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Intergranular and Pitting Corrosion Susceptibilities of a Supermartensitic Stainless Steel Weldment

J.M. Aquino,,* C.A. DellaRovere,** and S.E. Kuri**

ABSTRACT
Degree of sensitization and pitting corrosion potential of a supermartensitic stainless steel weldment were measured and compared. An improvement in the degree of sensitization and in the pitting corrosion potential, from the base metal to the weld metal, was found in the electron beam weldment. The heat-affected zone showed a degree of sensitization level as low as the one in the weld metal, most likely from the chromium carbide precipitate redissolution; however, the -ferrite phase was responsible for an intense corrosion attack next to the fusion line of the heat-affected zone. The pitting potential yielded high values when the degree of sensitization was low. This indicates that pits were preferentially nucleated at samples with high amounts of chromium-depleted zones. KEY WORdS: degree of sensitization, double loop-electrochemical potentiokinetic reactivation, electron beam weldments, intergranular corrosion, pitting corrosion, supermartensitic stainless steel

INTRODUCTION
Supermartensitic stainless steel (SMSS) arose in the 1990s as an attractive alternative to conventional carbon steel and to duplex stainless steel. It has two main advantages: low prices and high performance against corrosion. The main metallurgical characteris Submitted for publication February 11, 2010; in revised form, April 18, 2010. Corresponding author. E-mail: zeaquino@yahoo.com.br. * So Carlos Federal University, Chemistry Department, Rodovia Washington Lus, km 235, CEP 13565-905, So Carlos-SP, Brazil. ** So Carlos Federal University, Materials Engineering Department, Rodovia Washington Lus, km 235, CEP 13565-905, So CarlosSP, Brazil.

tics are low carbon contents up to 0.01%, nickel contents up to 6%, and molybdenum contents up to 3%. The low carbon level improved the material weldability and led to a decrease in the precipitates, mainly chromium carbide. Consequently, a more corrosionresistant material should be expected when considering intergranular stress corrosion cracking (IGSCC), which is the most common problem that occurs in martensitic stainless steels (MSS). However, the literature1 has shown that SMSS is susceptible to this type of corrosion problem, which was described in a simulated heat-affected zone (HAZ). The cracks seemed to propagate along prior austenite grain boundaries, where the chromium carbide precipitated. In welded joints, the precipitation process is likely to occur in the HAZ due to the thermal heat gradient generation provided by the welding apparatus,2,3 and to the time in which the material remains close to the fusion4 temperature and the precipitation5 temperature. Carbide precipitates also occur as a result of the combination of the carbon matrix saturation and the tempering effect of subsequent welding passes; however, this process is not expected to occur in the single pass welded joints.3 Chromium carbide precipitates, and other types of precipitates like Fe2Mo6 and inclusions in stainless steel, lead to a corrosion attack susceptibility. Particularly, the intergranular corrosion is a selective process that occurs in sensitized regions as a result of inadequate heat treatments, weldings, or high-temperature services.7 In the classical sensitization process, chromium carbides precipitate at grain boundaries leading to a consequent chromium impoverishment in the

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TAbLe 1 Chemical Composition (mass%) of the Supermartensitic Stainless Steel

C Si Mn P S Cr Ni Mo Ti V Cu O N 0.007 0.07 1.6 0.007 0.003 11.4 6.1 2.6 0.02 0.05 0.5 0.01 0.01

TAbLe 2 Electron Beam Welding Parameters

Parameters Vacuum Welding voltage Working distance Welding speed Welding current Heat input Conditions 1 mbar 60 kV 50 mm 7 mm/s 195 mA 1.6 kJ/mm

adjacent matrix. The other type of sensitization process refers to the martensite-induced sensitization caused by the chromium carbide precipitates in the martensitic lath boundaries.7-8 This last process leads to an intergranular corrosion attack. Pitting corrosion also may be influenced by chromium-depleted zones as well as in the proximity of manganese sulfide (MnS) inclusions.9-14 According to the literature,3,5,15 the HAZ of conventional multipass welds processes is often a critical point regarding intergranular and pitting corrosion. However, weldings produced by high-energy density processes, such as the electron beam (EB), can promote a diminishment in the chromium carbide precipitates,5 because of the very rapid processes of heating and cooling. These intrinsic characteristics lead to high-quality weldments, especially concerning the HAZ, as demonstrated in the literature.16-17 Consequently, the goal of the present work was to measure the degree of sensitization (DOS) through the double loop-electrochemical potentiokinetic reactivation (DL-EPR) technique as well as the pitting potential through the polarization curves of an autogenous SMSS weldment.

