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Carney, Casey S.

Publications and source records attributed to Carney, Casey S..

High-Temperature Corrosion of Chromia-Forming Ni-Based Alloys in CO 2 Containing Impurities

Future technologies require structural materials resistant to environmental degradation in high-temperature CO 2 -rich environments. In this work, we exposed several commercially available Ni-based alloys (230, 263, 282, 617, 625, and 740H) to atmospheric pressure gases intended to simulate the compositions expected in future direct-fired supercritical CO 2 power cycles. The alloys were exposed to 95% CO 2 + 4% H 2 O + 1% O 2 and the same gas containing 0.1% SO 2 at temperatures of 600, 650, 700, 750, and 800 °C for 2500 h. With minor exceptions, chromia scales formed on all alloys at all temperatures in the SO 2 -free gas, yielding parabolic growth rates that followed an Arrhenius temperature dependence. Behavior in the SO 2 -containing gas was more complex. Generally, the alloys performed well at temperatures of 650, 750, and 800 °C. While some alloys further performed relatively well across the whole temperature range, several of the alloys experienced chromia failure resulting in non-protective duplex oxide scales and high oxidation rates, at temperatures of 600 and 700 °C. Deviation from protective behavior was associated with internal sulfide formation and, additionally for the case of 600 °C, external sulfate formation. Extensive carburization accompanied growth of the non-protective duplex oxide scales, which made it more difficult for the alloy to recover after initiation of the sulfur-induced accelerated corrosion process. The thermodynamic and kinetic factors influencing the accelerated corrosion in the presence of sulfur are discussed. The results suggest that caution is required when assessing compatibility of Ni-based alloys for CO 2 -based systems when sulfur-based impurities are expected.

36 MATERIALS SCIENCE↗

Effect of pressure on high-temperature oxidation of Ni alloys in supercritical CO 2 containing impurities

Direct supercritical CO 2 (sCO 2 ) power cycles require structural materials compatible with hot sCO 2 containing high levels of water and oxygen impurities. Chromia-forming Ni-based superalloys, which are leading candidates at temperatures > 600 °C, have shown good compatibility in pure sCO 2 , however potential impurity effects are not well understood. In this report we exposed several commercial Ni-based alloys to 95%CO 2 -4%H 2 O-(1-3)%O 2 at 750 °C and 0.1 or 20 MPa for 2500 h. Protective chromia scales formed in all cases. Nevertheless, water vapor-assisted oxide volatilization clearly occurred at high pressure. The volatilization rates decreased with time, but still represent a potentially serious compatibility issue in real, high-velocity, sCO 2 systems.

36 MATERIALS SCIENCE↗

Carburization susceptibility of chromia-forming alloys in high-temperature CO 2

It is generally believed that when a chromia scale forms in high-temperature CO 2 environments, carbon uptake of alloys is nearly eliminated, thereby preventing carburization and associated degradation of properties. We quantitively assess this notion through careful examination of several chromia-forming Ni-based and Fe-based commercial alloys after long-term (10,000-h) exposures to CO 2 and air at 700°C. Here, small but measurable carbon uptake ensued independent of alloy base metal (Ni/Fe), alloy crystal structure (FCC/BCC), and chromia growth rate. The rate for Ni-based alloys was strongly dependent on Si and Mn content, highlighting the need to understand possible long-term effects on mechanical properties.

