Search Results for austenite grain boundaries

The precipitation behavior of various phases in austenitic heat-resistant model steels, including the Fe 2 Nb Laves phase (C14 structure) on grain boundaries (GB) and grain interiors (GI), and the Ni 3 Nb metastable γ“ phase and stable δ phase on GI, was investigated through experimental study at different temperatures and thermokinetic calculation. The steel samples were prepared by arc melting followed by 65% cold rolling. Subsequently, the samples were solution treated within the γ single-phase region to control the grain size to approximately 150 μm. Aging of the solution-treated samples was carried out at temperatures ranging from 973 K to 1473 K for up to 3600 hours. Microstructural observations were conducted using FE-SEM, and the chemical compositions of the γ matrix and precipitates of Laves and δ phases were analyzed using EPMA. The precipitation modeling was performed using MatCalc software, utilizing a thermodynamic database constructed by our research group to calculate the chemical potential of each phase. Classical nucleation theory was applied for nucleation, while the SFFK model was employed for the growth and coarsening stages. Distinct phases were defined for grain boundary and grain interior Laves phase, with all precipitates assumed to have spherical morphology in the calculations. The precipitation start time was defined as the time when the precipitate fraction reached 1%. Experimental results indicated that above 973 K, Laves phase nucleation primarily occurred on grain boundaries before extending into the grain interior, with the nose temperature located around 1273 K. To replicate the experimentally determined Time-Temperature-Precipitation (TTP) diagram, interaction parameters among elements were adjusted. Additionally, by introducing lower interfacial energy between the γ matrix and Laves phase, the TTP diagram was successfully reproduced via calculation, suggesting relative stability at the interface.

A newly developed ferritic heat-resistant steel; 9Cr-3W-3Co-Nd-B steel has higher creep rupture strength both in the base metal and welded joints than the conventional high-Cr ferritic heat-resistant steels. The creep rupture strengths of 9Cr-3W-3Co-Nd-B steel welded joints were below the lower limit of the base metal in long-term creep stage more than 20,000 hours. The creep rupture position was heat-affected zone (HAZ) from 1.0 to 1.5 mm apart from the fusion line on the welded joint specimen ruptured at 34,966 hours. The equiaxed subgrains and coarsened precipitates were observed in HAZ of the ruptured specimen. In order to clarify the creep fracture mechanism of the welded joints, the microstructures of HAZ were simulated by heat cycle of weld, then observed by EBSD analysis. Fine austenite grains formed along the prior austenite grain boundaries in the material heated just above A C3 transformation temperature, however there were no fine grains such as conventional steel welded joints. The prior austenite grain boundaries were unclear in the material heated at 1050 °C. The creep rupture life of the material heated at just above A C3 transformation temperature exceeded the lower limit of base metal and there was no remarkable degradation, although it was shorter than the other simulated materials. It is, therefore, concluded that the creep fracture of 9Cr-3W-3Co-Nd-B steel welded joint in long-term stage occurred at HAZ heated at from just above A C3 transformation temperature to 1050 °C. It is speculated that the fine austenite grains formed along the prior austenite grain boundaries and inhomogeneous microstructures cause the coarsening precipitates and recovery of lath structure during long-term creep deformation.

Microstructure change during creep at 650°C has been examined for a high-B 9%Cr steel by FIB-SEM serial sectioning 3D observation, Nano-SIMS, SEM, EBSD and TEM. The precipitates formed in the steel were M 23 C 6 , Laves phase, and a quite small amount of MX. For as-tempered steel, precipitation of M 23 C 6 on the prior austenite grain boundaries was clearly found, while precipitation of the Laves phase was not confirmed during tempering. The volume fraction of the Laves phase gradually increased with elapsed time, while M 23 C 6 appeared to increase once and decrease afterward, based on the comparison between the 2,754 h ruptured sample and the 15,426 h ruptured sample. Nano-SIMS measurements have revealed that B segregates on the prior austenite grain boundaries during normalizing, and it dissolves into M 23 C 6 .

