Intergranular Corrosion Research Articles

Microstructure, Hardness, Wear Resistance, and Corrosion Resistance of As-Cast and Laser-Deposited FeCoNiCrAl0.8Cu0.5Si0.5 High Entropy Alloy

FeCoNiCrAl0.8Cu0.5Si0.5 high-entropy alloys were fabricated using vacuum induction melting and laser deposition processes, followed by a comparison of the structural and mechanical properties of two distinct sample types. The as-cast FeCoNiCrAl0.8Cu0.5Si0.5 alloy is comprised of BCC1, BCC2, and Cr3Si phases, while the laser-deposited alloy primarily features BCC1 and BCC2 phases. Microstructural analysis revealed that the as-cast alloy exhibits a dendritic morphology with secondary dendritic arms and densely packed grains, and the laser-deposited alloy displays a dendritic structure without the formation of granular interdendritic regions. For mechanical properties, the as-cast FeCoNiCrAl0.8Cu0.5Si0.5 alloy demonstrated higher hardness than the as-deposited alloy, with values of 586 HV0.2 and 557 HV0.2, respectively. The wear rate for the as-cast alloy was observed at 3.5 × 10−7 mm3/Nm, with abrasive wear being the primary wear mechanism. Conversely, the as-deposited alloy had a wear rate of 9.0 × 10−7 mm3/Nm, characterized by adhesive wear. The cast alloy exhibited an icorr of 4.062 μA·cm−2, with pitting as the form of corrosion. The laser-deposited alloy showed an icorr of 3.621 μA·cm−2, with both pitting and intergranular corrosion observed. The laser-deposited alloy demonstrated improved corrosion resistance. The investigation of their microstructure and mechanical properties demonstrates the application potential of FeCoNiCrAl0.8Cu0.5Si0.5 alloys in scenarios requiring high hardness and enhanced wear resistance.

Correlating corrosion modes with the microstructure of the 2XXX series alloys: A comparative approach

In this study, the localized corrosion susceptibility of AA2050‐T84, AA2198‐T851, and AA2024‐T3 alloys was compared by immersion in three test solutions, specifically sodium chloride solution (3.5% NaCl), EXCO solution, according to ASTM G34‐18, and a solution for intergranular corrosion (IGC) test recommended by ASTM G110‐15 and via scanning vibrating electrode technique (SVET). The results showed higher susceptibility of AA2050‐T84 alloy to all types of corrosion tested compared to the other studied 2XXX series alloys. Corrosion penetration was deeper in the AA2050‐T84 due to its microstructural characteristics as a difference in the micrometric Cu‐Rich intermetallic particle distribution on the surface and related to the distribution of the T1 (Al2CuLi) phase.

Effect of rare earth element Y content on microstructure, magnetic properties, and electrochemical properties of the as-annealed FeCoNiAl0.2Yx high-entropy alloys

FeCoNi high-entropy alloy (HEA) is widely used in the aerospace and chemical industry. However, the strength and corrosion resistance of the alloy still need to be improved. In this paper, FeCoNiAl0.2Yx (x = 0, 0.05, 0.1, 0.2, and 0.3 in mole ratio) high entropy alloys with different contents of rare earth (RE) element yttrium (Y) were prepared by the vacuum arc melting method, and then the alloys were subjected to annealing treatment at 800 °C/2h. The microstructure, hardness, magnetism, and corrosion performance of FeCoNiAl0.2Yx HEAs in the annealed state with different contents of element Y were analyzed. The results show that the annealed FeCoNiAl0.2Yx HEAs without the addition of element Y and after the addition of element Y both were composed of a face-centered cubic phase. The alloy showed a dendritic structure inside. The element Y was solidly dissolved in the alloys to refine the microstructure of the alloys, and the dendrites were gradually refined with the addition of Y. The Y element caused the phenomenon of lattice distortion inside the alloys, which led to the increase in the alloys’ hardness. The alloy with x = 0.2 showed the greatest exchange of magnetic atoms and the alloy with x = 0.05 showed the lowest coercivity. The alloy with x = 0.1 showed the lowest self-corrosion current density, the broadest passivation zone, the densest dendrites, the smallest grain spacing, and the weakest tendency for intergranular corrosion. The present study shows that the introduction of element Y improves the microstructural morphology, hardness, magnetism, and corrosion properties of FeCoNiAl0.2Yx HEAs in the annealed state.

