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.     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

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.     

Isothermal kinetics and relaxation recovery of high-frequency shear modulus in the course of structural relaxation of Pd<Subscript>40</Subscript>Cu<Subscript>30</Subscript>Ni<Subscript>10</Subscript>P<Subscript>20</Subscript> bulk glass

Isothermal kinetics of relaxation of the high-frequency (1.4 MHz) shear modulus during structural relaxation of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass below the glass transition temperature is studied by an in situ method of contactless electromagnetic acoustic transformation. The kinetic law of relaxation is established. It is shown that quenching of aged samples from the supercooled liquid state leads to a decrease in the absolute value of shear modulus to below the initial value; the degree of subsequent isothermal relaxation of the modulus may be several times higher than the initial value. Possible reasons for relaxation and recovery of the shear modulus are considered.     

Response of the electrical resistivity and magnetoresistance of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films to biaxial compressive mechanical (001) or (110) strains

The behavior of the electrical resistivity and magnetoresistance of 40-to 120-nm-thick La_0.67Ca_0.33MnO₃ films grown on differently oriented lanthanum aluminate substrates was studied. The cell volume in thin (40 nm) La_0.67Ca_0.33MnO₃ films grown coherently on (001)LaAlO₃ was found to be substantially smaller. Mechanical stress relaxation in biaxially strained La_0.67Ca_0.33MnO₃ films is accompanied by an increase in the cell volume. The temperatures at which the electrical resistivity and magnetoresistance in biaxially strained La_0.67Ca_0.33MnO₃ films were maximum can differ by 60–70 K from those observed in bulk single crystals.     

High-precision measurements of the compressibility and the electrical resistivity of bulk <Emphasis Type="Italic">g</Emphasis>-As<Subscript>2</Subscript>Te<Subscript>3</Subscript> glasses at a hydrostatic pressure up to 8.5 GPa

High-precision studies of the volume and the electrical resistivity of g-As₂Te₃ glasses at a high hydrostatic pressure up to 8.5 GPa at room temperature are performed. The glasses exhibit elastic behavior in compression only at a pressure up to 1 GPa, and a diffuse structural transformation and inelastic density relaxation (logarithmic in time) begin at higher pressures. When the pressure increases further, the relaxation rate passes through a sharp maximum at 2.5 GPa, which is accompanied by softening the relaxing bulk modulus, and then decreases, being noticeable up to the maximum pressure. When pressure is relieved, an unusual inflection point is observed in the baric dependence of the bulk modulus near 4 GPa. The polyamorphic transformation is only partly reversible and the residual densification after pressure release is 2%. In compression, the electrical resistivity of the g-As₂Te₃ glasses decreases exponentially with increasing pressure (at a pressure up to 2 GPa); then, it decreases faster by almost three orders of magnitude in the pressure range 2–3.5 GPa. At a pressure of 5 GPa, the electrical resistivity reaches 10^–3 Ω cm, which is characteristic of a metallic state; this resistivity continues to decrease with increasing pressure and reaches 1.7 × 10^–4 Ω cm at 8.1 GPa. The reverse metal–semiconductor transition occurs at a pressure of 3 GPa when pressure is relieved. When the pressure is decreased to atmospheric pressure, the electrical resistivity of the glasses is below the initial pressure by two–three orders of magnitude. Under normal conditions, both the volume and the electrical resistivity relax to quasi-equilibrium values in several months. Comparative structural and Raman spectroscopy investigations demonstrate that the glasses subjected to high pressure have the maximum chemical order. The glasses with a higher order have a lower electrical resistivity. The polyamorphism in the As₂Te₃ glasses is caused by both structural changes and chemical ordering. The g-As₂Te₃ compound is the first example of glasses, where the reversible metallization under pressure has been studied under hydrostatic conditions.     

Structural and electrical properties of KCa<Subscript>2</Subscript>Nb<Subscript>5</Subscript>O<Subscript>15</Subscript> ceramics

A polycrystalline sample of KCa₂Nb₅O₁₅ with tungsten bronze structure was prepared by a mixed oxide method at high temperature. A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound shows a uniform grain distribution throughout the surface of the sample. Studies of temperature variation on dielectric response at various frequencies show that the compound has a transition temperature well above the room temperature (i.e., 105°C), which was confirmed by the polarization measurement. Electrical properties of the material have been studied using a complex impedance spectroscopy (CIS) technique in a wide temperature (31–500°C) and frequency (10²–10⁶ Hz) range that showed only bulk contribution and non-Debye type relaxation processes in the material. The activation energy of the compound (calculated from both the loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers. A possible ‘hopping’ mechanism for electrical transport processes in the system is evident from the modulus analysis. A plot of dc conductivity (bulk) with temperature variation demonstrates that the compound exhibits Arrhenius type of electrical conductivity.      

Impedance spectroscopy study of Pb<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

The lead pyrophosphate, Pb₂P₂O₇, compound was prepared by conventional solid-state reaction and identified by X-ray powder diffractometer. Pb₂P₂O₇ has a triclinic structure whose electrical properties were studied using impedance spectroscopy technique. Both impedance and modulus analysis exhibit the grain and grain boundary contribution to the electrical response of the sample. The temperature dependence of the bulk and grain boundary conductivity were found to obey the Arrhenius law with activation energies E _g = 0.66 eV and E _gb = 0.67 eV, respectively. The scaling behavior of the imaginary part of the complex impedance suggests that the relaxation describes the same mechanism at various temperatures.     

