Optimisation of long-term creep strength of martensitic steels

Besides the reduction of greenhouse gases the increase of thermal efficiency is one of the major goals in modern material development for process and power plants. Increasing the steam inlet temperatures and pressures is at present the favoured method to increase the thermal efficiency. For the realization of 700°C power plants, new creep resistant ferritic-martensitic 9–12 wt. % Cr steels are required to be applied in the 650°C temperature range. An important task for the optimization of long term creep properties is the characterization of the changes in the microstructure during creep exposure. A sufficient long term creep strength is based on a small initial size and slow coarsening of the M₂₃C₆ precipitates as well as the dynamic precipitation of small V(C, N) particles along with the absence of Z-phase. The paper describes the R&D activities of the MPA University of Stuttgart in the frame work of national and international research projects aimed at the development and long term characterisation of optimised martensitic steels with higher long term creep strength.     

Creep deformation properties of creep strength enhanced ferritic steels

Creep deformation properties of creep strength enhanced ferritic steels were investigated. Good linear relationships between creep strain vs. time and creep rate vs. time were observed within a transient stage in a double logarithmic plot. It was appropriately expressed by a power law rather than exponential law, logarithmic law and Blackburn’s equation. With decrease in stress, a magnitude of creep strain at the onset of accelerating creep stage decreased from about 2% in the short-term to less than 1% in the long-term. Life fraction of the time to specific strain of 1% creep strain and 1% total strain, to time to rupture tended to increase with decrease in stress. A time to 1% total strain, that is a parameter for design of high temperature components, was observed in the transient creep stage in the short-term regime, however, it shifted to the accelerating creep stage in the long-term regime. Difference in stress dependence of the minimum creep rate was observed in the high- and low-stress regimes with a boundary condition of 50% of 0.2% offset yield stress. Stress dependence of the minimum creep rate in the high stress regime was equivalent to a strain rate dependence of flow stress observed in tensile test, and a magnitude of stress exponent, n, in the high stress regime decreased with increase in temperature from 20 at 550°C to 10 at 700°C. On the other hand, n value in the low stress regime was about 5, and creep deformation in the low stress regime was considered to be controlled by dislocation climb.     

Microstructure characteristics of 12Cr ferritic/martensitic steels with various yttrium

12Cr ferritic/martensitic steels with 0, 0.1 wt%, 0.2 wt% and 0.3 wt% theoretical yttrium(Y) additions were fabricated by vacuum inducting melting and casting method. Solubilities of Y in the 12Cr steels are0.027, 0.078 and 0.17 for 12Cr-0.1 Y, 12Cr-0.2 Y and 12Cr-0.3 Y, respectively. Phase transformations and microstructure characteristics under different heat-treatment schedules were investigated. The starting temperature of ferrite-to-austenite transformation A~(c1) are maintained about 850℃, but the finishing temperature of ferrite-to-austenite transformation A~(c3) are about 950, 970, 980 and 1000℃ for 12Cr-0 Y,12Cr-0.1 Y, 12Cr-0.2 Y and 12Cr-0.3 Y, respectively, which indicates that A~(c3) increases gradually with the addition of Y. Martensite accompanied with a few δ-ferrite is the dominant structure in all the steels. The amount of δ-ferrite shows a strong dependence with the Y content and austenitizing temperature. Area fraction of δ-ferrite increases with the content of Y, which is the ferrite favouring element. The minimum amount of δ-ferrite are achieved at 950℃ for 12Cr-0 Y, 12Cr-0.1 Y, 12Cr-0.2 Y and 1000℃ for 12Cr-0.3 Y.Besides, more carbides precipitate along the martensite laths and grain boundaries in the Y-bearing steel due to the redistribution of carbon between austenite and ferrite resulting from the ferrite favouring element of Y.     

