Hot corrosion of TBC-coated components upon combustion of low-sulfur fuels

Gas turbine reliability is a crucial requirement for passenger safety in aviation and a secure energy supply. Hence, corrosive degradation of combustor parts, vanes, and blades in gas turbines must be prevented. One of the most severe forms of corrosion is alkali-sulfate-induced hot corrosion, which is associated with internal sulfidation of components and is usually anticipated to fade in importance in the absence of sulfur. However, the literature suggests that hot corrosion might still occur in low-sulfur combustion gases. In this study, established thermodynamic modeling methods are used to analyze the low-sulfur hot corrosion regime. Liquid sodium chromate is found to be stable in these conditions. A comparison of calculation results and engine findings suggests that high alkali levels can negatively impact thermal barrier coating life even if sulfur is absent in the fuel. Laboratory tests are carried out to validate the chromate formation on MCrAlY-coated specimens. It is shown that molten sodium chromate can alter the oxidation behavior of MCrAlY, promoting the formation of voluminous spinel. This represents a new and different form of hot corrosion compared to type I hot corrosion.     

Potential influence of microorganisms on the corrosion of carbon steel in the French high- and intermediate-level long-lived radioactive waste disposal context

In the context of the high-level radioactive waste disposal CIGEO, the corrosion rate due to microbially influenced corrosion (MIC) has to be evaluated. In France, it is envisaged to dispose of high- and intermediate-level long-lived radioactive waste at a depth of 500 m in a deep geological disposal, drilled in the Callovo-Oxfordian claystone (Cox) formation. To do so, a carbon steel casing will be inserted inside disposal cells, which are horizontal tunnels drilled in the Cox. A specific cement grout will be injected between the carbon steel casing and the claystone. A study was conducted to evaluate the possibility of MIC on carbon steel in the foreseeable high radioactive waste disposal. The corrosiveness of various environments was investigated at 50°C and 80°C with or without microorganisms enriched from samples of Andra's underground research laboratory. The monitoring of corrosion during the experiments was ensured using gravimetric method and real-time corrosion monitoring using sensors based on the measurements of the electrical resistance. The corrosion data were completed with microbiological analyses including cultural and molecular characterizations.     

The corrosion of mild and stainless steel in alkaline anaerobic conditions representing the Belgian “supercontainer” concept and the Swiss L/ILW repository

Deep geological repositories for radioactive waste contain metallic materials, either used to construct disposal canisters or as low-/intermediate-level waste (L/ILW). The safety relevance of corrosion is linked to canister lifetime in the former case and gas generation in the latter. More specifically, the Belgian “supercontainer” concept envisages mild steel for the used fuel disposal canister, and in the case of the Swiss L/ILW repository, mild steels are the largest metallic waste component due to the decommissioning of civilian power-generating facilities. For these circumstances, the corrosion environment is dominated by the chemistry of cement, which is used as buffer or backfill material. The corrosion behaviour of mild steel in anoxic environments was studied through the analysis of the hydrogen end-product. Hydrogen analysis was conducted by periodically purging the cell head-space and analysing the gas using a solid-state hydrogen sensor. While this method is limited to providing only uniform corrosion rates averaged over periods of time, ranging from weeks to months, it provides excellent resolution and sensitivity. The test cell environments were matched against the anticipated Belgian high-level waste and Swiss L/ILW repository environments, and also against experiments that have been conducted by other researchers for comparative purposes. Samples were exposed to synthetic cement pore waters, representing fresh and degraded cement. In young cement waters, the formation of initial corrosion products resulted in steel wire corrosion rates of the order of µm/year, which, at 80°C rapidly declined to ∼10 nm/year. In contrast, SA516 grade 70 steel plate corroded much more slowly under similar conditions. In aged cement waters, initial corrosion rates were higher but declined faster towards a longer-term rate of ∼10 nm/year. 316L stainless steel, embedded in cementitious material, corroded at a rate of <1 nm/year at 50°C.     