EXPERIMENTAL Procedures
Electrochemical measurements were performed for samples of base metals (BM), HAZ, and weld met-

als (WM) of a high-alloy SMSS weldment, which was welded by an electron beam in a low-vacuum chamber. The full penetration butt weld was done between two 20-mm-thick plates, previously hot-rolled and tempered at 600C for 10 min. The welding was done in a single pass without metal filler wire additions. No postweld heat treatment was applied. Tables 1 and 2 show the chemical composition of the plate and the welding operation conditions, respectively. X-ray diffraction measurements were done to identify and quantify the austenitic and martensitic/ ferrite phases presented in the SMSS. The full details are described in other papers.16-17 The 1-mm-thick samples were extracted by electroerosion from the inner part of the weldment middle, as schematically shown in Figure 1. The extraction procedure was conducted after etching the weldment with a Villelas reagent or with a mixture of hydrochloric acid/nitric acid (HCl/HNO3, 3:1). Subsequently, the corresponding weldment regions were identified through an optical microscopic analysis. The electrochemical investigation in the distinct weldment regions intends to disregard any galvanic influence of other regions. The electrochemical measurements in the HAZ sample were not accomplished in separate regions since that sample is characterized by a heterogeneous microstructure. Testing samples were mounted in polyester resin, attempting to avoid the presence of crevices after the electric contact. The exposed area was 0.40 cm2. Before the electrochemical measurements, the samples were wet-grinded on 600 silicon carbide (SiC) paper, washed with distilled water, and immersed in the electrochemical cell. The testing solution for the DL-EPR measurements was composed of reagent-grade 0.5 mol/L sulfuric acid (H2SO4) and 0.01 mol/L potassium thiocyanate (KSCN). Polarization curves were obtained after two steps. First, the working electrode was sub-

(a)

(b)

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FiGUre 1. Sample extraction schematic representation of an electron beam weldment single pass: (a) welded joint, (b) weldment slice extracted by electroerosion, and (c) testing samples having dimensions of 10 by 5 by 1 mm. Regions 1, 2, and 3 refer to the BM, HAZ, and WM. The asterisk indicates where the electrochemical testings were done.

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jected to open-circuit conditions until a steady-state potential (Ecorr) was reached. This was accomplished in 30 min. Then, an anodic potentiodynamic sweeping rate of 1.67 mV/s, from 100 mV/Ecorr to 600 mV vs. saturated calomel electrode (SCE), was imposed. At 600 mV (passive vertex potential), the potential scanning was reversed back to 100 mV/Ecorr. At least four curves for each sample region were done to obtain good reproducibility. The DL-EPR testing results were expressed in the current densities ratio, iR/ia, which was used to evaluate the DOS.18 The iR term is the reactivation current density (maximum current density in the cathodic scan), and the ia term is the activation current density (maximum current density in the anodic scan). A 3.56 mass% reagent-grade sodium chloride (NaCl) solution was used for the pitting potential determination. Polarization curves were obtained after the Ecorr was reached. That occurred in 35 min. Then, a potentiodynamic sweeping rate of 1 mV/s, from 100 mV/Ecorr to a potential slightly above the pitting potential, was imposed. The pitting potential was determined when a sharp and sudden rise in the current density occurred. A minimum of five curves were done for each sample region. All measurements were performed in distilled water, which was naturally aerated. The temperature was held at 25C. A conventional electrochemical cell that was composed of a platinum counter electrode and a SCE, connected to a potentiostat, was used. Scanning electron microscopy (SEM) images were obtained in all the weldment samples after the electrochemical measurements. To obtain clear and detailed images, a pretreatment in 1 m alumina (Al2O3) was completed.

