Steam turbine materials and corrosion

Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions. Current goals of the U.S. Department of Energy’s Advanced Power Systems Initiatives include coal generation at 60% efficiency, which would require steam temperatures of up to 760°C. This research examines the steamside oxidation of alloys for use in USC systems, with emphasis placed on applications in high- and intermediate-pressure turbines. The list of alloys being examined is discussed, including the addition of new alloys to the study. These include alloy 625, selected because of its use as one of the two alloys used for turbine rotors, valves, casings, blading and bolts in the European AD700 full-scale demonstration plant (Scholven Unit F). The other alloy, alloy 617, is already one of the alloys currently being examined by this project. Other new alloys to the study are the three round robin alloys in the UK-US collaboration: alloys 740, TP347HFG, and T92. Progress on the project is presented on cyclic oxidation in 50% air – 50% water vapor, furnace exposures in moist air, and thermogravimetric analysis in argon with oxygen saturated steam. An update on the progress towards obtaining an apparatus for high pressure exposures is given

Degradation of solid oxide fuel cell metallic interconnects in fuels containing sulfur

Hydrogen is the main fuel for all types of fuel cells except direct methanol fuel cells. Hydrogen can be generated from all manner of fossil fuels, including coal, natural gas, diesel, gasoline, other hydrocarbons, and oxygenates (e.g., methanol, ethanol, butanol, etc.). Impurities in the fuel can cause significant performance problems and sulfur, in particular, can decrease the cell performance of fuel cells, including solid oxide fuel cells (SOFC). In the SOFC, the high (800-1000°C) operating temperature yields advantages (e.g., internal fuel reforming) and disadvantages (e.g., material selection and degradation problems). Significant progress in reducing the operating temperature of the SOFC from ~1000 ºC to ~750 ºC may allow less expensive metallic materials to be used for interconnects and as balance of plant (BOP) materials. This paper provides insight on the material performance of nickel, ferritic steels, and nickel-based alloys in fuels containing sulfur, primarily in the form of H2S, and seeks to quantify the extent of possible degradation due to sulfur in the gas stream

Effects of CO2 and H2S on corrosion of martensitic steels in brines at low temperature

Corrosion studies were conducted for martensitic carbon steels in 5 wt% NaCl brine solutions at 4°C and 10 MPa (1,450 psi). These studies simulated different subsurface environments relevant to Arctic drilling. Here, two high-strength martensitic carbon steels, S-135 and UD-165, were studied in three different environments: (1) a CO2-NaCl-H2O solution with a CO2:H2O molar ratio of 0.312 in the whole system, (2) an H2SNaCl- H2O solution with an H2S:H2O molar ratio of 3.12 × 10−4, and (3) a CO2-H2S-NaCl-H2O solution with the same acid gas to water ratios as environments 1 and 2. Results from the CO2+H2S mixed environment indicated that sour corrosion mechanism was dominant when the CO2:H2S molar ratio was 1,000. This impact of a small amount of H2S on the corrosion mechanism could be attributed to the specific adsorption of H2S on the steel surface. Electrochemical and mass loss measurements showed a distinct drop in the corrosion rate (CR) by more than one order of magnitude when transitioning from sweet to sour corrosion. This inhibiting effect on CR was attributed to the formation of a protective sulfide thin film

Corrosion behavior of 13Cr casing steel in cement-synthetic pore solution exposed to high pressure CO2 and H2S

The electrochemical corrosion behavior of grade L-80, type 13Cr casing steel was investigated in cement-synthetic pore solution (CSPS) exposed to CO2 and H2S using in-situ electrochemical methods and ex-situ surface analyses at 85 and 200 °C, respectively. Total system pressure was 10 MPa. Corrosion rates increased significantly when the temperature increased from 85 to 200 °C. Limiting current behavior was observed for the anode reaction, while charge-transfer control was observed for the cathode reaction. Surface analyses revealed the presence of CaCO3 on the surface at both temperatures and FeCO3-like deposits at 200 °C

Quantitative X-ray microanalysis of submicron carbide formation in chromium (III) oxide rich scale

This paper discusses the chemical microanalysis techniques adapted to identify the precipitates that form on the surface of, or within, the oxide scale of a Fe-22Cr ferritic steel during exposure to a carbon-monoxide rich environment at 750C for 800 hours. Examination of oxidized test coupons revealed the presence of a fiber like structure at the surface, shown in figure 1. Other studies have reported that these structures are carbon precipitates

Understanding and Controlling Cu-Catalyzed Graphene Nucleation: The Role of Impurities, Roughness, and Oxygen Scavenging