The microstructures of two 9% chromium steels, P92 (30 ppm B) and B2 (100 ppm B), after heat treatment and after long-term creep deformation at 600°C were quantitatively investigated by means of transmission electron microscopy and boron trace autoradiography. The aim of the study was to show the boron distribution and identify the influence of boron on precipitation processes taking place in both steels during long-term creep exposure. The incorporation of boron into the M 23 C 6 precipitates in both steels was demonstrated. In P92 steel (30 ppm B), boron was distributed preferentially on prior austenite grain boundaries and hardly visible on the sub-grain boundaries. In the steel B2 doped with 100 ppm B, boron was densely distributed on prior austenite grain- and sub-grain boundaries as well as within martensite laths. Quantitative TEM metallography and boron trace autoradiography investigation showed that boron retarded the growth of M 23 C 6 by forming borocarbides M 23 (C, B) 6 , thereby significantly improving the creep rupture strength of boron doped 9% chromium steels.

Microstructural analyses by FE-SEM and TEM were performed on a ferritic heat-resisting steel that contained 12mass% chromium and 2mass% tungsten to characterize its multi-scale structure, consisting of prior austenite grains, packets, blocks, subgrains and precipitates. The size distributions of the block, subgrains and precipitates were quantitatively evaluated before and after a creep-fatigue test to relate them to their creep-fatigue property. Our results showed that the occupancy of precipitates on prior austenite grain boundaries increased markedly and subgrains became coarse during the creep-fatigue test, while block size did not change. It is suggested that the growth of grain boundary precipitates and coarse subgrains plays an important role in the intergranular fracture mechanism caused by creep-fatigue.

Long-term creep strength property of creep strength enhanced ferritic steels was investigated. Stress dependence of minimum creep rate was divided into two regimes with a boundary condition of macroscopic elastic limit which corresponds to 50% of 0.2% offset yield stress (Half Yield). High rupture ductility was observed in the high stress regime above Half Yield, and it was considered to be caused by relatively easy creep deformation throughout grain interior with the assistance of external stress. Grades T23, T/P92 and T/P122 steels represented marked drop in rupture ductility at half yield with decrease in stress. It was considered to be caused by inhomogeneous recovery at the vicinity of prior austenite grain boundary, because creep deformation was concentrated in a tiny recovered area. High creep rupture ductility of Grade P23 steel should be associated with its lower creep strength. It was supposed that recovery of tempered martensitic microstructure of T91 steel was faster than those of the other steels and as a result of that it indicated significant drop in long-term creep rupture strength and relatively high creep rupture ductility. The long-term creep rupture strength at 600°C of Grade 91 steel decreased with increase in nickel content and nickel was considered to be one of the detrimental factors reducing microstructural stability and long-term creep strength. The causes affecting recovery of microstructure should be elucidated in order to obtain a good combination of creep strength and rupture ductility for long-term.

Recently, a γ’ precipitation strengthened Ni-base superalloy, USC141, was developed for 700°C class A-USC boiler tubes as well as turbine blades. In boiler tube application, the creep rupture strength of USC141 was much higher than that of Alloy617, and the 105 hours’ creep rupture strength of USC141 was estimated to be about 180MPa at 700°C. This is because fine γ’ particles precipitate in austenite grains and some kinds of intermetallic compounds and carbides precipitate along austenite grain boundaries during creep tests. Good coal ash corrosion resistance is also required for tubes at around 700°C. It is known that coal ash corrosion resistance depends on the contents of Cr and Mo in Ni-base superalloys. Therefore the effect of Cr and Mo contents in USC141 on coal ash corrosion resistance, tensile properties, and creep rupture strengths were investigated. As a result, the modified USC141 containing not less than 23% Cr and not more than 7% Mo showed better hot corrosion resistance than the original USC141. This modified alloy also showed almost the same mechanical properties as the original one. Furthermore the trial production of the modified USC141 tubes is now in progress.

