Structural behaviour of Pd40Cu30Ni10P20 metallic glass under high pressure

The structural behaviour of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass as a function of hydrostatic pressure up to 47.4 GPa was investigated by means of in situ high energy synchrotron X-ray diffraction patterns. Monotonic changes are observed in the diffraction data without any indication of a phase transition. In real space all maxima of the atomic pair correlation function including the nearest neighbour distance are decreasing and scale with pressure. The volume as function of hydrostatic pressure is extracted from the diffraction data. For the largest hydrostatic pressure of 47.4 GPa the volume is reduced by 18%. The bulk modulus B₀ = 178 GPa was calculated from the diffraction data. The dependence of volume on pressure of Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass can be well described by the Birch–Murnaghan equation of state.     

Excellent mechanical properties of metastable c-WN fabricated at high pressure and high temperature

Tungsten nitrides (WNs) are promising functional materials with high hardness, but the greatest challenge is to synthesize stoichiometric and bulk materials. In this paper, bulk tungsten mononitride (c-WN) with sodium chloride structure, which is a metastable phase, has been successfully synthesized at high pressure and high temperature (HPHT) using W₃N₄ as precursor. It is found that synergistic effect of pressure and temperature was useful to control the complete decomposition of W₃N₄ and to suppress further decomposing of as-synthesized c-WN. The compression ability and Vickers hardness were investigated by in situ high pressure X-ray diffraction (XRD) and Vickers microhardness tests, respectively. It is worth noting that the bulk modulus of c-WN is 422.9 ± 6.7 GPa, which is comparable to diamond. The Vickers hardness, 29 GPa obtained under an applied load of 0.49 N, is nearly 45% higher than that of TiN which is widely used as hard wear protective coatings. The excellent mechanical properties of c-WN may be ascribed to strong pd hybridization which has been further proved by XPS.     

Synthesis and compressive behavior of Cr2GeC up to 48 GPa

M_n+1AX_n compounds have gathered huge momentum because of its exciting properties. In this paper we report the synthesis of ternary layered ceramic Cr₂GeC, a 211 M_n+1AX_n compound by hot-pressing. Scanning electron microscopy and X-ray diffraction have been employed to characterize the new synthesized phase. High-pressure compressibility of Cr₂GeC were measured using diamond anvil cell and synchrotron radiation at room temperature up to 48 GPa. No phase transformation was observed in the experimental pressure range. The bulk modulus of Cr₂GeC calculated using the Birch–Murnaghan equation of state is 169 ± 3 GPa, with K′ = 3.05 ± 0.15.     

Structure-property relations of arc-evaporated Al-Cr-Si-N coatings

The addition of silicon to the widely used aluminum-containing transition metal nitrides is promising for the synthesis of hard and thermally stable films with good oxidation resistance. For that reason, Al-Cr-Si-N coatings were deposited by reactive cathodic arc-evaporation under industrial conditions from Al₇₀Cr_30 − xSi_x (x = 0, 1, 2, 5 at.%) targets at substrate bias voltages ranging from − 40 V to − 150 V. The structure of the well adherent coatings was investigated by X-ray diffraction and Raman spectroscopy, which indicated at higher Al/Cr ratio > 1.9 an increased tendency of the metastable face-centered cubic solid solution of AlN in CrN to separate into a cubic-hexagonal phase mixture. At higher bias voltages, this effect is gradually inverted and the single cubic phase can be retained. X-ray photoelectron spectroscopy revealed dominant Si-N bonds suggesting either a substitutional solid solution or a separate Si-N phase. Mechanical properties, i.e. hardness and elastic modulus, measured by indentation together with stress evolution demonstrate the beneficial effect of the conservation of the metastable cubic phase.     

