Motivated by frequently reported deviations from stoichiometry in cubic transition metal nitride (TMNx) thin films, the effect of N-vacancy concentration on the elastic properties of cubic TiNx, ZrNx, VNx, NbNx, and MoNx (0.72 & LE; x & LE; 1.00) is systematically studied by density functional theory (DFT) calculations. The predictions are validated experimentally for VNx (0.77 & LE; x & LE; 0.97). The DFT results indicate that the elastic behavior of the TMNx depends on both the N-vacancy concentration and the valence electron concentration (VEC) of the transition metal: While TiNx and ZrNx exhibit vacancy-induced reductions in elastic modulus, VNx and NbNx show an increase. These trends can be rationalized by considering vacancy-induced changes in elastic anisotropy and bonding. While introduction of N-vacancies in TiNx results in a significant reduction of elastic modulus along all directions and a lower average bond strength of Ti-N, the vacancy-induced reduction in [001] direction of VNx is overcompensated by the higher stiffness along [011] and [111] directions, resulting in a higher average bond strength of V-N. To validate the predicted vacancy-induced changes in elasticity experimentally, close-to-singlecrystal VNx (0.77 & LE; x & LE; 0.97) are grown on MgO(001) substrates. As the N-content is reduced, the relaxed lattice parameter a0, as probed by X-ray diffraction, decreases from 4.128 & ANGS; to 4.096 & ANGS;. This reduction in lattice parameter is accompanied by an anomalous 11% increase in elastic modulus, as determined by nanoindentation. As the experimental data agree with the predictions, the elasticity enhancement in VNx upon N-vacancy formation can be understood based on the concomitant changes in elastic anisotropy and bonding.

Refractory transition-metal diborides (TMB2) are candidates for extreme environments due to melting points above 3000 degrees C, excellent hardness, good chemical stability, and thermal and electrical conductivity. However, they typically suffer from rapid high-temperature oxidation. Here, we study the effect of Al addition on the oxidation properties of sputter-deposited TiB2-rich Ti1-xAlxBy thin films and demonstrate that alloying the films with Al significantly increases the oxidation resistance with a slight decrease in hardness. TiB2.4 layers are deposited by dc magnetron sputtering (DCMS) from a TiB2 target, while Ti1-xAlxBy alloy films are grown by hybrid high-power impulse and dc magnetron co-sputtering (Al-HiPIMS/TiB2-DCMS). All as-deposited films exhibit columnar structure. The column boundaries of TiB2.4 are B-rich, while Ti0.68Al0.32B1.35 alloys have Ti-rich columns surrounded by a Ti(1-x)Al(x)By tissue phase which is predominantly Al rich. Air-annealing TiB2.4 at temperatures above 500 degrees C leads to the formation of oxide scales that do not contain B and mostly consist of a rutile-TiO2 (s) phase. The resulting oxidation products are highly porous due to the evaporation of B2O3 (g) phase as well as the coarsening of TiO2 crystallites. This poor oxidation resistance is significantly improved by alloying with Al. While air-annealing at 800 degrees C for 0.5 h results in the formation of an similar to 1900-nm oxide scale on TiB2.4, the thickness of the scale formed on the Ti0.68Al0.32B1.35 alloys is similar to 470 nm. The enhanced oxidation resistance is attributed to the formation of a dense, protective Al-containing oxide scale that considerably decreases the oxygen diffusion rate by suppressing the oxide-crystallites coarsening. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The effect of low-energy ion irradiation on the nanolaminated Ti3AlC2 is investigated by means of X-ray diffraction, transmission electron microscopy, electron energy loss and X-ray absorption spectroscopy. The chemical sensitivity and local order probing from core-loss edges provide new insights into the structural modifications induced under irradiation. From the analysis of the C K energy loss near-edge structure and Al K X-ray absorption near-edge structure by ab initio calculations, the influence of the layered structure of this compound on the irradiation damage is demonstrated, and damage is found to be preferentially localized in the aluminum planes of the structure. On the basis of comparisons between calculations and experimental spectra, a structural model is proposed for the irradiated state. This study emphasizes the utility of core-loss fine structure analysis to enhance understanding of ion irradiation-induced damage in complex crystalline materials.

The effect of varying nitrogen vacancies on the growth, microstructure, spinodal decomposition and hardness values of predominantly single crystal cubic phase c-(Ti1-xAlx)N-y films was investigated. Epitaxial c-(Ti1-xAlx)N-y films with y = 0.67, 0.79, and 0.92 were grown on MgO(001) and MgO(111) substrates by magnetron sputter deposition. High N vacancy c-(Ti1-xAlx)N-0.67 films deposited on MgO(111) contained coherently oriented w-(0001) structures while segregated conical structures were observed on the films grown on MgO(001). High resolution STEM images revealed that the N-deficient growth conditions induced segregation with small compositional fluctuations that increase with the number of N vacancies. Similarly, strain map analysis of the epitaxial c-(Ti1-xAlx)N-y (001) and (111) films show fluctuations in strain concentration that scales with the number of N vacancies and increases during annealing. The spinodal decomposition coarsening rate of the epitaxial c-(Ti1-xAlx)N-y films was observed to increase with decreasing N vacancies. Nanoindentation showed decreasing trends in hardness of the as-deposited films as the N vacancies increase. Isothermal post-anneal at 1100 degrees C in vacuum for 120 min revealed a continuation in the increase in hardness for the film with the largest number of N vacancies (y = 0.67) while the hardness decreased for the films with y = 0.79 and 0.92. These results suggest that nitrogen-deficient depositions of c-(Ti1-xAlx)N-y films help to promote a self-organized phase segregation, while higher N vacancies generally increase the coherency strain which delays the coarsening process and can influence the hardness at high temperatures. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd.

Transition-metal (TM) carbides are an important class of hard, protective coating materials; however, their brittleness often limits potential applications. We use density functional theory to investigate the possibility of improving ductility by forming pseudobinary cubic (MMC)-M-1-C-2 alloys, for which M-1 = Ti or V and M-2 = W or Mo. The alloying elements are chosen based on previous results showing improved ductility of the corresponding pseudobinary nitride alloys with respect to their parent compounds. While commonly-used empirical criteria do not indicate enhanced ductility in the carbide alloys, calculated stress/strain curves along known slip systems, supported by electronic structure analyses, indicate ductile behavior for VMoC. As VMoC layers are sheared along the 1 (1) over bar0 direction on {111} planes, the stress initially increases linearly up to a yield point where the accumulated stress is partially dissipated. With further increase in strain, the stress increases again until fracture occurs. A similar mechanical behavior is observed for the corresponding TM nitride VMoN, known to be a ductile ceramic material [1]. Thus, our results show that VMoC is a TM carbide alloy which may be both hard and ductile, i.e. tough. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ta4AlC3, a new member of the Mn+1AXn-phase family, has been synthesized and characterized (n = 1-3, M = early transition metal, A = A-group element, and X = C and/or N). Phase determination by Rietveld refinement of synchrotron X-ray diffraction data shows that Ta4AlC3 belongs to the P63/mmc space group with a and c lattice parameters of 3.10884 ± 0.00004 Å and 24.0776 ± 0.0004 Å, respectively. This is shown to be the α-polymorph of Ta4AlC3, with the same structure as Ti4AlN3. Lattice imaging by high-resolution transmission electron microscopy demonstrates the characteristic MAX-phase stacking of α-Ta4AlC3. Three modes of mechanical deformation of α-Ta4AlC3 are observed: lattice bending, kinking and delamination. © 2007.

