Search Results for chromium diffusion

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.

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.

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.

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.

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.

The recently developed 12%Cr steel VM12-SHC is characterized by very good creep properties at temperatures up to 620°C. This new material development exhibits an excellent oxidation resistance in steam atmospheres at the typical application temperature but also at temperatures up to 650°C. In comparison to the existing 9% Cr grades T/P91 and T/P92, VM12-SHC steel opens due to its excellent oxidation behavior, new possibilities for its application as a heat exchanger boiler component. It was found that outside its application temperature range VM12-SHC also shows, as all 9-12%Cr steels, the appearance of the so called Z-phase. This effect was investigated to understand its influence on creep properties of this class of ferritic/martensitic steels aiming at controlling the microstructure stabilities for future grade developments. Creep testing has been carried out in the temperature range between 525°C and 700°C. Selected crept specimens have been investigated using light optical microscopy, SEM with EDX and TEM. In this study, the oxidation behavior of a number of typical martensitic 9-12%Cr steels was compared with the newly developed 12% Cr steel VM12-SHC. The compositions and morphologies of oxide scales formed after 5000 h exposure steels in simulated steam environments as function of temperature were characterized by light optical metallography and scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX).

The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are sponsoring the “Boiler Materials for Ultrasupercritical Coal Power Plants” program. This program is aimed at identifying, evaluating, and qualifying the materials needed for the construction of critical components for coal-fired boilers capable of operating at much higher efficiencies than the current generation of supercritical plants. Operation at ultrasupercritical (USC) conditions (steam temperatures up to 760°C (1400°F)) will necessitate the use of new advanced ferritic materials, austenitic stainless steels and nickel-based alloys. As well as possessing the required mechanical properties and fireside corrosion resistance, these materials must also exhibit acceptable steamside oxidation resistance. As part of the DOE/OCDO program, steamside oxidation testing is being performed at the Babcock & Wilcox Research Center. More than thirty ferritic, austenitic and nickel-based materials have been exposed for up to 4,000 hours in flowing steam at temperatures between 650°C (1202°F) and 800°C (1472°F). In addition to wrought materials, steamside oxidation tests have been conducted on weld metals, coated materials and materials given special surface treatments. Exposed specimens were evaluated to determine oxidation kinetics and oxide morphology. High chromium ferritic, austenitic and nickel-based alloys displayed very good oxidation behavior over the entire temperature range due to the formation of a dense chromium oxide. With increasing steam temperature, low chromium ferritic materials experienced breakaway oxidation, and low chromium austenitic materials experienced significant oxide exfoliation. Special surface treatments that were applied to these materials appeared to have a beneficial effect on their oxidation behavior.

Most effective method to increase the boiler efficiency and decrease emissions is to increase the steam temperature of modern coal-fired power plants. The increase in the steam temperature of the AUSC power plants will require higher grade heat-resistant materials to support the long-term safety and service reliability of power plants. The corrosion resistance of alloys is one of the most important factors for the application in AUSC power plants.

Advanced ultra-supercritical (USC) steam power plants promise higher efficiencies and lower emissions. The U.S. Department of Energy (DOE) aims to achieve 60% efficiency in coal-based power generation, requiring steam temperatures of up to 760°C. This study presents ongoing research on the oxidation behavior of candidate materials for advanced steam turbines, with a focus on estimating chromium evaporation rates from protective chromia scales. Due to the high velocities and pressures in advanced steam turbines, evaporation rates of CrO 2 (OH) 2 (g) are predicted to reach up to 5 × 10 −8 kg m −2 s −1 at 760°C and 34.5 MPa, corresponding to a solid chromium loss of approximately 0.077 mm per year.

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.

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.

Higher steam temperature in steam power plants increases their thermal efficiency. Thus there is a strong demand for new materials with better creep and corrosion resistance at higher temperatures, while retaining the thermal flexibility of martensitic steels. Z-phase strengthened 12% Cr steels have been developed to meet the 923 K (650°C) challenge in these power plants. Ta, Nb, or V forms Z-phase together with Cr and N. A new trial steel was produced based on combining Ta and Nb to form Z-phase. It was shown that Z-phase was formed with a composition corresponding to Cr1+x(Nb,Ta)1-xN. The Nb/Ta ratio in Z-phase precipitates was higher than that in MX precipitates. Z-phase precipitates based on Ta and Nb were coarser than precipitates in a similar trial steel based on Ta alone.

Research has demonstrated that creep damage in power plant steels is directly linked to grain boundary precipitates, which serve as nucleation sites for cavities and micro-cracks. The formation of M 23 C 6 carbides along grain boundaries creates chromium-depleted zones vulnerable to corrosion and significantly reduces creep life due to rapid coarsening. Through combined Monte Carlo grain boundary precipitation kinetics and continuum creep damage modeling, researchers have predicted that increasing the proportion of MX-type particles could enhance creep performance. This hypothesis was tested using hafnium-containing steel, which showed improved creep and corrosion properties in 9% Cr steels. Ion implantation of Hafnium into thin foils of 9 wt% Cr ferritic steel resulted in two new types of precipitates: hafnium carbide (MX-type) and a Cr-V rich nitride (M 2 N). The hafnium carbide particles, identified through convergent beam diffraction and microanalysis, appeared in significantly higher volume fractions compared to VN in conventional ferritic steels. Additionally, Hafnium was found to eliminate M 23 C 6 grain boundary precipitates, resulting in increased matrix chromium concentration, reduced grain boundary chromium depletion, and enhanced resistance to intergranular corrosion cracking.

