Search Results for nitrogen

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.

Various carbon and nitrogen free martensitic alloys were produced for the application which required long time creep properties at high temperatures. But they were easy transformed to austenite phase before the creep tests because of low Ac1 temperature. In this paper, a new attempt has been demonstrated using carbon and nitrogen free austenitic alloys strengthened by intermetallic compounds. We choose Fe-12Ni-9Co-10W-9Cr-0.005B based alloy. Furthermore, we discussed about creep characteristics among the wide range of the testing conditions more over 700°C and steam oxidation resistance to confirm the possibility of the alloys for the future USC power plants under the severe environments.

For last half century the development of creep strength enhanced ferritic steels has been continued and presently ASME grades 91, 92 and 122 extremely stronger than conventional low alloy steels have extensively been used worldwide in high efficient power plants. However the use of these creep strength enhanced 9-12%Cr steels is limited to around 630°C or 650°C at maximum in terms of high temperature strength and oxidation resistance. Consequently the appearance of ferritic steels standing up to higher temperature of around 700°C to substitute of high strength austenitic steels is strongly desired. Under the state, the addition of high nitrogen to ferritic steels is attracting considerable attention because of improving high temperature strength and oxidation resistance of them. This work was done to evaluate the oxidation resistance of high nitrogen steels and to investigate the effect nitrogen and microstructure on oxidation resistance using 9-15%Cr steels with about 0.3% nitrogen manufactured by means of Pressurized Electro- Slag Remelting (PESR) method in comparison with ASME grades 91 and 122. As a result, high nitrogen ferritic steels showed excellent oxidation resistance comparing with nitrogen-free steels and ASME grades 91 and 122. The oxidation resistance of 9%Cr ferritic steels depends on the nitrogen content in the each steel. That is, the weight gain decreases with an increase in nitrogen content. Moreover, the oxide scale of high nitrogen steel contained a high concentration of Cr. It is conjectured that, in high temperature oxidation, nitrogen plays a key role in promoting the formation of the oxide scale which has high concentration of Cr, inhibiting oxidation from proceeding. And also it was found that the oxidation resistance of the high nitrogen steels does not depend greatly on Cr content but on their microstructure. The oxidation resistance of high nitrogen ferritic heat-resistant steels increased as the fraction of martensite structure increased. These results indicate for high nitrogen steels Cr diffusion along grain boundaries is further promoted resulting in the formation of protective oxide scale having high Cr concentration. Furthermore as new findings it was confirmed that the Cr diffusion in substrate of steels to form Cr concentrated oxide scale on the metal surface is accelerated by nitrogen while suppressed by carbon in matrix of steel.

9-12%Cr martensitic steels can be applied to the next highest temperature components such as boiler tracts, steam pipelines and turbines of advanced ultra-supercritical power plants with steam temperatures of 650°C. New 10%Cr martensitic steels with high B and low N contents can be a worthy candidate for use in production because it has superior creep resistance. At the same time, resistance to cyclic and dynamic loads is very important. In this work, we studied the low cycle fatigue (LCF) properties at room and elevated (500-650°C) temperatures and Charpy impact toughness at temperatures ranging from -196…100°C of advanced 10% Cr martensitic steel with high B and low N contents. The effect of new alloying scheme and corresponding peculiarities of M 23 C 6 carbides on the low cycle fatigue resistance and impact toughness of the 10%Cr martensitic steel is analyzed. It is revealed that fine and densely distributed carbides has no effect on the fatigue resistance except for the slight improvement of fatigue life at small strain amplitudes and shift the ductile-brittle transition temperature (DBTT) to higher but satisfactory value of +10°C as compared to other high-chromium martensitic steels.

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.

