Creep resistance of Fe–Ni–Cr heat resistant alloys for reformer tube applications

Relations between microstructure, phase transformations and creep resistance of austenitic Fe–Ni–Cr alloys are investigated. As-cast alloys with different silicon contents and an ex-service tube are submitted to laboratory agings to trigger specific phase transformations, and subsequently creep-tested at 950°C under stresses of 24–48?MPa. As-cast microstructures contain interdendritic chromium-rich M₇C₃ carbides with niobium-rich MC carbides. After aging at 950°C, primary M₇C₃ carbides transform into chromium-rich M₂₃C₆ carbides, associated to a loss in creep strength. The G phase present in the ex-service alloy is reversed into MC carbides by a heat treatment at 1100°C, associated to a slight decrease in creep resistance. Besides, the addition of silicon is highly detrimental to creep strength. Results can be used for alloy design.     

Effect of thermal exposure on the stability of carbides in Ni-Cr-W based superalloy

The microstructure evolutions of Ni-Cr-W based superalloy during thermal exposure have been investigated systematically. M₆C carbides in the alloy decompose into M₂₃C₆ carbides at temperatures from 650 to 1000 °C due to its high content of Cr. The M₆C carbides decompose dramatically from 800 to 900 °C. At temperatures up to 1000 °C, a few M₂₃C₆ carbides form on the surface of M₆C carbides. The decomposition behavior of primary M₆C can be explained by the following reaction: M₆C → M₂₃C₆ + Me (W, Ni, Cr, Mo). At temperatures below 900 °C, coarse lamellar M₂₃C₆ carbides precipitate at the grain boundaries. The carbide lamellae line almost perpendicular to the grain boundaries. While the temperature is above 1000 °C, discrete M₂₃C₆ carbides precipitate at the grain boundaries. Moreover, there are lots of small M₂₃C₆ particles precipitated around M₆C carbides from 650 to 1000 °C.     

Formation of Re-containing Carbides in a Second Generation Directionally Solidi¯ed Ni Base Superalloy

The precipitates at grain boundary in a directionally solidified Ni base superalloy after heat treatment, aging at 975°C, and creep rupture test have been characterized. Besides the primary MC carbides and fine particles of μ phase, the Re-containing M₂₃C₆ was observed. The precipitation kinetics revealed that the formation of M₂₃C₆ was associated with the dissolution of μ phase and MC carbides. TEM image shows that the continuous precipitation of M₂₃C₆ particles effectively hinders the dislocation movement and strengthens the grain boundaries. The high strength of the alloy suggests that M₂₃C₆ carbides are beneficial to the properties although Re as an important matrix strengthening element was consumed.     

Formation of lamellar M23C6 on and near twin boundaries in austenitic stainless steels

Thin foil electron microscopy studies were made on the precipitation of lamellar M₂₃C₆ during aging at 973 K and 1073 K in water-quenched specimens of two austenitic stainless steels. After the precipitation on incoherent twin boundaries M₂₃C₆ formed on coherent twin boundaries and in the regions adjacent to incoherent twin boundaries. These precipitates showed lamellar morphology and were aligned in a specific manner with respect to the twin boundaries. Such lamellar precipitates were absent in the specimens which were isothermally treated at 1073 K after being transferred from the solution treatment temperature. The lamellar morphology of M₂₃C₆ is suggested to be developed by the influence of residual specific stress field around twin boundaries resulted from quenching.     

