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Face-centred cubic (fcc-) Mo–N and Ta–N exhibit an inherent driving force for vacancy formation. To study their interaction and effects on structural evolution and mechanical properties, we synthesised Mo–Ta–N coatings by reactive magnetron sputtering using nitrogen-to-total pressure ratios, pN2/pT, of 0.32 and 0.69.Low pN2/pT results in high concentration of N vacancies, which stabilise single-phase fcc-Mo1-xTaxNy up to x = 0.76. These solid solutions follow the MoN0.5–Ta0.875N0.875 quasi-binary tie line. Compressive residual stresses, σ, indentation hardness, H, and toughness, KC, increase with Ta content, reaching their maxima of (on average) -2.0 GPa, 28 GPa, and 7.0 MPa√m, respectively, within the x range 0.38–0.69. Higher Ta contents favour higher concentration of metal vacancies deteriorating the properties.High pN2/pT favours the formation of fcc-Mo1-xTaxNy rich in metal vacancies, which however always coexists with a hexagonal phase. Within the x range 0.33–0.66, the fraction of the hexagonal phase is negligible, and σ, H, and KC deviate from −1.0 GPa, 28 GPa, and 2.9 MPa√m, respectively, within the error of measurements.The combination of experimental and theoretical studies demonstrates the power of point defects in stabilising desired crystal structures and improving mechanical properties through the thereby tuned atomic configuration.

Density Functional Theory applying the generalised gradient approximation is used to study the phase stability of (AlxCr1−x)2O3 solid solutions in the context of physical vapour deposition (PVD). Our results show that the energy of formation for the hexagonal α phase is lower than for the metastable cubic γ and B1-like phases–independent of the Al content x. Even though this suggests higher stability of the α phase, its synthesis by physical vapour deposition is difficult for temperatures below 800 °C. Aluminium oxide and Al-rich oxides typically exhibit a multi-phased, cubic-dominated structure. Using a model system of (Al0.69Cr0.31)2O3 which experimentally yields larger fractions of the desired hexagonal α phase, we show that point defects strongly influence the energetic relationships. Since defects and in particular point defects, are unavoidably present in PVD coatings, they are important factors and can strongly influence the stability regions. We explicitly show that defects with low formation energies (e.g. metal Frenkel pairs) are strongly preferred in the cubic phases, hence a reasonable factor contributing to the observed thermodynamically anomalous phase composition.

Despite growing environmental concern, combustion engines are projected to stay the main technology of transportation for many years, so will unpopular S- and P- containing additives in lubricating oils. Therefore, it is essential to maximize efficiency and minimize the harmful impacts of these additives in the meantime. Coatings based on Mo and W hold great promise as they can chemically interact with S-bearing additives and form low friction tribofilms like MoS2 and in particular WS2. Here we highlight the reaction pathways involving first the formation of oxide intermediates, followed by the generation of a highly protective and low-shear transition metal disulfide tribofilm on a tailored WN-based coating, affording coefficients of friction as low as 0.05 combined with an extraordinary wear protection (i.e., no measurable wear on sliding surfaces even after 100 h of testing). High resolution TEM and Raman spectroscopy confirm the formation of WS2 sheets and hence the huge potential of these coatings for lubricated surfaces. Keywords: In-situ WS2, Coating-lubricant interaction, Tungsten nitride, Thin film, Tribofilm

Tailoring vacancies is a feasible way to improve the mechanical properties of ceramics. However, high concentrations of vacancies usually compromise the strength (or hardness). We show that a high elasticity and flexural strength could be achieved simultaneously using a nitride superlattice architecture with disordered anion vacancies up to 50%. Enhanced mechanical properties primarily result from a distinctive deformation mechanism in superlattice ceramics, i.e., unit-cell disturbances. Such a disturbance substantially relieves local high-stress concentration, thus enhancing deformability. No dislocation activity involved also rationalizes its high strength. The work renders a unique understanding of the deformation and strengthening/toughening mechanism in nitride ceramics., (© 2023. The Author(s).)

