Vibrational and electronic properties of the amorphous systems Ni<Subscript>44</Subscript>Nb<Subscript>56</Subscript>, Ni<Subscript>62</Subscript>Nb<Subscript>38</Subscript>, and Cu<Subscript>33</Subscript>Zr<Subscript>67</Subscript> as derived from specific heat measurements

The specific heats of the amorphous systems Ni₄₄Nb₅₆, Ni₆₂Nb₃₈, and Cu₃₃Zr₆₇ were studied in the temperature range 3–273 K. The data obtained allow one to isolate the contribution due to atomic vibrations from the experimentally measured specific heat, to determine the density of electronic states at the Fermi level and the temperature dependence of the characteristic Debye parameter Θ over a broad temperature range, and to calculate a few frequency moments that characterize the vibrational spectrum. The information derived on the average characteristics of vibrational spectra is in good agreement with earlier data on inelastic neutron scattering. In transferring from Ni₄₄Nb₅₆ to Ni₆₂Nb₃₈, the density of electronic states at the Fermi level decreases and the characteristic vibrational frequencies increase. The density of electronic states at the Fermi level for Cu₃₃Zr₆₇ is close to that for Ni₆₂Nb₃₈. The characteristic frequencies of the vibrational spectrum of the Cu₃₃Zr₆₇ system are substantially lower (by 30%) than those of the Ni₄₄Nb₅₆ and Ni₆₂Nb₃₈ systems.     

Molecular dynamics study of structure and glass forming ability of Zr<Subscript>70</Subscript>Pd<Subscript>30</Subscript> alloy

In this study, the temperature effects on the structural evolution of theZr₇₀Pd₃₀ binary alloy in the glassy and liquid states werestudied using the molecular dynamics simulations based on the many-body type tight-bindingpotential. We considered the following properties in detail: the temperature dependence ofthe volume, the partial and total pair distribution functions and the simulated glasstransition temperature. The effects of the cooling rates on the glass transitiontemperature were examined. The Wendt-Abraham parameter was calculated to determine theglass transition temperature of Zr₇₀Pd₃₀ glassy alloy. The pair analysis technique ofHoneycutt-Andersen was applied to define local atomic arrangements produced from moleculardynamics simulations. The results show that the icosahedral ordering in glassy state hasbeen composed during quenching period, and the simulated glass transition temperature andthe total pair distribution functions are in good agreement with the experimental data.     

Formation,thermal stability and mechanical properties of Ti<Subscript>42.5</Subscript>Zr<Subscript>7.5</Subscript>Cu<Subscript>40</Subscript>Ni<Subscript>5</Subscript>Sn<Subscript>5</Subscript> bulk metallic glass

Ti_42.5Zr_7.5Cu₄₀Ni₅Sn₅ bulk metallic glass with a critical diameter of 4 mm was fabricated by the conventional copper mould casting method. The supercooled liquid region ΔT _x, reduced glass transition temperature T _rg, γ parameter, and δ parameter of the alloy were measured to be 63.9 K, 0.561, 0.393, and 1.400, respectively, implying that the alloy has an excellent glass-forming ability. The bulk metallic glass exhibits high compressive fracture strength of 2162 MPa with distinct plastic strain of 0.9%. The fracture surface consists mainly of vein-like patterns, typical of bulk glassy alloys. Supported by the Program for New Century Excellent Talents in University of China and the National Natural Science Foundation of China (NSFC)(Grant No. 50771040)     

Mechanical alloying of Ni<Subscript>80</Subscript>Ta<Subscript>20</Subscript> and Ni<Subscript>80</Subscript>Nb<Subscript>20</Subscript>. Crystallization of the amorphous phase

The sequence and crystallization kinetics of the amorphous phase have been analyzed by differential scanning calorimetry and X-ray diffraction for mechanochemically activated Ni₈₀Ta₂₀ and Ni₈₀Nb₂₀ samples. The formation of equilibrium products from the amorphous phase occurs through the formation of metastable products of the A3 type. The kinetic parameters (activation energy and reaction order) and thermodynamic characteristics of this process are determined. Crystallization of the amorphous phase for the Ni₈₀Ta₂₀ and Ni₈₀Nb₂₀ systems occurs due to the growth of existing nuclei through the polymorphic and eutectic mechanisms, respectively. The thermal effects of the synthesis of equilibrium products from a mechanochemically activated mixture of components are identified.     