36 MATERIALS SCIENCE↗

Oxidation Behavior of Welded Fe-Based and Ni-Based Alloys in Supercritical CO 2

Next-generation supercritical CO 2 (sCO 2 ) power cycles will require different classes of alloy throughout the operational temperatures to optimize tradeoff of creep strength, oxidation performance and cost. This will necessitate joining methods such as welding, which might pose compatibility concerns at the joined interfaces. In this study, similar and dissimilar metal welds were generated from a variety of candidate alloys for sCO 2 systems including ferritic/martensitic steels, austenitic steels, and Ni-based superalloys. Samples were extracted from different regions of the welds and exposed to sCO 2 at 550 °C and 20 MPa for 2500 h, then characterized to understand their behavior in this environment. Unsurprisingly, the local oxidation behavior was largely dictated by the Cr content in the underlying metal. High-Cr austenitic steels and Ni alloys formed slow-growing Cr-rich oxide scales with minimal carburization of the underlying metal, while low-Cr ferritic/martensitic steels formed fast-growing Fe-rich oxide scales with significant carburization. Most welds did not show any unusual oxidation behavior at the interfaces, considering the local Cr content. The one exception was the 347H similar metal weld, where a larger grain size and complex grain structure in the fusion zone led to a significantly higher rate of Fe-rich oxide nodule formation compared to the base metal. This suggests that microstructural changes at joined interfaces can play an important role on the oxidation-limited lifetimes in future sCO 2 systems. The composition changes across the interfaces enabled study of the effect of Fe on the growth rate of Cr-rich oxides and of the origins of the sub-surface recrystallization zone that forms beneath them.

36 MATERIALS SCIENCE↗

High-temperature oxidation of transient-liquid phase bonded Ni-based alloys in 1 bar and 250 bar carbon dioxide

Compact microchannel heat exchanger designs for supercritical CO 2 power cycles are valued for equipment size reduction and increased heat transfer. They can be fabricated via transient-liquid phase (TLP) bonding, which utilizes a lower melting point interlayer for bonding facilitation of etched thin plates. Haynes 230 and 282 TLP bonded stacks were exposed to high-purity CO 2 at 1 bar/700 °C to 4000 h and 250 bar/720 °C (supercritical) to 1500 h. All samples obeyed parabolic kinetics after an oxide buildup stage of 500-1000 h. Mass gains were similar for the base and TLP bonded alloys, and oxide thicknesses and scales did not significantly differ around the TLP bond regions. Furthermore, there were some slight oxide compositional differences for the H282 TLP samples at 250 bar. There was a slight pressure effect on mass gain, as samples exposed at the higher pressure experienced higher initial mass gains, but then slower continued oxide growth.

36 MATERIALS SCIENCE↗

Effect of Surface Finish on High-Temperature Oxidation of Steels in CO 2 , Supercritical CO 2 , and Air

Current and future power systems require steels resistant to high-temperature oxidation in CO 2 -rich environments. The introduction of structural defects by various surface treatments can profoundly affect the oxidation/corrosion behavior of steels in many environments. This effect is largely unexplored for steels exposed to high-temperature CO 2 , which is the focus of this work. We prepared Grade 22, Grade 91, 347H, and 310S steels with three different surface finishes, ranging from little to substantial surface damage, and exposed the steels to 1 bar CO 2 , 200 bar supercritical CO 2 , and laboratory air at 550 °C for up to 1500 h. Surface finish had little impact on the oxidation behavior of low-Cr (2 wt%) Grade 22 and high-Cr (25 wt%) 310S steels. In contrast, intermediate-Cr steels Grade 91 (8 wt%) and 347H (17 wt%) generally showed improved oxidation and carburization resistance with increasing extent of surface damage, which was attributed to the delay or prevention of the onset of Fe-rich oxide nodule growth. Comparison between exposure environments suggests that this effect is more complex for CO 2 compared to air and that it is additionally affected by CO 2 pressure. In conclusion, the results suggest that surface treatments should be considered as one approach to achieve improved corrosion resistance in high-temperature CO 2 , particularly for steels containing Cr levels near the transition that is required to form and maintain a protective Cr-rich oxide scale.

36 MATERIALS SCIENCE↗

Simulated fireside corrosion of T91 in oxy-combustion systems with an emphasis on coal/biomass environments

Oxy-combustion is the burning of a fuel in oxygen rather than air for the ease of capture of CO2 for reuse or sequestration. Corrosion issues associated with the change in heat exchanger tube operating environment (replacement of most of the N 2 with CO 2 and potentially higher SO x levels) from air- to oxy-combustion were examined. The ferritic-martensitic alloy T91 was used in accelerated fireside corrosion tests using several different gas compositions and ash deposit overcoats to simulate air-fired, oxy-fired coal, and oxy-fired co-fired coal/biomass conditions. Initial corrosion was observed after 240 h of exposure by examining cross-sections with retained ash. Metal section losses were determined after exposures of up to 1440 h at 600-700 °C. Severe corrosion was observed, and a corrosion response with respect to ash deposit chemistry was observed. Corrosion response differences with respect to gas phase chemistry were minimal. Alloy-oxide scale-ash morphologies were consistent with oxide fluxing mechanisms.

