Corrosion Science 48 (2006) 522530 www.elsevier.

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Short Communication

Hydrogen embrittlement of duplex stainless steel under cathodic protection in acidic articial sea water in the presence of sulphide ions
F. Zucchi *, V. Grassi, C. Monticelli, G. Trabanelli
` Corrosion Study Centre A. Dacco, Chemistry Department, University of Ferrara, L.Borsari 46, I-44100 Ferrara, Italy Received 13 May 2004; accepted 5 January 2005 Available online 8 March 2005

Abstract By slow strain rate technique, hydrogen embrittlement (HE) of a 2205 duplex stainless steel was studied in deaerated acidic (pH 6.5) articial sea water, in the absence and in presence of sulphide ions (130 ppm). Strain rate tests (1 106 s1) were performed on specimens polarized at 0.9; 1.0 and 1.2 VSCE at 25 0.1 C. HE was evaluated by R, the ratio between the % elongation to fracture in the aggressive solution and in air. Duplex stainless steel were subjected to HE in acidic articial sea water at 0.9 VSCE. HE increased at 1.0 VSCE but it was reduced at 1.2 VSCE. This decrease was attributed to the inuence of a calcareous deposit. Sulphide ions at 1 ppm were sucient to stimulate HE of duplex stainless steel. The higher the sulphide amount and the more negative the cathodic potential, the higher HE was. In the presence of S2, the shielding eect of the calcareous deposit was not evident. 2005 Elsevier Ltd. All rights reserved.
Keywords: Hydrogen embrittlement; Duplex stainless steel; Acidic articial sea water; Sulphide ions; Cathodic protection; Slow strain rate test

Corresponding author. Tel.: +39 0532 291135; fax: +39 0532 240709. E-mail address: zhf@unife.it (F. Zucchi).

0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2005.01.004

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1. Introduction Duplex stainless steels (DSS) are widely utilized in the petroleum industry, in oil and gas production and transmission, because of their good mechanical properties, their pitting and stress corrosion cracking resistance in chloride solutions, also in the presence of hydrogen sulphide [16]. DSS are susceptible to failure by hydrogen embrittlement (HE) in particular conditions of hydrogen charging, temperature, composition and stress [79]. In oil and gas production, hydrogen can be generated by galvanic coupling between DSS tubing and carbon steel casing downhole. In this case the aggressive solution consists of sour brine with the pH in the range 3.54.5 at elevated temperatures. Another source of hydrogen derives from the cathodic protection of pipelines in sea water. The corrosion behaviour of DSS, at dierent potentials and in more or less concentrated chloride solutions polluted by hydrogen sulphide, has been investigated by dierent authors [1017]. Griths and Turnbull [17] studied the eect of coupling DSS with steel in 3.5% NaCl in the presence of dierent concentrations of hydrogen sulphide at 80 C. Nevertheless, the behaviour of cathodically protected DSS in natural or articial sea water has not been frequently investigated. The aim of this paper was to determine by slow strain rate test (SSRT) the HE on SAF2205 DSS under cathodic protection in acidic articial sea water (AASW), in the absence or in presence of sulphide ions.

2. Experimental SSRT were performed on SAF2205 DSS specimens, machined from a 1.5 mm thick sheet, with gauge length of 35 8 mm. The specimen surface was prepared with emery paper up to No. 800. Tests were performed at a nominal strain rate of 1 106 s1. The susceptibility to HE was evaluated by the parameter R, the ratio between % elongation to fracture in the aggressive solution and in air. The specimens were inserted into a 1 l capacity double wall Pyrex glass cell, connected to a thermostat to maintain the temperature at 25 0.1 C. A glass pH-electrode and a saturated calomel electrode (SCE) were inserted into the cell, together with a tube for continuous nitrogen bubbling, a glass bridge, closed with a glass frit, connecting the Pt counter electrode compartment. The aggressive solution was an acidic, pH 6.5, articial sea water (AASW, ASTM D-1141-50T), which was deaerated by nitrogen bubbling during the night in a 10 l reservoir and was continuously recirculated in the cell by a magnetic drive pump. Solutions containing 1, 10 and 30 ppm of sulphide ions were prepared by adding a concentrated solution of Na2S 9H2O to deaerated AASW. In order to maintain the initial concentration of sulphides, which was checked by iodometric titration, the correct amount of the concentrated sulphide solution was added each day.