Accelerated corrosion tests of a contact pair austenitic stainless steel – titanium alloy

The results of accelerated corrosion tests of a pair of austenitic stainless steel — titanium alloy under conditions of elevated temperatures and high concentrations of corrosive agents are presented, conditions for the developing the mechanism of local corrosion being the same. The proposed approach included provoking the appearance of microstress concentrators by three-point loading of test samples with subsequent forced development of local types of corrosion through simultaneous exposure to an increased concentration of corrosive agents and temperatures at a fixed exposure in an autoclave. The results of modeling the corrosion process in a titanium alloy being in contact with stainless steel are assessed proceeding from the data obtained from metallographic studies of the state of surface layers of the metal and the morphology of corrosion products on prepared sections of the surface of templates cut from the samples under study. We considred a pair of steel 08Kh18N10T — titanium alloy VT-5. It is shown that the contact of samples under conditions of accelerated corrosion tests does not lead to a significant development of local types of corrosion of the titanium alloy. On the contrary, analysis of the state of the surface layers of the samples of stainless steel revealed the presence of deep corrosion pits, triggering the intergranular corrosion. In this case, corrosion of austenitic steel, both in the presence and in the absence of contact with titanium, proceeded in three stages: the initiation and fusion of pitting; formation of knife corrosion ulcers; propagation of intergranular cracks into the depth of steel. The proposed methodology of corrosion testing can be used to predict the possible nature of the development of metal corrosion under operating conditions that form local zones of static stresses in structural materials, and for prompt response to extend the design life of the equipment at thermal and nuclear power facilities.

The Effect of Self-Healing Microcapsules in Corrosion Testing on Magnesium AZ31 Alloy and Fibre Metal Laminates

Fibre metal laminates (FMLs) are the most interesting composite materials of the past decade. They possess the properties of both polymer composites and metallic alloys. However, there is a problem with corrosion when the outer layers are made of aluminium or magnesium. The electrochemical changes that occur during the corrosion process and the mechanisms associated with the corrosion phenomenon are still being investigated. Recently, self-healing phenomena have emerged as a useful approach to prevent corrosion. However, there is limited research on the combination of FMLs and self-healing layers. Therefore, the main purpose of this article is to evaluate the self-healing ability of a magnesium/PEO layer based on microcapsules in a corrosion environment. It was observed that the corrosion mechanism in magnesium alloys is very complex. However, the use of a barrier layer with PEO treatment and microcapsules yielded positive anti-corrosion results. The FML samples were subjected to a 6-week corrosion test, and the addition of microcapsules to the layers showed positive results. In contrast, the samples without microcapsules exhibited intergranular corrosion. In the future, comprehensive tests using self-healing microcapsules in FMLs could greatly enhance their anti-corrosion properties and improve the integrity of the structure.

Enhancing the corrosion resistance of high Mo S31254 super austenitic stainless steel using grain boundary engineering

