Laves phases are intermetallic phases well known for their excellent strength at high temperatures but also for their pronounced brittleness at low temperatures. Especially in high-alloyed steels, Laves phases were long time regarded as detrimental phases as they were found to embrittle the material. Perusing the more recent literature, it seems the negative opinion about the Laves phases has changed during the last years. It is reported that, if the precipitation morphology is properly controlled, transition metal-based Laves phases can act as effective strengthening phases in heat resistant steels without causing embrittlement. For a targeted materials development, the mechanical properties of pure Laves phases should be known. However, the basic knowledge and understanding of the mechanical behavior of Laves phases is very limited. Here we present an overview of experimental results obtained by micromechanical testing of single-crystalline NbCo 2 Laves phase samples with varying crystal structure, orientation, and composition. For this purpose, diffusion layers with concentration gradients covering the complete homogeneity ranges of the hexagonal C14, cubic C15 and hexagonal C36 NbCo 2 Laves phases were grown by the diffusion couple technique. The hardness and Young's modulus of NbCo 2 were probed by nanoindentation scans along the concentration gradient. Single-phase and single crystalline microcantilevers and micropillars of the NbCo 2 Laves phase with different compositions were cut in the diffusion layers by focused ion beam milling. The fracture toughness and the critical resolved shear stress (CRSS) were measured by in-situ microcantilever bending tests and micropillar compression tests, respectively. The hardness, Young's modulus and CRSS are nearly constant within the extended composition range of the cubic C15 Laves phase, but clearly decrease when the composition approaches the boundaries of the homogeneity range where the C15 structure transforms to the off stoichiometric, hexagonal C36 and C14 structure on the Co-rich and Nb-rich, respectively. In contrast, microcantilever fracture tests do not show this effect but indicate that the fracture toughness is independent of crystal structure and chemical composition of the NbCo 2 Laves phase.

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.

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.

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 creep strength and ductility of Grade P22 steel (2¼ Cr) was measured at 600°C under standard uniaxial tensile conditions at 150MPa. Test specimens were prepared by solution heat treatment at austenitization temperatures ranging from 900°C - 1200°C followed by normalization at 900°C before continuous air cooling to room temperature. In addition to specimens tested in the solution treated state, creep tests were also performed after tempering. The variable austenitization temperatures gave rise to different prior austenite grain (PAG) sizes, which in turn influenced the crystallographic packet and block boundary misorientation angle distribution. The latter parameters were measured using electron backscattered diffraction which also allowed partial reconstruction of the PAG boundaries. The time to creep failure at 600°C increased as function of PAG size up to approximately 70µm, but significantly decreased when the average prior austenite grain size measured approximately 108 µm. However, the minimum creep rate decreased even up to the largest PAG size with corresponding decrease in creep ductility. The stability of the crystallographic packet and block boundaries influences the high strength-low ductility for the large PAGs in comparison to the dominant effect of PAG boundaries at the smallest grain size where extensive recovery and recrystallization reduces creep strength.

9-10%Cr-3%Co martensitic steels are the prospective materials for elements of boilers, tubes and pipes for fossil power plants which are able to work at ultra-supercritical parameters of steam (T=620-650°C, P=25-30 MPa). The effect of creep on the microstructure of the 10 wt.%Cr-3Co- 3W-0.2Re martensitic steel was investigated in the condition of 650°C and an applied stress of 140 MPa, time to rupture was more than 8500 h. Previously, this steel was subjected to the normalizing at 1050°C and tempering at 770°C. This heat treatment provided the hierarchical tempered martensite lath structure with the mean size of prior austenite grains of 59 μm and with high dislocation density (2×10 14 m -2 ) within martensitic laths. Boundary M 23 C 6 and M 6 C carbides and randomly distributed within matrix Nb-rich MX carbonitrides were detected after final heat treatment. The addition of Re in the steel studied positively affected creep at 650°C/140 MPa and stabilized the tempered martensite lath structure formed during 770°C-tempering. The formation of the subgrains in the gage section was accompanied by the coarsening of M 23 C 6 carbides and precipitations of Laves phase with fine sizes during creep. No depletion of Re and Co from the solid solution during creep was revealed whereas W content decreased from 3 to 1 wt.% for first 500 h of creep. Reasons of improved creep as well as mechanisms of grain boundary pinning by precipitates are discussed.

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.

Modified 9Cr-1Mo steel (ASTM Gr.91) is widely used in components of fossil fueled power plants around the world today. This grade of steel has however been shown to exhibit significant variations in creep life and creep ductility, which has led to premature in-service failures. The aim of this work is to define potential metallurgical risk factors that lead to this variation in performance. To achieve this, a set of creep test samples that represent a wide range in this variation of creep behavior in this steel grade have been studied in detail. As a first stage in this characterization the macro-scale chemical homogeneity of the materials were mapped using micro-XRF. Understanding the segregation behavior also allows quantification of microstructural parameters in both segregated and non-segregated areas enabling the variations to be determined. For example this showed a significant increase in the number per unit area of Laves phase particles in high compared with low Mo content areas. To study the effect of MX particles on segregation a methodology combining SEM and TEM was employed. This involved chemically mapping the larger V containing particles using EDS in the SEM in segregated and unsegregated areas and then comparing the results to site-specific TEM analysis. This analysis showed that although the average size of the V containing samples is in the expected 0-50 nm size range, these particles in some samples had a wide size distribution range, which significantly overlaps with the M 23 C 6 size distribution range. This together with the segregation characteristics has important implications for determining meaningful quantitative microstructural data from these microstructurally complex materials.

