Anodic behaviour of supermartensitic stainless steel weldments

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

The corrosion resistance evaluation was carried out in a supermartensitic stainless steel weldment through anodic polarisation curves and through corrosion rate measurements in an acidic medium. The electrochemical measurements were carried out separately in the base metal samples, the heat affected zone and the weld metal of electron beam weldments. An improvement was found in the corrosion resistance from the base metal to the weld metal.
Keywords: Supermartensitic stainless steel, Electron beam weldments, Anodic polarisation, Corrosion rates, Linear polarisation

Introduction
Supermartensitic stainless steel (SMSS) arose in the 1990s as an attractive alternative to the traditional carbon steel and the duplex stainless steel. Its low production and maintenance costs, combined with high levels of corrosion resistance, have made its use even more attractive, mainly in gas and petroleum production lines.1 The term super is related to the improvement in the mechanical, the welding and the corrosion properties when comparing them to a conventional martensitic stainless steel. The main metallurgical changes refer to an increase in the molybdenum content up to 3%, and up to 6% in the nickel content. A decrease in the carbon content to levels as low as 0?01% was conducted to improve the weldability and, consequently, to decrease the precipitation tendency of the carbides, once the conventional martensitic stainless steel is not normally welded. The precipitation of such carbides leads to sensitisation and to hydrogen embrittlement as a consequence of the chromium impoverishment in the adjacent matrix. This precipitation process is likely to occur especially in the heat affected zone (HAZ) of the weldments due to the thermal heat gradient generation provided by the welding apparatus.2 Precipitation of chromium carbides in the HAZ of supermartensitic stainless steels occur due to the tempering effects occasioned by the preceding welding pass. Thus, top and single pass weldments are not susceptible to precipitation.2,3 Pitting corrosion may occur due to the susceptible sites of chromium impoverishment as reported in the literature.46 However, the literature7 shows that the HAZ is not the most susceptible region in relation to pitting corrosion. Furthermore, the HAZ microstructure does not seem to inuence the HAZ pit nucleation.8 The inuences of the stainless steel chemical composition9 and of its heat treatments10 are of special concern
Materials Engineering Department, Sa o Carlos Federal University (UFSCar), Rodovia Washington Lu s, km 235, CEP 13565-905, Sa o Carlos, SP, Brazil *Corresponding author, email zeaquino@yahoo.com.br

regarding the SMSS due to its adjustment of hardness and consequently the corrosion resistance. Polarisation curves generally show how the chemical composition and the heat treatment processes are inuencing the performance of the materials. In the last years, with the development and improvement of new welding processes, it was possible to produce high quality weldments with excellent performance and, without the application of pre- or postwelding heat treatments.11 Electron beam welding is inserted in this context as a main process because, in a single pass, it combines high welding velocities to a narrow HAZ of a few millimetres. Thus, the aim of this work was to evaluate and to compare the corrosion resistance of supermartensitic stainless steel weldment distinct regions, made through an electron beam welding. The weldment is composed of the base metal (BM), the HAZ and the weld metal (WM).

Experimental
Electrochemical measurements were carried out separately in the samples of BM, HAZ, and WM; in two types of supermartensitic stainless steel that were welded by electron beam welding in a chamber of low vacuum. The full penetration butt weld was made between two 20 mm thick plates, which were previously hot rolled and tempered at 600uC. The welding was made in two passes using a matching ller wire metal, commercially known as Thermanit 13/06Mo. The 1 mm thick test specimens were extracted by electroerosion from the inner part of the weldment top. First, the weldment was etched with a Villelas reagent or a mixture of HCl/ HNO3 (3 : 1). Then, the sample extraction was conducted after the identication of the characteristic microstructures through an optical microscopic analysis. The electrochemical investigation of the samples was carried out in distinct regions to disregard any galvanic inuence of other regions. Tables 1 and 2 show the chemical composition of the plates, the ller wire and the welding parameters respectively. The test samples were mounted in polyester resin to avoid the presence of crevices after the electric contact.
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Published by Maney on behalf of the Institute Received 9 October 2007; accepted 9 May 2008 DOI 10.1179/174329408X326515

