Both non-destructive and traditional microsectioning techniques have been used to measure the oxide thickness of steam grown oxides between two close contacting surfaces. Different power plant materials, nickel based alloys and ferritic-martensitic steels, were exposed to steam oxidation at temperatures ranging from 650 °C up to 750 °C and periods from 500 h to 3000 h. Ultrasonic measurements of thickness, based on the speed of sound in the oxide, were performed and compared to optical thickness measurements based on conventional metallographic microsectioning with promising results. Improvements on the measurement resolution have been practically demonstrated with oxides down to 65 μm thickness being measured successfully.

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.

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.

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.

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.

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.

Laboratory-scale tests are frequently used to generate understanding of high-temperature oxidation phenomena, to characterise and rank the performance of existing, future materials and coatings. Tests within the laboratory have the advantage of being well controlled, monitored and offer the opportunity of simplification which enables the study of individual parameters through isolating them from other factors, such as temperature transients. The influence of pressure on the oxidation of power plant materials has always been considered to be less significant than the effects of temperature and Cr content, but still remains a subject of differing opinions. Experimental efforts, reported in the literature, to measure the influence of steam pressure on the rate of oxidation have not produced very consistent or conclusive results. To examine this further a series of high pressure steam oxidation exposures have been conducted in a high pressure flowing steam loop, exposing a range of materials to flowing steam at 650 and 700 °C and pressure of 25, 50 and 60 bar. Data is presented for ferritic-martensitic alloys showing the effect of increasing pressure on the mass change and oxide thickness of these alloys in the flowing steam loop. In addition the effect observed on the diffusion of aluminium from an aluminised coating in these alloys is also presented and the differences in the extent of diffusion discussed.

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.

Structural alloy corrosion is a major concern for the design and operation of supercritical carbon dioxide (sCO 2 ) power cycles. Looking towards the future of sCO 2 system development, the ability to measure real-time alloy corrosion would be invaluable to informing operation and maintenance of these systems. Sandia has recently explored methods available for in-situ alloy corrosion monitoring. Electrical resistance (ER) was chosen for initial tests due the operational simplicity and commercial availability. A series of long duration (>1000 hours) experiments have recently been completed at a range of temperatures (400-700°C) using ER probes made from four important structural alloys (C1010 Carbon Steel, 410ss, 304L, 316L) being considered for sCO 2 systems. Results from these tests are presented, including correlations between the probe measured corrosion rate to that for witness coupons of the same alloys.

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.

Using oxygen, rather than air, in coal-fired boilers has been studied for several years as a strategy to reduce NOx and concentrate CO 2 for capture. In combination with flue gas recirculation, higher levels of CO 2 are expected but increased H 2 O and SO 2 levels also may occur. In order to understand the role of substrate composition on corrosion, a combination of commercial and model alloys were investigated with synthetic coal ash and gas compositions simulating air- and oxyfiring environments. Exposure temperatures ranged from 600°-800°C to cover current operating temperatures up to advanced ultrasupercritical conditions. Using 500h exposures, no consistent negative effect was found for switching to the oxy-firing environment with the same synthetic ash. For model Fe-Cr alloys, 30%Cr was needed to form a thin protective reaction product across this temperature range. Among the commercial stainless steels, 310-type stainless steel showed low reaction rates with the maximum attack at 650°C. At higher temperatures, the depth of attack on Fe-base type 310 stainless steel was less than for Ni-base alloy 740. Initially, this difference was attributed to the Al and Ti additions in alloy 740. However, cast and hot rolled model Ni-18Cr and -22Cr alloys with various Al and Ti additions showed decreased metal loss with increasing Al and Ti additions in the oxy-firing environment at 700° and 800°C. As expected, metal loss was very sensitive to Cr content. A second set of model alloys also examined the effect of Co and Mo.

To improve the efficiency of fossil fuel power plants the operating temperatures and pressures need to be increased. However, at high temperatures the steam side oxidation resistance becomes a critical issue for the steels used especially at the final stages of superheaters and reheaters. Apart from the chemical composition of the material, surface condition is a major factor affecting the oxidation resistance in steam and supercritical water. In this paper, stainless boiler steels (UNS S34710, S31035, S31042, and S30942) are investigated for oxidation resistance in flowing supercritical water. Tests were conducted in an autoclave environment (250 bar, with 125 ppb dissolved oxygen and a pH of 7) at 625°C, 650°C and 675°C for up to 1000 h. Materials were tested with as-delivered, shot peened, milled or spark eroded and ground surface finish. The results show a strong influence of surface finish at the early stages of oxidation. Oxides formed on cold worked surfaces were more adherent and much thinner than on a spark eroded and ground surface. This effect was stronger than the influence of temperature or alloy composition within the tested ranges.

Because of the problems experienced with steam-side oxide scale exfoliation in commercial power plants, there has been increased interest in understanding the steam oxidation resistance of 300- series stainless steels such as 347H and 304H. Model alloys were used in an attempt to understand the effect of varying Ni (9-12%) and Cr (16-20%) on steam oxidation resistance at 650°C. However, the model alloys generally showed superior oxidation resistance than commercial alloys of similar composition. Several surface engineering solutions also were investigated. The commercially favored solution is shot peening. Laboratory steam testing at 650°C found that annealing temperatures of ≥850°C eliminated the benefit of shot peening and a correlation was observed with starting hardness in the peened region. This effect of annealing has implications for the fabrication of shot peened tubing. Another route to improving oxidation resistance is the use of oxidation resistant diffusion coatings, which can be deposited inexpensively by a vapor slurry process. Uniform coatings were deposited on short tube sections and annealed at 1065°C to retain good 650°C creep properties. The coating was thicker than has been investigated in laboratory processes resulting in increased brittleness when the coating was assessed using 4-point bending.

