[en] A high-refractory Ni-based superalloy prototype was melted on a research scale while simulating industry practices. Ingots were vacuum induction melted and subjected to a computationally optimized homogenization heat treatment prior to fabrication which consisted of forging and hot rolling. Failure of one of the ingots at the early stage of the forging process was attributed to the precipitation of the β-NiAl phase during melting which stabilized the eutectic constituent.

[en] The need for materials with superior thermal and mechanical properties while mitigating cost increases interest in new complex alloy compositions which brings challenges to manufacturing processes. In this investigation, vacuum induction melting (VIM) and electroslag remelting (ESR) of a novel tantalum (Ta)-containing martensitic steel was performed using standard industry practices at a laboratory scale. A 25 pct loss of Ta was measured from the VIM electrode to the ESR ingot using X-ray fluorescence. Several tools were used for broad characterization of the ingots, including LECO for chemistry analysis, scanning electron microscopy, and electron probe microanalysis for observation of the precipitate and inclusion phases post-VIM and post-ESR as well as computational modeling of the ESR process for the calculation of macrosegregation and inclusion travel. It was found that a significant amount of Ta₂O₅ inclusions formed during VIM and were transferred to the slag during ESR. While ESR was particularly successful at decreasing the number density of inclusions by 95 pct, additional efforts are needed with regard to vacuum leak rate and purity of stock material when melting novel advanced steels.

[en] Segregation of solute elements occurs in nearly all metal alloys during solidification. The resultant elemental partitioning can severely degrade as-cast material properties and lead to difficulties during post-processing (e.g., hot shorts and incipient melting). Many cast articles are subjected to a homogenization heat treatment in order to minimize segregation and improve their performance. Traditionally, homogenization heat treatments are based upon past practice or time-consuming trial and error experiments. Through the use of thermodynamic and kinetic modeling software, NETL has designed a systematic method to optimize homogenization heat treatments. Use of the method allows engineers and researchers to homogenize casting chemistries to levels appropriate for a given application. The method also allows for the adjustment of heat treatment schedules to fit limitations on in-house equipment (capability, reliability, etc.) while maintaining clear numeric targets for segregation reduction. In this approach, the Scheil module within Thermo-Calc is used to predict the as-cast segregation present within an alloy, and then diffusion controlled transformations is used to model homogenization kinetics as a function of time and temperature. Examples of computationally designed heat treatments and verification of their effects on segregation and properties of real castings are presented.

[en] The interfacial energies of three twin boundaries with low-index boundary planes: prismatic (1 0 1-bar 0), basal O-terminated (0001), and basal Cr-terminated (0001), and the segregation energies of five doping elements (Ce, Hf, La, Y and Zr) have been calculated as a function of temperature. The static energies at 0 K were obtained through first-principles calculations and the energies at finite temperatures were derived based on the Debye model. The calculation results show that both the interfacial and segregation energies decrease as temperature increases and the segregation energies are found to be proportional to the ionic size mismatch and the interfacial energy. Our combined approaches suggest an efficient and less computationally intensive way to derive grain boundary energetics at finite temperatures. (paper)

[en] Phase stability is an important design parameter for Ni-based superalloys to be used in future advanced ultra-supercritical (AUSC) power plants as exposure times in this type of environment are considerable. In this investigation, microstructures based on candidate alloy 263 were obtained with varying amounts of η precipitates using isothermal exposure at 800 °C for times ranging from 1000 h to 10,000 h. The effect of η phase stability on the creep properties was determined using creep specimens isothermally aged at 800 °C for 8 h, 3000 h, 5000 h and 10,000 h prior to creep screening. The creep life was found to exponentially decrease with increasing density of η phase while the elongation to failure was found to increase. Furthermore, the minimum creep rate was related to the density of η phase; a relationship that did not depend on the alloy formulation. Modification to the Ti and Al concentrations slowed down the γ′ to η transformation while doubling the γ′ fraction after standard heat treatment. By modifying the Ti and Al content, and thereby improving γ′ stability over η, the creep lives of specimens isothermally aged for up to 5000 h were greater than that of the nominal alloy in its standard aged condition.

[en] High-entropy alloys (HEAs), a novel class of metal alloys, have been receiving increasing attention from the scientific community. HEAs have the potential to be used in critical load-bearing applications in replacement of conventional alloys such as stainless steel and nickel-base superalloys. Tensile experiments at quasi-static to dynamic strain rates (10⁻⁴-10³ s⁻¹) were performed on two single-phase face-centered cubic HEAs, CoCrFeNi and CoCrFeMnNi. Electron backscatter diffraction was used to study the microstructure of the samples before the experiments, and transmission electron microscopy was performed postmortem. The dominant deformation mechanisms were dislocation slip at quasi-static strain rates with the addition of deformation nano-twins at dynamic strain rates. Ultimate dynamic tensile strength and ductility improved with the increase in strain rate, which can be attributed to the activation of deformation nano-twins in HEAs. CoCrFeNi and CoCrFeMnNi both have low stacking fault energies, which could promote twinning at high strain rates to accommodate plastic deformation. The strain rate sensitivity of the flow stress increased with increasing strain rate, beginning with negligible strain rate sensitivity in the quasi-static range to high strain rate sensitivity in the dynamic range. CoCrFeMnNi showed greater strain rate sensitivity of flow stress. CoCrFeNi, with less configurational entropy, had higher mechanical properties and strain-hardening rates compared to CoCrFeMnNi, which was attributed to the weakening effect of the addition of Mn on the solid solution hardening.

