CORROSION SCIENCE SECTION

Localized Corrosion Susceptibility of Supermartensitic Stainless Steel in Welded Joints

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

ABSTRACT
Supermartensitic stainless steels is known for its better weldability and corrosion resistance compared to the conventional martensitic, mainly due to its lower carbon content. This enables the production of welded joints with superior resistance to hydrogen embrittlement and to sensitization, particularly in the heat-affected zone. These characteristics can be optimized with the production of weldments using high-power density processes, such as electron beam welding. This process creates a narrow heat-affected zone with a high thermal gradient, which makes it less susceptible to precipitation, particularly to chromium carbides. Thus, its pitting potential is improved. KEY WORDS: electron beam weldments, pitting corrosion, supermartensitic stainless steel

INTRODUCTION
Supermartensitic stainless steel was developed as an alternative to the traditional carbon and duplex stainless steels, which combine low production and maintenance costs with excellent mechanical and corrosion properties. They are mainly used in gas and petroleum production lines.1 The main metallurgical characteristic of this material, which is a subclass of the conventional martensitic, is the increase in nickel content between 4%
Submitted for publication April 2007; in revised form, September 2007. Corresponding author. E-mail: dsek@power.ufscar.br. * Federal University of So Carlos (UFSCar), Materials Engineering Department, Rod. Washington Luiz, km 235, CEP 13565-905, So Carlos-SP, Brazil.

to 6%, and the reduction in carbon content as low as 0.01%. The reduced carbon content led to an improvement in the materials weldability.2 This was reected in a decreased tendency to hydrogen embrittlement and sensitization. Sensitization involves the formation of chromium-depleted zones resulting from precipitation of chromium carbides, particularly in the heataffected zone (HAZ) of weldments.3 According to the literature,4-7 sensitized regions are more susceptible to pitting corrosion. Thus, the HAZ of multipass welds is often a critical point in the pitting resistance, since this promotes the precipitation of chromium carbides.3,8 Nevertheless, welds produced by high-energy density processes, such as electron beam, are more efcient because they involve a single pass at high welding velocity and a narrow HAZ without the necessity of a postweld heat treatment.9 Thus, this microstructure has a lower pitting susceptibility. The goal of this work was to measure and compare the localized corrosion susceptibilities, by means of pitting potential determinations using potentiodynamic polarization measurements, in a supermartensitic stainless steel joint, comprised of the base metal (BM), HAZ, and weld metal (WM).

EXPERIMENTAL PROCEDURES
Localized corrosion measurements were done separately in samples of the BM, HAZ, and WM for two types of supermartensitic stainless steel that were welded by an electron beam in a low vacuum chamber. The full-penetration butt weld was made between 20-mm-thick plates, previously hot-rolled and tem-

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TABLE 1 Chemical Composition (mass%) of Steels and Filler 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 Cr 12.6 11.4 12.3 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

TABLE 2 Electron Beam Welding Parameters for the Top Pass

Parameters Vacuum Welding voltage Working distance Welding speed Root opening Wire feed rate Welding current Heat input Conditions 1 mbar 60 kV 50 mm 7 mm/s 0.5 mm 3.78 m/min 130 mA 1.1 kJ/mm

curves for each sample region was done to guarantee good reproducibility. The presence of pits was conrmed by scanning electron microscopy. Metallography using Villelas reagent was conducted to analyze the microstructural sites where pits nucleated and grew.

RESULTS AND DISCUSSION

Figures 1(a) through (c) show the initial microstructures corresponding to the BM, HAZ, and WM. The microstructural appearance of steels A and B was similar, only differing in contents relative to the metallurgical phases presented. The BM is mainly composed of quenched and tempered martensite, retained austenite (A = 11.1% and B = 39.0%, which can only be detected using transmission electron microscopy8), and some -ferrite stringers parallel to the rolling direction.11 The heterogeneous microstructure characteristic of the HAZ (relative to grain size) is composed mainly of tempered and quenched martensite, retained austenite (A = 5.5% and B = 4.3%), and -ferrite, located next to the fusion line. The WM, which was solidied rapidly as a result of the high cooling rates, consisted mainly of quenched martensite and retained austenite (A = 26.4% and B = 18.5%). The low level of retained austenite in the HAZ is a consequence of martensitic transformation induced by thermal strain.12 Figures 2(a) through (c) show polarization curves obtained for the determination of the pitting potential in the separate regions of the joint. Analyzing the curves for the three regions of the weld joint, it can be noted that they show similar behavior. None of the curves show an active-passive transition, indicating that the materials were passivated in the electrolyte. This fact was corroborated by the lower current density of about 106 A/cm2. As the potential is increased, some current density oscillations appeared, which, according to the literature,13-15 is attributed to nucleation and metastable growth events of pits that are soon repassivated. The repassivation phenomenon occurred at lower potentials, well below the pitting potential. The incidence of these events decreased with time because of the decrease, or saturation, in the sites available for pit nucleation.13-14 According to Kimura, et al.,16 retained austenite has no inuence on the pitting potential, even though this metallurgical phase promotes carbon and nitro-

