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.

Nickel-base alloys were exposed to flowing supercritical CO 2 (P = 20MPa) at temperatures of 700 to 1000°C for up to 1000 h. For comparison, 316L stainless steel was similarly exposed at 650°C. To simulate likely service conditions, tubular samples of each alloy were internally pressurised by flowing CO 2 , inducing hoop stresses up to 35 MPa in the tube walls. Materials tested were Haynes alloys 188, 230 and 282, plus HR120 and HR160. These alloys developed chromia scales and, to different extents, an internal oxidation zone. In addition, chromium-rich carbides precipitated within the alloys. Air aging experiments enabled a distinction between carburisation reactions and carbide precipitation as a result of alloy equilibration. The stainless steel was much less resistant to CO 2 attack, rapidly entering breakaway corrosion, developing an external iron-rich oxide scale and internal carburisation. Results are discussed with reference to alloy chromium diffusion and carbon permeation of oxide scales.

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.

The INCONEL filler metals 72 and 72M have been utilized significantly for weld overlay protection of superheaters and reheaters, offering enhanced corrosion and erosion resistance in this service. Laboratory data conducted under simulated low-NOx combustion conditions, field exposure experience, and laboratory analysis (microstructure, chemical composition, overlay thickness measurements, micro-hardness) of field-exposed samples indicate that these overlay materials are also attractive options as protective overlays for water wall tubes in low-NOx boilers. Data and field observations will be compared for INCONEL filler metals 72, 72M, 625 and 622.

Coal burning power companies are currently considering FeAlCr weld overlay claddings for corrosion protection of waterwall boiler tubes located in their furnaces. Previous studies have shown that these FeAlCr coatings exhibit excellent high-temperature corrosion resistance in several types of low NOx environments. In the present study, the susceptibility of FeAlCr weld overlay claddings to hydrogen cracking was evaluated using a gas-tungsten arc welding (GTAW) process. Microsegregation of alloying elements was determined for the FeAlCr welds and compared to a currently used Ni-based superalloy. Long-term gaseous corrosion testing of select weld overlays was conducted along with the Ni-based superalloy in a gaseous oxidizing/sulfidizing corrosion environment at 500°C. The sample weight gains were used along with analysis of the corrosion scale morphologies to determine the corrosion resistance of the coatings. It was found that although there were slight differences in the corrosion behavior of the selected FeAlCr weld coatings, all FeAlCr based alloys exhibited superior corrosion resistance to the Ni-based superalloy during exposures up to 2000 hours.

Ni-38Cr-3.8Al has high hardness and high corrosion resistance with good hot workability, and therefore, it has been applied on various applications. However, in order to expand further application, it is important to understand the high temperature properties. Then, this study focused on the high temperature properties such as thermal phase stability, hardness, tensile property, creep property and hot corrosion resistance. As the result of studies, we found that the thermal phase stability of (γ/α-Cr) lamellar structure and the high temperature properties were strongly influenced by the temperature. Although the high temperature properties, except for creep property, of Ni-38Cr-3.8Al were superior to those of conventional Ni-based superalloys, the properties were dramatically degraded beyond 973 K. This is because the lamellar structure begins to collapse around 973 K due to the thermal stability of the lamellar structure. The hot corrosion resistance of Ni-38Cr-3.8Al was superior to that of conventional Ni-based superalloys, however, the advantage disappeared around 1073 K. These results indicate that Ni-38Cr-3.8Al is capable as a heat resistant material which is required the hot corrosion resistance rather than a heat resistant material with high strength at high temperature.

Prior to utilizing new advanced materials in coal power plants, a large number of experimental testing is required. Test procedures are needed in specialized high temperature laboratories with state of the art facilities and precise, accurate analytical equipment capable of performing tests at a variety of temperatures and environments. In this study, the results of a unique technique involving salt spray testing at high temperatures are presented. The Haynes 282 gamma – prime (γ’) strengthened alloy fabricated by means of three different manufacturing processes: HAYNES 282 WROUGHT alloy, Haynes 282-SINT alloy, and finally Haynes 282-CAST alloy have been tested. The materials have been exposed to a salt spray corrosion atmosphere using 1% NaCl - 1% Na 2 SO 4 . Post exposure investigations have included SEM, EDS and XRD examinations. The test using salt spray of 1% NaCl - 1% Na 2 SO 4 water solution at 550 °C for 500 hours indicted no influence on the corrosion products formation, where Cr 2 O 3 has been developed in all three alloys, whereas NiO has been found only in Haynes 282-CAST material. On the other hand, it has been found that the fabrication process of HAYNES 282 alloy strongly influences the corrosion products formation under the high temperature exposures.

