Sigma Phase Formation Research Articles

Improved creep strength of alumina-forming austenitic heat-resistant steels through W addition

We investigated the effect of W addition on the creep and precipitation behavior of alumina-forming austenitic (AFA) heat-resistant steels at 700°C and 160MPa. Our results showed that the creep rupture time of the W containing AFA (WAFA) increased more than that of the AFA due to enhanced precipitation hardening of Laves phase and suppression of sigma phase formation. W increased the volume fraction of Laves phase and enhanced precipitation hardening by higher driving force for the precipitation and affinity of the Laves phase. Therefore most W were consumed for the precipitation of the Laves phase, however Mo content contributed to the precipitation of M23C6 as well as precipitation of Laves phase due to the lower affinity of Laves phase. The M23C6 in AFA contained enough Mo to form the sigma phase, which served as an initiation site for cavitation and crack propagation. The sigma phase grew and coarsened at the expense of M23C6 and Mo-rich Laves phase to match the stoichiometric composition of the sigma phase, and finally creep strength of AFA was greatly reduced.

Sigma Phase in Superduplex Stainless Steel: Formation, Kinetics and Microstructural Path

The superduplex stainless steels (SDSS) are widely used in chemical, oil and gas industries, to pipelines and storage material facilities. In welding process or working in temperature elevated, secondary phases may appear in the form of precipitates, as the sigma phase (σ) which is an intermetallic compound. This compound is harmful to the properties of steel, deteriorating its mechanical properties, such as decreasing corrosion resistance and toughness. In this paper it is analyzed the formation, kinetics and microstructural evolution of sigma phase in SDSS UNS S32750 after isothermal aging at 700oC, 750oC and 800oC. In this work sigma phase kinetics is studied by JMAK theory and by two microstructural path descriptors, SV, interfacial area per unit of volume between sigma phase and austenite, and , mean chord length of sigma, both in function of the VV, volumetric fraction of sigma, known in the literature as microstructural partial path (MP). The MP formulation is common in recrystallization studies, but so far has not been used in the sigma phase precipitation studies, being applied here for the first time. The results indicated that the sigma phase nucleates by site saturation with anisotropic linear impingement. This means that sigma phase nucleates on edges.

The Effect of Surface Preparation on the Precipitation of Sigma During High Temperature Exposure of S32205 Duplex Stainless Steel

Although the formation of sigma phase in duplex stainless steels is reasonably well documented, the effect of surface finish on its formation rate in surface regions has not been previously noted. The growth of the sigma phase precipitated in the subsurface region (to a maximum depth of 120 μm) has been quantified after heat treatment of S32205 duplex stainless steel at 1073 K (800 °C) and 1173 K (900 °C) after preparation to two surface finishes. Here, results are presented that show that there is a change in the rate of sigma phase formation in the surface region of the material, with a coarser surface finish leading to a greater depth of precipitation at a given time and temperature of heat treatment. The growth rate and morphology of the precipitated sigma has been examined and explored in conjunction with thermodynamic equilibrium phase calculations.

On the formation of stripe, sigma, and honeycomb phases in a core-corona system.

Using Monte Carlo simulations and free-energy calculations, we investigate the phase behaviour of a two-dimensional core-corona system. We model this system as particles consisting of an impenetrable hard core of diameter σHD surrounded by a purely repulsive soft corona of diameter δ = 1.95σHD. At low densities, we observe the spontaneous formation of a phase with a stripe texture as well as a honeycomb-like phase driven by both energy and entropy considerations. At high densities, we find that a two-dimensional analogue of the periodic sigma phase, considered as an approximant of dodecagonal quasicrystals, is energetically stabilised with respect to two distinct dodecagonal quasicrystals, namely, a square-triangle tiling and a square-triangle-shield tiling. We also find the formation of stable hexagonal phases at three distinct density ranges, which are energetically driven, i.e. by minimising the overlap of coronas. Furthermore, our calculations show that the low-density dodecagonal quasicrystal that was previously reported by Dotera et al., [Nature, 2014, 506, 208] is kinetically formed in the coexistence region between the honeycomb and the medium-density hexagonal phase.