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An optical microscope was used to observe the gauge sections while a scanning electron microscope (SEM) was used to examine the fracture zone.

3. Results 3.1. AASW Fig. 1 gathers the stress/strain (r/e) curves measured in AASW on DSS specimens at Ecorr or polarized at the various potentials; the r/e curve of the specimen in air is also shown. Table 1 reports the results of the duplicated tests in acidic articial sea water. The value of the percentage elongation to fracture (er%) in air and in AASW at Ecorr was the same (43%), testifying the absence of HE susceptibility of DSS in this condition. er% decreased to 34% at 0.9 VSCE and to 32.6% at 1.0 VSCE, but it increased to 37% at 1.2 VSCE. The R values were 0.80 for the specimens polarized at 0.9 VSCE, 0.76 for those at 1.0 VSCE and 0.86 for those polarized at 1.2 VSCE.

900 800 700 600

( MPa )

500 400 300 200 100 0 0 5 10 15 20 25 30 35 -1.0 -0.9 -1.2

Ecorr Air

40

45

%
Fig. 1. Stress/strain (r/e) curves measured on specimen in air and in AASW at Ecorr and polarized at 0.9, 1.0, 1.2 VSCE.

Table 1 Percentage elongation to fracture in air and in acidic articial sea water at dierent cathodic potentials Air AASW Ecorr e% (mean) 42.343.5 (42.9) 42.142.9 (42.5) 0.9 VSCE 33.534.9 (34.2) 1.0 VSCE 32.233.0 (32.6) 1.2 VSCE 36.236.838.3 (37.1)

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Fig. 2. Presence of secondary cracks in a gauge section.

Fig. 3. Macrography of the specimen cracked at 1.2 VSCE.

Metallographic observation of the gauge sections showed the presence of many secondary cracks in all the specimens (Fig. 2). The er% increase at 1.2 VSCE was attributed to the calcareous deposit formation. At cathodic potentials the surface pH rapidly augmented, thus provoking the formation of a calcareous deposit, which interfered with the hydrogen evolution process. In the macrography of the specimen cracked at 1.2 VSCE the presence of a nonuniform layer of white products was evident (Fig. 3). XRD analysis showed that the white deposit was chiey brucite, Mg(OH)2. 3.2. Inuence of sulde ions As an example, Fig. 4 shows the r/e curves recorded at 1.0 VSCE in AASW in the absence and in presence of 1, 10 and 30 ppm of sulphide ions. The eect of sulphide concentration was evident. The % elongation to fracture decreased from 33% in AASW to 25% with the addition of 30 ppm of sulphide, while 1 ppm of sulphide ions was sucient to enhance the HE susceptibility of DSS.

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(MPa)

500 400 300 200 100 0 0 5 10 15 20 25 30 35 40 45 30ppm 10ppm 1ppm AASW Air

%
Fig. 4. Stress/strain curves measured on specimen in AASW and in AASW added of 1, 10 and 30 ppm of sulde ions, polarized at 1.0 VSCE.

90 85 80 75
--

AASW

R%

70 65 60 55 50 45 -0.8 -0.9 -1.0 -1.1

+ 1ppm S

+ 10ppm S

--

+ 30ppm S

--

-1.2

-1.3

Potential (VSCE)
Fig. 5. R values calculated from the SSRT performed in AASW and in AASW added of 1, 10 and 30 ppm of sulde ions at the dierent cathodic potentials.

In Fig. 5, the R values calculated from the SSRT performed in AASW with the addition of 1, 10 and 30 ppm of sulphide ions at the dierent cathodic potentials are reported and compared with those in unpolluted AASW. At all the potentials the presence of sulphide ions produced a decrease in R values and this eect was more evident at more negative potentials and at higher pollutant concentrations.

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Fig. 6. Macrography of the specimen polarized at 1.2 VSCE in AASW + 1 ppm S2.

