Physical properties of icosahedral and glassy Pd−U−Si alloys

The transformations of glassy Pd₆₀U₂₀Si₂₀ alloys into an icosahedral state with quasicrystalline order and into the crystalline state have been studied by differential scanning calorimetry and X-ray diffraction. In addition, the electrical resistivity, the Hall coefficient and the magnetic susceptibility have been measured to high temperatures. The electronic structure has been investigated by photoelectron spectroscopy and the top surface layers have been probed by ion scattering spectroscopy. The physical properties in the icosahedral and glassy phase are similar. Comparisons with other uranium rich or dilute alloys are made in order to study the valence change or the development of a magnetic moment for uranium. Finally, the novel scanning tunneling microscope has been used to study the topography and the local tunneling barrier height with the aim of correlating micromorphology with local chemical structure.Dedicated to professor Harry Thomas on the occasion of his 60th birthday     

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.     

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.     

Calorimetric investigation of electronic and lattice excitations of the icosahedral quasicrystal in the range of moderate temperatures

The precise measurements of the specific heat and the linear expansion coefficient of polygrain samples of the ordered icosahedral phase Al₆₃Cu₂₅Fe₁₂ have been performed in the temperature range 1.8–400.0 K. The deviations from the Grüneisen law, according to which the temperature dependences of the lattice specific heat at constant volume and the linear expansion coefficient are identical to each other, have been analyzed. The proofs that the specific heat of the quasicrystals contains latent electronic and lattice contributions of the Schottky type have been obtained. The revealed contributions can be thermodynamic consequences of the fractal energy spectra.     

Local order of icosahedral quasicrystals studied by Mössbauer spectroscopy

Thermodynamically stable Al-Cu-Fe and Fe-doped ferromagnetic Al-Cu-Ge-Mn icosahedral quasicrystals are studied by⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffraction experiments. Al₆₅Cu₂₀Fe₁₅ quasicrystalline alloy was subjected to a mechanical grinding (MG) for up to 800 hours in a ball mill. Presence of the amorphous phase which co-exists with the quasicrystalline one is revealed in the early stage of MG. Mössbauer measurements were performed on icosahedral Al₄₀Cu_10–x Ge₂₅Mn₂₅Fe _x quasicrystal (x0.1; 3) in a temperature range from 10 K to 548 K. It was found that a magnetic transition occurs at about 30 K which is far belowT _c reported in the literature. It is concluded that AlGeMn ferromagnet which is present in the samples does not affect the magnetic transition observed and the transition is an intrinsic property of the Al-Cu-Ge-Mn host alloy.Samples of icosahedral quasicrystals were kindly provided by Profs. A. Inoue, T. Masumoto and P. H. Shingu. Ball milling was performed in Kyoto University by a courtesy of Prof. P. H. Shingu. This work was supported by the project for priority areas on properties of quasicrystals (No. 01630003) from the Japanese Ministry of Education, Science and Culture.     

Low-energy lattice excitations in the decagonal Al-Ni-Fe and icosahedral Al-Cu-Fe quasicrystals and the (Al,Si)-Cu-Fe cubic phase

The specific heat of decagonal Al_71.3Ni_24.0Fe_4.7 and icosahedral Al₆₂Cu_25.5Fe_12.5 quasicrystals and the Al_55.0Si_7.0Cu_25.5Fe_12.5 cubic phase approximating the structure of the icosahedral alloy has been studied in the temperature range 4.2–40.0 K. All the three compounds exhibit low coefficients of the electronic heat capacity and pronounced deviations of the low-temperature lattice heat capacity from a cubic temperature law in the range 5–10 K. The results obtained by the thermodynamic method and inelastic neutron scattering have been compared and analyzed. It has been established that, at energies ɛ < 14 meV, the spectral density of thermal vibrations in the icosahedral quasicrystal is substantially higher than those in the cubic approximant and in decagonal quasicrystal.     

