Alloy 718 is one of the most useful heat-resistant alloys for important device components that require high-temperature properties. In order to obtain excellent mechanical properties, it is necessary to form fine grains, for which the pinning effect of the δ phase can be used in some cases. To precipitate a sufficient amount for the pinning effect, time-consuming isothermal heat treatments are required. Thus, a metallurgical method with a shortened holding time would improve production efficiency considerably. Our goal is to optimize the forging process to control grain size by utilizing the δ phase, and the purpose of this study was to investigate the influence of the initial microstructure of the precipitated γ″ phase on δ-phase precipitation behavior in Alloy 718. As a solute treatment, Alloy 718 was heated at 1050 °C for 4 h, followed by heating of some samples at 870 °C for 10 h to precipitate the γ″ phase. The specimen with precipitated γ″ phase showed more precipitated δ phase than that under the solute condition by comparing results of heating at 915 °C. This suggested that utilizing the γ″ phase promoted δ-phase precipitation, and it is thus expected to shorten the heat treatment time for δ-phase precipitation.

The microstructural evolution has been investigated for an 18Cr-12Ni stainless steel (347HFG) that has been subject to a thermo-mechanical treatment to obtain a fine grain size (ASTM 7-10). In particular, sigma phase precipitation and growth has been evaluated. Samples of 347HFG stainless steel have been isothermally heat treated to reproduce and accelerate the ageing conditions experienced in-service at temperatures between 600 and 750 °C for up to 10,000 hours. Results have shown that sigma phase is precipitated at triple points and along grain boundaries after as little as 1000 hours which is contrary to thermodynamic predictions. In addition X-ray diffraction (XRD) and image analysis has been carried out to semi-quantitatively measure the amount of sigma phase present. The area fraction of sigma has been found to be 2.77 and 2.23 percent at 700 and 750 °C respectively. This is a higher volume fraction of sigma phase than has been previously observed in regular 347H at these conditions. It is thought that this is due to the reduced grain size that has provided an increase in nucleation sites and diffusion paths that can enhance the precipitation and growth of sigma phase. The results from this study are discussed with regards to the effect of precipitation on the service life of a 347HFG stainless steel tube operating in advanced supercritical boilers.

Precipitation of Z-phase, Cr(V,Nb)N, is known to negatively affect creep properties of 9-12%Cr steels for power plant applications as it dissolves finely distributed MX particles, (V,Nb)N, especially in high Cr steels. As the Z-phase precipitates slowly as large particles, this causes a net drop in precipitation strengthening. Two model alloys containing 9 and 12%Cr, but otherwise having similar composition, were produced in order to quantify the difference in Z-phase precipitation speed at different Cr levels. The nitride precipitation behavior was followed at different temperatures using TEM and XRD, allowing for a quantification of the Z-phase precipitation. The Z-phase was found to precipitate 20-50 times faster in the 12%Cr steel compared to 9%Cr steel in the temperature range 600- 650°C. The transformation of MX into Z-phase was followed in a Ta containing alloy without V or Nb. In this alloy the Z-phase precipitates very quickly, and thus appears as finely distributed particles which have the same strengthening effect as MX particles. Investigations using atomic resolution microscopy showed how Cr diffuses from the matrix into the TaN MX particles and gradually transforms them both chemically and crystallographically into Z-phase CrTaN particles.

Effects of alloying additions of Ti or Mo to a simplified chemical composition of the γ′′-Ni 3 Nb strengthened type Ni-based alloy 718 on the precipitation mode of δ-Ni 3 Nb phase were investigated to aim at designing grain boundaries using the δ phase for raising temperature capability of the γ′′ strengthened Ni-based wrought alloys. In the base alloy of Ni-22Cr-16Fe-3.5Nb, the δ phase precipitated at the grain boundaries of the matrix phase in a platelet form by continuous precipitation mode at temperatures above 1273K (1000°C) but in a lamellar morphology by discontinuous precipitation mode below that temperature. The boundary temperature where the continuous/discontinuous precipitation mode changes was raised by addition of 1 % Ti and lowered by addition of 5% Mo. The increase in the boundary temperature by Ti addition can be considered to have occurred by an increase in the solvus temperature of γ′′ phase. The decrease in the boundary temperature by Mo addition can be interpreted by the reduction of the strain energy caused by the coherent γ′′ precipitates and/or the volume change by the formation of δ phase from the γ/γ′′ phases, which may promote the continuous precipitation with respect to the discontinuous precipitation.

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.