Specific heat and electrical resistivity of an icosahedral-structure Zr<Subscript>70</Subscript>Pd<Subscript>30</Subscript> alloy and of its amorphous and crystalline analogs

Binary icosahedral and crystalline phases of the Zr₇₀Pd₃₀ alloy were obtained in crystallization from the amorphous state during heat treatment. The specific heat and electrical resistivity of the icosahedral, amorphous, and crystalline phases were measured and compared. An increase in the electronic density of states on the Fermi surface, lattice softening, and an increase in the electron-phonon coupling constant were observed to occur with decreasing structural order. Despite the high valence electron density in the icosahedral phase, where the electronic densities of states are twice those in the crystal, the electrical resistivity of the icosahedral phase is ～50 times as high. Superconductivity was observed for the first time in the icosahedral phase of a binary system of transition metal atoms, Zr₇₀Pd₃₀.     

Compression behavior of Zr<Subscript>41</Subscript>Ti<Subscript>14</Subscript>Cu<Subscript>12.5</Subscript>Ni<Subscript>10</Subscript>Be<Subscript>22.5</Subscript> bulk metallic glass up to 24 GPa

The compression of a Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (BMG) is investigated at room temperature up to 24 GPa using in-situ high pressure energy dispersive X-ray diffraction with a synchrotron radiation source. The pressure-induced structural relaxation is exhibited. It is found that below about 8 GPa, the existence of excess free volume contributes to the rapid structural relaxation, which gives rise to the rapid volumetric change, and the structural relaxation results in the structural stiffness under higher pressure.     

Structural relaxation of Zr<Subscript>41</Subscript>Ti<Subscript>14</Subscript>Cu<Subscript>12.5</Subscript>Ni<Subscript>10</Subscript>Be<Subscript>22.5</Subscript> bulk metallic glass under high pressure

Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (BMG) is annealed at 573 K under 3 GPa and its structural relaxation is investigated by X-ray diffraction, ultrasonic study, compression as well as sliding wear measurements. It is found that after the ZrTiCuNiBe BMG sample was annealed under high pressure, the mechanical properties were improved. Moreover, theBMG with relaxed structure exhibits markedly different acoustic properties. These results are attributed to the fact that relaxation under high-pressure results in a microstructural transformation in the BMG.     

Higher order elastic moduli of the bulk metallic glass Zr<Subscript>52.5</Subscript>Ti<Subscript>5</Subscript>Cu<Subscript>17.9</Subscript>Ni<Subscript>14.6</Subscript>Al<Subscript>10</Subscript>

The effect of elastic loading on the velocity of propagation of acoustic waves in a solid is calculated (to the second order in the applied load). The results of the calculations and the experimental data on the effect of uniaxial loading on the propagation of ultrasonic waves in the bulk metallic glass Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ are used to estimate the third-order and fourth-order elastic moduli.     

Glass-forming ability and thermal stability of Fe<Subscript>62</Subscript>Nb<Subscript>8−x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>30</Subscript> and Fe<Subscript>72</Subscript>Zr<Subscript>8</Subscript>B<Subscript>20</Subscript> amorphous alloys?

Glass-forming ability (GFA) and thermal stability of Fe₆₂Nb₈B₃₀, Fe₆₂Nb₆Zr₂B₃₀ and Fe₇₂Zr₈B₂₀ at % amorphous alloys were investigated by calorimetric (DSC and DTA) measurements. The crystallization kinetics was studied by DSC in the mode of continuous versus linear heating and it was found that both the glass transition temperature, T _g , and the crystallization peak temperature, T _p , display strong dependence on the heating rate. The partial replacement of Nb by Zr leads to lower T _g and T _x temperatures and causes a decrease of the supercooled liquid region. JMA analysis of isothermal transformation data measured between T _g and T _x suggests that the crystallization of the Fe₆₂Nb₈B₃₀ and Fe₆₂Nb₆Zr₂B₃₀ amorphous alloys take place by three-dimensional growth with constant nucleation rate. Nb enhances the precipitation of the metastable Fe₂₃B₆ phase and stabilizes it up to the third crystallization stage. Zr addition increases the lattice constant of Fe₂₃B₆ and, at the same time, decreases the grain size.     

