Effect of the la concentration on the dielectric and optical properties of the transparent ferroelectric ceramics 75PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-25PbTiO<Subscript>3</Subscript>

The dielectric, optical, and electro-optical properties of transparent ferroelectric ceramics 75PbMg_1/3Nb_2/3O₃-25PbTiO₃ (75PMN-25PT) with different La concentrations (2, 3, and 4 at %) have been studied. It has been shown that all the samples under study undergo a diffuse phase transition, and the degree of diffuseness increases with an increase in the La concentration. The temperature dependences of the optical transmission in different regimes of applying an electric field and the quadratic electro-optical effect have been investigated. It has been found that, at room temperature, the maximum electro-optical effect is observed in the ceramics with a La concentration of 3 at %. This is explained by the fact that the measurement temperature is close to the Vogel-Fulcher temperature at which the minimum electric field is required to induce ferroelectric states from the relaxor phase.     

Acoustic emission and thermal expansion of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> and Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> crystals

The temperature dependence of the elongation per unit length for Pb(Mg_1/3Nb_2/3)O₃ crystals unannealed after growth and mechanical treatment is investigated in the course of thermocycling. It is revealed that this dependence deviates from linear behavior at temperatures below 350°C. The observed deviation is characteristic of relaxors, is very small in the first cycle, increases with increasing number n of thermocycles, and reaches saturation at n≥3. In the first cycle, a narrow maximum of the acoustic emission activity is observed in the vicinity of 350°C. In the course of thermocycling, the intensity of this maximum decreases and becomes zero at n>3. For (1?x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ crystals, the dependence of the temperature of this acoustic emission maximum on x exhibits a minimum. It is assumed that the phenomena observed are associated with the phase strain hardening due to local phase transitions occurring in compositionally ordered and polar nanoregions.     

Peculiarities of the dielectric,elastic, and anelastic properties of the PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> ferroelectromagnet at the antiferromagnetic phase transition

Peculiarities in the behavior of the dielectric, elastic, and anelastic properties of the PbFe_1/2Nb_1/2O₃ ceramic ferroelectromagnet have been found and investigated near the antiferromagnetic phase transition (Néel temperature T _N = 160 K). It is established that the transition to the antiferromagnetic phase leads to a decrease in the permittivity and elastic compliance. The anomaly of permittivity found near T _N indicates the presence of magnetoelectric interaction in the magnetically ordered phase.     

Dielectric dispersion and magnetic properties of Ba-modified Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>

The polycrystalline samples of Ba-modified Pb(Fe_1/2Nb_1/2)O₃ (i.e., (Pb_1-xBa_x)(Fe_1/2Nb_1/2)O₃ PBFN, with x=0,0.05,0.07) were synthesized by a mechanosynthesis (i.e., high-energy ball milling) route followed by a mixed oxide method. Structural analysis provides the information on formation of single-phase orthorhombic structure on substitution of a small amount (x=0.07) of Ba at the Pb-site of Pb(Fe_0.50Nb_0.50)O₃ (PFN). The ferroelectric–paraelectric phase transition in PFN was observed at 383 K, which decreases on increasing Ba-concentration in PBFN. Detailed studies of dielectric properties of PBFW show the following: (i) diffuse phase transition, (ii) low loss tangent, (iii) low activation energy, and (iv) low frequency dielectric dispersion. An anomaly in the ac conductivity was found very close to phase transition temperature. The activation energy is found to decrease from 0.19 to 0.01 eV on increasing Ba-concentration to 7% (x=0.07). Temperature field-dependent magnetization measurements of all the samples showed antiferromagnetic transition at ∼15 K (for x=0.07). PBFN sample showed a slight increase in the coercivity (i.e., from 400 Oe (PFN) to 500 Oe (PBFN, for x=0.07) at 2 K. PACS 61.10.Nz; 68.37.Hk; 75.50.Ss; 75.60.Ej; 77.22.Ch; 77.22.Gm     

Statistical mechanics of cation ordering in PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

A model Hamiltonian for B cation ordering (Sc-Nb(Ta)) in PbSc_1/2Nb_1/2O₃ and PbSc_1/2Ta_1/2O₃ solid solutions is constructed. The parameters of the model Hamiltonian are determined from the ab initio calculation within the ionic crystal model with allowance made for the deformability and the dipole and quadrupole polarizabilities of the ions. The temperatures of the phase transition due to the ordering of the B cations are calculated by the Monte Carlo method in the mean-field and cluster approximations. The phase transition temperatures calculated by the Monte Carlo method (1920 K for PbSc_1/2Ta_1/2O₃ and 1810 K for PbSc_1/2Nb_1/2O₃) are consistent with the experimental data (1770 and 1450 K, respectively). The thermodynamic properties of the cation ordering are investigated using the Monte Carlo method.     