More efficient, sustainable, flexible and cost-effective energy technologies are strongly needed to fulfil the new challenges of the German “Energiewende”. For a reduction of consumed primary resources higher efficiency steam cycles with increased operating parameters, pressure and temperature, are mandatory. Hence, advanced materials are needed. The present study focuses on stainless, high strength, ferritic (non-martensitic) steel grades, regarding thermal treatment effects on particle evolution. The heat treatment includes variations, e.g. a two phase pre heat treatment. Effects of the treatment were analysed and connected to creep performance. Experiments at differently heat treated materials show promising improvement of creep performance. These results can be linked to the stability and evolution of strengthening Laves phase particles.

The microstructures and mechanical properties of T122 steel used for superheater tube of the boiler in a 1000 MW ultra supercritical power plant after service for 83,000h at 590℃ were investigated, and compared with data of that served for 56,000h in previous studies. The results show that compared with T122 tube sample service for 56,000h, the tensile properties at room temperature and the size of precipitated phase exhibit few differences, but the lath martensites features are apparent, and the Brinell hardness value are obviously higher. SEM and TEM experiments show that the substructure is still dominated by lath martensite. A few lath martensites recover, subgrains appear and equiaxe, and the dislocation density in grains is relatively low. A large number of second-phase particles precipitated at boundaries of original austenite grains and lath martensite phases, which are mainly M 23 C 6 and Laves phases.

In order to understand the microstructural evolution during service that 9Cr steels experience it is important to be able to quantify key microstructural parameters that define the characteristics of the secondary phases (e.g. precipitated phases and inclusions) and the steel matrix. The average size of M 23 C 6 , Laves phase and MX particles in these materials have been reported in many studies, however comparability between these studies is compromised by variations in technique and different/incomplete reporting of procedure. This paper provides guidelines on what is required to accurately measure these parameters in a reproducible way, taking into account macro-scale chemical heterogeneities and the statistical number of particles required to make meaningful measurements. Although international standards do exist for inclusion analysis, these standards were not developed to measure the number per unit area of hard particles that can act as creep cavity nucleation sites. In this work a standardized approach for measuring inclusions from this perspective is proposed. In addition the associated need to understand the segregation characteristics of the material are described, which in addition to defining the area that needs to be analysed to measure the average number of inclusions per unit area, also allows the maximum number of inclusions per unit area to be determined, a parameter which is more likely to define the damage tolerance of the material.

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

Development of the advanced USC (A-USC) boiler technology has been promoted in recent years, which targets 700°C steam condition. HR6W (Ni-23Cr-7W-Ti-Nb-25Fe) and HR35 (Ni-30Cr-6W-Ti-15Fe) have been developed for A-USC boiler tubes and pipes. The former alloy is mainly strengthened by Fe 2 W type Laves phase. The latter one employs precipitation strengthening of α-Cr phase in addition to Laves phase. Characteristic alloy design of both alloys, which does not use precipitation strengthening of γ′ phase (Ni 3 Al), leads to superior ductility and resistance to stress-relaxation cracking. Stability of creep strength and microstructure has been confirmed by long-term creep rupture tests. The 100,000h average creep rupture strength of HR6W is 85MPa at 700C. That of HR35 is 126MPa at 700°C which is comparable with conventional Alloy617. Tubes of both alloys have been evaluated by the component test in Japanese national A-USC project with γ′ hardened Alloy617 and Alloy263. Detailed creep strength, deformation behavior and microstructural evolution of these alloys are described from the viewpoint of the difference in strengthening mechanisms. Capability of these alloys for A-USC boiler materials has been demonstrated by the component test in the commercial coal fired boiler as the part of the A-USC project.

A new alloy design concept for creep- and corrosion-resistant, fully ferritic alloys was proposed for high-temperature structural applications in current/future fossil-fired power plants. The alloys, based on the Fe-30Cr-3Al (in weight percent) system with minor alloying additions of Nb, W, Si, Zr and/or Y, were designed for corrosion resistance though high Cr content, steam oxidation resistance through alumina-scale formation, and high-temperature creep performance through fine particle dispersion of Fe 2 (Nb,W)-type Laves phase in the BCC-Fe matrix. Theses alloys are targeted for use in harsh environments such as combustion and/or steam containing atmospheres at 700°C or greater. The alloys, consisting of Fe-30Cr-3Al-1Nb-6W with minor alloying additions, exhibited a successful combination of oxidation, corrosion, and creep resistances comparable or superior to those of commercially available heat resistant austenitic stainless steels. An optimized thermo-mechanical treatment combined with selected minor alloying additions resulted in a refined grain structure with high thermal stability even at 1200°C, which improved room-temperature ductility without sacrificing the creep performance. The mechanism of grain refinement in the alloy system is discussed.

