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.

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.

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 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.

The paper deals with microstructural evolution in the AISI 316LN + 0.1 wt.% Nb steel during long-term creep exposure at 600 and 625°C. The following minor phases formed: Z-phase (NbCrN), M 23 C 6 , M6X (Cr3Ni2SiX type), η-Laves (Fe2Mo type) and σ-phase. M6X gradually replaced M 23 C 6 carbides. Primary Z-phase particles were present in the matrix after solution annealing, while secondary Z-phase particles formed during creep. Precipitation of Z-phase was more intensive at 625°C. The dimensional stability of Z-phase particles was excellent and these particles had a positive effect on the minimum creep rate. However, niobium also accelerated the formation and coarsening of σ-phase, η-Laves and M6X. Coarse particles, especially of σ-phase, facilitated the development of creep damage, which resulted in poor long-term creep ductility.

Materials with a higher creep strength and sensitization resistance superior to those of 347AP are required in complex refinery such as delayed coker. To optimize material designing, the effect of B addition on the Z phase-strengthened steels has been investigated. B addition significantly improved the creep strength of steel containing Nb despite the absence of M 23 C 6 , whereas the creep strength of steel without Nb showed only a slight change with B addition. The size of Z phase was smaller in the Nb-containing steel with B content than that in B-free steel. It was suggested that the refinement of Z phase contributed to the creep strengthening by B addition in steels containing Nb.

A 10%Cr martensitic steel with 3%Co and 0.008%B exhibits extremely long creep rupture time of approximately 40000 h under an applied stress of 120 MPa at a temperature of 650°C. The steel’s microstructure after creep tests interrupted at different creep stages was examined by transmission and scanning electron microscopy. It was shown that superior creep resistance of this steel was attributed to slow increase in creep rate at the first stage of tertiary creep whereas the rapid acceleration of creep rate took place only at the short second stage of tertiary creep. Transition from minimum creep rate stage to tertiary creep was found to be accompanied by coarsening of Laves phase particles, whereas M 23 C 6 – type carbides demonstrated high coarsening resistance under creep condition. Strain-induced formation of Z-phase does not affect the creep strength under applied stress of 120 MPa due to nanoscale size of Z-phase particles.

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.

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.

COST FB2 steel alloyed with boron is currently the best available martensitic 9% Cr steel for turbine shafts subjected to steam temperatures up to 620°C and meanwhile introduced into production for application in commercial power plants. Currently several development programs are running to develop materials for further increase of application temperature up to 650°C. For realization of a 650ºC power plant not only creep strength, but also resistance against steam oxidation must be improved by increase of Cr content up to 11-12%. In the past all attempts to develop stable creep resistant martensitic 11-12% Cr steels for 650°C failed due to breakdown in long-term creep strength. Therefore new alloy concepts have been developed by replacing the fine nitride strengthening particles by controlled and accelerated precipitation of the more stable Z phase. Therefore the European project “Z-Ultra” was launched for further development and manufacture of this new alloy type. Saarschmiede participates in this project and contributed by manufacturing trial melts, boiler tubes and a large scale turbine rotor forging. Production experience and test results are presented. In order to exceed the temperature limit of 650°C, only nickel base alloys can be used. One of the most promising candidate alloys for rotor forgings subjected to steam temperatures of 700°C is Alloy 617, which was already intensively investigated. For still higher temperatures in the range of 750°C only γ‘-precipitation hardened nickel base alloys, such as Alloy 263, can be applied. Therefore the “NextGenPower” project was launched and aimed at manufacture and demonstration of parts from Ni-based alloys for application in steam power plants at 750°C. One of the main goals was to develop turbine rotor materials and to demonstrate manufacturability of forgings for full scale turbine rotor parts. Contributing to this project, Saarschmiede has produced for the first time a large rotor forging in the Ni base Alloy 263. Numeric simulations of ingot manufacture, forging and heat treatment have been performed and a large trial rotor forging in Alloy 263 with a diameter of 1000 mm was successfully produced from a triple melt ingot. Experiences in manufacture and test results are presented.

Advanced austenitic stainless steels, such as Super 304H, have been used in reheater and superheater tubes in supercritical and ultra-supercritical power plants for many years now. It is important to characterize the microstructure of ex-service reheater and superheater tubes as this will help researchers understand the long-term microstructural evolution and degradation of the material, which can impact the performance and lifetime of the components that are in service. In this research, the microstructure of an ex-service Super 304H reheater tube that has been in service for 99,000 hours at an approximate metal temperature of 873K (600°C) has been characterized. The characterization techniques used were electron microscopy-based and included imaging and chemical analysis techniques. Seven phases were observed as a result of the characterization work. The phases observed were MX carbonitrides rich in niobium, copper-rich particles, M 23 C 6 , sigma phase, Z phase, a cored phase, and a BCC phase.

