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

To save fossil fuel resources and to reduce CO 2 emissions, considerable effort has been directed toward researching and developing heat-resistant materials that can help in improving the energy efficiency of thermal power plants by increasing their operational temperature and pressure conditions. Instead of conventional 9-12Cr ferritic heat-resistant steels with a tempered martensitic microstructure, we developed “Precipitation Strengthened 15Cr Ferritic Steel” based on a new material design concept: a solid-solution treated ferrite matrix strengthened by precipitates. Creep tests for 15Cr-1Mo-6W-3Co-V-Nb steels with ferrite matrix strengthened by a mainly Laves phase (Fe 2 W) showed that the creep strengths of 15Cr ferritic steel at temperatures ranging from 923 K to 1023 K were twice as high as those of conventional 9Cr ferric heat-resistant steel. 15Cr steels have higher steam oxidation resistance than that of conventional steel in the same temperature range as the creep tests. Thus, the new material design concept of heat-resistant steel pro- vides improved creep strength and steam oxidation resistance. We are attempting to determine the optimum compositions, especially that of carbon, in order to improve the high-temperature creep strength.

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.

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.

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.

700°C advanced ultra-supercritical system and supercritical CO 2 turbine system are developed for high efficiency turbine systems for next generation. This study covered the feasibility of creep life assessment of γ’-Ni 3 (Al,Ti) precipitation strengthened Ni-based superalloy rotor material, TOS1X-2, a modified alloy of UNS N06617 for these systems, based on hardness measurement method. It was found that the hardness of TOS1X-2 was governed by the change in precipitation strengthening and strain hardening during creep. The clear relationship between hardness increase in crept portion and macroscopic creep strain was observed, suggesting that it might be possible to estimate the creep strain or initiation of acceleration from hardness measurement. Microstructure inhomogeneity and microstructure evolutions during creep especially focused on dispersion of creep strain were characterized by EBSD quantitative analysis. It was found that creep strain was accumulated along the grain boundary, while it was relatively absent in coarse grains with low Schmid factor of {111} <110> slip system in fcc structure. The upper limit of hardness scatter band is thought to be important, since it represents the local and critical creep damage of the alloy.

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.

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.

To achieve the necessary creep-rupture lifetimes at the temperatures and pressures associated with advanced ultrasupercritical (A-USC) steam conditions (100,000 h at 100 MPa and 760°C), precipitation-strengthened nickel-based alloys are required for the superheater and reheater tubing in A-USC boilers. Two alloys were considered to have potential for this application: Inconel 740 and Haynes 282 alloy. In support of this application, creep-rupture testing of several heats of Inconel 740 was conducted over a range of temperatures and stresses to develop confidence in qualitatively predicting creep lifetimes under conditions relevant to A-USC steam conditions, with the longest rupture times exceeding 30,000 h. For comparison, the creep-rupture behavior of Haynes 282 alloy was mapped as a function of temperature and stress, but with a significantly smaller dataset. Only a small difference in creep-rupture results between Inconel 740 and Inconel 740H was found although the latter alloy showed significantly greater resistance to η phase formation during testing. Little effect of prior aging treatments (for setting the γ′ precipitate structure) on creep-rupture behavior was observed. Results from a modified power law analysis showed that, while both Inconel 740 and Haynes 282 are projected to meet the A-USC lifetime requirements, the latter offered the potential for better long-term creep resistance.

In order to study the effect of precipitation strengthening by MX precipitates on the restriction of microstructure degradation in 9 mass% Cr ferritic heat-resistant steels, V, Nb additioned model steels were evaluated by microstructure analysis through TEM and EBSD with reference to the creep test and creep interrupting test. VN precipitation increased the creep strength if the content was higher than 0.02%. Simultaneous addition of Nb and V in the specimen resulted in the complex NbC-VN precipitates even in the as-heat-treated specimens. The coherent and fine-needle-type VN was also detected in the steel. These precipitates are expected to increase the creep strength according to the creep strain curves. V variation up to 0.02% did not affect the crystallographic character of the grain boundary in the as-heat-treated specimens. Nb variation affected the crystallographic character of the grain boundary significantly because of the grain refinement effect of NbC. VN precipitation during the creep test restricted the crystallographic misorientation-angle-profile degradation. Integrating all intragranular precipitates, VN, restricts the crystallographic degradation significantly. The long-term creep test results and the precise precipitation analysis will be disclosed by the presentation.

High nitrogen steel was manufactured by solid state nitriding and Laminate- rolling at laboratory to study the nitride morphology and creep properties through the TEM, EPMA and creep strain test. Nitriding made the nitride dispersing steels possible. Solid state nitriding of thin plates and those laminate rolling enabled the high nitrogen containing thick plate steel. Precipitated coarse nitrides during the nitriding resolved by normalizing and re-precipitated by tempering finely. Needle type VN was detected in V containing high nitrogen steels. Its coherency seems to affect the creep strength significantly. V precipitated steels indicated the higher creep strength than the steels without VN precipitation. Thermodynamically stable precipitates like VN increases the creep rupture strength. Ti and Zr containing high nitrogen steels also will be evaluated and discussed by the presentation.

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.