Study on microstructure and properties of centrifugal casting 35Cr45NiNb+MA furnace tubes during service

In the present study, the microstructure evolution of 35Cr45NiNb+MA ethylene cracking furnace tubes during service and its effect on the properties were investigated. According to the results, in the early stage of service, the skeletal M₇C₃ and vermicular NbC were transformed into blocky M₂₃C₆ and G phase (Ni₁₆Nb₆Si₇), respectively, accompanied with many dispersed M₂₃C₆ secondary carbides. With the extension of service time, M₂₃C₆ carbides on the grain boundaries were transformed into M₇C₃ with high stacking fault structure and coarsened, and the blocky G phase was transformed into granular NbC. The yield strength and ultimate tensile strength of the aging furnace tubes decreased by 9%-18%, yet the elongation after fracture decreased significantly from 10.0%-14.0% to 3.0%-5.0%. The hardness of the carburized zone of the carburized tubes increased by 10%-17%, and the rupture time decreased by 45%-75% under the test condition of 1100℃ and 16MPa. Finally, the evolution map was summarized.     

Microstructural evolution in bainite,martensite, and δ ferrite of low activation Cr–2W ferritic steels

Abstract

The microstructural evolution in (2–15)Cr–2W–0·1C (wt-%) firritic steels after quenching, tempering, and subsequent prolonged aging was investigated, using mainly transmission electron microscopy. The steels examined were low induced radioactivation ferritic steels for fusion reactor structures. With increasing Cr concentration, the matrix phase changed from bainite to martensite and a dual phase of martensite and δ ferrite. During tempering, homogeneous precipitation of fine W₂C rich carbides occurred in bainite and martensite, causing secondary hardening between 673 and 823 K. With increasing tempering temperature, dislocation density decreased and carbides had a tendency to precipitate preferentially along interfaces such as bainite or martensite subgrain boundaries. During aging at high temperature, carbides increased in size and carbide reaction from W₂C and M₆C to stable M₂₃C₆ occurred. No carbide formed in δ ferrite. The precipitation sequence of carbides was analogous to that in conventional Cr–Mo steels.

MST/1049     

Formation of the reversed austenite during intercritical tempering in a Fe-13%Cr-4%Ni-Mo martensitic stainless steel

Formation of the reversed austenite obtained by intercritical tempering has been studied via transmission electron microscopy (TEM) in a Fe-13%Cr-4%Ni-Mo low carbon martensitic stainless steel. It is found that the precipitation of M₂₃C₆ carbides along the martensite lath boundaries will result in Ni-enrichment in the adjacent region. The reversed austenite forms with the Ni-enrichment region as the nucleation sites, keeps a cube-cube orientation relationship with the M₂₃C₆ carbides and bears the Kurdjumov-Sachs (K-S) relationship with the martensite. Moreover, the reversed austenite formed inside the martensite laths is also confirmed. The mechanism for formation of the reversed austenite is discussed in detail.     

Structure of centrifugally cast austenitic stainless steels: Part 2 Effects of Nb,Ti, and Zr

Abstract

The microstructures of several centrifugally cast stainless steels containing strong carbide formers (Nb, Ti, and Zr) have been examined as cast and after prolonged creep in the range 800–1000°C. These additions refine the eutectic carbide, changing the morphology and composition as illustrated by the behaviour of IN 519 (Fe–Ni–Cr–Nb) and IN 519 TZ (Fe–Ni–Cr–Nb–Ti–Zr). The carbides present have been identified by electron diffraction and by energy-dispersive X-ray analysis. During creep, the precipitation of both MC and M₂₃C₆ carbides was observed, the former being very much finer and very resistant to coarsening. The role of both the grain-boundary carbide networks and the matrix precipitation in determining the creep properties is discussed.

MST/136     

Static recovery of tempered lath martensite microstructures during long-term aging in 9-12% Cr heat resistant steels

Static recovery of tempered lath martensite microstructures of strength enhanced ferritic steels has been investigated during very long-term aging up to 2 × 10⁴ h at 650 °C for 3 steels containing 9 to 12% Cr. Static recovery of tempered lath martensite microstructure occurs after an incubation period for 1-2 × 10³ h in the steels. The static recovery is controlled by the loss of strengthening due to M₂₃C₆ precipitates, and disappearance of MX carbonitrides cannot be the main cause of the static recovery.     