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.

A new ferritic steel branded as Thor 115 has been developed to enhance high-temperature resistance. The steel design combines an improved oxidation resistance with long-term microstructural stability. The new alloy was extensively tested to assess the high-temperature time- dependent mechanical behavior (creep). The main strengthening mechanism is precipitation hardening by finely dispersed carbide (M 23 C 6 ) and nitride phases (MX). Information on the evolution of secondary phases and time-temperature-precipitation behavior of the alloy, essential to ensure long-term stability, was obtained by scanning transmission electron microscopy with energy dispersive spectroscopy, and by X-ray powder diffraction on specimens aged up to 50,000 hours. The material behavior was also tested in service conditions, to validate the laboratory results: Thor 115 tubing was installed in a HRSG power plant, directly exposed to turbine flue gasses. Tubing samples were progressively extracted, analyzed and compared with laboratory specimens in similar condition. This research shows the performance of Thor 115 regarding steam oxidation and microstructure evolution up to 25,000 exposure hours in the field. So far, no oxide microstructure difference is found between the laboratory and on field tubing: in both cases, the oxide structure is magnetite/hematite and Cr-spinel layers and the oxide thickness values lay within the same scatter band. The evolution of precipitates in the new alloy confirms the retention of the strengthening by secondary phases, even after long-term exposure at high temperature. The deleterious conversion of nitrides into Z phase is shown to be in line with, or even slower than that of the comparable ASME grade 91 steel.

Creep properties and microstructural changes of 25Cr-20Ni-Nb-N steel (KA-SUS310J1TB) were investigated. Creep tests were performed under 20MPa to 380MPa at 600°C to 800°C. Time to rupture was from 53.5h to 23950h. At 650°C or higher, creep strength degraded in the long-term. Rupture elongation and reduction of area decreased with increasing time to rupture at 600°C to 800°C. The reduction of area was lower than 12% after creep rupture for more than 10000h. Creep voids and cracks were observed on grain boundaries in creep ruptured samples. The hardness of head portion of creep ruptured samples increased with increasing time to rupture at 600°C to 800°C. The hardness of gauge portion of creep ruptured samples was higher than that of as received sample. However, the hardness of gauge portion does not strongly depend on time to rupture. No precipitates were observed in as received sample. On the other hand, a large number of precipitates were confirmed after creep rupture at 600°C to 800°C. M 23 C 6 , sigma phase, eta nitride and Z phase were detected in creep ruptured samples. The precipitation was confirmed on grain boundaries after short-term creep. The precipitates were also formed inside grains after long-term creep. It was confirmed by optical microscope that the grain boundary seemed to have band-like structure after short-term creep exposure. The Cr depletion zone was detected around grain boundary after short-term creep exposure. The Cr depletion zone can be visible when Cr rich precipitates such as M 23 C 6 and sigma phase are formed on grain boundaries. However, the bandlike structure was not observed after long-term creep exposure because the Cr depletion zone became unclear after long-term creep exposure. Creep voids were formed on grain boundaries and at the interface between precipitates such as M 23 C 6 and sigma phase and matrix.

The development of 9-12% chromium steels during the last twenty years is reviewed. The significant increases in creep strength that have been achieved by minor alloying additions of V, Nb, W, Mo, N and B are discussed and the mechanisms by which the individual elements contribute to the long-term creep strength are evaluated. The basic strengthening is provided by the martensitic transformation that allows the formation of a sub-grain structure from the martensite laths. The sub-grain boundaries are stabilized by precipitates, mainly M 23 C 6 ; within the sub-grains, fine nitride and carbonitride precipitates interact with dislocations, thereby enhancing the strength. The relative contributions of the martensitic transformation and the various precipitates to the overall creep strength of the steels are assessed. Of particular importance for the long-term creep strength is the stability of the microstructure, especially the time dependent coarsening of the various precipitates and the possible formation of additional phases, such as Laves phase (Fe 2 (W,Mo) and the Z phase (CrNbN). It is shown that microstructural changes that occur during exposure at anticipated service temperatures have a large impact on the strength and these changes must be taken into account in the derivation of long-term design stresses. Finally, the potential for achieving further increases in the creep strength of 9-12% chromium steels is discussed, especially in view of the need for higher chromium contents to ensure adequate steam oxidation resistance.