A novel salt-bath nitrocarburizing process recently developed forms a lithium-iron compound-oxide layer on the surface of steel in concurrence with a nitride layer by adding lithium ions to the molten salt. This process has already been successfully applied to mass-produced products. However, the microstructure and its formation process of the surface layer in alloyed steels during the nitrocarburizing process have not yet been fully understood. In this study, we focus on the effect of Si and Cr, which are included in a common die steel, on the microstructure of an oxide layer of a nitrocarburized alloy. The alloys used in this study are Fe-0.4wt%C, Fe-0.4wt%C-2.0wt%Si, and Fe-0.4wt%C-2.0wt%Cr. These alloys were arc melted into button ingots under an Ar atmosphere. The ingots were annealed at 1123 K for 1.0 h, followed by air cooling and double tempering at 873 K, similar to the heat treatments employed to hot-die steels. Salt-bath nitrocarburizing was carried out at 823 K for 0.1-10 h. The microstructures of the cross-sectional surface layers of the samples were examined using an optical microscope and FE-SEM. Elemental mapping as well as phase identification of the surface layers were done by EDS, XRD, and GD-OES. In the Fe-C binary alloy, a thin continuous oxide layer of α-LiFeθ 2 formed first on the outermost surface, and a thick iron nitride layer developed underneath the oxide layer, with aligned oxide particles along the grain boundaries of the nitrogen compound layer. In the case of Si addition, the outermost oxide layer became thinner and an additional oxide layer consisting of α-LiFeθ 2 and (Li,Fe) 3 Siθ 4 formed between the outer oxide layer and nitrogen compound layer, and the formation of the oxide particles in the nitrogen compound layer was fully suppressed. In the case of Cr addition, internal oxide particles formed in the nitrogen compound layer, similar to those in the binary steel, although an continuous oxide layer of CrfN,O) formed in between those layers. On the basis of these results, the inner oxide layer formed with Si addition contributes to improving the frictional wear characteristics in die steels.

Creep properties of 9Cr heat resistant steels can be improved by the addition of boron and nitrogen to produce martensitic boron-nitrogen strengthened steels (MarBN). The joining of this material is a crucial consideration in the material design since welds can introduce relatively weak points in the structural material. In the present study, creep tests of a number of MarBN weld filler metals have been carried out to determine the effect of chemistry on the creep life of weld metal. The creep life of the weld metals was analysed, and the evolution of creep damage was investigated. Significant differences in the rupture life during creep have been observed as a function of boron, nitrogen and molybdenum concentrations in the weld consumable composition. Although the creep lives differed, the particle size and number in the failed creep tested specimens were similar, which indicates that there is a possible critical point for MarBN weld filler metal creep failure.

Tempered martensitic 9-12%Cr steels bearing tungsten, such as P92 and P122 showing higher creep rupture strength than the conventional steel P91, have been developed for thick section components in ultra-supercritical (USC) boilers. However, their creep strength is not sufficient for applying at the steam condition of 650°C/35MPa or above, which is a recent target condition in order to increase plant efficiency. The research and development project in NIMS on advanced high-Cr steels which can be applied at the steam condition of 650°C/35MPa as boiler components with large diameter and thick section has been carried out since 1997. In this project, it has been revealed that the addition of boron more than 0.01 mass% to the 0.08C-9Cr- 3W-3Co-V,Nb-<0.00ЗN steel remarkably improves creep strength. The boron enriched in M 23 C 6 carbides near prior-austenite grain boundaries suppresses coarsening of these carbides during creep deformation, leading to excellent microstructural stability and creep strength. Further improvement of creep strength is achieved by the addition of appropriate amount of nitrogen which enhances precipitation of fine MX. Excess addition of nitrogen to the high-B containing steel reduces creep rupture lives and ductility. The highest creep strength is obtained in the 0.08C-9Cr-3W-3Co-0.2V-0.05Nb-0.0139B-0.0079N (mass%) steel, resulting in excellent creep strength in comparison with that of P92 and P122. This steel shows good creep ductility even in the long term. It is, therefore, concluded that this high-B bearing 9Cr-3W-3Co-V,Nb steel with the addition of nitrogen in the order of 0.008 mass% is the promising candidate which shows superior creep strength without impairing creep ductility for thick section components in the 650°C-USC plant.

Nitridation is a high-temperature material degradation issue that can occur in air and in environments containing nitrogen, ammonia, etc., and in a variety of industrial processes. The nitridation behavior of several commercial nickel- and cobalt-based alloys is reviewed in this paper. The alloys include Haynes 230, Haynes 188, Haynes 625, Haynes 617, Haynes 214, Hastelloy X, and Haynes 233. The environments discussed are high-purity nitrogen gas between 871°C and 1250°C, 100% ammonia gas at 982°C and 1092°C, and a simulated combustion atmosphere at 982°C. The results showed that nitridation occurred in all the environments containing nitrogen. The nitridation attack was strongly influenced by the alloy compositions and the type of oxide formed (i.e., chromia or alumina), as some degree of oxidation was expected in the environments in which residual oxygen was present. Thermal cycling is briefly discussed because the integrity of protective oxides is also an important factor in resisting high-temperature oxidation and nitridation attack.