First-principles investigations on structural,elastic, thermodynamic and electronic properties of Ni3X (X = Al,Ga and Ge) under pressure

The structural, elastic, thermodynamic and electronic properties of L1₂-ordered intermetallic compounds Ni₃X (X = Al, Ga and Ge) under pressure range from 0 to 50 GPa with a step of 10 GPa have been investigated using first-principles method based on density functional theory (DFT). The calculated structural parameters of Ni₃X at zero pressure and zero temperature are consistent with the experimental data. The results of bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio v, anisotropy index A^U and Debye temperature Θ_D increase with the increase of external pressure. In addition, the Debye temperature of these compounds gradually reduce as the order of Ni₃Al > Ni₃Ga > Ni₃Ge. The ratio of shear modulus to bulk modulus G/B shows that the three binary compounds are ductile materials, and the ductility of Ni₃Al and Ni₃Ga can be improved with pressure going up, while Ni₃Ge is opposite. Finally, the pressure-dependent behavior of density of states, Mulliken charge and bond length are analyzed to explore the physical origin of the pressure effect on the structural, elastic and thermodynamic properties of Ni₃X.     

Preparation of polycrystalline cubic boron nitride compact by high-pressure infiltration using cemented carbide

Polycrystalline cubic boron nitride (PcBN) compacts, using the infiltrating method in situ by cemented carbide (WC–Co) substrate, were sintered under high temperature and high pressure (HPHT, 5.2 GPa, 1450 °C for 6 min). The microstructure morphology, phase composition and hardness of PcBN compacts were investigated by using scanning electron microscope (SEM), X-ray diffraction (XRD) and energy dispersive spectrometer (EDS). The experimental results show that the WC and Co from WC–Co substrate spread into cubic boron nitride (cBN) layer through melting permeability under HPHT. The binder phases of WC, MoCoB and Co₃W₃C realized the interface compound of PcBN compact, and the PcBN layer formed a dense concrete microstructure. Additionally the Vickers hardness of 29.3 GPa and cutting test were performed when sintered by using cBN grain size of 10–14 μm.     

Mn3Sb: a new L12-type intermetallic compound synthesized under high-pressure

A new intermetallic compound, Mn₃Sb, has been synthesized by direct reaction of elemental components at 6.2 GPa and 1000 °C for 30 min using a belt-type high-pressure apparatus. The compound crystallizes into a cubic structure with the space group Pm-3m, namely the L1₂-type (Cu₃Au-type) structure. The structure was refined by the Rietveld analysis of the powder X-ray diffraction data and the lattice constant was determined to be a=0.40017(2) nm. The compound exhibits metallic conductivity and weak ferromagnetism.     

Temperature dependence of the isothermal bulk modulus of TiB2

The temperature dependencies of the isothermal bulk modulus of TiB₂ above room temperature were calculated by using the equation for the Anderson- Grüneisen parameter (δ_T) and its solution by Garai and Laugier (J. Appl. Phys. 101, 023514 (2007)). The present calculations utilize the relevant experimental data for the pressure derivative of the isothermal bulk modulus, K′ as δ_T in addition to the volume thermal expansion coefficients (α_V). The temperature derivatives of the isothermal bulk modulus of TiB₂ obtained in 300–900 K, using the latest published thermal expansion coefficients are, 0.012–0.013 GPa/K, in good agreement with the corresponding experimental values. The results verify the present approach as a practical way to predict the bulk moduli of materials at high temperatures.     

First-principle calculations of structural,elastic and thermodynamic properties of Fe–B compounds

The structural, elastic and thermodynamic properties of FeB, Fe₂B, orthorhombic and tetrahedral Fe₃B, FeB₂ and FeB₄ iron borides are investigated by first-principle calculations. The elastic constants and polycrystalline elastic moduli of Fe–B compounds are usually large especially for FeB₂ and FeB₄, whose maximum elastic constant exceeds 700 GPa. All of the six compounds are mechanically stable. The Vickers hardness of FeB₂ is estimated to be 31.4 GPa. Fe₂B and FeB₂ are almost isotropic, while the other four compounds have certain degree of anisotropy. Thermodynamic properties of Fe–B compounds can be accurately predicted through quasi-harmonic approximation by taking the vibrational and electronic contributions into account. Orthorhombic Fe₃B is more stable than tetrahedral one and the phase transition pressure is estimated to be 8.3 GPa.     