The macrography of Fig. 6 shows the gauge section of a specimen polarized in AASW + 1 ppm S2 at 1.2 VSCE. White products were present on the surface and also inside the secondary cracks. The stimulating eect of sulphide on HE would seem to prevail on the shielding action of the calcareous deposit. The stimulating action of S2 on HE may be evidenced by the comparison of the gauge sections of specimens polarized at the same potentials in AASW, with or without S2. Fig. 7 shows the gauge sections of specimens polarized at 0.9 VSCE in unpolluted AASW and in AASW + 30 ppm S2. The number of secondary cracks of the latter specimen is higher than that in unpolluted AASW. The section of the cracked specimens, observed by metallographic microscope, clearly evidenced that the cracks started in the ferrite phase (Fig. 8). SEM observations were performed to examine the fracture zone. In all the polarized specimens the crack morphology was predominantly transgranular, as may be seen from the specimen tested in AASW at 1.2 VSCE (Fig. 9). The ferrite grains presented a cleavage mode, characteristic of HE, while in the austenite grains a rough stepwise

Fig. 7. Macrography of the specimen polarized at 0.9 VSCE in AASW (a) and in AASW + 30 ppm S2 (b).

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Fig. 8. Micrography of section of the cracked specimen polarized at 1.0 VSCE in AASW + 30 ppm S2.

Fig. 9. Micrography of the fracture zone of the specimen polarized at 1.2 VSCE in AASW.

Fig. 10. Micrography of the fracture zone of the specimen at Ecorr.

morphology of crack developed. The fracture zone of the specimens tested in AASW at Ecorr was completely ductile, characterized by dimples (Fig. 10).

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4. Discussion DSS suered HE when it was strained and cathodically polarized in deaerated AASW, as it was observed in 3.5% NaCl solutions [12]. HE eects were already evident at 0.9 VSCE, with cathodic current density of some lA/cm2, and they increased at 1.0 VSCE. These eects tended to decrease at 1.2 VSCE because of the calcareous deposit formation. Although the solution pH was maintained at about 6.5 by adding HCl, the pH at the metal/solution interface could reach high enough values to permit the precipitation of Mg(OH)2. This assumption was conrmed by the results of SSRT performed on the same DSS in deaerated, pH 6.5 buered, 3.5% NaCl solutions, where a regular increase in HE eects from 1.0 to 1.3 VSCE was observed [18]. It is well known that the diusion of hydrogen atoms through the austenitic phase is much slower than through the ferritic phase, while the solubility of hydrogen atoms in c phase is higher than in a phase. Alpha phase is readily embrittled by hydrogen, while c phase can be an obstacle to crack propagation. The micrographies of the secondary cracks clearly showed that all the cracks started in the a phase and during their progress they either avoided or were arrested by the austenite phase. By reducing the recombination rate of hydrogen atoms to hydrogen molecule, sulphide ions increase the adsorbed hydrogen on the surface and consequently the absorbed hydrogen. Sulphide ions (1 ppm) was sucient to increase HE susceptibility of DSS. This eect was increased by decreasing the applied potential and by increasing the sulphide ion concentration. It is noteworthy that the S2 stimulating action on HE prevailed over the shielding eect of the calcareous deposit. This fact conrms that the hydrogen uptake producing cracking is controlled by a local process which would be associated with lm rupture on the surface [17]. The eect of sulphide ions may be attributed to a much higher surface coverage of hydrogen atoms on the naked metal surface, induced by straining. In this way the concentration of hydrogen atoms locally rises beyond the threshold value necessary for cracking. The sulphide ion adsorption on the metal surface also reduces the repassivation rate so that the produced hydrogen amount during a lm rupture event is greater. SEM pictures of the fracture zone showed that the cracks, initiated on the ferrite phase, pass through the austenite phase, changing from a typical brittle cleavage in the former phase to roughly stepwise in the latter one. The austenite embrittlement was attributed to the e martensite formation under straining and hydrogen evolution [13]. Oltra et al. [19] demonstrated that the supply of hydrogen to the austenitic grains of DSS is controlled by localized damage occurring at the a/c boundary. The penetration of cleavage cracking from the hydrogen embrittled ferrite forms a crack embryo in the austenite. Hydrogen locally penetrates at the crack tip and along the slip planes, interacting with the dislocation mobility. This will lead to zig-zag microcracking in accordance with corrosion enhanced plasticity model [20] for the transgranular corrosion cracking of fcc materials.

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5. Conclusions At 25 C, SAF 2205 DSS was susceptible to HE in deaerated pH 6.5 AASW, when cathodically protected at 0.9 VSCE. Calcareous deposit formation at 1.2 VSCE partially reduced HE eects. The presence of sulphide ions, in the concentration range between 1 and 30 ppm, drastically increased HE susceptibility. The higher the S2 concentration and the more negative the cathodic potential, the higher this eect was.

Acknowledgement The authors wish to thank AvestaPolarit ABE AB for supplying the 2205 duplex stainless steel base material.

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