High hardness,low Young's modulus and low friction of nanocrystalline ZrW2 Laves phase and Zr1−xWx thin films

Zr_1?xW_x nanocrystalline films of Zr-W solid solutions and ZrW₂ Laves phase were synthesized by magnetron co-sputtering. Large values of the H/E ratio up to 0.09 are observed for grain sizes in the nanometer range along with a hardness above 10 GPa and Young's modulus below 230 GPa. H/E values are correlated with the developed surface of grain boundaries suggesting an elastic deformation mostly handled by the grain boundaries. This is associated to friction coefficients comparable to those of metallic glass surfaces. In contrast to fragile bulk Laves phases, no cracks were detected at the film surface after indentation and scratch test of nanocrystalline ZrW₂. The friction coefficient of such films against diamond tip was in the range 0.08–0.15, similarly to metallic glass surfaces.     

Investigations on structural,elastic, thermodynamic and electronic properties of TiN,Ti2N and Ti3N2 under high pressure by first-principles

The lattice parameters, cell volume, elastic constants, bulk modulus, shear modulus, Young's modulus and Poisson's ratio are calculated at zero pressure, and their values are in excellent agreement with the available data, for TiN, Ti₂N and Ti₃N₂. By using the elastic stability criteria, it is shown that the three structures are all stable. The brittle/ductile behaviors are assessed in the pressures from 0 GPa to 50 GPa. Our calculations present that the performances for TiN, Ti₂N and Ti₃N₂ become from brittle to ductile with pressure rise. The Debye temperature rises as pressure increase. With increasing N content, the enhancement of covalent interactions and decline of metallicity lead to the increase of the micro-hardness. Their constant volume heat capacities increase rapidly in the lower temperature, at a given pressure. At higher temperature, the heat capacities are close to the Dulong–Petit limit, and the heat capacities of TiN and Ti₂N are larger than that of c-BN. The thermal expansion coefficients of titanium nitrides are slightly larger than that of c-BN. The band structure and the total Density of States (DOS) are calculated at 0 GPa and 50 GPa. The results show that TiN and Ti₂N present metallic character. Ti₃N₂ present semiconducting character. The band structures have some discrepancies between 0 GPa and 50 GPa. The extent of energy dispersion increases slightly at 50 GPa, which means that the itinerant character of electrons becomes stronger at 50 GPa. The main bonding peaks of TiN, Ti₂N and Ti₃N₂ locate in the range from −10 to 10 eV, which originate from the contribution of valance electron numbers of Ti s, Ti p, Ti d, N s and N p orbits. We can also find that the pressure makes that the total DOS decrease at the Fermi level for Ti₂N. The bonding behavior of N–Ti compounds is a combination of covalent and ionic nature. As N content increases, valence band broadens, valence electron concentration increases, and covalent interactions become stronger. This is reflected in shortening of Ti–N bonds.     

Electrical and mechanical properties of diluted magnetic semiconductor Zn1−xMnxS nanocrystalline films

Nanostructured Zn_1−xMn_xS films (0 ⩽ x ⩽ 0.25) were deposited on glass substrates by simple resistive thermal evaporation technique. All the films were deposited at 300 K in a vacuum of 2 × 10⁻⁶ m bar. All the films temperature dependence of resistivity revealed semiconducting behaviour of the samples. Hot probe test revealed that all the samples exhibited n-type conductivity. The nanohardness of the films ranges from 4.7 to 9.9 GPa, Young’s modulus value ranging 69.7–94.2 GPa.     

Pressure-induced variation of structural,elastic, vibrational,electronic, thermodynamic properties and hardness of Ruthenium Carbides

Three of the five structures obtained from the evolutionary algorithm based structure search of Ruthenium Carbide systems in the stoichiometries RuC, Ru₂C and Ru₃C are relaxed at different pressures in the range 0–200 GPa and the pressure-induced variation of their structural, elastic, dynamical, electronic and thermodynamic properties as well as hardness is investigated in detail. No structural transition is present for these systems in this pressure range. RuC–Zinc blende is mechanically and dynamically unstable close to 100 GPa. RuC-Rhombohedral and Ru₃C-Hexagonal retain mechanical and dynamical stability up to 200 GPa. For all three systems the electronic bands and density of states spread out with pressure and the band gap increases with pressure for the semiconducting RuC–Zinc blende. From the computed IR spectrum of RuC–Zinc blende at 50 GPa it is noted that the IR frequency increases with pressure. Using a semi-empirical model for hardness it is estimated that hardness of all three systems consistently increases with pressure. The hardness of RuC–Zinc blende increases towards the superhard regime up to the limiting pressure of its mechanical stability while that of RuC-Rhombohedral becomes 30 GPa at the pressure of 150 GPa.     

