Pitting Corrosion Resistance and Repassivation Behavior of C-Bearing Duplex Stainless Steel

metals Article Pitting Corrosion Resistance and Repassivation Behavior of C-Bearing Duplex Stainless Steel Hanme Yoon 1,2, Heon-Young Ha 2,* , Tae-Ho Lee 2, Sung-Dae Kim 2, Jae Hoon Jang 2 , Joonoh Moon 2 and Namhyun Kang 1,* 1 Department of Materials Science and Engineering, Pusan National University, Busan 46241, Korea 2 Ferrous Alloy Department, Korea Institute of Materials Science, Changwon 51508, Korea * Correspondence: [email protected] (H.-Y.H.); [email protected] (N.K.); Tel.: +82-55-280-3422 (H.-Y.H.); +82-51-510-3274 (N.K.) Received: 24 July 2019; Accepted: 22 August 2019; Published: 26 August 2019 Abstract: The effects of C-substitution for part of the N content, on the pitting corrosion resistance and repassivation tendencies of duplex stainless steels (DSSs) were investigated. For this investigation, normal UNS S32205 containing N only (DSS-N) and the C-substituted DSS (DSS-NC) were fabricated. Microstructural analyses confirmed that the two DSSs had dual-phase microstructures without precipitates, and they possessed similar initial microstructure, including their grain sizes and phase fractions. Polarization and immersion tests performed in concentrated chloride solutions revealed that the DSS-NC was more resistant against stable pitting corrosion and possessed a higher repassivation tendency than the DSS-N. Furthermore, the corrosion pits initiated and propagated to a less corrosion resistant α phase. Polarization tests and corrosion depth measurements conducted in an HCl solution indicated that the DSS-NC exhibited lower galvanic corrosion rate between the α and γ phases than the DSS-N. Therefore, the growth rate of pit embryo was lowered in the DSS-NC, which shifted the potentials for the stable pit initiation and the pit extinction to the higher values. Keywords: duplex stainless steel; pitting corrosion; repassivation behavior; galvanic corrosion 1. Introduction The beneficial effects of alloying nitrogen (N) [1–9] and carbon (C) [10–20] on mechanical properties and resistance to the localized corrosion of austenite stainless steels (γ-SSs) are widely investigated, and their mechanistic roles in the performance improvements are well established. N and C are economical and strong γ formers, thus they can be used in the γ-SS in replacement of Ni. In addition, they improve the mechanical strength of γ-SS by solid solution strengthening with a minimal loss of elongation. Moreover, it is reported that alloying N and C enhances the resistance to localized corrosion by strengthening the protectiveness of the passive film. Therefore, various γ-SSs have been modified and newly developed by alloying N and/or C [2,4,5,7,10–12,15]. It is worth mentioning that the advantages of the alloying N and C can be manifested as long as they remain in solid solution state in the matrix. Because the alloyed N and C exceeding solubility limits is prone to form Cr-consuming precipitates, such as Cr2N[21–23] and Cr23C6 [19,24], which degrade both mechanical and corrosion properties, thermomechanical processing and welding for N and/or C-bearing γ-SSs should be managed with caution. Duplex stainless steels (DSSs) are a family of SSs consisting of equal volume of ferrite (α) and γ phases [25–28]. A combination of the α and γ phases exerts beneficial influences on mechanical properties and resistance to corrosion. DSSs are particularly well known for their outstanding resistance to stress corrosion cracking in Cl−-containing environments [29]. Moreover, DSSs generally contains less Ni content (1–7 wt%) than the commercial 300-series γ-SS (i.e., FeCrNi-based SS contains, generally Metals 2019, 9, 930; doi:10.3390/met9090930 www.mdpi.com/journal/metals Metals 2019, 9, 930 2 of 13 8–24 wt% Ni), thus DSSs are known to be more economical than FeCrNi-based γ-SSs. Because of the desirable performances and economic benefits, demand for the DSSs as structural materials shows a continuous increase in various industrial fields requiring high mechanical strength and corrosion resistance. Alloying N is frequently adopted for DSSs because of its advantages in performance improvement [25,30–34]. Thus, commercial DSSs including UNS S32101, UNS S32304, UNS S32205, and UNS S32750, contain 0.1–0.3 wt% N. However, alloying C to DSSs has rarely been attempted, although C is found to be beneficial to performances of γ-SSs, similarly to N. Generally, C content was carefully controlled to be less than 0.03 wt% for commercial DSSs, because DSSs can provide more sites to Cr23C6 precipitations such as phase boundaries than the γ-SS [19,35,36]. But as long as C remains in solid solution state, it is expected to take advantages of the alloying C in promoting the physico-chemical properties of DSSs, the possibility of which was supported by the previous