Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

Large quadratic electro-optic effect in K0.99Li0.01Ta0.60Nb0.40O3 single crystal

Single crystal paraelectric K_0.99Li_0.01Ta_0.60Nb_0.40O₃ is grown with a room-temperature Curie temperature (T_c). The parameters of the Sellmeier dispersion equation were determined. A large quadratic electro-optic (QEO) effect was observed. The QEO coefficient R₁₁ reaches as high as 2.48 × 10^?15 m² V^?2 around T_c. The induced refractive index change under an electric field of 500 V/mm is 40 times bigger than that of commonly used LiNbO₃. The large QEO coefficient makes single crystal K_0.99Li_0.01Ta_0.60Nb_0.40O₃ a promising candidate in optical devices.     

The ionic conductivity of Li6BaLa2M2O12 with coexisting Nb and Ta on the M sites

In a view to balancing cost and lithium ion conductivity, Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2) was prepared by solid-state reaction, and its corresponding AC impedances were tested at temperatures ranging from 20 to 250 °C in air. Li₆BaLa₂Ta₂O₁₂ exhibits the highest conductivity, 8.77?×?10^?6?S/cm, and the second highest is Li₆BaLa₂Nb₂O₁₂ with 6.69?×?10^?6?S/cm. Partial replacement of Ta with Nb cannot bestow the advantages of cost saving or the enhancement of lithium ion conductivity. X-ray diffraction patterns revealed a gradual change as an increasing amount of Nb replaces Ta in Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2), and it is thought that the trending of Nb and Ta to rest on the crystallographic planes is different.     

Li and Nb codoping in dielectric properties and phase transitions of KTaO3: Reentrant dipolar glass and long-range dipole ordering

Abstract

The highly polarizable perovskite-type oxide, KTaO₃ doped simultaneously with Li⁺ and Nb⁵⁺ (K_1?xLi_xTa_1?yNb_yO₃, KLTN), reveals unexpected properties and ordering effects. Studies of the dielectric permittivity ?'(T, f) (10—300K, 100Hz-1 MHz) for x = 0.0014 and y = 0.024 show collective dipolar ordering effects with a transition from paraelectric into a mixed phase (coexisting dipole-glass-like and long-range ordered ferroelectric phases) taking place near 39 K. At 15 K another phase transition into a reentrant dipolar glass-like state is observed. Such a sequence of transitions and the existence of a reentrant glass state are unknown for electrical dipolar systems.     

Investigating ionic mobility in solid solutions of Li x Na1 − x Ta y Nb1 − y O3 via Raman spectroscopy

The ionic mobility in Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions (SSes) is investigated by means of Raman spectroscopy. The average lifetime of an Li⁺ ion in the equilibrium position and the magnitude of the potential barrier are estimated from the temperature dependence of the line width corresponding to the vibrations of Li⁺ cations.     

Lithium-ionic diffusion and electrical conduction in the Li7La3Ta2O13 compounds

The electrical properties and the mechanism of lithium ionic diffusion in the Li₇La₃Ta₂O₁₃ compounds were investigated. The bulk and total conductivity at 300 K of the Li₇La₃Ta₂O₁₃ compound are about 3.3 × 10^? 6 S/cm and 2.6 × 10^? 6 S/cm, respectively. The activation energy of bulk and total conductivity is in the range of 0.38–0.4 eV. A prominent internal friction peak in Li₇La₃Ta₂O₁₃ compounds was observed around 280 K at 0.5 Hz, which is actually composed of two subpeaks (P₁ peak at lower temperature and P₂ peak at higher temperature). From the shift of peak position with frequency, the activation energy of 1.0 eV and the pre-exponential factor of relaxation time in the order of 10^? 18–10^? 21 s were obtained if one assumes Debye relaxation processes. These values of relaxation parameters strongly suggest the existence of interaction between the relaxation species (here lithium ions or vacancies). Based on the coupling model, the relaxation activation energies are deduced as 0.45 eV and the pre-exponential factor of relaxation time as 10^? 15 s. Judging from these relaxation parameters and the similarity of structure between Li₇La₃Ta₂O₁₃ and Li₅La₃Ta₂O₁₂ compounds, the P₁ and P₂ peaks are suggested to be related with the lithium ionic diffusion between 48g?48g and 24d?48g.     