Elastic stability and electronic structure of tantalum boride investigated via first-principles density functional calculations

The elastic properties, electronic structure and thermodynamic behavior of the TaB have been investigated for the first time in this work. Using first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT), the ground state properties and equation of state of TaB have been obtained. The average zero-pressure bulk modulus of TaB is 302 GPa. By analyzing the elastically anisotropic behavior and the relative structure parameters of TaB, we found that the crystal cell along the b-axis was more compressible than along the a and c axes. The calculated ratio of bulk modulus and shear modulus (B/G) for TaB is 1.58, demonstrating that TaB is rather brittle. From the elastic stiffness constants, we found that TaB in the Cmcm phase is mechanically stable. The calculated hardness of TaB is 28.6 GPa which is close to the previous data. Moreover, using the Gibbs 2 model, the thermodynamic properties such as the thermal expansion and Debye temperature of TaB have been obtained firstly. At the ambient temperature, the Debye temperatures of TaB are 792 K and 845 K from GGA calculation and LDA calculation, respectively.     

High strain rate sensitivity of hardness in quinary Ti-Zr-Hf-Cu-Ni high entropy metallic glass thin films

Quinary Ti-Zr-Hf-Cu-Ni high-entropy metallic glass thin films were produced by magnetron sputter deposition. Nanoindentation tests indicate that the deposited film exhibits a relatively large hardness of 10.4±0.6 GPa and a high elastic modulus of 131±11 GPa under the strain rate of 0.5 s⁻¹. Specifically, the strain rate sensitivity of hardness measured for the thin film is 0.05, the highest value reported for metallic glasses so far. Such high strain rate sensitivity of hardness is likely due to the high-entropy effect which stabilizes the amorphous structure with enhanced homogeneity.     

First-principles calculations on crystal structure and physical properties of rhenium dicarbide

Structural stability, elastic behavior, hardness, and chemical bonding of ideal stoichiometric rhenium dicarbide (ReC₂) in the ReB₂, ReSi₂, Hex-I, Hex-II, and Tet-I structures have been systematically studied using first-principles calculations. The results suggest that all these structures are mechanically stable and ultra-incompressible characterized by large bulk moduli. Formation enthalpy calculations demonstrated that they are metastable under ambient conditions, and the relative stability of the examined candidates decreases in the following sequence: Hex-I>Hex-II>ReB₂>Tet-I>ReSi₂. The hardness calculations showed that these structures are all hard materials, among which the Hex-I exhibits the largest Vickers hardness of 32.2 GPa, exceeding the hardness of α-SiO₂ (30.6 GPa) and β-Si₃N₄ (30.3 GPa). Density of states and electronic localization function analysis revealed that the strong C–C and C–Re covalent bonds are major driving forces for their high bulk and shear moduli as well as small Poisson's ratio.     

M/Li+(M = Mg2+, Zn2+, and Mn2+) ion-exchange on lithium ion-conducting perovskite-type oxides and their properties

Lithium ions of perovskite-type lithium ion conductor La_0.55Li_0.35TiO₃ were replaced by divalent Mg²⁺, Zn²⁺, and Mn²⁺ ions in an ion-exchange reaction using molten chlorides. The polycrystalline Mg-exchanged and Zn-exchanged samples are solid electrolytes for divalent Mg²⁺ and Zn²⁺ ions, whose dc ionic conductivities (σ = 2.0 × 10^− 6 S cm^− 1 at 558 K for the Mg-exchanged sample, La_0.56(2)Li_0.02(1)Mg_0.16(1)TiO_3.01(2) and σ = 1.7 × 10^− 6 S cm^− 1 at 708 K for the Zn-exchanged samples, La_0.55(1)Li_0.0037(2)Zn_0.15(1)TiO_2.98(2)) were compared to those of the known highest Mg²⁺ and Zn²⁺ inorganic solid electrolytes. The Mn-exchanged sample, then, showed paramagnetic behavior in the temperature range of 2 to 300 K. The Mn ions in the exchanged sample are divalent and the spin configuration is in high spin state (S = 5/2).     