Comparative study of the heat capacity of icosahedral quasicrystals in solid and liquid states

The heat capacity of icosahedral quasicrystals Al₆₃Cu₂₅Fe₁₂ and Al₆₂Cu_25.5Fe_12.5 has been studied at high temperatures up to 1700 K, which is by almost 400 K higher than the melting point of the material. It has been shown that the melt exhibits an excess heat capacity with respect to that determined by the Dulong-Petit law and that is a direct extension of the excess heat capacity of the solid state. It has been concluded that the excess heat capacity is related, as a whole, to the short-range order in the quasicrystal structure. This circumstance allows the identification of the orbital hybridization as the most probable mechanism of formation of the pseudogap in the electronic structure of the quasicrystals.     

Magnetic and transport properties of Pr2Pd3Si5

We have investigated the magnetic and transport properties of a new ternary intermetallic compound Pr₂Pd₃Si₅ which forms in U₂Co₃Si₅-type orthorhombic structure (space group Ibam). At low field (0.01 T) magnetic susceptibility exhibits an abrupt increase below 7 K and peaks at 5 K, revealing a magnetic phase transition. The onset of magnetic order is also confirmed by well defined anomalies in the specific heat and electrical resistivity data. Apart from the sharp λ-type anomaly, magnetic part of specific heat also shows a broad Schottky-type hump due to crystal field effect. Magnetoresistance data as a function of temperature exhibits a pronounced peak in paramagnetic state which could be interpreted in terms of crystal field effect and short-range ferromagnetic correlations.     

Magnetic susceptibility and characteristic features of the electronic structure of quasicrystalline alloys

Experiments are performed to determine the magnetic susceptibility of the icosahedral phase itself in the alloy Al₆₂Cu_25.5Fe_12.5 in the temperature range 3.9–1100 K. A new regularity is observed — the curves of the temperature dependences of the susceptibility and electrical conductivity are congruent. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 3, 206–210 (10 February 1999)     

The electrical resistivity of amorphous alloys at low temperatures

Measurements of the temperature- and magnetic field dependence of the electrical resistance of some metallic glasses are presented. The data obtained for Cu₅₇Zr₄₃, Cu₄₀Zr₆₀ and Pd₃₀Zr₇₀ demonstrate that deviations from the high temperature behaviour extrapolated to low temperatures are caused by superconducting effects. The paraconductivity which is strongly enhanced in amorphous alloys is shown to agree quite well with theoretical models. The normal state resistance does not saturate down to temperatures of about 2 K. It still exhibits a negative temperature coefficient of the resistivity.     

Decagonal quasicrystal in the Al–Pd–Mn system

Abstract

A stable decagonal quasicrystal in Al₇₀Pd_30?xMn_x alloys (x = 10–20) was examined by electron diffraction and high-resolution electron microscopy. The decagonal quasicrystalline grains are formed with definite crystallographic relationships to adjacent icosahedral and Al₃Mn crystalline grains. The structure of the decagonal phase, which is formed as the main phase at near Al₇₀Pd₁₀Mn₂₀ composition, is a mixture of decagonal quasicrystalline regions with some linear phason strain and microcrystalline regions. The structures of both regions may be interpreted in terms of quasiperiodic and periodic tilings, constructed with two types of bond lengths, S (about 2 nm) and L (= τ · S, where τ is the Golden ratio), of the same atom cluster with decagonal symmetry.     

Spin-glass behaviour of novel ternary uranium aluminide U3Co4+ x Al12− x (x = 0.55)

Experimental results on dc and ac susceptibility, magnetization and magnetic relaxation, specific heat, electrical resistivity and magnetoresistivity up to 8?T are reported for the novel ternary uranium aluminide U₃Co_4.55Al_11.45. The temperature dependence of the dc susceptibility shows a cusp at a characteristic temperature T _f?=?8–10?K that depends weakly on the applied magnetic field. The observed pronounced difference between the ZFC and FC magnetizations, as well as the decay in the remanent, both give evidence that a highly irreversible, frozen state is formed below T _f which is reminiscent of spin-glass behaviour. The real and imaginary parts of the ac susceptibility show that the corresponding T _f peaks are only slightly dependent on frequency. Electrical resistivity measured at zero and in fields up to 8?T indicates that the Kondo-like state becomes dominant at temperatures above T _f.     