Study of the ion mobility in a Li0.03Na0.97Ta0.4Nb0.6O3 solid solution by raman spectra

We have studied ion mobility in a Li_0.03Na_0.97Ta_0.4Nb_0.6O₃ solid solution by its Raman spectra. It has been revealed that, as the temperature of the solution is increased to approach the point of the phase transition to a state with a high conductivity with respect to lithium, the lines with frequencies at 77, 118, and 142 cm^?1, which refer, respectively, to librations of oxygen octahedra Nb(Ta)O6 as a whole and vibrations of Li and Na ions in octahedra, considerably broaden, decrease in intensity, and smear into the wing of the Rayleigh line. Remaining lines are preserved in the spectrum. We have observed that the width of the line with a frequency of 118 cm^?1 depends exponentially on temperature, while the width of the line with a frequency of 142 cm^?1 changes linearly with it, which makes it possible to attribute to the line with the frequency of 118 cm^?1 to vibrations of Li⁺ cations, whereas the line with the frequency of 142 cm^?1 should be attributed to vibrations of Na⁺ cations in AO₁₂ cuboctahedra. The average lifetime of Li⁺ ions in equilibrium positions and the jump barrier have been estimated to be ～8 × 10^?12 s and ～20 kJ/mol, respectively. This agrees well with the data in the literature on measurements of electric conductivity.     

The effect of some transition metal oxides on the physical properties of K0.5Na0.5Nb0.95Ta0.05O3 ceramics

Abstract

Both K_0.5Na_0.5Nb_0.95Ta_0.05O₃ (KNNTO) and (K_0.5Na_0.5Nb_0.95Ta_0.05O₃)_0.99-M_0.01, M = Co₃O₄ and Mn₂O₃ (M/KNNTO) Ferromagnetic behaviour was observed for some M/KNNTO compounds. The hardness and compressive strength of all investigated samples are given. Comparisons with similar materials are discussed. Ceramics were synthesised using a solid-state reaction method. X-ray diffraction patterns of all samples revealed that the crystal structure is orthorhombic. Field-emission scanning electron microscopy was performed. Polarisation hysteresis curves indicated a disruption of ferroelectric order with the addition of M into KNNTO ceramics. The dielectric properties of the investigated ceramics have been studied as a function of frequency and temperature.     

Concentration phase transitions in Li x Na1 − x Ta y Nb1 − y O3 solid solutions

The ferroelectric-antiferroelectric concentration phase transitions in solid solutions of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃, which are promising environmentally friendly (lead-free) ferropiezoelectric materials, are studied by means of Raman spectroscopy.     

Synthesis and crystallographic studies of garnet-related lithium-ion conductors Li6CaLa2Ta2O12 and Li6BaLa2Ta2O12

High-purity specimens of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ have been successfully synthesized by solid-state reactions. The analytical chemical compositions of these samples were in good agreement with the nominal compositions of Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂. The Rietveld refinements verified that these compounds have the garnet-type framework structure with the lattice constants of a = 12.725(2) Å for Li₆CaLa₂Ta₂O₁₂ and a = 13.001(4) Å for Li₆BaLa₂Ta₂O₁₂. All of the diffraction peaks of X-ray powder diffraction patterns were well indexed on the basis of cubic symmetry with space group Ia-3d. To make a search for Li sites, the electron density distributions were precisely examined by using the maximum entropy method. Li⁺ ions occupy partially two types of crystallographic site in these compounds: (i) tetrahedral 24d sites, and (ii) distorted octahedral 96h sites, the latter of which are the vacant sites of the ideal garnet-type structure. The present Li₆CaLa₂Ta₂O₁₂ and Li₆BaLa₂Ta₂O₁₂ samples exhibit the conductivity σ = 2.2 × 10^? 6 S cm^? 1 at 27 °C (E_a = 0.50 eV) and σ = 1.3 × 10^? 5 S cm^? 1 at 25 °C (E_a = 0.44 eV), respectively.     

（Na0.52K0.44Li0.04）Nb0.9-xSbxTa0.1O3 Lead-Free Piezoelectric Ceramics with High Performance and High Curie Temperature

（Na0.52K0.44Li0.04）Nb0.9-x Sbx Ta0.1O3 lead-free piezoelectric ceramics are prepared by a solid-state reaction method. With increasing Sb content, the transition temperature from orthorhombic to tetragonal polymorphic phase decreased. A composition （Na0.52K0.44Li0.04）Nb0.863Sb0.037Ta0.1O3 is found to possess excellent piezo- electric and electromechanical performances （d33 = 306pC/N, kp =48%, and kt=50%）, and high Curie temperature （Tc = 320 ℃）. These results indicate that （Na0.52K0.44Li0.04）Nb0.863Sb0.037 Ta0.1O3 is a promising lead-free piezoceramics replacement for lead zirconate titanate.     

