Tetrahedral structures with icosahedral order and their relation to quasicrystals

The possible existence of quasicrystals in tetrahedral phases is considered. It is shown that one of the well-known crystalline silicon phases (the BC8 phase or silicon III) is characterized by the icosahedral local order with three-quarters of the interatomic bonds being directed along the fivefold axes of an icosahedron. This crystal is considered as an approximant of an icosahedral quasicrystal. Higher order approximants and other tetrahedral structures related to quasicrystals are also constructed. It is shown that in these structures, the formation of the intrinsic phason disorder with the preservation of the energetically favorable coordination number four is possible. The ab initio quantum-mechanical calculations for carbon and silicon show that, although all the considered phases are metastable, their energies only slightly differ from the energies of the corresponding stable phases.     

Formation of icosahedral quasicrystals in (Ag,Au)-based ternary systems

We investigated the phase constitution of rapidly solidified (Ag,Au)-based ternary alloys at various compositions of (M,X)_85.7RE_14.3 (M = Ag, Au, X = Al,Ga,In, RE = Er,Lu). It is found that an icosahedral phase is formed at an average electrons per atom ratio close to 2.0 as well as at the composition ratio of (M,X)₆RE, suggesting that these factors have crucial roles in the stability of the icosahedral phases. It is also found that the trend of the icosahedral phase formation in the Au-based alloys is quite different from that in the Ag-based alloys.     

Formation and thermal stability of Pd-based bulk metallic glasses

The glass-forming ability and thermal stability of bulk glassy Pd₇₉Cu₆Si₁₀P₅ alloy were studied by substitution of Cu with Ag and with Au + Ag from 0 to 6 at.%. The results indicated that the small addition of Ag strongly affects the thermal stability and glass-forming ability of the Pd₇₉Cu₆Si₁₀P₅ alloy. The alloy doped with 4 at.% Ag (Pd₇₉Cu₂Ag₄Si₁₀P₅) exhibits the largest glass-forming ability among the Pd₇₉Cu_6−xAg_xSi₁₀P₅ (x = 0–6 at.%) alloys. The critical diameter for glass formation of this alloy reaches as large as 7 mm by copper mold casting. On the other hand, the multi-addition of Au + Ag does not increase the glass forming ability though the Ag and Au are similar in atomic size. The largest glass forming ability is obtained at 1 at.% Au + 2 at.% Ag among the Pd₇₉Cu_6−x−yAu_xAg_ySi₁₀P₅ (x = 1–4 at.%, y = 1–3 at.%) alloys. The critical diameter of this alloy is 5 mm by copper mold casting.     

Stability, atomic and electronic structure of icosahedral quasicrystals

Ab-initio investigations of the structure, stability, and of the electronic spectrum of isosahedral quasicrystals are presented.     

Partial spectra of atomic thermal vibrations in decagonal and icosahedral quasicrystals

The atomic dynamics of an Al-Ni-Fe decagonal quasicrystal and an Al-Cu-Fe icosahedral quasicrystal are investigated experimentally using the isotopic contrast method in inelastic neutron scattering. The partial spectra of thermal vibrations of copper, nickel, iron, and aluminum atoms in the decagonal and icosahedral quasicrystals are reconstructed directly from the experimental data without recourse to model concepts. The limiting energies and positions of the main features in the partial spectra of atomic thermal vibrations in decagonal and icosahedral quasicrystals are determined. It is established that, in the quasicrystals under investigation, the copper and nickel atoms are bound more weakly than the iron atoms and that the partial vibrational spectrum of aluminum atoms in the quasicrystals is considerably harder than the spectrum of pure metallic aluminum.     

Gorsky-Bragg-Williams theory of phase transitions in the approximants of icosahedral quasicrystals

The Gorsky-Bragg-Williams (GBW) theory has been modified to describe phase transitions caused by the ordering of two kinds of atoms in the even and the odd sublattices of the structures of icosahedral quasicrystals with the dodecahedral local order (DLO) and their approximants. The modified method is exemplified by numerical calculations of such phase transitions in the structures of several simplest approximants.     