In this study, a possibility of application of advanced 9%Cr steel containing 130 ppm boron for boiler components utilized at around 650 °C to higher temperature steam turbine rotor materials has been investigated by means of reduction in silicon promoting macro-segregation in the case of large size ingots, using laboratory heats. Tempered martensitic microstructure without proeutectoid ferrite in all steels studied is obtained even at the center position of a turbine rotor having a barrel diameter of 1.2 m despite lower amounts of nitrogen and silicon. The strength at room temperature is almost the same level of practical high Cr steels such as X13CrMoCoVNbNB 9-2-1 for ultrasuper critical steam turbine rotors. The toughness is sufficient for high temperature rotors in comparison with CrMoV steels utilized as sub-critical high pressure steam turbine components. The creep rupture strength of the steels is higher than that of the conventional 9-12Cr steels used at about 630 °C. The creep rupture strength of 9%Cr steel containing 130 ppm B, 95 ppm N, 0.07 % Si and 0.05 % Mn is the highest in the steels examined, and it is therefore a candidate steel for high temperature turbine rotors utilized at more than 630 °C. Co-precipitation of M 23 C 6 carbides and Laves phase is observed around the prior austenite grain boundaries after the heat treatments and the restraint of the carbide growth is also observed during creep exposure. An improvement in creep strength of the steels is presumed to have the relevance to the stabilization of the martensitic lath microstructure in the vicinity of those boundaries by such precipitates.

The addition of boron without the formation of any boron nitrides during normalizing heat treatment at high temperature minimizes the degradation in creep strength of both base metal and welded joints of 9Cr steel at 650 °C and long times. The enrichment of soluble boron near prior austenite grain boundaries (PAGBs) by the segregation is essential for the reduction of coarsening rate of M 23 C 6 carbides in the vicinity of PAGBs, enhancing boundary and subboundary hardening, and also for the production of same microstructure between the base metal and heat-affected-zone (HAZ) in welded joints, indicating no Type IV fracture in HAZ. Excess addition of boron and nitrogen promotes the formation of boron nitrides during normalizing, which reduces the soluble boron concentration and accelerates the degradation in creep rupture ductility at long times. 9Cr- 3W-3Co-VNb steel with 120 - 150 ppm boron and 60 - 90 ppm nitrogen (MARBN) exhibits not only much higher creep strength of base metal than Gr.92 but also substantially no degradation in creep strength due to Type IV fracture at 650 °C. The pre-oxidation treatment in Ar gas promotes the formation of protective Cr 2 O 3 scale on the surface of 9Cr steel, which significantly improves the oxidation resistance in steam at 650 °C.

To enhance long-term creep strength at 650°C, stabilization of the lath martensitic microstructure near prior austenite grain boundaries has been investigated for a 9Cr-3W-3Co-0.2V-0.05Nb steel. This was achieved by adding boron to stabilize M 23 C 6 carbides and dispersing fine MX nitrides. Creep tests were conducted at 650°C for up to approximately 3 × 10 4 hours. Adding a large amount of boron exceeding 0.01%, combined with minimized nitrogen, effectively stabilized the martensitic microstructure and improved long-term creep strength. The amount of available boron, free from boron nitrides and tungsten borides, is crucial for enhancing long-term creep strength. Reducing the carbon concentration below 0.02% led to a dispersion of nano-sized MX nitride particles along boundaries and in the matrix, resulting in excellent creep strength at 650°C. A critical issue for the 9Cr steel strengthened by MX nitrides is the formation of Z-phase, which degrades long-term creep strength. Excess nitrogen additions of 0.07 and 0.1% promoted Z-phase formation during creep. The formation of a protective Cr-rich oxide scale was achieved through a combination of Si addition and pre-oxidation treatment in argon, significantly improving the oxidation resistance in steam at 650°C.