Super austenitic stainless steel (SASSs) with a high Mo content exhibit excellent resistance to intergranular corrosion (IGC), Its mechanical properties mainly depend on solid solution strengthening. Meanwhile, grain boundary engineering (GBE) can simultaneously improve the corrosion resistance and mechanical properties of Mo-rich austenitic stainless steel using the resistance to IGC of Mo. However, recrystallization annealing is extremely difficult due to the sensitive precipitation of Cr-rich and Mo-rich precipitations in SASSs. Therefore, this study explores the effect of large deformation, high temperature, and short-time annealing on the corrosion resistance of SASSs. The results show that a recrystallized organization with an average grain size of 13.3 μm was prepared by 50% cold rolling deformation and 2 min high-temperature short-time annealing at 1150 °C. The highest percentage of Σ3 GBs is about 34%, the percentage of other low-energy GBs is relatively low (only about 6%), and the rest are random high-angle grain boundaries (RHAGBs), which account for about 60%. It can be seen the corrosion resistance of random GBs after GBE treatment is superior to that of solution treatment. Meanwhile, medium-temperature aging improved the resistance to IGC of SASSs, especially after aging at 450 ℃, a small amount of Mo is enriched along the GBs, which promotes the formation of Cr2O3 and Mo-rich oxides in the passivation film and improves the corrosion resistance. The above results provide guidance for improving the corrosion resistance of Mo-rich austenitic stainless steels.

Development of NiCrFeCoBX eutectic high entropy alloy coating by laser cladding: Investigation of microstructural, solidification, corrosion, and wear properties

Developing protective coatings resistant to corrosion and wear has always been a challenge in various industries. In this work, we processed NiCrFeCoBx (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6) high-entropy alloy by laser cladding on a GTD-111 superalloy. At B ≤ 0.3, the microstructure of the coating consisting of inter-dendritic FCC1 and FCC2 lamellae coupling was confirmed by XRD and SEM analysis. By increasing the value of B (B≥ 0.4), a coating with the phase structures of FCC1, FCC2, and MXBY was identified. The presence of Cr-rich borides (MXBY) was attributed to the enrichment of the eutectic composition with B and its segregation into interdendritic regions. With increasing B, more areas were created for inhomogeneous nucleation of dendrites from the melt, resulting in a finer eutectic structure with a higher volume fraction. The comparison between B0.1 and B0.6 samples showed that the hardness increased from 240 HV to 603 HV and the coefficient of friction decreased from 0.63 to 0.42. Raising the B value led to a drop in the corrosion current potential of the NiCrFeCoBX coating from −0.456 V to −0.895 V in a 3.5 % NaCl solution. Additionally, this shift altered the corrosion mechanism from pitting to intergranular corrosion. This was attributed to the high surface energy of the eutectic phase and the intensification of galvanic corrosion.

Improved Ability to Resist Corrosion of Selective-Laser-Melted Stainless Steel Based on Microstructure and Passivation Film Characteristics

The local corrosion resistance of forging and selective laser melting (SLM) 304 steels was explored by intergranular corrosion analysis, double-loop electrochemical potentiodynamic reactivation, dynamic polarization experimentation, structural analysis, and passivation film characteristics analysis. The ability to resist sensitization of SLM 304 steel is greater than that of forging 304 steel at a temperature of 650 °C for 9 h. Moreover, the pit corrosion resistance of forging and SLM 304 steels is weakened by sensitization, while the pit corrosion resistance of SLM 304 steel is much greater than that of forging steel. Therefore, SLM technology can improve the ability to resist sensitization and pit corrosion of 304 steel. Analysis showed that the ability to resist corrosion of the passivation film of SLM 304 steel is greater than that of forging steel. In addition, corrosion pits are easier to generate at the interface of forging steel and SLM 304 steel. The grain boundary corrosion of SLM 304 steel intensified while the corrosion of the melt pool boundaries weakened after the sensitization treatment, resulting in a decrease in pit corrosion resistance. The coupling effect of these different structures and passivation films decides the pit and sensitization resistance of forging and SLM 304 steels. Clarifying the corrosion mechanism of forging and SLM steels is of great significance for scientific research and the widespread use of SLM technology.