25Cr-20Ni-Nb-N (Tp310HCbN) steel is a promising austenitic steel for applications in superheater tubes in coal fired thermal power plants due to the high creep strength and oxidation resistance. In this work, the microstructural evolution of this material during heat treatment and thermal ageing has been investigated. The investigations were carried out by Light Optical Microscopy (LOM), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS). Besides, equilibrium and Scheil calculations were carried out using the thermodynamic software MatCalc to analyse the stable phases and the solidification process, respectively. Precipitation calculations during solution annealing and subsequent ageing at 650 and 750°C were performed to predict the phase fraction and precipitates radius up to 10.000h ageing time. SEM and TEM investigations of aged specimens revealed the presence of six different precipitates: M 23 C 6 , Cr 2 N, sigma, Z-phase, eta-phase (Cr 3 Ni 2 Si(C,N)) and Nb(C,N). These precipitates were predicted and confirmed by MatCalc simulations. The calculated phase fraction and mean radius show good agreement with experimental data. Finally, simulations of different Cr-, C- and N-content in Tp310HCbN were performed.

The Cr and W effect on the creep strength of ferritic steels were studied using the new strengthening hypothesis, precipitation strengthening mechanism, by examining the residual aligned precipitates consisting of W and Cr. In 2 mass% W-containing steel, the increase in Cr content up to 10 mass% resulted in the creep life extension. However, the Cr content higher than 11 mass% decreased the creep life. In 9 mass% Cr-containing steel, the increase in W content decreased the creep deformation rate with creep time. However, it also shortened the time to reach the minimum creep rate. Therefore, optimum Cr and W contents possibly resulted in the optimum alloy design. To understand the effect of W and Cr contents on creep strength, the precipitation strengthening hypothesis by the precipitates at the block boundary must be introduced. The residual aligned precipitation line is supposedly an effective obstacle for the dislocation motion at the interparticle space of the aligned precipitates. The new hypothesis will be activated after block boundary migration. It occurs during the acceleration creep period. On the basis of the hypothesis, creep strength was expressed as the summation of threshold creep stress and effective internal creep stress. According to the experimental data of microstructure recovery, the effective internal stress decreased with creep deformation and consequently vanished. In such cases, creep strength is decided only by the threshold stress of creep. Integrating all, we concluded that the creep deformation mechanism of ferritic creep-resistant steel possibly transits from the viscous dislocation gliding mode to the microstructure recovery driven type mode during the acceleration creep.

A novel multi-component, multi-particle, multi-phase precipitation model is used to predict the precipitation kinetics in complex 9-12% Cr steels investigated within the European COST project. These steels are used for tubes, pipes, casings and rotors in USC (ultra super critical) steam power plants for the 21 st century. In the computer simulations, the evolution of the precipitate microstructure is monitored during the entire fabrication heat treatment including casting, austenitizing, several annealing treatments. The main interest lies on the concurrent nucleation, growth, coarsening and dissolution of different types of precipitates.

This paper investigates the cause of premature failures in certain Grade 91 steel components used in UK power plants. The failures were linked to both low material hardness and specific chemical compositions that fell within ASTM specifications but had a low nitrogen-to-aluminum ratio (N:Al). The investigators examined eight material batches, including those involved in failures, new stock, and in-service components with similar properties. Testing confirmed these materials had lower creep resistance compared to standard Grade 91 steel. Microscopic analysis revealed the presence of large aluminum nitride precipitates, which limited the formation of beneficial vanadium nitride precipitates, leading to reduced creep strength. These findings suggest that even within the ASTM specification limits, a low N:Al ratio can negatively impact the performance of Grade 91 steel.

NiAl precipitates with the B2 structure are known to be effective in increasing the strength of ferritic heat-resistant steels. The strengthening mechanism by the NiAl precipitates was examined using Fe-21Al-2Ni and Fe-23Al-6Ni (at%) single crystals. As a result, the difference in primary slip system between the bcc matrix and the NiAl precipitates is responsible for strong hardening. The B2-NiAl phase was precipitated in the bcc matrix satisfying the cube-on-cube orientation relationship with small misfit strain. The primary slip direction of the bcc matrix and the NiAl precipitates are <111> and <001>, respectively. However, in the ferritic alloys, the NiAl precipitates were cut by paired 1/2<111> dislocations in the bcc matrix, resulting in the hardening. The size and volume fraction of the NiAl precipitates strongly influenced the strength. The stress increase by the NiAl precipitates was also discussed quantitatively based on the precipitation hardening theory. Based on the experimental results obtained by the single crystal study, we developed Fe-Al-Ni-Cr-Mo ferritic heat-resistant alloy containing the NiAl precipitates. The alloy exhibited excellent creep properties at 923 K.

Inconel alloy 740H is designated for boiler sueprheater/reheater tubes and main steam/header pipes application of advanced ultra-supercritical (A-USC) power plant at operating temperatures above 750°C. Microstructure evolution and precipitates stability in the samples of alloy 740H after creep-rupture test at 750°C, 800°C and 850°C were characterized in this paper by scanning electron microscopy, transmission electron microscopy and chemical phase analysis in details. The phase compositions of alloy 740H were also calculated by thermodynamic calculation. The research results indicate that the microstructure of this alloy keeps good thermal stability during creep-rupture test at 750°C, 800°C and 850°C. The precipitates are MC, M 23 C 6 and γ′ during creep-rupture test. The temperature of creep test has an important effect on the growth rate of γ′ phase. No harmful and brittle σ phase was found and also no γ′ to η transformation happened during creep. Thermodynamic calculations reveal almost all the major phases and their stable temperatures, fractions and compositions in the alloy. The calculated results of phase compositions are consistent with the results of chemical phase analysis. In brief, except of coarsening of γ′, Inconel alloy 740H maintains the very good structure stability at temperatures between 750°C and 850°C.

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.

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.