SCC susceptibility (Figure 8). Metallographic cross sections of X-60 steel fractured at 25C and 50C are shown in Figures 12 and 13, respectively. It seems that the cracks were predominantly transgranular in nature, but this could have been better shown with an etched specimen. Just as indicated by the polarization curve, that the corrosion rate increased as the temperature increased, the amount of corrosion products inside the cracks is more pronounced at 50C than at 25C, and the crack length was longer at 50C than at 25C, although this might be random. In any case, these pictures show the important role of anodic dissolu-

tion in the cracking process. For X-65 steel, no cracks were observed, only pits, just as shown in Figure 14, possibly because the cracks were polished away. It should be noted that the term pitting refers to the localized breakdown of a thin, protective passive lm. Such lms do not form on carbon steels at low potentials in acidic sour environments, so the observed attack might be better described as localized corrosion that occurs at a break in the somewhat protective iron sulde lm. The requirements for SSC based on the HE mechanism include a susceptible microstructure, a threshold level of hydrogen to induce cracking, and an applied or residual stress.14 First, it can be assumed that the failed round tensile bars used in the H2S study expose every weld microstructure directly to the test solution. In this study, environmental factors that enhanced hydrogen uptake by the welds also enhanced the SSC susceptibility. Thus, the tensile tests showed that these welds are highly susceptible to SCC (Figure 8), since in air the failure was completely ductile. In the testing solution the fracture mode was very brittle, with a very small percentage reduction in area values (%RA) (Figures 9 and 10), and there was a large number of cracks induced by the solution (Figures 11 through 13). Second, permeation studies have consistently shown that the H2S solution to produce hydrogen ux transients peaks at early times, and these measured uxes are directly proportional to surface hydrogen concentrations (Figure 5). Since the SSC susceptibility, ISCC, increases with temperature in the same fashion as the hydrogen concentration, Co, does, presumably HE would be most likely when the concentration of hydrogen is at a maximum. However, the corrosion current values observed in the polarization curves, Figures 4 and 5, were almost unaffected by temperature in the same fashion as the ISCC and Co values were. Additionally, the anodic Tafel

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(a)

(b)

FIGURE 11. Chemical composition of inclusions in X-60 and X-65 steels in fractured specimen by tensile tests.

FIGURE 12. Cross section of X-60 steel weldment fractured at 25C.

FIGURE 13. Cross section of X-60 steel weldment fractured at 50C.

slopes on the polarization curves were not affected by the temperature, which may indicate that the HE is the main mechanism explaining why there might be failures observed in this study, and the anodic dissolution component plays a secondary role, i.e., providing electrons for the reduction of hydrogen. Asahi, et. al.,12 for instance, using the four-point bend tests and hydrogen permeation measurements, also found that the cracking susceptibility and the hydrogen uptake of a steel increased as the H2S concentration and the temperature increased, and with a decrease in the pH value, concluding that the SSC mechanism was HE. Grifths and Turnbull,14 performing SSRT experiments and hydrogen permeation measurements, also found that the cracking susceptibility increased with the amount of hydrogen uptake, and the latter increased with a decrease in the pH, increasing the H2S concentration and the cathodic current charging, concluding the presence of an HE mechanism, and nding a threshold total hydrogen content for cracking under SSRT conditions between 100 ppm and

FIGURE 14. Cross section of X-65 steel weldment fractured at 50C.

250 ppm for the alloy tested. Thus, it seems that the most likely mechanism in the SSC susceptibility of X-60 and X-65 weldments is HE, but anodic dissolu-

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tion plays a secondary role. However, more research is necessary to clarify this point.

REFERENCES
1. J.L. Dawson, J.W. Palmer, P.J. Moreland, G.E. Dicken, Advances in Corrosion Control and Materials in Oil and Gas Production, European Federation of Corrosion Publications, no. 6, P.S. Jackman, L.M. Smith, eds. (Great Britain: IOM Communications Ltd., 1999), p. 155-169. 2. NACE MR0175, Sulde Stress Cracking Resistance Metallic Materials for Oileld Equipment (Houston, TX: NACE International, 2005), p. 1-40. 3. NACE TM0177, Laboratory Testing of Metals for Resistance to Sulde Stress Cracking and Stress Corrosion Cracking in H2S Environments (Houston, TX: NACE, 2005). 4. J.C. Charbonnier, H. Margot-Marette, F. Moussy, D. Bridoux, C. Perdrix, Rev. Mtal. 1 (1988): p. 91-105. 5. A. Gingell, X. Garat, Advances in Corrosion Control and Materials in Oil and Gas Production, European Federation of Corrosion Publications, no. 6, eds. P.S. Jackman, L.M. Smith (Great Britain: IOM Communications Ltd., 1999), p. 127-134. 6. G. Echaniz, C. Morales, T. Perez, Advances in Corrosion Control and Materials in Oil and Gas Production, European Federation of Corrosion Publications, no. 6, eds. P.S. Jackman, L.M. Smith (Great Britain: IOM Communications Ltd., 1999), p. 135-140. 7. H.-Y. Liou, R.-I. Hsieh, W.-T. Tsai, Corros. Sci. 44 (2002): p. 2,841-2,856. 8. M.A.V. Devanathan, Z. Stachurski, Proc. R. Soc. London A 270 (1962): p. 90. 9. A.R. Bhatti, M.E. Saggese, D.N. Hawkins, J.A. Whiteman, M.S. Golding, Welding Journal 63 (1984): p. 224-230. 10. R.E. Dolby, Factors Controlling Weld Toughness-The Present Position, Pt. II-Weld Metals, The Welding Institute Members Report 14/1976/M (1976). 11. P.R. Kirkwood, Met. Constr. 5 (1978): p. 260-264. 12. H. Asahi, M. Ueno, T. Yonezawa, Corrosion 50, 7 (1994): p. 537. 13. ASTM G 1, Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens, in Annual Book of ASTM Standards (West Conshohocken, PA: ASTM International, 1999). 14. A.J. Grifths, A. Turnbull, Corrosion 53, 9 (1997): p. 700.

CONCLUSIONS
The effects of temperature on the corrosion rate, hydrogen uptake, and SSC susceptibility of X-60 and X-65 weldments has been investigated. The most important results are as follows: The corrosion rate, taken as Icorr, for X-60 weldment, increased with an increase in temperature from 25C to 50C, but not for X-65. The amount of hydrogen uptake for the weldments increased with an increase in temperature from 25C to 50C. The SSC susceptibility also increased with an increase in temperature for both weldments from 25C to 50C. The most likely mechanism for the cracking susceptibility of X-60 and X-65 weldments in H2S solutions seems to be HE, and anodic dissolution seems to play a secondary role in the cracking mechanism, but more research is necessary.

ACKNOWLEDGMENTS
The authors acknowledge DGEP-UNAM and CONACYT, from Mexico, for their nancial support.

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