Prospects for 12Cr martensitic creep resistant steels for 650℃steam power plant

In the last three decades new stronger modified 9%Cr steels have been introduced in new power plants with steam parameters up to 300 bar(1 bar =10~5 Pa) and 600℃. In order to further increase the steam parameters of steel based power plants up to a target value of 650℃/ 325 bar it is necessary to double the creep strength compared with todays strongest 9%Cr steels,and at the same time the resistance against steam oxidation must be improved by adding 12%Cr to the steel. However,so far all attempts to make stronger 12%Cr steels have been unsuccessful because the high chromium content introduced severe microstructure instabilities in the tested steels.Recently,it was found that the microstructure instabilities in 11%- 12%Cr steels can be explained by the precipitation of coarse Cr(V,Nb)N Z-phases, which dissolve fine(V,Nb)N nitrides. A new possibility to use the Z-phase for strengthening of 12%Cr steels has been identified,and the development of stable strong martensitic 12%Cr steels based on this concept is expected to allow the construction of 325 bar/ 650℃steam power plants all based on steel.     

Contributions from research on irradiated ferritic/martensitic steels to materials science and engineering

Ferritic and martensitic steels are finding increased application for structural components in several reactor systems. Low-alloy steels have long been used for pressure vessels in light water fission reactors. Martensitic stainless steels are finding increasing usage in liquid metal fast breeder reactors and are being considered for fusion reactor applications when such systems become commercially viable. Recent efforts have evaluated the applicability of oxide dispersion-strengthened ferritic steels. Experiments on the effect of irradiation on these steels provide several examples where contributions are being made to materials science and engineering. Examples are given demonstrating improvements in basic understanding, small specimen test procedure development, and alloy development. This paper is based on a presentation made in the symposium “Irradiation-Enhanced Materials Science and Engineering” presented as part of the ASM INTERNATIONAL 75th Anniversary celebration at the 1988 World Materials Congress in Chicago, IL, September 25–29, 1988, under the auspices of the Nuclear Materials Committee of TMS-AIME and ASM-MSD.     

Contributions from research on irradiated ferritic/martensitic steels to materials science and engineering

Ferritic and martensitic steels are finding increased application for structural components in several reactor systems. Low-alloy steels have long been used for pressure vessels in light water fission reactors. Martensitic stainless steels are finding increasing usage in liquid metal fast breeder reactors and are being considered for fusion reactor applications when such systems become commercially viable. Recent efforts have evaluated the applicability of oxide dispersion-strengthened ferritic steels. Experiments on the effect of irradiation on these steels provide several examples where contributions are being made to materials science and engineering. Examples are given demonstrating improvements in basic understanding, small specimen test procedure development, and alloy development. This paper is based on a presentation made in the symposium “Irradiation-Enhanced Materials Science and Engineering” presented as part of the ASM INTERNATIONAL 75th Anniversary celebration at the 1988 World Materials Congress in Chicago, IL, September 25–29, 1988, under the auspices of the Nuclear Materials Committee of TMS-AIME and ASM-MSD.     

Microstructure characteristics of 12Cr ferritic/martensitic steels with various yttrium additions

12Cr ferritic/martensitic steels with 0, 0.1 wt%, 0.2 wt% and 0.3 wt% theoretical yttrium (Y) additions were fabricated by vacuum inducting melting and casting method. Solubilities of Y in the 12Cr steels are 0.027, 0.078 and 0.17 for 12Cr-0.1Y, 12Cr-0.2Y and 12Cr-0.3Y, respectively. Phase transformations and microstructure characteristics under different heat-treatment schedules were investigated. The starting temperature of ferrite-to-austenite transformation A_c1 are maintained about 850 °C, but the finishing temperature of ferrite-to-austenite transformation A_c3 are about 950, 970, 980 and 1000 °C for 12Cr-0Y, 12Cr-0.1Y, 12Cr-0.2Y and 12Cr-0.3Y, respectively, which indicates that A_c3 increases gradually with the addition of Y. Martensite accompanied with a few δ-ferrite is the dominant structure in all the steels. The amount of δ-ferrite shows a strong dependence with the Y content and austenitizing temperature. Area fraction of δ-ferrite increases with the content of Y, which is the ferrite favouring element. The minimum amount of δ-ferrite are achieved at 950 °C for 12Cr-0Y, 12Cr-0.1Y, 12Cr-0.2Y and 1000 °C for 12Cr-0.3Y. Besides, more carbides precipitate along the martensite laths and grain boundaries in the Y-bearing steel due to the redistribution of carbon between austenite and ferrite resulting from the ferrite favouring element of Y.     