Joint properties of ultra thin 430M2 ferritic stainless steel sheets by friction stir welding using pinless tool

In this study, friction stir butt welding of ultra thin 430M2 ferritic stainless steel sheets with satisfactory joint properties has been achieved using a pinless WC-Co tool. Friction stir welding was carried out at a tool rotational speed of 900rpm and a travel speed of 96mm/min. FSW joints were welded completely without any unwelded zone resulting from smooth material flow, despite of being adopted pinless tool. It was revealed that the maximum tensile strength of FSW welds was 468MPa, equivalent to the tensile strength of base metal. Notably, it was found that sigma phase formation in FSW welds is suppressed compared with that of arc welds, resulting in improving joint strength. These results suggest that the low input process of FSW is an effective substitute for the conventional fusion welding GTAW in ultra thin ferritic stainless steel plate.

Dry Sliding Wear Behavior of Super Duplex Stainless Steel AISI 2507: a Statistical Approach

Abstract The dry sliding wear behavior of heat-treated super duplex stainless steel AISI 2507 was examined by taking pin-on-disc type of wear-test rig. Independent parameters, namely applied load, sliding distance, and sliding speed, influence mainly the wear rate of super duplex stainless steel. The said material was heat treated to a temperature of 850°C for 1 hour followed by water quenching. The heat treatment was carried out to precipitate the secondary sigma phase formation. Experiments were conducted to study the influence of independent parameters set at three factor levels using the L27 orthogonal array of the Taguchi experimental design on the wear rate. Statistical significance of both individual and combined factor effects was determined for specific wear rate. Surface plots were drawn to explain the behavior of independent variables on the measured wear rate. Statistically, the models were validated using the analysis of variance test. Multiple non-linear regression equations were derived for wear rate expressed as non-linear functions of independent variables. Further, the prediction accuracy of the developed regression equation was tested with the actual experiments. The independent parameters responsible for the desired minimum wear rate were determined by using the desirability function approach. The worn-out surface characteristics obtained for the minimum wear rate was examined using the scanning electron microscope. The desired smooth surface was obtained for the determined optimal condition by desirability function approach.

Sigma phases in an 11%Cr ferritic/martensitic steel with the normalized and tempered condition

At the present time 9–12% Cr ferritic/martensitic (F/M) steels with target operating temperatures up to 650°C and higher are being developed in order to further increase thermal efficiency so as to reduce coal consumption and air pollution. An 11% Cr F/M steel was prepared by reference to the nominal chemical composition of SAVE12 steel with an expected maximum use temperature of 650°C. The precipitate phases of the 11% Cr F/M steel normalized at 1050°C for 0.5h and tempered at 780°C for 1.5h were investigated by transmission electron microscopy. Except for Cr-/Cr-Fe-Co-rich M23C6, Nb-/V-/Ta-Nb-/Nd-rich MX, Fe-rich M5C2, Co-rich M3C and Fe-Co-rich M6C phases previously identified in the steel, two types of sigma phases consisting of σ-FeCr and σ-FeCrW were found to be also present in the normalized and tempered steel. Identified σ-FeCr and σ-FeCrW phases have a simple tetragonal crystal structure with estimated lattice parameters a/c=0.8713/0.4986 and 0.9119/0.5053nm, respectively. The compositions in atomic pct of the observed sigma phases were determined to be approximately 50Fe-50Cr for the σ-FeCr, and 30Fe-55Cr-10W in addition to a small amount of Ta, Co and Mn for the σ-FeCrW. The sigma phases in the steel exhibit various blocky morphologies, and appear to have a smaller amount compared with the dominant phases Cr-rich M23C6 and Nb-/V-/Ta-Nb-rich MX of the steel. The σ-FeCr phase in the steel was found to precipitate at δ-ferrite/martensite boundaries, suggesting that δ-ferrite may rapidly induce the formation of sigma phase at δ-ferrite/martensite boundaries in high Cr F/M steels containing δ-ferrite. The formation mechanism of sigma phases in the steel is also discussed in terms of the presence of δ-ferrite, M23C6 precipitation, precipitation/dissolution of M2X, and steel composition.