Mechanical characterization of hotplate synthesized vanadium oxide nanobelts

Vanadium oxide nanobelts have been synthesized on Si or SiN substrates by simply heating vanadium foils on a hotplate. As-grown nanobelts were characterized as V₂O₅·nH₂O (0.3 < n < 1.7) layer structures containing water molecular intercalation. Using an electromechanical resonance method, the Young’s modulus of the nanobelts was measured in situ in a scanning electron microscope. It was found that the Young’s modulus of as-grown nanobelts varied between 5.6 and 98 GPa, with a typical Q-factor of 120. Such scattered values were attributed to the different contents of water molecules in the nanobelts. After annealing at 450 °C in vacuum, the nanobelts were converted to α-V₂O₅ phase and a polycrystalline structure was observed. The Young’s modulus of the annealed nanobelts showed more consistent values at an average of 28.9 GPa, lower than the calculated modulus of bulk α-V₂O₅ at 68 GPa.     

Structure,phase stability and elastic properties in the Ti1–xZrxN thin-film system: Experimental and computational studies

The composition-dependence of the structure and elastic properties of ternary Ti_1–xZr_xN alloys is systematically investigated by combining thin film growth and ab initio calculations. Single-phase Ti_1–xZr_xN thin films (0 ? x ? 1) with a rocksalt structure have been deposited using dc reactive magnetron sputtering at T_s = 300 °C in Ar/N₂ plasma discharges. The structure, stress state and phase stability upon thermal annealing were studied by X-ray diffraction (XRD), while the acoustic and elastic properties were measured using Brillouin light spectroscopy, picosecond ultrasonics and nanoindentation. First-principles pseudopotential calculations of the total energy, lattice constants, bulk modulus, and single-crystal elastic constants C_ij for several cubic ordered structures of Ti_1–xZr_xN alloys were also carried out. The positive values of the computed formation energies indicate that the homogeneous Ti_1–xZr_xN alloys can be only stabilized at high temperatures. However, the magnetron-sputtered thin films were found to retain their as-grown single-phase cubic structure during post-deposition annealing at 850 °C for 3 h. The calculated equilibrium lattice parameters are in good agreement with the stress-free lattice parameters a₀ determined experimentally from XRD using the sin²ψ method: they both exhibit a positive deviation from Vegard-like linear interpolation. The calculated bulk modulus, elastic constants and Poisson’s ratio gradually decrease from TiN to ZrN. These computed values were used to interpret the experimentally derived elastic constants and Young’s modulus as functions of composition.     

Structural and mechanical properties of corundum and cubic (AlxCr1−x)2+yO3−y coatings grown by reactive cathodic arc evaporation in as-deposited and annealed states

Coatings of (Al_xCr_1?x)_2+yO_3?y with 0.51 ? x ? 0.84 and 0.1 ? y ? 0.5 were deposited on hard cemented carbide 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 differed from that of the facing targets by up to 11%. 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 active target during deposition. The corundum phase was promoted by high Cr content and high O₂ flow per target, while the cubic phase was observed mostly 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 with TiAlN coatings.     

Nanocrystalline Al3Ni2 alloy with high hardness produced by mechanical alloying and high-pressure hot-pressing consolidation

An elemental powder mixture corresponding to Al₃Ni₂ phase stoichiometry was subjected to mechanical alloying. A metastable nanocrystalline AlNi intermetallic phase with the mean crystallite size of 12 nm was formed upon milling. Heating of the synthesised powder in a calorimeter up to 720 °C caused phase transformation into an equilibrium Al₃Ni₂ intermetallic phase with the mean crystallite size of 41 nm. The product of mechanical alloying was consolidated at 1000 °C under the pressure of 5 GPa and 7.7 GPa. During consolidation, a phase transformation analogous with the one observed in the course of heating in the calorimeter took place. Both bulk materials have nanocrystalline structure with mean crystallite size of 67 nm and 58 nm, the smaller one in the sample consolidated under the higher pressure. The hardness of the produced Al₃Ni₂ intermetallic is 8.81 GPa (898 HV1) and 8.72 GPa (887 HV1), while the specific yield strength, estimated using the Tabor relation, is 624 kNm/kg and 617 kNm/kg for the sample hot-pressed under 5 GPa and 7.7 GPa respectively. On the basis of the obtained results, we can assume that the quality of consolidation with preserving a nanocrystalline structure is satisfactory and the hardness as well as the estimated specific yield strength of the produced materials are relatively high.     