Influence of Thermal Aging Treatments on Intergranular Corrosion and Cyclic Oxidation Behavior of Low Nickel and Nickel-Free Austenitic Stainless Steels

Influence of Thermal Aging Treatments on Intergranular Corrosion and Cyclic Oxidation Behavior of Low Nickel and Nickel-Free Austenitic Stainless Steels

Evaluation of Sensitization Behaviors on the Heat-Affected Zone of Austenitic Stainless Steel Weld by Thermal Cycles of Actual Multi-pass Welding

The sensitization behavior of the welding heat affected zone (HAZ) in austenitic stainless steels (SSs) was investigated through simulated thermal cycles emulating actual multi-pass welding processes using the Gleeble simulator. The tests were performed with austenitic SSs, considering carbon contents, heat input, and distance from the fusion line to determine the thermal cycle conditions of the HAZ. Higher carbon content led to increased sensitization (degree of sensitization, DOS) values, while the influence of the thermal cycle in the final weld pass was that even though it was rapidly heated to over 1000 °C and cooled at a rapid rate, the DOS value decreased due to partial carbide dissolution and chromium diffusion. Therefore, effective management of the final thermal cycle in the HAZ contributes to improved intergranular stress corrosion cracking resistance. Even with prolonged exposure of the HAZ to the sensitization region, the discovery that corrosion resistance improves when the final heating cycle reaches 1000 °C underscores the importance of HAZ heat cycle management and provides valuable insights for materials engineering and industrial applications.Graphical abstract

A novel surface grain boundary engineering approach to improving corrosion resistance of a high-N and Ni-free austenitic stainless steel

Grain boundary engineering (GBE) can effectively improve the corrosion resistance of materials, but the traditional thermal-mechanical process still exhibits some limitations. In the present work, a novel surface spinning strengthening (3 S) technology followed by heat treatment was applied to modify the microstructure near the surface (∼ 400 μm) of a high-N Ni-free austenitic stainless steel. Under an optimal condition of annealing at 1323 K for 60 min after 3 S, the fraction of special boundaries mainly involving Σ3 boundaries in GBE layer was significantly improved from 48.3 % to 69.1 %, thus achieving excellent resistances to intergranular corrosion and stress corrosion cracking.

Intergranular corrosion in AA5083 alloy: The influence of grain boundary segregation and its detection via TEM

The influence of grain boundary segregation on corrosion behaviour of AA5083 alloy remains unclear. In the present work, the segregation in both as-received and sensitized AA5083 alloys was examined via transmission electron microscopy (TEM). The influence of TEM specimen preparation methods on grain boundary segregation detection was explored. It is revealed that focussed ion beam (FIB) is reliable for the detection of grain boundary segregation. Further, the influence of grain boundary segregation on intergranular corrosion (IGC) of AA5083 alloy was examined. It is indicated that Mg segregation at grain boundary is decisive for IGC development in AA5083-H116 alloy, which also benefits IGC development in sensitized AA5083-H116 alloy by increasing the continuity of grain boundary micro-chemistry.

Study on the quenching sensitivity of corrosion properties in 7199 aluminum alloy

This study used electrochemical corrosion, intergranular corrosion (IGC), and exfoliation corrosion tests, as well as microscopic observations of the microstructure and first-principles calculations, to investigate the effect of different quenching rates on the microstructure and corrosion properties of the 7199 alloy. The results show that as the quenching rate decreases, the size, Zn, and Mg content of precipitated phases at grain boundaries (GBs), as well as the width of the precipitation-free zone (PFZ), increase, resulting in a decrease in corrosion properties. During slow quenching, the η phase (MgZn2) at the GBs continuously absorbs surrounding Zn and Mg atoms, causing Zn and Mg atom depletion near the GBs. This results in the formation of a wide PFZ. Enlargement of the η phase and PFZ at the GBs leads to anodic dissolution channels, allowing for rapid corrosion expansion along the GBs. Additionally, at slow quenching rates, not only does the η phase precipitate at the subgrain boundaries (SGBs) but also the T and S phases. In corrosive environments, the η phase is more prone to corrosion than the T and S phases. Electron work function calculations show that the S phase has the highest corrosion potential, whereas the η phase has the lowest. As a result, SGBs containing T and S phases are unlikely to serve as corrosion pathways. Corrosion preferentially extends along SGBs containing η phases.