pered at 600C, using a matching ller metal in two passes. The chemical composition of the plates and consumable, and the welding parameters, are shown in Tables 1 and 2, respectively. The test specimens consisted of samples extracted by electroerosion, from the inner part of the top of the weldment. X-ray diffraction measurements were conducted in the extracted samples for identication and quantication of the austenitic () and martensitic ()/ferritic () phases presented in the joint, according to ASTM E975.10 The analyses were carried out separately in the BM, HAZ, and WM of the two types of steel. The analyses were a 2- with a continuous sweep rate equal to 2 degrees per min in a range of 5 degrees to 120 degrees. A copper lament was used (K = 1.542). The test specimens for the electrochemical experiments were mounted in polyester resin, with care to avoid the presence of crevices. The exposed area was 0.403 cm2. The samples were wet-grinded with 600 silicon carbide (SiC) paper before polarization measurements. The electrolyte used in the electrochemical tests was a 3.56 mass% reagent-grade sodium chloride (NaCl) in distilled water, naturally aerated at 24C. An electrochemical cell composed of three electrodes was used with a platinum counter electrode and a saturated calomel reference electrode (SCE). Polarization curves were obtained by the working electrode immersion in the electrolyte until a steadystate corrosion potential, Ecorr, was reached, which was accomplished after 30 min to 40 min. Then, a potentiodynamic sweep rate of 1 mV/s was used starting from 100 mV, below Ecorr, to a potential slightly above the pitting potential, characterized by a sharp and sudden rise in the current density. A minimum of ve

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(a)

(a)

(b)

(b)

(c)
FIGURE 1. Weldment microstructure: (a) BM of steel B, (b) HAZ of steel A, and (c) WM of steel B.

(c)
FIGURE 2. Polarization curves obtained to determine the pitting potentials of steels A and B: (a) BM, (b) HAZ, and (c) WM.

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FIGURE 3. Pitting potential comparison for steels A and B.

gen dissolution, which avoid precipitation of these elements with chromium and molybdenum, and hence decreasing the sites available for pit nucleation. On the other hand, results presented by Bilmes, et al.,17 showed that an increase in the austenite content shifts the pitting potential to a nobler value. This is caused by the less-pronounced precipitation of carbides/nitrides, as mentioned above. Nevertheless, results obtained in this study for the BM are not conclusive, regarding the effect of retained austenite on the pitting potential, because both steels showed the same pit potentials (Figure 3) with different austenite contents. The presence of -ferrite increases the pit susceptibility because it promotes the formation of chromium-depleted zones by precipitation of chromium nitrides or carbides.3,8,11 Others susceptible sites could include the prior austenitic grain boundaries or the tempered martensitic matrix, where carbide precipitation also occurs. Molybdenum content was not a critical factor in the differentiation of pitting potential of steels A and

B, because, as stated in the literature,15,18-19 molybdenum additions of approximately 1 wt% is sufcient to achieve an adequate resistance to localized corrosion in neutral environments. Further additions of this element do not improve the pit resistance signicantly. Furthermore, the difference in contents of Mo presented in steels A and B (Table 1) could not be sufciently high to result in a perceptible difference in the pitting potential. It suggests that the localized corrosion resistance does not depend solely on the chemical composition. Microstructure and thermal treatments also exert a large inuence. Figure 4 shows a representative secondary electron image of a pit formed in the BM. Pits appeared to nucleate and grew randomly through the microstructure, as expected from the homogenous microstructure. Another aspect to be considered is the relatively large diameter of the pits formed, approximately 80 m, which makes it difcult to determine the region from where the pit resulted. In the HAZ, the pitting potential for steel A was higher than for steel B, as shown in Figure 3. This difference indicates that the thermal gradient created by the electron beam weld produced different microstructural transformations in steels, because of their different chemical composition (mainly chromium). The microstructural changes in steels A and B led to an increase in the pitting potential compared to the BM region (Figure 3), which is attributable to the redissolution of chromium carbide precipitates.20 This occurs because of the high temperatures reached in the HAZ by this type of process. This increased the chromium content in the matrix, which was higher for steel A, making its pitting potential nobler. Figure 5 shows a pit formed in the HAZ next to the fusion line. For steel B, nucleation and growth of the pits followed a random distribution, whereas for steel A, pits grew near the boundary with the BM. This preferential nucleation in steel A strongly supports the carbides redissolution mechanism, which

FIGURE 4. Pit morphology in the BM of steel A.

FIGURE 5. Pit morphology in the HAZ of steel B.

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results in an increase in solid solution of the chromium content next to the fusion line. For steel A, which has a lower chromium content and pits randomly, it can be concluded that chromium replenishment from redissolution was not sufcient to ensure better pitting resistance, even close to the fusion line. The WM was the least susceptible region for localized corrosion as indicated by the high pitting potentials whose values were above 200 mVSCE (Figure 3). This could be attributed to the low level of precipitates, due to the quenching process that resulted in a typical microstructure of quenched martensite. According to the literature,16 the pitting potential of quenched martensite is higher than for tempered martensite. In comparison with results obtained with other welding processes,21 where welds showed lower pitting resistance, electron beam welding is superior. Figure 6 shows a representative secondary electron image of a pit in the WM. As observed for the BM, pits formed in this region also followed a random distribution relative to nucleation and growth, as a result of the homogenous microstructure. Another aspect that emphasizes the nobler pit potential attained by the WM was the much lower pit density in this region than that in the HAZ and BM.

FIGURE 6. Pit morphology in the WM of steel A.

CONCLUSIONS
The BM was the most susceptible region to localized corrosion because of its tempered microstructure. The WM showed the highest pitting resistance as a result of the quenched martensite produced by welding. The weld thermal cycle produced redissolution of chromium carbides and/or nitrides in the HAZ, improving the pitting potential relative to the BM.

ACKNOWLEDGMENTS
The authors acknowledge the nancial support provided by Coordenao de Aperfeioamento de Pessoal de Nvel Superior (CAPES), and C.R. Ribeiro for supplying the steel samples.
REFERENCES
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