Search Results for oxide structure

Oxide scale formation in the inner bore of steam tubing has been identified as a key metric for determining operational parameters and life expectancy of modern boiler systems. Grade 91 tubing is commonly used for the construction of key components within boiler systems designed for power generation operating in the temperature range of 500 to 650 °C. Standard laboratory test procedures involve grinding the surface of test coupons to homogenise their surface structure and improve experimental consistency, however, data presented here shows a discrepancy between laboratory and industrial practices that has long term implications on scale growth kinetics and morphological development. Microstructural analysis of both virgin and ex-service tubing reveals the presence of a pre-existing oxide structure that is incorporated into the inwardly growing scale and is implicated in the formation of multiple laminar void networks. These void networks influence thermal diffusivity across the scale and may function as regions of spallation initiation and propagation.

This paper describes the steam oxidation behavior of two 18Cr-8Ni austenitic fine-grained stainless steels, TP347HFG and SUPER304H, which have been developed for ultra-supercritical (USC) boilers. A field exposure test was conducted by installing these tubes, along with comparative materials, in the tertiary superheater of a utility power boiler. After periodic service, the fine-grained tubes were removed to examine their steam oxidation behavior. Examination of the steam oxidation scale on the inner surface of the tubes indicated an extremely low scale growth rate for the fine-grained steels, even after 10 years of service. The oxidation structure is discussed and compared with conventional materials, TP321H and TP347H. Accelerated steam oxidation tests were conducted using an oxidation test with saturated dissolved oxygen concentration. The combination of fine-grained steel and a shot-peening layer exhibits high steam oxidation resistance at 700°C or higher temperatures.

A new ferritic steel branded as Thor 115 has been developed to enhance high-temperature resistance. The steel design combines an improved oxidation resistance with long-term microstructural stability. The new alloy was extensively tested to assess the high-temperature time- dependent mechanical behavior (creep). The main strengthening mechanism is precipitation hardening by finely dispersed carbide (M 23 C 6 ) and nitride phases (MX). Information on the evolution of secondary phases and time-temperature-precipitation behavior of the alloy, essential to ensure long-term stability, was obtained by scanning transmission electron microscopy with energy dispersive spectroscopy, and by X-ray powder diffraction on specimens aged up to 50,000 hours. The material behavior was also tested in service conditions, to validate the laboratory results: Thor 115 tubing was installed in a HRSG power plant, directly exposed to turbine flue gasses. Tubing samples were progressively extracted, analyzed and compared with laboratory specimens in similar condition. This research shows the performance of Thor 115 regarding steam oxidation and microstructure evolution up to 25,000 exposure hours in the field. So far, no oxide microstructure difference is found between the laboratory and on field tubing: in both cases, the oxide structure is magnetite/hematite and Cr-spinel layers and the oxide thickness values lay within the same scatter band. The evolution of precipitates in the new alloy confirms the retention of the strengthening by secondary phases, even after long-term exposure at high temperature. The deleterious conversion of nitrides into Z phase is shown to be in line with, or even slower than that of the comparable ASME grade 91 steel.

The drive for increased efficiency and carbon reduction in next-generation boilers is pushing conventional materials to their limits in terms of strength and oxidation resistance. While traditional isothermal testing of simple coupons provides some insight into material performance, it fails to accurately represent the heat transfer conditions present in operational boilers. This paper introduces a novel test method designed to evaluate the degradation of candidate materials under more realistic heat flux conditions. The method, applied to tubular specimens using both laboratory air and steam as cooling media, demonstrates a significant impact of thermal gradients on material performance. Initial comparisons between tubular heat flux specimens and flat isothermal specimens of 15Mo3 revealed increased oxidation kinetics and altered oxide morphology under heat flux conditions. The paper details the design of this heat flux test, presents results from initial work on 15Mo3 under air and steam conditions, and includes findings from further studies on oxides formed on 2-1/4Cr material under both heat flux and isothermal conditions. This research represents a crucial step toward more accurate prediction of material behavior in next-generation boiler designs.

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.

