Fireside Corrosion of Heat Exchanger Materials for Advanced Solid Fuel Fired Power Plants

To address the challenge of climate change, future energy systems need to have reduced greenhouse gas emissions and increased efficiencies. For solid fuel fired combustion plants, one route towards achieving this is to increase the system’s steam temperatures and pressures. Another route is to co-fire renewable fuels (such as biomass) with coals. Fireside corrosion performance of two candidate superheater/reheater alloys has been characterised at higher heat exchanger surface temperature. Samples of the alloys (a stainless steel, Sanicro 25 and a nickel-based alloy, IN740) were exposed in fireside corrosion tests at 650 °C, 700 °C and 750 °C, in controlled atmosphere furnaces using the ‘deposit recoat’ test method to simulate superheater/reheater exposure for 1000 h. After exposure, the samples were analysed using dimensional metrology to determine the extent and distributions of corrosion damage in terms of surface recession and internal damage. At 650 °C, the stainless steel and nickel-based alloy performed similarly, while at 700 °C and above, the median damage to the steel was at least 3 times greater than for the nickel-based alloy. Optical and electronic microscopy studies were used to study samples’ damage morphologies after exposure. Intergranular damage and pits were found in sample cross sections, while chromium depletion was found in areas with internal damage. For high-temperature applications, the higher cost of the nickel-based alloy could be offset by the longer life they would allow in plant with higher operating temperatures.

Mechanical Stress Effects on 550 °C Hot Corrosion Propagation Rates in Precipitation Hardened Ni-Base Superalloys: CMSX-4, CM247LC DS and IN6203DS

Combinations of temperature, stress and hot corrosion may cause environmentally-assisted cracking in precipitation-hardened Ni-base superalloys, which is little understood. This research aims to increase current understanding by investigating the effects of mechanical stress on the hot corrosion propagation rate during corrosion-fatigue testing of CMSX-4, CM247LC DS and IN6203DS. The parameters used during the tests included a high R-ratio, high frequency, and a temperature of 550 °C. The results showed CMSX-4 experienced a predictable increase in the hot corrosion rate, CM247LC DS also experienced increased rates, but no obvious trend was apparent; whilst IN6203DS showed no evidence of an increased rate. These different behaviours appear to be a result of an interaction between the mechanical stress and microstructural features, which include gamma-prime volume fractions in both the matrix and eutectic regions, along with the distribution of the eutectic structure. The different behaviours in the hot corrosion propagation rate subsequently affected the respective corrosion fatigue results, with both CMSX-4 and CM247LC DS experiencing fracture but with significantly more scatter involved in the CM247LC DS results. All IN6203DS corrosion-fatigue specimens completed the respective tests without fracture and showed no evidence of cracking. It, therefore, appears that precipitation hardened Ni-base superalloys, which are susceptible to environmentally-assisted cracking, also experience increased hot corrosion propagation rates.

Influence of Water Vapor and Temperature on the Oxide Scale Growth and Alpha-Case Formation in Ti-6Al-4V Alloy

The Ti-6Al-4V alloy is extensively used in aerospace, automotive and biomaterial applications. In the aerospace industry, the service temperature of Ti-6Al-4V is currently limited to 350 °C due to its insufficient oxidation resistance. Oxidation at higher temperatures causes the formation of a fast-growing oxide scale and an oxygen-enriched subsurface layer, which is known as the “alpha-case.” Additionally, the effect of water vapor on the oxidation behavior is critical. In the present study, the oxidation behavior of Ti-6Al-4V in dry air and air containing 10 vol.% H2O at 500, 600 and 700 °C for up to 500 h has been investigated. The main focus of this study is the examination of the different oxide scale morphologies along with the oxygen enrichment in the subsurface zone. It has been observed that spallation of the oxide scale is more severe in a water vapor-containing environment. In dry air, the oxide morphology shows the typical layered TiO2/Al2O3 structure after exposure at 700 °C for 300 h, while Al2O3 precipitates are present in the outermost part of the TiO2 scale when oxidized in wet air. This indicates that the solubility and diffusivity of Al3+ ions in TiO2 are influenced by water vapor. In addition, the extent of oxygen enrichment in the subsurface zone (alpha-case) as a function of temperature and time is determined by nanoindentation profiles. It was shown that in contrast to the scale formation, the alpha-case thickness is not affected by the presence of water vapor in the atmosphere.

Protective Alumina Scale Growth at 900 °C for a Ni- and Cr-Free Co-Base Model Alloy with γ/γ’-Microstructure: Synergistic Effects by Combining Shot-Peening and Halogenation

The oxidation resistance of novel γ/γ’-strengthened Co-base superalloys is clearly outmatched by their Ni-base counterparts within the high-temperature regime. Therefore, surface modification strategies to foster protective alumina growth seem auspicious. This study elucidates the impact of fluorination and shot-peening on protective alumina formation at 900 °C for a quaternary Co-base model alloy (Co-Al-W-Ta system) which is well known for an exceptionally low inherent oxidation resistance. Time-resolved isothermal gravimetric analysis (TGA) in synthetic air, detailed electron microscopic analysis, and X-ray diffraction (XRD) were used. For polished samples, no pronounced enhancement of oxidation resistance could be obtained by halogenation. However, in case of shot-peened samples (halogen-free), an increased tendency for alumina formation is found compared to polished surfaces. The very early stages of oxidation were identified to be especially crucial with respect to sustainable protective scale growth. Most noteworthy is the observation of a strong synergistic effect derived by a combination of halogenation and shot-peening, leading to significantly increased oxidation resistance.

High Temperature Oxidation Performance of an Additively Manufactured Mo–9Si–8B Alloy

As reported in previous studies, the processing of Mo–Si–B alloys using additive manufacturing (AM) techniques, like directed energy deposition (DED) shows a high technical feasibility. The present work investigates the cyclic oxidation performance of an AM DED Mo–9Si–8B alloy. Depending on the temperature (800 °C, 1100 °C, 1300 °C), the oxidation mechanisms vary, which is due to different reactions at the surface of the alloys accompanied with mass changes of samples. These mass changes can be explained on the basis of microstructural investigations. However, compared to a powder metallurgically processed Mo–9Si–8B alloy, the AM-DED alloy shows competitive oxidation performance at potential application temperatures of 1100 °C and 1300 °C, while a catastrophic materials degradation occurs at 800 °C as also observed in other Mo-rich Mo–Si–B alloys.