Inherent brittleness, which easily leads to crack formation and propagation during use, is a serious problem for protective ceramic thin-film applications. Superlattice architectures, with alternating nm-thick layers of typically softer/stiffer materials, have been proven powerful method to improve the mechanical performance of, e.g., cubic transition metal nitride ceramics. Using high-throughput first-principles calculations, we propose that superlattice structures hold promise also for enhancing mechanical properties and fracture resistance of transition metal diborides with two competing hexagonal phases, [Formula: see text] and [Formula: see text]. We study 264 possible combinations of [Formula: see text], [Formula: see text] or [Formula: see text] MB[Formula: see text] (where M [Formula: see text] Al or group 3-6 transition metal) diboride superlattices. Based on energetic stability considerations, together with restrictions for lattice and shear modulus mismatch ([Formula: see text], [Formula: see text] GPa), we select 33 superlattice systems for further investigations. The identified systems are analysed in terms of mechanical stability and elastic constants, [Formula: see text], where the latter provide indication of in-plane vs. out-of-plane strength ([Formula: see text], [Formula: see text]) and ductility ([Formula: see text], [Formula: see text]). The superlattice ability to resist brittle cleavage along interfaces is estimated by Griffith's formula for fracture toughness. The [Formula: see text]-type TiB[Formula: see text]/MB[Formula: see text] (M [Formula: see text] Mo, W), HfB[Formula: see text]/WB[Formula: see text], VB[Formula: see text]/MB[Formula: see text] (M [Formula: see text] Cr, Mo), NbB[Formula: see text]/MB[Formula: see text] (M [Formula: see text] Mo, W), and [Formula: see text]-type AlB[Formula: see text]/MB[Formula: see text] (M [Formula: see text] Nb, Ta, Mo, W), are suggested as the most promising candidates providing atomic-scale basis for enhanced toughness and resistance to crack growth., (© 2023. Springer Nature Limited.)

Differential scanning calorimetry and Raman spectroscopy were used to study the nonisothermal and isothermal crystallization behavior of amorphous indomethacin powders (with particle sizes ranging from 50 to 1000 µm) and their dependence on long-term storage conditions, either 0-100 days stored freely at laboratory ambient temperatures and humidity or placed in a desiccator at 10 °C. Whereas the γ-form polymorph always dominated, the accelerated formation of the α-form was observed in situations of heightened mobility (higher temperature and heating rate), increased amounts of mechanically induced defects, and prolonged free-surface nucleation. A complex crystallization behavior with two separated crystal growth modes (originating from either the mechanical defects or the free surface) was identified both isothermally and nonisothermally. The diffusionless glass-crystal (GC) crystal growth was found to proceed during the long-term storage at 10 °C and zero humidity, at the rate of ~100 µm of the γ-form surface crystalline layer being formed in 100 days. Storage at the laboratory temperature (still below the glass transition temperature) and humidity led only to a negligible/nondetectable GC growth for the fine indomethacin powders (particle size below ~150 µm), indicating a marked suppression of GC growth by the high density of mechanical defects under these conditions. The freely stored bulk material with no mechanical damage and a smooth surface exhibited zero traces of GC growth (as confirmed by microscopy) after >150 days of storage. The accuracy of the kinetic predictions of the indomethacin crystallization behavior was rather poor due to the combined influences of the mechanical defects, competing nucleation, and crystal growth processes of the two polymorphic phases as well as the GC growth complex dependence on the storage conditions within the vicinity of the glass transition temperature. Performing paired isothermal and nonisothermal kinetic measurements is thus highly recommended in macroscopic crystallization studies of drugs with similarly complicated crystal growth behaviors.

We have performed a quantum-mechanical study of a B2 phase of Fe 70 Al 30 alloy with and without antiphase boundaries (APBs) with the {001} crystallographic orientation of APB interfaces. We used a supercell approach with the atoms distributed according to the special quasi-random structure (SQS) concept. Our study was motivated by experimental findings by Murakami et al. (Nature Comm. 5 (2014) 4133) who reported significantly higher magnetic flux density from A2-phase interlayers at the thermally-induced APBs in Fe 70 Al 30 and suggested that the ferromagnetism is stabilized by the disorder in the A2 phase. Our computational study of sharp APBs (without any A2-phase interlayer) indicates that they have moderate APB energies (≈0.1 J/m 2 ) and cannot explain the experimentally detected increase in the ferromagnetism because they often induce a ferro-to-ferrimagnetic transition. When studying thermal APBs, we introduce a few atomic layers of A2 phase of Fe 70 Al 30 into the interface of sharp APBs. The averaged computed magnetic moment of Fe atoms in the whole B2/A2 nanocomposite is then increased by 11.5% w.r.t. the B2 phase. The A2 phase itself (treated separately as a bulk) has the total magnetic moment even higher, by 17.5%, and this increase also applies if the A2 phase at APBs is sufficiently thick (the experimental value is 2-3 nm). We link the changes in the magnetism to the facts that (i) the Al atoms in the first nearest neighbor (1NN) shell of Fe atoms nonlinearly reduce their magnetic moments and (ii) there are on average less Al atoms in the 1NN shell of Fe atoms in the A2 phase. These effects synergically combine with the influence of APBs which provide local atomic configurations not existing in an APB-free bulk. The identified mechanism of increasing the magnetic properties by introducing APBs with disordered phases can be used as a designing principle when developing new magnetic materials.

