Nano-sized precipitates in 11 % Cr ferritic-martensitic steel after thermomechanical treatment

9 %–12 % Cr ferritic/martensitic steels with a good long-term creep strength at temperatures up to 650 °C and higher are being developed in order to increase steam temperature of coal-fired power plants.Thermomechanical treatment can effectively enhance the mechanical properties of high-Cr ferritic/martensitic steels mainly due to plenty of nano-sized precipitates produced by thermomechanical treatment. Nano-sized precipitates in an 11 % Cr ferritic/martensitic steel produced by a thermomechanical treatment, including warm rolling at 650 °C plus tempering at 650 °C for 1 h, were investigated by transmission electron microscopy. The average size of precipitates in the steel after the thermomechanical treatment was determined to be about 30 nm in diameter, which is only one-third of the average size of precipitates in the steel with the normalized and tempered condition. A large number of Cr-rich precipitates having an average diameter of about 25 nm in the steel produced by the thermomechanical treatment were identified as Cr-rich M₂C carbide with a hexagonal crystal structure, rather than M₂₃C₆ or MX phase. The plenty of nano-sized Cr-rich M₂C carbides were dominant phase in the steel after the thermomechanical treatment. The reason why prior precipitate phase formed in the steel during the thermomechanical treatment was Cr-rich M₂C carbide is also discussed.     

Effect of alloying on interfacial energy of precipitation/matrix in high-chromium martensitic steels

The effect of cobalt, tungsten, and boron on interfacial energy of precipitate/ferritic matrix in the 9% Cr martensitic steels on the base of creep tests at 650 °C under different applied stresses ranging from 80 to 220 MPa was investigated. An interfacial energy of M₂₃C₆ carbides, the Laves phase particles, and MX carbonitrides was estimated by comparison of theoretical curves obtained by Prisma software for the model steels for the exposure time of 2 × 10⁴ h with experimental data measured by TEM in the gage sections of crept specimens. Addition of 3 wt% Co to Co-free 9Cr2W steel led to about 1.7 times increase in the interfacial energy of M₂₃C₆ carbides and MX carbonitrides, whereas Co did not effect on the interfacial energy of the Laves phase. Increasing W from 1.5 to 3 wt% in the Co-containing steels led to increase in the interfacial energy of the Laves phase up to 0.78 J m^?2 under long-term exposure, whereas it did not effect on the interfacial energy of M₂₃C₆ carbides and MX carbonitrides. In the steel with increased B up to 0.012 wt% and decreased N to 0.007 wt%, a strong decrease in the interfacial energy of M₂₃C₆ carbides to 0.12 J m^?2 occurred. Change in the interfacial energy of the precipitates was analyzed in comparison with coarsening rate constant.     

Decomposition modes of austenite in 9Cr–W–V–Ta reduced activation ferritic–martensitic steels

The present paper presents the results of an extensive electron microscopy investigation on the decomposition modes of high temperature austenite in 9Cr–W–V–Ta reduced activation ferritic–martensitic steels. Although the displacive martensitic transformation is predominant on austenitisation, low volume fraction of Fe rich M₃C or M₂₃C₆ precipitates formed, when the tungsten content exceeded 1 wt-%. The compositional inhomogeneity introduced in the austenite by the nature, chemistry and kinetics of dissolution of the pre-existing carbides is dependent on the steel composition and austenitisation conditions. The extent of repartitioning of tungsten between M₂₃C₆ and ferrite largely influences the kinetics of austenite and martensite transformation, for the same austenitisation conditions. Supporting evidence from calorimetry analysis is also presented.     

Investigations of ferritic/martensitic super heat resistant 11‐12 %Cr steels for 650 °C power plants

The investigations of advanced ferritic/martensitic 11–12 %Cr steels for 650 °C power plant components focus on the improvement of high‐temperature creep properties with respect to chemical composition. The claim of the DFG research work was the development of new heat‐resistant 12 %Cr ferritic‐martensitic steels with sufficient creep and oxidation resistance for a 650 °C application by using basic principles and concepts of physical metallurgy on the basis of the state of art and to overcome the usual trial and error industrial alloy development. Efforts are focussed on a 100,000h creep strength of 100MPa at 650 °C in combination with a sufficient corrosion resistance by a Cr content of 12 % with contents 4‐5 %W, 3.4‐5,5 %Co, V, B and 1 %Cu as well as the choice of Ta or Ti instead of Nb. The results demonstrate that the aim is not to realize with the used alloying concept. In the long term range all 12 %Cr melts have a lower creep rupture strength than the advanced 9 %Cr piping steel P92. A high creep strength could be reached with a 0.06 % Ta alloyed 11 %Cr melt, which is in addition alloyed with a higher C and B content and as well as with lower W and Co portions. The results indicate in accordance with the finding of other steel researcher that a lower Cr content allows more effectiveness for the alloying partners respectively for the generation of more stable precipitates.     

