A diffuse phase transition study on Ba substituted (Na0.5Bi0.5)TiO3 ferroelectric ceramic

Polycrystalline perovskite lead free material (Na_0.5Bi_0.5)_0.91Ba_0.090TiO₃ was prepared by solid state reaction method. The crystal structure examined by X-ray powder diffraction indicates that the material was single phase with tetragonal structure. Dielectric studies exhibit a diffuse phase transition and characterized by a strong temperature and frequency dispersion of permittivity which relates cation disorder at A-site and exhibits relaxor behaviour. The dielectric relaxation has been modeled using the Vogel-Fulcher relationship, the calculated activation energy found to be E_a = 0.021 eV. Complex impedance analysis indicates the system undergoing a polydispersive non-Debye type relaxation. Also, used to characterize grain and grain-boundary resistivities of Ba substituted (Na_0.5Bi_0.5)TiO₃ ceramic. The phenomenon was also interpreted by accounting for microstructural differences. The corresponding relaxation times were also used to confirm the interpretation of complex impedance spectra. Overlapping of grain boundary and electrode relaxation processes can be separated above about 4000 C. Electrical modulus spectroscopy studies have been performed. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K¹) have been calculated using Almond and West formalism.     

Electrical conduction and dielectric relaxation process in Ce0.8Y0.2O1.9 electrolyte system

In this work, we present the electrical conductivity and dielectric relaxation studies of 20 mol% yttria doped ceria (Ce_0.8Y_0.2O_1.9) electrolyte prepared by mechanical milling technique. The ac conductivity was found to obey the universal dielectric response at low temperatures. At high temperatures, the conductivity value estimated from the high frequency plateau agreed with the bulk conductivity (σ_b) obtained form the impedance spectra and the low frequency plateau value agreed with the grain boundary conductivity (σ_gb). Temperature dependence of σ_b and σ_gb gives the activation energies for conduction in the bulk and grain boundary. Two relaxation peaks were observed in the tan delta spectra; the high frequency relaxation peak is due to the bulk conduction and the low frequency peak result from the grain boundary conduction. The migration energy E_M and the energy required for the creation of free oxygen vacancies assisting oxide ion migration E_O is estimated from the resonant frequency and maxima of the tan delta spectra of these relaxation peaks. The sums of these two values in the low and high frequency peaks are nearly equal to the activation energies obtained from the bulk and grain boundary conductivity plot.     

Microstructures and electrical responses of pure and chromium-doped CaCu3Ti4O12 ceramics

Pure and chromium-doped CCTO (CaCu₃Ti₄O₁₂) ceramics were prepared by a conventional solid-state reaction method, and the effects of chromium doping on the microstructures and electrical properties of these ceramics were investigated. Efficient crystalline phase formation accompanied by dopant-induced lattice constant expansion was confirmed through X-ray diffraction studies. Scanning electron microscopy (SEM) results show that doping effectively enhanced grain growth or densification, which should increase the complex permittivity. The dielectric constant reached a value as high as 20,000 (at 1 kHz) at a chromium-doping concentration of 3%. The electrical relaxation and dc conductivity of the pure and chromium-doped CCTO ceramics were measured in the 300-500 K temperature range, and the electrical data were analyzed in the framework of the dielectric as well as the electric modulus formalisms. The obtained activation energy associated with the electrical relaxation, determined from the electric modulus spectra, was 0.50-0.60 eV, which was very close to the value of the activation energy for dc conductivity (0.50 ± 0.05 eV). These results suggest that the movement of oxygen vacancies at the grain boundaries is responsible for both the conduction and relaxation processes. The short-range hopping of oxygen vacancies as “polarons” is similar to the reorientation of the dipole and leads to dielectric relaxation. The proposed explanation of the electric properties of pure and chromium-doped CCTO ceramics is supported by the data from the impedance spectrum.     