Oxidation behaviour and phase transformations of an interconnect material in simulated anode environment of intermediate temperature solid oxide fuel cells

The oxidation behaviour and the phase transformations associated with high temperature exposure of a commercial ferritic interconnect steel, Crofer 22 H, was studied in a simulated solid oxide fuel cell (SOFC) anode atmosphere at 700 °C. Special emphasis was placed on the formation of the intermetallic sigma phase. No sigma phase was detected in the bulk alloy after 500 h of exposure of bare specimens. However, specimens which were pre-coated with a layer of nickel showed formation of an interdiffusion zone after as little as 2 h of exposure and sigma phase formation occurred after 10 h. The presence of the nickel layer, which simulates the contact between ferritic steel interconnects and a nickel mesh in a SOFC results in the formation of an austenitic zone and accelerated formation of a σ-phase rich layer at the ferrite/austenite interface. The ferritic steel is transformed into austenite due to the inward diffusion of nickel, σ-phase started to nucleate at the transformed austenite grain boundaries. The nucleation is enhanced by an increased Cr/Fe-ratio at that interface due to more pronounced diffusion of Fe, compared to Cr, in the direction of the Ni-layer. Different possible mechanisms for the nucleation and growth of σ-phase were identified. The experimental results led to the conclusion that sigma nucleates in the austenite and grows following an isothermal eutectoid-like decomposition. The kinetics of σ-phase formation and the depth of the interdiffusion zone were found to follow a traditional diffusion relationship. It was observed that as the Ni-concentration increases the sigma-phase re-dissolves and thus the zone which, contains sigma phase moves deeper into the ferritic steel with exposure time. Interdiffusion processes between the nickel layer and the ferritic steel result not only in accelerated formation of σ-phase but also in the formation of Cr-rich oxides within the nickel layer.

Effect of multipass TIG welding on the corrosion resistance and microstructure of a super duplex stainless steel

This is a study of the effect of repetitive TIG (tungsten inert gas) welding passes, melting and remelting the same material volume on microstructure and corrosion resistance of 2507 (EN 1.4410) super duplex stainless steel. One to four weld passes were autogenously (no filler added) applied on a plate using two different arc energies and with pure argon shielding gas. Sensitization testing showed that multipass remelting resulted in significant loss of corrosion resistance of the weld metal, in base material next to the fusion boundary, and in a zone 1 to 4 mm from the fusion boundary. Metallography revealed the main reasons for sensitization to be a ferrite‐rich weld metal and precipitation of nitrides in the weld metal, and adjacent heat affected zone together with sigma phase formation at some distance from the fusion boundary. Corrosion properties cannot be significantly restored by a post weld heat treatment. Using filler metals with higher nickel contents and nitrogen containing shielding gases, are therefore, recommended. Welding with a higher heat input and fewer passes, in some cases, can also decrease the risk of formation of secondary phases and possible corrosion attack.

Effect of Cooling Rate on the Corrosion Behavior of As-Cast SAF 2205 Duplex Stainless Steel after Solution Annealing Treatment

The formation of intermetallic phases alters the properties of duplex stainless steel and is therefore a crucial factor in its performance. For example, the formation of sigma phase in duplex steel increases its brittleness and decreases its corrosion resistance because this phase consumes chromium and molybdenum in solid solution, thus leading to the depletion of these elements in the matrix. This study investigated the corrosion resistance of as-cast SAF 2205 duplex stainless steel after solution annealing treatment at 1100 °C for 240 minutes, under varying cooling rates. The objective was to evaluate the correlation between cooling condition, microstructural changes and corrosion resistance based on cyclic potentiodynamic polarization tests and double loop electrochemical potentiokinetic reactivation (DL-EPR) measurements. The results revealed a significant reduction in the corrosion resistance of a slowly cooled sample, which presented an increase in the degree of Cr (Qr / Qa) depletion resulting from the formation of sigma phase.

