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.     

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.     

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.     

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.     

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.     

Structural and electronic properties of Ni<Subscript>5</Subscript>Nb<Subscript>3</Subscript>Zr<Subscript>5</Subscript> clusters as a local structural unit of Ni-Nb-Zr glassy alloys

We calculate electronic states of fifty icosahedral Ni₅Nb₃Zr₅ clusters and optimize their structures by first principles calculations within the generalized gradient approximation. Based on the energetic stability and the atomic configuration, we search for some candidates for the local structural units of Ni₃₆Nb₂₄Zr₄₀ glassy alloys by comparing with the experimental data measured by the XAFS method. The Ni-centered icosahedral Ni₅Nb₃Zr₅ clusters containing a Nb-triangle are proposed as the structural units, which in turn combine into local structures of the glassy alloy.     

EXAFS analysis of Zr-based quasicrystals

The character of transformation of the local environment of zirconium and palladium atoms in Zr₇₀Pd₃₀ binary alloy at a transition from the amorphous state to the quasicrystalline and crystalline states and in Zr₇₀Be₃₀ and Zr₈₀Pt₂₀ binary alloys at a transition from the amorphous to the quasicrystalline state have been investigated by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray diffraction. The parameters of the zirconium, palladium, and platinum local environment are determined, and the general features and differences in the local atomic rearrangement during formation of icosahedral clusters around zirconium atoms in these three compounds are established.     

Effect of heat treatment on the structure and elastic properties of a bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass

The effect of heat treatment over the range from room temperature to 500°C on the elastic properties of a bulk amorphous Pd₄₀Cu₃₀Ni₁₀P₂₀ alloy was studied. It is shown that the increase in the shear modulus under crystallization of the alloy is two-staged and that the most significant increase in the modulus occurs at the second stage. The obtained results are compared to the x-ray structural data. It is also found that the density characteristics of the as-cast material change very slightly during the transformation from the amorphous to the crystal state, with the density decreasing slightly due to crystallization.     

Magnetic,thermal, and electrical properties of an Ni<Subscript>45.37</Subscript>Mn<Subscript>40.91</Subscript>In<Subscript>13.72</Subscript> Heusler alloy

The magnetization, the electrical resistivity, the specific heat, the thermal conductivity, and the thermal diffusion of a polycrystalline Heusler alloy Ni_45.37Mn_40.91In_13.72 sample are studied. Anomalies, which are related to the coexistence of martensite and austenite phases and the change in their ratio induced by a magnetic field and temperature, are revealed and interpreted. The behavior of the properties of the alloy near Curie temperature T_C also demonstrates signs of a structural transition, which suggests that the detected transition is a first-order magnetostructural phase transition. The nontrivial behavior of specific heat detected near the martensite transformation temperatures is partly related to a change in the electron density of states near the Fermi level. The peculiar peak of phonon thermal conductivity near the martensitic transformation is interpreted as a consequence of the appearance of additional soft phonon modes, which contribute to the specific heat and the thermal conductivity.     

Shear viscosity of the Pd<Subscript>40</Subscript>Cu<Subscript>40</Subscript>P<Subscript>20</Subscript> metallic glass under conditions of isochronous heating below the glass transition temperature

The shear viscosity is measured under conditions of isochronous (linear) heating below the glass transition temperature of the Pd₄₀Cu₄₀P₂₀ metallic glass, which is characterized by the polymorphic crystallization into the Pd₂Cu₂P tetragonal phase with a lower density than the initial glass. It is shown that the rate dependence of the shear viscosity can be interpreted as a result of the irreversible structural relaxation by analogy with the case of the previously studied metallic glasses despite the unusual ratio of the densities of the material in noncrystalline and crystalline states.     

Phase Transitions in a Mixture of Amorphous C<Subscript>60</Subscript> and C<Subscript>70</Subscript> Fullerene Phases at High Temperatures and Pressures

Phase transitions in two types of amorphous fullerene phases (C₆₀–C₇₀ (50/50) mixtures and an amorpous C₇₀ fullerene phase) are studied via neutron diffraction at pressures of 2–8 GPa and temperatures of 200–1100°C. Fullerenes are amorphized by grinding in a ball mill and sintered under quasi-hydrostatic pressure in a toroidal-type chamber. Diffraction studies are performed ex situ. It is shown that the amorphous phase of fullerenes retains its structure at temperatures of 200–500°C, and amorphous graphite is formed at 800–1100°C with a subsequent transition to crystalline graphite. This process is slow in a mixture of fullerenes, compared to C₇₀ fullerene. According to neutron diffraction data, the amorphous graphite formed from amorphous fullerene phases has anisotropy that is much weaker in a fullerene mixture.     