Laves phases are intermetallic phases well known for their excellent strength at high temperatures but also for their pronounced brittleness at low temperatures. Especially in high-alloyed steels, Laves phases were long time regarded as detrimental phases as they were found to embrittle the material. Perusing the more recent literature, it seems the negative opinion about the Laves phases has changed during the last years. It is reported that, if the precipitation morphology is properly controlled, transition metal-based Laves phases can act as effective strengthening phases in heat resistant steels without causing embrittlement. For a targeted materials development, the mechanical properties of pure Laves phases should be known. However, the basic knowledge and understanding of the mechanical behavior of Laves phases is very limited. Here we present an overview of experimental results obtained by micromechanical testing of single-crystalline NbCo 2 Laves phase samples with varying crystal structure, orientation, and composition. For this purpose, diffusion layers with concentration gradients covering the complete homogeneity ranges of the hexagonal C14, cubic C15 and hexagonal C36 NbCo 2 Laves phases were grown by the diffusion couple technique. The hardness and Young's modulus of NbCo 2 were probed by nanoindentation scans along the concentration gradient. Single-phase and single crystalline microcantilevers and micropillars of the NbCo 2 Laves phase with different compositions were cut in the diffusion layers by focused ion beam milling. The fracture toughness and the critical resolved shear stress (CRSS) were measured by in-situ microcantilever bending tests and micropillar compression tests, respectively. The hardness, Young's modulus and CRSS are nearly constant within the extended composition range of the cubic C15 Laves phase, but clearly decrease when the composition approaches the boundaries of the homogeneity range where the C15 structure transforms to the off stoichiometric, hexagonal C36 and C14 structure on the Co-rich and Nb-rich, respectively. In contrast, microcantilever fracture tests do not show this effect but indicate that the fracture toughness is independent of crystal structure and chemical composition of the NbCo 2 Laves phase.

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

The size and distribution of the Laves phase particles in a 9.85Cr-3Co-3W-0.13Mo-0.17Re- 0.03Ni-0.23V-0.07Nb-0.1C-0.002N-0.008B steel subjected to creep rupture test at 650°C under an applied stresses of 160-200 MPa with a step of 20 MPa were studied. After heat treatment consisting of normalizing of 1050°C and tempering of 770°C, M 23 C 6 and Fe 3 W 3 C carbides with the mean sizes of 67±7 and 40±5 nm, respectively, were revealed along the boundaries of prior austenite grains and martensitic laths whereas round NbX carbonitrides were found within martensitic laths. During creep metastable Fe 3 W 3 C carbides dissolved and the stable Laves phase particles precipitated; volume fraction of Laves phase increases with time. The Laves phase particles nucleated on the interfacial boundaries Fe 3 W 3 C/ferrite during first 100 h of creep and provided effective stabilization of tempered martensitic lath structure until their mean size less than 150 nm.

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.

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.

Components such as tubes, pipes and headers used in power generation plants are operated in a creep regime and have a finite life. During partial replacement, creep exhausted materials are often welded to virgin materials with superior properties. The aim of this study was to identify a suitable weld filler material to join creep aged X20CrMoV12-1 to a virgin P91 (X10CrMoVNbV9-1) steel. Two dissimilar joints were welded using the gas tungsten arc welding (GTAW) process for the root passes, and manual metal arc (MMA) welding for filling and capping. The X20 and the P91 fillers were selected for joining the pipes. The samples were further heat treated at 755°C to stress relief the samples. Microstructural evolution and mechanical properties of the weld metals were evaluated. The average hardness of X20 weld metal (264 HV10) was higher than the hardness measurement of P91 weld metal (206 HV10). The difference in hardness was attributed to the high carbon content in X20 material. The characterisation results revealed that the use of either X20 or P91 weld filler for a butt weld of creep aged X20 and virgin P91 pipes material does not have a distinct effect on the creep life and creep crack propagation mechanism. Both weld fillers (X20 and P91) are deemed to be suitable because limited interdiffusion (<10 μm) of chromium and carbon at the dissimilar weld interface was observed across the fusion line. The presence of a carbon ‘denuded’ zone was limited to <10 μm in width, based on the results from local measurements of the precipitate phase fractions using image analysis and from elemental analysis using EDS. However the nanoindentation hardness measurements across the fusion line could not detect any ‘soft’ zone at the dissimilar weld interface. The effect of the minute denuded zone was also not evident when the samples were subjected to nanoindentation hardness testing, tensile mechanical testing, Small Punch Creep Test (SPCT) and cross weld uniaxial creep testing.

In order to develop an Fe/Ni dissimilar-weld rotor structure for an Advanced Ultra Super Critical turbine, fundamental studies on the metallurgical properties of Fe/Ni welds are needed. In the work reported in this paper, we studied the microstructure evolution and creep rupture properties of Fe/Ni weld joints with different compositions. Investigation of thermally aged Fe/Ni diffusion couples revealed that Fe-based ferritic steel and Alloy 617 weld joints with a large difference in Cr content showed strong C diffusion at the weld interface. This decreased the creep rupture life of the weld joint, caused by coarsening of a martensitic structure near the interface. Analysis using Fe/Ni diffusion couples and thermodynamic calculations suggested that the driving force of C diffusion is the chemical potential gradient at the interface, and the difference in Cr content between Fe and Ni accelerates the C diffusion.