Inconel Filler Metal 72 (FM 72) and Incoclad 671/800H co-extruded tubing have been successfully used for over 20 years to protect boiler tubing from high-temperature degradation. A newer alloy, FM 72M, offers superior weldability and the lowest corrosion rate in simulated low NOx environments. Both FM 72 and 72M show promise in addressing challenges like circumferential cracking and corrosion fatigue in waterwall tubing overlays. Additionally, 72M’s superior wear resistance makes it ideal for replacing erosion shields in superheater and reheater tubing. Beyond improved protection, these alloys exhibit increased hardness and thermal conductivity over time, leading to reduced temperature difference across the tube wall and consequently, enhanced boiler efficiency and lower maintenance costs. This paper discusses the historical selection of optimal alloys for waterwall and upper boiler tubing overlays, analyzes past failure mechanisms, and highlights the key properties of successful choices like FM 72 and 72M.

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.

Creep strength of Grade 91 steels has been reviewed and allowable stress of the steels has been revised several times. Allowable stress regulated in ASME Boiler and Pressure Vessel Code of the steels with thickness of 3 inches and above was reduced in 1993, based on the re-evaluation with long-term creep rupture data collected from around the world. After steam leakage from long seam weld of hot reheat pipe made from Grade 122 steel in 2004, creep rupture strength of the creep strength enhanced ferritic (CSEF) steels has been reviewed by means of region splitting method in consideration of 50% of 0.2% offset yield stress (half yield) at the temperature, in the committee sponsored by the Ministry of Economy, Trade and Industry (METI) of Japanese Government. Allowable stresses in the Japanese technical standard of Grade 91 steels have been reduced in 2007 according to the above review. In 2010, additional long-term creep rupture data of the CSEF steels has been collected and the re-evaluation of creep rupture strength of the steels has been conducted by the committee supported by the Federation of Electric Power Companies of Japan, and reduction of allowable stress has been repeated in 2014. Regardless of the previous revision, additional reduction of the allowable stress of Grade 91 steels has been proposed by the review conducted in 2015 by the same committee as 2010. Further reduction of creep rupture strength of Grade 91 steels has been caused mainly by the additional creep rupture data of the low strength materials. A remaining of segregation of alloying elements has been revealed as one of the causes of lowered creep rupture strength. Improvement in creep strength may be expected by reducing segregation, since diffusional phenomena at the elevated temperatures is promoted by concentration gradient due to segregation which increases driving force of diffusion. It has been expected, consequently, that the creep strength and allowable stress of Grade 91 steels can be increased by proper process of fabrication to obtain a homogenized material free from undue segregation.

Additive manufacturing (AM) is a process where, as the name suggests, material is added during production, in contrast to techniques such as machining, where material is removed. With metals, AM processes involve localised melting of a powder or wire in specific locations to produce a part, layer by layer. AM techniques have recently been applied to the repair of gas turbine blades. These components are often produced from nickel-based superalloys, a group of materials which possess excellent mechanical properties at high temperatures. However, although the microstructural and mechanical property evolution during the high temperature exposure of conventionally produced superalloy materials is reasonably well understood, the effects of prolonged high temperature exposure on AM material are less well known. This research is concerned with the microstructures of components produced using AM techniques and an examination of the effect of subsequent high temperature exposures. In particular, the paper will focus on the differences between cast and SLM IN939 as a function of heat treatment and subsequent ageing, including differences in grain structure and precipitate size, distribution and morphology, quantified using advanced electron microscopy techniques.

The use of high-nickel superalloys has greatly increased among many industries. This is especially the case for advanced coal-fired boilers, where the latest high temperature designs will require materials capable of withstanding much higher operating temperatures and pressures than current designs. Inconel alloy 740H (UNS N07740) is a new nickel- based alloy that serves as a candidate for steam header pipe and super-heater tubing in coal-fired boilers. Alloy 740H has been shown to be capable of withstanding the extreme operating conditions of an advanced ultra-super-critical (AUSC) boiler, which is the latest boiler design, currently under development. As with all high nickel alloys, welding of alloy 740H can be very challenging, even to an experienced welder. Weldability challenges are compounded when considering that the alloy may be used in steam headers, where critical, thick-section and stub-to-header weld joints are present. This paper is intended to describe the proper procedures developed over years of study that will allow for ASME code quality welds in alloy 740H with matching composition filler metals.

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.