Due to their excellent high temperature oxidation resistance, utilities worldwide are adopting advanced austenitic stainless steels (A-ASS) for critical plant components, such as heat exchangers, as they aim to achieve higher operating conditions. However, challenges may be encountered in developing life assessment and life management strategies for such components. This is because conventional methods used for life assessment, such as measuring steam side oxide scale thickness in ferritic and conventional austenitic material to predict tube metal temperature, may not be successfully applied to A-ASS. In such instances, tracking the formation and evolution of microstructural features during service, may offer a possible method to predict the temperature of these steels. For such metallurgy based lifing strategy to be successful, it is essential to develop a good understanding of microstructure evolution in these steels. In this work one heat of Super 304H, that has been creep tested at 600°C, 650°C and 700°C, with applied stress ranging from 110 to 340 MPa, is characterized using a combination of advanced characterization tools and image analysis methods. The amount of sigma phase formed at the gauge and grip sections of the samples is quantified and the methodology used to quantify this phase is presented. From the results, a time-temperature-transformation diagram for sigma formation is developed.

MoSiBTiC alloy is a promising material for advanced aerospace applications and next generation high pressure turbine blades in jet engines and gas turbines. It mainly consists of Mo solid solution, TiC and Mo 5 SiB 2 phases and has creep strength much stronger than Ni-base superalloys and better than SiC/SiC ceramic matrix composites. Furthermore, the fracture toughness of the alloy is much better (>15 MPa(m) 1/2 ) than Mo-Si-B ternary alloys (<10 MPa(m) 1/2 ) even if the volume fraction of Mo solid solution is less than 50 %. The improvement of fracture toughness would be caused not only by the continuity of Mo solid solution in solidification microstructure but also by TiC phase affecting as a fracture-resistant phase. In order to understand the microstructure evolution during solidification and the effect of TiC phase on the fracture toughness of the MoSiBTiC alloy, Mo-Ti-C ternary model alloys are dealt with in this study. Then, (1) liquidus surface projection and (2) isothermal section and the elastic moduli of TiC phase in equilibrium with Mo solid solution were focused on. The obtained liquidus surface projection suggests that the ternary transition peritectic reaction (L+ Mo 2 C->Mo+TiC) takes place in Mo-rich region. At 1800 °C, TiC phase in equilibrium with Mo phase contains at least 20.2 at% Mo and the Mo/TiC/Mo 2 C three phase region should exist around Mo-15Ti-10C.

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.

A trial weld joint of COST F and COST FB2 steels was produced using the GTAW HOT-WIRE method in conditions used in industry for production of welding steam turbine rotors. Conventional long-term creep tests (CCT) to the rupture of this weldment and the base materials were carried out at temperatures ranging from 550 °C to 650 °C in the stress range from 70 to 220 MPa (the longest time to rupture was above 52,000 hours). Creep rupture strength was evaluated using Larson-Miller parameter model. Assessment of microstructure was correlated with the creep strength. Precipitation of Laves phase and structure recovery during creep exposures were the main reasons for the failure which occurred in the heat affected zone of steel COST F. The recently developed simulative accelerated creep testing (ACT) on thermal-mechanical simulator allows the microstructural transformation of creep-resisting materials in a relatively short time to a state resembling that of multiyear application under creep conditions. ACT of samples machined from various positions in the weldment was performed at 600 °C under 100 MPa. Changes in the hardness and the microstructures of the samples, which underwent both types of creep tests, were compared. Small sample creep test (SPCT), another alternative method how to obtain information about the creep properties of materials when only a limited amount of test material is at disposal, were performed. It was shown that the same stress-temperature dependence and relationships are valid in the SPCT as in the CCT. Using a simple load-based conversion factor between the SPCT test and the CCT test with the same time to rupture, the results of both test types can be unified.

Interstitial carbon (C) in β-Ti, α-Ti, α 2 -Ti 3 Al and γ-TiAl phases present in the γ-TiAl alloys with and without substitutional elements (M: transition element) is quantitatively analyzed using soft X-ray emission spectroscopy (SXES), in order to reveal the effect of solute carbon on the phase equilibria. SXES for carbon analysis was used and the peak intensity of the second reflection of carbon Kα is analyzed using the fully homogenized sample having different C content under the optimum condition to make the accurate calibration curves. The obtained calibration curve is in an accuracy of ± 0.07 at. % C. In all heat treated alloys, no carbide is observed. In Ti-Al binary system, the α+γ phase region shifts toward higher Ti side, and the volume fraction of γ phase increases slightly with the carbon addition. In all system, carbon preferentially partitions into the α phase, followed by less partitioning in the γ and β phases in order. The carbon content in the β phase remains unchanged of almost 0.05 at. % regardless of carbon addition in Ti-Al-V system and the partition coefficient of carbon between the α and γ phases becomes larger in Ti-Al-V system than that in TiAl binary system.