Magnetic properties of a monocrystalline quasicrystal in the Al-Pd-Mn system

Magnetic susceptibility of a monocrystalline icosahedral Al_70.2Pd_21.3Mn_8.5 quasicrystal was measured over the temperature range from 4 to 1100 K. The susceptibility was found to include the temperature-independent diamagnetic contribution, the temperature-dependent Curie’s contribution, and the contribution from the Pauli paramagnetism of an electron system with energy gap. An analysis of the low-temperature susceptibility revealed the presence of about 0.008% of ions with magnetic moment 4µ_B in the quasicrystal at 4 K. It is assumed that the ions with uncompensated magnetic moments appear near the structural vacancies in the quasicrystal lattice. The energy gap between the valence and conduction bands is estimated at Δ=0.64 eV, and the effective mass of charge carriers is equal to approximately 70 electron masses.     

Nuclear magnetic resonance in icosahedral Al-Pd-Mn alloys

²⁷Al and⁵⁵Mn nuclear magnetic resonance shift,K, and²⁷Al spin lattice relaxation time,T ₁, have been measured for the six-dimensional face-centered icosahedral quasicrystals, Al_75-x Pd₁₅Mn_10+x withx=0, 2 and7. The Al₇₅Pd₁₅Mn₁₀ quasicrystal exhibits a temperature independent Knight shiftK and(T ₁ T)^–1=0.022±0.002 (K s)^–1 in a temperature range from room temperature to 5 K because there exist no Mn atoms with local magnetic moment. The replacement of Al with Mn drastically decreases the²⁷AlK, the⁵⁵MnK andT ₁ of²⁷Al, andthe²⁷AlK becomes negative. There is an additional contribution to the spin lattice relaxation time independent of temperature. This is considered to be due to the presence of a localized magnetic moment in the replaced Mn atoms.     

Electrical transport, magnetic and thermal properties of icosahedral Al–Pd–Mn quasicrystals

We report measurements of electrical resistivity (ρ), Hall coefficient (R_H), magnetization (M) and specific heat (C_p(T)) of high-quality icosahedral Al_70.4Pd_20.8Mn_8.8 phases with different thermal treatment. An improvement in the quasi-crystallinity upon the annealing treatment caused a drastic increase in ρ up to 7000 μΩ cm accompanied by a very small electronic specific heat coefficient γ. The low temperature ρ(T) data has been analyzed in terms of weak localization and electron–electron interaction effects. The Hall resistivity (ρ_H) is found to be strongly temperature-dependent and varies linearly with the magnetization (M) for the same field and temperature. Magnetization measurement reveals that more conductive samples are more magnetic and vice versa. Magnetic susceptibility (χ) data of all the annealed samples agrees with the Curie–Weiss-like behavior implying the existence of localized moments. The negative Curie–Weiss temperature (θ) indicates strong antiferromagnetic coupling between individual Mn atoms. The magnetic Mn concentration is found to be small, ranging from 1.73×10^-4 for the less magnetic sample studied up to 3×10^-3 for the more magnetic one. The small electronic specific heat coefficient obtained for all the samples suggests a significant reduction in the electronic density of states (DOS) at the Fermi level (E_F) upon thermal annealing treatment.     