Stainless steels suited for solution nitriding

Solution nitriding is a new heat treatment to yield a high nitrogen case on stainless steels at 1100 ± 50°C. Combining experimental results and thermodynamic calculation steels are selected to give a hard martensitic or high strength austenitic case. Especially developed steels are discussed as well as the suitability of standard grades. A martensitic case is combined with a martensitic core in steel Cr13C0.2 and with a softer ferritic‐martensitic core in steel Cr13C0.1. The nitrogen content of an austenitic case increases with the Cr/Ni ratio, e.g. in the order of Cr17Ni12Mo2, Cr18Ni10, Cr22Ni5Mo3N0.2. The duplex microstructure of the latter provides the highest yield strength in the core. It is essential to stay clear of the austenite/austenite + M₂N boundary and avoid precipitates which deteriorate the fatigue and corrosion resistance. Seventeen steels are assessed in this report.     

Creep damage and grain boundary precipitation in power plant metals

Abstract

There is clear evidence that creep damage in power plant steels is associated with grain boundary precipitates. These particles provide favourable nucleation sites for creep damage such as grain boundary cavities and microcracks. Monte Carlo based grain boundary precipitation kinetics is combined with continuum creep damage mechanics (CDM) to model both the microstructural evolution and creep behaviour in power plant metals. It is found that grain boundary precipitates, such as M₂₃C₆ in most Cr containing ferritic steels, are harmful to the creep properties of the material, in line with experimental observations. It is also found that to improve the creep behaviour of the material, means should be found either to increase the proportion of MX type particles, such as VN, or to decrease or remove the larger grain boundary precipitates, such as M₂₃C₆. Hafnium has been ion implanted into thin foils of a 9 wt-%Cr ferritic steel to study the effect of hafnium on the grain boundary precipitation kinetics. It is found that the implantation of hafnium to the steel completely prohibits the formation of the common grain boundary M₂₃C₆ particles. Instead, two new types of precipitates are formed. One is hafnium carbide, which is an MX type precipitate, and is very small in size and has a much higher volume fraction as compared with the volume fraction of VN in conventional power plant ferritic steels. The other is Cr- and V-rich nitride of formula M₂N. CDM modelling shows that implantation of hafnium can markedly improve the creep property of the material. In addition, the replacement of M₂₃C₆ with hafnium carbide increases the concentration of Cr in the matrix and is expected to improve the intergranular corrosion resistance of the material.     

Precipitation in 9Cr–1Mo steel after creep deformation

The carbides present after creep testing a 9Cr–1Mo steel at 566 °C over a range of stress levels giving rupture times of up to 7300 h have been characterized and identified using a transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron diffraction. The initial carbide precipitates present were M₇C_3, (NbV)C and VC and it was determined that M₆C carbide precipitates were present in all specimens after elevated temperature exposure for greater than approximately 1700 h. No precipitation of M₂₃C₆ was detected. The evolutionary sequence from the initially present carbides during high temperature exposure involved the formation of the stable M₆C carbide directly, without the intermediate formation of M₂₃C₆, as is reported to occur in other Cr–Mo steels.     

Precipitate design for creep strengthening of 9% Cr tempered martensitic steel for ultra-supercritical power plants

Abstract

It is crucial for the carbon concentration of 9% Cr steel to be reduced to a very low level, so as to promote the formation of MX nitrides rich in vanadium as very fine and thermally stable particles to enable prolonged periods of exposure at elevated temperatures and also to eliminate Cr-rich carbides M₂₃C₆. Sub-boundary hardening, which is inversely proportional to the width of laths and blocks, is shown to be the most important strengthening mechanism for creep and is enhanced by the fine dispersion of precipitates along boundaries. The suppression of particle coarsening during creep and the maintenance of a homogeneous distribution of M₂₃C₆ carbides near prior austenite grain boundaries, which precipitate during tempering and are less fine, are effective for preventing the long-term degradation of creep strength and for improving long-term creep strength. This can be achieved by the addition of boron. The steels considered in this paper exhibit higher creep strength at 650 °C than existing high-strength steels used for thick section boiler components.     