A model based on a concept of “fraction of exfoliated area” as a function of oxide scale strain energy was developed to predict the extent of exfoliation of steam-side scale from boiler tube superheater loops. As compared with the Armitt diagram, which can be used to predict when scale damage and exfoliation would be likely to occur, a “fraction of exfoliated area” approach provides an estimation of mass of scale released and the fraction of tube likely to be blocked by the exfoliation. This paper gives results for the extent of blockage expected in a single bend of a superheater loop was predicted as a function of operating time, bend geometry, and outlet steam temperature under realistic service conditions that include outages. The deposits of exfoliated scale were assumed to be distributed horizontally the tubes bends. Three types of bends were considered: regular bends, short bends, and hairpin bends. The progressive increase in steam and tube temperatures along a single loop of superheater tubing and the ensuing variation of oxide scale thickness are considered. Numerical simulation results for a superheater loop made of TP347H austenitic steel indicated that tube blockage fractions larger than 50% are likely to occur within the first two years of boiler operation (with regularly scheduled outages) for outlet tube temperatures of 540-570°C, which is consistent with practical experience. Higher blockage fractions were predicted for tubes with hairpin bends than for tubes with regular bends, of length that are larger than five internal tube diameters. Finally, the blockage model presented can be used with some confidence to devise operating schedules for managing the consequences of oxide scale exfoliation based on projections of time to some critical blockage fraction for specific boiler operating conditions.

A new martensitic steel for power generation applications was developed: Tenaris High Oxidation Resistance (Thor) is an evolution of the popular ASTM grade 91, offering improved steam oxidation resistance and better long-term microstructural stability, with equal or better creep strength. Thanks to its design philosophy, based on consolidated metallurgical knowledge of microstructural evolution mechanisms, and an extensive development performed in the last decade, Thor was engineered to overcome limitations in the use of ASTM grade 91, above 600 °C, particularly related to scale growth and liftoff. After laboratory development, Thor was successfully validated at the industrial level. Several heats up to 80 metric tons were cast at the steel shop, hot rolled to tubes of various dimensions, and heat treated. Trial heats underwent extensive characterization, including deep microstructural examination, mechanical testing in the as-received condition and after ageing, long-term creep and steam oxidation testing. This paper presents an overview of metallurgical characterization performed on laboratory and industrial Thor material, including microstructural examination and mechanical testing in time-independent and time-dependent regimes. Data relevant to the behavior and the performance of Thor steel are also included.

Traditional laboratory steam experiments are conducted at ambient pressure with water of variable chemistry. In order to better understand the effect of steam pressure and water chemistry, a new recirculating, controlled chemistry water loop with a 650°C autoclave was constructed. The initial experiments included two different water chemistries at 550° and 650°C. Two 500-h cycles were performed using oxygenated (OT, pH ~9 and ~100 ppb O 2 ) or all-volatile treated (AVT, pH ~9 and <10 ppb O 2 ) water conditions at each temperature. Coupons exposed included Fe-(9-11)%Cr and conventional and advanced austenitic steels as well as shot peened type 304H stainless steel. Compared to ambient steam exposures, the oxides formed after 1,000 h were similar in thickness for each of the alloy classes but appeared to have a different microstructure, particularly for the outer Fe-rich layer. An initial attempt was made to quantify the scale adhesion in the two environments.

Long-term performance of high temperature alloys is critically linked to the oxidation behavior in power generation applications in wet air and steam. As power generation systems move towards higher efficiency operation, nextgeneration fossil, nuclear and concentrating solar power plants are considering supercritical CO 2 cycle above 700°C. Wrought solid solution strengthened and precipitations strengthened alloys are leading candidates for both steam and Supercritical CO 2 power cycles. This study evaluates the cyclic oxidation behavior of HAYNES 230, 282, and 625 alloys in wet air, flowing laboratory air, steam and in 1 and 300 bar Supercritical CO 2 at ~750°C for duration of 1000 -10,000h. Test samples were thermally cycled for various times at temperature followed by cooling to room temperature. Alloy performances were assessed by analyzing the weight change behavior and extent of attack. The results clearly demonstrated the effects of alloy composition and environment on the long-term cyclic oxidation resistance. The extents of attack varied from alloy to alloy but none of the alloys underwent catastrophic corrosion and no significant internal carburization was observed in supercritical CO 2 . The performance of these alloys indicates that these materials are compatible not only in oxidizing environments, but also in Supercritical CO 2 environments for extended service operation.

Austenitic heat resistant steels are one of the most promising materials to be applied around 650°C, due to its superior creep strength than conventional ferritic steels and lower material cost than Ni based superalloys. The problem of austenitic steels is its high thermal expansion coefficient (CTE), which leads to high deformation and stress when applied in rotors, casings, blades and bolts. To develop low CTE austenitic steels together with high temperature strength, we chose the gamma-prime strengthened austenitic steel, A-286, as the base composition, and decreased the CTE by introducing the invar effect. The developed alloy, Fe-40Ni-6Cr-Mo-V-Ti-Al-C-B, showed low CTE comparable to conventional ferritic steels. This is mainly due to its high Ni and low Cr composition, which the invar effect is prone even at high temperature region. This alloy showed higher yield strength, higher creep rupture strength and better oxidation resistance than conventional high Cr ferritic steels and austenitic steels. The 2 ton ESR ingot was forged or hot rolled without defects, and the blade trial manufacturing was successfully done. This alloy is one of the best candidates for USC and A-USC turbine components.

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.

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.