Crevice corrosion behaviour of superaustenitic stainless steels: Dynamic electrochemical impedance spectroscopy and atomic force microscopy studies

Potentiodynamic anodic polarisation and dynamic electrochemical impedance spectroscopic (DEIS) measurements were carried out for 316L SS, alloy 33 and alloy 24 in natural sea water in order to assess their crevice corrosion resistance. DEIS measurements were performed from open circuit potential to dissolution potential. It was shown that the impedance measurements in potentiodynamic conditions allow simultaneous investigation of changes in passive layer structure. The impedance spectra of various potential regions were also discussed. The surface morphology of the alloys after crevice corrosion studies were studied using optical microscope and atomic force microscopy (AFM).     

Determination of susceptibility to intergranular corrosion and electrochemical reactivation behaviour of AISI 316L type stainless steel

In this study, double loop electrochemical potentiokinetic reactivation (DLEPR) test was applied to determine the degree of sensitization in 316L type stainless steel, where obtained results were correlated with revealed microstructures after oxalic acid test and weight loss measurements of Streicher and Huey acid tests. Best agreement was provided with test parameters which are 1 M H₂SO₄ and 0.005 M KSCN at 0.833 mV/s scan rate at 30 °C. Specimens were classified structurally as absence of chromium carbides - step, no single grain completely surrounded by carbides - dual and one or more grain completely surrounded by carbides - ditch, in the as-etched structure, if the I_r:I_a (×100) ratios were obtained to be between 0 and 0.2, 0.2 and 5.0 and 5.0 and higher, respectively. It was also found that at high KSCN concentrations, reactivation current profile skewed to higher potentials where this was attributed the formation of metastable pits, during the anodic scan of the test procedure.     

Effect of ageing heat treatments on the microstructure and intergranular corrosion of powder metallurgy duplex stainless steels

The influence of ageing heat treatments (675 and 875 °C for 1.5 to 48 h) on the microstructure and intergranular corrosion resistance of sintered in nitrogen duplex stainless steels was investigated. The materials were obtained by sintering mixtures of austenitic AISI 316L and ferritic AISI 430L powders. Corrosion behaviour was evaluated by using electrochemical techniques. The beneficial effect of nitrogen on corrosion behaviour of solution annealed samples was established. During ageing, secondary phases were precipitated and the intergranular and transgranular corrosion resistance significantly decreased though repassivation was observed in specimens aged at 875 °C for times up to 8 h.     

Wear behavior of a ferritic stainless steel with carbides manufactured through powder metallurgy

A ferritic stainless steel has been manufactured through the powder metallurgy (P/M) route: uniaxial pressing and sintering. The sintering process was carried out in vacuum, at 1215 °C for 30 min. After sintering, materials showed nearly 90% of density. A complete metallographic study was carried out using optical microscopy and scanning electron microscopy (SEM). Wear behavior was evaluated using a “pin on disk” test according to ASTM Standard G99. Eight test conditions were studied, varying the load (5 and 10 N), the speed (0.1 and 0.4 m/s), and the counter-material (chromium steel and a martensitic stainless steel). The sliding distance was 400 m, and tests were carried out on polished materials, with less than 30% of relative humidity. Moreover, wear tracks were observed by SEM in order to understand the wear processes involved, which depend mainly on the counter-material.     

奥氏体不锈钢焊接接头晶间腐蚀断裂分析

核电站管道大多采用奥氏体铁素体不锈钢制成,以主管道为例,多数采用焊接方式进行连接。在现场应用之前,需要进行工艺评定的焊接和检验,以验证焊接接头是否满足高温、高压、高腐蚀的性能要求。晶间腐蚀按照标准RCCM+RCCM2000补遗中MC1312.3中B法处理后,在弯曲过程出现裂纹,对比试样也出现裂纹,难以判定是否是晶间腐蚀造成的裂纹缺陷。利用金相方法观察出现裂纹的试样,结合力学性能试验和化学成分进行分析得出,弯曲受检面产生的裂纹不是由晶间腐蚀造成的。     

粉末冶金高氮超级奥氏体不锈钢的开发

采用气雾化法制备高氮超级奥氏体不锈钢粉末,利用热等静压成形。结果表明,热等静压后,材料完全致密,而σ及Cr2 N两相的析出导致材料塑性、韧性及耐蚀性显著下降。材料经1200℃×1 h固溶处理后,力学性能及耐蚀性能大大提高,抗拉强度Rm为1050 MPa、屈服强度Rp0.2为735 MPa,伸长率A为57.0%,自腐蚀电位Ecorr为0.946 V。     

