Search Results for oxidation behavior

For high-strength steels developed at the National Institute for Materials Science (NIMS) in Japan, a dispersion of nano-sized MX nitride particles along boundaries and in the matrix is achieved by reducing carbon concentration below 0.02%. This structure results in excellent creep strength at 923K, approximately two orders of magnitude longer rupture time than P92. Additionally, adding a large amount of boron exceeding 0.01% combined with minimized nitrogen effectively improves creep rupture strength by stabilizing the martensitic microstructure during creep. Efforts have been made to enhance the steam oxidation resistance of these 9Cr steels strengthened by boron and fine MX nitrides. A combination of 0.7% Si, 40-60 ppm S, and pre-oxidation treatment was applied. Steam oxidation tests were conducted at 923K for up to 4000h. Pre-oxidation treatment in argon gas at 973K for 50h significantly improved oxidation resistance in steam at 923K by forming a protective Cr-rich oxide layer. The pre-oxidized steels exhibited much lower mass gain in steam at 923K than Mod.9Cr-1Mo steel at 873K, and lower than T91 at 873K after 1000h. After 4000h, their mass gain was about zero, much lower than P91 at 873K and 923K. SEM/EDS analysis and low mass gain suggest a protective Cr-rich oxide scale formed on the pre-oxidized steel surface, exhibiting excellent oxidation resistance in steam at 923K.

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.

High Cr ferritic steels have been developed for the large components of fossil power plants due to their excellent creep resistance, low thermal expansion, and good oxidation resistance. Development works to improve the operating temperature of these steels mainly focused on the high mechanical properties such as solid solution strengthening and precipitation hardening. However, the knowledge of the correlation between Laves phase precipitation and oxidation behavior has not clarified yet on 9Cr ferritic steels. This research will be focused on the effect of precipitation of Laves phase on steam oxidation behavior of Fe-9Cr alloy at 923 K. Niobium was chosen as the third element to the Fe- 9Cr binary system. Steam oxidation test of Fe-9Cr (mass%) alloy and Fe-9Cr-2Nb (mass%) alloy were carried out at 923 K in Ar-15%H 2 O mixture for up to 172.8 ks. X-ray diffraction confirms the oxide mainly consist of wüstite on the Fe-9Cr in the initial stage while on Nb added samples magnetite was dominated. The results show that the Fe-9Cr- 2Nb alloy has a slower oxidation rate than the Fe-9Cr alloy after oxidized for 172.8 ks

The current work presented a study of isothermal-oxidation behavior of the additive manufactured (AM) Alloy718 in air at 800°C. The oxidation behavior of Alloy718 specimens produced by selective laser melting (SLM) and electron beam melting (EBM) process were comparatively examined. No significant differences were observed in oxidation kinetics while different microstructures of the oxide scale were found. Coarse and columnar chromia grains developed on SLM specimens, whereas the chromia scale of EBM specimens consisted of extremely fine grains. Glow Discharge Optical Emission Spectrometry (GD-OES) analysis revealed that SLM specimens contain a higher content of Ti in chromia compared with EBM specimens. Process-induced supersaturation in SLM specimens might lead to a relatively high concentration of Ti in the chromia, which may affect the grain morphology of oxide scale in the SLM specimen.

Because of the problems experienced with steam-side oxidation in commercial power plants, there has been continuing interest in better understanding the steam oxidation behavior of creep strength enhanced ferritic steels such as grades 23, 24 and 91 as well as 300-series stainless steels such as 347H and 304H. Analysis of field-exposed tubes has provided information on the oxidation reaction products but relatively few specimens are available and there is limited information about the kinetics. Specimens have included tube sections with a shot peened surface, a treatment that is now widely used for austenitic boiler tubes. To complement this information, additional laboratory studies have been conducted in 1bar steam at 600°-650°C on coupons cut from conventional and shot-peened tubing. Exposures of 1-15 kh provide some information on the steam oxidation kinetics for the various alloys classes. While shot-peened type 304H retained its beneficial effect on oxidation resistance past 10,000 h at 600° and 625°C, the benefit appeared to decline after similar exposures at 650°C.