Physical attributes of multicomponent materials of a given chemical composition are determined by atomic arrangement at property-relevant length scales. A potential route to access a vast array of atomic configurations for material property tuning is by synthesis of multicomponent thin films using vapor fluxes with their deposition pattern modulated in the sub-monolayer regime. However, the applicability of this route for creating new functional materials is impeded by the fact that a fundamental understanding of the combined effect of sub-monolayer flux modulation, kinetics and thermodynamics on atomic arrangement is not available in the literature. Here we present a research strategy and verify its viability for addressing the aforementioned gap in knowledge. This strategy encompasses thin film synthesis using a route that generates multi-atomic fluxes with sub-monolayer resolution and precision over a wide range of experimental conditions, deterministic growth simulations and nanoscale micro structural probes. Investigations are focused on structure formation within the archetype immiscible Ag-Cu binary system, revealing that atomic arrangement at different length scales is governed by the arrival pattern of the film forming species, in conjunction with diffusion of near-surface Ag atoms to encapsulate 3D Cu islands growing on 2D Ag layers. The knowledge generated and the methodology presented herein provides the scientific foundation for tailoring atomic arrangement and physical properties in a wide range of miscible and immiscible multinary systems. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The thermal stability of Ti₃SiC₂(0 0 0 1) thin films is studied by in situ X-ray diffraction analysis during vacuum furnace annealing in combination with X-ray photoelectron spectroscopy, transmission electron microscopy and scanning transmission electron microscopy with energy dispersive X-ray analysis. The films are found to be stable during annealing at temperatures up to ∼1000 °C for 25 h. Annealing at 1100–1200 °C results in the rapid decomposition of Ti₃SiC₂ by Si out-diffusion along the basal planes via domain boundaries to the free surface with subsequent evaporation. As a consequence, the material shrinks by the relaxation of the Ti₃C₂ slabs and, it is proposed, by an in-diffusion of O into the empty Si-mirror planes. The phase transformation process is followed by the detwinning of the as-relaxed Ti₃C₂ slabs into (1 1 1)-oriented TiC_0.67 layers, which begin recrystallizing at 1300 °C. Ab initio calculations are provided supporting the presented decomposition mechanisms.

The influence of Ti content on crystallinity and bonding of Cr–Ti–C thin films deposited by magnetron sputtering have been studied by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy. Our results show that binary Cr–C films without Ti exhibit an amorphous structure with two non-crystalline components; amorphous CrC_x and amorphous C (a-C). The addition of 10–20 at.% Ti leads to the crystallization of the amorphous CrC_x and the formation of a metastable cubic (Cr_1−xTi_x)Cy phase. The observation was explained based on the tendency of the 3d transition metals to form crystalline carbide films. The mechanical properties of the films determined by nanoindentation and microindentation were found to be strongly dependent on the film composition in terms of hardness, elasticity modulus, hardness/elasticity ratio and crack development.

Motivated by density functional theory (DFT)-derived ductility indicators for face centered cubic (fcc, rocksalt) structured TiN/MoN0.5 superlattices and Ti0.5Mo0.5N0.75 solid solutions, TiN/MoNy superlattice (SL) thin films with bilayer periods lambda of 2.4, 3.9, 6.6, 9.9, and 23.0 nm and corresponding solid solutions were developed by DC reactive magnetron sputtering. These SLs allow for improved hardness H and critical fracture toughness K-IC, with both peaking at the same bilayer period lambda of 9.9 nm (where the MoN0.5 layers crystallize with the ordered beta-Mo2N phase); H = 34.8 +/- 1.6 GPa and K-IC = 4.1 +/- 0.2 MPa root m. The correspondingly prepared fcc-Ti0.5Mo0.5N0.77 solid solution has H = 31.4 +/- 1.5 GPa and K-IC = 3.3 +/- 0.2 MPa root m. Thus, especially the fracture toughness shows a significant superlattice effect. This is suggested by DFT-by the increase of the Cauchy pressure from -19 to + 20 GPa for the 001-direction (while that in the 100-direction remained high, above 83 GPa) upon increasing lambda from 3 to 4 nm.& nbsp;Together, experimental and computational investigations prove the importance of optimized bilayer periods for highest strength and fracture toughness, as well as optimized N-content for the solid solutions.

The influence of the Mn content on the elastic properties of face centered cubic Fe-Mn alloys was studied using the combinatorial approach. Fe-Mn thin films with a graded chemical composition were synthesized. Nanoindentation experiments were carried out to investigate the elastic properties as a function of the Mn content. As the Mn content increases from similar to 23 to similar to 39 at.%, the average bulk modulus varies from 143 to 105 GPa. Ab initio calculations served to probe the impact of magnetic effects on the elastic properties. The magnetic state description with disordered local moments yields the best agreement with the experimental results, whereas with non-magnetic and antiferromagnetic configurations the bulk modulus is overestimated. The strong impact of the magnetic configuration may be understood based on the differences in the chemical bonding and the magnetovolume effect. It is suggested that, owing to minute energy differences of competing antiferromagnetic configurations, a mixture of these with a "notional magnetic disorder" is present, which is in fact well described by the disordered local moments model. These results show that the combinatorial thin film synthesis with subsequent nanoindentation is an appropriate tool for investigating the elastic properties of Fe-Mn alloys systematically as a function of the chemical composition, to validate theoretical models.

We have studied the influence of Al and Si additions on the elastic properties of face-centered cubic (fcc) Fe-Mn random alloys with Fe/Mn ratios of 4.00 and 2.33 using ab initio calculations. When Al is added up to 8 at.% the shearing elastic constants (C-11-C-12)/2 and C-44 decrease, resulting in a drop of similar to 20% in shear and similar to 19% in Youngs modulus. In fcc Fe-Mn-Si alloys, the trends in the elastic constants are similar, but less drastic, with a similar to 7% shear and similar to 6% Youngs modulus decrease when Si is added up to 8 at.%. The Fe/Mn ratio exhibits a minor influence on the shear and Youngs modulus values at constant Al and Si contents. To assess the quality of the ab initio data Fe-Mn-Al and Fe-Mn-Si thin films with an fcc structure were combinatorially synthesized and the elastic properties measured using nanoindentation. For both systems the measured and calculated lattice parameters are in good agreement. Although the measured Youngs modulus data showed significant scatter due to the high surface roughness, they are in good agreement with the predicted values. For the Fe-Mn-Al system the calculations generally underestimate the experimental data by similar to 15%. For the Fe-Mn-Si system the calculated data are in general lower by similar to 10% than the experimentally determined values. The presented results are of relevance for multicomponent alloy design, since the effect of Si and Al addition on the elastic properties of Fe-Mn alloys can be predicted based on ab initio data.