Influence of secondary carbides precipitation and transformation on the secondary hardening of laser melted high chromium steel

The influence of secondary carbides precipitation and transformation on the secondary hardening of laser melted high chromium steels was analyzed by means of scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The microstructure of laser melted high chromium steel is composed of austenite with supersaturated carbon and alloy elements and granular interdendritic carbides of type M₂₃C₆. Secondary hardening of the laser melted layer begins at 450 °C after tempering, and the hardness reaches a peak of 672HV at 560 °C and then decreases gradually. After tempering at 560 °C, a large amount of lamellar martensite was formed in the laser melted layer with a small quantity of thin lamellar M₃C cementite due to the martensitic decomposition. The stripy carbides precipitating at the grain boundaries were determined to be complex hexagonal M₇C₃ carbides and face centered cubic M₂₃C₆ carbides. In addition, the granular M₂₃C₆ carbides and fine rod-like shaped M₇C₃ carbides coexisted within the dendrites. As a result, the combined effects of martensitic transformation, ultrafine carbide precipitations, and dislocation strengthening result in the secondary hardening of the laser melted layer when the samples were tempered at 560 °C.     

Effect of alloying on interfacial energy of precipitation/matrix in high-chromium martensitic steels

The effect of cobalt, tungsten, and boron on interfacial energy of precipitate/ferritic matrix in the 9% Cr martensitic steels on the base of creep tests at 650 °C under different applied stresses ranging from 80 to 220 MPa was investigated. An interfacial energy of M₂₃C₆ carbides, the Laves phase particles, and MX carbonitrides was estimated by comparison of theoretical curves obtained by Prisma software for the model steels for the exposure time of 2 × 10⁴ h with experimental data measured by TEM in the gage sections of crept specimens. Addition of 3 wt% Co to Co-free 9Cr2W steel led to about 1.7 times increase in the interfacial energy of M₂₃C₆ carbides and MX carbonitrides, whereas Co did not effect on the interfacial energy of the Laves phase. Increasing W from 1.5 to 3 wt% in the Co-containing steels led to increase in the interfacial energy of the Laves phase up to 0.78 J m^?2 under long-term exposure, whereas it did not effect on the interfacial energy of M₂₃C₆ carbides and MX carbonitrides. In the steel with increased B up to 0.012 wt% and decreased N to 0.007 wt%, a strong decrease in the interfacial energy of M₂₃C₆ carbides to 0.12 J m^?2 occurred. Change in the interfacial energy of the precipitates was analyzed in comparison with coarsening rate constant.     

Precipitates change of ferritic‐martensitic 11 % chromium steel under short‐term creep

A ferritic‐martensitic (FM) 11 % chromium steel with final heat treatment was subjected to a short‐term creep test at a stress of 150 MPa and 600 °C for 1100 h in order to study the change of precipitates in the steel during the creep test. Except for Nb‐rich metall carbides (MC, M₂₃C₆) and Laves phases, Fe‐W‐Cr‐rich M₆C (based on Fe₃W₃C) carbides forming during the creep test were also identified in the crept steel by electron diffraction and x‐ray diffraction in combination with energy dispersive x‐ray analysis of extraction carbon replicas. The identified M₆C carbides have a fcc crystal structure, a metallic element composition of approximately 44Fe, 32 W, and 20Cr in atomic %, and large sizes ranging from 100 nm to 300 nm in diameter. The M₆C carbides are a dominant phase in the crept steel. M₆X precipitates are generally not easy to form during high temperature creep, even if it is a long‐term creep, in ferritic‐martensitic 9–12 % chromium steels with a final heat treatment. The present work provides the evidence for the M₆C carbides forming during short‐term creep in ferritic‐martensitic high chromium steels. The formation of the M₆C carbides was discussed.     