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RESULTS AND DISCUSSION

Figures 2(a) through (c) show the BM, HAZ, and WM initial microstructures. Tempered martensite is the main metallurgical phase presented in the BM as well as in the HAZ. Retained austenite was presented in all the weldment regions (BM ~ 39%, HAZ ~ 5%, and WM ~ 30%). -ferrite was detected in the BM and next to the HAZ fusion line. Quenched martensite was the microstructural phase mainly presented in the WM as a result of the rapid cooling rate of the fusion welding process. Additionally, the HAZ exhibited the most morphological variability in relation to the grain size as a result of its thermal history. Figure 3 illustrates the DL-EPR typical curves that are representative of the weldment regions. The BM sample exhibited very similar activation and reactivation current densities, which led to a high DOS (iR/ia = 6.4 101). In the BM polarization curve shown in Figure 3, there is the formation of two oxidation peaks in the anodic and cathodic voltage scans. There

(c)
FiGUre 2. Weldment optical micrographs: (a) BM, (b) HAZ (next to the fusion line), and (c) WM.

are numerous cases in the literature in which two oxidation peaks have been observed during the anodic8,19-23 and cathodic18,24 polarization scans. The HAZ and WM sample curves showed a very similar behavior in relation to the iR and ia current densities. As those regions exhibited lower iR values in comparison to the BM sample values, their DOS remained very low (iR/ia = 5 103 and 8 103 for the HAZ and WM samples, respectively).

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FiGUre 3. Representative DL-EPR curves for the BM, HAZ, and WM regions. The scanning potential direction is indicated herein. Passive vertex potential is at 600 mV. The ia and iR current densities are indicated for the BM curve.

Figure 4(a) shows the BM sample microstructure after the DL-EPR testing. An intense corrosion attack can be observed in the grain boundaries and inside the grains. This is a consequence of the tempering heat treatment, which led to a chromium carbide precipitation. This thermal process is known to be harmful to the corrosion resistance of martensitic stainless steel.25 Figures 4(b) and (c) show the HAZ microstructure in the middle (1 mm from the fusion line) and next to the fusion line, respectively, after the DL-EPR testing. There is no evidence of a significant corrosion attack in the middle of the HAZ, as shown in Figure 4(b). On the other hand, an intense corrosion attack is observed in the HAZ next to the fusion line, specifically adjacent to the -ferrite phase (which is the clearest phase in Figure 4[c]). This may be attributed to a lower carbon solubility in the -ferrite phase,26 which resulted in the matrix supersaturation and the consequent chromium carbide precipitation adjacent to that phase. Furthermore, as the -ferrite phase is enriched mainly in chromium and molybdenum elements, it did not suffer a corrosion attack. The differences in the corrosion attack levels are related to the thermal gradient generated in the HAZ region distinct zones,2,15 having a consequent microstructural change as well as a chromium carbide precipitation. Furthermore, the high heat input of the electron beam welding process also promoted the chromium carbide precipitate redissolution5 in the middle of the HAZ, having a consequent chromium replenishment in the solid solution matrix.4 Another possibility, as reported in the literature,5 refers to the short period in which the material remains in the precipitation temperature zone. That period varies according to the welding technique used.

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FiGUre 4. SEM micrographs after a DL-EPR testing: (a) BM, (b) HAZ middle (1 mm from the fusion line), (c) HAZ next to the fusion line, and (d) WM. The samples were previously polished with 1 m alumina.

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(a)

FiGUre 5. Representative polarization curves (in NaCl solution) for the BM, HAZ, and WM regions.