The physical properties of hard and superhard nanocomposite thin films are strongly dependent on their nanostructure. Here, we present the results of an investigation of nanostructural evolution and the resulting mechanical properties of (Zr1-xSix)N-y films, with 0 less than= x less than= 1 and 1 less than= y less than= 1.27, grown on MgO(0 0 1) and Al2O3(0 0 0 1) substrates at temperatures T-s = 500-900 degrees C by reactive magnetron sputter deposition from Zr and Si targets. X-ray diffraction and transmission electron microscopy (TEM) results show that there is a T-s/composition window in which stoichiometric Zr-Si-N and amorphous a-Si3N4 phases mutually segregate and self-organize into encapsulated 3-5 um wide ZrN-rich (Zr1-xSix)N columns which extend along the growth direction with a strong (002) texture. Lattice-resolved scanning TEM and energy-dispersive X-ray spectroscopy reveal that the (Zr1-xSix)N-y nanocolumns are separated by a bilayer tissue phase consisting of a thin crystalline SiNy-rich (Zr1-xSix)N-y layer with an a-Si3N4 overlayer. Incorporation of metastable SiN into NaCl-structure ZrN leads to an enhanced nanoindentation hardness H which is a function of T-s and film composition. For nanocomposites with composition (Zr(0.8)Sio(0.2))N-1.14 (10 at.% Si) H, increases from 26 GPa at 500 degrees C to 37 GPa at 900 degrees C. For comparison, the hardness of epitaxial ZrN/MgO(0 0 1) layers grown at T-s = 800 degrees C is 24 GPa. (C) 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The lattice strain tensor evolution for single bulk grains of austenite and ferrite in a duplex stainless steel during tensile loading to 0.02 applied strain has been investigated using in situ high-energy X-ray measurements and finite-element modeling. Single-grain X-ray diffraction lattice strain data for the eight austenite and seven ferrite grains measured show a large variation of residual lattice strains, which evolves upon deformation to the point where some grains with comparable crystallographic orientations have lattice strains different by 1.5 × 10⁻³, corresponding to a stress of 300 MPa. The finite-element simulations of the 15 measured grains in three different spatial arrangements confirmed the complex deformation constraint and importance of local grain environment.

The Ti-B-N system offers a wide range of possible meta(stable) phases, making it interesting for science and industry. However, the solubility for B within the face-centered cubic (fcc)-TiN lattice is rather limited and less studied, especially without forming B-rich phases. Therefore, we address how chemistries along the TiN-TiB2 or TiN-TiB tie-line influence this B-solubility. The variation between these two tie-lines is realized through non-reactive co-sputtering of a TiN, TiB2, and Ti target. We show that for variations along the TiN-TiB tie-line, even 8.9 at.% B (equivalent to 19.3 at.% non-metal fractions) can fully be incorporated into the fcc-TiNy lattice without forming other B-containing phases. The combination of detailed microstructural characterization through X-ray diffraction and transmission electron microscopy with ab initio calculations of fcc-Ti1-xNBx, fcc-TiN1-xBx, and fcc-TiN1-2xBx solid solutions indicates that B essentially substitutes N. The single-phase fcc-TiB0.17N0.69 (the highest B-containing sample along the TiN-TiB tie-line studied) exhibits the highest hardness H of 37.1 +/- 1.9 GPa combined with the highest fracture toughness K-IC of 3.0 +/- 0.2 MPa<middle dot>m(1/2) among the samples studied. These are markedly above those of B-free TiN0.87 having H = 29.2 +/- 2.1 GPa and K-IC = 2.7 +/-<0.1 MPa<middle dot>m(1/2).

In this study, we propose a new concept for achieving metastable ternary transition metal nitride solid solutions, focusing on face centered cubic (fcc) structured Ti(N,B) as a model system. Combining non-reactive magnetron sputtering with computational analysis, we develop a microalloying strategy to manipulate the metallic sublattice, thereby influencing the solubility of B in the non-metal sublattice. We show that imposed tensile strain on the fcc-TiN lattice facilitates the solubility of B, with a 1.5 % strain enabling the incorporation of similar to 28.5 at.% B at the non-metal sublattice. Conversely, compressive strain hinders the formation of the fcc-Ti(N,B) solid solution, highlighting the importance of lattice manipulation in controlling solubility. At the same time, our experimental findings reveal that adding larger atoms, such as Zr, to the metal sublattice enhances the solubility of B in fcc-TiN more effectively (similar to 2 at.% Zr proves to be sufficient to solute 10 at.% B in the fcc-TiN lattice) than smaller atoms, like Cr or similar-sized Ti atoms. The size effect of the alloying atoms on the B solubility is further supported by radial distribution function analysis, showing lower local lattice distortions for Zr compared to Cr.

Microscopic incompatibility-induced stresses in a duplex stainless steel undergoing plastic deformation are elucidated using a visco-plastic self-consistent model. The model considers not only the grain-orientation-dependent stresses and phase-to-phase interactions, but also texture evolution during deformation. The parameters used for describing the micromechanical behavior of the two-phase polycrystalline material are directly derived from the neutron diffraction data. A reliable prediction of the evolution of grain orientation distributions for both phases at small deformations is achieved after considering various micromechanical interactions of the studied material. © 2007 Acta Materialia Inc.

Heterophase interfaces play a crucial role in deformation microstructures and thus govern mechanical properties of multilayered composites. Here, we fabricated Ti/Nb multilayers by accumulative roll bonding (ARB) where shear bands became predominant with increasing rolling cycles. To explore correlation between micromechanical behavior and mechanical properties of the composites with various lamellar morphologies, in-situ high-energy X-ray diffraction tensile tests were performed. The results quantitatively reveal that the rapid strengthening of the composites with increasing ARB cycles mainly originates from the Nb layers strengthened by dislocations, grain boundaries and heterophase interfaces, and the {211} grains mostly contribute to the global strain hardening. The softer Ti grains also extend global strain hardening to a wide range and postpone necking. Furthermore, complete stress state analysis show that in the presence of extensive shear bands, significant load partitioning between the neighboring metals leads to triaxial stresses in each constituent and dislocations tend to slip along the shear direction. This promotes dislocation multiplication and motion, which is conducive to overall strength enhancement while maintaining a satisfactory ductility. These findings elucidate the effect of strong constraints of the interfaces on mechanical properties, which provides a fundamental understanding of load partitioning and strengthening mechanisms of the multilayers processed by multiple ARB cycles.