Wear-resistant Ti–B–N nanocomposite coatings synthesized by reactive cathodic arc evaporation

Wear-resistant Ti–B–N coatings have been synthesized by reactive arc evaporation of Ti–TiB₂ compound cathodes in a commercial Oerlikon Balzers Rapid Coating System. Owing to the strong non-equilibrium conditions of the deposition method, a TiN–TiB_x phase mixture is observed at low N₂ partial pressures, as determined by elastic recoil detection analysis, X-ray diffraction, X-ray spectroscopy, transmission electron microscopy and selected area electron diffraction. The indicated formation of a metastable solid solution of B in face-centered cubic TiN gives rise to a maximum in hardness (>40 GPa) and wear resistance on the expense of increased compressive stresses. A further saturation of the nitrogen content results in the formation of a TiN–BN nanocomposite, where the BN phase fraction was tailored by the target composition (Ti/B ratio of 5/3 and 5/1). However, the amorphous nature of the BN phase does not support self-lubricious properties, showing friction coefficients of 0.7 ± 0.1 against alumina. The effect of an increased bias voltage on structure and morphology was investigated from −20 to −140 V and the thermal stability assessed in Ar and air by simultaneous thermal analysis up to 1400 °C.     

Enhanced mechanical properties due to structural changes induced by devitrification in Fe–Co–B–Si–Nb bulk metallic glass

Fe₃₆Co₃₆B_19.2Si_4.8Nb₄ bulk glassy rods were synthesized by copper mould casting. The effects of annealing treatments on the microstructure, elastic and mechanical properties of this alloy are investigated. Annealing below the glass transition temperature induces the formation of atomic clusters with pseudo-tenfold symmetry with a close relationship to the Fe₂₃B₆ phase. Annealing at sufficiently high temperatures promotes the formation of stable Fe₂B and FeB phases and Fe(Co) solid solution. The as-cast alloy exhibits ultra-high hardness (H > 14 GPa), high reduced Young’s modulus (E_r > 200 GPa) and good wear resistance. These properties are further enhanced after thermal treatments (H > 18 GPa and E_r > 260 GPa are achieved in the fully crystallized sample). The mechanical hardening is accompanied with an increase of the elastic recovery and a decrease of the Poisson’s ratio. The different microstructural mechanisms responsible for these annealing-induced changes in mechanical and elastic properties are discussed.     

Deposition and characterization of non-isostructural (Ti0.7Al0.3N)/(Ti0.3Al0.7N) multilayers

Non-isostructural Ti_0.7Al_0.3N(cubic B1)/Ti_0.3Al_0.7N(hexagonal B4) nanoscale multilayers were deposited by dc magnetron sputtering on steel substrates, with nominal periods of 6, 10, 20 and 40 nm. The structure, composition, periodicity, and interface abruptness of the samples were characterized by X-ray diffraction, glow discharge optical spectroscopy, medium energy ion scattering, and narrow resonant nuclear reaction profiling. The nanohardness and elastic modulus of the samples were determined, revealing superhardness of up to 57 GPa for the lowest nanoscale multilayer period. The H³/E² ratios were found to be superior to those of most metal nitride multilayers commonly used as protective coatings, which indicates a superior wear resistance for the present nanostructured coating. The results are discussed in terms of the present stage of understanding of nanoscale multilayer effects on the tribological properties of protective coatings.     