Impedance and electric modulus analysis of Sm-modified Pb(Zr0.55Ti0.45)1−x/4O3 ceramics

The polycrystalline ceramic samples of Pb_1−xSm_x(Zr_0.55Ti_0.45)_1−x/4O₃ (x = 0.00, 0.03, 0.06 and 0.09) were prepared by solid-state reaction technique at high temperature. Electric impedance (Z) and modulus (M) properties of the materials have been investigated within a wide range of temperature and frequency using complex impedance spectroscopy (CIS) technique. The complex impedance analysis has suggested the presence of mostly bulk resistive (grain) contributions in the materials. This bulk resistance is found to decrease with the increase in temperature. It indicates that the PSZT compounds exhibit a typical negative temperature coefficient of resistance (NTCR) behavior. The bulk contribution also exhibits an increasing trend with the increase in Sm³⁺ substitution to PZT. The complex modulus plots have confirmed the presence of grain (bulk) as well as grain boundary contributions in the materials. Both the complex impedance and modulus studies have suggested the presence of non-Debye type of relaxation in the materials.     

Origin of giant dielectric constant in Ba[(Fe1−xCox)1/2Nb1/2]O3

The X-ray diffraction Rietveld refinement of Ba[(Fe_1−xCo_x)_1/2Nb_1/2]O₃ with 0 ≤ X ≤ 1 shows cubic structure formation with space group P_m3_m. No distinct tilting of oxygen octahedron is observed. The dielectric measurement of such a cubic system exhibited giant values (?′ > 10⁴) in the temperature range of 298-483 K and frequency range of 10²-10⁵ Hz. An analysis of the permittivity, electric modulus, and electrical conductivity properties in these systems confirmed the presence of oxygen vacancies induced dipolar relaxation. Our investigations show that the observed extremely high dielectric constant values are predominantly the result of oxygen vacancies induced dipoles produced at the grain boundaries. Additional significant intrinsic contributions to the permittivity comes from the directly doped electrons at the unit cell, as indicated by the enhancement in the observed values of the permittivity on replacement of Fe³⁺ (3d⁵) by Co³⁺ (3d⁶). The contributions of the doped free charges and the oxygen vacancy induced dipoles are separated using the Jump Relaxation Model.     

Ferroelectric relaxor behavior and dielectric spectroscopic study of 0.99(Bi0.5Na0.5TiO3)-0.01(SrNb2O6) solid solution

0.99(Bi_0.5Na_0.5TiO₃)-0.01(SrNb₂O₆) was prepared by simple solid state reaction route. Material stabilized in rhombohedral perovskite phase with lattice constants a = 3.9060 Å, α = 89.86° and a_h = 5.4852 Å, c_h = 6.7335 Å for hexagonal unit cells. Density of material was found 5.52 g_m/cm³ (92.9% of theoretical one) in the sample sintered at 950 °C. The temperature dependent dielectric constant exhibits a broad peak at 538 K (?_m = 2270) at 1 kHz that shows frequency dependent shifts toward higher temperature - typical relaxor behavior. Modified Curie-Weiss law was used to fit the dielectric data that exhibits almost complete diffuse phase transition characteristics. The dielectric relaxation obeys the Vogel-Fulcher relationship with the freezing temperature 412.4 K. Significant dielectric dispersion is observed in low frequency regime in both components of dielectric response and a small dielectric relaxation peak is observed. Cole-Cole plots indicate polydispersive nature of the dielectric relaxation; the relaxation distribution increases with increase in temperature.     

