Steam-side oxidation and the resultant exfoliation of iron-based scales cause unplanned shutdowns at coal-fired power generation plants. Exfoliate removal is currently limited to frequent unit cycling to minimize the volume of exfoliated scale, upgrading a plant with a “blow down” system, or installing a higher alloy. This paper discusses the rate of steam-side oxidation on Type 304H stainless steel (304H) tube after shot peening the internal surface with commercially available techniques. Shot peening the ID of Type 304H austenitic stainless steel superheater tubes has been shown to improve the overall oxidation resistance in steam. Decreasing the oxidation rate directly impacts the volume of exfoliated scale. The adherent spinel scales are thinner and more robust than non-shot peened tubes of the same alloy. Most of the improved oxidation resistance can be attributed to the presence of a spinel oxide layer combined with a continuous chromia layer formed near the steam-touched surfaces. The presence of a continuous chromia layer vastly reduces the outward diffusion of iron and minimizes the formation of iron-based scales that exfoliate. This work showed that a uniform cold-worker layer along the tube ID has a profound effect on oxidation resistance. Incomplete coverage allows oxidation to proceed in the non-hardened regions at a rate comparable to the oxidation rate on unpeened Type 304H.

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.

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.

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.

Early supercritical units such as American Electric Power (AEP) Philo U6, the world’s first supercritical power plant, and Eddystone U1 successfully operated at ultrasupercritical (USC) levels. However due to the unavailability of metals that could tolerate these extreme temperatures, operation at these levels could not be sustained and units were operated for many years at reduced steam (supercritical) conditions. Today, recently developed creep strength enhanced ferritic (CSEF) steels, advanced austenitic stainless steels, and nickel based alloys are used in the components of the steam generator, turbine and piping systems that are exposed to high temperature steam. These materials can perform under these prolonged high temperature operating conditions, rendering USC no longer a goal, but a practical design basis. This paper identifies the engineering challenges associated with designing, constructing and operating the first USC unit in the United States, AEP’s John W. Turk, Jr. Power Plant (AEP Turk), including fabrication and installation requirements of CSEF alloys, fabrication and operating requirements for stainless steels, and life management of high temperature components

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.

For higher efficiency and competitive overall performance, it would be an advantage to be able to safely exceed the highest operational values, currently up to about 600-620°C/25-30 MPa in supercritical (SC) boiler plants. Under such operating conditions the oxidation resistance in SC water tends to limit the potential for further improvement of efficiency. The way to increase the oxidation resistance of traditional austenitic boiler tubes e.g. TP 347H is to do additional cold work on the boiler tube inner surface. In the current paper the effect of cold work on the oxidation resistance of TP347H and TP347HFG has been evaluated by shot peened samples with different parameters and subjecting those samples to supercritical oxidation exposure. The results show an improvement in the oxidation resistance of the alloys, especially in the large grained alloy TP347H. Also the uniformity of the deformation layer was seen to have an influence on the oxidation resistance, since the oxide nodules start to grow at locations with the thinnest or no deformation layer.

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.

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.

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.

Sanicro 25 material is approved for use in pressure vessels and boilers according ASME code case 2752, 2753 and VdTUV blatt 555. It shows higher creep rupture strength than any other austenitic stainless steels available today. It is a material for superheater and reheaters, enabling higher steam parameters of up to about 650 °C steam (ie about max 700 °C metal) without the need for expensive nickel based alloys. The aim of the present study is the investigation of the steam oxidation resistance of the Sanicro 25. The long term test was conducted in the temperature range 600 -750 °C up to 20 000 hours. The morphology of the oxide scale and the microstructure of the bulk material were investigated. In addition, the effect of surface finish and pressure on the steam oxidation were also studied.

Energy requirements and environmental concerns have promoted a development in higher-efficiency coal fired power technologies. Advanced ultra-super critical power plant with an efficiency of higher than 50% is the target in the near future. The materials to be used due to the tougher environments become therefore critical issues. This paper provides a review on a newly developed advanced high strength heat resistant austenitic stainless steel, Sandvik Sanicro 25, for this purpose. The material shows good resistance to steam oxidation and flue gas corrosion, and has higher creep rupture strength than any other austenitic stainless steels available today, and has recently obtained two AMSE code cases. This makes it an interesting option in higher pressures/temperature applications. In this paper, the material development, structure stability, creep strength, steam oxidation and hot corrosion behaviors, fabricability and weldability of this alloy have been discussed. The conclusion is that the Sanicro 25 is a potential candidate for superheaters and reheaters in higher-efficiency coal fired boilers i.e. for applications seeing up to 700°C material 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.

The United States Department of Energy (U.S. DOE) Office of Fossil Energy and the Ohio Coal Development Office (OCDO) have been the primary supporters of a U.S. effort to develop the materials technology necessary to build and operate an advanced-ultrasupercritical (A-USC) steam boiler and turbine with steam temperatures up to 760°C (1400°F). The program is made-up of two consortia representing the U.S. boiler and steam turbine manufacturers (Alstom, Babcock & Wilcox, Foster Wheeler, Riley Power, and GE Energy) and national laboratories (Oak Ridge National Laboratory and the National Energy Technology Laboratory) led by the Energy Industries of Ohio with the Electric Power Research Institute (EPRI) serving as the program technical lead. Over 10 years, the program has conducted extensive laboratory testing, shop fabrication studies, field corrosion tests, and design studies. Based on the successful development and deployment of materials as part of this program, the Coal Utilization Research Council (CURC) and EPRI roadmap has identified the need for further development of A-USC technology as the cornerstone of a host of fossil energy systems and CO 2 reduction strategies. This paper will present some of the key consortium successes and ongoing materials research in light of the next steps being developed to realize A-USC technology in the U.S. Key results include ASME Boiler and Pressure Vessel Code acceptance of Inconel 740/740H (CC2702), the operation of the world’s first 760°C (1400°F) steam corrosion test loop, and significant strides in turbine casting and forging activities. An example of how utilization of materials designed for 760°C (1400°F) can have advantages at 700°C (1300°F) will also be highlighted.

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.

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.