This work presents an investigation of the microstructure development during the application of the quenching and partitioning (Q&P) process to two stainless steels with different Mn content. The results are compared with calculations based on the constrained carbon equilibrium theory, paying special attention to the presence of reactions competing for the carbon available for partitioning and to the effect of alloying element segregation. Results show that chromium carbides must be considered when accounting for the carbon available for austenite stabilisation. Moreover, manganese/chromium segregation bands play an important role in the microstructure development, particularly in martensite formation, with important consequences in the microstructure development during the following processing steps.

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The effect of the heat treatment on the magnetism, magnetocaloric effect and microstructure formation has been systematically studied in Fe-rich (Mn,Fe)_y(P,Si) melt-spun ribbons (1.80 ≤ y ≤ 2.00). XRD, SEM and EDS measurements demonstrate that a metal deficiency prompts the stable (Mn,Fe)Si phase, whereas in the metal-rich region the (Mn,Fe)₃Si phase is formed. It is found that the annealing temperature influences the composition and lattice parameters of the (Mn,Fe)_y(P,Si) alloys, which greatly affects the Curie temperature (T_C). For the optimal metal/non-metal ratio y the magnetic entropy change (|ΔS_m|) is found to increase from 5.5 to 15.0 Jkg⁻¹K⁻¹ in a magnetic field change of 2 T by varying the annealing temperature from 1313 to 1433 K, indicating an enhancement of the first-order magnetic transition (FOMT). The presented results reveal that the secondary phase and magnetic properties in the (Mn,Fe)_y(P,Si) system can be tuned by varying the annealing temperature and by adjusting the metal/non-metal ratio y.

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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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To prevent premature triggering of the healing reaction in Mo-Si containing self-healing thermal barrier coating system, an oxygen impenetrable shell (α-Al₂O₃) around the sacrificial healing particles (MoSi₂) is desired. Here an encapsulation method is presented through selective oxidation of Al in Mo(Al_xSi_1-x)₂ particles. Healing particles of Mo(Al_xSi_1-x)₂ is designed in terms of alumina shell thickness, particle size and fraction Al dissolved. By replacing Si by Al in MoSi₂ up to the maximum solubility (x = 0.65) a strong crack healing ability is maintained (relative volume expansion ≥ 40 %). The formed exclusive α-Al₂O₃, featuring a two-layered structure, results from a counter-diffusion process along the grain boundaries, and its oxidation kinetics fits well with the 3D diffusion-Jander model. After 16 h exposure in gaseous ambient with a pO₂ of 5 × 10^-10 atm. at 1100 °C, a closed and dense shell of α-Al₂O₃ is formed with a thickness of about 1.3 µm. The oxide shell produced under this condition provided healing particles with significantly improved stability upon exposure to high pO₂ of 0.2 atm. at 1100 °C for 50 h. The particles after exposure feature an inner core of MoSi₂ with Al completely consumed and an oxide shell of α-Al₂O₃.

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The effect of Co and Ni doping on the structure, magnetic and magnetocaloric properties of Fe-rich (Mn,Fe)₂(P,Si) compounds was studied. With increasing Co and Ni content, both the Curie temperature (T_c) and the thermal hysteresis (ΔT_hys) decreased, whereas the hexagonal P-62 m crystal structure was maintained. A pronounced reduction in hysteresis was observed upon Co doping, while a significant reduction in Curie temperature was found upon Ni doping. Mössbauer spectroscopy measurements and DFT calculations indicated the substitution of Fe at the 3f site for both Co and Ni doping. Rietveld refinement of the X-ray diffraction data showed that Co substitute atoms in the main phase and the impurity phase, while Ni exhibits an affinity to the main phase. Magnetization measurements on the Co doped samples revealed an increase in magnetization for 2 at.% of Co, followed by a decrease for higher concentrations. DFT calculations showed that the magnetic moment on the 3f site is enhanced by Co substitution, whereas an opposite trend was observed for Ni substitution.

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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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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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Single-crystal copper films on sapphire have recently been reported upon in relation to graphene growth on these films. In the present paper the kinetics of the formation of single crystal copper films is investigated. We demonstrate the importance of heating the sapphire substrate in 1000 hPa oxygen, followed by a fast cooling prior to depositing the copper film. The importance of this treatment is tentatively explained by the dissolution of oxygen in sapphire and subsequent out-diffusion during recrystallization of the copper film to form a copper-oxide interface layer. Also, the importance of avoiding oxygen incorporation in the sputter deposited film is demonstrated.