The evolution of micro- and macrostresses in a duplex stainless steel during loading has been investigated in situ by X-ray diffraction. A 1.5 mm cold-rolled sheet of alloy SAF 2304 solution treated at 1050°C was studied. Owing to differences in the coefficient of thermal expansion between the two phases, compressive residual microstresses were found in the ferritic phase and balancing tensile microstresses in the austenitic phase. The initial microstresses were almost two times higher in the transverse direction compared to the rolling direction. During loading the microstresses increase in the macroscopic elastic regime but start to decrease slightly with increasing load in the macroscopic plastic regime. For instance, the microstresses along the rolling direction in the austenite increase from 60 MPa, at zero applied load, to 110 MPa, at an applied load of 530 MPa. At the applied load of 620 MPa a decrease of the microstress to 90 MPa was observed. During unloading from the plastic regime the microstresses increase by approximately 35 MPa in the direction of applied load but remain constant in the other directions. The initial stress state influences the stress evolution and even after 2.5% plastic strain the main contribution to the microstresses originates from the initial thermal stresses. Finite element simulations show stress variations within one phase and a strong influence of both the elastic and plastic anisotropy of the individual phases on the simulated stress state.

This paper examines the idea that reversible hysteresis in MAX phases is caused by the formation, growth and collapse of unstable, or incipient, kink bands. In situ X-ray diffraction of polycrystalline Ti3SiC2 in compression showed that residual elastic lattice strains developed during the first loading cycle and remained approximately constant afterwards. These residual strains were compressive in grains with a low Schmid factor and tensile in grains with a high Schmid factor, consistent with previous observations of plastically deformed hexagonal metals. In contrast, incipient kink bands would be expected to collapse completely, without any residual strain. Elastoplastic self-consistent simulations showed that reversible hysteresis is predicted if some grains yield by slip on the basal plane, while others remain predominantly elastic, giving both the experimentally observed magnitude of the work dissipated and its dependence on the maximum applied stress. The reversible hysteresis in single crystals was studied by cyclically indenting thin films of Ti3SiC2 and Ti3SiC2/TiC multilayers on Al2O3 substrates. The work dissipated in the multilayer films was greater than in Ti3SiC2 alone, despite the reduction in volume fraction of Ti3SiC2. Reversible hysteresis was also observed during indentation of single-crystal cubic MgO, demonstrating that this behaviour can occur if there are insufficient slip systems to accommodate the strain around the indentation. These results show that reversible hysteresis is associated with conventional dislocation flow, without the need for unstable kinking.

We report the stress relaxation behavior of arc-evaporated TiC_xN_1−x thin films during isothermal annealing between 350 and 900°C. Films with x=0, 0,15 and 0,45 each having an initial compressive intrinsic stress σ_int = -5.4 GPa were deposited by varying the substrate bias V_s and the gas composition. Annealing above the deposition temperature leads to a steep decrease in the magnitude of σ_int to a saturation stress value, which is a function of the annealing temperature. The corresponding apparent activation energies for stress relaxation are E_a=2.4, 2.9, and 3.1 eV, for x=0, 0,15 and 0,45 respectively. TiC_0.45N_0.55 films with a lower initial stress σ_int = -3 GPa obtained using a high substrate bias, show a higher activation energy E_a=4.2 eV.In all the films, stress relaxation is accompanied by a decrease in defect density indicated by the decreased width of X-ray diffraction peaks and decreased strain contrast in transmission electron micrographs. Correlation of these results with film hardness and microstructure measurements indicates that the stress relaxation is a result of point-defect annihilation taking place both during short-lived metal-ion surface collision cascades during deposition, and during post-deposition annealing by thermally activated processes. The difference in E_a for the films of the same composition deposited at different V_s suggests the existence of different types of point-defect configurations and recombination mechanisms.

Coatings of (Al_xC_r1-x)_2+yO_3-y with 0.51≤x≤0.84 and 0.1≤y≤0.5 were deposited on hard cemented carbides substrates in an industrial cathodic arc evaporation system from powder-metallurgy prepared Cr/Al targets in pure O₂ and O₂+N₂ atmospheres. The substrate temperature and bias in all the deposition runs were 575 °C and -120 V, respectively. The composition of the coatings measured by energy dispersive x-ray spectroscopy and elastic recoil detection analysis was the same as that of the targets. Microstructure analyses performed by symmetrical X-ray diffraction and transmission electron microscopy showed that corundum, cubic or mixed-phase coatings formed depending on the Cr/Al ratio of the coatings and O₂ flow per activetarget during deposition. The corundum phase was promoted by high Cr content and high O₂ flow per target, while the cubic phase was mostly observed for high Al content and low O₂ flow per active target. In situ annealing of the cubic coatings resulted in phase transformation from cubic to corundum completed in the temperature range of 900-1100 °C, while corundum coatings retained their structure in the same range of annealing temperatures. Nanoindentation hardness of the coatings with Cr/Al ratio < 0.4 was 26-28 GPa, regardless of the structure. Increasing the Cr content of the coatings resulted in increased hardness of 28-30 GPa for corundum coatings. Wear resistance testing in a turning operation showed that coatings of Al-Cr-O have improved resistance to crater wear at the cost of flank wear compared to TiAlN coatings.

Coatings of (CrxAl1-x)(delta)(O1-yNy)(xi) with 0.33 less than= x less than= 0.96, 0 less than= y less than= 1 and 0.63 less than= delta/xi less than= 1.30 were deposited using cathodic arc evaporation in N-2/O-2 reactive gas mixtures on 50 V negatively biased WC-10 wt.% Co substrates from different Cr and Al alloys with three different Cr/Al compositional ratios. For N-2 less than 63% of the total gas, ternary (Cr,Al)(2)O-3 films containing less than1 at.% of N forms; as determined by elastic recoil detection analysis. Increasing the N-2 fraction to 75% and above results in formation of quaternary oxynitride films. Phase analyses of the films by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy show the predominance of cubic Cr-Al-N and cubic-(Cr,Al)(2)O-3 solid solutions and secondary hexagonal alpha-(Cr,Al)(2)O-3 solid solution. High Cr and Al contents result in films with higher roughness, while high N and O contents result in smoother surfaces. Nanoindentation hardness measurements showed that Al-rich oxide or nitride films have hardness values of 24-28 GPa, whereas the oxynitride films have a hardness of similar to 30 GPa, regardless of the Cr and Al contents. Metal cutting performance tests showed that the good wear properties are mainly correlated to the oxygen-rich coatings, regardless of the cubic or corundum fractions.