Intergranular Attack of Low Carbon Steel in Molten Aluminum Chloride

AISI 1018 carbon steel exhibits intergranular attack in molten aluminum chloride. To explore grain boundary corrosion initiation and propagation, tests have been conducted on several iron-based alloys, heat treated to recrystallization temperature, and using molten aluminum chloride and its mixture with other molten chlorides environments. Pure iron, A106, and AISI 1018 carbon steel have been exposed to both pure aluminum chloride and ferric chloroaluminate melt in both their recrystallized and as-received, cold-worked conditions. Intergranular corrosion is observed in both 1018 and A106 carbon steels in all the salts whereas pure iron only shows pitting. Materials processing has varying effects on the corrosion depths of 1018 and A106 carbon steels. The grain boundary microchemistry of 1018 carbon steel is examined with in situ fracture Auger spectroscopy where molybdenum and carbon segregation are found, and a mechanism is proposed to explain the present corrosion phenomenon.

Effect of heat input on the microstructure and hardness of AISI 321 stainless steel welds using ER 347 filler metal

Stainless steel is widely used in various fields, one of which is AISI 321, which is used for high-temperature applications because of its high resistance to creep and intergranular corrosion. The type of filler metal and heat input on stainless steel welds play an essential role in determining the microstructure and mechanical properties of the welded joints. The purpose of this experiment was to evaluate the microstructure and mechanical properties of AISI 321 stainless steel welds with variations in heat input. This study is expected to explore the performance of this weld joint, which can be anticipated in relevant fields. The welding method used in this experiment was Gas Tungsten Arc Welding (GTAW) with ER 347 as filler metal. Welding was carried out on three samples with a heat input of 0.92 kJ/mm, 0.64 kJ/mm, and 0.52 kJ/mm, respectively. The tests included tensile strength, Vickers microhardness, and microstructure observations. The tensile test results showed that a fracture occurred in the Base Metal (BM) area, indicating that the strength of the weld joint was higher than that in the BM. The Vickers microhardness test results showed that the Weld Metal's hardness (WM) was the highest, followed by the Heat-Affected Zone (HAZ) and BM. The welding experiment that used three variations in heat input demonstrated that higher heat input lowered the hardness of the weld joint. The microstructure observation results around the fusion line demonstrated the presence of step and ditch structures. The ditch structure indicates intergranular corrosion.

Sensitization characteristics for type 445 ultra-pure ferritic stainless steel with an electrochemical reactivation method

The sensitization characteristics of type 445 ultra-pure ferritic stainless steel (FSS) under different aging conditions were investigated by the optimized double loop electrochemical potentiodynamic reactivation (DL-EPR) test and microstructure observation. The solution 2 mol L−1 H2SO4 + 0.01 mol L−1 KSCN +0.5 mol L−1 NaCl and a scan rate of 100 mV min−1 are suitable for the DL-EPR test of 445 FSS. With the change of aging temperature from 500 to 900 °C, the degree of sensitization (DOS) slightly increases at first and then decreases, which reaches a maximum value at about 700 °C. Under the aging condition at 700 °C for 10 min to 2 h, the DOS value gradually increases, but it is less than 3% due to the low intergranular corrosion susceptibility. The aging treatment at 700 °C results in the precipitation of Laves phase and (Nb, Ti)(C, N), but no Cr-carbides. The sensitization may be related to the segregation of Cr atoms around (Nb, Ti)-precipitates at the grain boundaries.

Localized corrosion of thermally aged Cu-containing Ni-13Cr-10Fe alloys: The role of Cu enrichment induced grain boundary sensitization

This study reports a new mechanism of grain boundary (GB) sensitization without precipitation of Cr-rich phases at GBs in Cu-containing Ni-Cr-Fe alloys. Copper segregation at GBs during annealing can deplete the boundaries of Cr due to the repulsive interaction between Cr and Cu. The depletion of passivating Cr along GBs can cause intergranular corrosion susceptibility, as evidenced by electrochemical testing and post-mortem morphological characterization. The implications of this new sensitization mechanism on the localized corrosion resistance of Cu-containing commercial alloys are discussed.