Synthesis and physicochemical properties of Li2 Me x Zr1 − x O3 − δ (Me = Nb,Ti; x = 0.05, 0.1) solid solutions

Complex lithium metallates Li₂ Me _x Zr_{1 ? x} O_{3 ? δ} (Me = Nb, Ti, x = 0.05, 0.1) with iso-and heterovalent substitutions for Zr⁴⁺ ions in lithium zirconate are synthesized for the first time using a citrate technique. The inclusion of Ti⁴⁺ and Nb⁵⁺ ions in the crystal structure of Li₂ZrO₃ is confirmed by means of X-ray diffraction and NMR. It is shown that in the temperature range of 750–820 K, Li₂Ti_0.1Zr_0.9O₃ solid solution has higher conductivity than phases of undoped lithium zirconate.     

Synthesis and electrochemical properties of Li8 − x Zr1 − x Nb x O6 solid solutions

New lithium-conducting solid solutions based on lithium orthozirconate have been synthesized by mutual doping of the related structures Li₈ZrO₆ and Li₇NbO₆. The main factor determining the increase in the electrical conductivity of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ solid solutions is the formation of lithium vacancies in the tetrahedral and octahedral layers. The practical stability of the Li_{8 ? x} Zr_{1 ? x} Nb _x O₆ ceramics to metallic lithium has been studied.     

Manifestation of a ferroelectric-antiferroelectric phase transition in Li<Subscript>0.12</Subscript>Na<Subscript>0.88</Subscript>Ta<Subscript>0.4</Subscript>Nb<Subscript>0.6</Subscript>O<Subscript>3</Subscript> in its Raman scattering spectra

The ferroelectric-antiferroelectric phase transition in the Li_0.12Na_0.88Ta_0.4Nb_0.6O₃ ceramic solid solution has been studied by the Raman scattering technique. As the temperature approached the transition point from below, we observed an appreciable broadening of the lines associated with the vibrations of the cations occupying octahedral and cubooctahedral cavities of the structure and with the oxygen network vibrations (which implies a substantial increase in disorder on the cation sublattices), as well as a decrease to zero intensity of the 875-cm^?1 line corresponding to stretch vibrations of the bridging oxygen in the BO₆ octahedral anion in the vicinity of the transition. The temperature dependence of the 875-cm_?1 line intensity near the transition was used to study the behavior of the phase transition order parameter η. The behavior of η was found to disagree markedly with the Landau theory of second-order phase transitions. It is shown that discrepancies originate from the increase in disorder in the niobium and tantalum sublattices in the Li_0.12Na_0.88Ta _y Nb_1-y O₃ solid solution system with increasing y. The order of the transition is lowered.     

Enhanced piezoelectric properties and lowered sintering temperature of Ba(Zr0.07Ti0.93)O3 by B2O3 addition

The effects of B₂O₃ doping on densification, ferroelectric, and piezoelectric properties of Ba(Zr_0.07Ti_0.93)O₃(BZT) ceramics were investigated. The addition of B₂O₃ to the ceramics lowered the sintering temperature by ∼200 °C as well as changed their microstructures. Higher B₂O₃ concentration caused a decrease in remanent polarization and coercive field, while the piezoelectric coefficient d₃₃ remained at a high value of 291 pC/N for the ceramic sample with 2 wt.% B₂O₃. The relationship between piezoelectric properties and ferroelectric constant was examined.     

E-T phase diagrams of a solid solution of the multicomponent PbZn1/3Nb2/3O3-PbMg1/3Nb2/3O3-PbNi1/3Nb2/3O3-PbTiO3 system near the morphotropic phase boundary

The specific features of the dielectric and pyroelectric responses of a solid solution in the barium-doped multicomponent yPbZn_1/3Nb_2/3O₃-mPbMg_1/3Nb_2/3O₃-nPbNi_1/3Nb_2/3O₃-xPbTiO₃ system of the composition y = 0.0982, m = 0.4541, n = 0.1477, and x = 0.3 near the morphotropic phase boundary have been investigated. It has been assumed that the maxima revealed in the dependences of the reversible permittivity on the electric field strength with both the forward and backward changes in the field (E ₌) are associated with the induced phase transition. Based on the experimental results, the E-T phase diagrams are constructed in the temperature range from ?100 to 150°C for different temperature-field regimes: (i) variation in the electric field E ₌ at a fixed temperature of the sample and (ii) variation in the temperature of the sample at a constant value of E ₌. It has been found that there is a singular point in the E-T phase diagram and that, in the vicinity of this point, the dielectric and pyroelectric responses of the studied ceramics exhibit specific features.     