V(0.5)Mo(0.5)Nx/MgO(001) alloys with the B1-NaCI structure are grown by ultra-high-vacuum reactive magnetron sputter deposition in 5 mTorr mixed Ar/N-2 atmospheres at temperatures T-s between 100 and 900 degrees C. Alloy films grown at T-s amp;lt;= 500 degrees C are polycrystalline with a strong 002 preferred orientation; layers grown at T-s amp;gt;= 700 degrees C are epitaxial single-crystals. The N/Metal composition ratio x ranges from 1.02 +/- 0.05 with T-s = 100-500 degrees C to 0.94 +/- 0.05 at 700 degrees C to 0.64 +/- 0.05 at T-s = 900 degrees C. N loss at higher growth temperatures leads to a corresponding decrease in the relaxed lattice parameter a(0) from 4.212 A with x = 1.02 to 4.175 angstrom at x = 0.94 to 4.120 angstrom with x = 0.64. V(0.5)Mo(0.5)Nx nanoindentation hardnesses H and elastic moduli E increase with increasing T-s, from 17 +/- 3 and 323 +/- 30 GPa at 100 degrees C to 26 +/- 1 and 370 +/- 10 GPa at 900 degrees C. Both polycrystalline and single-crystal V(0.5)Mo(0.5)Nx films exhibit higher toughnesses than that of the parent binary compound VN. V(0.5)Mo(0.5)Nx films deposited at higher Ts also exhibit enhanced wear resistance. Valence-band x-ray photoelectron spectroscopy analyses reveal an increased volume density of shear-sensitive d-t(2g) d-t(2g) metallic states for V(0.5)Mo(0.5)Nx compared to VN and the density of these orbitals increases with increasing deposition temperature, i.e., with increasing N-vacancy concentration.(C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Using a combination of experiments and density functional theory (DFT), we demonstrate the first example of vacancy-induced  toughening, in this case for epitaxial pseudobinary NaCl-structure substoichiometric V_0.5Mo_0.5N_x alloys, with N concentrations 0.55 ≤ x ≤ 1.03, grown by reactive magnetron sputter deposition. The nanoindentation hardness H(x) increases with increasing vacancy concentration from 17 GPa with x = 1.03 to 26 GPa with x = 0.55, while the elastic modulus E(x) remains essentially constant at 370 GPa. Scanning electron micrographs of indented regions show ductile plastic flow giving rise to material pile-up, rather than cracks as commonly observed for hard, but brittle, transition-metal nitrides. The increase in alloy hardness with an elastic  modulus which remains constant with decreasing x, combined with the observed material pile-up around nanoindents, DFT-calculated decrease in shear to bulk moduli ratios, and increased Cauchy pressures (C₁₂-C₄₄), reveals a trend toward vacancy-induced toughening. Moreover, DFT crystal orbital overlap population analyses are consistent with the above results.

Interfaces between components of a material govern its mechanical strength and fracture resistance. While a great number of interfaces is present in nanolayered materials, such as superlattices, their fundamental role during mechanical loading lacks understanding. Here we combine ab initio and classical molecular dynamics simulations, nanoindentation, and transmission electron microscopy to reveal atomistic mechanisms underlying plasticity and crack growth in B1 AlN(001)/TiN(001) superlattices under loading. The system is a model for modern refractory ceramics used as protective coatings. The simulations demonstrate an anisotropic response to uniaxial tensile deformation in principal crystallographic directions due to different strain-activated plastic deformation mechanisms. Superlattices strained orthogonal to (001) interfaces show modest plasticity and cleave parallel to AlN/TiN layers. Contrarily, B1-to-B3 or B1-to-B4(B-k) phase transformations in AlN facilitate a remarkable toughness enhancement upon in plane [110] and [100] tensile elongation, respectively. We verify the predictions experimentally and conclude that strain-induced crack growth-via loss of interface coherency, dislocation-pinning at interfaces, or layer interpenetration followed by formation of slip bands-can be hindered by controlling the thicknesses of the superlattice nanolayered components.

Structure and mechanical properties of nanoscale multilayers of ZrN/Zr0.63Al0.37N grown by reactive magnetron sputtering on MgO (0 0 1) substrates at a temperature of 700 degrees C are investigated as a function of the Zr0.63Al0.37N layer thickness. The Zr0.63Al0.37N undergoes in situ chemical segregation into ZrN-rich and AlN-rich domains. The AlN-rich domains undergo transition from cubic to wurtzite crystal structure as a function of Zr0.63Al0.37N layer thickness. Such structural transformation allows systematic variation of hardness as well as fracture resistance of the films. A maximum fracture resistance is achieved for 2 nm thick Zr0.63Al0.37N layers where the AlN-rich domains are epitaxially stabilized in the metastable cubic phase. The metastable cubic-AlN phase undergoes stress-induced transformation to wurtzite-AlN when subjected to indentation, which results in the enhanced fracture resistance. A maximum hardness of 34 GPa is obtained for 10 nm thick Zr0.63Al0.37N layers where the wurtzite-AlN and cubic-ZrN rich domains form semi-coherent interfaces.

Following our recent discovery of a new nanolaminated carbide, Mo2Ga2C, we herein present a detailed structural and chemical analysis of this phase based on ab initio calculations, X-ray photoelectron spectroscopy, high resolution scanning transmission electron microscopy, and neutron powder diffraction. Calculations suggest an energetically and dynamically stable structure for C in the octahedral sites between the Mo layers, with Ga bilayers - stacked in a simple hexagonal arrangement - between the Mo2C layers. The predicted elastic properties are below those of the related nanolaminate Mo2GaC. The predicted structure, including lattice parameters and atomic positions, is experimentally confirmed. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Reactive RF-magnetron sputtering is used to grow Cr0.28Zr0.10O0.61 coatings at 500 degrees C. Coatings are annealed at 750 degrees C, 810 degrees C, and 870 degrees C. The microstructure evolution of the pseudobinary oxide compound is characterized through high resolution state of the art HRSTEM and HREDX-maps, revealing the segregation of Cr and Zr on the nm scale. The as-deposited coating comprises cc-(Cr,Zr)(2)O-3 solid solution with a Zr-rich (Zr,Cr)O-x. amorphous phase. After annealing to 750 degrees C tetragonal ZrO2 nucleates and grows from the amorphous phase. The ZrO2 phase is stabilized in its tetragonal structure at these fairly low annealing temperatures, possibly due to the small grain size (below 30 nm). Correlated with the nucleation and growth of the tetragonal-ZrO2 phase is an increase in hardness, with a maximum hardness after annealing to 750 degrees C, followed by a decrease in hardness upon coarsening, bcc metallic Cr phase formation and loss of oxygen, during annealing to 870 degrees C. The observed phase segregation opens up future design routes for pseudobinary oxides with tunable microstructural and mechanical properties. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nanocomposite coatings consisting of Ag and TiCx (x andlt; 1) crystallites in a matrix of amorphous SiC were deposited by high-rate magnetron sputtering from Ti-Si-C-Ag compound targets. Different target compositions were used to achieve coatings with a Si content of similar to 13 at.%, while varying the C/Ti ratio and Ag content. Electron microscopy, helium ion microscopy, X-ray photoelectron spectroscopy and X-ray diffraction were employed to trace Ag segregation during deposition and possible decomposition of amorphous SiC. Eutectic interaction between Ag and Si is observed, and the Ag forms threading grains which coarsen with increased coating thickness. The coatings can be tailored for conductivity horizontally or vertically by controlling the shape and distribution of the Ag precipitates. Coatings were fabricated with hardness in the range 10-18 GPa and resistivity in the range 77-142 mu Omega cm.

The mechanical behaviour at room temperature of a single-crystal superalloy exposed to long term ageing at elevated temperature has been investigated, a topic important for the material’s resistance to thermal-mechanical fatigue. Specimens with several different crystallographic orientations were plastically deformed in either tension or compression before and after the long term furnace exposure. While the thermally activated degradation of the microstructure causes a reduction in yield limit of up to 25% for specimens initially deformed in the |001 and |011| directions, none or only moderate reduction was seen for specimens initially deformed along the |111| direction. This can be explained by the strong correlation between yield limit reduction and the amount of γ coarsening. By introducing an isotropic degradation function in a newly developed crystal plasticity model, the constitutive behaviour of both virgin and degraded materials has been described with good agreement with the experimental results.