The size and distribution of the Laves phase particles in a 9.85Cr-3Co-3W-0.13Mo-0.17Re- 0.03Ni-0.23V-0.07Nb-0.1C-0.002N-0.008B steel subjected to creep rupture test at 650°C under an applied stresses of 160-200 MPa with a step of 20 MPa were studied. After heat treatment consisting of normalizing of 1050°C and tempering of 770°C, M 23 C 6 and Fe 3 W 3 C carbides with the mean sizes of 67±7 and 40±5 nm, respectively, were revealed along the boundaries of prior austenite grains and martensitic laths whereas round NbX carbonitrides were found within martensitic laths. During creep metastable Fe 3 W 3 C carbides dissolved and the stable Laves phase particles precipitated; volume fraction of Laves phase increases with time. The Laves phase particles nucleated on the interfacial boundaries Fe 3 W 3 C/ferrite during first 100 h of creep and provided effective stabilization of tempered martensitic lath structure until their mean size less than 150 nm.

The formation of periodically arrayed rows of very fine Fe 2 Hf Laves phase particles was recently found in 9 wt. % chromium ferritic matrix through interphase precipitation along a reaction path of δ-ferrite → γ-austenite + Fe 2 Hf with a subsequent phase transformation of the γ phase into the α-ferrite phase. One of the problems on the formation of the fine Laves phase dispersion is a poor heat treatability; the interphase precipitation (δ-Fe→γ-Fe+Fe 2 Hf) is competitive with the precipitation of Laves phase from the δ phase in the eutectoid-type reaction pathway (δ→δ+Fe 2 Hf). In the present work, the effect of supersaturation on the precipitation of Laves phase from δ phase (δ→δ+Fe 2 Hf) and the δ→γ transformation in the reaction pathway was investigated by changing the Hf and Cr contents. The results obtained suggest that it is effective to have a high supersaturation for the precipitation of Laves phase and an adequately high supersaturation for the δ→γ transformation at the same time in order to widen the window of the interphase precipitation

Modern polycrystalline Ni-base superalloys for advanced gas turbine engines have been a key component that has contributed to technological advances in propulsion and power generation. As advanced turbine engine designs are beginning to necessitate the use of materials with temperature and strength capabilities beyond those exhibited by existing materials, new alloying concepts are required to replace conventional Ni-base superalloys with conventional γ-γ’ microstructures. The phase stability of various high Nb content Ni-base superalloys exhibiting γ-γ’-δ -η microstructures have been the subject of a number of recent investigations due to their promising physical and mechanical properties at elevated temperatures. Although high overall alloying levels of Nb, Ta and Ti are desirable for promoting high temperature strength in γ-γ’ Ni-base superalloys, excessive levels of these elements induce the formation of δ and η phases. The morphology, formation, and composition of precipitate phases in a number of experimental alloys spanning a broad range of compositions were explored to devise compositional relationships that can be used to predict the microstructural phase stability and facilitate the design of Ni-base superalloys.

In the present study, the precipitation kinetics of topologically close-packed (TCP) Fe 2 Nb Laves and geometrically close-packed (GCP) Ni 3 Nb phases is studied quantitatively in experimental alloys with different Ta / Nb+Ta ratio, to clarify the mec4hanism of the Ta effect. The microstructure of alloys is changed from Widmanstätten structure to lamellar structure due to discontinuous precipitation, with increasing Ta / Nb+Ta. It is confirmed that Ta partitions into both Fe 2 Nb Laves and Ni 3 Nb phases. However, two phases stability is changed by added Ta content. Ta accelerates the formation kinetics of the precipitates at grain boundaries, as well as γ“-GCP phase within grain interiors, due to increased supersaturation by Ta addition. Besides, Ta retards the transformation kinetics of metastable γ“-Ni 3 Nb to stable the δ-Ni 3 Nb phase. The results indicate that Ta decreases the driving force for the transformation of the δ-GCP phase.

Higher steam temperature in steam power plants increases their thermal efficiency. Thus there is a strong demand for new materials with better creep and corrosion resistance at higher temperatures, while retaining the thermal flexibility of martensitic steels. Z-phase strengthened 12% Cr steels have been developed to meet the 923 K (650°C) challenge in these power plants. Ta, Nb, or V forms Z-phase together with Cr and N. A new trial steel was produced based on combining Ta and Nb to form Z-phase. It was shown that Z-phase was formed with a composition corresponding to Cr1+x(Nb,Ta)1-xN. The Nb/Ta ratio in Z-phase precipitates was higher than that in MX precipitates. Z-phase precipitates based on Ta and Nb were coarser than precipitates in a similar trial steel based on Ta alone.