A new model-based creep equation for dispersion strengthened materials

The strongly stress-sensitive and temperature-dependent creep behaviour of dispersion strengthened materials cannot be described satisfactorily by current creep laws. In this paper a new creep equation is developed which considers as the rate-controlling event the thermally activated detachment of dislocations from dispersoid particles exerting an attractive force. The approach is motivated by recent TEM observations and theoretical calculations which strongly suggest that the “classical” view, according to which particles merely force dislocations to climb around them, is inadequate. The creep equation is applied to a dispersion-strengthened superalloy, two aluminium alloys and bubble-strengthened tungsten. Practical conclusions, regarding the optimum dispersoid size and alloy development, are drawn.     

Evolution of dislocation structure in martensitic steels: the subgrain size as a sensor for creep strain and residual creep life

The results on the evolution of the dislocation structure in martensitic CrMoV-steels published by two research groups are shown to be consistent: The steady state dislocation spacings vary in inverse proportion to shear modulus normalized stress, the subgrains grow with strain at a rate which is determined by the initial subgrain size w₀, the steady state subgrain size w_∞ and the strain rate, independent of the composition of the material. At constant stress and temperature the strain ? and the subgrain size w are uniquely related by ? = ?_wln[log(w₀ / w_∞)/log(w / w_∞)] with ?_w = 0.12. Thus w can be used as a sensor for strain and, if the relation between strain and time is known, for the residual creep life.     

The effect of temperature and microstructure on the creep damage found in low alloy ferritic steels

Constant strain rate tests at 10^-5 s^-1 have been carried out in the temperature range 723 to 973 K on two 1 1/2 pct Cr · 1/2 pct V ferritic steels, the first steel with a 20 pct bainite, 80 pct ferrite microstructure and the second with a fully ferritic structure. Measurements of the quantitative strain, ε_gb, due to grain boundary sliding (gbs), were made and in both steels the γ values (where γ = ε_gb/ε_T) increased with increasing temperature. In both structures, sliding was found to occur on all boundaries. A qualitative study of cavitation damage and final fracture mechanisms was also made. It is suggested that in the mixed structure, cavities are nucleated by gbs at carbides whereas in the fully ferritic structure, cavity nucleation is by the interaction of intragranular slip with a grain boundary. Optical observations showed that the large scale cavitation behavior was superficially very similar in both steels, but scanning electron microscope observations showed remarkable differences in the fine scale cavitation damage. The implications of these results are discussed in terms of the relationship between matrix deformation, grain boundary deformation and creep fracture. Formerly of the Department of Metallurgy, University of Manchester.     

Weldable and corrosion-resistant ferritic stainless steels

High-chromium ferritic stainless steels have been little used as materials of construction because they lose their corrosion resistance and ductility when welded. Good as-welded properties depend on controlling interstitial carbon and nitrogen. Three methods of achieving such control are described: 1) reducing the interstitials to critical low levels; 2) including weld ductilizing additives, which “soften” the matrix; 3) using additives to complex the interstitials. The third method is particularly useful, since it eases the requirements for raw-material purity and melting techniques to control carbon and nitrogen. This paper is based on a presentation made at a symposium on “New Developments in Ferritic and Duplex Stainless Steels,” held at the Fall Meeting in Cleveland, Ohio, on October 19, 1972, under the sponorship of the Corrosion Resistant Metals Committee of TMS-IMD and the Corrosion and Oxidation Activity of the ASM.     

Embrittlement of ferritic stainless steels

The mechanical properties and microstructures of commercial 11 to 29 pct Cr ferritic steels were examined as functions of aging times to 1000 h at 371, 482, and 593°C. Of the properties evaluated, changes in impact transition temperatures were the best measure of embrittlement. Embrittlement at 482°C occurs most rapidly in the 29 pct Cr alloy and somewhat more slowly in the stabilized 26 pct Cr alloy. The stabilized 18 pct Cr alloy embrittles much more slowly while little, if any, embrittlement was detected in a stabilizedll pct Cr alloy. Embrittlement at 482°C was characterized by a rapid change in properties followed by a plateau region and then further property changes. The early property change is attributed to precipitation of interstitial compounds and the later change to classic 475°C embrittlement. The onset of 475°C embrittlement in the two highest Cr alloys was accompanied by clustering of Cr atoms along {100} planes indicative of spinodal decomposition. Concurrent with clustering there was also a change from turbulent slip to a more planar slip along {110} planes. Some embrittlement was observed after longer exposures at 371°C which was attributed to a combination of 475°C embrittlement and the precipitation of interstitial compounds. Two of the alloys also embrittled at 593°C, accompanied by optically observable precipitates. The precipitate in the stabilized 18 pct Cr alloy was identified as Laves (Fe₂Ti) phase. One of the precipitates in the 29 pct Cr alloy was identified as sigma phase. Formerly with Allegheny Ludlum Steel Corporation.     