The DOS low level in the HAZ is surprisingly different from what is reported in the literature.27-29 However, studies considering welded joints are mainly carried out by using conventional welding processes. Thus, when dealing with non-conventional or highpower density welding processes, like the electron or laser beam welding, it is necessary to consider their different heat input, thermal gradient generated, and precipitation kinetics in the corrosion resistance performance. Regarding that, a little research on the SMSS as well as on its weldments that are done through high-power density processes is available. Figure 4(d) shows the WM microstructure after the DL-EPR testing. This region exhibited very small sites of corrosion attacks over its entire surface. There is no evidence of intergranular or intragranular corrosion attacks in the quenched martensite. The DOS low level is from the rapid solidification process provided by the EB welding,30 which apparently was too rapid for significant microsegregation of the alloy elements to occur. The stringers in the WM microstructure (clearer phase) are present over the entire WM microstructure; however, no sign of corrosion attack was observed adjacent to that phase. According to the literature,31 these stringers are associated with the -ferrite phase. Figure 5 shows representative polarization curves of the weldment regions for the pitting potential determination. None of the curves showed an active-passive transition behavior. The current density oscillations, below the pitting potential, were possibly because of the nucleation and metastable growth of pits that were repassivated soon.9-10 The pitting potential increased from the BM to the WM, with the HAZ having the highest value. This result supports the chromium precipitate redissolution process in the HAZ. Moreover, the metallurgical phases did not seem to exert influ-

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FiGUre 6. SEM micrographs of the pits formed after the polarization interruption at 10 mA/cm2: (a) BM, (b) HAZ middle (1 mm from the fusion line), and (c) WM. The samples were previously polished with 1 m alumina, and etched with Villelas reagent after the polarization.

ence in the pitting potential, particularly the austenitic phase, contrary to what has been reported.32 Figures 6(a) through (c) show scanning electron images of the BM, HAZ, and WM regions after the polarization testing. The HAZ sample was deteriorated during the grinding process and during the electrochemical measurements. The pits nucleated and grew randomly in those regions. Figure 7 shows different tendencies between the DOS and the pitting potential within the SMSS weldment. As the pitting potential increases, the DOS decreases, which leads to a more resistant region

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chromium depletion; however, it did not mean that pit nucleation and growth occurs, specifically, at chromium-impoverished regions.