studies on C-bearing γ-SSs [10–20]. This study investigated the effects of C on the corrosion properties of DSS. For this study, type UNS S32205 DSS in which some N content was substituted with C, and normal UNS S32205 DSS containing only N, were produced. The resistance to pitting corrosion of the DSSs was assessed, and the role of C-substitution in the corrosion properties was discussed in terms of the repassivation tendency and pit growth rate. 2. Materials and Methods In the present study, Fe-22Cr-5Ni-3Mo-1Mn-based (in wt%, type UNS S32205) DSSs containing different N and C contents were investigated. The detailed chemical compositions of the DSSs denoted as DSS-N and DSS-NC are given in Table1. Table 1. Chemical compositions (in wt%) of the investigated DSSs. Alloy Fe Cr Ni Mo Mn N C S P DSS-N 22.48 5.17 3.10 1.46 0.24 0.002 0.005 0.005 Balanced DSS-NC 22.43 5.18 3.14 1.46 0.13 0.090 0.006 0.004 The DSS ingots of 30 kg were produced by vacuum induction melting in Ar. Then they were homogenized at 1250 ◦C for 2 h in Ar gas and hot-rolled, followed by water quenching. The hot-rolled plates with a thickness of 2 mm of the DSS-N and DSS-NC were solution treated at 1150 ◦C and 1130 ◦C for 1 h, respectively, in order to obtain α + γ matrix without precipitates and to control the phase fraction (α:γ) to be 1:1. The temperatures for the solution treatments were determined based on the equilibrium phase fraction versus temperature diagram (Figure1), which was calculated using Thermo-Calc software (version 2017b, database TCFE 7.0, Stockholm, Sweden). Microstructures of the DSSs were examined using light optical microscopy (LOM, Epiphot, Nikon, Minato, Japan), scanning electron microscopy (SEM, IT-300, JEOL, Akishima, Japan), and electron backscatter diffraction (EBSD, HKL Nordlys Channel 5, Oxford Instruments, Abingdon, UK) in a SEM (JSM-7001F, JEOL, Akishima, Japan). For the LOM and SEM analyses, the specimens (10 mm 10 mm 2 mm) were mechanically polished using suspension containing 1 µm-sized × × diamond particles. The polished specimens were chemically etched in a mixed acid solution (20 mL HNO3 + 30 mL HCl + 50 mL deionized water) for 1–3 min [33,35,37,38], which allowed us to measure the phase fractions (α:γ) of the specimens. Then we electrochemically etched in a 40% HNO3 solution by applying 4.5 V for 20–30 s [39,40] in order to identify the grain boundaries. Based on the SEM images taken at 5 different locations, the phase fractions (α:γ in vol%) of the DSSs were measured by image analysis. For the EBSD analysis, the specimens were polished using colloidal silica with a particle size of 0.02 µm. The EBSD analysis was performed on a scanning area 120 100 µm. with a step × size of 0.5 µm, and the grain boundaries were identified with the critical misorientation angle of 10◦. Alloying element partitioning in the DSSs was examined by an energy dispersive X-ray spectroscope Metals 2019, 9, 930 3 of 13 (EDS)Metals 2019 equipped, 9, x FOR on PEER the REVIEW SEM, and the chemical compositions were quantitatively examined through3 of 14 electron probe micro analysis (EPMA, SX100, CAMECA, Gennevilliers, France). Figure 1. Equilibrium phase fractions of the (a) duplex stainless steel containing N only (DSS-N) and Figure 1. Equilibrium phase fractions of the (a) duplex stainless steel containing N only (DSS-N) and (b) duplex stainless steel containing N and C (DSS-NC) as functions of temperature, calculated using (b) duplex stainless steel containing N and C (DSS-NC) as functions of temperature, calculated using Thermo-Calc software (version 2017b, database TCFE 7.0). Thermo-Calc software (version 2017b, database TCFE 7.0). Pitting corrosion resistance and repassivation tendencies of the DSSs were assessed through linearMicrostructures and cyclic potentiodynamic of the DSSs were polarization examined tests using in NaCl light solutions. optical microscopy The polarization (LOM, tests Epiphot, were performedNikon, Minato, in a multi-neckJapan), scanning glass cell electron consisting micros of acopy saturated (SEM, calomelIT-300, referenceJEOL, Akishima, electrode Japan), (SCE), aand Pt plateelectron counter backscatter electrode, diffraction and a specimen (EBSD, servingHKL Nord as a workinglys Channel electrode. 5, Oxford The specimensInstruments, were Abingdon, mounted inUK) cold in a epoxy SEM resin(JSM-7001F, and ground JEOL, using Akishima, SiC emery Japan) paper. For ofthe up LOM to 2000 and grit.SEM The analyses, exposed the area specimens for the polarization(10 mm × 10 test mm was × 2 controlled mm) were to mechanically be 0.2 cm2 using polished electroplating using suspension tape. The containing tests were 1 performed µm-sized withdiamond a potentiostat particles. The (Reference600 polished specimens+, GAMRY, were Warminster, chemically PA, etched USA).

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