Due to a high degree of mixing between substrate and weld deposit, fusion welding of dissimilar metal joints functionally produce new, uncharacterized alloys. In the power generation industry, such mixing during the application of cobalt-based hardfacing has led to a disconcerting number of failures characterized by the hard overlay welds disbonding. Investigations into this failure mechanism point to the unknown alloy beneath the surface of the hardfacing layer transforming, hardening, and becoming brittle during service. This research describes a methodology for exploring a chemical space to identify alloy combinations that are expected to be safe from deleterious phase formation. Using thermodynamic modeling software and a stepped approach to potential chemistries, the entire phase stability space over the full extent of possible mixing between substrate and weld material can be studied. In this way diffusion effects – long term stability – can also be accounted for even in the case where mixing during application is controlled to a low level. Validation of predictions specific to the hardfacing system in the form of aged weld coupons is also included in this paper. Though the application of this methodology to the hardfacing problem is the focus of this paper, the method could be used in other weld- or diffusion- combinations that are expected to operate in a high temperature regime.

Coatings are an essential part of the materials system to protect the turbine blades from oxidation and corrosive attack during service. Inter-diffusion of alloying elements between a turbine blade substrate and their coatings is a potential concern for coated turbine blades at ever increasing operating temperatures because this can cause the formation of undesirable Secondary Reaction Zones (SRZs), which may degrade the mechanical properties of coated Ni-based superalloys. Understanding the effects of each element on the SRZ formation is essential in order to understand both the mechanism and inter-diffusion behaviour between coatings and substrates. In this research, a number of simpler aluminized ternary Ni-Al-X (where X is Co, Cr, Re, Ru or Ta) alloys were investigated in order to elucidate the separate effects of each element on the microstructural evolution, especially at the coating/substrate interface. The aluminized ternary alloys developed distinctive diffusion zones, depending on the third alloy element, ‘X’. Specifically, it has been found that both Ni-Al-Re and Ni-Al-Ta alloys developed a continuous SRZ-like diffusion layer. This diffusion zone persisted in the Ni-Al-Re alloys after high temperature exposure, indicating that Re has a stronger effect on SRZ formation than Ta.

While the water vapor content of the combustion gas in natural gas-fired land based turbines is ~10%, it can be 20-85% with coal-derived (syngas or H 2 ) fuels or innovative turbine concepts for more efficient carbon capture. Additional concepts envisage working fluids with high CO 2 contents to facilitate carbon capture and sequestration. To investigate the effects of changes in the gas composition on thermal barrier coating (TBC) lifetime, furnace cycling tests (1h cycles) were performed in air with 10, 50 and 90 vol.% water vapor and in CO 2 -10%H 2 O and compared to prior results in dry air or O 2 . Two types of TBCs were investigated: (1) diffusion bond coatings (Pt diffusion or simple or Pt-modified aluminide) with commercially vapor-deposited yttria-stabilized zirconia (YSZ) top coatings on second-generation superalloy N5 and N515 substrates and (2) high velocity oxygen fuel (HVOF) sprayed MCrAlYHfSi bond coatings with air-plasma sprayed YSZ top coatings on superalloy X4 or 1483 substrates. In both cases, a 20-50% decrease in coating lifetime was observed with the addition of water vapor for all but the Pt diffusion coatings which were unaffected by the environment. However, the higher water vapor contents in air did not further decrease the coating lifetime. Initial results for similar diffusion bond coatings in CO 2 -10%H 2 O do not show a significant decrease in lifetime due to the addition of CO 2 . Characterization of the failed coating microstructures showed only minor effects of water vapor and CO 2 additions that do not appear to account for the observed changes in lifetime. The current 50°-100°C de-rating of syngas-fired turbines is unlikely to be related to the presence of higher water vapor in the exhaust.

Simple and effective material examination methods are desired for the diffusion bonding process, so that bonding produced components, such as compact heat exchangers, can be used in nuclear applications. Optical microscopy of diffusion bond process samples is a quick way to examine diffusion bond-line microstructure and to evaluate material quality. The stacked nature of a diffusion bonded-block results in distinct regions of grain growth both at and away from the bond interface. Strong diffusion bond materials exhibit grain growth across the original bond interface plane, weak materials have little-to-no growth across. A series of 316H diffusion bonded specimens of differing quality and strength were examined using optical microscopy. The microstructure both at and away from the bond interface was examined over 15mm long sections of the bond-line. A metric for evaluating bond growth is proposed. This is defined as the Bond Line Growth Threshold (BLGT) and is evaluated as the percentage of the bond line with grains meeting the threshold. Here a fraction of the diffusion bond is considered bonded when its grains exceed a threshold of growth past the bond interface. The BLGT is determined through automated image processing methods.

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.