Surface spreading of intergranular corrosion on stainless steels

The spreading of intergranular corrosion was investigated using micrometer scale simulations and experimental verifications on sensitized stainless steel [UNS S30400]. The degree of sensitization, presence of a pit, and applied potential all affected spreading. The inputs used in the simulation were obtained from Fe-XCr(X = 10, 12, 14, 16 wt.%)-Mo-Ni alloys representing various grain boundary Cr depletion levels. Corroding grain boundaries and pits triggered corrosion of nearby sensitized boundaries due to Ohmic potential drop. Large connected clusters of corroding grain boundaries formed at high fractions of Cr-depleted grain boundaries. The metallurgical, electrochemical and geometric conditions for this behavior could be forecasted.     

Investigation of intergranular corrosion of 316L stainless steel diffusion bonded joint by electrochemical potentiokinetic reactivation

Electrochemical potentiokinetic reactivation technique (EPR) was employed to assess degree of sensitization in 316L stainless steel diffusion bonded joint (DBJ). The result showed the degree of sensitization of DBJ was much smaller than that of base material (BM). No chromium carbides precipitated at grain boundaries in DBJ after 100 h treatment at 650 °C, while chromium carbides could be seen clearly in the BM after 8 h treatment, indicating that DBJ has better intergranular corrosion resistance than BM. Diffusion bonding technique will not increase intergranular corrosion susceptibility of 316L DBJ. Reactivation potential has the biggest effect on sensitization.     

Improving the intergranular corrosion resistance of 304 stainless steel by grain boundary network control

The grain boundary network (GBN) was controlled by grain boundary engineering (GBE) in a 304 stainless steel. The total length proportion of Σ3ⁿ coincidence site lattice (CSL) boundaries was increased to more than 70% associating with the formation of large size highly twinned grain-cluster microstructure. Only coherent twin boundaries (Σ3_c) were found to be resistant to intergranular corrosion (IGC) and only such boundaries could be termed “special” ones. The improvement of resistance to IGC of the GBE specimen can be attributed to the large size grain-clusters associated with high proportion of the Σ3ⁿ boundaries and the interconnected Σ3ⁿ-type triple junctions.     

Inhibition effect of metal cations to intergranular stress corrosion cracking of sensitized Type 304 stainless steel

Inhibition effect of metal cation to intergranular stress corrosion cracking (IGSCC) of sensitized Type 304 stainless steel has been investigated by slow strain rate technique (SSRT) with a dynamic crack observation system. The SCC tests were conducted in fully-deaerated aqueous solutions containing various metal sulfates of 10⁻⁵ kmol/m³ at 95 °C. Metal cations of Na⁺, Ca²⁺, Mn²⁺ and Zn²⁺ were selected in this study, and were characterized by a hardness based on the hard and soft acids and bases (HSAB) concept. As a result, it was found that a hard metal cation in the test solution increased crack initiation time and decreased mean crack initiation frequency. In other words, metal cations with larger hardness have an ability of suppressing initiation process of the IGSCC. On the other hand, apparent mean crack velocity was independent of the hardness of metal cation. The finding that the metal cations with large hardness inhibit initiation of the IGSCC was able to be rationally explained on the basis of the passive film model combined with the HSAB concept.     

Influence of microstructure on the corrosion resistance of hyperduplex stainless steel

Hyperduplex UNS S32707 is a newly developed austenitic–ferritic stainless steel. The steel contains about 27%Cr, 7%Ni, 4.5%Mo, and 0.4%N, which results in a pitting resistance equivalent factor (PRE) equal to 49. In this study, the pitting corrosion resistance of this new grade of stainless steel was investigated by varying the microstructure using different thermal processes. The critical pitting temperature measurement and cyclic polarization tests confirm the high corrosion resistance of the hyperduplex steel in the solution treated condition. However, deleterious phases form easily during thermal processing and cause a drastic decrease in the corrosion resistance.     

Intergranular corrosion susceptibility in supermartensitic stainless steel weldments

The intergranular corrosion susceptibility in supermartensitic stainless steel (SMSS) weldments was investigated by the double loop – electrochemical potentiokinetic reactivation (DL-EPR) technique through the degree of sensitization (DOS). The results showed that the DOS decreased from the base metal (BM) to the weld metal (WM). The heat affected zone (HAZ) presented lower levels of DOS, despite of its complex precipitation mechanism along the HAZ length. Chromium carbide precipitate redissolution is likely to occur due to the attained temperature at certain regions of the HAZ during the electron beam welding (EBW). Scanning electron microscopy (SEM) images showed preferential oxidation sites in the BM microstructure.     