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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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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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Recently MoSi₂ sacrificial particles embedded in yttria partially stabilized zirconia (YPSZ)have been proposed as attractive healing agents to realize significant extension of the lifetime of the thermally loaded structures. Upon local fracture of the YPSZ, the embedded healing particles in the path and in the vicinity of the crack react with the oxygen atoms transported via the crack and first fill the crack with a viscous glassy silica phase (SiO₂). The subsequent reaction between this freshly formed SiO₂ and the existing tetragonal ZrO₂ of the YPSZ leads to the formation of rigid crystalline zircon (ZrSiO₄), which is key in the crack-healing mechanism of YPSZ based materials. The isothermal kinetics of the self-healing reaction and the mechanism of zircon formation from the decomposing MoSi₂ and the surrounding YPSZ were assessed via X-ray diffraction (XRD). The obtained results revealed that at 1100 °C the reaction between amorphous SiO₂ and YPSZ is completed after about 10 h. For a more accurate determination of the kinetics of the self-healing reaction, bilayer samples of YPSZ – MoSi₂ (with and without boron addition)were annealed in air over a temperature range of 1100–1300 °C. This led to the formation of a MoSi₂/amorphous (boro)silica/zircon/YPSZ multi-layer, which was investigated with scanning electron microscopy (SEM)and electron probe X-ray microanalysis (EPMA). Kinetic modeling of the growth of zircon and silica or borosilicate layers showed that zircon growth was dominated by the diffusion of Si⁴⁺ in zircon whereas the growth of the silica or borosilicate layer was controlled by oxygen diffusion. Moreover, a significant increase in the rate of ZrSiO₄ formation was observed due to the presence of B in the MoSi₂ particles.

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The Macroscopic Atom Model (MAM) is extended with the halogens to obtain formation enthalpies and molar volumes of halides. Molar volumes and electron densities were obtained with ab initio methods assuming a hypothetical metallic state. The electronegativity parameter and transformation enthalpy were obtained by linear extrapolation and regression analysis. Negative transformation enthalpies were introduced to obtain reliable values for the formation enthalpy of halides. Formation enthalpies of halides are computed within 25 kJ/mol·at and their molar volumes are underestimated by 20%. The MAM provides better estimates than models using Pauling electronegativity or Born-Haber cycle calculations assuming an ionic lattice of the Born-Haber type. The inclusion of the halogens in the MAM scheme has extended its application to both alloys and ionic compounds. This model can now predict their formation enthalpies and molar volumes, which is not the case in all other electronegativity schemes.

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When metals are mechanically loaded at elevated temperatures for extended periods of time, creep damage will occur in the form of cavities at grain boundaries. In the present experiments it is demonstrated that in binary iron-tungsten alloys creep damage can be self healed by selective precipitation of a W-rich phase inside these cavities. Using synchrotron X-ray nano-tomography the simultaneous evolution of creep cavitation and precipitation is visualized in 3D images with a resolution down to 30 nm. The degree of filling by precipitation is analysed for a large collection of individual creep cavities. Two clearly different types of behaviour are observed for isolated and linked cavities, where the isolated cavities can be filled completely, while the linked cavities continue to grow. The demonstrated self-healing potential of tungsten in iron-based metal alloys provides a new perspective on the role of W in high-temperature creep-resistant steels.@en

The influence of the prior austenite grain size (PAGS), varying between 6 and 185 μm, on the microstructural development of a low carbon steel during quenching and partitioning (Q&P) processing is investigated. The effect on the size and morphological aspects of the microconstituents is discussed based on the kinetics of carbon redistribution between martensite and austenite upon partitioning conditions of 400 °C and 50 s. Under fixed quenching and partitioning conditions, decreasing the PAGS leads to a more efficient carbon partitioning process through the smaller and more homogeneously distributed phases developed during the first quench. In contrast, the microstructural heterogeneity obtained with larger PAGSs makes it more difficult to control the degree of carbon enrichment in austenite during partitioning and thus the austenite stability. Additionally, large volumes of fresh martensite are more likely to form in the interior of large-scale austenite grains due to the incomplete carbon homogenisation process. To consider the PAGS in the design of Q&P microstructures the selection of an optimum fraction of primary martensite is proposed, which ensures the minimisation of fresh martensite in the final microstructure and the sufficient stabilisation of the austenite phase. This new methodology facilitates the applicability of the Q&P process providing a controlled and reproducible development of optimised Q&P microstructures.