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.

The present study presents a detailed investigation on the evolution of the microstructure during welding on virgin and long-term service exposed (creep aged 1 = 535°C; 16.1 MPa; 156 kh and creep aged 2 = 555°C; 17.0 MPa; 130 kh) 12% Cr (X20CrMoV11-1) martensitic steel. This study was carried out in order to understand the impact of welding on prior creep exposed Tempered martensite ferritic (TMF) steel and to explain the preferential failure of weldments in the fine grained heat affected zone (FGHAZ) of the creep aged material side instead of the new material side. Gleeble simulation (Tp = 980°C; heating rate = 200 °C/s; holding time = 4 seconds) of the FGHAZ was performed on the materials to create homogeneous microstructures for the investigation. Quantitative microstructural investigations were conducted on the parent plate and simulated FGHAZ materials using advanced electron microscopy to quantify: a) voids, b) dislocation density, c) sub-grains, and d) precipitates (M 23 C 6 , MX, Laves, Z-phase) in the materials. Semi-automated image analysis was performed using the image analysis software MIPARTM. The pre-existing creep voids in the creep aged parent material and the large M 23 C 6 carbides (Ø > 300 nm) in the FGHAZ after welding are proposed as the main microstructural contributions that could accelerate Type IV failure on the creep aged side of TMF steel weldments.

The recently developed 12%Cr steel VM12-SHC is characterized by very good creep properties at temperatures up to 620°C. This new material development exhibits an excellent oxidation resistance in steam atmospheres at the typical application temperature but also at temperatures up to 650°C. In comparison to the existing 9% Cr grades T/P91 and T/P92, VM12-SHC steel opens due to its excellent oxidation behavior, new possibilities for its application as a heat exchanger boiler component. It was found that outside its application temperature range VM12-SHC also shows, as all 9-12%Cr steels, the appearance of the so called Z-phase. This effect was investigated to understand its influence on creep properties of this class of ferritic/martensitic steels aiming at controlling the microstructure stabilities for future grade developments. Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected crept specimens have been investigated using light optical microscopy, SEM with EDX and TEM. In this study, the oxidation behavior of a number of typical martensitic 9-12%Cr steels was compared with the newly developed 12% Cr steel VM12-SHC. The compositions and morphologies of oxide scales formed after 5000 h exposure steels in simulated steam environments as function of temperature were characterized by light optical metallography and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX).

In order to clarify the effect of stress and strain on microstructural changes during creep for T91 steel, creep interrupted tests were performed at 600°C for 10000h, 20000h, 30000h, 50000h and 70000h. The steel studied was T91 steel with high Ni content (0.28mass%) in the range of specification. Changes of dislocation structure and precipitates distributions were observed for the grip and gauge portions of creep interrupted samples. The subgrain size gradually increased with increasing creep time up to 50000h in both the grip and gauge portions. However, the subgrain size abruptly increased after 50000h in the gauge portion as compared with the grip portion. Decrease in dislocation density inside subgrain was promoted in the gauge portion as compared with the grip portion. The size of M 23 C 6 gradually increased with increasing creep time up to 50000h in both the grip and gauge portions. The increase in M 23 C 6 size was accelerated after 50000h in the gauge portion as compared with the grip portion. The Z phase formation was promoted in the gauge portion as compared with the grip portion. The number density of all kinds of particles gradually decreased with increasing creep time in the gauge and grip potions. After 50000h, the number density rapidly decreased in the gauge portion as compared with the grip portion.

A new martensitic steel for power generation applications was developed: Tenaris High Oxidation Resistance (Thor) is an evolution of the popular ASTM grade 91, offering improved steam oxidation resistance and better long-term microstructural stability, with equal or better creep strength. Thanks to its design philosophy, based on consolidated metallurgical knowledge of microstructural evolution mechanisms, and an extensive development performed in the last decade, Thor was engineered to overcome limitations in the use of ASTM grade 91, above 600 °C, particularly related to scale growth and liftoff. After laboratory development, Thor was successfully validated at the industrial level. Several heats up to 80 metric tons were cast at the steel shop, hot rolled to tubes of various dimensions, and heat treated. Trial heats underwent extensive characterization, including deep microstructural examination, mechanical testing in the as-received condition and after ageing, long-term creep and steam oxidation testing. This paper presents an overview of metallurgical characterization performed on laboratory and industrial Thor material, including microstructural examination and mechanical testing in time-independent and time-dependent regimes. Data relevant to the behavior and the performance of Thor steel are also included.