Carbide types in an advanced microalloyed bainitic/ferritic Cr–Mo Steel – TEM observations and thermodynamic calculations

The strength and toughness of low alloyed ferritic/bainitic steels depend on their microstructure, which evolves during thermo‐mechanical treatments along the processing chain. Chromium‐molybdenum steel microstructures are complex. Therefore, only a limited number of attempts have been made to fully characterize carbide populations in such steels. In the present work, analytical transmission electron microscopy is employed to study the microstructure of a low alloyed chromium‐molybdenum steel, which features ferritic (F, mainly α‐iron and niobium‐carbides) and bainitic (B, α‐phase, dislocation, grain/subgrain boundaries, various M_xC_y carbides) regions. The crystal structure and chemical nature of more than 200 carbides are determined and their distributions in the two microstructural regions are analyzed. The present work shows how particles can be identified in an effective manner and how the microstructural findings can be interpreted on the basis of thermodynamic calculations.     

Carbide changes and sulphur segregation in erMa steel during creep

An investigation was carried out into microstructural changes at the grain boundary of interrupted creep-tested and long-term heated 2sCr-1Mo steel by means of transmission electron microscopy with energy dispersive X-ray spectrometry. Grain boundary precipitates alternated their types of M₇C3 carbides with M₆C carbides, and were spheroidized during creep or long-term heating. These carbide changes and spheroidization of precipitates were found to be accelerated by creep stress. Sulphur migrated to segregate at the interface between M₆ C and the matrix, while this phenomenon was not observed at the Ms3 carbide or precipitate-free grain boundary. Consequently it was considered that the intergranular creep damage in 2sCr-Mo steel was caused by a reduction in interfacial energy due to the sulphur segregation at the interface between the matrix and M₆C carbides.     

Influence of secondary carbides precipitation and transformation on the secondary hardening of laser melted high chromium steel

The influence of secondary carbides precipitation and transformation on the secondary hardening of laser melted high chromium steels was analyzed by means of scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The microstructure of laser melted high chromium steel is composed of austenite with supersaturated carbon and alloy elements and granular interdendritic carbides of type M₂₃C₆. Secondary hardening of the laser melted layer begins at 450 °C after tempering, and the hardness reaches a peak of 672HV at 560 °C and then decreases gradually. After tempering at 560 °C, a large amount of lamellar martensite was formed in the laser melted layer with a small quantity of thin lamellar M₃C cementite due to the martensitic decomposition. The stripy carbides precipitating at the grain boundaries were determined to be complex hexagonal M₇C₃ carbides and face centered cubic M₂₃C₆ carbides. In addition, the granular M₂₃C₆ carbides and fine rod-like shaped M₇C₃ carbides coexisted within the dendrites. As a result, the combined effects of martensitic transformation, ultrafine carbide precipitations, and dislocation strengthening result in the secondary hardening of the laser melted layer when the samples were tempered at 560 °C.     

Cyclic behaviour of 12% Cr ferritic‐martensitic steel upon long‐term on‐site service in power plants

The strain‐controlled and stress‐controlled low‐cycle fatigue behaviour of served 12% Cr ferritic–martensitic steel is conducted at room temperature. Continuous softening is observed at both control modes, and the fitting results show that the fatigue properties of 12% Cr steel are not reduced significantly after 230 000 h service at 550 °C/13.7 MPa. Scanning electron microscopy has been employed to investigate the microstructure evolution after long‐term service. It is proved that the decomposition of martensite laths structure and the coarsening of carbides at grain/lath boundaries are the main reasons why the pipe bursts after 180 000 h service at 550 °C/17.1 MPa. The fracture under both control modes has been observed by using scanning electron microscopy, and it indicates coarse carbides along grain/lath boundaries are favourable sites for micro‐crack nucleation and the secondary cracks along the fatigue striations are formed by the connection of micro‐cracks nucleated during fatigue behaviour.     