01 COAL, LIGNITE, AND PEAT↗

Structural Evolution of a Ni Alloy Surface During High-Temperature Oxidation

We show that considerable structural transformations occur at a Ni alloy surface during the transient stages of high-temperature oxidation. This was demonstrated by exposing the alloy to high-temperature CO 2 for short times at both atmospheric and supercritical pressures. A protective Cr-rich oxide layer formed after only 5 min at 700 °C and persisted for longer exposures up to 500 h. Voids formed and grew over time by the condensation of metal vacancies generated during oxidation, while the alloy surface recrystallized after sufficient oxidation had occurred. The oxygen potential established at the oxide/alloy interface led to oxidation along the newly formed grain boundaries as well as adjacent to and inside of the voids. Al, the most stable oxide-former and present at low concentration in the alloy, was preferentially oxidized in these regions. Furthermore, the results provide an improved understanding of the internal oxidation of Al and its role in enhancing scale adhesion for this class of Ni alloys.

20 FOSSIL-FUELED POWER PLANTS↗

Materials and Manufacturing Challenges for Compact Heat Exchangers of Supercritical CO2 Power Cycles

The supercritical CO2 (sCO2) power cycles rely heavily on heat recuperation to increase efficiency. Compact heat exchangers are proposed to reduce equipment size and enhance heat transfer between heat source and sCO2. Microchannel architectures in these heat exchangers are typically formed by a lamination process wherein channels are formed in layers of sheet material, which are then stacked and joined together using diffusion bonding, brazing, or transient-liquid-phase bonding (TLPB). TLPB of Ni-based superalloy (Alloy 230) sheets into stacks was investigated. Electron microscopy identified solidification shrinkage porosity on the bond line as the most common defect in the TLP bonded stacks. Tensile yield strengths of 76-86 % of the base alloy strength were obtained on bonded stacks. Scanning electron microscopy on the fracture surfaces indicated ductile failure mode in the bonded zone. Environmental stability of joined regions in Alloy 230 stacks was investigated by exposing to CO2 at 700°C for 1500 hours. Mass change and post-exposure microscopic analysis showed a corrosion behavior similar to the base material.

14 SOLAR ENERGY↗

Transient-Liquid-Phase Bonding of H230 Ni-Based Alloy Using Ni-P Interlayer: Microstructure and Mechanical Properties

Transient-liquid-phase bonding using Ni-P as an interlayer has been developed for H230 Ni-Cr-W solid-solution-strengthened Ni-based alloy. Two process parameters—composition of the interlayer and bonding time—have been varied to optimize the mechanical properties. H230 has been bonded into two sets of stacks (set I and II) for 8 and 4 hours using Ni-12P and Ni-6P interlayer, respectively, (wt pct) at 1423 K (1150 °C) and 12.7 MPa. The microstructure of both the stacks has three distinct regions—the joint centerline which showed the presence of pores, an isothermally solidified zone (ISZ) which did not have any carbide precipitates and base H230. Transmission electron microscopy and atom probe tomography showed a uniform microstructure, and an absence of any deleterious phases at the joint and in ISZ. Set I and set II had a yield strength of 76 and 86 pct of that of the H230 sheet, tested at 1023 K (750 °C). Here, the measured elongation at fracture was negligible, but the fracture surfaces revealed a ductile cup-and-cone-type fracture occurring through the ISZ/joint region. Examination of broken tensile samples revealed that the plastic strain was constrained to within one joint region through which fracture occurred.

14 SOLAR ENERGY↗