Development of microstructure during heat treatment of high carbon Cr–Mo steel

Abstract

Stainless steels containing enhanced chromium and carbon contents are particularly attractive for applications requiring improved wear and corrosion resistance. The as cast microstructure of such steels is composed mainly of ferritic matrix along with a network of interdendritic primary carbides. It has been shown that heat treatment of these steels results in microstructures that contain more than one type of carbide. A selective dissolution technique has been employed to isolate carbides from the matrix. Scanning electron microscope and X-ray diffraction studies of the as cast steels have shown that the primary carbides are essentially of M₇C₃ type, whereas in heat treated specimens both M₇C₃ (primary) and M₂₃C₆ (secondary) type carbides have been observed. The relative amounts of these carbides are found to be dependent on the heat treatment temperature. In addition, nucleation of austenite occurs above 950°C and at ～1250°C the matrix transforms entirely to austenite, which is retained completely on quenching to room temperature.     

Creep damage and grain boundary precipitation in power plant metals

Abstract

There is clear evidence that creep damage in power plant steels is associated with grain boundary precipitates. These particles provide favourable nucleation sites for creep damage such as grain boundary cavities and microcracks. Monte Carlo based grain boundary precipitation kinetics is combined with continuum creep damage mechanics (CDM) to model both the microstructural evolution and creep behaviour in power plant metals. It is found that grain boundary precipitates, such as M₂₃C₆ in most Cr containing ferritic steels, are harmful to the creep properties of the material, in line with experimental observations. It is also found that to improve the creep behaviour of the material, means should be found either to increase the proportion of MX type particles, such as VN, or to decrease or remove the larger grain boundary precipitates, such as M₂₃C₆. Hafnium has been ion implanted into thin foils of a 9 wt-%Cr ferritic steel to study the effect of hafnium on the grain boundary precipitation kinetics. It is found that the implantation of hafnium to the steel completely prohibits the formation of the common grain boundary M₂₃C₆ particles. Instead, two new types of precipitates are formed. One is hafnium carbide, which is an MX type precipitate, and is very small in size and has a much higher volume fraction as compared with the volume fraction of VN in conventional power plant ferritic steels. The other is Cr- and V-rich nitride of formula M₂N. CDM modelling shows that implantation of hafnium can markedly improve the creep property of the material. In addition, the replacement of M₂₃C₆ with hafnium carbide increases the concentration of Cr in the matrix and is expected to improve the intergranular corrosion resistance of the material.     

High-temperature mechanical properties of Inconel-625: role of carbides and delta phase

Based on the temperature sensitivity characteristics, high-temperature tensile tests were performed at different temperatures and after different solid solution treatments to investigate the effect of Cr-rich M₂₃C₆, Nb-rich MC and the delta phase on the mechanical properties of Inconel 625. The experimental results indicated that the Cr-rich M₂₃C₆ carbides and the Nb-rich MC carbides decomposed at 700°C, which could be the reason for resulting tensile strength anomaly that was observed in a narrow temperature range from 650 to 700°C during the tensile tests at different temperatures. For the samples subjected to a prior solid solution treatment, the size of the δ phase was found to increase with the solution treatment temperature, whereas the elongation at fracture decreased.     

Effects of vanadium on upper-nose temper embrittlement and other Mechanical properties of Cr–Ni–Mo low-alloy steels

Abstract

Large components manufactured from Cr–Mo–Ni low-alloy steels are usually heavily tempered for the purpose of stress relieving, with resultant undesirable loss of strength and the inception of upper-nose temper embrittlement (UNTE). This paper describes an investigation on the effects of vanadium additions and of variation in the molybdenum content on the properties of these heavily tempered steels. It is shown that the addition of vanadium to these steels leads to a substantial improvement in their strength without impairment of their ductility and toughness, and also to a marked improvement in their resistance to UNTE. An increase in the molybdenum content of the steel from 0·5 to 1·0% leads to a moderate improvement in its strength, but has an aggravating effect on its susceptibility to UNTE, as a result of an increase in the coarsening rate of the grain boundary carbides and the formation of unfavourable M₂₃C₆ and M_aC_b molybdenum-rich large carbides.

