Superconducting and normal state properties of Li1+x Ti2−x O4 spinel compounds. I. Preparation,crystallography, superconducting properties,electrical resistivity,dielectric behavior,and magnetic susceptibility

LiTi ₂ O ₄ is one end member of the homogeneity range of the spinel phase Li _1+x Ti _2–x O ₄ (0x1/3) and is superconducting at temperatures up to 13.7 K. Various measurements were carried out in order to characterize the superconducting and normal state properties of LiTi ₂ O ₄ and of other compositions within the homogeneity range of the spinel phase. These measurements establish LiTi ₂ O ₄ as ad-band superconductor and show thatT _c decreases to <1.5 K forx0.1. This disappearance of superconductivity with increasingx was found to be correlated with anomalous changes in the lattice parameter with composition, and, from electrical resistivity measurements, is tentatively attributed to the occurrence of a composition-induced metal-semiconductor transition atx0.1. The metallic character of LiTi ₂ O ₄ and the composition dependence of the observed electrical properties are shown to follow from crystallographic considerations.Research sponsored by the Air Force Office of Scientific Research, Air Force Systems Command, USAF, under AFOSR Contract Number AFOSR/F-44620-C-0017.     

Investigation of the lithium-rich boundary of the Li1+x Mn2−x O4 cubic spinel phase in air

Several compositions of the cubic spinel Li_1+x Mn_2?x O_4?δ phase in the lithium–manganese–oxygen (Li–Mn–O) system were synthesized at 700, 750, and 800 °C in air ( $ p_{{{\text{O}}_{2} }} $  = 0.2 atm) to investigate the Li-rich boundary of the cubic spinel phase at these temperatures. The lattice parameters of the several compositions were determined by Rietveld analysis of the measured X-ray patterns, and the Li and Mn contents of the samples were measured using inductively coupled plasma with optical emission spectroscopy (ICP-OES). A Vegard-like dependence of the measured lattice parameter of the cubic spinel phase with Li to Mn ratio exists in the homogeneity range of the cubic spinel. This dependence could be used to derive the boundary of the single phase cubic spinel field in the Li–Mn–O system at 700 and 750 °C at $ p_{{{\text{O}}_{2} }} $  = 0.2 atm and to estimate the Li-rich boundary at 800 °C. The results of the present study are compared with two other experimental studies on the homogeneity range of the cubic spinel phase in an attempt to resolve the contradiction between these two studies.     

Microstructure and dielectric properties of BaZr x Ti1−x O3 ceramics

The crystalline structure and dielectric properties of BaZr _x Ti_1−x O₃ ceramics with x = 0.05, 0.10, 0.15, and 0.20 were investigated. As zirconium increased, the a-axis lattice constant gradually increased, however, the c-axis lattice constant and c/a ratio gradually decreased. When x = 0.20, the crystal structures of the BZT ceramics are very close to cubic, different from the tetragonal structure when x < 0.20. The temperature dependence of the dielectric constant was studied and an enhanced diffuse phase transition behavior is found to be caused by the increased Zr content. The decreases of coercive electric field and remanent polarization were the result of increase of Zr/Ti ratio in BaZr _x Ti_1−x O₃.     

Subsolidus phase relations of Li2O–FeO–P2O5 system and the solid solubility of Li1+x Fe1−x PO4 compounds under Ar/H2 atmosphere

The phase relation of Li₂O–FeO–P₂O₅ ternary system under the 95 %Ar + 5 %H₂ atmosphere has been systematically investigated by X-ray diffraction (XRD), and there exist 8 binary compounds, 4 ternary compounds, 2 two-phase regions, and 17 three-phase regions. No other new lithium ferrous phosphates can be existed in the Li₂O–FeO–P₂O₅ ternary system under the 95 %Ar + 5 %H₂ atmosphere. In this system, the Li_1+x Fe_1?x PO₄ solid solution phase with the homogeneous range of ?0.15 ≤ x ≤ 0.06 is determined. Their corresponding lattice parameters are obtained by the refinement results, and the results show that the lattice parameters (a, b, c, V) vary linearly with the increasing amount of excess Li-ion (x > 0) or with the increasing amount of excess Fe-ion (x < 0). The phase diagram determined in this paper can provide more information about the phase relation of Li₂O–FeO–P₂O₅ ternary system and serve as a guide for the future investigation of lithium iron phosphates in this system.     

Low-temperature thermoelectric and magnetic properties of Ca3−x Bi x Co4O9+δ (0 ≤ x ≤ 0.30)

Polycrystalline samples of Ca_3?x Bi _x Co₄O_9+δ (x = 0.00, 0.05, 0.10, 0.15, 0.20 and 0.30) have been prepared by conventional solid-state synthesis. Thermopower of all the samples is positive, indicating that the predominant carriers are holes over the entire temperature range. The resistivity of all the samples, except the one with x = 0.30, exhibits nonmetal to metal transition (T _MI) in the low temperature regime. The resistivity results indicate that all the doped samples obey the variable range hopping in the low temperature regime. The T _MI and T ^* (transition temperature from Fermi liquid metal to incoherent metal) increase, and the slope of A value (Fermi-liquid transport coefficient) decreases with the increasing Bi content due to an increase in chemical pressure in the lattice. Among the samples, Ca_2.7Bi_0.3Co₄O_9+δ has the highest dimensionless figure of merit of 0.091 at 300 K. This value represents an improvement of about 135 % compared to the undoped Ca₃Co₄O_9+δ . Magnetic measurements indicate that all the samples exhibit a low-spin state of cobalt ion. The ferrimagnetic transition temperature is suppressed by the Bi dopant. These results suggest that Bi is an effective doping element for improving the thermoelectric properties of Ca₃Co₄O_9+δ .     

