Search Results for strengthening

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.

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

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

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

The development of materials technologies for piping and tubing in advanced ultrasupercritical (A-USC) power plants operating at steam temperatures above 700°C represents a critical engineering challenge. The 23Cr-45Ni-7W alloy (HR6W), originally developed in Japan as a high-strength tubing material for 650°C ultra-supercritical (USC) boilers, was systematically investigated to evaluate its potential for A-USC plant applications. Comparative research with γ-strengthened Alloy 617 revealed that the tungsten content is intimately correlated with Laves phase precipitation and plays a crucial role in controlling creep strength. Extensive creep rupture tests conducted at temperatures between 650-800°C for up to 60,000 hours demonstrated the alloy's long-term stability, with 105-hour extrapolated creep rupture strengths estimated at 88 MPa at 700°C and 64 MPa at 750°C. Microstructural observations after creep tests and aging confirmed the material's microstructural stability, which is closely linked to long-term creep strength and toughness. While Alloy 617 exhibited higher creep rupture strength at 700 and 750°C, the materials showed comparable performance at 800°C. Thermodynamic calculations and microstructural analysis revealed that the Laves phase in HR6W gradually decreases with increasing temperature, whereas the γ' phase in Alloy 617 rapidly diminishes and almost completely dissolves at 800°C, potentially causing an abrupt drop in creep strength above 750°C. After comprehensive evaluation of creep properties, microstructural stability, and other reported mechanical characteristics, including creep-fatigue resistance, HR6W emerges as a promising candidate for piping and tubing in A-USC power plants.

The creep resistance of 9-12% Cr steels is significantly influenced by the presence and stability of different precipitate populations. Numerous secondary phases grow, coarsen and, sometimes, dissolve again during heat treatment and service. Based on the software package MatCalc, the evolution of these precipitates during the thermal treatment of the COST 522 steel CB8 is simulated from the cooling process after cast solidification to heat treatment and service up to the aspired service life time of 100.000h. On basis of the results obtained from these simulations in combination with a newly implemented model for evaluation of the maximum threshold stress by particle strengthening, the strengthening effect of each individual precipitate phase, as well as the combined effect of all phases is evaluated - a quantification of the influence of Z-Phase formation on the long-term creep behaviour is thus made possible. This opens a wide field of application for alloy development and leads to a better understanding of the evolution of microstructural components as well as the mechanical properties of these complex alloys.

Ferritic 9-12 wt.% chromium steels are commonly used for thick-walled high-temperature components in thermal power plants, but they face two major limitations in high-temperature service. Firstly, a reduction in creep strength occurs after approximately 10,000 hours at service temperatures around 600°C, due to the dissolution of finely dispersed V-rich nitrides and the precipitation of coarse particles of the modified Z-phase, [(Cr,V,Nb)N]. Secondly, welded joints of nearly all ferritic steel grades are prone to premature creep failures in the fine-grained heat-affected zone, known as Type IV cracking, which results from a strength loss of up to 50% compared to the base material. This study describes the development of a 9Cr3W3CoVNb steel with added boron and controlled nitrogen content. Preliminary creep testing results up to 24,000 hours at 650°C show a significant improvement in creep strength compared to established ferritic 9Cr grades like P91 and P92, attributed to a reduced driving force for the precipitation of modified Z-phase particles. Crosswelds of the new 9Cr3W3CoVNbBN steel also demonstrate improved creep behavior at 650°C, with creep rupture strength comparable to the mean base material creep strength of the best commercially available grade P92.

In this study, the role of minor alloying additions in 347H stainless steels (UNS34709, ASTM A240/240M) on creep-rupture properties at 650-750°C and microstructure evolution during isothermal exposure at 750°C has been investigated, aiming to provide the experimental dataset as boundary conditions of physics-based modeling for material/component life prediction. Four different 347H heats containing various amounts of boron and nitrogen additions were prepared and evaluated. The combined additions of B and N are found to stabilize the strengthening secondary M 23 C 6 carbides and retarding the transition from M 23 C 6 to sigma phase precipitates during thermal exposure. The observed kinetics of microstructure evolution reasonably explains the improvement of creep-rupture properties of 347H stainless steels with the B and N additions.

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.

In this work, the effects of phosphorus addition on the creep properties and microstructural changes of wrought γ’-strengthened Ni-based superalloys (Haynes 282) were investigated, focusing on the effects of carbides precipitation. In an alloy with a phosphorus content of 8 ppm, precipitation of M 23 C 6 carbides was observed in both grain boundaries and the grain interior prior to the creep tests. Grain boundary coverage by carbide increased with phosphorus content up to approximately 30 ppm. On the other hand, the amount of M 23 C 6 in the grain interior decreased with phosphorus content. The results of the creep tests revealed the relationship between the time to rupture and the grain boundary coverage by carbides. The microstructure of the crept specimens showed the existence of misorientation at the vicinity of grain boundaries without carbides, as demonstrated via electron backscattered diffraction (EBSD) analysis. These results suggest that the observed improvement in the time to rupture is due to a grain-boundary precipitation strengthening mechanism caused by grain boundary carbides and that phosphorus content affects the precipitation behavior of M 23 C 6 carbides in the grain interior and grain boundaries. These behaviors were different between alloys with the single addition of phosphorus and alloys with the multiple addition of phosphorus and niobium.