Search for possible structures of cubic approximants of icosahedral quasicrystals

Admissible structures of the approximants are obtained within the model of the dodecahedral local order (DLO) with due regard for the constraints imposed by the space symmetry. It is shown that the number of cubic approximants of icosahedral quasicrystals having a certain order and dodecahedral local order is finite and that the number of positions that can be occupied by the atoms from the unit cells of an approximant of each order is also finite. The corresponding estimates from above are made. In particular, it is shown that there exists only one structure for the 1/?1 approximant. It is also shown that it is possible to determine all the structures for any approximant of any order. The corresponding algorithm of the exhaustive search for these structures is suggested. The implementation of this algorithm provided the determination of all the structures of the 0/1 approximants and also some possible structures of the 0/1 and 1/1 approximants. The tables of possible approximant structures can be useful in the studies of new phases having approximant structures.     

Precipitation of icosahedral quasicrystalline and crystalline approximant phases in Zr-Cu-(Co, Rh or Ir) metallic glasses

Zr₇₀Cu₃₀, Zr₇₀Cu₂₀Co₁₀, Zr₇₀Cu₂₀Rh₁₀ and Zr₇₀Cu₂₀Ir₁₀ glassy alloys were prepared by the single roller melt-spinning method and the crystallization process was studied by differential scanning calorimetry, X-ray diffraction and transmission electron microscopy, with an emphasis on the initial stage. The Zr₇₀Cu₃₀ metallic glass crystallizes through the direct precipitation of the stable crystalline phase from the matrix. The addition of Co, Rh and Ir to the Zr₇₀Cu₃₀ metallic glass induces the precipitation of metastable phases prior to the formation of the stable ones. The metastable phases are a Ti₂Ni-type compound for Zr₇₀Cu₂₀Co₁₀, a mixture of the Ti₂Ni-type compound and an icosahedral quasicrystalline phase (I-phase) for Zr₇₀Cu₂₀Rh₁₀, and the I-phase for Zr₇₀Cu₂₀Ir₁₀ metallic glasses. The different effects of Co, Rh and Ir addition are explained based on their difference in atomic radius.     

Approximants of icosahedral quasicrystals: Atomic structure, inherent defects, and superstructural ordering

The structural features of approximants of icosahedral and decagonal quasicrystals and new unusual approximants (rhombohedral AlPd and cubic Al₆₈Pd₂₀Ru₁₂) are considered. It is shown that most approximants can be described in terms of universal local ordering of atoms, in which the nearest neighbors of each atom occupy the vertices of an almost ideal dodecahedron: the so-called dodecahedral local ordering. A set of general atomic motifs in the approximants of different orders is found for quasicrystals of different types. It is shown that the dodecahedral local ordering can be easily described by the project method, in which the basis vectors directed along icosahedral threefold axes are used. Different types of defects inherent in dodecahedral local ordering are analyzed.     

Distortions of the atomic structure of 2/1 approximants of icosahedral quasicrystals

Ideal structures of several 2/1 approximants of icosahedral quasicrystals with the sp. gr. Pm \(\overline 3 \) and Pa \(\overline 3 \) have been constructed. It is shown that most atoms have dodecadhedral local coordination. The structural features of the crystals studied have been analyzed. It is found that displacements of atoms from ideal positions in real crystals tend to increase with an increase in the distance to the center of the approximant projection on the perpendicular space. Large displacements are generally related to the presence of very close neighbors in the ideal structure of the approximant. The importance of the investigation of approximants as a source of information about the structure of polyatomic nanoclusters is indicated.     

Static heterogeneity in metallic glasses and its correlation to physical properties

Glasses exhibit intriguing physical and mechanical properties resulting from their structure. We have investigated metal-glass dynamics using inelastic X-ray scattering and ultrasonic techniques for several Pd-, Pt-, and Zr-based glasses with varying fragility. In some cases we have observed a faster phase velocity at short wavelengths than long wavelengths, or positive dispersion. Here we apply elastic wave scattering theory to suggest that the behavior of acoustic phonons can be understood by considering the presence of intrinsic nanoscale elastic inhomogeneity with a certain correlation length, i.e., “static heterogeneity”. Furthermore, we suggest that such an elastic inhomogeneity could be the origin of many of the interesting physical and mechanical properties of metallic glasses.     

Dissoluble and degradable CaLi-based metallic glasses

We study the degradable and dissoluble features of a Ca-Li-Mg-Zn bulk metallic glass in pure water at room temperature. A remarkable degradable feature of the metallic glasses is that the degradation is controllable by changing the composition and components. The degradable metallic glasses with superior combined properties of polymer-like thermal plasticity at low temperature (40-70 °C), the ultralow elastic moduli comparable to that of human bones, and ultralow density (< 2 g/cm³) in known metallic glasses to date, and good machinability at a lower temperature in the supercooled liquid region could have potential applications. The metallic glasses also provide a model system to study the corrosion behavior in glasses.     