Thermodynamic properties of Ca1 − x Er x F2 + x and Ca1 − x Yb x F2 + x heterovalent solid solutions

The heat capacity of single crystals of the Ca_{1 ? x} Er _x F_{2 + x} (x = 0.05, 0.10) and Ca_0.95Yb_0.05F_2.05 fluorite solid solutions was determined by adiabatic calorimetry in the temperature range 55–300 K. The results were used to obtain temperature dependences of the Debye characteristic temperature, entropy, and enthalpy for the solid solutions.     

Low-temperature formation mechanism of double oxides Fe x Zr(Ti)1−0.75x O2−δ prepared from alkoxides and acetylacetonates

As a result of titanium and zirconium alcoholates hydrolysis in the presence of dissolved Fe(acac)₃, amorphous iron-containing gels have been synthesized. Their heat treatment has led to polycrystalline double oxides Fe _x Zr_1–0.75x O_2– (C) and Fe _x Ti_1–0.75x O_2– (T) formation. It has been shown that oxides (C) and (T) are likely to be solid solutions with 0.01<x<0.17 and 0.01<x<0.14, respectively. On the basis of X-ray diffraction and extended X-ray absorption fine structure data, iron-zirconium and iron-titanium crystallite models for gels and oxides have been proposed. It has been found that the crystallization process does not lead to a significant change in interatomic distances typical for local structures detected in gels.     

Dielectric properties of Na1 − x K x NbO3 and Na1 − x Li x NbO3 ceramics

The dielectric properties of solid solutions based on sodium potassium and sodium lithium niobates have been studied in wide ranges of temperatures (25–750°C), frequencies (25 to 10⁶ Hz), and electric fields (up to 30 kV/cm). We have identified solid-solution regions differing in the temperature and frequency dependences of the dielectric permittivity. It is reasonable to take into account the present results in device applications where wide variations in dc bias field and frequency are needed.     

Physical and electrical properties of MnO2-doped Pb(Zr x Ti1−x )O3 ceramics

The effects of composition on the physical property change in the phase coexistence region between the tetragonal and rhombohedral phases have been investigated as a function of zirconium concentration, x, for the MnO₂-doped Pb(Zr _x Ti_1–x )O₃ (0.40x0.60) ceramics. The relative amount of phase coexisting between the tetragonal and rhombohedral phases affects greatly both dielectric and piezoelectric properties as a function of zirconium concentration. However, there are no detectable changes between the apparent density and microstructure. Also, in the coexistence region, the relative amount of coexistence of the rhombohedral phase increases with MnO₂ addition. The inflection points of the dielectric constant shift to lower zirconium concentration in proportion to the MnO₂ addition, owing to the substitution effect on the PZT lattice site.     

Investigation of the functional properties of Mg x Ni1−x Fe2O4 ceramics

The paper presents a complex study of the effect of Mg substitution on the functional properties of Ni-ferrite ceramics prepared by self-combustion sol–gel method. The sintered ceramics have pure cubic spinel structures with an increase of the lattice parameter and the grain size with Mg content. The electrical properties of Mg _x Ni_1?x Fe₂O₄ (x = 0; 0.17; 0.34; 0.5; 0.66; 1) ceramics have been investigated. The complex impedance spectra suggest a grain boundary contribution in the conduction process and reveal that the real part of impedance and the imaginary component (reactance) increase with increasing the Mg amount. The temperature dependence of dielectric properties shows that the hopping of charge carriers is thermally activated. The resistivity as a function of frequency for different degree of humidity was also investigated. All the investigated samples show a typical ferrimagnetic character with a strong non-linearity, small coercitive field (~50 Oe) and a saturation field of ~1kOe, typical to the investigated Mg _x Ni_1?x Fe₂O₄ ceramics. The Curie temperature determined from magnetic susceptibility versus temperature dependences presents a decrease with the addition of non-magnetic Mg²⁺ ion concentration from 603 °C (for x = 0) to 384 °C (for x = 1).     

Thermoelectric properties of GdBaCo2−x Fe x O5+δ ceramics

The influence of Fe doping on the lattice structure and thermoelectric properties of GdBaCo_2?x Fe _x O_5+δ (x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) ceramics was studied from room temperature to 525 K. The results show that presence of Fe will increase both electrical resistivity and Seebeck coefficients of the samples. Due to the lattice misfit and carrier concentration reduction caused by Fe, the thermal conductivity of the sample decreases. The activation energy of conductivity is larger than that of thermopower calculated in the semiconductive region, which means that the conduction mechanism may be determined as a small polaron hopping model. The optimum Fe doping amount is x = 0.6, which results in a ZT value 0.02 at 373 K.     