Complex impedance analysis of (Y2O3 + CeO2)-YCr0.5Mn0.5O3 composite NTC ceramics

Ceramic compositions based on (aY₂O₃ + bCeO₂)-0.4YCr_0.5Mn_0.5O₃ (a + b = 0.6) were prepared by conventional solid state reaction at 1200 °C, and sintered under air atmosphere at 1600 °C. For 0 ≤ a < 0.6, XRD patterns have shown that the major phases presented in the calcined powders are Y₂O₃, CeO₂ and orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase, respectively. SEM and EDAX observations confirm the YCr_0.5Mn_0.5O₃ phases mostly exist at the grain, whereas the Y₂O₃ and CeO₂ phases mainly exist at the grain boundaries. Complex impedance analysis shows that, for 0 < a ≤ 0.6, single semicircular arc whose shape does not show any change with temperature. Nevertheless, for a = 0, two overlapping semicircular arcs are observed at and above 300 °C. The grain boundary properties exhibit thermistor parameters with a negative temperature coefficient characteristic. The relaxation behavior and conduction for the grain boundary could be due to a space-charge relaxation mechanism and oxygen vacancies, respectively.     

Enhanced magnetoelectric properties in Bi0.95Ho0.05FeO3 polycrystalline ceramics

Polycrystalline samples of Ho doped BiFeO₃ were prepared by solid state reaction method and effect of partial substitution of Ho on dielectric, magnetic and ferroelectric properties was studied. High temperature dielectric results show two dielectric anomalies both in ? and tan δ, out of which, anomaly at higher temperature (∼400 °C) could be ascribed to antiferromagnetic Néel temperature which, is a signature of magnetoelectric coupling. The magnetic moment is greatly improved and the maximum magnetization was found to be 0.736 emu/g. Saturated ferroelectric hysteresis loops were observed for Bi_0.95Ho_0.05FeO₃ with remnant polarization (P_r) = 1.59 μC/cm², maximum polarization (P_max) = 2.56 μC/cm² and coercivity (E_c) = 5.45 kV/cm. We have conducted comprehensive magnetoelectric and magnetodielectric properties at room temperature. Magnetic field induced ferroelectric hysteresis loop observed in Bi_0.95Ho_0.05FeO₃ is of prime importance.     

Dielectric properties of Cu substituted Ni0.5−xZn0.3Mg0.2Fe2O4 ferrites

Dielectric properties of Cu substituted Ni-Zn-Mg ferrite samples having the general formula Ni_0.5−xCu_xZn_0.3Mg_0.2Fe₂O₄ (where x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) synthesized by Pramanik method are reported. The single phase formation of the ferrites was confirmed by XRD technique. The lattice parameter is found to increase with increase in Cu content. Average grain size, obtained from SEM micrographs, is found to increase with increase in Cu content. Dielectric parameters were measured as a function of frequency at room temperature as well as at higher temperatures. The variation in dielectric constant (?′) with temperature at four different fixed frequencies viz. 1 kHz, 10 kHz, 100 kHz, and 1 MHz was also studied. The room temperature dielectric constant (?′) and dielectric loss (tan δ) are found to decrease with increase in frequency. The ac conductivity (σ_ac) is found to increase with increase in the frequency.     

Dielectric relaxation, conductivity behaviour and magnetic properties of Mg substituted Ni-Li ferrites

The dielectric properties of Mg substituted Ni-Li spinel ferrites synthesized by sol-gel auto combustion process have been studied using impedance measurements in the frequency range from 10 Hz to 10 MHz and in the temperature range from 310 K to 473 K. The effect of frequency, temperature and composition on dielectric constant (?′), dielectric loss (tan δ) and conductivity (σ) has been discussed in terms of hopping of charge carriers between Fe²⁺ and Fe³⁺ ions. The electrical modulus formulism has been employed to study the relaxation dynamics of charge carriers and the results indicate the presence of non-Debye type of relaxation in the present ferrites. Similar values of activation energies for dc conduction (E_dc) and for conductivity relaxation (E_M″) reveal that the mechanisms of electrical conduction and dielectric polarization are same in these ferrites. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of dynamical process for charge carriers. The saturation magnetization and coercivity have been calculated from the hysteresis loop measurements and show striking dependence on the composition.     

