Corrosion Science 52 (2010) 113117

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Role of nitrite addition in chloride stress corrosion cracking of a super duplex stainless steel
R.K. Singh Raman a,b,*, W.H. Siew a
a b

Department of Chemical Engineering, Monash University, Melbourne, Vic. 3800, Australia Department of Mechanical and Aerospace Engineering, Monash University, Melbourne, Vic. 3800, Australia

a r t i c l e

i n f o

a b s t r a c t
This paper presents the role of addition of nitrite ions in susceptibility of a super duplex stainless steel, SAF 2507 to stress corrosion cracking (SCC) in chloride environment, which has a particular industrial relevance. Slow strain rate testing (SSRT) in 30 wt.% MgCl2 solution established SCC susceptibility, as evidenced by post-SSRT fractography. However, the addition of nitrite has interesting inuence. At their lower concentrations, nitrite additions seem to decrease SCC susceptibility, whereas, at a higher concentration, it has an accelerating effect on SCC. Attempts have been made to understand this behaviour on the basis of the role of nitrite in passivation and pitting characteristics of SAF 2507 in chloride solution. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 31 August 2008 Accepted 18 August 2009 Available online 23 August 2009 Keywords: A. Stainless steel Stress corrosion cracking

1. Introduction Duplex stainless steels (DSS), which generally have a ferrite/ austenite volume ratio of 1:1, and their advanced varieties (viz., super DSS), show considerable resistance to pitting and stress corrosion cracking (SCC) and are used in environments where traditional austenitic stainless steels suffer chloride-SCC [1,2]. SAF 2507 (UNS S32750) is a highly alloyed duplex stainless steel with a Pitting Resistance Equivalent Number (PREN) of greater than 40. Duplex stainless steels achieve the considerably high resistance to pitting corrosion due mainly to their higher chromium, molybdenum and nitrogen contents, as compared to the traditional DSS varieties, such as SAF 2205 [3]. Common austenitic stainless steels (namely, UNS S30400 and S31600) are believed to be resistant to chloride-SCC at temperatures below 50 C [4,5] whereas temperature limits are considerably higher for the duplex grades (for example, a common duplex SS S31803 is reported to be immune to SCC in 3% NaCl at temperature up to 150 C [6]). Advanced duplex stainless steels (viz., super duplex SS UNS 32750) are immune to chloride-SCC up to still higher temperatures [4,5]. Superior SCC resistance of DSS in chloride media is attributed to the electrochemical and mechanical interactions of the two phases. Austenite, which is more susceptible to SCC, is cathodically protected by the ferrite [1,2], whereas, the ferrite, which is believed to be under compression due to keying effect [7] in the dual phase structure, is also protected from SCC (since SCC essentially requires tensile

* Corresponding author. Address: Department of Mechanical and Aerospace Engineering, Monash University, Building 31, Vic. 3800, Australia. Tel.: +61 3 9905 3671; fax: +61 3 9905 1825. E-mail address: Raman.Singh@eng.monash.edu.au (R.K. Singh Raman). 0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2009.08.041

stress). In fact, the improvement in the chloride-SCC resistance due to the presence of ferrite with austenite has been known in the case of weld metal region of austenitic stainless steel weldments. The presence of the retained ferrite (510%) in the weld metal and its absence in the base metal of the austenitic SS weldment accounts for the superior SCC resistance of the weld metal [8]. Superior SCC resistance of DSS to austenitic variety is also ascribed [9] to its resistance to grain boundary sensitization (i.e., formation of chromium carbide at the alloy grain boundaries, leaving the neighbouring area lean in Cr and susceptible to intergranular SCC). Owing to its proven resistance to chloride pitting and SCC, super duplex stainless steel, SAF 2507 was selected as the material of construction for vessels used for stripping vinyl chloride monomer in a PVC processing plant in Australia. During a maintenance inspection, alarmingly high instances of pitting (which is a wellknown SCC initiator) and SCC were observed. Pitting and SCC were believed to have initiated and accentuated particularly when nitrite/nitrate compounds were used as an alternative chemical for arresting certain chemical reactions in the stripping step, in order to economize the stripping operation. There are reports on the effect of a few anions, viz., chromates, sulphates, molybdates and nitrates on pitting and SCC behaviour of stainless steels in chloride solutions [1022]. A majority of these reports suggested an inhibiting effect of these anions on stainless steel pitting. However, these studies are all on austenitic stainless steels, and little work seems to have been conducted on the effect of nitrite/nitrate on pitting and stress corrosion cracking of SAF 2507 in chloride environments. This paper presents results of slow strain rate testing of super duplex stainless steel, SAF 2507, in chloride solutions with and without different levels of nitrite content.