This study explores methods to enhance the creep strength of 12%Cr martensitic/ferritic steels. The approach focuses on utilizing various precipitates to hinder microstructure coarsening and dislocation movement. A combination of Laves phase (slow precipitation) and MX carbonitrides (dislocation pinning) is used for sustained strengthening. Different MX-forming elements (V, Ta, Ti) are investigated to identify the optimal combination for high quantities of finely distributed strengthening particles. Additionally, cobalt and copper are employed to promote a fully martensitic microstructure and potentially slow down diffusion or provide nucleation sites for Laves phase precipitation. Long-term creep tests confirm the effectiveness of Laves phase precipitation, particularly with tungsten present. Tantalum's influence on both MX precipitation and the Laves phase is also observed. Combining multiple MX-forming elements (V/Ta, V/Ti, Ta/Ti) further improves creep strength, supported by predictions of high MX carbonitride formation from Thermo-Calc calculations. Partially replacing cobalt with copper (1%) also demonstrates positive effects on creep properties.

The complex nitride Z-phase, Cr(V,Nb)N, has recently been identified as a major cause for premature breakdown in creep strength of a number of new 9-12%Cr martensitic steels, especially the high Cr variants. A thermodynamic model of the Z-phase has been created based on the Thermo-Calc software. The model predicts the Z-phase to be stable in all of the new 9- 12%Cr martensitic steels, and this has generally been confirmed by experimental observations. Z-phase precipitation seems then to be a kinetic problem, and driving force calculations, using Thermo-Calc with the developed model, have been used to predict steel compositions, which could delay Z-phase precipitation. The model also predicted the existence of a new niobium free Z-phase variant, which has since been discovered in a niobium free 12CrMoV steel.

So-called Ni base dual two-phase intermetallic alloys are composed of primary Ni 3 Al (L1 2 ) phase precipitates among eutectoid microstructures consisting of the Ni 3 Al and Ni 3 V (D0 22 ) phases. In this article, microstructural refinement of an alloy with a nominal composition of Ni 75 Al 10 V 15 (in at.%) was attempted by various heat treatment processes. When the alloy was continuously cooled down after solution treatment, fine and cuboidal Ni 3 Al precipitates were developed by rapid cooling while coarse, rounded and coalesced Ni 3 Al precipitates were developed by slow cooling. When the alloy was isothermally annealed at temperatures above the eutectoid temperature, the morphology of the Ni 3 Al precipitates changed from fine and cuboidal one to large and rounded one with increase in annealing time. When the alloy was annealed at temperatures below the eutectoid temperature, the Ni 3 Al precipitates were grown keeping cuboidal morphology. The morphological change from the cuboidal to rounded Ni 3 Al precipitates was induced by the transition from the growth driven by elastic interaction energy between the precipitate and matrix to that by the surface energy of the precipitate. Fine and cuboidal Ni 3 Al precipitates generally resulted in high hardness.

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.

The nucleation and growth of precipitates such as Laves phases, carbides and nitrides reduce fracture toughness and high-temperature strength of high chromium steels used in thermal power plants. For this reason, to ensure a long-term plant reliability, it is important to estimate material deterioration by aging. The study presented in this paper involves micro structural evolution by thermal aging of COST-E, F, and FB2 steels, all turbine materials. The results indicate that the Laves phases and other precipitates can be separately detected and quantified by the electrochemical technique. The results also clarify the correlation between the amount of Laves phases precipitated and electrochemical polarization parameters.

This study examines the influence of carbon and austenite stabilizing elements (Ni, Mn, Co, Cu) on Laves phase precipitation, Fe 2 W formation, and creep rupture strength (CRS) in 9-12% Cr steels at 600-700°C. Nickel and manganese had minimal impact on Laves phase and coarse carbide formation up to 1% content. While cobalt increased Laves phase fraction at 650°C, it did not improve long-term CRS and even caused a rapid decrease in short-term CRS. Copper, on the other hand, promoted the precipitation of fine Cu-rich particles that acted as nucleation sites for Laves phase and M 23 C 6 carbide. This resulted in a different needle-like Laves phase morphology compared to the globular type observed in nickel and cobalt alloys, leading to improved CRS in the copper alloy. Increasing carbon content from 0.1% to 0.2% effectively suppressed Laves phase formation, as confirmed by Thermo-Calc calculations. Notably, for cobalt alloys with higher tungsten content, higher carbon content (0.09% to 0.19%) improved CRS at 650°C, whereas the opposite effect was observed in nickel and nickel-manganese alloys. Copper alloys maintained improving CRS trends even with increased carbon, leading to the overall best CRS performance among the tested alloys with 0.2% carbon.