Corrosion behaviors and mechanism of AlxCrFeMnCu high-entropy alloys in a 3.5 wt% NaCl solution

This study investigated the corrosion behavior of as-cast AlxCrFeMnCu (x = 0, 0.5, 1.0, 1.5, 2.0) high-entropy alloys (HEAs) in a 3.5 wt% NaCl solution at room temperature. The results indicated that the corrosion resistance of the AlxCrFeMnCu HEAs decreased with increasing Al content. Intergranular corrosion was the primary corrosion type for CrFeMnCu and Al0.5CrFeMnCu HEAs, while Al1.0CrFeMnCu, Al1.5CrFeMnCu, and Al2.0CrFeMnCu HEAs exhibited selective corrosion with enrichment of Al and Cu in the BCC2 phase. The XPS fitting calculations indicated that an increase in the molar ratio of Al led to a decrease in Cr2O3 content and an increase in Al2O3 content, which weakened the stability and protective properties of the passive film.

Microstructure and properties of a HIP manufactured SiCp reinforced high alloyed Al–Zn–Mg–Cu–Zr–Ti aluminum matrix composite

In this study, a hot isostatic pressing (HIP) manufactured SiC particles (SiCp) reinforced high alloyed Al–Zn–Mg–Cu–Zr–Ti aluminum matrix composite was fabricated through ball-milling, HIP, homogenization, hot extrusion, solution treatment, and aging treatment. The results showed the presence of an interfacial reaction layer, MgAl2O4, around the SiCp, which enhanced the bonding between the particles and the matrix. The aging treatment resulted in the formation of different aging precipitates, which were featured by GP zone for T4, GP zone + η' (metastable MgZn2) + η (stable MgZn2) for T6 and GP zone + η' (metastable MgZn2) for T6I4. The composite samples of T4, T6, and T6I4 exhibited different mechanical properties. Specifically, the elastic modulus was measured as 102.9, 103.4, and 102.3 GPa, the yield strength was 685.3, 598.1, and 619.7 MPa, the ultimate tensile strength was 713.6, 618.9, and 633.3 MPa, and the elongation was 2.2%, 1.8%, and 2.8%, respectively. Furthermore, the corrosion behavior of the composite was evaluated through electrochemical, intergranular corrosion, and exfoliation corrosion. The corrosion current density was found to be 3.17 × 10−7, 4.97 × 10−7, and 3.67 × 10−7 A cm−2, the corrosion potential was measured as −0.70, −0.81, and −0.56 V, and the maximum intergranular corrosion depth was 139.9, 167.8, and 106.2 μm for T4, T6, and T6I4, respectively. The severity of exfoliation corrosion varied, with T4 showing severe pitting, T6 exhibiting moderate pitting, and T6I4 displaying slight pitting. The strengthening mechanism and load transfer strengthening of the composites were discussed in detail based on theoretical calculations, and the anti-corrosion mechanisms were also analyzed.

The influence of microstructural evolutions on electrochemical corrosion and passive behavior in precipitation-strengthened high-entropy alloys

Effects of microstructural evolutions on electrochemical corrosion properties and passive film characteristics of precipitation-strengthened (Ni2Co2FeCr)92Al4Nb4 high-entropy alloys (HEAs) were investigated in a saline environment. Compared with single-phase FCC alloys, the appearance of nano-sized L12 particles increases the metastable pitting activities and slightly reduces the pitting potential, while the lamellar D019 phase further deteriorates the localized corrosion resistance. The chemical composition and oxide state of passive films are closely related to the different precipitation scenarios. The corrosion morphologies of the single-phase and L12-strengthened alloys are dominated by pitting, whereas the intergranular corrosion (IGC) and intragranular dealloying-like corrosion occur in the D019-strengthened alloy.