Synergistic microwave and structural studies of C-type Ho2Si2O7

Ho₂Si₂O₇ material exists in four polymorphs, a triclinic low temperature phase (type-B), a monoclinic modification (type-C), high temperature monoclinic (type-D), and high temperature orthorhombic modification (type-E). The structural properties are measured by XRD and the morphology is noted through scanning electron microscopy (SEM). The dc electrical resistivity (ρ) as a function of temperature and dielectric properties of C-type Ho₂Si₂O₇ in the microwave region is measured. The activation energy is calculated from ln ρ versus 1/k_BT plot. The activation energy is 0.119 ± 0.001 eV. Both the real (?′) and imaginary parts of permittivity (?″) decrease slightly as the frequency increases up to 1.5 GHz, after that ?′ increases while ?″ decreases as the frequency increases. At around 2.45 GHz, resonance is observed.     

Dielectric and magnetic behavior of BaCd2−xSrxFe16O27 W-type hexagonal ferrites

We have prepared BaCd_2−xSr_xFe₁₆O₂₇ (x = 0, 0.5, 1, 1.5 and 2.0) W-type hexagonal ferrites by standard ceramic method. In this work, the structural, dielectric and magnetic properties have been studied of the prepared samples. The XRD analysis of the samples reveals single phase behavior sintered at 1400 °C for 6 h. The saturation magnetization (M_s) shows increasing behavior with the increasing concentration of Sr²⁺. While the coercivity (H_c) decreases rapidly up to 409 G for x = 1.5 and then increases for (x > 1.5) due to the preference of Cd²⁺ for tetrahedral sites and the number of spin-down magnetic ions. The real and imaginary parts of the dielectric constant (?′,?″) and dielectric loss tangent (tan δ) are determined in the frequency range 0.1-10⁷ Hz. It is observed that both the real and imaginary parts of the dielectric constant and tan δ decrease with the increasing concentration of Sr²⁺, which is due to the contribution of Cd²⁺ ions in addition to Fe³⁺ and Fe²⁺ ions to interfacial polarization.     

Nanocrystals of a new complex perovskite dielectric Ba2TmSbO6

Nanocrystals of a new complex perovskites ceramic oxide, barium thulium antimony oxide - Ba₂TmSbO₆, were synthesized using a single step auto-ignition combustion process. The combustion product was single phase and composed of aggregates of nanocrystals of sizes in the range 20-50 nm. Ba₂TmSbO₆ crystallized in cubic perovskite structure with lattice parameter, a = 8.4101 Å. The polycrystalline fluffy combustion product was sintered to high density (∼97%) at ∼1450 °C for 4 h. Resistivity of the sintered specimen was ∼5 MΩ/cm. The Ba₂TmSbO₆ has dielectric constant (?′) and dielectric loss (tan δ) of 17 and ∼10⁻⁴ at 5 MHz; the new material would probably be developed as a low-loss dielectric material.     

Synthesis, characterization and electrical properties of CdI2 doped Al2O3 and TiO2 superionic conductors

Superionic conductors were prepared by admixing metallic oxides (alumina and titania) with cadmium iodide in different proportions using direct mixing method. The synthesized materials were characterized by various qualitative techniques such as XRD (X-ray diffraction), DSC (differential scanning calorimetry) and SEM (scanning electron microscopy). Pure CdI₂ shows the standard pattern which corresponds to β-phase stable at room temperature, however, the diffractograms of the mixtures shows two phase nature of the materials with no effect of the second phase on the peak positions of the first, i.e. CdI₂. DSC curves also confirmed the formation of composite. SEM micrographs show the presence of great number of space charge regions which are very important in creating a great number of surfaces which in turn act as additional sources of point defects. It was also found that the conductivity of CdI₂ increases with mole fractions of dopants till x = 0.5 for alumina and x = 0.3 for titania. Arrhenius equation was used to study the temperature dependence of electrical conductivity and the activation energy of pure cadmium iodide was found to be 0.792 eV.     

