Ionic conduction mechanism and relaxation studies of NaNbAlP<Subscript>3</Subscript>O<Subscript>12</Subscript> compound

The Na superionic conductor (NASICON) NaNbAlP₃O₁₂ compound was prepared by the conventional solid-state reaction method. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be a hexagonal phase at room temperature. The electrical conductivity was measured in the frequency range from 200 Hz to 5 MHz and temperatures between 573 and 773 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The analysis of Nyquist plots has revealed the contribution of three electrically active regions corresponding to the bulk mechanism, distribution of grain boundaries, and electrode processes. Besides, the frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. Temperature dependence of the power law exponent s strongly suggests that the non-overlapping small polaron tunneling (NSPT) model is the dominant transport process. The variation of the imaginary part of the complex modulus as a function of angular frequency at several temperatures shows a double relaxation peak suggesting the presence of grains and grain boundaries in the sample. An analysis of the dielectric constants ε″ and loss tangent tan (δ) with frequency shows a distribution of relaxation times.     

Shapiro steps in the torsion of a quasi-one-dimensional conductor TaS<Subscript>3</Subscript>

Features have been observed in the current dependences of the torsion angle, φ(I), for samples of a quasi-one-dimensional conductor TaS₃ irradiated by a high-frequency (HF) field. The features appear at the same current values as the Shapiro steps on the current-voltage characteristics, i.e., correspond to the synchronization of the motion of a charge-density wave (CDW) by the HF field. The shape of the features in the φ(I) dependences indicates a decrease in the inhomogeneous deformation of the CDW under the synchronization conditions. The investigation of torsion appears to be a highly sensitive method for determining the spatial coherence of the CDW.     

Magnetic properties of a quasi-one-dimensional NaFeGe<Subscript>2</Subscript>O<Subscript>6</Subscript> polycrystal

The magnetic properties of a synthesized dielectric NaFeGe₂O₆. polycrystal have been studied. The antiferromagnetic ordering of this compound below 15 K has been established. The Mössbauer spectrum at 300 K is a quadrupole doublet; it is characterized by an isomeric shift typical of the high-spin Fe³⁺ ion in the octahedral coordination and quadrupole splitting, which indicates distortion of the oxygen octahedron around the iron cation. Quasi-one-dimensionality of the sample magnetic structure is proved.     

Solitons in the spin-Peierls compound CuGeO <Subscript>3</Subscript>

We calculate the excitation gap, the soliton energy, and the soliton density at finite temperature, of the spin-1/2 one dimensional antiferromagnet coupled to phonons, using a self-consistent harmonic approximation, and the thermal-Green function technique. The spin degrees of freedom are represented by the phase Hamiltonian with the help of the boson representation of the spinless fermions. We estimate the critical field H_c above which begins the incommensurate phase. We also present a theoretical calculation for the specific heat in this phase. We use CuGeO₃ as an example of a compound where our theory could be applied. Received 22 October 2002 / Received in final form 21 January 2003 Published online 14 March 2003     

Electrical conduction mechanism in Fe<Subscript>70</Subscript>Pd<Subscript>30</Subscript> catalyzed multi-walled carbon nanotubes

Carbon nanotubes (CNTs) are synthesized by the catalytic decomposition of acetylene using low pressure chemical vapour deposition method (LPCVD) at 800 °C and at a chamber pressure of 10 Torr over a supported catalyst film of Fe₇₀Pd₃₀. Morphology of these CNTs is studied using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). From HRTEM image of these multi-walled carbon nanotubes (MWNTs), it is clear that these MWNTs do not possess a co-axial cylindrical structure, but are composed of imperfect and broken graphite cylinders of different sizes. The average diameter and length of the nanotubes varies between 20–70 nm and 5–60 μm respectively. Electrical transport measurements of these MWNTs are studied over a temperature range of 298–4.2 K. The results have been interpreted in terms of variable-range hopping (VRH) over the entire temperature range of 298–4.2 K. Three-dimensional variable-range hopping (VRH) is suggested for the temperature range (298–125 K), while two-dimensional VRH is observed for the temperature range (125–4.2 K).     

Fast ionic transport in Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>TiS<Subscript>2</Subscript>

The enthalpy of the subsystem of silver ions in the intercalation compounds Ag _x TiS₂ has been calculated from the electrochemically measured thermodynamic functions of the silver subsystem. The ionic conductivity and the coupled chemical diffusion coefficients for silver in the intercalation compound have been measured. The activation energy for diffusion of silver ions is determined and the obtained value is interpreted from analyzing the concentration dependence of the enthalpy of the ionic subsystem. The conclusion has been drawn that the high diffusion mobility is associated with the competition between the covalent and elastic interactions, which decreases the activation energy for diffusion of ions.     