Recovery of electrical-resistivity and viscoelasticity relaxation in thermally aged bulk Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> metallic glass

The structural relaxation of a bulk Pd₄₀Cu₃₀Ni₁₀P₂₀ metallic glass is studied by measuring the electrical resistivity and infralow-frequency (0.05 Hz) internal friction. It is demonstrated that the structural relaxation in thermally aged samples can be restored by quenching them from a supercooled liquid state. It is found that the degree of relaxation after quenching can exceed the initial one by several times.     

Thermodynamic and kinetic properties of an icosahedral quasicrystalline phase in the Al-Pd-Tc system

The properties of a quasicrystalline phase in the Al-Pd-Tc system are studied for the first time. X-ray investigations demonstrate that the quasicrystalline phase in the Al₇₀Pd₂₁Tc₉ alloy has a face-centered icosahedral quasi-lattice with parameter a=6.514 ?. Annealing experiments have revealed that this icosahedral phase is thermodynamically stable. The heat capacity of an Al₇₀Pd₂₁Tc₉ sample is measured in the temperature range 3–30 K. The electrical resistivity and magnetic susceptibility are determined in the temperature range 2–300 K. The electrical resistivity is found to be high (600 μΩ cm at room temperature), which is typical of quasicrystals. The temperature coefficient of electrical resistivity is small and positive at temperatures above 50 K and negative at temperatures below 50 K. The magnetic susceptibility has a weakly paramagnetic character. The coefficient of linear contribution to heat capacity (γ=0.24 mJ/(g-atom K²)) and the Debye characteristic temperature (Θ=410 K) are determined. The origin of the specific features in the vibrational spectrum of the quasicrystals is discussed. __________ Translated from Fizika Tverdogo Tela, Vol. 42, No. 12, 2000, pp. 2113–2119. Original Russian Text Copyright ? 2000 by Mikheeva, Panova, Teplov, Khlopkin, Chernoplekov, Shikov.     

Intrinsic metastability of low doped manganites: La<Subscript>0.8</Subscript>Ca<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> case

Transport properties of phase separated La_0.8Ca_0.2MnO₃ crystals in the aged highly resistive metastable state were studied. It was found that the coexistence of different ferromagnetic phases at low temperatures is sensitive to electric current/field. In a contrast with the previously studied low resistivity metastable states the high resistivity state exhibits positive magnetoresistance and significant current dependence of the resistivity even at temperatures much higher than the Curie temperature. Application of current pulses results in appearance of zero bias anomaly in the current dependent conductivity. Similarly to the low resistivity metastable states the memory of the resistivity can be erased only after heating of the sample to T_e ≈360 K. After one year storage at room temperature the La_0.8Ca_0.2MnO₃ samples show clear signatures of aging. The aged samples spontaneously evolute towards high resistivity states. The results are discussed in the context of a coexistence of two ferromagnetic phases with different orbital order and different conductivity. The metallic ferromagnetic phase seems to be less stable giving rise to the experimentally observed electric field effects and aging.     

Structural investigation of icosahedral Pd58.8U20.6Si20.6

The structure factors of the amorphous, icosahedral and crystalline Pd_58.8U_20.6Si_20.6 were measured with X-rays and neutrons. By comparing the radial distribution functions of the three phases, we find a similar short range order in the amorphous and icosahedral phase, but a different atomic arrangement in the crystalline phase. A magnetic long range order observed in the crystalline material is absent in the icosahedral phase.Dedicated to Professor Harry Thomas on the occasion of his 60th birthday     

Low-temperature electron properties of Heusler alloys Fe<Subscript>2</Subscript>VAl and Fe<Subscript>2</Subscript>CrAl: Effect of annealing

We present the results of measurements of low-temperature heat capacity, as well as electrical and magnetic properties of Heusler alloys Fe₂VAl and Fe₂CrAl prepared in different ways using various heat treatment regimes. The density of states at the Fermi level is estimated. A contribution of ferromagnetic clusters in the low-temperature heat capacity of the Fe₂VAl alloy is detected. The change in the number and volume of clusters as a result of annealing of an alloy affects the behavior of their low-temperature heat capacity, resistivity, and magnetic properties.     

