A study of intergranular corrosion of austenitic stainless steel by electrochemical potentiodynamic reactivation, electron back-scattering diffraction and cellular automaton

The impact of solution and sensitization treatments on the intergranular corrosion (IGC) of austenitic stainless steel (316) was studied by electrochemical potentiodynamic reactivation (EPR) test, and the results showed the degree of sensitization (DOS) decreased as solution treatment temperature and time went up, but it increased as sensitization temperature prolonged. Factors that affected IGC were investigated by field emission scanning electron microscope (FE-SEM) and electron back-scattering diffraction (EBSD). Furthermore, the precipitation evolution of Cr-rich carbides and the distribution of chromium concentration were simulated by cellular automaton (CA), clearly showing the effects of solution and sensitization treatments on IGC.     

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.     

Application of the modified electrochemical potentiodynamic reactivation method to detect susceptibility to intergranular corrosion of a newly developed lean duplex stainless steel LDX2101

The present work aimed at defining optimal conditions using double loop electrochemical potentiokinetic reactivation (DL-EPR) method for evaluating intergranular corrosion (IGC) susceptibility of lean duplex stainless steel (LDX2101) aged at 700 °C between 3 min and 300 h. The results demonstrated that the modified DL-EPR measurement (solution of 33% H₂SO₄ + 0.1% HCl at 20 °C and scan rate of 2.5 mV/s) could successfully characterize the interactions between precipitation, chromium depletion and IGC of LDX2101 with high sensitivity and reproducibility. In addition, there was no indication of healing because the effect of formation of chromium-enriched precipitates was more dominative than that of redistribution of chromium in depleted zones.     

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.     

Assessment of intergranular corrosion (IGC) in 316(N) stainless steel using electrochemical noise (EN) technique

In the present work, an attempt was made to demonstrate the use of electrochemical noise (EN) technique in assessment of intergranular corrosion (IGC) in 316(N) stainless steel (SS). Degree of sensitization (DOS) in the specimens aged at 923 K for 24, 40, 50 and 100 h was determined using double loop electrochemical potentiodynamic reactivation (DLEPR) technique. Immediately after applying a prior preconditioning treatment, current and potential noise measurements were made. The DOS was determined from standard deviation of current noise (σ_I) versus time plot and it was found to bear a good correlation with the values obtained by DLEPR. Shot noise analysis of the EN data confirmed the above results.     

Grain boundary structure and intergranular stress corrosion crack initiation in high temperature water of a thermally sensitised austenitic stainless steel,observed in situ

The development of an intergranular stress corrosion crack initiation site in thermally sensitised type 304 austenitic stainless steel has been observed in situ in high temperature oxygenated water using digital image correlation of time-resolved optical observations. The grain boundary normal stresses were calculated using the Schmid-Modified Grain Boundary Stress (SMGBS) model of Was et al., applying three-dimensional data for the grain boundary planes and grain orientations. The initiation site coincided with the most highly stressed sensitised boundary, demonstrating the importance of the combined contributions to crack initiation of grain boundary structure and plastic strain incompatibility.     

Effect of laser surface melting on intergranular corrosion behaviour of aged austenitic and duplex stainless steels

In the present study, the effect of laser surface melting (LSM) on intergranular corrosion behaviour of aged austenitic stainless steels (UNS S30400, S31603, S32100 and S34700) and aged duplex stainless steels (UNS S31803 and S32950) were investigated. LSM of the aged stainless steels was carried out using a 2.5 kW CW Nd:YAG laser. The microstructure of the aged stainless steels after LSM depends on their compositions. After LSM, the aged austenitic stainless steels mainly contain austenite (γ) with some ferrite (δ) as the minor phase, but the carbide phases are completely eliminated. For the aged duplex stainless steels after LSM, δ becomes the major phase and the δ/γ phase balance is disturbed, whereas the sigma (σ) phase is eliminated. The degree of sensitization (DOS) and corrosion morphology of the aged stainless steels before and after LSM were determined by the double loop electrochemical potentiokinetic reactivation (DL-EPR) using a potentiostat and SEM observation, respectively. Desensitization of the aged stainless steels has been successfully achieved by LSM and their intergranular corrosion resistance is found to be significantly enhanced as reflected by the decrease in DOS due to dissolution of the carbides or σ phase, which reduced Cr depletion or the possibility of solute segregation at the grain or phase boundaries, despite the presence of δ and disturbance of δ/γ phase balance.     