MST/390     

Carbide transformation in carburised zone of 25Cr35NiNb+MA alloy after high-temperature service

Microstructure evolution due to carburising of a 25Cr35NiNb+MA ethylene pyrolysis furnace tube was investigated after service for approximately 4 years. The microstructure of 25Cr35NiNb+MA alloy was examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) equipped with energy-dispersive X-ray spectroscopy and high-resolution transmission electron microscopy (TEM). The results revealed that M₂₃C₆ carbides of the 25Cr35NiNb+MA alloy had coarsened and transformed to M₇C₃ carbides with a heavily faulted structure during carburising. The content of M₇C₃ carbide increased closer to the inner wall. A large number of dislocations had been observed surrounding the carbides and some formed dislocation walls. The carbide transformation mechanism and the effect of the dislocation walls are discussed.     

Correlation between grain boundary misorientation and M23C6 precipitation behaviors in a wrought Ni-based superalloy

The correlation between the grain boundary misorientation and the precipitation behaviors of intergranular M₂₃C₆ carbides in a wrought Ni–Cr–W superalloy was investigated by using the electron backscattered diffraction (EBSD) technique. It was observed that the grain boundaries with a misorientation angle less than 20°, as well as all coincidence site lattice (CSL) boundaries, are immune to precipitation of the M₂₃C₆ carbides; in contrast, the random high-angle grain boundaries with a misorientation angle of 20°–40° provide preferential precipitation sites of the M₂₃C₆ carbides at the random high-angle grain boundaries with a higher misorientation angle of 55°–60°/[2 2 3] turn to retard precipitation of M₂₃C₆ carbides owing to their nature like the Σ3 grain boundaries and retard the precipitation of M₂₃C₆ carbides. The low-angle and certain random grain boundary segments induced by twins were found to interrupt the precipitation of the M₂₃C₆ carbides along the high-angle grain boundaries.     

Effect of M7C3→M23C6 transformation on fracture behaviour of cast ferritic stainless steels

Abstract

The fracture behaviour of three 29 wt-%Cr ferritic steels, two containing zirconium and titanium respectively, has been investigated in the as cast condition and after annealing at 660°C for different times up to 2210 h. The fracture energy and the mode of fracture depend on both the morphology and the nature of the eutectic, which consists of carbides and ferrite. In the as cast condition, fracture is predominantly transgranular cleavage and it can be associated with the discontinuous morphology of the M₇C₃ carbides present in the eutectic as coarse particles surrounded by the eutectic ferrite. After prolonged heating, the ambient fracture energy decreases and the interdendritic mode of fracture is enhanced. This change in fracture mechanism is associated with transformation of the M₇C₃ to M₂₃ C₆ carbides. The M₂₃ C₆ carbides, unlike the coarse M₇C₃ carbides, form a continuous network within the eutectic mixture and constitute an easy path for crack propagation. The zirconium and titanium additions result in a more massive morphology of the carbides in the eutectic mixture and accelerate the M₇C₃ to M₂₃C₆ transformation during the heat treatments, enhancing the interdendritic mode of fracture both in the as cast and in the annealed condition.

MST/1734     

Effect of long-term service exposure on microstructure and mechanical properties of Alloy 617

The present work was carried out to investigate the effect of long-term service exposure on microstructure and mechanical properties of a gas turbine hot gas path component, made of Alloy 617. The results showed significant service-induced microstructural changes, such as excessive grain boundary Cr-rich M₂₃C₆ carbides formation and some oxidation features in the exposed material in compare with the solution-annealed material. Also it was found that the yield strength and hardness of the alloy have increased while the ductility of the alloy has decreased. In the similar test conditions, the stress-rupture life of the exposed alloy decreased considerably compared to the solution-annealed sample, which could be attributed to the microstructural degradation, especially formation of continuous M₂₃C₆ carbides on grain boundaries.