The presented work summarizes the results of more than 10 years of research at TU Graz and TU Chemnitz and partners on a martensitic boron and nitrogen stabilized 9Cr3W3Co (MARBN) steel grade. The design philosophy of MARBN steels is presented and critical issues regarding boron and nitrogen balance are discussed. Microstructural characterization of two different laboratory heats, is presented and efforts in European projects towards an upscaling of melts are presented. Base material creep testing data at 650 °C up to 50.000 hours is presented and assessed to commercial alloys such as ASTM grades P91 and P92. An increase of creep rupture stress of more than +20% was recorded. Oxidation tests in steam at 650°C revealed an anomalous response of the material. Several specimens exhibited excellent oxidation resistance commonly only seen for grades of higher chromium content. The anomalous oxidation behaviour is identified and discussed, although the causes remain yet unclear. Results of manufacturing, characterization and testing of different MARBN welds, including gas-tungsten-arc-, gas-metal-arc-, friction stir and electron beam welds reveal a microstructure memory effect in the heat affected zone, so that no uniform fine-grained zone is present. The behaviour of crosswelds during long-term creep testing at 650 °C up to more than 32.000 hours is assessed and the susceptibility to Type IV cracking is discussed. The manuscript summarizes research of more than 10 years, presents current research activities on MARBN and describes open questions for an alloy identified as a promising martensitic steel grade for elevated temperature components.

The addition of boron without the formation of any boron nitrides during normalizing heat treatment at high temperature minimizes the degradation in creep strength of both base metal and welded joints of 9Cr steel at 650 °C and long times. The enrichment of soluble boron near prior austenite grain boundaries (PAGBs) by the segregation is essential for the reduction of coarsening rate of M 23 C 6 carbides in the vicinity of PAGBs, enhancing boundary and subboundary hardening, and also for the production of same microstructure between the base metal and heat-affected-zone (HAZ) in welded joints, indicating no Type IV fracture in HAZ. Excess addition of boron and nitrogen promotes the formation of boron nitrides during normalizing, which reduces the soluble boron concentration and accelerates the degradation in creep rupture ductility at long times. 9Cr- 3W-3Co-VNb steel with 120 - 150 ppm boron and 60 - 90 ppm nitrogen (MARBN) exhibits not only much higher creep strength of base metal than Gr.92 but also substantially no degradation in creep strength due to Type IV fracture at 650 °C. The pre-oxidation treatment in Ar gas promotes the formation of protective Cr 2 O 3 scale on the surface of 9Cr steel, which significantly improves the oxidation resistance in steam at 650 °C.

To enhance long-term creep strength at 650°C, stabilization of the lath martensitic microstructure near prior austenite grain boundaries has been investigated for a 9Cr-3W-3Co-0.2V-0.05Nb steel. This was achieved by adding boron to stabilize M 23 C 6 carbides and dispersing fine MX nitrides. Creep tests were conducted at 650°C for up to approximately 3 × 10 4 hours. Adding a large amount of boron exceeding 0.01%, combined with minimized nitrogen, effectively stabilized the martensitic microstructure and improved long-term creep strength. The amount of available boron, free from boron nitrides and tungsten borides, is crucial for enhancing long-term creep strength. Reducing the carbon concentration below 0.02% led to a dispersion of nano-sized MX nitride particles along boundaries and in the matrix, resulting in excellent creep strength at 650°C. A critical issue for the 9Cr steel strengthened by MX nitrides is the formation of Z-phase, which degrades long-term creep strength. Excess nitrogen additions of 0.07 and 0.1% promoted Z-phase formation during creep. The formation of a protective Cr-rich oxide scale was achieved through a combination of Si addition and pre-oxidation treatment in argon, significantly improving the oxidation resistance in steam at 650°C.