Corrosion behaviour of sensitized and unsensitized Alloy 900 (UNS 1.4462) in concentrated aqueous lithium bromide solutions at different temperatures

Duplex stainless steels can undergo microstructural changes if they are heated improperly. When that happens, duplex stainless steels are sensitized and intermetallic phases appear. The high Chromium and Molybdenum content promotes the formation of secondary phases as a consequence of the heat treatment. These secondary phases, which are rich in alloying elements, such as Cr and Mo, deplete these elements from the neighbouring phases, leading to a reduction in corrosion resistance. In order to study the influence of the secondary phases on the corrosion parameters, samples of duplex stainless steel, Alloy 900 (UNS 1.4462), have been heated in argon atmosphere at 825 °C for 1 h. The corrosion behaviour of sensitized and unsensitized Alloy 900 has been analyzed in a concentrated aqueous lithium bromide (LiBr) solution of 992 g/L by means of cyclic potentiodynamic curves. Secondary phase presence reduces the pitting potential value of Alloy 900. Besides, the pitting potential decreases with temperature. On the other hand, the corrosion potential and open circuit potential values increase with temperature and 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.     

Effect of chromium content on intergranular corrosion and precipitation of Ti-stabilized ferritic stainless steels

Intergranular corrosion (IGC) and precipitation of ferritic stainless steels (FSS) were investigated with change in Cr content from 11 wt.% to 17 wt.%. The increase in Cr content improved IGC resistance as temperature and time for the sensitization became higher and longer, respectively, but it did not prevent IGC. The analysis on the intergranular precipitates revealed that Cr segregation around fine intergranular TiC in developed all FSS regardless of Cr content. This Cr segregation is proposed to explain the Cr depletion for the cause of IGC in Ti-stabilized Cr FSS.     

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.     

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.     

Intergranular corrosion of welded joints of austenitic stainless steels studied by using an electrochemical minicell

An intergranular corrosion study of welded joints of austenitic stainless steels (AISI 304 and 316L) has been addressed. A specific small-scale electrochemical cell (minicell) has been used. Four different weldment zones have been studied. The electrochemical methods applied were the electrochemical potentiokinetic reactivation test and electrochemical potentiokinetic reactivation double loop test. These techniques showed that the HAZ was the most critical zone to intergranular corrosion for both materials. The weld metal was susceptible to interdendritic corrosion and the fusion line showed a mixture of intergranular and interdendritic corrosion. The effect of pre- and post-welding heat treatments for AISI 316L was analyzed. The HAZ was again the most critical zone in every heat treatment condition. The results were correlated to the microstructural features of the materials.     

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.     

Investigation of pitting corrosion of stainless steel by means of acoustic emission and potentiodynamic methods

Measurements of pitting corrosion by potentiodynamic method and also by acoustic emission technique were carried out simultaneously. Cumulative distribution function of pitting corrosion (CDF_P) occurrence was determined based on the results of potentiodynamic measurements. Independently cumulative distribution function of acoustic events (CDF_AE) was found. The correlation analysis of both distributions was also performed. The occurrence of pitting corrosion was checked by metallographic observation. The measurements proved that observable acoustic activity is an effect of hydrogen evolution inside the pits. The random character of acoustic events during polarization, statistical analysis and existence of pits are good confirmation.     

Kinetics of sharp intergranular corrosion fissures in AA7178

During service in structural aircraft applications, AA7178 has been found to develop sharp intergranular corrosion (IGC) fissures, a special form of attack. A new laboratory approach to quantify the kinetics of sharp IGC fissure growth was developed in this work. Sharp IGC fissures, similar to those formed in service, grew in samples that were given an electrochemical pre-treatment and then exposed in a humid environment. The time for the first sharp IGC fissure to penetrate the thin sample was determined by visual observation of the back side of the sample. The depth of the sharp IGC fissure was determined by serial sectioning. The kinetics measured by this approach did not represent the fastest rates, but rather the rates of long sharp IGC fissures. Relative humidity had no measurable effect on fissure kinetics, indicating that there was little connection of the local sharp IGC fissure region with the outside environment. AA7178 in the as-received and T7 conditions exhibited slower sharp IGC fissure rates than in the T6 condition. The sharp IGC fissures were found to be filled with corrosion products, which possibly exert a stress that could play an important role in driving fissure growth. It is suggested that the sharp IGC fissure could be a form of SCC.     