Use of Magnetic Barkhausen Noise (MBN) to Follow Up the Formation of Sigma Phase in Saf2205 (UNS S31803) Duplex Stainless Steel

Duplex stainless steels have a structure normally composed of austenite and ferrite in approximately equal proportions. In order to attain control of its fabrication processes and performance, it is important to understand its microstructural evolution, due to the formation of intermetallic phases such as sigma (σ) and chi (χ), which may cause a severe deterioration of mechanical properties. In the present study, the evolution of sigma phase during heat treatments at temperatures in which intermetallic phases can be formed (800oC-900°C) was studied using magnetic analyses on a SAF2205 (DIN 1.4462/UNS S31803) steel. A significant reduction of the intensity of Magnetic Barkhausen Noise (MBN) was observed with the increase of heat treatment time, indicating a decrease in the quantity of ferromagnetic phases. For 24-hour-long treatments, the Barkhausen Noise signal is almost completely enclosed by the background noise, indicating the existence of a very small volume fraction of ferrite. If proper calibration samples are to be produced, this technique may be a viable method for non-destructive evaluation of field components working under thermal conditions that may cause the formation of intermetallic phases.

Sigma phase detection in duplex stainless steel by induced magnetic field

Duplex stainless steels when subjected to temperatures above 600 ° C have its tenacity decreased by the formation of sigma phase. This phase has high hardness and is rich in chromium and reduces the matrix of this element. In this study, field line density measurements, obtained in the reversibility region of magnetic domains, and application of artificial neural networks are used to monitor the formation of this undesirable phase. Samples of a stainless steel SAF 2205 were subjected to aging at temperatures of 800 ° C and 900 ° C, in order to obtain different amounts of sigma phase. The amount of this phase was obtained by image processing and the density of field lines through a Hall Effect sensor. Charpy impact tests were performed. The field lines densities were used for training of an artificial neural network and correlated with the presence of sigma phase and embrittlement of the material. The results showed that the method was able to correlate the parameters studied with the presence of the sigma phase and toughness of the material studied in both temperatures.

Kinetic Study to Predict Sigma Phase Formation in Duplex Stainless Steels

This work presents an improved kinetic study of sigma phase formation during isothermal aging between 973 K and 1223 K (700 °C and 950 °C), based on Kolmogorov-Johnson-Mehl-Avrami (K-J-M-A) model, established from volume fraction of sigma phase determined in backscattered electron images over polished surfaces of aged samples. The kinetic study shows a change in the main mechanism of sigma formation between 973 K and 1173 K (700 °C and 900 °C), from a nucleation-governed stage to a diffusion-controlled growth-coarsening stage, confirmed by a double inclination in K-J-M-A plots and microstructural observations. A single inclination in K-J-M-A plots was observed for the 1223 K (950 °C) aging temperature, showing that kinetic behavior in this temperature is only related to diffusion-controlled growth of sigma phase. The estimated activation energies for the nucleation of sigma phase are close to the molybdenum diffusion in ferrite, probably the controlling mechanism of sigma phase nucleation. The proposed time-temperature-transformation (TTT) diagram shows a “double c curve” configuration, probably associated to the presence of chi-phase formed between 973 K and 1073 K (700 °C and 800 °C), which acts as heterogeneous nuclei for sigma phase formation in low aging temperatures.

Ab initio study of energetics and magnetism of sigma phase in Co–Mo and Fe–Mo systems

We analyse, from first-principles, the energetics and magnetic ordering of sigma phases in Co–Mo and Fe–Mo systems. Total energy differences between the sigma phase and Standard Element Reference (SER) structures are calculated in the whole concentration range at equilibrium volumes by means of the linear muffin-tin orbitals method in the atomic-sphere approximation (LMTO-ASA), the full-potential linearised augmented-plane waves (FLAPW) method and the pseudopotential approach. They are compared with the enthalpy of formation of sigma phase obtained from the phase equilibria calculations at higher temperature based on the semiempirical CALPHAD (CALculation of PHAse Diagram) method. It turns out that the binary sigma phases are more stable than the weighted average of the sigma phase of elemental constituents and that this stability for Fe–Mo is higher than for Co–Mo. On the other hand it was found that the binary sigma phases do not exhibit any stability with respect to the weighted average of the SER structures. The magnetic configurations in all systems are investigated and the stabilizing effect of magnetic order in sigma phase at 0 K is presented. It turns out that the atomic magnetic moment strongly depends on the type of occupied sublattice and total composition of the alloy.