Structural,elastic, electronic,and thermodynamic properties of intermetallic Zr2Cu: A first-principles study

Three competing structures (C11_b, C16 and E9₃) of intermetallic Zr₂Cu have been systematically investigated by first-principles calculations and quasi-harmonic Debye model. Both the calculated equation of states (EOS) and pressure–enthalpy results indicate a structural phase transition from C11_b to C16 phase at around 11–14 GPa. The calculated equilibrium crystal parameters and elastic constants are in consistence with available experimental or theoretical data. All three phases are mechanically stable according to the elastic stability criteria, and ductile according to Pugh's ratio, while the ambient-stable C11_b phase shows a higher elastic anisotropy. Furthermore, differences in the nature of bonding between three competing structures are uncovered by electron density topological analysis. C11_b Zr₂Cu possesses an intriguing pseudo BaFe₂As₂-type structure with the charge density maxima at Zr tetrahedral interstices serving as Fe-position pseudoatoms; C16 Zr₂Cu contains Zr-pair configurations bonded through bifurcated Zr–Zr bonding paths; while the E9₃ phase has only conventional straight bonding. Additionally, through quasi-harmonic Debye model, the pressure and temperature dependences of the bulk modulus, specific heat, Debye temperature, Grüneisen parameter and thermal expansion coefficient for three phases are obtained and discussed.     

Pressure-induced change in the order of the phase transition in lead titanate: Structural aspects

The crystal structure of lead titanate PbTiO₃ have been studied by energy-dispersive X-ray diffraction under pressures of 0–4 GPa in the temperature range of 300–950 K. At a temperature of T = 747 K, a structural phase transition from a ferroelectric tetragonal phase to a paraelectric cubic phase is observed. The application of pressure leads to a significant decrease in the phase transition temperature; under pressures of P ∼ 2 GPa, the type of the phase transition changes from the first to second order. In the low pressure range, the baric coefficient value is dTc/dP = −20(3) K/GPa; under pressures above 2 GPa, it increases up to −113(5) K/GPa.     

In situ synthesis of nanocrystalline intermetallic layer during surface plastic deformation of zirconium

By means of a surface plastic deformation method a nanocrystalline (NC) intermetallic compound was in situ synthesized on the surface layer of bulk zirconium (Zr). Hardened steel shots (composition: 1.0C, 1.5Cr, base Fe in wt.%) were used to conduct repetitive and multidirectional peening on the surface layer of Zr. The microstructure evolution of the surface layer was investigated by X-ray diffraction and scanning and transmission electron microscopy observations. The NC intermetallic layer of about 25 μm thick was observed and confirmed by concentration profiles of Zr, Fe and Cr, and was found to consist of the Fe_100 − xCr_x compound with an average grain size of 22 nm. The NC surface layer exhibited an extremely high average hardness of 10.2 GPa. The Zr base immediately next to the compound/Zr interface has a grain size of ∼ 250 nm, and a hardness of ∼ 3.4 GPa. The Fe_100 − xCr_x layer was found to securely adhere to the Zr base.     

Structural,electronic and elastic properties of noble metal sub-nitrides M2N (M = Ru,Rh, Pd)

Ab initio calculations are performed to investigate the structural stability, electronic structure and elastic properties of noble metal sub-nitrides M₂N (M = Ru, Rh, Pd). The metal nitrides, Ru₂N and Rh₂N are found to be stable in anti-fluorite structure, whereas Pd₂N is stable in tetragonal structure. In Ru₂N and Rh₂N, structural phase transition is predicted from antifluorite to orthorhombic phase whereas tetragonal to antifluorite and then antifluorite to pyrite phase transitions are predicted in Pd₂N under high pressure. The electronic structure reveals that these nitrides are metallic. The calculated elastic constants indicate that these materials are mechanically stable at ambient condition. The Debye temperature values are reported for all the phases of these nitrides. The high bulk modulus indicates that these materials are super hard materials. They are ductile in nature at normal and high pressures. The bonding nature of these materials is found to be a mixture of covalent, metallic and ionic attribution at ambient condition.