The Advanced Ultrasupercritical (A-USC) power plants are aimed to operate at steam inlet temperatures greater than 700°C; consequently, a complete materials overhaul is needed for the next-generation power plants. HAYNES 282, a gamma-prime strengthened alloy, is among the leading candidates because of its unique combination of properties, superior creep and LCF strength, fabricability and thermal stability. It is currently being evaluated in wrought and cast forms for A-USC turbine rotors, casings, boiler tubings, header, and valves. The candidate materials for A-USC applications not only require oxidation resistance for steam cycles but fireside corrosion resistance to coal ash is also of an extreme importance. In order to study the effect of both environments on the performance of 282 alloy, the alloy was exposed for extended periods in various oxidizing environments, such as air, air plus water vapor (10%), and 17bar steam up to 900°C. The fireside corrosion resistance of 282 alloy was evaluated at 700°C in synthetic coal ash and at 843°C in alkali salt deposits in a controlled gaseous environment.

The oxidation resistance of 9-12% chromium steels in steam-containing environments simulating the service conditions of steam power plant has been investigated for exposure times ranging from 1 h up to 10 000 h. For characterizing the oxidation behavior, the results of gravimetric studies were combined with data obtained from a number of analysis techniques, such as optical metallography, SEM/EDX and LRS. Different mechanisms of oxidation were observed for the various steels in different temperature regimes, exposure times and exposure conditions. The cracking and spallation of scales was correlated with the type, morphology and growth of pores and voids in the scale and could be influenced by the steel microstructure. For some steels, the steam oxidation resistance increased with increasing exposure temperature. The oxidation rates only slightly depend on the exact water vapor content in the test gas but can be strongly affected by the gas flow rates.

This study investigates the growth kinetics and spallation behavior of oxide scales formed under steam environments on alloys used in high-temperature plants. The influence of alloy composition is analyzed using two approaches: an empirical model based on the concept of “chromium equivalent” and a neural network model. Both models demonstrate a good correlation with experimental results when sufficient data is available to generate the model parameters. However, there is insufficient data on scale spallation to develop similar models describing the influence of alloy composition on this phenomenon.

The oxidation behavior of X20 steel in steam environments was studied isothermally between 580-640°C. Initially, the magnetite (Fe 3 O 4 ) phase formed on the surface. With increasing time and temperature, the hematite (Fe 2 O 3 ) phase formed. The oxide scale consisted of an inner layer divided from an outer layer by the original metal surface. A Cr-rich area was observed beneath the original metal surface. Oxide scales formed on a serviced boiler tube at 540°C for 7000h were also analyzed and found to be similar in oxide phase composition to those formed on X20 steel under laboratory conditions. However, differences existed in the microstructure and distribution of the Cr-rich area within the oxide scale. It was concluded that the oxidation mechanism under field conditions differs from that under laboratory conditions.

CWT (combined water treatment) was introduced in Japan in 1990 and over 50 power generation boilers are now in operation. However, the effect of oxygenated treatment on the steam oxidation of the ferritic-martensitic steels and austenitic stainless steels that are used for superheaters and reheaters is currently far from clear. In this study, laboratory tests were used to examine the effect of the oxygen level of the feed water on the scale growth and the scale exfoliation propensity of T91 ferritic-martensitic steel and 300-series austenitic stainless steels, as represented by TP316H and TP347H (coarse- and fine-grained, respectively). The oxygen level of the feed water had little effect on the steam oxidation rates of all the steels tested. Hematite (Fe 2 O 3 ) formed in the outer layer of the oxide scales on both the ferritic and austenitic steels and is considered to have been encouraged in the simulated CWT atmosphere. The adhesion strength of the oxide scale formed on T91 in the simulated CWT atmosphere, that is, scale in which hematite was present, was lower than that of the oxide scale formed in the simulated AVT (all volatile treatment) atmosphere. The oxidation rate of fine-grained TP347H was confirmed to be slower than that of coarse-grained TP316H. Hematite significantly influenced the scale exfoliation of the austenitic steels and the critical oxide thickness for exfoliation decreased with increasing proportion of hematite in the outer scale.

The high-temperature oxidation of Fe-9Cr-1Mo steel in a CO 2 environment, with varying oxygen content (0.6-3%), was investigated at 700°C. While the steel heavily oxidized in pure CO 2 , the oxidation mass gain decreased significantly with increasing oxygen content. Microscopic analysis revealed the formation of Fe-rich nodules with an internal Cr-carbide layer beneath them. Notably, the number of nodules decreased with increasing oxygen content but remained independent of the oxidation time. To explain these observations, the authors propose that “intrinsic” defects within the initially formed protective Cr 2 O 3 scale facilitated gas permeation. This mechanism is believed to be responsible for the observed dependence of nodule formation on the oxygen content in the gas mixtures.

