The parabolic growth rate constant (k_p) of high-temperature oxidation of steels is predicted via a data analytics approach. Four machine learning models including Artificial Neural Networks, Random Forest, k-Nearest Neighbors, and Support Vector Regression are trained to establish the relations between the input features (composition and temperature) and the target value (k_p). The models are evaluated by the indices: Mean Absolute Error, Mean Squared Error, Root Mean Squared Error and Coefficient of Determination. The steel composition regarding Cr and Ni content and the temperature were the most significant input features controlling the oxidation kinetics.

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Mo(Al_xSi_1-x)₂ alloy with x in the range of 0.35–0.65 were prepared by a one-step spark plasma sintering. To study the exclusive formation of an α-Al₂O₃ scale, oxidation experiments were conducted in low and high oxygen partial pressure ambient at 1373 K; viz.: 10⁻¹⁴ and 0.21 atm. The oxidation kinetics follows a parabolic rate law after a transient period. A counter-diffusion process of O and Al along grain boundaries of Al₂O₃ scale is responsible for the equiaxed and columnar grain growth based on a two-layered microstructure. The formation of a dense equiaxed α-Al₂O₃ layer contributes to excellent oxidation resistance.

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The thermal diffusivity and conductivity of dense and porous binary composites having an insulating and conducting phase were studied across its entire composition range. Experimental evaluation has been performed with MoSi₂ particles embedded into yttria partially stabilized zirconia (YPSZ) as prepared by spark plasma sintering (SPS). The thermal diffusivity of the composites was measured with Flash Thermography (FT) and Laser Flash Analysis (LFA) techniques. Subsequently, the thermal conductivity was determined with the measured heat capacity and density of the composites. The actual volume fraction of the conducting phase of the composites was determined with image analysis of X-ray maps recorded with scanning electron microscopy (SEM). The phases present and their density were determined with X-ray diffractometry (XRD) using Rietveld refinement. The thermal diffusivity increases with increasing volume fraction of MoSi₂. Porosity reduces the thermal diffusivity, but the effect diminishes with high volume fractions MoSi₂. The thermal diffusivity as a function of the MoSi₂ volume fraction of the YPSZ composites is captured by modelling, which includes the porosity effect and the high conductivity paths due to the percolation of the conductive phase.

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Boron containing MoSi₂ is a promising material for applications at high temperature, but the oxidation mechanism is still unclear. In this work, the high temperature (1100 °C) oxidation of B doped MoSi₂ in synthetic air has been investigated. A (boro)silicate layer is formed on the surface of the alloy, which features a mixture of amorphous SiO₂ and cristobalite. After an initial transient period, the oxidation kinetics follows a parabolic growth rate law. The growth rate constant of the oxide layer is enhanced by the boron in the alloy by 90 % per at.% B. The increase in growth rate is associated with boron mitigating the formation of cristobalite thereby promoting the formation of amorphous SiO₂.

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High-temperature oxidation of steels can be relatively fast when exposed to air. Consequently, elucidating the effect of different parameters on the oxidation mechanism and kinetics is challenging. In this study, short-time oxidation was investigated to determine the oxidation mechanism, the affecting parameters, and the linear-to-parabolic growth transition of different Fe–Mn alloys in various oxygen partial pressures (10–30 kPa) and gas flow rates (26.6 and 53.3 sccm) in a temperature range of 950–1150 °C. Oxidation kinetics was investigated using a thermogravimetric analyzer (TGA) under controlled atmosphere. Linear oxide growth was observed within the first 20 minutes of oxidation. The linear rate constant was significantly increased by increasing the oxygen partial pressure or the flow rate of the oxidizing gas. The morphology of the oxide layer was determined by scanning electron microscopy (SEM). The crystal structure of the oxides formed was followed by in-situ X-ray diffraction (XRD), confirming that the growing layer consists of wustite mainly, which upon slow cooling to room temperature, transformed into magnetite. Energy-dispersive X-ray spectroscopy (EDS) showed that the atomic ratio of Fe+Mn to O was ~ 1.03:1 in the oxide scale, corresponding to Fe(Mn)O formation. Based on the characterization and a model for linear growth kinetics, it is concluded that the oxidation rate is controlled by the diffusion of oxidizing molecules through the gas layer to the sample’s surface. The findings led to a better understanding of initial oxidation behavior and provided a pathway for improved insight into the high-temperature oxidation behavior for more complex alloys.

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MXenes are a new family of 2D carbides or nitrides that have attracted attention due to their layered structure, tunable surface groups and high electrical conductivity. Here, we report for the first time that the Ti₂CT_x MXene catalyses the selective oxidative dehydrogenation of n-butane to butenes and 1,3-butadiene. This catalyst showed higher intrinsic activity compared to a commercial TiC and TiO₂ samples in terms of C₄ olefin formation rate. We propose that the stabilisation of structural vacancies and the change in composition (from a carbide to a mixed phase oxide) in the MXene causes its higher catalytic activity. These vacancies can lead to a higher concentration of unpaired electrons in the MXene-derived material, enhancing its nucleophilic properties and favouring the production of olefins.