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1 Microstructure of supermartensitic stainless steel weldment: a B steel BM, b B steel HAZ next to fusion line and c A steel WM

The exposed area was 0?403 cm2. Before the polarisation measurement, the electrode was wet grinded on a 600 silicon carbide paper and immersed in the cell without drying it. A conventional electrochemical cell composed of three electrodes was used with a platinum counter electrode as well as a satured calomel reference electrode. A Solartron SI 1287 A model potentiostat was used as well as a 0?05 mol L21 sulphuric acid solution, in distilled water, naturally aerated at 25uC. The polarisation measurement was carried out after a period in which the open circuit potential Ecorr reached a stable value; which occurred in 25 min. Then, the cathodicanodic potentiodynamic polarisation started. The sweep rate employed was 10 mV s21, starting from a potential of 100 mV below Ecorr, to a potential of 1?2VSCE. At least four curves were drawn for each weldment sample region. The corrosion rate measurement, in millimetres per year, was carried out through the linear polarisation method, in which a potentiodynamic sweep rate of 0?1667 mV s21 was xed in a range of 10 mV, in relation to the open circuit potential. The time required to reach such a potential was 30 min.

Results and discussion

Figure 1 shows some of the initial microstructures corresponding to the BM, the HAZ, and the WM of the A and B steels. The microstructural appearance is similar among the equal regions of both steels. Among their distinct regions, the only difference is in the contents relative to the metallurgical phases presented. Tempered martensite is mainly presented in the BM as well as in the HAZ while quenched martensite is a characteristic of the WM. Additionally, retained austenite was detected in all the weldment samples using Xray diffraction measurement. d ferrite was presented in the BM grain boundaries and also next to the fusion line in the HAZ. Figure 2 shows the curves that resulted from the polarisation in the sulphuric acid medium to the distinct regions of the supermartensitic stainless steel. The curve shapes indicate an activepassive behaviour, in which
Table 1 Chemical composition of steel and ller metal, Material A B Filler C 0.02 0.007 0.012 Si 0.3 0.07 0.45 Mn 0.9 1.6 0.65 P 0.03 0.007 0.005 S 0.004 0.003 0.005
12

the open circuit potentials remained close within the regions. The HAZ critical current density of the A and B steels was the lowest due to the redissolution of chromium carbide precipitates.13 That occurred during the welding procedure. As this is a high energy density process, it promotes a high temperature gradient, in a narrow zone, proper to the precipitate dissolution. Consequently, the HAZ was chromium replenished to a certain extent that increased its corrosion resistance. The redissolution process also supports the lower passive and the secondary passive current densities obtained for these samples. In the WM, the critical current density was similar to the BM one in the A and B steels. Even though they both have similar chemical composition, this was intriguing once those regions were submitted to a complete different heat treatment when comparing it to the BM. While the WM was submitted to a rapid solidication process,14 the BM was submitted to a tempering treatment which is known to depreciate the corrosion properties.10 Thus, one possible reason for this controversy is the initial formation of a nonadherent passive lm followed by an adherent one. It is supposed that, once this lm is formed, the passive current density remains on the same levels as the HAZ ones. Another interpretation for that discrepancy would be referred as a kinetic dependence on the anodic behaviour during the potential sweep rate. This will be shown later. The BM presented the highest critical current density as a result of its tempering heat treatment that yielded in
Table 2 Electron beam welding parameters for top pass12 Parameters Vacuum, mbar Welding voltage, kV Working distance, mm Welding speed, mm s21 Root opening, mm Wire feed rate, m min21 Welding current, mA Heat input, kJ mm21 mass% Ni 5.1 6.1 6.4 Mo 1.8 2.6 2.6 Ti 0.01 0.02 V 0.05 0.05 Cu 0.3 0.5 O 0.01 0.01 0.008 N 0.01 0.01 0.01 Conditions 1 60 50 7 0.5 3.78 130 1.1