Microstructures and nano mechanical properties of the metal tungsten film

The W film was prepared on 1045 steel by magnetron sputtering, with the thickness of 2 μm, its surface and cross-section morphologies were investigated with SEM, and the phase structure was analyzed with XRD. X-ray stress determinator was utilized to measure its residual stress, and the nano-hardness and elastic modulus of the film were surveyed by nano-indentation tester. The results show that the surface of W film is very compact and smooth; the particles arranged regularly, the granularity of the thin film is about 1 μm. The microcracks, cavities and desquamation were not found in the film and interface, and the bonding between the W film and substrate is well. The XRD results showed that the W film had a body-centered cubic structure, the lattice constant: a = 0.316 nm, the growth preferred orientations are (1 1 0) and (2 2 0). The compressive stress (−169 MPa) was found on the surface. The average nano-hardness and elastic modulus of W film are 15.22 GPa, 176.64 GPa, respectively, and the mechanical properties of W film are well.     

Significant enhancement of electrical transport properties of thermoelectric Ca3Co4O9+δ through Yb doping

We report the significant enhancement of the power factor of Ca₃Co₄O_9+δ through Yb doping. The pellets were prepared by pressing under 0.5 GPa and 2 GPa. The highest power factor of 553 μW m^?1 K^?2 due to the significant increase of electrical conductivity was obtained for Ca_2.9Yb_0.1Co₄O_9+δ pressed at 0.5 GPa. This is 2.3 times higher than that of Ca₃Co₄O_9+δ (246 μW m^?1 K^?2). Nanostructure examinations show that the pellets pressed at 0.5 and 2 GPa have different nano-lamella structures. This work suggests that Yb is an effective doping element for enhancing the electrical transport properties of Ca₃Co₄O_9+δ, and the optimum doping level is related to the nanostructure of the bulk pellets.     

Optical and electrical properties of Ge-implanted SiO2 layers on n-Si and p-Si

Ge ions of 100 keV were implanted into a 120 nm-thick SiO₂ layer on n-Si at room temperature while those of 80 keV were into the same SiO₂ layer on p-Si. Samples were, subsequently, annealed at 500°C for 2 h to effectively induce radiative defects in the SiO₂. Maximum intensities of sharp violet photoluminescence (PL) from the SiO₂/n-Si and the SiO₂/p-Si samples were observed when the samples have been implanted with doses of 1×10¹⁶ and 5×10¹⁵ cm⁻², respectively. According to current–voltage (I–V) characteristics, the defect-related samples exhibit large leakage currents with electroluminescence (EL) at only reverse bias region regardless of the type of substrate. Nanocrystal-related samples obtained by an annealing at 1100°C for 4 h show the leakage at both the reverse and the forward region.     

Structural,electronic and mechanical properties of alkaline earth metal oxides MO (M=Be,Mg, Ca,Sr, Ba)

The structural, electronic and mechanical properties of alkaline earth metal oxides MO (M=Be, Mg, Ca, Sr, Ba) in the cubic (B1, B2 and B3) phases and in the wurtzite (B4) phase are investigated using density functional theory calculations as implemented in VASP code. The lattice constants, cohesive energy, bulk modulus, band structures and the density of states are computed. The calculated lattice parameters are in good agreement with the experimental and the other available theoretical results. Electronic structure reveals that all the five alkaline earth metal oxides exhibit semiconducting behavior at zero pressure. The estimated band gaps for the stable wurtzite phase of BeO is 7.2 eV and for the stable cubic NaCl phases of MgO, CaO, SrO and BaO are 4.436 eV, 4.166 eV, 4.013 eV, and 2.274 eV respectively. A pressure induced structural phase transition occurs from wurtzite (B4) to NaCl (B1) phase in BeO at 112.1 GPa and from NaCl (B1) to CsCl (B2) phase in MgO at 514.9 GPa, in CaO at 61.3 GPa, in SrO at 42 GPa and in BaO at 14.5 GPa. The elastic constants are computed at zero and elevated pressures for the B4 and B1 phases for BeO and for the B1 and B2 phases in the case of the other oxides in order to investigate their mechanical stability, anisotropy and hardness. The sound velocities and the Debye temperatures are calculated for all the oxides using the computed elastic constants.     