Magnetic ordering of Fe atoms in icosahedral Al70−x BxPd30−y Fey quasicrystals

Novel icosahedral quasicrystals, in which Fe atoms possess a magnetic moment, have been found in Al_70?x B_xPd_30?y Fe_y compounds with 5<x<10 and 10<y<20. The compounds have ferromagnetic properties, and their Curie temperature ranges between 280 and 340 K, the saturation magnetization σ _s(5 K)≈7.5 emu/g. It follows from Mössbauer spectra that only a fraction of Fe atoms (12 to 15%) are magnetically ordered at 4.2 K, and the mean saturation field 〈H _hf〉=96 kOe. The isomer shift values confirm that the atomic volume of magnetic Fe sites is larger than that of nonmagnetic Fe sites. The magnetic properties of these quasicrystals can be interpreted in terms of large magnetic clusters with a size of 185 to 290 Å. This size correspond to about 4×10⁴ “unit cells,” hence the magnetic state can be described in terms of bulk parameters. The localized magnetic moment of Fe atoms is tentatively ascribed to bonding between Fe and B, similarly to that in the amorphous Fe_～50B_～50 alloy.     

Electrical transport and magnetic ordering in R 2Ti3Ge4 (R=Dy, Ho and Er) compounds

New R ₂Ti₃Ge₄ (R=Dy, Ho and Er) intermetallic compounds have been synthesized and characterized by X-ray diffraction and low temperature ac magnetic susceptibility, electrical resistivity and thermoelectric power measurements were carried out. The compounds crystallize in the parent, Sm₅Ge₄-type orthorhombic structure (space group Pnma) and lanthanide contraction is observed as one moves along the rare-earth series. The changeover from paramagnetic to antiferromagnetic phase happens at low temperatures and the ordering temperature scales with the de Gennes factor. The electrical resistivity is metallic with a negative curvature above 100 K. Thermopower displays a weak maximum at temperatures less than 50 K signifying the possible phonon and magnon drag effects.     

High temperature magnetic ordering in La2RuO5

Magnetic susceptibility, heat capacity and electrical resistivity measurements have been carried out on a new ruthenate, La₂RuO₅ (monoclinic, space group P2₁/c) which reveal that this compound is a magnetic semiconductor with a high magnetic ordering temperature of 170 K. The entropy associated with the magnetic transition is 8.3 J/mol K close to that expected for the low spin (S=1) state of Ru⁴⁺ ions. The low temperatures specific heat coefficient γ is found to be nearly zero consistent with the semiconducting nature of the compound. The magnetic ordering temperature of La₂RuO₅ is comparable to the highest known Curie temperature of another ruthenate, namely, metallic SrRuO₃, and in both these compounds the nominal charge state of Ru is 4+.     

Delocalization of the Ce 4f shell in amorphous Ce75.5Co24.5

The amorphous alloy Ce_75.5Co_24.5 prepared by melt spinning has been studied through measurements of the magnetic susceptibility, magnetization, electrical resistivity, thermoelectric power and specific heat. The results are interpreted in terms of a homogeneous intermediate valence state of the Ce ions. This is inferred from a temperature-independent magnetic susceptibility at low temperature and the absence of magnetic ordering, a large linear term in the specific heat, and aT ² dependence of the electrical resistivity at low temperature followed by a steep increase with temperature up to 50 K. At this temperature, the thermoelectric power displays a maximum. The intrinsic properties are partially obscured at low temperatures by a contribution from roughly a few percent of magnetic impurities, presumably Ce³⁺ ions. They manifest themselves by an increase of the susceptibility towards low temperatures and by a broad Schottky-like contribution to the specific heat resulting from the excitation of magnetic clusters.Dedicated to Prof. Dr. S. Methfessel on the occasion of his 60th birthday     

Electrical resistivity and crystallization behaviour of icosahedral Al51Cu12.5Mg36.5

Samples consisting of icosahedral Al₅₁Cu_12.5Mg_36.5 were produced by melt-spinning and characterized by X-ray and electron diffraction. DSC measurements confirm the transition from the quasicrystalline to the crystalline state to be exothermic. The electrical conductivity shows two steps at about 600 K due to crystallization processes. The magnetoresistance at 4.2 K exhibits the typical shape of the quantum interference correction.