Anomalous magnetoresistivity of the superconducting Zr<Subscript>80</Subscript>Pt<Subscript>20</Subscript> system in quasicrystalline and amorphous states

The binary icosahedral Zr₈₀Pt₂₀ system has been synthesized during the crystallization of an initially amorphous alloy fabricated by melt quenching on the surface of a rotating copper wheel. The temperature and field dependences of the electrical resistivity and magnetoresistivity of the icosahedral and amorphous phases are studied and compared in a temperature range of 1.5–300 K and magnetic fields up to 8 T. Superconductivity has been detected for the first time in the icosahedral and amorphous phases of the Zr₈₀Pt₂₀ system. For both phases, the magnetoresistivity is positive and depends anomalously on the magnetic field. The anomalous behavior of magnetoresistivity is satisfactorily described by the theory of weak localization and electron-electron interaction in three-dimensional disordered systems, which takes into account electron scattering by superconducting fluctuations. The absolute values and temperature dependences of the electron-electron interaction constant and the times of inelastic scattering of conduction electrons are estimated for the icosahedral and amorphous phases of this binary system.     

Gamma irradiation effects on structural and optical properties of amorphous and crystalline Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> thin films

The structural and optical properties of RF sputtered Nb₂O₅ thin films are studied before and after gamma irradiation. The films are subjected to structural and surface morphological analyses by using X-ray (XRD) and field emission scanning electron microscope techniques. In the wavelength range of 300–2000 nm, the optical parameters for amorphous and crystalline Nb₂O₅ thin films are estimated at differently exposed γ-irradiation doses (0, 50, 100 and 200 kGy). The optical constants, such as optical energy band gap, absorption coefficient, refractive index and oscillators parameters of amorphous and crystalline Nb₂O₅ thin films are calculated. The optical band gaps of γ-irradiated amorphous and crystalline Nb₂O₅ thin films are determined. In the non-absorbing region, the real part of the refractive index of amorphous and crystalline Nb₂O₅ thin films slightly increases with the increase in the exposed γ-irradiation dose.     

Effect of nanocrystallization on the mechanical and magnetic properties of finemet-type alloy (Fe<Subscript>78.5</Subscript>Si<Subscript>13.5</Subscript>B<Subscript>9</Subscript>Nb<Subscript>3</Subscript>Cu<Subscript>1</Subscript>)

The kinetics of primary crystallization and the effect of structural parameters of the precipitating nanocrystalline α-phase Fe-Si on changes in microhardness, coercive force, and saturation magnetization in an amorphous Finemet-type 5BDSR alloy (Fe_78.5Si_13.5B₉Nb₃Cu₁) obtained by melt quenching are studied. It is found that both an increase in bulk density and an increase in the average nanoparticle size contribute to the hardening of the amorphous/nanocrystalline alloy.     

Features of the formation of an oxide layer on the surface of amorphous Zr<Subscript>41.2</Subscript>Ti<Subscript>13.8</Subscript>Cu<Subscript>12.5</Subscript>Ni<Subscript>10.0</Subscript>Be<Subscript>22.5</Subscript> alloy

Field investigations were performed into the nature of oxidation of Zr_41.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 alloy (Vitreloy-1), a new alloy highly promising for in -vessel mirrors of the ITER (International Thermonuclear Experimental Reactor). The main methods of investigation were X-ray photoelectron spectroscopy and multi-angle ellipsometry. The resistance of the optical properties of Vitreloy-1 against radiation impact was explained by the oxidation of the surface layer, based on the features of the diffusion process in amorphous alloys and of interaction between amorphous metal alloys with hydrogen.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

Magnetic resonance in Pb<Subscript>x</Subscript>Nb<Subscript>y</Subscript>O<Subscript>z</Subscript> ceramics as a system containing chemical fluctuation regions

Simulation of the chemical fluctuation regions in PMN-like relaxors through growth of the Pb_xNb_yO_z eramics was performed. Different Pb_xNb_yO_z clusters (chemically and structurally) coexist in such ceramics. Hole polaron and bipolaron (Cr³⁺-two polaronic-hole) paramagnetic complexes were considered for explanation of the EPR spectra in Pb_xNb_yO_z ceramics. Dynamical averaging, light-induced effects, and significant effects of reduction treatment giving the coexistence of Nb⁵⁺ and Nb³⁺ ions, as well as of a strong internal magnetic field, were discovered in this ceramics. The latter could be related to antiferromagnetic phase realization in Pb_xNb_yO_z clusters containing a sufficiently high concentration of magnetic Nb³⁺ host lattice ions. Such a situation leads to antiferromagnetic resonance on Nb³⁺ ions, as well as to EPR of Cr³⁺-related paramagnetic complexes in a Nb³⁺-induced internal magnetic field. Charge transfer vibronic excitons (CTVE) in free and in CTVE phase states were detected in Pb_xNb_yO_z ceramics by photoluminescence studies.     