We have performed quantum-mechanical calculations to examine the impact of disorder on thermodynamic, structural and electronic (magnetic) properties of Fe-Al systems with vacancies. A series of supercells was used and their properties were computed employing density-functional theory (DFT) as implemented in the VASP package. Our case study is primarily aimed at a disordered solid solution Fe 81.25 Al 18.75 but we have compared our results also with those obtained for the ordered Fe 3 Al intermetallic compound for which experimental data exist in literature. Both phases are found in Fe-Al-based superalloys. The Fe-18.75at.%Al solid solution was simulated using special quasirandom structures (SQS) in three different disordered states with a different distribution of Al atoms. In particular, we have considered a general disordered case (an A2-like variant), the case without the first nearest neighbor Al-Al pairs (a B2-like distribution of atoms) and also the case without both the first and second nearest neighbor Al-Al pairs (the D0 3 -like variant, in fact, an Fe-rich Fe 3 Al phase). The vacancy formation energies as well as the volumes of (fully relaxed) supercells with vacancies showed a large scatter for the disordered systems. The vacancy formation energies decrease with increasing concentration of Al atoms in the first coordination shell around the vacancy (an anti-correlation) for all disordered cases studied. The computed volumes of vacancies were found significantly lower (by 25-60%) when compared with the equilibrium volume of the missing atoms in their elemental states. Lastly, we have analyzed interactions between the vacancies and the Fe atoms and evaluated vacancy-induced changes in local magnetic moments of Fe atoms.

First-principles evolutionary algorithms are employed to shed light on the phase stability of Al⁻Nb intermetallics. While the tetragonal Al₃Nb and AlNb₂ structures are correctly identified as stable, the experimentally reported Laves phase of AlNb₃ yields soft phonon modes implying its dynamical instability at 0 K. The soft phonon modes do not disappear even upon elevating the temperature in the simulation up to 1500 K. X-Ray diffraction patterns recorded for our powder-metallurgically produced arc cathodes, however, clearly show that the AlNb₃ phase exists. We propose that AlNb₃ is dynamically stabilised by ordered antisite defects at the Al sublattice, leading also to a shift of the Nb content from 75 to ∼81 at.%. Unlike the defect-free AlNb₃, the antisite-stabilised variant hence falls into the compositional range consistent with our CALPHAD-based phase diagram as well as with the previous reports.

Quantum-mechanical calculations are applied to examine magnetic and electronic properties of phases appearing in binary Fe-Al-based nanocomposites. The calculations are carried out using the Vienna Ab-initio Simulation Package which implements density functional theory and generalized gradient approximation. The focus is on a disordered solid solution with 18.75 at. % Al in body-centered-cubic ferromagnetic iron, so-called α -phase, and an ordered intermetallic compound Fe 3 Al with the D0 3 structure. In order to reveal the impact of the actual atomic distribution in the disordered Fe-Al α -phase three different special quasi-random structures with or without the 1st and/or 2nd nearest-neighbor Al-Al pairs are used. According to our calculations, energy decreases when eliminating the 1st and 2nd nearest neighbor Al-Al pairs. On the other hand, the local magnetic moments of the Fe atoms decrease with Al concentration in the 1st coordination sphere and increase if the concentration of Al atoms increases in the 2nd one. Furthermore, when simulating Fe-Al/Fe 3 Al nanocomposites (superlattices), changes of local magnetic moments of the Fe atoms up to 0.5 μ B are predicted. These changes very sensitively depend on both the distribution of atoms and the crystallographic orientation of the interfaces.

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