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The surface oxidation and wettability of Mn and Si-alloyed steel after annealing at different conditions are studied with scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and a so-called de-wetting method. After exposure at 950 °C for 1 hour in an Ar + 5 vol pct H₂ gas atmosphere with dew points (DP) ranging from – 40 °C to 10 °C, oxides were observed along the grain boundaries or dispersed on the surface for the Fe–1.8 Mn steels while a continuous oxides layer was formed on Fe–1.9 Mn–0.94 Si steels (composition in weight fractions). The oxides formed at different DPs were predicted based on thermodynamic calculations. (Fe,Mn)O was formed on Fe–1.8 Mn steel at the whole range of DPs, while the oxide phase on Fe–1.9 Mn–0.94 Si steel depends on the DP. At low-DP SiO₂ were formed and with increasing the DP (Fe,Mn)SiO₃ or (Fe,Mn)SiO₃ + (Fe,Mn)₂SiO₄ were formed and finally (Fe,Mn)₂SiO₄ were formed. An increase of the fraction of Fe in the oxide with increasing DP for both steels was observed with XPS analysis. As a measure for the surface wettability, the contact angle of Pb droplets on the annealed steels surfaces was determined with SEM and image analysis software. Also, the contact angle of Pb on pure Fe and on the Mn and Si alloyed steels free of surface oxides was measured for comparison. The results show that the contact angle of Pb on the steel surfaces after annealing decreases with increasing DP. This improved wettability with increasing dew point is related to the Fe fraction of the oxides formed on the surface.

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Repetitive heating and cooling cycles inevitably cause crack damage of hot gas components of gas turbine engines, such as blades and vanes. In this study the self-healing capacity is investigated of mullite + ytterbium monosilicate (Yb₂SiO₅) as EBC material with Ti₂AlC MAX phase particles embedded as a crack-healing agent. The effect of Ti₂AlC in the EBC was compared with the self-healing ability of the mullite + Yb₂SiO₅ material. After introducing cracks by Vickers indentation on the surface of each sample, crack healing was realized by controlling the temperature and time during the post-heat-treatment process. For the mullite + Yb₂SiO₅ composite with Ti₂AlC particles, crack healing occurred at 1000 °C, while in the case of the mullite + Yb₂SiO₅ composite without Ti₂AlC, a sustained temperature of 1300 °C or higher was required. Compared with the healing of the mullite + Yb₂SiO₅ composite by the formation of a eutectic phase, the addition of Ti₂AlC promoted healing via the oxidation of Ti and Al. Notably, the surface formation of a ternary oxide of Ti–Yb–O was confirmed, which completely covered the damage area. Consequently, the addition of a Ti₂AlC MAX phase to the EBC composite resulted in a complete strength recovery, while the mullite + Yb₂SiO₅ composite without Ti₂AlC showed a strength recovery of about 80%. Furthermore, by analyzing the indentation load–displacement curve to indicate the role of Ti₂AlC, the addition of Ti₂AlC improved both the hardness and stiffness of the composite.

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Autonomous healing of creep-induced grain boundary cavities by Au-rich and W-rich precipitates was studied in a Fe-3Au-4W (wt pct) alloy at a fixed temperature of 823 K (550 °C) with different applied stresses. The ternary alloy, with two supersaturated healing solutes, serves as a model system to study the interplay between two separate healing agents. The creep properties are evaluated and compared with those of the previously studied Fe-Au and Fe-W binary systems. The microstructures of the creep-failed samples are studied by electron microscopy to investigate the cavity filling behavior and the mass transfer of supersaturated solute to the defect sites. Compared to the Fe-Au and Fe-W alloys, the new Fe-Au-W alloy has the lowest steady-state strain rate and the longest lifetime. The site-selective filling of the creep-induced cavities is attributed to two different categories of precipitates: micron-sized Au-rich precipitates and nano-sized W-rich precipitates. The Au-rich precipitates are found capable to fully heal the cavities, while the W-rich precipitates show only a limited degree of healing. The two types of precipitates show a reluctance to coexistence, and the formation of W-rich precipitates is suppressed strongly. A model is proposed to describe the competitive healing behavior of the Au-rich and W-rich precipitates.