Diffusion aluminide coatings have been evaluated as a strategy for improving the oxidation resistance of austenitic and ferritic-martensitic (FM) steels, particularly in the presence of steam or water vapor. The objective was to evaluate the strengths and weaknesses of these coatings and quantify their performance and lifetime. Long-term diffusion and oxidation experiments were conducted to study the behavior of various model diffusion coatings and produce a better data set for lifetime predictions. The key findings are that (1) thin coatings (<50μm) with relatively low Al contents appear to be more effective because they avoid high thermal expansion intermetallic phases and have less strain energy to nucleate a crack; and (2) the low Al reservoir in a thin coating and the loss of Al due to interdiffusion are not problematic because the low service temperatures of FM steels (<600°C) and, for austenitic steels at higher temperatures, the phase boundary between the ferritic coating-austenitic substrate inhibits Al interdiffusion. Unresolved issues center on the effect of the coating on the mechanical properties of the substrate including the reaction of N in the alloy with Al.

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.

Titanium is extensively utilized in the aerospace industry due to its low density and excellent mechanical and chemical properties. Given that components in this sector are exposed to temperatures up to 873 K, representing 45% of the metal's melting point, understanding the mechanical properties in this temperature range is crucial for ensuring flight safety. This study focuses on examining the creep behavior of pure titanium to gain insights into its fundamental mechanical response. Creep was observed to occur at stresses exceeding micro-yielding levels around 297 K, primarily attributed to overcoming the pinning effect caused by interstitial atoms. Interestingly, at intermediate temperatures, an inverted primary creep phenomenon was noted, with an activation energy of approximately 240 kJ/mol within this range. This value, significantly larger than those associated with lattice or dislocation-core diffusions, suggests the potential movement of dislocations with interstitial atoms, similar to the diffusion of oxygen or nitrogen within titanium. Moreover, fracture strain exceeded 80% at temperatures surpassing 673 K, possibly resulting from grain boundary diffusion mechanisms akin to superplasticity. The activation energy for this mechanism, at 97 kJ/mol, is adequate for activating grain boundary deformation at intermediate temperatures.

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 study explores methods to enhance the creep strength of 12%Cr martensitic/ferritic steels. The approach focuses on utilizing various precipitates to hinder microstructure coarsening and dislocation movement. A combination of Laves phase (slow precipitation) and MX carbonitrides (dislocation pinning) is used for sustained strengthening. Different MX-forming elements (V, Ta, Ti) are investigated to identify the optimal combination for high quantities of finely distributed strengthening particles. Additionally, cobalt and copper are employed to promote a fully martensitic microstructure and potentially slow down diffusion or provide nucleation sites for Laves phase precipitation. Long-term creep tests confirm the effectiveness of Laves phase precipitation, particularly with tungsten present. Tantalum's influence on both MX precipitation and the Laves phase is also observed. Combining multiple MX-forming elements (V/Ta, V/Ti, Ta/Ti) further improves creep strength, supported by predictions of high MX carbonitride formation from Thermo-Calc calculations. Partially replacing cobalt with copper (1%) also demonstrates positive effects on creep properties.

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.

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.

Ti alloys are used as compressor blades and disks in jet engines due to their high specific strength and good oxidation resistance at operation temperature. However, Ti alloys cannot be used above 600 °C because creep properties and oxidation resistance deteriorate. To overcome the above problems, the effect of alloying element on oxidation resistance was investigated and it was found that Sn deteriorated oxidation resistance and Nb improved oxidation resistance. Then, we have attempted to design new Ti alloys without Sn, but including Nb because Nb improved oxidation resistance. To expect solid-solution hardening, Zr was also added to the alloys. In this study, the creep behavior of Ti-10Al-2Nb-2Zr and Ti-10Al-2Nb-2Zr-0.5Si alloys was investigated. The creep test was performed at temperature range between 550 and 650 °C and stress range between 137 and 240 MPa. The stress exponent and the activation energy for creep were analyzed using an Arrhenius equation. The stress exponent was 5.9 and 3.4, and the activation energy was 290 and 272 kJ/mol for Ti-10Al-2Nb-2Zr and Ti-10Al-2Nb-2Zr-0.5Si, respectively. This indicates the creep deformation mechanism is dislocation (high-temperature power law) creep governed by lattice diffusion.

Precipitation of Z-phase, Cr(V,Nb)N, is known to negatively affect creep properties of 9-12%Cr steels for power plant applications as it dissolves finely distributed MX particles, (V,Nb)N, especially in high Cr steels. As the Z-phase precipitates slowly as large particles, this causes a net drop in precipitation strengthening. Two model alloys containing 9 and 12%Cr, but otherwise having similar composition, were produced in order to quantify the difference in Z-phase precipitation speed at different Cr levels. The nitride precipitation behavior was followed at different temperatures using TEM and XRD, allowing for a quantification of the Z-phase precipitation. The Z-phase was found to precipitate 20-50 times faster in the 12%Cr steel compared to 9%Cr steel in the temperature range 600- 650°C. The transformation of MX into Z-phase was followed in a Ta containing alloy without V or Nb. In this alloy the Z-phase precipitates very quickly, and thus appears as finely distributed particles which have the same strengthening effect as MX particles. Investigations using atomic resolution microscopy showed how Cr diffuses from the matrix into the TaN MX particles and gradually transforms them both chemically and crystallographically into Z-phase CrTaN particles.