Extensive research and development has been undertaken in the UK on MarBN steels. These were first proposed by Professor Fujio Abe from NIMS in Japan. Within the UK, progress has been made towards commercialisation of MarBN-type steel through a series of Government funded industrial collaborative projects (IMPACT, IMPEL, INMAP and IMPULSE). As part of the IMPACT project, which was led by Uniper Technologies, boiler tubes were manufactured from the MarBN steel developed within the project, IBN1, and installed on the reheater drums of Units 2 and 3 of Ratcliffe-on-Soar Power Station. The trial tubes were constructed with small sections of Grade 91 tubing on either side of the IBN1 to allow direct comparison after the service exposure. This is the world’s first use of a MarBN steel on a full-scale operational power plant. In September 2018 the first tube was removed having accumulated 11,727 hours operation and 397 starts. This paper reports microstructural and oxidation analysis, that has been undertaken by Loughborough University as part of IMPULSE project, and outlines future work to be carried out.

The effect of gas impurities on corrosion behavior of candidate Fe- and Ni-base alloys (SS 316LN, Alloy 800HT, Alloy 600) in high temperature CO 2 environment was investigated in consideration of actual S-CO 2 cycle applications. Preliminary testing in research and industrial grade S-CO 2 at 600 °C (20 MPa) for 1000 h showed that oxidation rates were significantly reduced in industrial-grade S-CO 2 environment. Meanwhile, controlled tests with individual impurity additions such as CH 4 , CO, and O 2 in research-grade CO 2 were performed. The results indicated that CH 4 and CO additions did not seem to significantly affect oxidation rates. On the other hand, O 2 addition resulted in lower weight gains for all alloys, suggesting that O 2 may be primarily affecting corrosion behavior.

The growth behavior of oxide scale in a laboratory steam environment has been conducted for the shot-peened 18Cr-8Ni stainless steels differing in grain size. Both steels (fine grained and coarse grained) have demonstrated almost the same steam oxidation behavior reacted at 700°C for up to 2000h, which had excellent oxidation resistance due to formation of a protective Cr 2 O 3 scale. After the exposure of 4000h, however, nodule-like oxide occurred on the coarse grained steel, while the fine grained steel still remained the uniform Cr 2 O 3 scale. These behaviors well explained in terms of changes of the outward Cr flux due to recovery and recrystallization of the deformed structure. This result has proven that the shot-peened tube composed of fine grain structure is capable of combat against the steam oxidation at high temperatures.

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.

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.

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.

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.

A new alloy design concept for creep- and corrosion-resistant, fully ferritic alloys was proposed for high-temperature structural applications in current/future fossil-fired power plants. The alloys, based on the Fe-30Cr-3Al (in weight percent) system with minor alloying additions of Nb, W, Si, Zr and/or Y, were designed for corrosion resistance though high Cr content, steam oxidation resistance through alumina-scale formation, and high-temperature creep performance through fine particle dispersion of Fe 2 (Nb,W)-type Laves phase in the BCC-Fe matrix. Theses alloys are targeted for use in harsh environments such as combustion and/or steam containing atmospheres at 700°C or greater. The alloys, consisting of Fe-30Cr-3Al-1Nb-6W with minor alloying additions, exhibited a successful combination of oxidation, corrosion, and creep resistances comparable or superior to those of commercially available heat resistant austenitic stainless steels. An optimized thermo-mechanical treatment combined with selected minor alloying additions resulted in a refined grain structure with high thermal stability even at 1200°C, which improved room-temperature ductility without sacrificing the creep performance. The mechanism of grain refinement in the alloy system is discussed.

Understanding of the thermomechanical processing that affects microstructures is important to develop new alloys, because the mechanical properties of Ti alloys depend on the microstructures. In our previous study, we found Sn deteriorated the oxidation resistance, while Nb improved the oxidation resistance. Then, we have focused on Ti-Al-Nb-Zr alloys which Nb was added instead of Sn. Zr was added for solid solution strengthening. In this study, the formation of microstructures by thermomechanical processing and the effect of microstructure on the mechanical properties were investigated using the Ti-13Al-2Nb-2Zr (at%) alloy. The samples heat-treated in the β+α phase followed by furnace cooling after processed in the β+α phase formed the equiaxed or the ellipsoid α phase surrounded by the β phase. On the other hand, the sample heat-treated in the β+α phase followed by furnace cooling after processed in the β phase formed the lamellar microstructure. The compression strengths of the equiaxed α structure processed at two temperatures in the β+α phase were almost the same. While creep life of the bi-modal structure was drastically changed by processing temperature.