Fast ionic conduction in cubic hafnium garnet Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Hf<Subscript>2</Subscript>O<Subscript>12</Subscript>

A new member of the family of garnets with fast lithium ion conduction has been found with the composition Li₇La₃Hf₂O₁₂. The anion arrangement corresponds to the oxygen framework in garnets, e.g., in Ca₃Fe₂Si₃O₁₂. Hafnium is coordinated octahedrally while the lanthanum environment can be described as a distorted cube. Lithium occupies a large number of positions with tetrahedral, trigonal planar, and metaprismatic coordination. Li₇La₃Hf₂O₁₂ shows a lithium bulk ion conductivity of 2.4 × 10⁻⁴ Ω⁻¹ cm⁻¹ at room temperature with an activation energy of 0.29 eV.     

Modulated magnetic structure in quasi-one-dimensional clinopyroxene NaFeGe<Subscript>2</Subscript>O<Subscript>6</Subscript>

The magnetic structure of the NaFeGe₂O₆ monoclinic compound has been experimentally investigated using the elastic scattering of neutrons. At a temperature of 1.6 K, an incommensurate magnetic structure has been observed in the form of an antiferromagnetic helix formed by a pairs of the spins of the Fe³⁺ ions with helical modulation in the ac plane of the crystal lattice. The wave vector of the magnetic structure has been determined and its temperature behavior has been studied. The analysis of the temperature dependences of the specific heat and susceptibility, as well as the isotherms of the field dependence of the magnetization, has revealed the existence of not only the order-disorder magnetic phase transition at the point T _N = 13 K, but also an additional magnetic phase transition at the point T _c = 11.5 K, which is assumingly an orientation phase transition.     

Thermal stability of EuMnO<Subscript>3</Subscript> compound

We determine the low-oxygen border of the region of homogeneity for the compound showing the pressure of oxygen and temperrature at which it is possible to obtain materials based on EuMnO₃ with various useful properties. It is established that under conditions of low oxygen pressures, EuMnO₃ dissociates according to the reaction EuMnO₃ = 1/2Eu₂O₃ + MnO + 1/4O₂ in the temperature range of 973–1190 K. We determine temperature dependences of the equilibrium pressure of oxygen and the changes in free Gibbs energy for this reaction. The thermodynamic parameters for the formation of EuMnO₃ from its elements are calculated on the basis of our experimental data.     

Incommensurate helical magnetic order in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> quasi-one-dimensional compounds

The results of the measurements of the ^{6, 7}Li and ²³Na nuclear magnetic resonance (NMR) and ^{63, 65}Cu nuclear quadrupole resonance in LiCu₂O₂ and NaCu₂O₂ quasi-one-dimensional compounds with a spin chains in the paramagnetic and magnetically ordered states are presented. The shape of the NMR line below T _c = 24 and 13 K for LiCu₂O₂ and NaCu₂O₂, respectively, is characteristic of the incommensurate static modulation of the local magnetic field matching with the incommensurate spiral modulation of the magnetic moments. The differences in the shape of the NMR spectra of ²³Na and ⁷Li are discussed in terms of the features of the crystal structure of LiCu₂O₂ and NaCu₂O₂.     

Long-range magnetic order in quasi-one-dimensional NaCrSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and NaCrGe<Subscript>2</Subscript>O<Subscript>6</Subscript> metal oxides

Formation of a long-range magnetic order is observed at low temperatures in NaCrSi₂O₆ and NaCrGe₂O₆ quasi-one-dimensional metal oxide compounds with a pyroxene structure. The first of these compounds, NaCrSi₂O₆, is an antiferromagnet with the Néel temperature T _N =3 K, while the second, NaCrGe₂O₆, is a ferromagnet with the Curie temperature T _C =6 K. From the measurements of magnetization and specific heat of these compounds, the main parameters of their magnetic subsystems are determined. In NaCrSi₂O₆, a spin-flip transition is observed. A change in the type of magnetic order that accompanies the replacement of Si by Ge can be attributed to a change in the parameters of the competing direct antiferromagnetic Cr-Cr and indirect ferromagnetic Cr-O-Cr interactions in isolated chains of CrO₆ octahedra.     

Specific heat of quasi-one-dimensional superionic LiCuVO<Subscript>4</Subscript>

The specific heat at constant pressure of polycrystalline LiCuVO₄ has been measured at temperatures of 80 to 310 K. The data obtained corroborate the earlier conclusion that this material is a superionic.     