Effects of inclusions on the precipitation of chi phases and intergranular corrosion resistance of hyper duplex stainless steel

During the initial stage of aging heat treatment at 850 °C, inclusions such as (Cr, Mn, Al) oxides and (Cr, Mn, Al, Fe) oxides of a hyper duplex stainless steel act as preferential precipitation sites for the chi phase like ferrite/austenite phase boundaries and ferrite/ferrite grain boundaries. The chi phase is precipitated around the inclusions due to the blocking and piling up the alloying elements such as Mo and W around the inclusions. The precipitation of Mo and W enriched chi phase around the inclusions decreases the intergranular corrosion resistance due to the formation of Mo and W depleted zones.     

Influence of high temperature softening and solid solution on intergranular corrosion susceptibility of Super304H stainless steel

Thermos-mechanical processes were investigated to suppress the high intergranular corrosion sensitivity of Super304H austenitic stainless steel. The microstructure and grain boundary character distribution were characterised, respectively, by scanning electron microscope and electron backscatter diffraction analysis. The degree of sensitisation (DOS) was evaluated by the double-loop electrochemical polarisation reactivation test. The results show that the bulk primary Nb(C,N) particles were dissolved more into the matrix after high temperature softening at 1300°C for more than 30 min and the special boundaries (∑ ≤ 29) maintained at the same level as the as-received state after solid solution at 1150°C. The DOS was decreased after high-temperature softening and solid solution treatments, which was attributed mainly to the dissolution of primary bulk Nb(C,N) phase during high-temperature softening and the dispersive precipitation of the secondary fine Nb(C,N) phase during solid solution, which had effectively consumed carbon.     

Detection and characterisation of intergranular stress‐corrosion cracking on austenitic stainless steel

Intergranular stress‐corrosion cracking (IGSCC) on a sensitised type AISI 304 stainless steel specimen was monitored simultaneously by acoustic emission, electrochemical noise, elongation measurements and a digital imaging system. The specimen was exposed to an aqueous sodium thiosulphate solution in combination with a constant load. It was established that before the final fracture two large cracks and numerous smaller cracks had developed. Detection and characterisation of the stress‐corrosion processes which generated these cracks are discussed. The results confirm and generalise previously established correlations between various parameters obtained by the implemented characterisation methods and IGSCC processes. Additionally, a clear differentiation between crack related and crack non‐related AE signals was made based on an analysis of the AE signals. The relationship between the crack lengths calculated by means of digital image correlation analysis and the electrochemical current noise was also established.     

Pitting and crevice corrosion of superaustenitic stainless steels

Superaustenites are mainly used in offshore applications, oil production and chemical industry. Most important types of localised corrosion of these steels are pitting and crevice corrosion. Investigated materials were N08028, S31254 and three modified alloys. Chromium content of investigated alloys varied between 20 and 27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1 and 0.36% and copper between 0 and 1.1%. For means of comparison stainless steel AISI 316L has been included in the study. Pitting and crevice corrosion of these highly corrosion resistant steels has been investigated by use of standardized tests. Critical pitting temperature and critical crevice temperatures were determined according to ASTM G 48, Methods C and D, respectively. Electrochemical measurements for determination of pitting potentials were done according to ASTM G 61 as well as for determination of critical pitting temperatures according to ASTM G 150. Results are presented as function of MARC (Measure of alloying for resistance to corrosion) defined by Speidel since linear correlation coefficients were higher when compared to conventional PREN. Results obtained by different testing methods must not be compared directly. Every test however is sensitive to microstructural defects like precipitations and segregations that decrease corrosion resistance. The higher alloyed a material is, the higher is its tendency to form microstructural defects, and the more difficult is it to reach its theoretical corrosion resistance at given chemical composition.     

Microstructure and intergranular corrosion resistance of UNS S17400 (17-4PH) stainless steel

UNS S17400 or 17-4PH is a precipitation hardening martensitic stainless steel with many industrial applications. Quite different mechanical properties can be produced in this material by varying the aging temperature. In this work, the influence of aging temperature on the intergranular corrosion susceptibility was evaluated by electrochemical and metallographic tests. The microstructural features were investigated by X-ray diffraction, optical and scanning electron microscopy. Intergranular chromium carbide precipitation occurs in specimens aged at high temperatures, although NbC carbides were also observed. The results obtained by double loop electrochemical potentiodynamic reactivation tests (DL-EPR) show that the susceptibility to intergranular corrosion resistance increases with the increase of aging temperature. Healing due to Cr diffusion in the 600-650 °C range was not observed by DL-EPR tests.