In the “Boiler Materials for Ultrasupercritical Coal Power Plants” program, sponsored by the U.S. Department of Energy and the Ohio Coal Development Office, various materials are being assessed for their suitability in the high-temperature, high-pressure environment of advanced ultrasupercritical (A-USC) boilers. Beyond mechanical properties and fireside corrosion resistance, these materials must also exhibit adequate steamside oxidation and exfoliation resistance. A comprehensive database of steamside oxidation test results at temperatures relevant to A-USC conditions has been compiled over recent years. These tests have been conducted on ferritic and austenitic materials with chromium content ranging from 2 to 26%. The specimens were evaluated for oxidation kinetics and oxide morphology. The findings indicate that steamside oxidation behavior is significantly affected by temperature, the chromium content of the material, and the ability of chromium to diffuse through the material's crystallographic lattice structure. Additionally, surface treatments have been applied to enhance the steamside oxidation resistance of certain materials. While these treatments have shown potential, their effectiveness can be limited by the operational temperatures.

In fossil-fired boilers, combustion-generated thermal energy transfers to the working fluid via exchanger tubes, where an internal oxide layer forms over time, reducing thermal conductivity and raising metal temperatures. This self-activating process accelerates creep damage, significantly shortening component lifespan. Boiler design codes set Maximum Allowable Stresses based on mechanical properties, primarily creep resistance, but oxidation effects are only indirectly considered through “design temperature” selection—an approach inadequate for next-generation high-performance boilers with increasingly severe steam conditions. This paper highlights the need to integrate oxidation behavior into the design of advanced heat-exchanging components by examining the impact of steam oxidation on tube lifespan, including oxide layer growth, metal loss, temperature rise, and reduced creep rupture time, with thermal flux effects illustrated through examples. It also compares the behavior of two 9-12Cr% steels: Grade 92, known for strong creep resistance, and VM12, which offers superior oxidation resistance. Additionally, it proposes a revised “design temperature” expression incorporating oxidation resistance performance indices and exchanger thermal characteristics. The study concludes by emphasizing the need for further research into oxidation kinetics, thermal properties, and oxide layer exfoliation mechanisms.

Over the past two decades there has been considerable interest in the development of coatings with finer microstructures approaching nanometer scale because these coatings are more resistant to high-temperature oxidation and corrosion than their counterpart conventional coatings. Long-term cyclic oxidation behavior of nanocrystalline FeCrNiAl and NiCrAl coatings were evaluated at different temperatures and the results showed that ultra-fine grain structure promoted selective oxidation of Al during thermal exposure. The protective Al2O3 scale formed on these coatings with Al content as low as 3 wt.% and exhibited excellent spallation resistance during thermal cycling. The nanocrystalline NiCrAl coating showed significantly higher oxidation resistance compared to the conventional plasma sprayed NiCoCrAlY and PWA 286 coatings. However, the Al content in the nanocrystalline coatings was consumed in relatively short time due to inward and outward diffusion of Al. Variation of oxide-scale spallation resistance during thermal cycling and the rate of Al consumption between the nanocrystalline and plasma sprayed coatings are compared.

Oxyfuel combustion is considered as one of the most promising technologies to facilitate CO 2 capture from flue gases. In oxyfuel combustion, the fuel is burned in a mixture of oxygen and recirculated flue gas. Flue gas recirculation increases the levels of fireside CO 2 , SO 2 , Cl and moisture, and thus promotes fouling and corrosion. In this paper the corrosion performance of two superheater austenitic stainless steels (UNS S34710 and S31035) and one Ni base alloy (UNS N06617) has been determined in laboratory tests under simulated oxyfuel conditions with and without a synthetic carbonate based deposits (CaCO 3 - 15 wt% CaSO 4 , CaCO 3 - 14wt% CaSO 4 - 1 KCl) at 650 and 720°C up to 1000 hours. No carburization of the metal substrate was observed after exposure to simulated oxyfuel gas atmospheres without deposit, although some carbon enrichment was detected near the oxide metal interface. At 720°C a very thin oxide formed on all alloy surfaces while the weight changes were negative. This negative weight change observed is due to chromium evaporation in the moist testing condition. At the presence of deposits, corrosion accelerated and considerable metal loss of austenitic alloys was observed at 720°C. In addition, clear carburization of austenitic steel UNS S34710 occurred.

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.

In order to assist in developing mechanistic and computational models for understanding the performance of current Fe-base waterwall tubing, characterization has been performed on three field-exposed low alloy steel waterwall tubes. The waterside oxide thickness was characterized using standard metallographic techniques. Alloy and oxide chemical composition was characterized using electron microprobe analysis. Waterside scale thickness was measured as a function of location. Agreement between the measured and predicted values based on likely rate constants was poor.