Synthesis,thermal and electrical behavior of the superprotonic conductor phase in Rb<Subscript>3</Subscript>(HSeO<Subscript>4</Subscript>)<Subscript>2.5</Subscript>(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>0.5</Subscript> compound

The Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound was prepared and its thermal behavior and electric properties were investigated. The thermogravimetry (TGA) analysis and the differential scanning calorimetric (DSC) show the presence of a structural phase transition of the title compounds at 374 K which is confirmed by the variation of fp and σ_dc as a function of temperature. The complex impedance of the Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound has been investigated in the temperature range of 295–453 K and in the frequency range 209 Hz–1 MHz. The impedance plots show 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 Rp and constant phase elements CPE₁ in series with fractal capacity CPE₂. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The conductivity dc follows the Arrhenius relation. The near value of activation energies obtained from the analysis of modulus, conductivity data, and circuit equivalent confirm that the transport is through the ion hopping mechanism, dominated by the motion of the H⁺ proton in the structure of the investigated materials.     

Anomalous polarization characteristics of magnetic resonance in a quasi-one-dimensional CuGeO<Subscript>3</Subscript>: Co magnet

Doping of CuGeO₃ by 2% Co was found to cause a new magnetic resonance, which has anomalous polarization characteristics. In the Faraday geometry, where a microwave field B _ω is directed along certain crystallographic directions, this mode is suppressed, which indicates that the character of magnetic oscillations in this mode differs strongly from standard spin precession. This resonance coexists with the EPR on Cu²⁺ chains and is likely to be caused by an unknown collective mode of magnetic oscillations of an antiferromagnetic quantum S = 1/2 spin chain.     

Metastable quasi-one-dimensional ensembles of C<Subscript>8</Subscript> clusters

The geometric and energy characteristics of quasi-one-dimensional ensembles of metastable carbon clusters C₈ are calculated using the molecular dynamics method with an empirical interatomic potential. The decay activation energy and the lifetime of the metastable state are determined.     

Metal-insulator transition in whiskers of the NbS<Subscript>3</Subscript> quasi-one-dimensional conductor under pressure

The effect of pressure on the conduction of the NbS₃ quasi-one-dimensional conductor is studied. A pressure-induced insulator-metal transition is observed. The transition is accompanied by an increase in conductivity by six orders of magnitude at room temperature. Under pressures of 3–4 GPa, an additional phase transition appears in the temperature dependences of resistance. This transition manifests itself in an increase in the local conduction activation energy. The quantity dln(R)/d(1/T) reaches its maximum under pressures of 4–5 GPa, and the temperature position of the maximum of dln(R)/d(1/T) depends on the pressure as T* ≈ 7.5P + 202 K.     

Comparative Study of the Magnetoelectric Effect in HoAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and HoGa<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Single Crystals

The comparative study of the magnetoelectric properties and magnetostriction of HoGa₃(BO₃)₄ and HoAl₃(BO₃)₄ single crystals has been carried out. The investigated compounds exhibit qualitatively similar magnetodielectric and inverse magnetoelectric ME _E effects with the close absolute values, which is indicative of the weak effect of a nonmagnetic metal ion. On the contrary, the magnetostriction of the galloborate has been found to be threefold higher than that of the alumoborate. In addition, the difference between the qualitative behaviors of magnetostriction has been established: the magnetic-field dependence of magnetostriction for the alumoborate has the maximum near 70 kOe at T = 4.2 K, while the galloborate magnetostriction has no maximum and does not saturate in a field of 140 kOe.     

NMR spectrum in a Mn<Subscript>3</Subscript>Al<Subscript>2</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> noncollinear antiferromagnet

The dependence of the NMR frequencies on the external magnetic field in a Mn₃Al₂Ge₃O₁₂ non-collinear 12-sublattice antiferromgnet is calculated using the exchange approximation for the spin dynamics.     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.     

Thermodynamic properties and structure of oxyfluorides Rb<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript> and K<Subscript>2</Subscript>NaMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

According to the results of calorimetric and structural studies, the Fm{ie1202-1}m phase in K₂NaMoO₃F₃ remains stable at least to 100 K. No ferroelectric transformation assumed earlier has been revealed in a series of Rb₂KMoO₃F₃ samples prepared using various technologies. Only a phase transition of nonferroelectric origin has been observed near 195 K, and its thermodynamic characteristics have been determined. An analysis of the stability of the cubic structure of molybdenum fluorine-oxygen elpasolites-cryolites has been performed in the framework of the hypothesis on strengths of interatomic bonds. The barocaloric effect in Rb₂KMoO₃F₃ has been estimated.