Vibrational and electronic characteristics of Zr<Subscript>70</Subscript>Pd<Subscript>30</Subscript>, Zr<Subscript>80</Subscript>Pt<Subscript>20</Subscript> icosahedral quasicrystals and their amorphous Counterparts

The heat capacity of Zr₇₀Pd₃₀ and Zr₈₀Pt₂₀ icosahedral quasicrystals and their amorphous counterparts is studied in the temperature range 1.5–500 K in order to establish a correlation between the short-range atomic order and the physical properties of these compounds. A comparison of the data made it possible to reveal changes in the vibrational spectra within the low-and high-energy ranges, as well as in the density of states, superconducting characteristics, electron-phonon interaction, and anharmonicity of the lattice thermal vibrations and to calculate the main average frequencies (moments) characterizing the vibrational spectra. The lower superconducting transition temperature T _c of the quasicrystals as compared to that of the amorphous counterparts can be associated with the decrease in the density of states on the Fermi surface, the hardening of the phonon spectrum, and the weakening of the electron-phonon coupling.     

Dielectric investigations in Sr<Subscript>0.75</Subscript>Ba<Subscript>0.25</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6</Subscript> relaxor ferroelectric thin films

The dielectric properties of Sr_0.75Ba_0.25Nb₂O₆ relaxor ferroelectric thin films were carefully analyzed. In contrast to bulk samples which present three distinct dielectric relaxation phenomena Sr_0.75Ba_0.25Nb₂O₆ thin films present only two of them. The suppression of the third anomaly can be mainly attributed to the narrow grain size distribution of nanograins and weak tensile strains imposed to the film from the substrate. The whole set of results point to the interpretation of a dielectric response characteristic of mesoscopic structure, which is composed of clusters and nanodomains.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

Symmetry-dependent Mn-magnetism in Al<Subscript>69.8</Subscript>Pd<Subscript>12.1</Subscript>Mn<Subscript>18.1</Subscript>

We investigated the stability of magnetic moments in Al_69.8Pd_12.1Mn_18.1. This alloy exists in both, the icosahedral (i) and the decagonal (d) quasicrystalline form. The transition from the i- to the d-phase is achieved by a simple heat treatment. We present the results of measurements of the ²⁷Al NMR-response, the dc magnetic susceptibility, and the low-temperature specific heat of both phases. In the icosahedral compound, the majority of the Mn ions carries a magnetic moment. Their number is reduced by approximately a factor of two by transforming the alloy to its decagonal variety. For both compounds, we have indications for two different local environments of the Al nuclei. The first reflects a low density of states of conduction electrons and a weak coupling of the Al nuclei to the Mn-moments. The second type of environment implies a large d-electron density of states at the Fermi level and a strong coupling to the magnetic Mn moments. Spin-glass freezing transitions are observed at T^deca_f=12 K for the decagonal, and T^ico_f=19 K for the icosahedral phase.     

Crystallization kinetics of Al<Subscript>86</Subscript>Ni<Subscript>8</Subscript>Ho<Subscript>6</Subscript> amorphous alloy

We investigate the processes of crystallization and determined the structure and thermal properties of Al₈₆Ni₈Ho₆ amorphous alloy in a wide temperature range. A three-stage nature of the crystallization process upon heating to a temperature of 700 K is found. According to data of high-temperature X-ray diffraction analysis, the crystallization of an Al₈₆Ni₈Ho₆ amorphous ribbon is rather complex: aluminum crystallites grow in the amorphous phase to a temperature of 470 K, a Ho₃Ni₅Al₁₉ phase is formed above 563 K, and a HoAl₃ phase appears above 598 K. The phases of Ho₃Ni₅Al₁₉ and HoAl₃ are retained up to a temperature of 723 K. A three-stage kinetic model of the crystallization process with the reaction sequence is proposed based on calculations by multivariate nonlinear regression. The values of the total activation energy for each crystallization stage reach 239, 378, and 247 kJ/mol.