Speciation of copper in high chloride concentrations,in the context of corrosion of copper canisters

Canisters with a cast iron insert for mechanical strength and a 50-mm thick copper shell as corrosion protection are planned to be used for disposal of spent nuclear fuel in Sweden and Finland. Chloride can be considered “beneficial”, as it promotes active dissolution of copper rather than passivation (which might result in pitting), but a high concentration of chloride in solution would increase the driving force for corrosion through the formation of soluble copper chloro complexes. Thermodynamic calculations are performed in this study with the PHREEQC software and three of its accompanying databases, and a comparison with experimental data is performed to select the database to be used when evaluating repository performance. The activity coefficient models are given special attention. For the assessment of chloride-assisted corrosion of a KBS-3 canister, chloride concentrations pessimistically up to 5 mol/kg are used (in Finland and Sweden, the groundwater and bentonite porewater chloride concentrations are not expected to exceed 1 mol/kg). The resulting copper solubilities are then considered in different mass transport cases.     

Application limits and sensitisation behaviour of the manganese- and nitrogen-alloyed austenitic stainless steel P2000 (X13CrMnMoN18-14-3)

Nickel-free high-nitrogen-alloyed stainless steels like the P2000 (X13CrMnMoN18-14-3) were developed to enhance the strength and corrosion resistance of austenitic stainless steels like 304 and 316 while keeping the typical high ductility. The mechanical and corrosive properties of P2000 were investigated and compared with 304 and 316 to highlight the application opportunities of this new alloy. The microstructure of the solution-annealed condition was characterised by electron backscatter diffraction and the mechanical properties were studied by uniaxial tensile tests, Charpy impact tests and hardness measurements. The passivation behaviour was analysed using the electrochemical potentiodynamic reactivation, whereas the pitting corrosion resistance was compared by pitting potentials and pitting temperatures. However, secondary thermal influences or suboptimal heat treatment can impair the corrosion resistance due to the precipitation of secondary phases and the resulting sensitisation. Thermodynamic calculations and artificial ageing treatment in the range of 500–900°C for up to 100 h were used to determine critical time–temperature parameters for sensitisation. The microstructure of the various aged states was evaluated by scanning electron microscopy and compared with the degrading corrosion resistance characterised by the KorroPad method.     

Microstructural and electrical changes in Ca0.9R0.1CeNbMoO8 (R = Y,Sm, Nd,La) ceramics induced by rare-earth ion doping

Rare-earth ions doped Ca_0.9R_0.1CeNbMoO₈ (R = Y, Sm, Nd, La) ceramics have been successfully prepared by solid-state method, and their modifications to the microstructure and electrical properties are also investigated. The rare-earth ions doped ceramics exhibit the scheelite structure. With the increase in the radius of rare-earth ions, the lattice distortion and bond interaction will be enhanced, and the consistency of grain size will be reduced. The ceramics exhibit negative temperature coefficient (NTC) thermistor characteristics in the temperature range of 473 K-1273 K, and the activation energy decreases with the increase of the radius of rare-earth ions. Rare-earth ions doping can increase the content of Ce³⁺ ions and promote the conductivity of ceramics. Except for Sm³⁺-doped ceramics, the high-temperature aging rate of other ceramics is less than 2%. The existence of some metastable Sm²⁺ ions in Sm³⁺-doped ceramics not only increases the activation energy, but also reduces the high-temperature stability of the ceramics.     

杂化包覆玄武岩鳞片/环氧涂料制备与性能

本文在环氧涂料中添加玄武岩鳞片，提高其防腐蚀性能。针对玄武岩鳞片的团聚问题，通过机械力化学改性工艺，采用正硅酸四乙酯、HY-311型钛酸酯偶联剂、E-44型环氧树脂对玄武岩鳞片进行杂化包覆，结果表明，杂化包覆后玄武岩鳞片的沉降时间从2h提高至96 h。杂化包覆玄武岩鳞片添加量为20%涂层的性能最优，附着力为13.40 MPa，耐盐雾时间为2000 h，在3.5%NaCl溶液中浸泡2000 h后，0.01 Hz的阻抗模值仍然有5.15×109 Ω·cm2。     

A theoretical and experimental study of phosphate ester inhibitors for AISI 1018 in carbon dioxide-saturated 3.5 wt% NaCl solution

Phosphate ester was investigated as a corrosion inhibitor for AISI 1018 carbon steel in carbon dioxide-saturated chloride solutions at different temperatures and pressures. The corrosion tests were realized by electrochemical techniques, weight loss measurements, bubble tests, and a high-pressure/high-temperature autoclave system. The corrosion tests demonstrated that the investigated molecule is an excellent corrosion inhibitor. The inhibiting effect is even bigger at high pressure and temperature than at atmospheric pressure and room temperature. The thermodynamic parameters were calculated and determined to obey the Langmuir isotherm. Polarization studies revealed that the evaluated inhibitor is a mixed type.