The mechanism by which Cu catalyst pretreatments control graphene nucleation density in scalable chemical vapor deposition (CVD) is systematically explored. The intrinsic and extrinsic carbon contamination in the Cu foil is identified by time-of-flight secondary ion mass spectrometry as a major factor influencing graphene nucleation and growth. By selectively oxidizing the backside of the Cu foil prior to graphene growth, a drastic reduction of the graphene nucleation density by 6 orders of magnitude can be obtained. This approach decouples surface roughness effects and at the same time allows us to trace the scavenging effect of oxygen on deleterious carbon impurities as it permeates through the Cu bulk. Parallels to well-known processes in Cu metallurgy are discussed. We also put into context the relative effectiveness and underlying mechanisms of the most widely used Cu pretreatments, including wet etching and electropolishing, allowing a rationalization of current literature and determination of the relevant parameter space for graphene growth. Taking into account the wider CVD growth parameter space, guidelines are discussed for high-throughput manufacturing of "electronic-quality" monolayer graphene films with domain size exceeding 1 mm, suitable for emerging industrial applications, such as electronics and photonics.This research was supported by the ERC under grant InsituNANO (279342), the EPSRC under grant GRAPHTED (EP/K016636/1), and the Innovation R&D programme of the National Measurement System of the U.K. Department of Business, Innovation and Skills (project number 118616)

High temperature electrochemical corrosion rate probes

Corrosion occurs in the high temperature sections of energy production plants due to a number of factors: ash deposition, coal composition, thermal gradients, and low NOx conditions, among others. Electrochemical corrosion rate (ECR) probes have been shown to operate in high temperature gaseous environments that are similar to those found in fossil fuel combustors. ECR probes are rarely used in energy production plants at the present time, but if they were more fully understood, corrosion could become a process variable at the control of plant operators. Research is being conducted to understand the nature of these probes. Factors being considered are values selected for the Stern-Geary constant, the effect of internal corrosion, and the presence of conductive corrosion scales and ash deposits. The nature of ECR probes will be explored in a number of different atmospheres and with different electrolytes (ash and corrosion product). Corrosion rates measured using an electrochemical multi-technique capabilities instrument will be compared to those measured using the linear polarization resistance (LPR) technique. In future experiments, electrochemical corrosion rates will be compared to penetration corrosion rates determined using optical profilometry measurements

Corrosion behavior of iron and nickel base alloys under solid oxide fuel cell exposure conditions

Topography and phase composition of the scales formed on commercial ferritic stainless steels and experimental low CTE nickel-based alloys were studied in atmospheres simulating solid oxide fuel cell (SOFC) environments. The materials were studied under dual environment conditions with air on one side of the sample and carbon monoxide on the other side at 750°C. Surface characterization techniques, such as scanning electron microscopy and X-ray diffraction analysis were used in this study

Oxidation of advanced steam turbine alloys

Advanced or ultra supercritical (USC) steam power plants offer the promise of higher efficiencies and lower emissions. Current goals of the U.S. Department of Energy’s Advanced Power Systems Initiatives include coal generation at 60% efficiency, which would require steam temperatures of up to 760°C. This research examines the steamside oxidation of advanced alloys for use in USC systems, with emphasis placed on alloys for high- and intermediate-pressure turbine sections

Corrosion probes for fireside monitoring in coal-fired boilers

Corrosion probes are being developed and combined with an existing measurement technology to provide a tool for assessing the extent of corrosion of metallic materials on the fireside in coal-fired boilers. The successful development of this technology will provide power plant operators the ability to (1) accurately monitor metal loss in critical regions of the boiler, such as waterwalls, superheaters, and reheaters; and (2) use corrosion rates as process variables. In the former, corrosion data could be used to schedule maintenance periods and in the later, processes can be altered to decrease corrosion rates. The research approach involves laboratory research in simulated environments that will lead to field tests of corrosion probes in coal-fired boilers. Laboratory research has already shown that electrochemically-measured corrosion rates for ash-covered metals are similar to actual mass loss corrosion rates. Electrochemical tests conducted using a potentiostat show the corrosion reaction of ash-covered probes at 500?C to be electrochemical in nature. Corrosion rates measured are similar to those from an automated corrosion monitoring system. Tests of corrosion probes made with mild steel, 304L stainless steel (SS), and 316L SS sensors showed that corrosion of the sensors in a very aggressive incinerator ash was controlled by the ash and not by the alloy content. Corrosion rates in nitrogen atmospheres tended to decrease slowly with time. The addition of oxygen-containing gases, oxygen and carbon dioxide to nitrogen caused a more rapid decrease in corrosion rate, while the addition of water vapor increased the corrosion rate