Cr 12.6 11.4 12.3

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2 Potentiodynamic polarisation curves at 10 mV s21: a A steel and b B steel

a chromium carbide precipitation, having consequently, a generation of chromium depleted regions that are more prone to corrosion. Another aspect that arose in the activepassive region of the polarisation curves of Fig. 2 was the so called second anodic current maximum. According to literature,1520 there are innumerous interpretations for this occurrence, which are: (i) nickel enrichment on the surface (ii) adsorbed hydrogen oxidation (iii) Fe2z ions effect (iv) chromium depleted zones effect (v) microstructural and compositional effects. To separate and to investigate the origin of the supermartensitic stainless steel second current density maximum peak, a new set of polarisation curves was drawn in the weldment samples using a potential sweep rate of 1 mV s21, though. Figure 3 shows the polarisation curves obtained for A and B steels. Considering this new condition, only the second anodic maximum of the BM samples has been separated. In the B steel HAZ, that peak disappeared or melted into one, as observed in Fig. 2b. In the WM, the second anodic maximum did not even appear in any of the sweep rates used. This suggests that the potential sweep rates inuence the anodic behaviour, particularly in the development of a second maximum current, as observed in Figs. 2 and 3. Furthermore, this occurrence seems to be inuenced by the microstructure and thermal history of the different weldment regions.

In relation to the WM, it could be veried that the critical current density shown in the polarisation curves of 1 mV s21, decreased almost ten times, remaining close to the HAZ one, shown in Fig. 3. This characteristic suggests that the anodic behaviour of the WM region is susceptible to changes in the potential sweep rate. In addition to the two critical current density separation, a morphological analysis through capturing some secondary electron images was carried out by SEM, in the BM region of A and B steels. The image was obtained after the interruption of the potential sweep at 20?27VSCE and z0?17VSCE, as indicated by the arrows in Fig. 3a. This procedure aimed to conrm the expected interpretation of the second anodic current maximum through the effect of chromium depleted zones. This occurrence is likely to happen in martensitic stainless steel. Furthermore, tempering treatments strongly contribute to that effect. Figure 4 shows secondary electron images of the microstructures revealed in the A steel BM. A typically martensitic microstructure is observed in both images. However, a signicant difference between the micrographs obtained in the different points of Fig. 3a was not detected. That difference could not be credited to the preferential corrosion attack which was originated on the second anodic current density. The same occurrence was observed on B steel, indicating that the expected effects on the chromium depleted zones were not conrmed in the supermartensitic stainless steels, according to the used experimental techniques.

3 Potentiodynamic polarisation curves at 1 mV s21: a A steel and b B steel; arrows indicate interruption of sweep rate to analyse microstructure through SEM

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4 A steel BM microstructure after potentiodynamic polarisation at 1 mV s21: a rst arrow (E<20?27VSCE) and b second arrow (E<z0?17VSCE) are depicted in Fig. 3a

Figure 5 shows the corrosion rate measurements that are relative to the generalised corrosion on the weldment region. Uniform corrosion was evaluated due to the lower chromium content (12%) on those steels. The heat treatments which the weldments were submitted to lead to the precipitation of the chromium carbides, and consequently, to a further decrease in that element in the solid solution. A pronounced reduction on the corrosion rate from the BM to the WM, in A and B steels, can be observed in the experimental values. Furthermore, the decrease in the corrosion rate in B steel is greater than in A steel due to a total content higher in corrosion resistance elements as well as to its lower carbon content for those regions of the weldments were submitted to the same heat treatments. The BM stood as the most susceptible region to the generalised corrosion, as a result of its tempering thermal treatment, which caused a chromium carbide precipitation having a consequent reduction of this element in the solid solution. Similar to the polarisation curves, the WM samples showed a potential sweep dependence and, this time, they remained at the lowest susceptible region concerning the uniform corrosion. This fact is quite plausible as expected on the rapid process of fusion and solidication.14 It also guarantees the presence of chemical elements in solid solution; therefore, it improves the corrosion properties. The HAZ redissolution process, as described above, presented corrosion rate levels comparable to that one on the WM due to the chromium replenishment in the

former region. The value obtained to the A steel HAZ was charted only after doing a single measurement of the sample due to its deterioration because of the grinding process. However, it is expected that the A steel HAZ follows the same behaviour of the B steel HAZ.

