A paste, which contains Pt or Pt-xIr (x = 0-30 at%) alloy nano-powder was sprayed on some Ni-based single crystal superalloys. Then the annealing diffusion treatment at 1100 °C for 1 h in flowing Ar atmosphere was conducted to develop Pt and Pt-Ir diffusion coatings. Cyclic oxidation tests were carried out at 1150 °C in still air in order to investigate the thermal stability and oxidation behavior of the coatings and they were compared with electroplated diffusion coatings. It was found that Ir can retard the formation of voids in both the coatings and substrates. In addition, by replacing the electroplating method to the paste coating method, the crack problem due to the brittle feature of electroplated Pt-Ir coatings could be solved. Therefore, the Pt-Ir diffusion coating prepared by the paste- coating method is promising as the bond-coat material due to suppression of voids, cracks and stable Al 2 O 3 on the surface. The Pt-Ir paste diffusion coatings introduced above have several further advantages: they are easy to recoat, cause less damage to substrates, and offer comparable oxidation resistance. Thus, the method can be applicable to the remanufacturing of blades, which may extend the life of components. The future aspect of the paste coating will also be discussed.

A major cost contributor of P91 pipe welding is the vital requirement of ensuring proper protection of the root or first pass of the weld from oxidation through the use of an inert gas blanket, i.e. backing gas. The necessity for oxidation protection negatively impacts the cost of both weld set-up and the actual welding process of P91 pipe fabrication. In an effort to decrease the associated costs of welding P91, Fluor Corporation has invested in significant research and extensive field-testing to develop the wire/gas mixture that contributes to the breakthrough in welding P91 with “No Backing Gas (NBG)”. Combining this novel technique with the semiautomatic GMAW-S (using inverter technology with a controlled transfer) eliminates all cost associated with the need to provide a backing gas, including installation of purge dams, backing gas, and man-hours associated with implementing these activities.

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.

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

The 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.

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.

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.

This paper investigates the combined effect of shot peening and pre-oxidation treatment in air on the subsequent steam oxidation resistance of Modified 9Cr-1Mo steel with different sulfur contents. Cast steel balls (50-180 μm diameter) and pure Cr (50-230 μm diameter) were used for shot peening durations of 5-50 seconds. After shot peening, pre-oxidation was performed in air at 973K for 3.6ks. Then, oxidation testing was conducted in steam at 923K for up to 3.6Ms. Only the combination of Cr shot peening and pre-oxidation treatment facilitated the formation of a protective Cr-rich oxide scale on the specimen surface during pre-oxidation. This Cr-rich oxide scale remained stable during subsequent steam oxidation, resulting in excellent oxidation resistance of the steel.

Model alloys of Fe-20Cr and Ni-20Cr (all compositions in weight %) and variants containing small amounts of Si or Mn were exposed to Ar-20CO 2 and Ar-20CO 2 -H 2 O (volume %) at 650 or 700°C. Protective Cr 2 O 3 scale was more readily formed on Fe-20Cr than Ni-20Cr, as a result of the different alloy diffusion coefficients. Silicon additions slowed chromia scale growth, promoting passivation of both alloy types. Water vapour accelerated chromia scaling, but slowed NiO growth.

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.

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.

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.

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.

During commissioning of recently built modern, and highly efficient coal-fired power plants, cracks were detected after very short time of operation within the welds of membrane walls made from alloy T24. The root cause analysis revealed transgranular and mostly intergranular cracks adjacent to the heat affected zone beside weld joints. At that time, the degradation mechanism was rather unclear, which led to an extended root cause analysis for clarification of these failures. The environmentally assisted cracking behavior of alloy T24 in oxygenated high-temperature water was determined by an experimental test program. Hereby, the cracking of 2½% chromium steel T24 and 1% chromium steel T12 were determined in high-temperature water depending on the effect of water chemistry parameters such as dissolved oxygen content, pH, and temperature, but also with respect to the mechanical load component by residual stresses and the microstructure. The results clearly show that the cracking of this low-alloy steel in oxygenated high-temperature water is driven by the dissolved oxygen content and the breakdown of the passive corrosion protective oxide scale on the specimens by mechanical degradation of the oxide scale as fracture due to straining. The results give further evidence that a reduction of the residual stresses by a stress relief heat treatment of the boiler in combination with the strict compliance of the limits for dissolved oxygen content in the feed water according to water chemistry standards are effective countermeasures to prevent environmentally assisted cracking of T24 membrane wall butt welds during plastic strain transients.

The addition of boron without the formation of any boron nitrides during normalizing heat treatment at high temperature minimizes the degradation in creep strength of both base metal and welded joints of 9Cr steel at 650 °C and long times. The enrichment of soluble boron near prior austenite grain boundaries (PAGBs) by the segregation is essential for the reduction of coarsening rate of M 23 C 6 carbides in the vicinity of PAGBs, enhancing boundary and subboundary hardening, and also for the production of same microstructure between the base metal and heat-affected-zone (HAZ) in welded joints, indicating no Type IV fracture in HAZ. Excess addition of boron and nitrogen promotes the formation of boron nitrides during normalizing, which reduces the soluble boron concentration and accelerates the degradation in creep rupture ductility at long times. 9Cr- 3W-3Co-VNb steel with 120 - 150 ppm boron and 60 - 90 ppm nitrogen (MARBN) exhibits not only much higher creep strength of base metal than Gr.92 but also substantially no degradation in creep strength due to Type IV fracture at 650 °C. The pre-oxidation treatment in Ar gas promotes the formation of protective Cr 2 O 3 scale on the surface of 9Cr steel, which significantly improves the oxidation resistance in steam at 650 °C.

An iron aluminide (Fe 3 Al) intermetallic coating was deposited onto F22 (2.25Cr-1Mo) steel substrate using a JP-5000 high velocity oxy-fuel (HVOF) thermal spray system. The as-sprayed coating was characterized by electron microscopy, X-ray diffraction, oxidation, and adhesion. Fe 3 Al coated steel specimens were exposed to a mixed oxidizing/sulfidizing environment of N 2 -10%CO-5%CO 2 -2%H 2 O-0.12%H 2 S (by volume) at 500, 600, 700, and 800°C for approximately seven days. All specimens gained mass after exposure, inversely proportional to temperature increases. Representative cross-sectioned specimens from each temperature underwent scanning electron microscopy (SEM) and X-ray mapping examination. Results are presented in terms of corrosion weight gain and product formation. The research evaluated the effectiveness of an HVOF-sprayed Fe 3 Al coating in protecting a steel substrate exposed to a fossil energy environment.

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.

Tests show that Inconel Filler Metal 72 overlay and/or Incoclad alloys 671/800HT are two material solutions that will provide adequate corrosion and erosion protection for superheater and reheater tubes in low-NOx boilers. This paper gives an overview of the corrosion issues involved in these applications and presents test data for these materials.

The power generation industry's need to extend run times between scheduled outages and to control maintenance budgets has increased reliance on advanced wear protection technologies to lengthen equipment life while maintaining clean, quality power production. This paper summarizes field erosion experiments conducted by the Electric Power Research Institute (EPRI) and the Tennessee Valley Authority (TVA) Kingston Power Plant on one of the plant's induced draft fans, testing several wear protection materials to reduce severe wear and extend intervals between planned outage cycles. Test results showed brazed tungsten carbide cladding's superiority in this extreme environment, successfully increasing the dirty gas fan run time from 5-8 months to over 30 months by cladding fan blades. Independent reviews of severe wear protection methods on low NOx burners and superheater boiler tubes with similar results are also presented.