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.      

Ionic displacements and structure of disordered PbFe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript>

A sequence of structural models of unit cells of complex oxides with perovskite-type structure has been constructed to refine the average structure of PbFe_1/2Nb_1/2O₃ (PFN) at temperatures above the ferroelectric Curie point (T _C ～ 110°C). Owing to the analysis of the probability theory considerations, each model is characterized by only two positional fitting parameters. With the use of the intensities of 95 symmetrically independent X-ray reflections from a PFN single crystal at 160°C, a model with the R factor below 3% (K = 2.44%) was chosen. The ravine method has been used to verify the existence of a single minimum for the R factor with respect to the fitting parameter.     

Lattice dynamics and ferroelectric instability in ordered and disordered PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

The dynamic Born charges and the frequency spectra of lattice oscillations in the crystals of ordered and disordered PbSc_1/2Ta_1/2O₃ (PST) and PbSc_1/2Nb_1/2O₃ (PSN) solid solutions have been calculated within the framework of the generalized Gordon-Kim model with allowance for the dipole and quadrupole polarizabilities. The phonon spectra of both compounds contain ferroelectric soft modes. The influence of various interactions on the magnitude of dynamic charges and ferroelectric instability in PSN and PST solid solutions has been studied and it is shown that both these charges and the ferroelectric instability are determined by the competition between long-range dipole-dipole interactions and short-range dipole-charge interactions, the determining role played by the interaction of Nb (Ta) cations and oxygen anions in the Nb-O (Ta-O) bond direction.     

Study of ferroelectric phase transitions in disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> and PbSc<Subscript>1/2</Subscript>Ta<Subscript>1/2</Subscript>O<Subscript>3</Subscript> solid solutions

Ferroelectric phase transitions and thermodynamic properties of disordered PbSc_1/2Ta_1/2O₃ and PbSc_1/2Nb_1/2O₃ solid solutions have been investigated by the Monte Carlo method. The parameters of the effective Hamiltonian were calculated within the generalized Gordon-Kim model. The obtained values of the phase-transition temperatures and spontaneous polarization are in satisfactory agreement with the experimental data.     

Phase transition and electrical properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)(Nb<Subscript>1-x</Subscript>Ta<Subscript>x</Subscript>)O<Subscript>3</Subscript> lead-free piezoelectric ceramics

(K_0.5Na_0.5)(Nb_1-xTa_x)O₃ lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique. The results of X-ray diffraction reveal that Ta⁵⁺ diffuses into the K_0.5Na_0.5NbO₃ lattices to form a solid solution with an orthorhombic perovskite structure. Because of the high melting temperature of KTaO₃, the (K_0.5Na_0.5)(Nb_1-xTa_x)O₃ ceramics can be sintered at higher temperatures. The partial substitution of Ta⁵⁺ for the B-site ion Nb⁵⁺ decreases both paraelectric/cubic–ferroelectric/tetragonal and ferroelectric/tetragonal–ferroelectric/orthorhombic phase transition temperatures, T_C and T_O-T. It also induces a relaxor phase transition and weakens the ferroelectricity of the ceramics. The ceramics become ‘softened’, leading to improvements in d₃₃, k_p, k_t and ε_r and a decease in E_c, Q_m and N_p. The ceramics with x=0.075–0.15 become optimum, having d₃₃=127–151 pC/N, k_p=0.43–0.44, k_t=0.43–0.44, ε_r=541–712, tanδ=1.75–2.48% and T_C=378–329 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Electro-optical polarization mode dispersion in PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> single crystals

The polarization mode dispersion induced by an external ac electric field in PbMg_1/3Nb_2/3O₃ single crystals is studied experimentally at frequencies of 10⁴–10⁷ Hz. It is established that the discovered electro-optical polarization mode dispersion (EPMD) displays anomalous properties related to the orientation of the induced dipole moments in microregions of the crystal. Analytical expressions describing the peculiarities of the physical properties of relaxors giving rise to the EPMD are obtained.     

Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Heat capacity study of relaxor PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> in a wide temperature range

Heat capacity of the PbMg_1/3Nb_2/3O₃ compound is measured using the methods of adiabatic and differential scanning calorimetry in the temperature range 80–750 K. Two blurred anomalies on the C _p (T) dependence are observed in wide temperature intervals of 200–400 K and 500–700 K. The results of studies are discussed together with data on the structure and phonon spectrum in the framework of spherical random bond-random field model.     

Effect of Ba-substitution on the structure and properties of Pb<Subscript>0.8</Subscript>Ba<Subscript>0.2</Subscript>[(In<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>]O<Subscript>3</Subscript> ceramics

Ferroelectric ceramics with formula Pb_0.8Ba_0.2[(In_1/2Nb_1/2)_1-xTi_x]O₃ (PBINT) (x=0.0,0.1,0.2,0.3,0.4 and 0.5) were prepared via a two-step solid state reaction method. It was found that ceramics with compositions in the range of x=0.0∼0.3 showed a pseudo-cubic structure, whereas the ceramic with x=0.5 displayed a tetragonal structure. All compositions showed significant frequency dispersion in their dielectric properties. The remanent polarization P_r as well as the coercive field E_c, measured at room temperature, increases with the Ti content. The experimental results obtained in this system are summarized into a phase diagram, with the morphotropic phase boundary (MPB) located at x=0.4. Compared with the Pb[(In_1/2Nb_1/2)_1-xTi_x]O₃ solid solution system, incorporating Ba in the A-site leads to a significant decrease in the dielectric maximum temperature T_max, a suppression of the dielectric relaxation parameter γ, and a shift of the MPB composition to a higher Ti content. PACS 77.84.Dy; 77.80.Bh; 77.22.Ch     

Enhanced electrochemical properties and thermal stability of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by surface modification with Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>

Layered LiNi_1/3Co_1/3Mn_1/3O₂ cathode material is synthesized via a sol-gel method and subsequently surface-modified with Eu₂O₃ layer by a wet chemical process. The effect of Eu₂O₃ coating on the electrochemical performances and thermal stability of LiNi_1/3Co_1/3Mn_1/3O₂@Eu₂O₃ cells is investigated systematically by the charge/discharge testing, cyclic voltammograms, AC impedance spectroscopy, and DSC measurements, respectively. In comparison, the Eu₂O₃-coated sample demonstrates better electrochemical performances and thermal stability than that of the pristine one. After 100 cycles at 1C, the Eu₂O₃-coated LiNi_1/3Co_1/3Mn_1/3O₂ cathode demonstrates stable cyclability with capacity retention of 92.9 %, which is higher than that (75.5 %) of the pristine one in voltage range 3.0–4.6 V. Analysis from the electrochemical measurements reveals that the remarkably improved performances of the surface-modified composites are mainly ascribed to the presence of Eu₂O₃-coating layer, which could efficiently suppress the undesirable side reaction and increasing impedance, and enhance the structural stability of active material.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Synthesis and electrochemical properties of P2-Na<Subscript>2/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>2/3</Subscript>O<Subscript>2</Subscript>

The pure phase P2-Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g^?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g^?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na_2/3Ni_1/3Mn_2/3O₂ is a potential cathode material for sodium-ion batteries.     

Local structure of disordered PbSc<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>O<Subscript>3</Subscript> in the region of the diffuse tetragonal phase-rhombohedral phase transition

The local structure of the ferroelectric-relaxor PbSc_1/2Nb_1/2O₃ in the temperature range from 550 to 220 K has been investigated using ⁴⁵Sc nuclear magnetic resonance. It has been found that, in the paraelectric phase at temperatures below 550 K, the crystal consists of regions of an ordered elpasolite structure and inclusions of the disordered tetragonal perovskite phase with displacements along directions of the [001] type. The relative weight of the tetragonal structure in the region of the paraelectric phase is approximately equal to 0.28. Below the temperature of the phase transition from the disordered modification to the polar phase, the relative weight of the tetragonal phase decreases with decreasing temperature. The tetragonal structure is replaced by the trigonal polar structure. In a wide temperature range (∼50 K), there exists a heterophase structure that is characteristic of relaxors. Note that the correlation length of displacements in the tetragonal phase should be very small to explain the absence of indications of the existence of this phase in the diffraction data.