An electrochemical framework to explain the intergranular stress corrosion behavior in two Al-Cu-Mg-Ag alloys as a function of aging

A modified version of the Cu-depletion electrochemical framework was used to explain the metallurgical factor causal to intergranular stress corrosion cracking (IGSCC) susceptibility in two Al-Cu-Mg-Ag alloys (i.e., Al-5.0%Cu-0.8%Mg-0.5%Ag and Al-5.4%Cu-0.5%Mg-0.5%Ag). This framework was also used to explain the specific cases of IGSCC susceptibility in the under-aged condition and increased IGSCC resistance with over-aging. Susceptibility in the under-aged and T8 (peak-aged) conditions is consistent with the grain boundary Cu-depletion mechanism and high concentrations of Cu in solid solution in grain interiors. Improvement in resistance to IGSCC of the over-aged T8+ condition (i.e., T8 temper followed by an additional thermal exposure of 5000 h at 107.2 °C) can be explained by elimination of the differential Cu concentration adjacent to the grain boundary compared to that of the grain interior. The resultant leveling of Cu concentration leads to the suppression of a preferential dissolution path at the grain boundaries associated with IGSCC.     

Combined effect of resistance spot welding and post-welding sensitization on the degree of sensitization of AISI 304 stainless steel

This work studies the combined effect of resistance spot welding (RSW) and post-welding sensitization on the degree of sensitization (DOS) of AISI 304 stainless steel (SS) by using EPR and DLEPR tests. The combined effect of RSW and post-welding sensitization at 750 °C gives rise to an overall DOS that: (i) is lower than that of the state without prior welding; (ii) that decreases initially with increasing sensitization time but then increases. This behaviour is due to the fact that the interdendritic corrosion (IDC) located in the weld metal decreases with increasing sensitization time.     

Martensitic transformation in an intergranular corrosion area of austenitic stainless steel during thermal cycling

An oxidation-assisted martensitic phase transformation was observed in an austenitic stainless steel after thermal cycling up to 970 °C in air in a solar thermal steam reformer. The intergranular corrosion areas were investigated by electron backscatter diffraction (EBSD), transmission Kikuchi diffraction (TKD) and transmission electron microscopy (TEM). The structural-and-chemical maps revealed that within intergranular corrosion areas this martensitic transformation primarily occurs in oxidation-induced chromium-depleted zones, rather than due to only sensitization. This displacive transformation may also play a significant role in the rate at which intergranular corrosion takes place.     

The study of intergranular corrosion in aircraft aluminium alloys using X-ray tomography

Atmospheric corrosion is one of the leading causes of structural damage to aircraft. Of particular importance is pitting and intergranular corrosion, which can develop into fatigue cracks, stress corrosion cracks, or exfoliation. Therefore it is of interest to the Australian Defence Force (ADF) to understand how corrosion ensues in susceptible aircraft aluminium alloys, such as AA2024-T351 and 7050-T7451. However, there are many difficulties in measuring the extent of intergranular corrosion, since it is predominantly hidden below the surface. Traditionally, cross-sectioning has been used to view and measure the depth of attack. In the present work, 2 mm diameter pin specimens were contaminated with a droplet of 3.5% NaCl and exposed to constant humidity that resulted in intergranular corrosion. X-ray computed tomography was then used to non-destructively assess the depth and volume of corrosion both as a function of time in 97% relative humidity, and as a function of relative humidity after 168 h exposure. Both corrosion depth and volume increased with time, but there was evidence for a limiting depth in AA2024. Depth and volume also increased with relative humidity of the environment, for which the time-of-wetness and oxygen concentration of the droplets were considered the important factors in driving the corrosion process.