Correlation between AC magnetic susceptibility and pitting behaviour of sigma-phase containing duplex stainless steel

Purpose – The purpose of this paper is to characterize the pitting behaviour of sigma-phase-containing duplex stainless steel and investigate the correlation between magnetic susceptibility and pitting potentials. Design/methodology/approach – Use an alternating current (AC) magnetic susceptometer to trace the change in magnetic susceptibility associated with sigma phase formation and systematic study of the effects of sigma precipitation on pitting parameters as obtained using the anodic potentiodynamic polarization test. Findings – The precipitation of sigma phase impairs the general and pitting corrosion resistance of duplex stainless steel. The pitting potential, the corrosion potential and the AC magnetic susceptibility have good correlations. Unlike the pitting potential and the corrosion potential, the passive current and the corrosion current do not seem to possess any trend with annealing time. Originality/value – The correlation between AC magnetic susceptibility and pitting parameters has not been reported in the literature before.

Effect of Cooling Rate on the Corrosion Behavior of As-Cast SAF 2205 Duplex Stainless Steel After Solution Annealing Treatment

The formation of intermetallic phases alters the properties of duplex stainless steel and is therefore a crucial factor in its performance. For example, the formation of sigma phase in duplex steel increases its brittleness and decreases its corrosion resistance because this phase consumes chromium and molybdenum in solid solution, thus leading to the depletion of these elements in the matrix. This study investigated the corrosion resistance of as-cast SAF 2205 duplex stainless steel after solution annealing treatment at 1100 °C for 240 minutes, under varying cooling rates. The objective was to evaluate the correlation between cooling condition, microstructural changes and corrosion resistance based on cyclic potentiodynamic polarization and double loop electrochemical potentiokinetic reactivation (DL-EPR) measurements. The results revealed a significant reduction in the corrosion resistance of a slowly cooled sample, which presented an increase in the degree of Cr (Qr / Qa) depletion resulting from the formation of sigma phase.

Degradation of mechanical and corrosion resistance properties of AISI 317L steel exposed at 550°C

Abstract The use of austenitic stainless steel type AISI 317L has increased in the last years, in substitution to AISI 316L and other austenitic grades. The higher Mo content (3.0 wt.%. at least) gives higher corrosion resistance to AISI 317L. However, some concern arises when this material is selected to high temperature process services in refineries. Microstructural changes such as chromium carbide precipitation and sigma phase formation may occur in prolonged exposure above 450 °C. In this work, the microstructure evolution of AISI 317L steel during aging at 550 °C was analyzed. Thermodynamic calculations with Thermocalc® and detailed microstructural analysis were performed in steel plate base metal and in weld metal produced by GTAW process. The aging for 200, 300 and 400 h promoted gradual embrittlement and deterioration of corrosion resistance of both weld and base metal. The results show that the selection of AISI 317L steel to services where temperatures can reach 550 °C is not recommended.

Gas tungsten arc welding and friction stir welding of ultrafine grained AISI 304L stainless steel: Microstructural and mechanical behavior characterization