Mechanical characteristics of solution grown potassium zinc chloride crystals doped with lithium ions

Results of indentation-induced hardness testing studies on potassium zinc chloride crystals doped with Li⁺ ions, leading to an understanding of their mechanical behaviour, are presented. The Vickers hardness of these crystals for (1 0 0), (0 1 0) and (0 0 1) planes in the load range 20–160 g were studied. Load-independent values of hardness are estimated for the three crystallographic planes by applying Hays-Kendall’s and Li-Bradt models. The results showed that: (1) for the three crystallographic planes the load-independent hardness obtained by Li-Bradt model is higher than that predicted by Hays-Kendall’s, approach; (2) the load independent hardness of the (0 0 1) plane is higher than that of both (1 0 0) and (0 1 0) planes, (3) the values of load-independent hardness depend on Li⁺ concentrations in the K₂ZnCl₄ crystals, (4) the variations of crack length and crack morphology are described for studied crystal planes.     

Synthesis and crystallographic studies of garnet-related lithium-ion conductors Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12

High-purity specimens of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ have been successfully synthesized by solid-state reactions. The analytical chemical compositions of these samples were in good agreement with the nominal compositions of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂. The Rietveld refinements verified that these compounds have the garnet-type framework structure with the lattice constants of a = 12.725(2) Å for Li₆CaLa₂Ta₂O₁₂ and a = 13.001(4) Å for Li₆BaLa₂Ta₂O₁₂. All of the diffraction peaks of X-ray powder diffraction patterns were well indexed on the basis of cubic symmetry with space group Ia-3d. To make a search for Li sites, the electron density distributions were precisely examined by using the maximum entropy method. Li⁺ ions occupy partially two types of crystallographic site in these compounds: (i) tetrahedral 24d sites, and (ii) distorted octahedral 96h sites, the latter of which are the vacant sites of the ideal garnet-type structure. The present Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ samples exhibit the conductivity σ = 2.2 × 10^? 6 S cm^? 1 at 27 °C (E_a = 0.50 eV) and σ = 1.3 × 10^? 5 S cm^? 1 at 25 °C (E_a = 0.44 eV), respectively.     

Theoretical investigation of the electronic structure and structural phase stability of CeGa2 under pressure

Recently, Chandra Shekar et al. (Phys. Stat. Sol. B 241(2004)2893), studied the structural stability of CeGa₂ under high pressure up to ∼32 GPa and reported a structural transition from hexagonal AlB₂-type to omega trigonal-type starting at ∼16 GPa with a volume collapse of ∼6%. The high-pressure omega triginal phase is found to coexist with the parent phase up to 32 GPa. In this paper, we report the results of our band structure calculations on this system as a function of reduced volume by the tight-binding linear muffin–tin orbital (TB-LMTO) method, in order to look into this structural transition and to understand it in terms of changes in its electronic structure. Our calculations indicate a structural transition at ∼30.6 GPa with a volume collapse of 3.5%, in good agreement with the experimental results. The possible mechanism of the phase transition may be due to f→d electron transfer under pressure. The theoretically calculated ground-state properties, namely the lattice parameters and the bulk modulus are also in good agreement with the experimental values.     

Superconductivity in Nb2InC

In this work the Nb₂InC phase is investigated by X-ray diffraction, heat capacity, magnetic and resistivity measurements. Polycrystalline samples with Nb₂InC nominal compositions were prepared by solid state reaction. X-ray powder patterns suggest that all peaks can be indexed with the hexagonal phase of Cr₂AlC prototype. The electrical resistance as a function of temperature for Nb₂InC shows superconducting behavior below 7.5 K. The M(H) data show typical type-II superconductivity with H_C1 ～ 90 Oe at 1.8 K. The specific heat data are consistent with bulk superconductivity. The Sommerfeld constant is estimated as γ ～ 12.6 mJ mol^?1 K^?1.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.     