A combined pilot-scale combustion test and long-term laboratory study investigated the impact of oxy-firing on corrosion in coal-fired boilers. Four coals were burned under both air and oxy-firing conditions with identical heat input, with oxy-firing using flue gas recirculation unlike air-firing. Despite higher SO 2 and HCl concentrations in oxy-firing, laboratory tests showed no increase in corrosion rates compared to air-firing. This is attributed to several factors: (1) Reduced diffusion: High CO 2 in oxy-firing densified the gas phase, leading to slower diffusion of corrosive species within the deposit. (2) Lower initial sulfate: Oxy-fired deposits initially contained less sulfate, a key hot corrosion culprit, due to the presence of carbonate. (3) Reduced basicity: CO 2 and HCl reduced the basicity of sulfate melts, leading to decreased dissolution of metal oxides and mitigating hot corrosion. (4) Limited carbonate/chloride formation: The formation of less corrosive carbonate and chloride solutes was restricted by low O 2 and SO 3 near the metal surface. These findings suggest that oxy-firing may not pose a greater corrosion risk than air-firing for boiler materials.

The steam oxidation behaviour of boiler tubes and steam piping components is a limiting factor for improving the efficiency of the current power plants. Spallation of the oxide scales formed during service can cause serious damage to the turbine blades. Vallourec has implemented an innovative solution based on an aluminum diffusion coating applied on the inner surface of the T/P92 steel. The functionality of this coating is to protect the tubular components against spallation and increase the actual operating temperature of the metallic components. In the present study, the newly developed VALIORTM T/P92 product was tested at the EDF La Maxe power plant (France) under 167b and 545°C (steam temperature). After 3500h operation, the tubes were removed and characterized by Light Optical Metallography (LOM), Scanning Electron Microscopy (SEM), with Energy Dispersive X-ray spectrometry (EDX) and X-Ray Diffraction (XRD). The results highlight the excellent oxidation resistance of VALIORTM T/P92 product by the formation of a protective aluminum oxide scale. In addition, no enhanced oxidation was observed on the areas close to the welds. These results are compared with the results obtained from laboratory steam oxidation testing performed on a 9%Cr T/P92 steel with and without VALIORTM coating exposed in Ar-50%H 2 O at 650°C.

The use of the bainitic class of creep strength enhanced ferritic steels T/P23 and T24 has increased over the last decade in a wide range of applications including replacement headers, superheater and reheater tubing and in waterwall tubing. Many issues have been reported in one or both of these materials including hydrogen induced cracking, reheat cracking and stress corrosion cracking. To appropriately address these issues, work has been initiated that includes a literature review, development of a database of phase transformation temperatures, investigation of tempering behavior, and an analysis of the effect of phase transformation on residual stresses. Such information will be provided in the context of understanding why these two materials appear highly susceptible to these cracking mechanisms.

The measurement of damage from high temperature solid particle erosion (HTSPE) can be a lengthy process within the laboratory with many lab-based systems requiring sequential heat and cooling of the test piece to enable mass and/or scar volume measurements to be made ex situ. Over the last few years a new lab-based system has been in development at the National Physical Laboratory which has the ability to measure the mass and volume change of eroded samples in situ without the need to cool the sample. Results have previously been shown demonstrating the in situ mass measurement, more recently the in situ volume measurement capability has been added and used to evaluate the erosion performance of additively manufactured materials. Selective laser melting (SLM) is an advanced manufacturing method which is growing in popularity and application. It offers the ability to manufacture low volume complex parts and has been used in rapid prototyping. As the technique has developed there is increasing interest to take advantage of the ability to manufacture complex parts in one piece, which in some case can be more cost and time effective than traditional manufacturing routes. For all the benefits of SLM there are some constraints on the process, these include porosity and defects in the materials such as ‘kissing bonds’, surface roughness, trapped powder and microstructural variation. These features of the processing route may have implications for component performance such as strength, fatigue resistance wear and erosion. To investigate this further SLM IN718 has been used to evaluate factors such as surface roughness, microstructure and morphology on the erosion performance as measured in situ and compared with conventional produced wrought IN718 material.

The influence of holding time during tempering on the long-term creep rupture strength of mod.9Cr-1Mo steel was investigated in this study, so as to elucidate proper heat treatment for boiler applications. Tempering was conducted at 770°C for 0.5h, 1h, 3h, 10h and 100h for the test materials, after re-normalization at 1050°C for 1h in all cases. Creep rupture tests were conducted at 600°C, and ruptured specimens were investigated to better understand the microstructural changes, including changes in the number density of precipitates, in order to observe and discuss their creep strength. All creep rupture test results for materials tempered within 10h exceeded the average creep strength of T91. Shorter tempering times such as 0.5h and 1h were clearly correlated with longer time to rupture at 600°C under 80MPa to 100MPa stress conditions. Reduction of area in creep-ruptured specimens decreased principally with lowered creep stress. Materials tempered for 0.5h and 100h showed the lowest reduction of area at 90MPa and 100MPa respectively, and their reduction of area recovered at lower than those stress levels. These stresses, showing minimum reduction of area, met inflection stress in the creep rupture strength curve.