Achieving long-term stability of the tempered martensite is considered crucial for increasing the creep resistance of steels at elevated temperatures above 700°C. It is noted that at low stress levels, the creep deformation of the tempered martensite proceeds heterogeneously around prior austenite grain boundaries, as excess dislocations inside the grain are difficult to rearrange. This paper presents a new approach using carbon-free martensitic alloys strengthened by intermetallic compounds. An iron-nickel-cobalt martensite matrix with Laves phase as the precipitate is selected. The creep characteristics are discussed across a wide range of testing conditions, and the thermal cycle test behavior is examined to evaluate the potential of these alloys for future ultrasupercritical power plants operating in severe environments.

A 9Cr-3W-3Co-VNbBN steel, designated MARBN ( MAR tensitic 9Cr steel strengthened by B oron and N itrides), has been alloy-designed and subjected to long-term creep and oxidation tests for application to thick section boiler components in USC power plant at 650 o C. The stabilization of lath martensitic microstructure in the vicinity of prior austenite grain boundaries (PAGBs) is essential for the improvement of long-term creep strength. This can be achieved by the combined addition of 140ppm boron and 80ppm nitrogen without any formation of boron nitrides during normalizing at high temperature. The addition of small amount of boron reduces the rate of Ostwald ripening of M 23 C 6 carbides in the vicinity of PAGBs during creep, resulting in stabilization of martensitic microstructure. The stabilization of martensitic microstructure retards the onset of acceleration creep, resulting in a decrease in minimum creep rate and an increase in creep life. The addition of small amount of nitrogen causes the precipitation of fine MX, which further decreases the creep rates in the transient region. The addition of boron also suppresses the Type IV creep-fracture in welded joints by suppressing grain refinement in heat affected zone. The formation of protective Cr 2 O 3 scale is achieved on the surface of 9Cr steel by several methods, such as pre-oxidation treatment in Ar gas, Cr shot-peening and coating of thin layer of Ni-Cr alloy, which significantly improves the oxidation resistance of 9Cr steel in steam at 650 o C. Production of a large diameter and thick section pipe and also fabrication of welds of the pipe have successfully been performed from a 3 ton ingot of MARBN.

Two Z-phase strengthened test steels with similar chemical composition were studied. The main difference in composition is the addition of 1 wt% Cu into one of the steels (referred to as “ZCu”). Mechanical testing was performed. The impact strength is very different: 3 J vs. 46.3 J, for the original and the Z-Cu steel, respectively. In the original steel that contains no Cu, much more Laves-phase (Fe 2 (W,Mo)) precipitates had formed along the prior austenite grain boundaries than in the steel with Cu addition. This is believed to be the reason for the difference in impact strength. Furthermore, the Cu addition also influenced the morphology of Laves-phase precipitates; fine rod-shaped instead of coarse equiaxed Laves-phase particles were observed in Z-Cu steel in comparison to the original steel. No partitioning of Cu into the Laves-phase particles was detected by using atom probe tomography (APT). The main function of Cu seems to be the formation of Cu precipitates that act as nucleation site for Laves-phase.

Tempered martensitic 9-12%Cr steels bearing tungsten, such as P92 and P122 showing higher creep rupture strength than the conventional steel P91, have been developed for thick section components in ultra-supercritical (USC) boilers. However, their creep strength is not sufficient for applying at the steam condition of 650°C/35MPa or above, which is a recent target condition in order to increase plant efficiency. The research and development project in NIMS on advanced high-Cr steels which can be applied at the steam condition of 650°C/35MPa as boiler components with large diameter and thick section has been carried out since 1997. In this project, it has been revealed that the addition of boron more than 0.01 mass% to the 0.08C-9Cr- 3W-3Co-V,Nb-<0.00ЗN steel remarkably improves creep strength. The boron enriched in M 23 C 6 carbides near prior-austenite grain boundaries suppresses coarsening of these carbides during creep deformation, leading to excellent microstructural stability and creep strength. Further improvement of creep strength is achieved by the addition of appropriate amount of nitrogen which enhances precipitation of fine MX. Excess addition of nitrogen to the high-B containing steel reduces creep rupture lives and ductility. The highest creep strength is obtained in the 0.08C-9Cr-3W-3Co-0.2V-0.05Nb-0.0139B-0.0079N (mass%) steel, resulting in excellent creep strength in comparison with that of P92 and P122. This steel shows good creep ductility even in the long term. It is, therefore, concluded that this high-B bearing 9Cr-3W-3Co-V,Nb steel with the addition of nitrogen in the order of 0.008 mass% is the promising candidate which shows superior creep strength without impairing creep ductility for thick section components in the 650°C-USC plant.