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R.K. Singh Raman, W.H. Siew / Corrosion Science 52 (2010) 113117 Table 2 Solutions used for electrochemical experiments to characterize the effects of nitrite anions. Volume of 1 M NaNO2 added to 250 mL 30 wt.% MgCl2 0 10 20 40 Concentration of NO2 anions (ppm) 0 1400 2800 5600 Cl:NO2 ratio 160:1 80:1 40:1

2. Experimental The chemical composition of DSS SAF 2507 plates used in the present study was analysed (Table 1). Microstructure of the duly polished steel surface was revealed by electrochemical etching (etchant: 10 wt.% oxalic acid, voltage: 20 V, current: 5 A, time: 100 s) and observed by optical microscopy. Slow strain rate testing (SSRT) rigs used for the present study were equipped with autoclaves for conducting tests using chloride solutions at high temperatures and pressures. With the use of a variable speed motor, the rigs provide different constant crosshead speeds as the motor speed are varied from 10% to 100% of the full motor speed, which correspond to various strain rates in the range of 107 s1. SSRT specimens were machined perpendicular to the rolling direction of the plate. Uniaxial cylindrical tensile specimens of 8.0 0.2 mm outer diameter (OD) with a gauge section of 3.0 0.2 mm OD and 20.0 0.2 mm length were used. The gauge section was polished in the longitudinal direction progressively to a 1200 grit nish, rinsed with acetone/water and air dried. A layer of Teon tape was applied on the specimens except for their gauge sections. After a nal rinse with acetone, the specimen was immediately mounted in the autoclave which was then lled with different test solutions at 180 C. While 30 wt.% MgCl2 (2.23 105 ppm Cl) constituted the primary test solution, some of the tests solutions were added with various concentrations of nitrite (in ppm by weight), in order to achieve different chloride-to-nitrite ratios, as described in Table 2. All solutions were prepared using laboratory grade chemicals and distilled water. While immersed in the test solution and subjected to straining at a constant rate, tensile stress was measured using a load cell and recorded every 10 min by a data-taker. All tests were conducted under open circuit potential conditions and the tensile specimen insulated from the grips and autoclave body by using appropriate Teon and ceramic insulators. Fractographic examinations of specimens after completion of SSRT tests were carried out using scanning electron microscopy (SEM) in order to characterize the presence of features of SCC. 3. Results and discussion Etched microstructure of the duplex stainless steel (shown in Fig. 1) shows elongated grains of austenite and ferrite in the rolling direction. Two sets of SSRT experiments were carried out: (a) for identifying the strain rate or the range of strain rates that produces SCC in plain 30% MgCl2 solution, and (b) for comparison of SCC susceptibility in 30% MgCl2, with and without nitrite addition (at a strain rate as identied through the rst set of experiments). 3.1. Slow strain rate testing at various strain rates Fig. 1 presents the force vs. time curves of SAF 2507 tensile specimens tested at 180 C at 30%, 40% and 70% of the full motor speeds, which, respectively, correspond to the strain rates of 3.7 107, 5.3 107 and 10.6 107 s1. It is evident from Fig. 2 that time to failure (tf) is considerably lower for 30% and 70% motor speeds in comparison to that at 40% motor speed. While the shorter tf at 70% motor speed may simply be associated with
Table 1 Chemical composition (wt.%) of SAF 2507 super duplex stainless steel plate. Elements Wt.% C 0.02 Cr 24.6 Ni 6.52 Mn 0.83 Mo 3.8 N 0.27