The effect of fine precipitate particles on the creep behaviour of ferritic model steels -I. Experiments

In view of efforts to develop ferritic creep resistant steels for applications above 600°C the effect of fine precipitate particles on the creep behaviour of ferritic model steels was studied as a function of stress, temperature and particle distribution. The chosen model steels contained 20% Cr (by mass), up to 0.9% Nb and up to 0.1 % C to produce NbC volume fractions up to 0.8% with particle sizes of about 0.1 μm (order of magnitude). The alloys and structures are briefly described (NbC solubility, precipitation and ageing behaviour, recrystallization and grain growth, oxidation resistance) as well as the mechanical short-term behaviour. The creep behaviour was studied between 600°C and 800°C (with emphasis on 700°C) at strain rates between 10^?11 and 10^?6 s^?1 with times to rupture up to 20000 h. The creep resistance of the model steels at 700°C (for a strain rate of 10^?8s^?1) increases with increasing NbC content from about 5 MN/m² for the alloy without NbC to about 50 MN/m² for the alloys with 0.6% or 0.8% NbC. The analysis of the obtained results is the subject of the second part of this report.     

Ferritic/martensitic steels for advanced nuclear reactors

Design concepts for the next generation of nuclear power reactors include water-cooled, gas-cooled, and liquid-metal-cooled reactors. Reactor conditions for several designs offer challenges for engineers and designers concerning which structural and cladding materials to use. Depending on operating conditions, some designs favor elevated-temperature ferritic/martensitic steels for in-core and out-of core applications. Such steels have been investigated in previous work on international fast reactor and fusion reactor research programs. Steels from these fission and fusion programs will provide reference materials for future fission applications. In addition, new elevated-temperature steels have been developed in recent years for conventional power systems that also need to be considered.     

A creep technique for monitoring MnS precipitation in Si steels

A newly developed creep method is described for investigating the kinetics of manganese sulfide precipitation in two Si steels at hot working temperatures. The method was also applied to a Ti steel, in which the precipitation kinetics were previously determined using a stress relaxation technique. Prior to loading, the specimens are solution-treated for half an hour and then immediately cooled to the test temperature. A constant stress is applied to the sample by means of a computerized MTS machine, and the strain is recorded continuously during testing. The resulting creep rate is sensitive to the occurrence of precipitation; thus, the slope of the true strain-log (time) curve decreases immediately after the initiation and increases on the completion of precipitation. The precipitation-time-temperature (PTT) diagrams determined in this way on the three tested steels are of classical C shape. Because higher dislocation densities and internal stress levels are maintained, the present technique is more effective for monitoring the precipitation events occurring in both austenitic and ferritic phases than the previously developed stress relaxation method. formerly with the Department of Metallurgical Engineering, McGill University.     

Grain structure of bainitic and martensitic steels

In contrast to austenitic and ferritic microstructures, in the case of bainite and martensite the identification of that structural unit representing a grain is less straightforward. There is a general agreement in the literature that the γ → α-transformation follows the Kurdjumow-Sachs relationship (KSR). For the complex microstructures resulting, however, the investigations include practically exclusively lath-type structures. These relatively simple structures may be described as follows. Within the original austenite grain there are several lath packets with only a few variants of the KSR occuring within one bainite or martensite packet. Opinions diverge with regard to the relative orientations within a packet and thus the type of grain boundaries occurring. Most authors, however, agree that a micro-structural unit – such as the grain in the ferrite structure – which determines both the yield strength and toughness properties, does not exist in lath-type structures, and that the yield strength mainly depends on the lath dimensions. The toughness properties, especially the transition temperature, are governed by the packet size, and possibly by the width of the co-variant packet.