Low thermal expansion precipitation strengthening Ni-base superalloy, Ni-20Cr-10Mo-1.2Al-1.6Ti alloy (USC141TM), was developed for 700°C class A-USC steam turbine material by Hitachi, Ltd and Hitachi Metals, Ltd. USC141 is usually solution treated and then aged to increase high temperature strength for turbine blades and bolts. As the estimated 105h creep rupture strength at 700°C is about 180MPa, USC141 could also be expected to apply for boiler tubes. On the other hand, this alloy seems to be only solution treated to apply for boiler tubes because tubes are usually jointed by welding and bended by cold working and thus tube alloys should have low hardness before welding and bending and should be used as solution treated. In this study, the creep properties of USC141 as solution treated was evaluated, and the results and microstructures after creep tests were compared with those as aged. As a result, USC141 as solution treated exhibited almost as same creep rupture properties as that as aged because precipitation at grain boundaries and in grains gradually increased at testing temperatures around 700°C. Furthermore seamless tubes of USC141 were produced and various properties including creep properties are now being evaluated.

Increasing demand on efficiency and power output of steam generators leads to new designs of welded rotors. The reason for rotor welding is the large size of rotors, which are difficult to produce in a single piece. Secondly, as there are varying operation conditions along the rotor length. In a heterogeneous rotor, several materials appropriate for local service conditions can be used. At the rotor service temperatures, creep properties are crucial for successful design. The weakest point of every welded component is the heat affected zone. Therefore, the creep properties of a heterogeneous weld are subject of the investigation herein the current study, a heterogeneous weld of COST F and COST FB2 materials is investigated. The welding was performed by multi pass technique with overlaying welding beads that applied several heating cycles to heat affected zone. Metallographic investigation of the weld was performed and the weakest microstructure spots were detected. With the use of FEM simulation, appropriate heating/cooling cycles were obtained for the detected weak points. The temperature cycles obtained were subsequently applied to both base materials under laboratory conditions by induction heating. Creep properties of these materials were investigated. The influence of the initial base material’s grain size was also considered in the investigation. Two heating/cooling schedules were applied to both base materials with two grain sizes. Altogether, 8 different microstructures were examined in short term creep tests and the results were summarized.

Microstructural change of 10 % Cr steel trial forgings subjected to different heat treatment conditions which aim to improve the creep rupture strength and microstructural stability during creep was investigated. Creep rupture strength of the forging subjected to the quality heat treatment with the austenitizing temperature of 1090° C is higher than that of the forging solution treated at 1050°C, however, the difference of creep rupture strength is reduced in the long-term region around 40,000 h. Decrease in creep rupture ductility of the forging until 43,300 h is not observed. Progress of the martensite lath recovery in the forging solution-treated at 1090°C is slower than that in the forging austenitized at 1050°C. Higher temperature solution treatment suppresses the recovery of lath structures. Formations of Z-phase are found in the specimens creep-ruptured at 37,300 h in the forging solution-treated at 1050°C and at 43,400 h in the forging austenitized at 1090°C. Z-phase precipitation behavior in this steel is delayed in comparison with the boiler materials, regardless of austenitizing temperature.