In the present study, an ultrafine grained (UFG) AISI 304L stainless steel with the average grain size of 650nm was successfully welded by both gas tungsten arc welding (GTAW) and friction stir welding (FSW). GTAW was applied without any filler metal. FSW was also performed at a constant rotational speed of 630rpm and different welding speeds from 20 to 80mm/min. Microstructural characterization was carried out by High Resolution Scanning Electron Microscopy (HRSEM) with Electron Backscattered Diffraction (EBSD) and Transmission Electron Microscopy (TEM). Nanoindentation, microhardness measurements and tensile tests were also performed to study the mechanical properties of the base metal and weldments. The results showed that the solidification mode in the GTAW welded sample is FA (ferrite–austenite) type with the microstructure consisting of an austenite matrix embedded with lath type and skeletal type ferrite. The nugget zone microstructure in the FSW welded samples consisted of equiaxed dynamically recrystallized austenite grains with some amount of elongated delta ferrite. Sigma phase precipitates were formed in the region ahead the rotating tool during the heating cycle of FSW, which were finally fragmented into nanometric particles and distributed in the weld nugget. Also there is a high possibility that the existing delta ferrite in the microstructure rapidly transforms into sigma phase particles during the short thermal cycle of FSW. These suggest that high strain and deformation during FSW can promote sigma phase formation. The final austenite grain size in the nugget zone was found to decrease with increasing Zener–Hollomon parameter, which was obtained quantitatively by measuring the peak temperature, calculating the strain rate during FSW and exact examination of hot deformation activation energy by considering the actual grain size before the occurrence of dynamic recrystallization. Mechanical properties observations showed that the welding efficiency of the FSW welded sample is around 70%, which is more than 20% higher than the GTAW welded sample.

Sigma-phase formation in high chromium ferritic steels at 650 °C

A binary Fe–30wt.%Cr alloy and corresponding ternary alloys containing manganese, molybdenum or tungsten were studied with respect to σ-phase formation at 650°C. Although even after 3000h exposure complete equilibration was not attained, the presence of tungsten and especially molybdenum was found to promote σ-phase formation. More extensive σ-phase formation was observed in the tungsten and especially in the molybdenum-containing alloys than in the binary and manganese-containing alloy. Apparently the bulk free energy decrease driving the nucleation of σ-phase is substantially larger when tungsten or molybdenum are present in the alloy.The presence of a nickel layer, to simulate the contact between ferritic steel interconnects and nickel mesh in a Solid Oxide Fuel Cell (SOFC) results in the formation of an austenitic zone and in accelerated formation of a σ-phase rich layer at the ferrite/austenite interface, due to interdiffusion processes. This interface acts as a highly efficient heterogeneity for the nucleation of σ-phase. The nucleation is enhanced by an increased Cr/Fe-ratio at that interface. Several possible modes for the growth of the σ layer were identified but the available experimental data were not sufficient to distinguish among these. The σ-rich layer, which appears to act as an interdiffusion barrier, is thicker in the case of the binary Fe–Cr and the Fe–Cr–Mn alloy than for the molybdenum- or tungsten-rich alloys.The results show that the stability range of σ-phase is larger than indicated by the presently used thermodynamic data bases.

Analysis of ferrite formed in 321 grade austenitic stainless steel

A significant fraction of ferrite has been identified in a 321 grade austenitic stainless steel in the solution heat treated condition. The microstructures were analysed using electron backscatter diffraction, energy dispersive X-ray spectroscopy and X-ray diffraction (XRD) and the stability of the ferrite investigated using heat treatments in a tube furnace, dilatometry and high temperature XRD. The ferrite dissolved ∼800°C, then formed again on cooling at temperatures under 200°C. Thermodynamic predictions showed a significant ferrite content at room temperature under equilibrium conditions, and the DeLong diagrams predict an austenite+martensite microstructure in the cast condition. Sensitivity analysis on the DeLong diagram has shown that the nitrogen content had a large effect on the austenite stability. The instability of the austenite and the subsequent transformation to ferrite on cooling can be attributed to low nitrogen content measured in the as received material. It was found that thermal aging of the material caused further transformation of austenite to ferrite as well as the formation of sigma phase that appears higher in nitrogen than the matrix phases. The diffusion of nitrogen into sigma phase may cause instability of the austenite, which could cause further transformation of austenite to ferrite on cooling from the aging temperature. The transformation of austenite to ferrite is known to be accompanied by an increase in volume, which may be of relevance to components made with tight dimensional tolerances.