Martensitic transformation and electrical properties of a Ni<Subscript>2.14</Subscript>Mn<Subscript>0.81</Subscript>Fe<Subscript>0.05</Subscript>Ga alloy in its different structural states

Phase transformations in a Ni_2.14Mn_0.81Fe_0.05Ga alloy in different structural states are studied from the temperature dependences of its electrical resistivity. The dependences obtained indicate that, in the coarse-grained state, this alloy undergoes two structural phase transformations: intermartensitic modulation transformation and martensite-austenite transformation. In the nanocrystalline state, these transformations are absent. The recrystallization of a nanocrystalline sample at 773 K for 30 min results in the martensite-austenite transformation; however, the phase transformation related to a change in the martensite modulation period does not occur in this state. The resistivity is shown to depend on the structural state of the alloy.     

Structural evolutions of the mechanically alloyed Al<Subscript>70</Subscript>Cu<Subscript>20</Subscript>Fe<Subscript>10</Subscript> powders

Elemental mixtures of Al, Cu, Fe powders with the nominal composition of Al₇₀Cu₂₀Fe₁₀ were mechanically alloyed in a planetary ball mill for 80 h. Subsequent annealing of the as-milled powders were performed at 600–800°C temperature range for 4 h. Structural characteristics of the mechanically alloyed Al₇₀Cu₂₀Fe₁₀ powders with the milling time and the heat treatment were investigated by X-ray diffraction (XRD), differential scanning calorimeter (DSC) and differential thermal analysis (DTA). Mechanical alloying of the Al₇₀Cu₂₀Fe₁₀ did not result in the formation of icosahedral quasicrystalline phase (i-phase) and a long time milling resulted in the formation of β-Al(Cu,Fe) solid solution phase (β-phase). The i-phase was observed only for short-time milled powders after heat treatment above 600°C. The β-phase was one of the major phases in the Al₇₀Cu₂₀Fe₁₀ alloy. The w-Al₇Cu₂Fe₁ phase (w-phase) was obtained only after heat treatment of the short-time milled and unmilled samples. The present investigation indicated that a suitable technique to obtain a large amount of quasicrystalline powders is to use a combination of short-time milling and subsequent annealing.     

Electronic Structure of Oxygen Vacancies in the Orthorhombic Noncentrosymmetric Phase Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The electronic structure of stoichiometric and oxygen-depleted Hf_0.5Zr_0.5O₂ in the orthorhombic noncentrosymmetric phase has been studied by X-ray photoelectron spectroscopy and quantum-chemical simulation based on the density functional theory. It has been established that the ion-etching-induced peak in the photoelectron emission spectrum with the energy above the top of the o-Hf_0.5Zr_0.5O₂ valence band is due to oxygen vacancies. A method of estimating the density of oxygen vacancies from the comparison of the experimental and theoretical photoelectron spectra of the valence band has been proposed. It has been established that oxygen polyvacancies in o-Hf_0.5Zr_0.5O₂ are not formed: the energetically favorable spatial arrangement of oxygen vacancies in a crystal corresponds to noninteracting oxygen vacancies distant from each other.     

Short-Range Order in Amorphous and Crystalline Ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The microstructures of amorphous and polycrystalline ferroelectric Hf_0.5Zr_0.5O₂ films are studied by X-ray spectroscopy and ellipsometry. EXAFS spectra demonstrate that the amorphous film consists of an “incompletely mixed” solid solution of metallic oxides HfO₂ and ZrO₂. After rapid thermal annealing, the mixed Hf_0.5Zr_0.5O₂ oxide films have a more ordered polycrystalline structure, and individual Hf and Zr monoxide islands are formed in the films. These islands are several nanometers in size and have a structure that is similar to the monoclinic structure of HfO₂ and ZrO₂. The presence of the HfO₂ and ZrO₂ phases in the Hf_0.5Zr_0.5O₂ films is also detected by ellipsometry.