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Pd–Cu alloys have been investigated as promising candidates for hydrogen separation membranes. Surface segregation influences the long-term performance of these membranes since their catalytic effect is mainly controlled by the surface composition. In the present research, surface segregation of Pd-40 at.% Cu alloy in vacuum and various gas atmospheres (H₂, CO and CO₂) was investigated with both XPS and LEISS probing different depths below the surface. Adsorption of H₂ and CO on the surface has a significant impact and the surface segregation trend can be reversed as compared to segregation in vacuum, however, CO₂ has almost no influence on the segregation behaviour. A thermodynamic model is also presented to explain these phenomena and to understand surface segregation behaviour of binary alloys in various gas atmospheres. The results can be considered as basic guidelines to design novel alloys for hydrogen separation membranes and predict their long-term performance under actual working conditions.

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Ternary alloys have been developed for a wide range of applications and surface segregation of ternary alloys has a decisive impact on their performance. Different from binary alloys, in which surface energy is usually the dominant factor, the interaction between solute elements has a noticeable effect on the surface segregation behavior of ternary alloys. As a practical example, Pd-based ternary alloys have been proposed as promising candidates for hydrogen separation membranes due to their excellent permeability and selectivity. In the present work, surface segregation of Pd-Cu-Ag and Pd-Cu-Mo ternary alloys in both vacuum and hydrogen atmosphere is investigated. X-ray photoelectron spectroscopy and low energy ion scattering spectroscopy analyses reveal that the segregation trend of the outermost atomic layer is not always the same as that of the near-surface region. A thermodynamic model is developed to describe the surface segregation of ternary alloys. The results of the model are in good qualitative agreement with experimental results. Furthermore, calculations for other ternary alloy systems confirm that the model provides a simple but universal method for surface segregation in ternary alloys. The results can also be considered as basic guidelines to design novel ternary alloys for various applications.

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MAX (Mn+1AXn) phases are layered carbides or nitrides with a high thermal and mechanical bulk stability. Recently, it was shown that their surface structure can be modified to form a thin non-stoichiometric oxide layer, which can catalyze the oxidative dehydrogenation of butane. Here, the use of a Ti2AlC MAX phase as a support for cobalt oxide was explored for the dry reforming of butane with CO2, comparing this new catalyst to more traditional materials. The catalyst was active and selective to synthesis gas. Although the surface structure changed during the reaction, the activity remained stable. Under the same conditions, a titania-supported cobalt oxide catalyst gave low activity and stability due to the agglomeration of cobalt oxide particles. The Co3O4/Al2O3 catalyst was active, but the acidic surface led to a faster deactivation. The less acidic surface of the Ti2AlC was better at inhibiting coke formation. Thanks to their thermal stability and acid-base properties, MAX phases are promising supports for CO2 conversion reactions.@en

Bones of humans and animals combine two unique features, namely: they are brittle yet have a very high fracture toughness linked to the tortuosity of the crack path and they have the ability to repeatedly heal local fissures such that full recovery of overall mechanical properties is obtained even if the local bone structure is irreversibly changed by the healing process. Here it is demonstrated that Ti₂AlC MAX phase metallo-ceramics also having a bone-like hierarchical microstructure and also failing along zig-zag fracture surfaces similarly demonstrate repeated full strength and toughness recovery at room temperature, even though the (high temperature) healing reaction involves the local formation of dense and brittle alumina within the crack. Full recovery of the fracture toughness depends on the healed zone thickness and process zone size formed in the alumina reaction product. A 3-dimensional finite element method (FEM) analysis of the data obtained from a newly designed wedge splitting test allowed full extraction of the local fracture properties of the healed cracks.

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Abstract: The precipitation of supersaturated solutes at free surfaces in ternary Fe–3Au–4W and binary Fe–3Au and Fe–4W alloys (composition in weight percentage) for different ageing times was investigated at a temperature of 700 °C. The time evolution of the surface precipitation is compared among the three alloys to investigate the interplay between the Au and W solutes in the ternary system. The Au-rich grain-interior surface precipitates show a similar size and kinetics in the Fe–Au–W and Fe–Au alloys, while the W-rich grain-interior surface precipitates show a smaller size and a higher number density in the Fe–Au–W alloy compared to the Fe–W alloy. The kinetics of the precipitation on the external free surface for the ternary Fe–Au–W alloy is compared to the previously studied precipitation on the internal surfaces of the grain-boundary cavities during creep loading of the same alloy. Graphical abstract: [Figure not available: see fulltext.]

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The ultra-high temperature ablation of a polycrystalline, fully dense, predominantly single phase MoAlB ceramic discs under an oxyacetylene flame is examined. The linear ablation rate decreases from 1.3 μm/s during the first 30 s to - 0.7 μm/s after 60 s when the surface temperature reached about 2050 °C (with a flame temperature around 3000 °C). Up to 60 s, the MoAlB is ablation resistant due to the formation of a protective and viscous surface Al2O3 layer. As the ablation time is prolonged, the protective Al2O3 scale becomes porous and is almost fully destroyed at the central ablation region after 120 s. This accelerates the formation of large amounts of volatile species (mainly B and Mo oxides), resulting in a reduction in the ablation resistance.@en