The microstructural features of shear localization, generated by a high-strain-rate deformation (similar to 10(5) s(-1)), of a twinning-induced plasticity (TWIP) steel containing about 17.5 wt.% Mn were well characterized by means of optical microscopy, transmission electron microscopy and electron backscatter diffraction. The high deformation rate was obtained by a ballistic impact penetration test on the TWIP steel sheet. In addition to the deformation twins observed as the main microstructural characterization in the matrix, some shear bands consisting of complex microstructures were also evidenced in the highly deformed area. Inside the shear band, there exist a large region of amorphous phase and a smooth transition zone that also contains nanocrystalline phases. The grain size decreases gradually in the transition zone, changing from a coarse scale (andgt;100 nm) to a fine scale (andlt;10 nm) adjacent to the amorphous region. The coexistence of the amorphous state and the fine-scaled nanocrystalline phase clearly suggests that melting inside the shear bands occurred, which is corroborated by calculations showing a very high rise in temperature due to localized plastic deformation and extremely rapid cooling by heat dissipation into the specimen.

The hardness and fracture toughness of high-temperature wear-resistant transition metal aluminum nitride multilayer films depend largely on the constituting layer ' s structure, compositional modulation, morphology, and interface coherency. We present a study on 1-micron thick multilayered films consisting of stacked layers of TiN and Zr 0.37 Al 0.63 N 1.09 , each layer being 10 nm thick. The films were grown using ion-assisted reactive magnetron sputtering on MgO(001) and Si(001) at substrate temperatures ranging from ambient to 900 degrees C. By increasing growth temperature, we found that the ZrAlN layers transition from near amorphous to nanocrystalline wurtzite to decomposed c-ZrN and w-AlN domains. Concurrently, the TiN layers exhibit strong fiber texture, polycrystallinity, and epitaxial growth carried by the ZrN domains. Both hardness and fracture stress, evaluated by nanoindentation and micromechanical tests, increase with temperature from H=24 GPa M g O , 23 GPa Si to 36 GPa M g O , 30 GPa Si , and sigma F Si = 6.1-7.7 GPa, respectively. An improved fracture toughness of K IC =2.4-2.8 MPa root m is related to different toughening mechanisms for the various microstructures. The difference in hardness between the substrates is related to compressive stress due to the deposition conditions and thermal contraction. The superior fracture stress is attributed to dense multilayers, free from macroscopic defects due to ion-assisted growth. After being deposited at 200 degrees C, the multilayers remained thermally stable when vacuum annealed for 15 hours at 900 degrees C, with no significant change in phase composition or hardness. The improved hardness, toughness, and temperature stability of the otherwise brittle nitrides are promising for industrial applications.

We measure the stacking fault energy of a set of 20 at% Cr-austenitic stainless steels by means of transmission electron microscopy using the weak beam dark field imaging technique and the isolated dislocations method. The measurements are analyzed together with first principles calculations. The results show that experiment and theory agree very well for the investigated concentration range of Mn (0-8%) and Ni (11-30%). The calculations show that simultaneous relaxation of atomic and spin degrees of freedom is important in order to find the, global energy minimum for these materials. Our results clearly show the great potential of the weak beam dark field technique to obtain accurate measurements of the stacking fault energy of austenitic steels and that the reliable predictability of first principles calculations can be used to design new steels with optimized mechanical properties. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Neutron strain scanning measurements on a eutectoid steel rod that has been subjected to standard industrial coiling and straightening operations are presented. Strains were determined non-destructively using two different diffractometers, one at a steady-state neutron source and the other at a pulsed spallation neutron source, with measurements made in both the ferrite and cementite components of the pearlitic microstructure. The residual stress state is explained in terms of a simplified analytical model for a two-phase material, which takes into account the successive loading operations contributing to residual stress. The results show that residual stresses generated by bending–straightening operations are significant and are likely to play an important role in the mechanical properties of the final wires.

High hardness and toughness are generally considered mutually exclusive properties for single-crystal ceramics. Combining experiments and ab initio molecular dynamics (AIMD) atomistic simulations at room temperature, we demonstrate that both the hardness and toughness of single-crystal NaCl-structure VNx/MgO(001) thin films are simultaneously enhanced through the incorporation of anion vacancies. Nanoindentation results show that VN0.8, here considered as representative understoichiometric VNx system, is approximate to 20% harder, as well as more resistant to fracture than stoichiometric VN samples. AIMD modeling of VN and VN0.8 supercells subjected to [001] and [110] elongation reveal that the tensile strengths of the two materials are similar. Nevertheless, while the stoichiometric VN phase cleaves in a brittle manner at tensile yield points, the understoichiometric compound activates transformation-toughening mechanisms that dissipate accumulated stresses. AIMD simulations also show that VN0.8 exhibits an initially greater resistance to both {110} &lt; 1 (1) over bar0 &gt; and {111} &lt; 1 (1) over bar0 &gt; shear deformation than VN. However, for progressively increasing shear strains, the VN0.8 mechanical behavior gradually evolves from harder to more ductile than VN. The transition is mediated by anion vacancies, which facilitate {110} &lt; 1 (1) over bar0 &gt; and {111} &lt; 1 (1) over bar0 &gt; lattice slip by reducing activation shear stresses by as much as 35%. Electronic-structure analyses show that the two-regime hard/tough mechanical response of VN0.8 primarily stems from its intrinsic ability to transfer d electrons between 2nd-neighbor and 4th-neighbor (i.e., across vacancy sites) V-V metallic states. Our work offers a route for electronic-structure design of hard materials in which a plastic mechanical response is triggered with loading. (C) 2020 Acta Materialia Inc. Published by Elsevier Ltd.