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The melting and dripping behaviour of an iron ore pellet bed mixed with nut coke are investigated through a series of quenching, melting and dripping experiments. In the melting bed of iron ore pellets, nut coke acts as a frame to maintain the passage for the gas flow. The iron carburisation level of the pellet shell is found to control the melting temperature of the pellet bed. Simultaneous and layer-wise melting is observed for the pellet bed with and without mixed nut coke, respectively.

In the case of pellet bed mixed with nut coke, the liquid dripping starts at a lower temperature (1500°C) compared to the case when nut coke is absent (1518°C). Subsequently, a steady rate of liquid dripping is observed for the pellet bed mixed with nut coke. However, in the case of the pellet bed without nut coke, most of the liquid drips (~50 wt%) at high temperature (1550°C). The difference in carbon content of the quenched pellets and the dripped metal reveals that a substantial iron carburisation occurs when liquid iron flows over the regular coke particles.

The nut coke is noticed to consumed preferentially in place of the regular coke. Additionally, the total coke consumption decreases with an increase in nut coke addition in the pellet bed. These results give support for more extensive use of nut coke as a replacement of the regular coke in the ironmaking blast furnace.@en

A wedge loaded testing methodology to determine the fracture energy and strength of (semi-) brittle (metallo-)ceramics is presented. The methodology combines a tailored specimen geometry and a comprehensive finite element analysis based on cohesive zone modelling. The use of a simulation-based approach to extract both fracture strength and energy from experimental data avoids the inherent inaccuracies found in closed-form expressions that rely on a priori assumptions about the deformation field. Results from wedge splitting tests on Ti3SiC2 and Ti2AlC (MAX phase) materials are used to illustrate the procedure. The simulation-based approach is further validated by comparing the fracture strength and fracture energies predicted by the proposed method and those indicated by a conventional four-point bending fracture toughness test (ASTM standard). The new protocol offers the possibility to measure not only the fracture properties of brittle material in its pristine state but also in the healed state.@en

A fast and generic scheme is proposed to calculate the work of adhesion between two different materials or the cohesive energy between two crystal planes in a material. These calculations make use of the regular solution theory. This theory is extended to describe chemical interactions between atoms at either side of an interface. The so-called regular solution parameter is estimated from thermodynamic values tabulated or solution enthalpies obtained from a macroscopic atom model (MAM). Complex surface definitions at either side of an interface, both in composition and position of atoms, can be dealt with. The proposed scheme has been used to calculate the work of adhesion between M2AlC (M = Ti, V, Cr) type MAX phases and α-Al2O3. Next, the cohesive energy of the MAX-phases and alumina were determined. The cohesion of the M2AlC type MAX-phase is the weakest bond present in the M2AlC- α-Al2O3 systems.@en

To date, the research aimed at creating a high-temperature alumina (Al₂O₃) grade capable of autonomously repairing crack damage focussed on the use of SiC particles which turns to SiO₂ as the healing agent. The present work presents an unbiased selection procedure to determine other attractive substances and phases which could serve as an effective healing agent for healing at high temperatures. The selection process is based on an analysis of the requested characteristics of the oxide to fill the crack (melting point, adhesion to the alumina matrix and thermal mismatch) as well as those of the healing agent prior to being activated (melting point, volume expansion upon oxidation and thermal mismatch). Application of all selection criteria resulted in identifying granular Ti, Cr, Zr, Nb, Hf, TiC, TiN, Cr₃C₂, Cr₂N, ZrN, NbC and NbN as promising agents for autonomous healing of alumina when used in air at high temperatures.

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We have investigated the autonomous repair of creep damage by site-selective precipitation in a binary Fe-Mo alloy (6.2 wt pct Mo) during constant-stress creep tests at temperatures of 813 K, 823 K, and 838 K (540 °C, 550 °C, and 565 °C). Scanning electron microscopy studies on the morphology of the creep-failed samples reveal irregularly formed deposits that show a close spatial correlation with the creep cavities, indicating the filling of creep cavities at grain boundaries by precipitation of the Fe₂Mo Laves phase. Complementary transmission electron microscopy and atom probe tomography have been used to characterize the precipitation mechanism and the segregation at grain boundaries in detail.

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