NMR study and electrical properties investigation of Zn<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The α-Zn₂P₂O₇ compound was obtained by conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, solid state ³¹P NMR MAS, and electrical impedance spectroscopy. The solid state ³¹P MAS NMR, performed at 121.49 MHz, shows three isotropic resonances at −21.1, −18.8, and −15.8 ppm, confirming the non-equivalency of the three PO₄ groups in the α-Zn₂P₂O₇ form. They are characterized by different chemical shift tensor parameters with the local geometrical features of the tetrahedra. Electrical impedance measurements of β-Zn₂P₂O₇, form stable for temperature greater than 403 K, were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The AC conductivity obeys the universal power law. The approximation type correlated barrier hopping model explains the universal behavior of the n exponent. The impedance plane plot shows semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The simulated spectra show a good correlation with the experimental data.     

Magnetically controlled thermoelastic martensite transformations and properties of a fine-grained Ni<Subscript>54</Subscript>Mn<Subscript>21</Subscript>Ga<Subscript>25</Subscript> alloy

Comparative studies of physical characteristics (the electrical resistivity, the magnetic susceptibility, the magnetization, the bending deformation, and the degree of shape recovery during subsequent heating) of the Ni₅₄Mn₂₁Ga₂₅ ferromagnetic alloy as-cast and rapidly quenched from melt have been performed in the temperature range 2–400 K. The results are compared to the results of studying the structural–phase transformations by transmission and scanning electron microscopy and X-ray diffraction. It is found that the rapid quenching influences the microstructure, the magnetic state, the critical temperatures, and the specific features of thermoelastic martensite transformations in the alloy. It is found that the resource of the alloy plasticity and thermomechanical bending cyclic stability demonstrates a record-breaking increase in the intercritical temperature range and during subsequent heating.     

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.     

Effect of uniaxial tension and hydrostatic compression on the geometry and morphology of amorphous Fe<Subscript>77</Subscript>Ni<Subscript>1</Subscript>Si<Subscript>9</Subscript>B<Subscript>13</Subscript> alloy ribbon surface

The effect of hydrostatic pressure and uniaxial compression on the relief of an amorphous Fe₇₇Ni₁Si₉B₁₃ alloy ribbon surface was studied using scanning tunneling and atomic-force microscopy. The fracture surfaces of samples were also studied. It is found that both the initial surfaces and the surfaces of samples subjected to hydrostatic compression or tension, as well as fracture surfaces, are fractal or multifractal, but their fractality parameters are different. Hydrostatic pressure decreases the surface roughness and the average fractal dimension of the surface on both sides of the ribbons. The dependence of the surface fractal characteristics on tension is more complex. Prior to the occurrence of a “critical event” on the surface (formation of a deformation band or a through crack), the Hölder index and the half-width of the singularity spectrum decrease. The correlation is discussed between the fractal characteristics of the ribbon surface and those of a fracture surface, and the role of an excess free volume in the initiation of fracture of amorphous alloys is analyzed.     

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.     

Impedance spectroscopy study of Na<Subscript>1/2</Subscript>Sm<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> ceramic

Complex impedance analysis of a valence-compensated perovskite ceramic oxide Na_1/2Sm_1/2TiO₃, prepared by a mixed oxide (solid-state reaction) method, has been carried out. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be an orthorhombic phase at room temperature. In a scanning electron microscope, grains separated by well-defined boundaries are visible, which is in good agreement with that of impedance analysis. Alternating current impedance measurements were made over a wide temperature range (31–400 °C) in an air atmosphere. Complex impedance and modulus plots helped to separate out the contributions of grain and grain boundaries to the overall polarization or electrical behavior. The physical structure of the samples was visualized most prominently at higher temperatures (275 °C) from the Nyquist plots showing inter- and intragranular impedance present in the material. The frequency dependence of electrical data is also analyzed in the framework of the conductivity and modulus formalisms. The bulk resistance, evaluated from the impedance spectrum, was observed to decrease with rise in temperature, showing a typical negative temperature coefficient of resistance-type behavior like that of semiconductors. The modulus mechanism indicates the non-Debye type of conductivity relaxation in the materials, which is supported by the impedance data. PACS 77.22.Ch; 77.22.Ej; 77.22.Gm; 77.22.Jp; 77.84.Bw     

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.     

Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

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.     

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.     

Two-dimensional electron gas at the interface of Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> ferroelectric and LaMnO<Subscript>3</Subscript> antiferomagnet

The temperature dependence of the electrical resistance has been studied for heterostructures formed by antiferromagnetic LaMnO₃ single crystals of different orientations with epitaxial films of ferroelectric Ba_0.8Sr_0.2TiO₃ deposited onto them. The measured electrical resistance is compared to that exhibited by LaMnO₃ single crystals without the films. It is found that, in the samples with the film, for which the axis of polarization in the ferroelectric is directed along the perpendicular to the surface of the single crystal, the electrical resistance decreases significantly with temperature, exhibiting metallic behavior below 160 K. The numerical simulations of the structural and electronic characteristics of the BaTiO₃/LaMnO₃ ferroelectric?antiferromagnet heterostructure has been performed. The transition to the state with two-dimensional electron gas at the interface is demonstrated.     

Concentration quenching anomalies of activated Y<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Pr<Superscript>3+</Superscript> nanocrystal luminescence

For the fist time in Y₂SiO₅:Pr³⁺ nanocrystals, the ordered stage in the ¹ D ₂ luminescence decay curves for Pr³⁺ ions has been observed at anomalously low doped ion concentration (0.5 at %). This effect is caused by preferred location of the activator ions in the near-surface layer of the nanocrystal that provides the relaxation of elastic tension arising due to the difference of ionic radii of Pr³⁺ and Y³⁺ ions. Concentration quenching of Pr³⁺ luminescence is caused by the cooperative cross-relaxation.