Synthesis and characterization of excess magnesium MgB2 superconductor under inert carbon environment

The structural, transport and magnetic properties of MgB₂ superconductor heavily blended with Mg is studied. The samples are synthesized with a new approach in both, pressed carbon environment and in flowing argon. The excess magnesium used is observed to play dual role: one being the prevention of Mg losses during the synthesis process and hence maintaining the stoichiometry of MgB₂ phase, and second being the formation of Mg milieu probably all around the MgB₂ grains to give a dense structure. Excess Mg also improves the grain connectivity by going into the pores and there by minimizing the insulating junctions. The residual resistivity of the sample is observed to decrease from 57.02 μΩ cm to 10.042 μΩ cm as it is progressively filled with superconductor–normal–superconductor (SNS) type junctions amongst the grains by the virtue of increased magnesium content. The synthesized samples devoid of porosity show the superconducting transition, T_c in the range of 39–34 K as of clean MgB₂ samples, though overloaded with Mg. The excess Mg resulted in enhanced critical current density, J_c from 6.8 × 10³ A cm^?2 to 5.9 × 10⁴ A cm^?2 at 20 K and 10 kOe, with reasonable decrease in the superconducting transition. Thus our samples being overloaded with Mg impart mechanical strength and competitive superconducting properties, which forms a part of interest.     

Mg0.9Zr0.1B2/Cu wires were successfully synthesized by SHS method in the air

Mg_0.9Zr_0.1B₂/Cu wires were successfully synthesized by powder-in-tube (PIT) techniques with self-propagating high-temperature synthesis (SHS) method. We loaded the mixed of Mg, Zr and B power into Cu tube. The tube was drawn to a wire and each end of the tube was sealed by the sealant, then rolled into solenoid with 1.5 cm diameter. The wire was heated up to 270 °C in a furnace with general air pressure, then, ignited the wire with electric arc from one of the end, the self-propagating reaction was completed in 2.0–2.5 s. Finally, the prepared wire was followed by furnace cooling to room temperature. The sample was examined using XRD, SEM, and magnetization measurements. The experiments show that there are small MgCu₂ and boron-rich phases inner sheath wall of copper tube. The magnesium oxide is small in the sample. So, PIT technologies with SHS method is effective in stopping the volatile and oxidize of magnesium. The J_c results show that Mg_0.9Zr_0.1B₂/Cu wires samples which were synthesized by SHS method are better than those sintered for 1 h and Cu clad pure MgB₂ wire. The highest J_c of the prepared Mg_0.9Zr_0.1B₂/Cu wire by SHS method in the air is 5.1 × 10⁵ A/cm² (5 K, 0.5 T), 1.4 × 10⁵ A/cm² (20 K, 1 T) and 4.3 × 10⁴ A/cm² (30 K, 0.5 T).     

Mechanical characterization of melt-textured Y0.95Er0.05Ba2Cu3O7−δ superconductor prepared in air

The effect of Er substitution on the mechanical properties of ab- and a(b)c-planes of melt-textured YBa₂Cu₃O_7?δ is reported in the present work. The non-oxygenated samples were characterized by scanning electron microscopy, X-ray diffraction and mechanical properties by instrumented indentation and conventional Vickers indentation whereas the superconducting properties were determined by resistivity measurements on oxygenated samples. The X-ray pattern and EDS analysis revealed the presence of Y-123, Y-211 and BaCeO₃ phases. Er substitution up to 5 wt.% did not affect the superconducting properties. No difference in hardness was observed for the ab- and a(b)c-planes. Elastic modulus of the a(b)c-plane was 10% higher than of the ab-plane. Differences in indentation fracture toughness obtained by conventional Vickers indentation of the ab- and a(b)c-planes was observed. The addition of 5 wt.% of Er did not affect significantly the mechanical properties of melt-textured samples when compared with pure melt-textured YBa₂Cu₃O_7?δ.