Fig. 1. Etched microstructure of the duplex stainless steel used in the present study.

the strain rate, the considerable longer tf for the specimen tested at 40%, in comparison to the specimen tested at 30% motor is a clear indication of SCC at 30% motor speed. Indeed, the SEM fractography revealed the features of intergranular SCC on a considerable fraction of the fracture surfaces of specimens tested at 30% motor speeds (Fig. 3). The remainder of the fracture surfaces of these specimens had features indicative of ductile failure (i.e., ductile dimples, as shown in Fig. 4). On the other hand, the entire fracture surface of the specimens tested at 40% and 70% motor speed only had ductile dimples (similar to the features shown in Fig. 4), i.e., no areas with features of intergranular cracking was detected on these specimens. These results suggest 30% motor speed (i.e., strain rates of 3.7 107 s1) to be suitable for causing intergranular cracking to SAF 2507 while immersed in 30% MgCl2 at 180 C. 3.2. Slow strain rate testing: role of nitrite addition SSRT runs carried out using plain 30 wt.% MgCl2 solution at 180 C have clearly resulted in intergranular SCC when a motor speed of 30% (i.e., a strain rate of 3.7 107 s1) was employed (as reported in Section 3.1). Hence, all the SSRT tests for investigating the role of nitrite addition to the 30 wt.% MgCl2 solution were carried out only at 30% motor speed. Fig. 5 presents the force versus time curves plotted with experimental runs in parafn oil and plain MgCl2 solution, as well as in the MgCl2 solution added with 1400, 2800 and 5600 ppm (by wt.) of NO2 anions. The run in parafn oil represents failure of the tensile specimen exclusively by mechanical overload, with a failure

Cu 0.13

P 0.02

Si 0.38

Al <0.01

S <0.01

Fe Balance

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6000

5000

70% motor speed

40% motor speed

4000

Force (N)

30% motor speed

3000

2000

1000

0 0 20 40 60 80 100 Time (hours) 120 140 160 180

Fig. 2. Force vs. time SSRT curves of SAF 2507 in 30 wt.% MgCl2 solution at 180 C, at different strain rates.

Fig. 4. A representative SEM fractograph showing purely ductile failure. Fig. 3. SEM fractograph of SAF 2507 tested at 30% motor speed (3.7 10 s ) in 30 wt.% MgCl2 at 180 C, showing intergranular SCC over considerable fraction of the fracture surface.
7 1

time of 245 h, and a maximum achieved force of approximately 5500 N. With MgCl2 in place of parafn oil, both failure time and maximum load decreased considerably to approximately 40 h and 3800 N, respectively, indicating chloride stress corrosion cracking, which is consistent with the results shown in Fig. 2. SEM fractograph of the specimen was also consistent with the feature for intergranular cracking (similar to that shown in Fig. 3), conrming SCC. Addition of lower levels of NO2 (i.e., 1400 and 2800 ppm) appears to inhibit SCC, with failure times approaching the values as for the SSRT runs in parafn, suggesting absence of SCC. SEM fractography corroborates the absence of SCC, as only ductile dimples were observed over the entire fracture surface (as shown in Fig. 6). However, addition of a higher concentration of NO2 (i.e., 5600 ppm) clearly shows an accelerated failure as compared to SSRT runs in parafn and chloride solution with 1400 and