According to ASME Case N-888-3, Similar and Dissimilar Metal Welding Using Ambient Temperature SMAW or Machine GTAW Temper Bead Technique, a 48 hr waiting period before conducting the final nondestructive examination (NDE) is required when ferritic filler weld metal is used. The purpose of the 48 hr hold is to confirm the absence of hydrogen-induced cracking in the temper bead heat-affected zone. In previous research, the effect of post-weld heat treatment (PWHT) and temper bead welding (TBW) on the hydrogen-induced cracking (HIC) susceptibility in the coarse-grained heat-affected zone (CGHAZ) in welds of SA-508, P-No. 3 Group 3, pressure vessel steel was investigated using the Delayed Hydrogen Cracking Test (DHCT). In that previous study, the Gleeble thermomechanical simulator was used to generate six CGHAZ microstructural conditions: as-welded (AW), PWHT, and AW with single a TBW reheat at 675, 700, 725, and 735°C. Hydrogen was introduced to the specimen through cathodic charging under in situ constant tensile stress. The HIC susceptibility for these microstructures was ranked by the DHCT at a diffusible hydrogen level significantly exceeding typical GTAW and SMAW processes. The work described in this paper investigates the susceptibility to HIC of these same CGHAZ microstructures with DHCT at variable current densities, further ranking each condition. Test results were analyzed by fracture surface examination of failed tests, and cross-section microstructural analysis under a scanning electron microscope (SEM). Future steps include evaluating critical hydrogen content levels using gas chromatography for each condition. The results from this study will be used to consider potential elimination of the NDE hold time requirement in Case N-888-3 when ferritic weld metal is used.

The localized creep failure in the heat-affected zone (HAZ) of Grade 91 steel weldments has been identified as one of the most important factors causing significantly shortened service lifetime and structural integrity issues of welded components in advanced fossil and nuclear power plants. To conduct a reliable creep lifetime assessment, a new engineering assessment approach has been developed by incorporating the experimentally determined local properties of the heterogeneous HAZ. By creep testing a purposely simulated HAZ specimen with in situ digital image correlation (DIC) technique, the highly gradient creep properties across the HAZ of Grade 91 steel was quantitatively measured. A physical creep cavitation constitutive model was proposed to investigate the local creep deformation and damage accumulation within the heterogeneous HAZ, which takes into account the nucleation of creep cavities and their growth by both grain boundary diffusion and creep deformation. The relationship among the local material property, creep strain accumulation, and evolution characteristic of creep cavities was established. The approach was then utilized to investigate the creep response and subsequent life for an ex-service 9% Cr steel weldment by incorporating the effects of pre-existing damages which developed and accumulated during long-term services. The predicted results exhibited quantitative agreement with the DIC measurement in terms of both nominal/local creep deformation as well as the subsequent life under the test conditions at 650 and 80 MPa.

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 microstructural evolution has been investigated for an 18Cr-12Ni stainless steel (347HFG) that has been subject to a thermo-mechanical treatment to obtain a fine grain size (ASTM 7-10). In particular, sigma phase precipitation and growth has been evaluated. Samples of 347HFG stainless steel have been isothermally heat treated to reproduce and accelerate the ageing conditions experienced in-service at temperatures between 600 and 750 °C for up to 10,000 hours. Results have shown that sigma phase is precipitated at triple points and along grain boundaries after as little as 1000 hours which is contrary to thermodynamic predictions. In addition X-ray diffraction (XRD) and image analysis has been carried out to semi-quantitatively measure the amount of sigma phase present. The area fraction of sigma has been found to be 2.77 and 2.23 percent at 700 and 750 °C respectively. This is a higher volume fraction of sigma phase than has been previously observed in regular 347H at these conditions. It is thought that this is due to the reduced grain size that has provided an increase in nucleation sites and diffusion paths that can enhance the precipitation and growth of sigma phase. The results from this study are discussed with regards to the effect of precipitation on the service life of a 347HFG stainless steel tube operating in advanced supercritical boilers.

Diffusion bonded compact heat exchangers have exceptionally high heat transfer efficiency and might significantly improve the performance and reduce the cost of supercritical carbon-dioxide Brayton cycle power plants using high temperature heat sources, like high temperature nuclear reactors and concentrating solar power plants. While these heat exchangers have an excellent service history for lower temperature applications, considerable uncertainty remains on the performance of diffusion bonded material operating in the creep regime. This paper describes a microstructural modeling framework to explore the plausible mechanisms that may explain the reduced creep ductility and strength of diffusion bonded material, compared to wrought material. The crystal plasticity finite element method (CPFEM) is used to study factors affecting bond strength in polycrystals mimicking diffusion bonded microstructures. Additionally, the phase field method is also employed to simulate the grain growth and recrystallization at the bond line to model the bonding process and CPFEM is used to predict the resulting material performance to connect processing parameters to the expected creep life and ductility of the material, and to study potential means to improve the structural reliability of the material and the resulting components by optimizing the material processing parameters.

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.