ACKNOWLEDGMENTS
The authors acknowledge the financial support provided by CAPES, and C.R. Ribeiro for supplying the steel samples.
REFERENCES
1. H. Nakamichi, K. Sato, Y. Miyata, M. Kimura, K. Masamura, Corros. Sci. 50 (2008): p. 309. 2. O.M. Akselsen, G. Rorvik, P.E. Kvaale, C. van der Eijk, Weld. J. 83 (2004): p. 160. 3. E. Ladanova, J.K. Solberg, T. Rogne, Corros. Eng., Sci. Technol. 41 (2006): p. 143. 4. P.H.S. Cardoso, C. Kwietniewski, J.P. Porto, A. Reguly, T.R. Strohaecker, Mater. Sci. Eng. A 351 (2003): p. 1. 5. H.T. Lee, J.L. Wu, Corros. Sci. 51 (2009): p. 439. 6. V. Vodarek, M. Tvrdy, A. Korgak, Inzynieria Materialowa 5 (2001): p. 939. 7. V. Kain, K. Chandra, K.N. Adhe, P.K. De, Corrosion 62 (2005): p. 587. 8. N. Alonso, M. Magri, I.G.S. Falleiros, Corrosion 55 (1999): p. 769. 9. G.T. Burstein, S.P. Vines, J. Electrochem. Soc. 148 (2001): p. B504. 10. G.S. Frankel, J. Electrochem. Soc. 145 (1998): p. 2186. 11. C.O.A. Olsson, D. Landolt, Electrochim. Acta 48 (2003): p. 1093. 12. I. Reynaud-Laporte, M. Vayer, J.P. Kauffmann, R. Erre, Microsc. Microanal. M. 8 (1997): p. 175. 13. M.P. Ryan, D.E. Williams, R.J. Chater, B.M. Hutton, D.S. McPhail, Nature 415 (2002): p. 770. 14. T.L.S.L. Wijesinghe, D.J. Blackwood, Corros. Sci. 49 (2007): p. 1755. 15. J. Enerhaug, O. Grong, U.M. Steinsmo, Sci. Technol. Weld. Joint. 6 (2001): p. 330. 16. J.M. Aquino, C.A. Della Rovere, S.E. Kuri, Corrosion 64 (2008): p. 35. 17. J.M. Aquino, C.A. Della Rovere, S.E. Kuri, Corros. Sci. 51 (2009): p. 2316. 18. V. Chal, R. Stefec, Electrochim. Acta 46 (2001): p. 3867. 19. L. Felloni, S.S. Traverso, G.L. Zucchini, G.P. Cammarota, Corros. Sci. 13 (1973): p. 773. 20. A.A. Hermas, M.S. Morad, K. Ogura, Corros. Sci. 41 (1999): p. 2251. 21. O.L. Riggs, Jr., Corrosion 31 (1975): p. 413. 22. M.B. Rockel, Corrosion 27 (1971): p. 95. 23. J.M. Aquino, C.A. Della Rovere, S.E. Kuri, J. Corros. Eng. Sci. Technol. 45 (2010): p. 150. 24. V. Chal, M. Blahetov, J. Hubckov, Z. Krhutov, S. Lasek, K. Mazanec, Corrosion and Structural Testing of Martensitic Steels by Electrochemical Polarization Method, Proc. Supermartensitic Stainless Steels, held October 3-4 (Brussels, Belgium: Welding Institute, 2002), p. 83. 25. J.E. Truman, Br. Corros. J. 11 (1976): p. 92. 26. E. Folkhard, Welding Metallurgy of Stainless Steel, 1st ed. (New York, NY: Spring-Verlag, 1988), p. 14. 27. L. Coudreuse, V. Ligier, C. Lojewski, P. Toussaint, Environmental Induced Cracking (SSC and SCC) in Supermartensitic Stainless Steels (SMSS), Proc. Supermartensitic Stainless Steels, held October 3-4 (Brussels, Belgium: Welding Institute, 2002), p. 163. 28. C. Garcia, M.P. de Tiedra, Y. Blanco, O. Martin, F. Martin, Corros. Sci. 50 (2008): p. 2390. 29. T. Rogne, M. Svenning, Intergranular Corrosion of Supermartensitic Stainless SteelA High Temperature Mechanism? Proc. Supermartensitic Stainless Steels, held October 3-4 (Brussels, Belgium: Welding Institute, 2002), p. 178. 30. S.A. David, S.S. Babu, J.M. Vitek, J. Miner. Met. Mater. Soc. 55 (2003): p. 14. 31. P. Bala Srinivasan, S.W. Sharkawy, W. Dietzel, Mater. Sci. Eng. A 385 (2004): p. 6. 32. P.D. Bilmes, C.L. Llorente, L. Saire Huamn, L.M. Gassa, C.A. Gervasi, Corros. Sci. 48 (2006): p. 3261.

FiGUre 7. Pitting potential and DOS values within the SMSS weldment.

considering precipitation and corrosion. Moreover, it seems that the pit nucleation and growth is more difficult to occur (high potentials) at low sensitized regions. These results are very similar to the ones reported in the literature17 using a metal filler wire during the EB welding of a SMSS.

CONCLUSIONS
v The heat treatment was a fundamental parameter when considering the corrosion resistance. The BM exhibited the highest sensitization degree and an intensive corrosion attack over the microstructure. The WM was not susceptible to an intergranular corrosion attack as a result of its high fusion and solidification processes. The HAZ showed an intensive precipitation near the fusion line, where the -ferrite phase nucleated and grew. In the middle of the HAZ region, the precipitation was reduced because of the chromium carbide precipitate redissolution provided by the heat generation of the welding apparatus. That showed the HAZ of a single pass electron beam welding was susceptible to precipitation. The welding technique influenced the temperature gradient in the precipitation and in the dissolution mechanism of the chromium carbide precipitates. The micro structure was also important when considering the alloy element microsegregation, as observed in the precipitation adjacent to the -ferrite phase in the HAZ sample. v The pitting corrosion and the DOS exhibited almost the same corrosion behavior within the weldment regions. The HAZ showed the highest pitting potential resulting from the chromium carbide redissolution. The pits showed a random nucleation and growth within the distinct weldment regions. v An inverse tendency between the pitting potential and the DOS was obtained: low levels of sensitization led to higher pit potentials. It means that pit nucleation and growth are likely to occur at regions with

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