2800 ppm NO2 (Fig. 5), suggesting SCC failure. SEM fractography conrmed the presence of intergranular SCC (Fig. 7). A duplicate SSRT run that was carried out to ascertain reproducibility of the observed behaviour of increase in SCC susceptibility at higher NO2 content, as opposed to inhibition at lower NO2 content of 30 wt.% MgCl2 solution, conrmed the behaviour (Fig. 5). SCC susceptibility is often represented as the ratio of ductility (measures as elongation, time to failure (tf) or reduction of area) in the test environment and that in an inert environment. In Fig. 8, ratios of tf in chloride solutions (with different levels of NO2) and in parafn oil (inert) have been plotted against the NO2 content of the chloride solution. SCC susceptibility appears to have dual dependence on the presence of nitrite anions in the chloride environment. At a NO2 concentration of 5600 ppm, SCC susceptibility is considerably enhanced whereas, at lower nitrite concentrations, the susceptibility decreases substantially. At this stage, a concrete explanation for the dual behaviour has not been achieved. However, there are a few reports/mechanisms on the role of nitrate ions in inhibiting the pitting susceptibility of stain-

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6000

paraffin oil

5000
1400 ppm NO2-

4000 Force, N

2800 ppm NO2No NO2-

3000

2000

5600 ppm NO2-, run 2 5600 ppm NO2-, run 1

1000

0 0 50 100 150 Time, hours

Fig. 5. Force vs. time SSRT curves for SAF 2507 in 30 wt.% MgCl2 with different concentrations of NO2 at 180 C.

200

250

300

1.2

tf (corrosive) / tf (inert)

1 0.8 0.6 0.4 0.2 0 0 2000 4000 Nitite concentration, ppm (wt) 6000

Fig. 8. A plot of SCC susceptibility (expressed as ratios of time to failure (tf) in chloride solutions and in parafn oil) against the NO2 content of the chloride solution. Fig. 6. SEM fractograph of SAF 2507 tested at 30% motor speed (3.7 107 s1) in 30 wt.% MgCl2 with 1400 ppm NO2 at 180 C, representative of ductile dimples, present over the entire fracture surface.

Fig. 7. SEM fractograph of SAF 2507 tested at 30% motor speed (3.7 107 s1) in 30 wt.% MgCl2 with 5600 ppm NaNO2 at 180 C, showing intergranular crack propagation.

less steels in chloride solution. Since, both nitrite and nitrate may have similar inhibiting effects, as well as since pitting is one of the common modes for SCC crack initiation, it may be pertinent to understand the role of nitrate/nitrite in pitting. A study by Newman and Ajjawi [12] on the inuence of nitrate in growth of an articial pit suggests that nitrate induces passivation under a salt lm at certain potentials which depends on the nitrate-to-chloride ratio. In a subsequent paper, Newman and Shahrabi [10] have suggested that the electro-reduction of nitrate anions may contribute to nitrogen enrichment on the active dissolution sites, improving pitting resistance. This model is consistent with the widely accepted view on improvement in pitting resistance of nitrogen bearing stainless steels. Presuming that nitrite can be expected to have inhibiting effects on pitting similar to that by nitrate, as well as presuming that pitting is the mode of SCC crack initiation in the present study, the observed improvement in SCC as a result of addition of lower levels of NO2 (i.e., 1400 and 2800 ppm) seems to nd an explanation. Features of pitting were observed (Fig. 9) when the surfaces of the gauge section of the failed specimens were examined by SEM. The increased SCC susceptibility in the solution with a higher nitrite concentration (5600 ppm) can possibly be explained if such a concentration could be proved to cause instability in the passive lm at the crack-tip. It has not been possible to carry out high tem-

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authors at a low temperature strongly support the change from the inhibiting effect of nitrite addition to the accelerating effect. A comparison of the anodic polarization curve for SAF 2507 in a plain chloride solution with the curve in the solution with 100 ppm NO2 clearly shows a considerable improvement in pitting resistance as a result of the NO2 addition (as evident from the shift in the pitting potential, shown in Fig. 10). However, at a considerably higher NO2 concentration (viz., 1000 ppm) in the chloride solution, the passivation characteristics appears to begin to be signicantly disturbed, whereas at a still higher concentration (2000 ppm), the passivation characteristics is considerably disturbed (Fig. 10). 4. Conclusions As established by slow strain rate testing (SSRT) of a super duplex stainless steel, SAF 2507, at various strain rates, in 30% MagCl2 solution at 180 C, with and without various NO2 additions, and the post-SSRT fractography:
Fig. 9. SEM microscopy of gauge section of the failed specimens showing features of pitting.