Intensity and width of bragg reflections from imperfect icosahedral quasicrystals obtained by simulating atomic growth

The Bragg reflections from icosahedral quasicrystals obtained in the course of a computer experiment on the simulation of crystal growth have been studied. The computer experiments based on the theory developed earlier allow one to “grow” in a computer the imperfect quasicrystals of nanometer dimensions. It is shown that the absolute value of the structure factor can be close to the maximum possible one for crystals, i.e., to the structure factor in the case where all the atoms scatter in phase. The spectral width of Bragg reflections is studied, and it is shown that the reflection width depends not only on the quasicrystal dimensions in the physical space but, also, on the perpendicular component of the reciprocal-lattice vectors. The data obtained are compared with the known experimental data.     

Kinetics of strain relaxation in metallic glasses

Torque relaxation and strain recovery measurements under linear heating for three Fe-, Ni- and Co-based metallic glasses are presented. Torque relaxation is determined by the pre-annealing temperature, T_a: at T < T_a, the degree of relaxation is small and high-rate torque relaxation starts near T_a. Analogously, high-rate strain recovery starts near the temperature of preliminary homogeneous deformation. The temperatures where high-rate stress relaxation and strain recovery begins are calculated in the framework of an activation energy spectrum model and are consistent with experiment. A homogeneous-flow model is developed which qualitatively explains macroscopically reversible behaviour as a result of directed irreversible microscopic relaxation events with distributed activation energies.     

Coring micron- and milli-scale holes in metallic glasses

Metallic glasses (MGs) combined with copper cores possess many advantages in precision casting and coring of alloys. In this study, inner holes with different dimensions and complex sectional shapes were fabricated through direct casting and coring in MGs. The MG castings show good surface finish and the cored inner holes exhibit high aspect ratios larger than 80 while holding a tight dimension tolerance. The dimensional deviation was proved to originate mainly from the contraction disagreement between castings and copper cores by comparing their thermal expansion coefficients and simulating the solidification and cooling processes, while other factors may also contribute to it. The results are expected to provide a convenient and economical way in the near net-shape fabrication of inner holes in metallic devices and in the assembly of MG components.     

Dynamic mechanical properties of metallic glasses

Dynamic mechanical properties of two metallic glasses, Fe₄₀Ni₄₀P₁₄B₆ and Fe₃₂Ni₃₆Cr₁₄P₁₂B₆, have been studied at frequencies ranging from 0.1 to 3 kHz and at temperatures between ? 160 and 390°C. Each of the samples exhibits an internal friction maximum at about ?20°C with activation energies of 25 and 34 kcal/mol. A possible mechanism for the low-temperature internal friction peak is suggested.     

Stability of Ni-based bulk metallic glasses

Several ternary (Ni_xNb_ySn_z) refractory alloy glasses (RAGs) were studied at elevated temperatures in order to assess the stability of the amorphous state, i.e. devitrification, and to identify subsequent phase transformations in these materials. differential scanning calorimetry (DSC) experiments indicated a complex phase transformation sequence with several distinct crystallization and melting events being recorded above the glass transition temperature, T_g. Below T_g the RAG samples were studied with an in situ environmental X-ray furnace facility, which allowed step-wise isothermal ramping experiments commencing at a temperature below the reduced temperature of T/T_g ≈ 0.80. Distinct crystalline phases were observed when T/T_g ≈ 0.84 for ternary RAG alloys, while similar experiments on Zr-based Vit 106 glass alloys did not reveal any apparent phase separation until T/T_g ≈ 0.96. The phase separation kinetics followed an Arrhenius type of relationship with Ni₃Sn, and Nb₂O₅ being the principle crystalline precipitates.     

Positron annihilation in thermally treated metallic glasses

The positron lifetime dependence on the annealing temperature has been studied for two transition metal-metalloid glasses (FeNi-based and Co-based). Small variations of the lifetime observed after annealing below crystallization temperature are attributed to elimination of the structural defects inherent in the as-quenched metallic glasses. More abrupt changes at higher temperatures are ascribed to crystallization processes which lead to polycrystalline phases. Differences in positron lifetime between annealed FeNi-based and Co-based metallic glasses are discussed.