We present theoretical prediction and experimental evidence of a new MAX phase alloy, Mo2ScAlC2, with out-of-plane chemical order. Evaluation of phase stability was performed by ab initio calculations based on Density Functional Theory, suggesting that chemical order in the alloy promotes a stable phase, with a formation enthalpy of -24 meV/atom, as opposed to the predicted unstable Mo3AlC2 and Sc3AlC2. Bulk synthesis of Mo2ScAlC2 is achieved by mixing elemental powders of Mo, Sc, Al and graphite which are heated to 1700 degrees C. High resolution transmission electron microscopy reveals a chemically ordered structure consistent with theoretical predictions with one Sc layer sandwiched between two Mo-C layers. The two-dimensional derivative, the MXene, is produced by selective etching of the Al-layers in hydrofluoric acid, resulting in the corresponding chemically ordered Mo2ScC2, i.e. the first Sc-containing MXene. The here presented results expands the attainable range of MXene compositions and widens the prospects for property tuning. (C)2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Obtaining high hardness combined with enhanced toughness represents one of the current challenges in material design of hard ceramic protective coatings. In this work, we combine experimental and ab initio density functional theory (DFT) analysis of the mechanical properties of Ti-Al-Nb-N coatings to validate the results of previous theoretical investigations predicting enhanced toughness in TiAIN-based systems highly alloyed (amp;gt;25 at. %) with nitrides of pentavalent VB group elements Nb, Ta, and V. As-deposited Ti1-x-yAlxNbyN coatings (y = 0 divided by 0.61) exhibit single phase cubic sodium chloride (B1) structure identified as TiAl(Nb)N solid solutions. The highest hardness,similar to 32.5 +/- 2 GPa, and the highest Youngs modulus, similar to 442 GPa, are obtained in Nb-free Ti0.46Al0.54N exhibiting pronounced 111 growth-orientation. Additions of Nb in the coatings promote texture evolution toward 200. Nanoindentation measurements demonstrate that alloying TiAlN with NbN yields significantly decreased elastic stiffness, from 442 to similar to 358 divided by 389 GPa, while the hardness remains approximately constant (between 28 +/- 2 and 31 +/- 3 GPa) for all Nb contents. DFT calculations and electronic structure analyses reveal that alloying dramatically reduces shear resistances due to enhanced d-d second-neighbor metallic bonding while retaining strong metal-N bonds which change from being primarily ionic (TiAlN) to more covalent (TiAlNbN) in nature. Overall, Nb substitutions are found to improve ductility of TiAlN-based alloys at the cost of slight losses in hardness, equating to enhanced toughness. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

We report on phase and strain changes in Ti_1-xAl_xN (0 ≤ x ≤ 0.61) coatings on cutting tools during turning recorded in operando by high-energy x-ray diffractometry. Orthogonal cutting of AISI 4140 steel was performed with cutting speeds of 360–370 m/min. Four positions along the tool rake face were investigated as a function of time in cut. Formation of γ-Fe in the chip reveals that the temperature exceeds 727 °C between the tool edge and the middle of the contact area when the feed rate is 0.06 mm/rev. Spinodal decomposition and formation of wurtzite AlN occurs at the positions of the tool with the highest temperature for the x ≥ 0.48 coatings. The strain evolution in the chip reveals that the mechanical stress is largest closest to the tool edge and that it decreases with time in cut for all analyzed positions on the rake face. The strain evolution in the coating varies between coatings and position on the rake face of the tool and is affected by thermal stress as well as the applied mechanical stress. Amongst others, the strain evolution is influenced by defect annihilation and, for the coatings with highest Al-content (x ≥ 0.48), phase changes.

Understanding the nucleation and growth of polycrystalline thin films is a long-standing goal. Numerous studies have been done to determine the grain size, stress, and the ideal crystallographic orientation in films. The majority of past studies have either employed an ex-situ methodology or only monitor the development of macroscopic stress in real-time. There has never been any research done on the simultaneous changes in crystallographic texture, grain size, and microscopic stress in polycrystalline thin films. In this study, we investigated the generation and temporal evolution of texture, grain size, and internal stress in cathodic arc evaporated Al0.50Ti0.50N thin films using a bespoke deposition apparatus designed for use with 2-dimensional synchrotron x-ray diffraction technique. The influence of the substrate temperature is investigated in terms of the emergence and development of texture, grain size and stress evolution. A dynamic evolution of the crystallographic texture is observed as the overall film thickness varies. We clearly resolved two regime of films growth based on stress evolution. Beyond a threshold grain size (similar to 14 nm), the stress scales inversely to the average grain sizes, and as the film thickness increases, immediate compressive stress relaxation was seen. An extensive ex-situ evaluation of thin films using electron microscopies and electron diffraction was performed to support the in-situ x-ray diffraction results.

In the present work, we have studied the decomposition of arc evaporated Ti_0.55Al_0.45N and Ti_0.36Al_0.64N during heat treatment in vacuum by in-situ synchrotron wide angle x-ray scattering primarily to characterize the kinetics of the phase transformation of AlN from the cubic NaCl-structure to the hexagonal wurtzite-structure. In addition, in-situ small angle x-ray scattering measurements were conducted to explore details of the wavelength evolution of the spinodal decomposition, thus providing information about the critical size of the c-AlN rich domains prior to the onset of the h-AlN transformation. We report the fractional cubic to hexagonal transformation of AlN in Ti_1-xAl_xN as a function of time and extract activation energies between 320 and 350 kJ/mol dependent on alloy composition. The onset of the hexagonal transformation occurs at about 50 K lower temperature in Ti_0.36Al_0.64N compared to Ti_0.55Al_0.45N where the high Al content alloy also has a significantly higher transformation rate. A critical wavelength for the cubic domains of about 13 nm was observed for both alloys. Scanning transmission electron microscopy shows a c-TiN/h-AlN microstructure with a striking morphology resemblance to the c-TiN/c-AlN microstructure present prior to the hexagonal transformation.

The atomic structure and local composition of high quality epitaxial substoichiometric titanium diboride (TiB1.9) thin film, deposited by unbalanced magnetron sputtering, were studied using analytical high-resolution scanning transmission electron microscopy, density functional theory, and image simulations. The unpaired Ti is pinpointed to inclusion of Ti-based stacking faults within a few atomic layers, which terminates the {1 (1) over bar 00} prismatic planes of the crystal structure and attributed to the absence of B between Ti planes that locally relaxes the structure. This mechanism allows the line compound to accommodate off-stoichiometry and remain a line compound between defects. The planar defects are embedded in otherwise stoichiometric TiB2 and are delineated by insertion of dislocations. An accompanied decrease in Ti-Ti bond lengths along and across the faults is observed. (c) 2020ActaMaterialiaInc. PublishedbyElsevierLtd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)

The thermal stability of Al_1−xIn_xN (0 ⩽ x ⩽ 1) layers was investigated by scanning transmission electron microscopy (STEM) imaging, electron diffraction, and monochromated valence electron energy loss spectroscopy during in situ annealing from 750 to 950 °C. The results show two distinct decomposition paths for the layers richest in In (Al_0.28In_0.72N and Al_0.41In_0.59N) that independently lead to transformation of the layers into an In-deficient, nanocrystalline and a porous structure. The In-richest layer (Al_0.28In_0.72N) decomposes at 750 °C, where the decomposition process is initiated by In forming at grain boundaries and is characterized by an activation energy of 0.62 eV. The loss of In from the Al_0.41In_0.59N layer was initiated at 800 °C through continuous desorption. No In clusters were observed during this decomposition process, which is characterized by an activation energy of 1.95 eV. Finally, layers richest in Al (Al_0.82In_0.18N and Al_0.71In_0.29N) were found to resist thermal annealing, although the initial stages of decomposition were observed for the Al_0.71In_0.29N layer.

The development of phase stress and grain-orientation-dependent stress under uniaxial compression was investigated in a duplex stainless steel consisting of austenite and ferrite. Using in situ neutron diffraction measurements, the strain response of several h k l planes to the applied compressive stress was mapped as a function of applied stress and sample direction. Analysis based on the experimental results and elastoplastic self-consistent simulations shows that phase stresses of thermal origin further increase during elastic loading but decrease with increased plastic deformation. Grain-orientation-dependent stresses become significant in both austenite and ferrite after loading into the plastic region. After unloading from the plastic regime, a considerable intergranular stress remains in the austenitic phase and dominates over the phase stress. This study provides fundamental experimental inputs for future micromechanical modeling aiming at the evaluation and prediction of the mechanical performance of multiphase materials. © 2006 Acta Materialia Inc.