1.4

(1) SAF 2507 suffers intergranular stress corrosion cracking (SCC) at strain rates of 3.7 107 and no SCC at higher strain rates. (2) Additions of 1400 and 2800 ppm of NO2 solution effectively suppress susceptibility to chloride-SCC. (3) Addition of 5600 ppm NO2 accelerates susceptibility to chloride-SCC.

1.2

2000ppm nitrite

1
100ppm nitrite 1000ppm nitrite

Acknowledgement Authors are grateful to the Australian Research Council and the PVC manufacturing company, Australian Vinyls, for the Linkage grant, which enabled the work presented in this paper. References
[1] N. Neilsen, Corrosion 20 (1964) 105. [2] S. Shimodaira, M. Takano, Y. Taleizawa, H. Kamida, SCC and Hydrogen Embrittlement of Iron-base Alloys, Pub: NACE, 1977, p. 1003. [3] A.J. Sedriks, Corrosion of Stainless Steels, John Wiley & Sons, Inc., 1996. [4] S. Bernhardsson, Duplex Stainless Steel 91, Les Edition de Physique, Les Ulis, France, 1991, p. 185. [5] J.E. Truman, H.W. Kirby, Metallurgia Aug (1965) 67. [6] R. Francis, Duplex stainless steels 94, paper KIV, in: T.G. Gooch (Ed.), TWI, Cambridge, UK, 1994. [7] I.A. Ward, L.H. Keys, Stainless Steels 84, Gothenberg, 1984. [8] T.G. Gooch, Doc.IIS/IIW-783-83, p. 64. [9] J.O. Nilsson, A. Wilson, Mater. Sci. Technol. 9 (1993) 545. [10] R.C. Newman, T. Shahrabi, Corros. Sci. 27 (8) (1987) 827838. [11] Y. Zuo, H. Wang, J. Zhao, J. Xiong, Corros. Sci. 44 (2002) 1324. [12] R.C. Newman, M.A.A. Ajjawi, Corros. Sci. 26 (12) (1986) 10571063. [13] H.H. Uhlig, J.E.W. Cook, J. Electrochem. Soc. 116 (2) (1969) 173177. [14] H.P. Leckie, H.H. Uhlig, J. Electrochem. Soc. 113 (12) (1966) 12621267. [15] R.L. Jones, Corrosion 31 (12) (1975) 431433. [16] H. Hirano, N. Aoki, T. Kurosawa, Corrosion 39 (1983) 314322. [17] G.O. Illevbare, K.J. King, S.R. Gordon, H.A. Elayat, G.E. Gdowski, T.S.E. Summers, 206th Meeting of The Electrochemical Society, Honolulu, HI, 2004. [18] S.A.M. Refaey, S.S.A. El-Rehim, F. Taha, M.B. Saleh, R.A. Ahmed, Appl. Surf. Sci. 158 (2000) 190196. [19] V.K. Gouda, S.M. Sayed, Corros. Sci. 13 (1973) 841852. [20] J.A. Bardwell, G.I. Sproule, D.F. Mitchell, B. Macdougall, M.J. Graham, J. Chem. Soc. Faraday Trans. 87 (7) (1991) 10111019. [21] C.C. Pu, J.K. Wu, Corros. Prev. Control 50 (4) (2003) 155156. [22] W.H. Siew, R.K. Singh Raman, Monash University, unpublished data.

0.8

Potential, V (vs SCE)

No nitrite

0.6

0.4

0.2

-0.2

-0.4

-10

-8

-6

-4

-2

log (Current Density), A/cm2

Fig. 10. Anodic polarization curves of SAF 2507 in 0.1 M NaCl with 0, 100, 1000 and 2000 ppm NO2, at 95 C.

perature electrochemical experiments, in order to generate the necessary pitting data at 180 C for validating the inhibiting and accelerating effects of nitrite, respectively, at the low and high nitrite concentrations. However, the pitting data generated by the