Microstructural evolution in bainite,martensite, and δ ferrite of low activation Cr–2W ferritic steels

Abstract

The microstructural evolution in (2–15)Cr–2W–0·1C (wt-%) firritic steels after quenching, tempering, and subsequent prolonged aging was investigated, using mainly transmission electron microscopy. The steels examined were low induced radioactivation ferritic steels for fusion reactor structures. With increasing Cr concentration, the matrix phase changed from bainite to martensite and a dual phase of martensite and δ ferrite. During tempering, homogeneous precipitation of fine W₂C rich carbides occurred in bainite and martensite, causing secondary hardening between 673 and 823 K. With increasing tempering temperature, dislocation density decreased and carbides had a tendency to precipitate preferentially along interfaces such as bainite or martensite subgrain boundaries. During aging at high temperature, carbides increased in size and carbide reaction from W₂C and M₆C to stable M₂₃C₆ occurred. No carbide formed in δ ferrite. The precipitation sequence of carbides was analogous to that in conventional Cr–Mo steels.

MST/1049     

Microstructural characterisation of vacuum sintered T42 powder metallurgy high-speed steel after heat treatments

High-speed steel powders (T42 grade) have been uniaxially cold-pressed and vacuum sintered to full density. Subsequently, the material was heat treated following an austenitising + quenching + multitempering route or alternatively austenitising + isothermal annealing. The isothermal annealing route was designed in order to attain a hardness value of ～50 Rockwell C (HRC) (adequate for structural applications) while the multitempering parameters were selected to obtain this value and also the maximum hardening of the material (～66 HRC). Microstructural characterisation has been carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The microstructure consists of a ferrous (martensitic or ferritic) matrix with a distribution of second phase particles corresponding to nanometric and submicrometric secondary carbides precipitated during heat treatment together with primary carbides. The identification of those secondary precipitates (mainly M₃C, M₆C and M₂₃C₆ carbides) has allowed understanding the microstructural evolution of T42 high-speed steel under different processing conditions.     

Development of microstructure during heat treatment of high carbon Cr–Mo steel

Abstract

Stainless steels containing enhanced chromium and carbon contents are particularly attractive for applications requiring improved wear and corrosion resistance. The as cast microstructure of such steels is composed mainly of ferritic matrix along with a network of interdendritic primary carbides. It has been shown that heat treatment of these steels results in microstructures that contain more than one type of carbide. A selective dissolution technique has been employed to isolate carbides from the matrix. Scanning electron microscope and X-ray diffraction studies of the as cast steels have shown that the primary carbides are essentially of M₇C₃ type, whereas in heat treated specimens both M₇C₃ (primary) and M₂₃C₆ (secondary) type carbides have been observed. The relative amounts of these carbides are found to be dependent on the heat treatment temperature. In addition, nucleation of austenite occurs above 950°C and at ～1250°C the matrix transforms entirely to austenite, which is retained completely on quenching to room temperature.     

High temperature stability of 2.25Cr-1Mo steel during creep

The creep rapture behaviour of 2.25Cr—1Mo steel in air and in a salt mixture was studied. The salt coating, which can form a liquid phase at the test temperatures, increased the creep rate and reduced the rupture life of the material. The coating reduced the available cross-section of the material by removing the surface layers, thereby resulting in a reduction of the rupture life. Cross-sections of coated samples showed an outer oxide layer comprising oxide of the metal and precipitates of sulphide at the metal/oxide interface. This subsurface penetration of the corrodants was responsible for the early failure of the coated samples. This is typical of hot corrosion mechanisms. The formation of various carbides like M₂₃C₆ and M₆C, as observed by transmission electron microscopy, during creep reduced the creep strength of the material both in air and in the coated state. Increasing temperature enhanced the formation of these carbides with a consequent decrease in creep strength. Applied stress did not seem to play much of a role in the degree of carbide precipitation.     

Teilkohärente Ausscheidungen in einer Eisen‐Chrom‐Kohlenstoff‐Legierung

Semicoherent precipitates in a Fe‐Cr‐C alloy Precipitation processes in ferromagnetic materials can be recorded very well by measuring the sensitive coercive field strength. It should be tested, whether also semicoherent precipitates have a sufficient clear interaction with Bloch‐walls. For this purpose the mild‐magnetic alloy X1FeCr25 served. To carry out the evidence sensitively, a method based on differences between H_C^t (heat‐treated state at T = 600…︁700°C) – H_C⁰ (quenched state from high temperature) = Δ H_C was used. A quantitative record of the amount of precipitates (as particle size) is possible by a decomposition parameter Δ H_C/Δ t. Plate‐like β′‐precipitates with planes {100}∥{100} in the α‐Fe solid solution have been proved by transmission electron microscopic investigations; this is the preparation state for the transition into the stable fcc phase M₂₃C₆. As a result, the quantitative electron microscopic proof of the β′‐phase can be supported by magnetic measurements, qualitatively and quantitatively. The estimated values of the activation energy for the process in the 1st maximum of precipitation in X1FeCr25 are higher than for the stable phases as the orthorhombic M₃C or the cubic complex M₆C in other steels and give a hint to the difficult processes related to nucleation as to the transition into M₂₃C₆.     