The nonstoichiometry and physical properties of the Nd1−x Ca1+x FeO4−y system

The solid solutions of the Nd_1–x Ca_1+x FeO_4–y system for compositions ofx=0.000,0.125, 0.250,0.375, and 0.500 are prepared by drip pyrolysis. XRD analysis shows all the solid solutions are tetragonal I_4/mmm. The Fe⁴⁺ ratio to the total Fe ions or value has a maximum for the compositionx=0.375. From the X-ray powder diffraction analysis and the Mössbauer spectroscopy, the distortion and symmetry change of oxygen octahedra of Fe ions are observed. The structural change of oxygen octahedra of Fe ions strongly affects the physical properties. The solid solution whenx=0.000 shows a weak ferromagnetic behaviour due to the spin canting of the distorted octahedra. The other solid solutions withx=0.125, 0.250, 0.375, and 0.500 show a paramagnetic behaviour over room temperature. The decrease of the magnetic transition temperature is due to the distortion of oxygen octahedra of Fe ions and the existence of the Fe⁴⁺ ion. The formation site of oxygen vacancies plays an important role in the conductivity of the Nd_1–x Ca_1+x FeO_4–y system. Although the oxygen vacancies in [Nd, Ca]-O layer have little effect on conductivity, the oxygen vacancies in the FeO₂ plane of the perovskite layer act as electron trapping sites and thus increase the activation energy.     

Structural elastic and thermal properties of Sr x Cd1−x O mixed compounds — a theoretical approach

In the present paper, the structural and mechanical properties of alkaline earth oxides mixed compound Sr _x Cd_1?x O (0 ? x ? 1) under high pressure have been reported. An extended interaction potential (EIP) model, including the zero point vibrational energy effect, has been developed for this study. Phase transition pressures are associated with a sudden collapse in volume. Phase transition pressure and associated volume collapses [ΔV (Pt)/V(0)] calculated from this approach are in good agreement with the experimental values for the parent compounds (x = 0 and x = 1). The results for the mixed crystal counterparts are also in fair agreement with experimental data generated from the application of Vegard’s law to the data for the parent compounds.     

Normal state properties of lithiated YBa2Cu3O7−x samples

Measurements of the resistivity in the normal state of lithiated YBa₂Cu₃O_7−x are reported. At low x_Li-values (<0.06), lithium substitutes copper of the CuO₂ planes. The samples are metallic; a progressive localization of the charge carriers is observed. In the intermediate concentration range, lithium occupies both copper sites planes and chains which leads to a two-phased system; the slope dϱ/dT is nearly independent of temperature. In the concentrated range, lithium is in the chain site. The resistivity behaviour is well described by the simple relation with ρ₀T₀=10Ω.cm.K, a result which is consistent with a single YBCO₆-type phase.     

Room-temperature multiferroic properties and magnetoelectric coupling in Bi4−x Sm x Ti3−x Co x O12−δ ceramics

We present the structural, dielectric, ferroelectric, magnetic and magnetoelectric studies of lead free; single phase Bi_4?x Sm _x Ti_3?x Co _x O_12?δ (0 ≤ x ≤ 0.07) ceramics, synthesized using a standard solid-state reaction technique. Raman spectroscopy analysis reveals the relaxation of distortion in TiO₆ octahedron. Field emission scanning electron microscopy confirmed the growth of plate-like grains. It is observed that with the substitution of Sm³⁺ and Co³⁺ ions the dielectric constant, loss tangent and ferroelectric transition temperature decreases. Electrical dc resistivity, remnant polarization and magnetization increases with increasing Sm³⁺ and Co³⁺ contents. The magnetoelectric coupling co-efficient, α = 0.65 mV cm^?1 Oe^?1 is realized for Bi_4?x Sm _x Ti_3?x Co _x O_12?δ (x = 0.07) ceramic sample. Our results clearly demonstrate the lead free, multiferroic nature of Sm/Co-substituted Bi₄Ti₃O₁₂, which may find useful application in designing cost-effective electromagnetic devices.     

The dielectic response of K x Al x Ti8−x O16 and K x Mg x/2 Ti8−x/2 O16

Materials of the hollandite structure with the general formulae K_x Al_x Ti_8–x O₁₆ and K_x Mg_x/2 Ti_8–x/2 O₁₆ have been synthesized in the composition range 1.6x2.0 and their dielectric properties have been measured in the temperature range 77 to 800 K and the frequency range 10^–3 to 10⁶ Hz. The observed response shows a whole range of features characteristic for both charge carrier and dipolar polarization processes and these are seen as being associated with the one-dimensional transport in channels in the hollandite structure. At low temperatures the dominant response is the universal dielectric relation in which the loss follows the law x() ^n–1, with the exponent n<1 and equal specifically to approximately 0.7. This is followed at 120 to 180 K by a distinct loss peak superimposed on the above law, and finally at higher temperatures by a region of strong dispersion which is associated with strongly interacting many-body processes between charged carriers restricted by defects to move in limited regions of the channels.