The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are sponsoring the “Boiler Materials for Ultrasupercritical Coal Power Plants” program. This program is aimed at identifying, evaluating, and qualifying the materials needed for the construction of critical components for coal-fired boilers capable of operating at much higher efficiencies than the current generation of supercritical plants. Operation at ultrasupercritical (USC) conditions (steam temperatures up to 760°C (1400°F)) will necessitate the use of new advanced ferritic materials, austenitic stainless steels and nickel-based alloys. As well as possessing the required mechanical properties and fireside corrosion resistance, these materials must also exhibit acceptable steamside oxidation resistance. As part of the DOE/OCDO program, steamside oxidation testing is being performed at the Babcock & Wilcox Research Center. More than thirty ferritic, austenitic and nickel-based materials have been exposed for up to 4,000 hours in flowing steam at temperatures between 650°C (1202°F) and 800°C (1472°F). In addition to wrought materials, steamside oxidation tests have been conducted on weld metals, coated materials and materials given special surface treatments. Exposed specimens were evaluated to determine oxidation kinetics and oxide morphology. High chromium ferritic, austenitic and nickel-based alloys displayed very good oxidation behavior over the entire temperature range due to the formation of a dense chromium oxide. With increasing steam temperature, low chromium ferritic materials experienced breakaway oxidation, and low chromium austenitic materials experienced significant oxide exfoliation. Special surface treatments that were applied to these materials appeared to have a beneficial effect on their oxidation behavior.

Reducing emissions and increasing economic competitiveness require more efficient steam power plants that utilize fossil fuels. One of the major challenges in designing these plants is the availability of materials that can stand the supercritical and ultra-supercritical steam conditions at a competitive cost. There are several programs around the world developing new ferritic and austenitic steels for superheater and reheater tubes exposed to the advanced steam conditions. The new steels must possess properties better than current steels in terms of creep strength, steamside oxidation resistance, fireside corrosion resistance, and thermal fatigue resistance. This paper introduces a series of experimental 9%Cr steels containing Cu, Co, and Ti. Stability of the phases in the new steels is discussed and compared to the phases in the commercially available materials. The steels were tested under both the dry and moist conditions at 650°C for their cyclical oxidation resistance. Results of oxidation tests are presented. Under the moist conditions, the experimental steels exhibited significantly less mass gain compared to the commercial P91 steel. Microstructural characterization of the scale revealed different oxide compositions.

Oxide scale growth kinetics of 1.25Cr-0.5Mo and 2.25Cr-1Mo steels have been investigated and oxide scales have been characterized. In spite of the considerable difference in chromium contents of the two steels, their oxidation kinetics have been found to be similar. The similarity in oxidation behavior has been associated with formation of a protective innermost layer of silicon rich oxide in the case of 1.25Cr-0.5Mo steel and absence of such a layer in the case of 2.25Cr-1Mo steel, suggesting predominating role of Si over Cr.

Advanced ultra-supercritical (USC) steam power plants promise higher efficiencies and lower emissions. The U.S. Department of Energy (DOE) aims to achieve 60% efficiency in coal-based power generation, requiring steam temperatures of up to 760°C. This study presents ongoing research on the oxidation behavior of candidate materials for advanced steam turbines, with a focus on estimating chromium evaporation rates from protective chromia scales. Due to the high velocities and pressures in advanced steam turbines, evaporation rates of CrO 2 (OH) 2 (g) are predicted to reach up to 5 × 10 −8 kg m −2 s −1 at 760°C and 34.5 MPa, corresponding to a solid chromium loss of approximately 0.077 mm per year.

Cast nickel-based superalloys used as structural materials for gas turbine parts need to withstand high temperatures and dynamic mechanical loads. When in contact with ambient air, the formation of protective oxide scales causes a depletion of γ’-precipitates in the surface-near region and leaves a weakened microstructure. This environmentally based degradation of the material might be accelerated under cyclic thermal exposure. In this paper, the cyclic oxidation behavior of two cast nickel-based superalloys and one single crystalline variant are investigated: C1023, CM-247 LC and M-247 SX. Exposure tests were carried out under both isothermal and cyclic conditions in air at 850 °C, 950 °C and 1050 °C for times up to 120 h to investigate the impact of thermal cycling. The differences in oxidation mechanisms are analyzed phenomenologically via light and electron microscopy and brought in correlation with the oxidation kinetics, determined based on net mass change and depletion zone growth. An assessment of the impact of precipitation loss on local mechanical strength is attempted via nano-indentation method. The found relations can be transferred onto an acceleration of crack growth under creep-fatigue and thermo-mechanical fatigue conditions.