Conclusion
The anodic behaviour of supermartensitic stainless steel weldments showed a corrosion resistance improvement from the BM to the WM, where the chemical composition as well as the heat treatments exerted a signicant inuence. The high critical current density of the BM suggests that this region is the most susceptible to oxidation, probably due to carbide precipitation as a result of the heat treatment, which was conrmed in the tests of uniform corrosion. The WM region showed a potential sweep rate dependence in its anodic behaviour, presenting current density values at 1 mV s21 that were more representative in that region. The passive current density showed the same tendency of the critical one, where the BM exhibited a poor performance. The polarisation curves carried at 1 mV s21 were efcient in the separation of the second anodic current maximum in the BM samples, meanwhile this occurrence does not seem to be related to microstructural effects. There is evidence of the same behaviour in the HAZ samples; however, it was not established. The welded regions exhibited a signicant susceptibility regarding the uniform corrosion, presenting rates of 0?5 mm per year to the BM due to its tempering heat treatment. The WM was the less susceptible within the regions as a consequence of the high cooling rates on the welding process. The levels of the HAZ samples were also a consequence of the high thermal gradient on the welding process.

Acknowledgements
The authors thank the financial support provided by CAPES and Dr C. R. Ribeiro for supplying the steel samples.

References
5 Corrosion rates within supermartensitic stainless steel weldment region
1. L. M. Smith and M. Celant: Proc. Conf. on Supermartensitic stainless steels, Brussels, Belgium, May 1999, Belgian Welding Institute, 6673.

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2. E. Ladanova, J. K. Solberg and T. Rogne: Corros. Eng. Sci. Technol., 2006, 41, 143151. 3. E. Ladanova and J. K. Solberg: Proc. Conf. on Supermartensitic stainless steels, Brussels, Belgium, October 2002, Belgian Welding Institute, 205214. 4. M. Vayer, I. Reynaud and R. Erre: J. Mater. Sci., 2000, 35, 2581 2587. 5. M. P. Ryan, D. E. Williams, R. J. Chater, B. M. Hutton and D. S. McPhail: Nature, 2002, 415, 770774. 6. I. Reynaud-Laporte, M. Vayer, J. P. Kauffmann and R. Erre: Microsc. Microanal. Microstruct., 1997, 8, 175185. 7. J. M. Aquino, C. A. Della Rovere and S. E. Kuri: Corrosion, 2008, 64, 3539. 8. J. Enerhaug, O. Grong and U. M. Steinsmo: Sci. Technol. Weld. Joining, 2001, 6, 330338. 9. A. A. Ono, N. Alonso and A. P. Tschiptschin: ISIJ Int., 1996, 36, 813817. 10. J. E. Truman: Br. Corros. J., 1976, 11, 9296. 11. Z. Sun and R. Karppi: J. Mater. Process. Technol., 1996, 59, 257 267.

12. C. R. Ribeiro: Avaliac a o de processos de soldagem por feixe de ele trons de baixo va cuo e por fricc a o radial em ac os inoxida veis supermartens ticos. PhD thesis, Federal University of Sa o Carlos, Sa o Paulo, Brazil, 2003. 13. P. H. S. Cardoso, C. Kwietniewski, J. P. Porto, A. Reguly and T. R. Strohaecker: Mater. Sci. Eng. A, 2003, A351, 1 8. 14. S. A. David, S. S. Babu and J. M. Vitek: J. Miner. Met. Mater. Soc., 2003, 55, 1420. 15. M. B. Rockel: Corrosion, 1971, 27, 95103. 16. O. L. Riggs, Jr: Corrosion, 1975, 31, 413415. 17. M. Magri and N. Alonso: Congresso Brasileiro de Corrosa o, Vol. 1, 129139; 1993, Rio de Janeiro, Brazilian Association of Corrosion. 18. A. A. Hermas, M. S. Morad and K. Ogura: Corros. Sci., 1999, 41, 22512266. 19. L. Felloni, S. S. Traverso, G. L. Zucchini and G. P. Cammarota: Corros. Sci., 1973, 13, 773779. 20. N. Alonso, M. Magri and I. G. S. Falleiros: Corrosion, 1999, 55, 769778.

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