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

By utilizing computational thermodynamics in a Design of Experiments approach, it was possible to design and manufacture nickel-base superalloys that are strengthened by the eta phase (Ni3Ti), and that contain no gamma prime (Ni3Al,Ti). The compositions are similar to NIMONIC 263, and should be cost-effective, and have more stable microstructures. By varying the aging temperature, the precipitates took on either cellular or Widmanstätten morphologies. The Widmanstätten-based microstructure is thermally stable at high temperatures, and was found to have superior ductility, so development efforts were focused on that microstructure. High temperature tensile test and creep test results indicated that the performance of the new alloys was competitive with NIMONIC 263. SEM and TEM microscopy were utilized to determine the deformation mechanisms during creep.

Alumina-forming austenitic stainless steels (AFAs) are potential materials for boiler/steam turbine applications in next generation fossil fuel power plants. They display a combination of good high temperature creep strength, excellent oxidation resistance and low cost. A recently-developed AFA alloy based on Fe-14Cr-32Ni-3Nb-3Al-2Ti (wt.%) shows better creep performance than a commercially-available Fe-based superalloy. In this paper we used scanning electron microscopy and transmission electron microscopy to study the fracture surfaces and cracking behavior in relation to the precipitates present in creep failure samples of this alloy tested at either 750°C/100 MPa or 700°C/170 MPa. It was found that most cracks are formed along the grain boundaries with precipitate-free zones beside the grain boundaries potentially providing the path for propagation of cracks.

Martensitic 9Cr steels have been developed which are strengthened by boron in order to stabilize the microstructure and improve their long-term creep strength. Boron plays a key role in these steels by stabilising the martensitic laths by decreasing the coarsening rate of M 23 C 6 carbides, which act as pinning points in the microstructure. In this work two modified FB2 steel forgings are compared. Both forgings have similar compositions but one underwent an additional remelting process during manufacture. Creep tests showed that this additional processing step resulted in a significant increase in time to failure. In order to investigate the effect of the processing route on microstructural evolution during aging and creep, a range of advanced electron microscopy techniques have been used including ion beam induced secondary electron imaging and High Angle Annular Dark Field (HAADF) imaging in the Scanning Transmission Electron Microscope. These techniques have enabled the particle population characteristics of all the second phase particles (M 23 C 6 , Laves phase, BN and MX) to be quantified for materials from both forging processes. These quantitative data have enabled a better understanding of how the processing route affects the microstructural evolution of FB2 steels.

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.

Prior to utilizing new advanced materials in coal power plants, a large number of experimental testing is required. Test procedures are needed in specialized high temperature laboratories with state of the art facilities and precise, accurate analytical equipment capable of performing tests at a variety of temperatures and environments. In this study, the results of a unique technique involving salt spray testing at high temperatures are presented. The Haynes 282 gamma – prime (γ’) strengthened alloy fabricated by means of three different manufacturing processes: HAYNES 282 WROUGHT alloy, Haynes 282-SINT alloy, and finally Haynes 282-CAST alloy have been tested. The materials have been exposed to a salt spray corrosion atmosphere using 1% NaCl - 1% Na 2 SO 4 . Post exposure investigations have included SEM, EDS and XRD examinations. The test using salt spray of 1% NaCl - 1% Na 2 SO 4 water solution at 550 °C for 500 hours indicted no influence on the corrosion products formation, where Cr 2 O 3 has been developed in all three alloys, whereas NiO has been found only in Haynes 282-CAST material. On the other hand, it has been found that the fabrication process of HAYNES 282 alloy strongly influences the corrosion products formation under the high temperature exposures.

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

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.

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.

Recent advances in materials technology for boilers materials in the advanced USC (A-USC) power plants have been reviewed based on the experiences from the strengthening and degradation of long term creep properties and the relevant microstructural evolution in the advanced high Cr ferritic steels. P122 and P92 type steels are considered to exhibit the long term creep strength degradation over 600°C, which is mainly due to the instability of the martensitic microstructure strengthened too much by MX carbonitrides. This can be modified by reducing the precipitation of VN nitride and by optimizing the Cr content of the steels. An Fe-Ni based alloy, HR6W strengthened by the Fe2W type Laves phase is found to be a marginal strength level material with good ductility at high temperatures over 700°C and to be used for a large diameter heavy wall thick piping such as main steam pipe and hot reheat pipe in A-USC plants, while Ni-Co based alloys such as Alloys 617 and 263 strengthened by a large amount of the y’ phase are found to be the high strength candidate materials for superheater and reheater tubes, although they are prone to relaxation cracking after welding and to grain boundary embrittlement during long term creep exposure. A new Ni based alloy, HR35 strengthened by a-Cr phase and other intermetallic phases has been proposed for piping application, which is specially designed for a good resistance to relaxation cracking as well as high strength and a good resistance to steam oxidation and fire-side corrosion at high temperatures over 700°C.