Ultrahigh-vacuum dual-target reactive magnetron sputtering, in a mixed Ar/N2 discharge was used to deposit epitaxial single-crystal MAX phase Ti2AlN(0 0 0 1) thin films, without seed layers, onto Al2O3(0 0 0 1) substrates kept at 1050 °C. By varying the N2 partial pressure a narrow process window was identified for the growth of single-crystal Ti2AlN. The film microstructure was characterized by a combination of X-ray diffraction, spherical aberration (Cs) corrected transmission electron microscopy (TEM), high-resolution image simulation and high-resolution scanning TEM. Nitrogen-depleted deposition conditions resulted in the concurrent formation of N-free Ti-Al intermetallics at the film/substrate interface and a steady-state growth of Ti2AlN together with N-free intermetallic phases. At higher N2 partial pressures the growth assumes a columnar epitaxial nature. 1 Å resolution of the lattice enabling location of all elements in the Ti2AlN unit cell is demonstrated. © 2007 Acta Materialia Inc.

Fe-Cr system attracts lot of attention in condensed matter physics due to its technological importance and extraordinary physics related to a non-trivial interplay between magnetic and chemical interactions. However, the effect of multicomponent alloying on the properties of Fe-Cr alloys are less studied. We have calculated the mixing enthalpy, magnetic moments, effective chemical, strain-induced and magnetic exchange interactions to investigate the alloying effect of Ni, Mn, Mo on the phase stability of the ferromagnetic bcc Fe Cr system at zero K. We demonstrate that the alloying reduces the stability of Fe-Cr alloys and expands the region of spinodal decomposition. At the same time, the mixing enthalpy in ternary Fe100-c-05CrcNi05 alloys indicates a stability of solid solution phase up to 6 at. % Cr. In Fem(100-c-07)CrNi(05)Mn(01)Mo(01) alloys, we did not find any alloy composition that has negative enthalpy of formation. Analyzing magnetic and electronic properties of the alloys and investigating magnetic, chemical and strain-induced interactions in the studied systems, we provide physically transparent picture of the main factors leading to the destabilization of the Fe-Cr solid solutions by the multicomponent alloying with Ni, Mn, Mo. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Traditional age hardening mechanisms in refractory ceramics consist of precipitation of fine particles. These processes are vital for widespread wear-resistant coating applications. Here, we report novel Guinier-Preston zone hardening, previously only known to operate in soft light-metal alloys, taking place in refractory ceramics like multicomponent nitrides. The added superhardening, discovered in thin films of Ti-Al-W-N upon high temperature annealing, comes from the formation of atomic-plane-thick W disks populating {111} planes of the cubic matrix, as observed by atomically resolved high resolution scanning transmission electron microscopy and corroborated by ab initio calculations and molecular dynamics simulations. Guinier-Preston zone hardening concurrent with spinodal decomposition is projected to exist in a range of other ceramic solid solutions and thus provides a new approach for the development of advanced materials with outstanding mechanical properties and higher operational temperature range for the future demanding applications.

Hard refractory transition-metal nitrides possess unique combinations of outstanding mechanical and physical properties, but are typically brittle. Recent experimental results demonstrated that single-crystal NaCI-structure (B1) V0.5Mo0.5N pseudobinary solid solutions are both hard (similar to 20 GPa) and ductile; that is, they exhibit toughness, which is unusual for ceramics. However, key atomic-scale mechanisms underlying this inherent toughness are unknown. Here, I carry out density-functional ab initio molecular dynamics (AIMD) simulations at room temperature to identify atomistic processes and associated changes in the electronic structure which control strength, plasticity, and fracture in V0.5Mo0.5N, as well as reference B1 TiN, subject to amp;lt;001amp;gt; and amp;lt;110amp;gt; tensile deformation. AIMD simulations reveal that V0.5Mo0.5N is considerably tougher than TiN owing to its ability to (i) isotropically redistribute mechanical stresses within the elastic regime, (ii) dissipate the accumulated strain energy by activating local structural transformations beyond the yield point. In direct contrast, TiN breaks in brittle manner when applied stresses reach its tensile strength. Charge transfer maps show that the adaptive mechanical response of V0.5Mo0.5N originates from highly populated d-d metallic-states, which allow for counterbalancing the destabilization induced via tensile deformation by enabling formation of new chemical bonds. The high ionic character and electron-localization in TiN precludes the possibility of modifying bonding geometries to accommodate the accumulated stresses, thus suddenly causing materials fracture for relatively low strain values. 

We use density functional theory calculations to explore the effects of alloying cubic TiN and VN with transition metals M = Nb, Ta, Mo, W in 50% concentrations. The obtained ternaries are predicted to become supertough as they are shown to be harder and significantly more ductile compared to the reference binaries. The primary electronic mechanism of this supertoughening effect is shown in a comprehensive electronic structure analysis of these compounds to be the increased valence electron concentration intrinsic to these ternaries. Our investigations reveal the complex nature of chemical bonding in these compounds, which ultimately explains the observed selective response to stress. The findings presented in this paper thus offer a design route for the synthesis of supertough transition metal nitride alloys via valence electron concentration tuning.

We carry out density functional theory calculations to compare the energetics of layer glide, as well as stress vs. strain curves, for cubic Ti0.5W0.5N pseudobinary alloys and reference B1-structure TiN. Irrespective of the degree of ordering on the metal sublattice, the hardness and stiffness of Ti0.5W0.5, as estimated by stress strain results and resistance to layer glide, are comparable to that of the parent binary TiN, while ductility is considerably enhanced. After an initial elastic response to an applied load, the pseudobinary alloy deforms plastically, thus releasing accumulated mechanical stress. In contrast, stress continues to increase linearly with strain in TiN. Layer glide in Ti0.5W0.5N is promoted by a high valence-electron concentration which enables the formation of strong metallic bonds within the slip direction upon deformation. [1111-oriented Ti0.5W0.5N layers characterized by high local metal-sublattice ordering exhibit low resistance to slip along &lt; 110 &gt; directions due to energetically favored formation of (111) hexagonal stacking faults. This is consistent with the positive formation energy of &lt; 111 &gt;-ordered Tio.5W0.5N with respect to mixing of cubic-BI TiN and hexagonal WC-structure WN. In the cubic pseudobinary alloy, slip occurs parallel, as well as orthogonal, to the resolved applied stress at the interface between layers with the lowest friction. We suggest that analogous structural metastability (mixing cubic and hexagonal TM nitride binary phases) and electronic (high valence electron concentration) effects are responsible for the enhanced toughness recently demonstrated experimentally for cubic single-crystal pseudobinary V0.5W0.5N and V0.5MocoN epitaxial layers. (c) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.