Towards improved ODS steels: A comparative high‐temperature low‐cycle fatigue study

Within the frame of this work, the mechanical behaviour of a bimodal ferritic 12Cr‐ODS steel as well as of a ferritic‐martensitic 9Cr‐ODS steel under alternating load conditions was investigated. In general, strain‐controlled low‐cycle fatigue tests at 550°C and 650°C revealed similar cyclic stress response. At elevated temperatures, the two steels manifest transitional stages, ie, cyclic softening and/or hardening corresponding to the small fraction of the cyclic life, which is followed by a linear cyclic softening stage that occupies the major fraction of the cyclic life until failure. However, it is clearly seen that the presence of the nano‐sized oxide particles is certainly beneficial, as the degree of cyclic softening is significantly reduced compared with non‐ODS steels. Besides, it is found that both applied strain amplitude and testing temperature show a strong influence on the cyclic stress response. It is observed that the degree of linear cyclic softening in both steels increases with increasing strain amplitude and decreasing test temperature. The effect of temperature on inelastic strain and hence lifetime becomes more pronounced with decreasing applied strain amplitude. When analysing the lifetime behaviour of both ODS steels in terms of inelastic strain energy calculations, it is found that comparable inelastic strain energies lead to similar lifetimes at 550°C. At 650°C, however, the higher inelastic strain energies of 12Cr‐ODS steel result in significant lower lifetimes compared with those of the 9Cr‐ODS steel. The strong degradation of the cyclic properties of the 12Cr‐ODS steel is obviously linked to the fact that the initial hardening response appears significantly more pronounced at 650°C than at 550°C. Finally, the obtained results depict that the 9Cr‐ODS steel offers higher number of cycles to failure at 650°C, compared with other novel ODS steels described in literature.     

Quantification of precipitates in a 10%Cr steel using TEM and EFTEM

Abstract

Modern (9–12)%Cr steels designated for power plants with higher steam parameters show a pronounced time dependent change in microstructure during purely thermal or creep stress exposure at temperatures around 600°C that determines their properties in service. In addition to other microstructural parameters, the state of the precipitates plays an important role for microstructural stability which is a prerequisite for long term creep strength. In order to support theoretical studies on precipitation growth and coarsening with more reliable experimental data, in this study a method is introduced for the quantification of the state of precipitates in (9–12)%Cr steels which is based on the application of different TEM methods. Therefore up to about 33 000 h aged specimens of the martensitic cast alloy G-X12CrMoWVNbN-10-1-1 were investigated by means of electron microscopy. The application of energy filtering transmission electron microscopy (EFTEM) allowed a reliable quantitative distinction between M₂₃C₆, VN, and Laves phases to establish the size distribution of these precipitates in different specimens conditions.     

Decarburization in 0·5Cr–0·5Mo–0·25V steel and its effects on creep and microstructure

Abstract

Many high–temperature creep tests are performed on low–chromium, ferritic steels in an uncontrolled atmosphere. Examination of creep rupture specimens of 0·5Cr–0·5Mo–0·25V steel tested in air has shown that decarburization accompanies oxidation and is an important factor in accelerating the failure of creep tests in air. Similarly, pre-aging in air reduces the creep life more than pre-aging in a capsule. There is also evidence that decarburization is accelerated during straining. Measurements of surface carbon contents in 10 mm thick blocks heat treated in air at 600–700°C have given an apparent activation energy for decarburization of about 250 kJ mol^?1, at least twice that for carbon diffusing in ferrite. However, this value is still below that for creep, so the influence of decarburization on creep life is expected to increase at lower temperatures. Structural observations are discussed in relation to loss of carbon and are related to creep behaviour. Secondary precipitation was observed after low-temperature treatments in aged encapsulated specimens, but not in specimens aged in air. This is attributed to the loss of carbon in the air aged specimens, which also showed a decrease in the M₃C content. The iron content of M₃C particles depends on carbon content as well as aging time.

MST/40