As part of the Boiler Materials for Ultrasupercritical Coal Power Plants program, sponsored by the United States (U.S.) Department of Energy (DOE) and the Ohio Coal Development Office (OCDO), the steamside oxidation and oxide exfoliation behavior of candidate alloys have been thoroughly evaluated in steam at temperatures between 620°C and 800°C (1148°F and 1472°F) for times up to 10,000 hours. The results from this test program indicate that the oxidation rates and oxide morphologies associated with steamside oxidation are a strong function of the crystallographic lattice structure and the chromium content of the material. Oxide exfoliation correlates to oxide thickness. The time required to reach the critical oxide thickness for exfoliation can be estimated based on oxidation kinetic relationships. For austenitic stainless steels, shot peening is effective in reducing steamside oxidation/exfoliation, but the efficacy of this technique is limited by the operating temperature. Nickel-based alloys exhibit very low oxidation/exfoliation rates, but have a propensity to form aluminum/titanium oxides along near surface grain boundaries.

High efficiency in power generation is not only desirable because of economical reasons but also for enhanced environmental performance meaning reduced quantity of forming ash and emissions. In modern medium to large size plants, improvements require supercritical steam values. Furthermore, in future there will be an increasing share of renewables, such as wind and solar power, which will enhance the fluctuation of supply with the consequence that other power sources will have to compensate by operating in a more demanding cyclic or ramping mode. The next generation plant will need to operate at higher temperatures and pressure cycles coupled with demanding hot corrosion and oxidation environments. Such an operation will significantly influence the performance of materials used for boilers and heat exchanger components by accelerating oxidation rates and lowering mechanical properties like creep resistance. The paper discusses the oxidation behaviour of San25, 800H and alloy 263 in supercritical water at temperatures 650 and 700 °C at 250 bar, and compares the changes of mechanical properties of materials at these temperatures.

Advances in materials for power plants include not only new materials with higher-temperature capabilities, but also the use of current materials at increasingly higher temperatures. This latter activity builds on extensive experience of the performance of the various alloys, and provides a basis for identifying changes in alloy behavior with increasing temperature as well as understanding the factors that ultimately determine the maximum use temperatures of the different alloy classes. This paper presents results from an effort to model the exfoliation processes of steam-side oxide scales in a manner that describes as accurately as possible the evolution of strains in oxides growing inside small-diameter tubes subjected to large thermal gradients and to thermal transients typical of normal steam boiler operation. One way of portraying the results of such calculations is by plotting the evolving strains in a given oxide scale on an ‘Exfoliation Diagram’ (of the type pioneered by Manning et al. of the British Central Electricity Research Laboratory) to determine the earliest time at which the trajectory of these strains intersects a criterion for scale failure. Understanding of how such ‘strain trajectories’ differ among different alloys and are affected by the major variables associated with boiler operation has the potential to suggest boiler operating strategies to manage scale exfoliation, as well as to highlight the mode of scale failure and the limitations of each alloy. Preliminary results are presented of the strain trajectories calculated for alloys T22, T91, and TP347 subjected to the conditions experienced by superheaters under assumed boiler operating scenarios. For all three alloys the earliest predicted scale failures were associated with the increased strains developed during a boiler shut-down event; indeed, in the cases considered it appeared unlikely that scale failure would occur in any practically meaningful time due to strains accumulated during operation in a load-following mode in the absence of a shut down. The accuracy of the algorithms used for the kinetics of oxide growth appeared to be a very important consideration, especially for alloy TP347 for which large effects on oxide growth rate are known to occur with changes in alloy grain size and surface cold work.

The oxide exfoliation is one of the main problems that cause the explosion of superheater or reheater, which threaten the safety of power plant units, but there is no direct test method of the particle concentration of the scales in high temperature steam. Based on the study of ferromagnetic and optical characteristics of scales, the technology and equipment were developed for on-line measurement based on magnetic sensitivity and granularity behavior. Through numerical simulation and dynamic simulation experiments of scale movement under high temperature and high pressure steam, calculating method of the particle concertation of scales in the main steam or reheated steam pipeline was retrieved by local sampling concentration.