[en] Highlights: • Incorporation of Mn into CrFeCoNi impairs corrosion resistance of the solid solution. • The CPT for CrMnFeCoNi was much lower than that of CrFeCoNi. • Pits on the surface of the CrMnFeCoNi were larger and deeper than those on CrFeCoNi. • Alternative EIS data representation provides accurate information about corrosion. -- Abstract: The electrochemical behavior and susceptibility to pitting corrosion of CrFeCoNi and CrMnFeCoNi high entropy alloys were studied in a 0.1 M NaCl solution at temperatures ranging from 25 to 75 °C. Electrochemical measurements revealed that CrMnFeCoNi is more susceptible to oxide film breakdown and localized corrosion compared to CrFeCoNi. Post corrosion microscopic observations showed severe pitting corrosion for CrMnFeCoNi in higher temperatures compared to CrFeCoNi. Based on in-depth XPS profile measurements on the remaining oxide films, this behavior was attributed to the depletion of Cr in the oxide film and detrimental presence of Mn in the matrix solid solution of CrMnFeCoNi.

[en] The effect of Si contamination when using B to improve the creep properties of a Ni-based superalloy was investigated using advanced characterization techniques and first-principles simulations on alloys with high and low B levels with varying Si contents. The positive effect of B segregation along grain boundaries on the creep properties was mitigated by the presence of Si which showed a similar segregation preference. Density functional theory calculations were used for validation by calculating grain boundary cleavage energies. Silicon was shown to decrease grain boundary cohesion which offsets the positive effect of B.

[en] Highlights: • Deformation below 1130 °C leads to partially recrystallized microstructures. • Higher temperatures enhance the driving force for dislocation and boundary mobility. • The strain rate controls the dominant softening mechanism above 1130 °C. • The γ' precipitates strongly affect the accuracy of the Zener-Hollomon parameter. • Zener-Hollomon model can be used to identify regions of different flow mechanisms. -- Abstract: The deformation behavior of a novel Ni-based superalloy was investigated using isothermal compression on a Gleeble system at temperatures between 1050 and 1210 °C with strain rates between 0.001 and 0.1 s⁻¹. Flow-stress curves and electron backscatter diffraction maps were employed to experimentally identify the various flow mechanisms operative during deformation. Deformation at temperatures below 1130 °C presented strong work hardening with limited restoration during dynamic softening leading to partially recrystallized microstructures. Increasing the deformation temperature to and above 1130 °C enhanced the driving force for dislocation and grain boundary mobility thereby enabling dynamic recovery (DRV) and dynamic recrystallization (DRX) mechanisms to better operate. The influence of the strain rate was more evident during deformation at these temperatures. Increasing the strain rate from 0.001 s⁻¹ to 0.1 s⁻¹ resulted in a transition in dominant softening mechanism from DRV to DRX. Flow stress modeling using the Zener-Hollomon parameter was performed to obtain the activation energy and the constitutive equation for hot deformation of the alloy. Strong changes in flow behavior affected the accuracy of the flow stress model, and thus, the model was used alternatively to identify deformation parameters associated with various flow regimes. In doing so, the activation energy and the other equation constants were obtained for each deformation mechanism observed experimentally.

[en] Highlights: ►Oxidation products of Ni-based superalloy were studied in oxy-fuel combustion conditions. ► An oxidation-induced phase transformation occurred in the subsurface region. ► One of the two product phases was not in the Ni database of Thermo-Calc. ► This unknown phase is an ordered derivative of FCC structure of Ni–Ti(–Ta) system. ► This phase is likely detrimental to the mechanical integrity of the alloy in use. - Abstract: In the integration of oxy-fuel combustion to turbine power generation system, turbine alloys are exposed to high temperature and an atmosphere comprised of steam, CO₂ and O₂. While surface and internal oxidation of the alloy takes place, the microstructure in the subsurface region also changes due to oxidation. In this study, bare metal coupons of Ni-base superalloys were exposed in oxy-fuel combustion environment for up to 1000 h and the oxidation-related microstructures were examined. Phase transformation occurred in the subsurface region in Ni-based superalloy and led to twinning. The transformation product phases were analyzed through thermodynamic equilibrium calculations and various electron microscopy techniques, including scanning electron microscopy (SEM), orientation imaging microscopy (OIM) and transmission electron microscopy (TEM). The mechanism by which the phase transformation and the formation of the microstructure occurred was also discussed. The possible effects of the product phases on the performance of the alloy in service were discussed.