The effect of Cr content on the creep strength at 650°C was examined with high Cr heat resistant steels for the USC high-temperature rotor shafts. The amount of Cr was varied from 8.5% to 11.5%, and then, the alloying effect of Cr was investigated on the stability of the precipitates at 650°C. Within the present range of the Cr content, the short-term creep rupture life under the higher applied stress increased with the Cr content in the steels, whereas the long-term creep rupture life under the lower applied stress decreased with the Cr content in the steels. For example, under the applied stress of 98MPa, the 9%Cr steel exhibited the longest creep rupture life among the experimental steels. Also, it was found from the experiment using the extracted residues that the degree of solution strengthening and the sorts of precipitates scarcely changed regardless of the Cr content in the steels. The Laves phase precipitated finely in the lath was enlarged in the 11.5%Cr steel even after a short-term creep. This result indicates that the coarsening of precipitates such as the Laves phase promotes the recovery of the lath in the early stage of creep deformation. It was suggested that 9%Cr is desirable content in the ferritic steel for suppressing the degradation of creep strength in 98MPa at 650°C.

The long-term performance of superheater super 304h tube during the normal service of an ultra-supercritical 1000mw thermal power unit was tracked and analyzed, and the metallographic structure and performance of the original tube sample and tubes after 23,400h, 56,000h, 64,000 h, 70,000 h and 80,000 h service were tested. The results show that the tensile strength, yield strength and post-break elongation meet the requirements of ASME SA213 S30432 after long-term service, but the impact toughness decreases significantly. The metallographic organization is composed of the original complete austenite structure and gradually changes to the austenite + twin + second phase precipitates. With the extension of time, the number of second phases of coarseness in the crystal and the crystal boundary increases, and the degree of chain distribution increases. The precipitation phase on the grain boundary is dominated by M 23 C 6 , and there are several mx phases dominated by NbC and densely distributed copper phases in the crystal. The service environment produces a high magnetic equivalent and magnetic induction of the material, the reason is that there are strips of martensite on both sides of the grain boundary, and the number of martensite increases with the length of service.

High Cr ferritic steels have been developed for the large components of fossil power plants due to their excellent creep resistance, low thermal expansion, and good oxidation resistance. Development works to improve the operating temperature of these steels mainly focused on the high mechanical properties such as solid solution strengthening and precipitation hardening. However, the knowledge of the correlation between Laves phase precipitation and oxidation behavior has not clarified yet on 9Cr ferritic steels. This research will be focused on the effect of precipitation of Laves phase on steam oxidation behavior of Fe-9Cr alloy at 923 K. Niobium was chosen as the third element to the Fe- 9Cr binary system. Steam oxidation test of Fe-9Cr (mass%) alloy and Fe-9Cr-2Nb (mass%) alloy were carried out at 923 K in Ar-15%H 2 O mixture for up to 172.8 ks. X-ray diffraction confirms the oxide mainly consist of wüstite on the Fe-9Cr in the initial stage while on Nb added samples magnetite was dominated. The results show that the Fe-9Cr- 2Nb alloy has a slower oxidation rate than the Fe-9Cr alloy after oxidized for 172.8 ks

Constricted steam oxidation resistance and finite microstructural stability limits the use of 9 - 12 wt.-% chromium ferritic-martensitic steels to steam temperatures of about 620 °C. Newly developed 12 wt.-% Cr steels are prone to Z-phase precipitation, which occurs at the expense of the strengthening precipitates, and therefore suffer an accelerated decline in strength during longterm operation. While the concept of ferritic-martensitic chromium steels thus seems to hit technological limitations, further improvement in steam power plant efficiency necessitates a further increase of steam pressure and temperature. Furthermore increasing integration of intermitting renewable energy technologies in electrical power generation poses a great challenge for supply security, which has to be ensured on the basis of conventional power plant processes. Besides improved efficiency for resource preservation, load flexibility, thermal cycling capability and downtime corrosion resistance will play key roles in the design of tailored materials for future energy technology. Under these preconditions a paradigm shift in alloy development towards improvement of cyclic steam oxidation and downtime corrosion resistance in combination with adequate creep and thermomechanical fatigue strength seems to be mandatory. The steam oxidation, mechanical and thermomechanical properties of fully ferritic 18 - 24 wt.-% chromium model alloys, strengthened by the precipitation of intermetallic (Fe,Cr,Si)2(Nb,W) Laves phase particles, indicate the potential of this type of alloys as candidate materials for application in highly efficient and highly flexible future supercritical steam power plants.