In thermal power plants, weldments of all currently used martensitic 9% chromium steels are prone to Type IV cracking in the fine-grained region of the heat-affected zone (HAZ). Japanese researchers have introduced a new martensitic steel for ultra-supercritical (USC) steam conditions that demonstrates resistance to Type IV cracking. This study compares a modified version of this boron-nitrogen balanced advanced 9Cr-3W-3Co steel with CB2, the most promising 9% Cr steel developed through the European research initiative COST, in terms of weldability. The HAZ was analyzed using the "Heat-Affected Zone Simulation" technique with a Gleeble 1500 thermo-mechanical simulator. Basic optical microscopy was complemented by advanced electron microscopy techniques, including energy-filtered TEM (EFTEM), electron energy loss spectroscopy (EELS), electron backscatter diffraction (EBSD), and energy-dispersive X-ray analysis (EDX). Phase transformations in the HAZ were directly observed using in situ X-ray diffraction with synchrotron radiation at the Advanced Photon Source (APS) of Argonne National Laboratory, IL, USA. Although both steels exhibited similar transformation behavior, their resulting microstructures after the weld thermal cycle differed significantly. At peak temperatures above 1200°C, delta ferrite formed and remained stable down to room temperature due to rapid cooling in both steels. While CB2 exhibited conventional coarse-grained (CG), fine-grained (FG), and intercritical HAZ regions, the boron-nitrogen balanced 9Cr steel did not develop a fine-grained HAZ. Since Type IV cracking primarily occurs in the FGHAZ, this alloy shows strong potential for eliminating Type IV cracking as a major life-limiting factor in heat-resistant steel weldments.

Boron and nitride additions are emerging as a promising design concept for stabilizing the microstructure of creep-resistant martensitic high-chromium steels. This approach, known as MarBN steel (martensitic steel strengthened by boron and nitrogen), combines the benefits of solid solution strengthening from boron with precipitation strengthening from nitrides. However, initial welding trials revealed challenges in achieving a uniform fine-grained region in the heat-affected zone (HAZ), which is crucial for mitigating Type IV cracking and ensuring creep strength. Despite these initial hurdles, preliminary creep test results for welded joints have been encouraging. This study presents an improved MarBN steel formulation and its investigation through uniaxial creep tests. Base material and welded joints were subjected to creep tests at 650°C for up to 25,000 hours under varying stress levels. The analysis focused not only on the creep strength of both the base material and welded joints but also on the evolution of damage. Advanced techniques like synchrotron micro-tomography and electron backscatter diffraction were employed to understand the underlying creep damage mechanisms. By combining long-term creep testing data with 3D damage investigation using synchrotron micro-tomography, this work offers a novel perspective on the fundamental failure mechanisms occurring at elevated temperatures within the HAZ of welded joints in these advanced steels.

Ferritic 9-12 wt.% chromium steels are commonly used for thick-walled high-temperature components in thermal power plants, but they face two major limitations in high-temperature service. Firstly, a reduction in creep strength occurs after approximately 10,000 hours at service temperatures around 600°C, due to the dissolution of finely dispersed V-rich nitrides and the precipitation of coarse particles of the modified Z-phase, [(Cr,V,Nb)N]. Secondly, welded joints of nearly all ferritic steel grades are prone to premature creep failures in the fine-grained heat-affected zone, known as Type IV cracking, which results from a strength loss of up to 50% compared to the base material. This study describes the development of a 9Cr3W3CoVNb steel with added boron and controlled nitrogen content. Preliminary creep testing results up to 24,000 hours at 650°C show a significant improvement in creep strength compared to established ferritic 9Cr grades like P91 and P92, attributed to a reduced driving force for the precipitation of modified Z-phase particles. Crosswelds of the new 9Cr3W3CoVNbBN steel also demonstrate improved creep behavior at 650°C, with creep rupture strength comparable to the mean base material creep strength of the best commercially available grade P92.