This study investigated the creep rupture strength and microstructure evolution in welded joints of high-boron, low-nitrogen 9Cr steels developed by NIMS. The welds were fabricated using the GTAW process and Inconel-type filler metal on steel plates with varying boron content (47-180 ppm). Creep rupture tests were conducted at 923K for up to 10,000 hours. Despite their higher boron content, these steels exhibited good weldability. Welded joints of the boron steel displayed superior creep properties compared to conventional high-chromium ferritic steel welds like P92 and P122. Notably, no Type IV failures were observed during creep testing. Welding introduced a large-grained microstructure in the heat-affected zone (HAZ) heated to the austenite transformation temperature (Ac3 HAZ). This contrasts with the grain refinement observed in the same region of conventional heat-resistant steel welds. Interestingly, the grain size in this large microstructure was nearly identical to that of the base metal. Analysis of the simulated Ac3 HAZ revealed crystal orientation distributions almost identical to those of the original specimen. This suggests a regeneration of the original austenite structure during the alpha-to-gamma phase transformation. Simulated Ac3 HAZ structures of the boron steel achieved creep life nearly equivalent to the base metal. The suppression of Type IV failure and improved creep resistance in welded joints of the boron steels are likely attributed to the large-grained HAZ microstructures and stabilization of M 23 C 6 precipitates. The optimal boron content for achieving the best creep resistance in welded joints appears to lie between 90 and 130 ppm, combined with minimized nitrogen content.

A 9Cr-3W-3Co-VNbBN steel, designated MARBN ( MAR tensitic 9Cr steel strengthened by B oron and N itrides), has been alloy-designed and subjected to long-term creep and oxidation tests for application to thick section boiler components in USC power plant at 650 o C. The stabilization of lath martensitic microstructure in the vicinity of prior austenite grain boundaries (PAGBs) is essential for the improvement of long-term creep strength. This can be achieved by the combined addition of 140ppm boron and 80ppm nitrogen without any formation of boron nitrides during normalizing at high temperature. The addition of small amount of boron reduces the rate of Ostwald ripening of M 23 C 6 carbides in the vicinity of PAGBs during creep, resulting in stabilization of martensitic microstructure. The stabilization of martensitic microstructure retards the onset of acceleration creep, resulting in a decrease in minimum creep rate and an increase in creep life. The addition of small amount of nitrogen causes the precipitation of fine MX, which further decreases the creep rates in the transient region. The addition of boron also suppresses the Type IV creep-fracture in welded joints by suppressing grain refinement in heat affected zone. The formation of protective Cr 2 O 3 scale is achieved on the surface of 9Cr steel by several methods, such as pre-oxidation treatment in Ar gas, Cr shot-peening and coating of thin layer of Ni-Cr alloy, which significantly improves the oxidation resistance of 9Cr steel in steam at 650 o C. Production of a large diameter and thick section pipe and also fabrication of welds of the pipe have successfully been performed from a 3 ton ingot of MARBN.

In thermal power plants, weldments of all currently used martensitic 9% chromium steels are prone to Type IV cracking in the fine-grained region of the heat-affected zone (HAZ). Japanese researchers have introduced a new martensitic steel for ultra-supercritical (USC) steam conditions that demonstrates resistance to Type IV cracking. This study compares a modified version of this boron-nitrogen balanced advanced 9Cr-3W-3Co steel with CB2, the most promising 9% Cr steel developed through the European research initiative COST, in terms of weldability. The HAZ was analyzed using the "Heat-Affected Zone Simulation" technique with a Gleeble 1500 thermo-mechanical simulator. Basic optical microscopy was complemented by advanced electron microscopy techniques, including energy-filtered TEM (EFTEM), electron energy loss spectroscopy (EELS), electron backscatter diffraction (EBSD), and energy-dispersive X-ray analysis (EDX). Phase transformations in the HAZ were directly observed using in situ X-ray diffraction with synchrotron radiation at the Advanced Photon Source (APS) of Argonne National Laboratory, IL, USA. Although both steels exhibited similar transformation behavior, their resulting microstructures after the weld thermal cycle differed significantly. At peak temperatures above 1200°C, delta ferrite formed and remained stable down to room temperature due to rapid cooling in both steels. While CB2 exhibited conventional coarse-grained (CG), fine-grained (FG), and intercritical HAZ regions, the boron-nitrogen balanced 9Cr steel did not develop a fine-grained HAZ. Since Type IV cracking primarily occurs in the FGHAZ, this alloy shows strong potential for eliminating Type IV cracking as a major life-limiting factor in heat-resistant steel weldments.