Dielectric response of PVC polymer loaded with Ba0.3Na0.7Ti0.3Nb0.7O3 ceramic powder

Dielectric response of poly(vinyl chloride), (PVC), loaded with different amount of Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ (BNTN) ceramic powders was investigated in frequency range 100 Hz–1 MHz and temperature range 100–450 K. Ceramic solid solution of barium titanate and sodium niobate with composition Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ was obtained from BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅ by conventional method. Powders were prepared by grinding of ceramics. The obtained ceramics, used to produce BNTN–PVC composites, are characterized by the relaxor behaviour with a broad peak of dielectric permittivity ε′ at T _m ≈ 230 K. The microstructure of the powders was observed and the grain size was estimated using scanning electron microscope Hitachi S-4700. The EDS analysis confirms the qualitative and quantitative chemical composition of powders and ceramics. The BNTN–PVC composite samples of 0-3 connectivity were prepared from ceramic and polymer powders by hot-pressing method. The dielectric response of the composites displays features originated from the PVC polymer modified by those of BNTN ceramics. The relaxation time of the α-process of PVC obeys the Vogel–Fulcher law and decreases with increasing volume fraction of the ceramics.     

Heat capacity of the 0.7PbNi1/3Nb2/3O3-0.3PbTiO3 ferroelectric ceramics

The temperature dependence of the heat capacity of the 0.7PbNi_1/3Nb_2/3O₃-0.3PbTiO₃ compound has been studied in the temperature range 120?C800 K. The temperature dependence of the heat capacity C _p has two diffuse anomalies in the temperature ranges 250?C450 K and 450?C650 K and a ?? anomaly at temperatures T ?? 225 K. The results are discussed with inclusion of the dielectric and structural data.     

High-temperature thermoelectric characteristics of B-site substituted Yb0.1Ca0.9Mn1−x Nb x O3 system (0≤x≤0.1)

The thermoelectric performance of Yb_0.1Ca_0.9MnO₃ doped with Nb⁵⁺ at B-site is investigated in this paper. It is found that there is a phase transition from O-type to O*-type orthorhombic structure with increasing of Nb doping content, which indicates that the structure distortion becomes more seriously. Since the electron–phonon interaction can be enhanced by the structure distortion, the small polaron formation is promoted in Yb_0.1Ca_0.9Mn_1?x Nb _x O₃ with increasing Nb content. In the whole measured temperature range, the electrical conductivity can be fitted very well by the adiabatic small polaron hopping model. The activated energy E _α is ascending with increasing Nb content. The temperature dependence of Seebeck coefficient S of Yb_0.1Ca_0.9Mn_1?x Nb _x O₃ shows that the S is basically inversive to the charge carrier concentration. S(T) can be fitted well by the Cutler and Mott model, which indicates that the density of state around the Fermi level is strongly affected by Nb-doping at B-site. It is contrary to those of CaMnO₃ and RE_0.1Ca_0.9MnO₃, when Nb content x>0.05, the |S| and σ show a same tendency of the temperature dependence.     

High-temperature impedance spectroscopy of BaFe0.5Nb0.5O3 ceramics doped with Bi0.5Na0.5TiO3

Bi_0.5Na_0.5TiO₃ (BNT)-doped BaFe_0.5Nb_0.5O₃ (BFN) ceramics were synthesized by a two-step solid-state reaction. Temperature dependence of dielectric properties measured at different frequencies was investigated over broad temperature and frequency ranges. Impedance spectroscopy and universal dielectric response were employed to study the relaxation behavior and conductivity mechanism of the ceramics in a frequency range from 40 Hz to 100 MHz and a temperature range from 300 K to 800 K. The complex plane impedance data revealed the bulk and grain boundary contributions toward conductivity processes in the form of semicircular arcs. The high-temperature conductivity of ceramics is attributable to thermally activated second ionized oxygen vacancy.