With nearly half of the world's electricity generation fueled by coal and an increasing focus on limiting carbon dioxide emissions, several technologies are being evaluated and developed to capture and prevent such emissions while continuing to use this primary fossil energy resource. One method aimed at facilitating the capture and processing of the resulting carbon dioxide product is oxy-combustion. With appropriate adjustments to the process, the approach is applicable to both new and existing power plants. In oxy-combustion, rather than introducing ambient air to the system for burning the fuel, oxygen is separated from the nitrogen and used alone. Without the nitrogen from the air to dilute the flue gas, the flue gas volume leaving the system is significantly reduced and consists primarily of carbon dioxide and water vapor. Once the water vapor is reduced by condensation, the purification and compression processes otherwise required for carbon dioxide transport and sequestration are significantly reduced. As an introduction to and overview of this technology, the paper summarizes the basic concepts and system variations, for both new boiler and retrofit applications, and also serves as an organized review of subsystem issues identified in recent literature and publications. Topics such as the air separation units, flue gas recirculation, burners and combustion, furnace performance, emissions, air infiltration issues, and materials issues are introduced.

In advanced ultra-supercritical (A-USC) power plants, which operate at steam temperatures of 700 °C or higher, there is a need to replace 9 to 12Cr martensitic steels with high-strength nickel-base superalloys or austenitic steels for components exposed to the highest temperatures. However, due to the high cost of nickel-base superalloys, it is desirable to use 9 to 12% Cr martensitic steels for components exposed to slightly lower temperatures, ideally expanding their use up to 650 °C. Key challenges in developing ferritic steels for 650 °C USC boilers include enhancing oxidation resistance and long-term creep rupture strength, particularly in welded joints where resistance to Type IV cracking is critical for constructing thick-section boiler components. The current research aims to investigate the creep deformation behavior and microstructure evolution during creep for base metals and heat-affected-zone (HAZ) simulated specimens of tempered martensitic 9Cr steels, including 9Cr-boron steel and conventional steels like grade 91 and 92. The study discusses the creep strengthening mechanisms and factors influencing creep life. It proposes an alloy design strategy that combines boron strengthening and MX nitride strengthening, avoiding the formation of boron nitrides during normalizing heat treatment, to improve the creep strength of both base metal and welded joints.

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.

Along with rapid development of thermal power industry in mainland China, problems in metal materials of fossil power units also change quickly. Through efforts, problems such as bursting due to steam side oxide scale exfoliation and blocking of boiler tubes, and finned tube weld cracking of low alloy steel water wall have been solved basically or greatly alleviated. However, with rapid promotion of capacity and parameters of fossil power units, some problems still occur occasionally or have not been properly solved, such as weld cracks of larger-dimension thick-wall components, and water wall high temperature corrosion after low-nitrogen combustion retrofitting.

In this study, a possibility of application of advanced 9%Cr steel containing 130 ppm boron for boiler components utilized at around 650 °C to higher temperature steam turbine rotor materials has been investigated by means of reduction in silicon promoting macro-segregation in the case of large size ingots, using laboratory heats. Tempered martensitic microstructure without proeutectoid ferrite in all steels studied is obtained even at the center position of a turbine rotor having a barrel diameter of 1.2 m despite lower amounts of nitrogen and silicon. The strength at room temperature is almost the same level of practical high Cr steels such as X13CrMoCoVNbNB 9-2-1 for ultrasuper critical steam turbine rotors. The toughness is sufficient for high temperature rotors in comparison with CrMoV steels utilized as sub-critical high pressure steam turbine components. The creep rupture strength of the steels is higher than that of the conventional 9-12Cr steels used at about 630 °C. The creep rupture strength of 9%Cr steel containing 130 ppm B, 95 ppm N, 0.07 % Si and 0.05 % Mn is the highest in the steels examined, and it is therefore a candidate steel for high temperature turbine rotors utilized at more than 630 °C. Co-precipitation of M 23 C 6 carbides and Laves phase is observed around the prior austenite grain boundaries after the heat treatments and the restraint of the carbide growth is also observed during creep exposure. An improvement in creep strength of the steels is presumed to have the relevance to the stabilization of the martensitic lath microstructure in the vicinity of those boundaries by such precipitates.