Study of structural, dielectric and electrical behavior of (1 − x)Ba(Fe0.5Nb0.5)O3-xSrTiO3 ceramics

Polycrystalline samples of BaFe_0.5Nb_0.5O₃ and (1 − x)Ba(Fe_0.5Nb_0.5)O₃-xSrTiO₃ [referred as BFN and BFN-ST respectively] (x = 0.00, 0.15 and 0.20) have been synthesized by a high-temperature solid-state reaction technique. The XRD patterns of the BFN and BFN-ST at room temperature show a monoclinic phase. The microstructure of the ceramics was examined by the scanning electron microscopy (SEM) and shows the polycrystalline nature of the samples with different grain sizes, which are inhomogeneously distributed through the sample surface. Detailed studies of dielectric and impedance properties of the materials in a wide range of frequency (100 Hz-5 MHz) and temperatures (30-270 °C) showed that properties are strongly temperature and frequency dependent. Complex Argand plane plot of ?″ against ?′, usually called Cole-Cole plots is used to check the polydispersive nature of relaxation phenomena in above mentioned compounds. Relaxation phenomena of non-Debye type have been observed in the BFN and BFN-ST ceramics, as confirmed by the Cole-Cole plots.     

Impedance spectroscopy and dielectric properties of Ce and La substituted Pb0.7Sr0.3(Fe0.012Ti0.988)O3 nanoparticles

We present the structural, microstructural, dielectric and impedance behavior of Pb_0.7Sr_0.3[(Fe_2/3Ce_1/3)_0.012Ti_0.988]O₃ (PSFCT) and Pb_0.7Sr_0.3[(Fe_2/3La_1/3)_0.012Ti_0.988]O₃ (PSFLT) nanoparticles. These nanoparticles were prepared by a chemical synthesis route using polyvinyl alcohol as surfactant. The X-ray diffraction pattern shows polycrystalline nature with coexistence of tetragonal and cubic phase in both PSFCT and PSFLT nanoparticles. The average particle size has been measured using Scherer's relation. The average particle sizes also measured by TEM are 10 and 11 nm, and by SEM 9 and 12 nm, respectively, of PSFCT and PSFLT nanoparticles. By measuring the value of relative permittivity (?′) and loss (tan δ) at lower frequency, the dielectric properties show Maxwell-Wagner type interfacial polarization. However, due to nano size effect of PSFCT and PSFLT, dispersionless dielectric response has been observed up to higher frequency of 15 MHz. The frequency dependent real (Z′) and imaginary (Z″) parts of impedance confirmed the variation which was observed in dielectric properties. The values of resistance of grain boundaries, R_gb is higher than grains, R_g indicates that the effect of grain boundaries is dominant on electrical properties when the size of nanoparticles is quite small.     

Structure and electrical properties of MnO2-doped Sr2−xCaxNaNb5O15 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics Sr_2−xCa_xNaNb₅O₁₅ + y wt% MnO₂have been prepared by the conventional solid state reaction method. Our results reveal that Ca²⁺and Mn ions have entered into the Sr₂NaNb₅O₁₅ lattices to form a solid solution with tungsten-bronze structure. The substitution of Ca²⁺ induces a decrease in piezoelectric coefficient d₃₃, electromechanical coupling factors k_p and k_t, while, the addition of Mn ions decreases the sintering temperature and effectively promotes the densification of the ceramics. The effect of substitution of Ca²⁺and Mn ions on the structure, electrical properties and diffused phase changing were investigated systematically. For the ceramic with x = 0.05 and y = 0.5, the piezoelectric, dielectric and ferroelectric properties become optimum, giving a piezoelectric coefficient d₃₃ = 190 pC/N, electromechanical coupling factors k_p = 13.4% and k_t = 36.5%, ?_r = 2123, loss tangent tan δ = 0.038, remanent polarization P_r = 4.76 μC/cm², coercive field E_c = 12.68 kV/cm, and Curie temperature T_c = 260 °C.     

Dielectric and microwave properties of ZrO2 doped CaO-SiO2-B2O3 ceramic matrix composites

The behavior of dielectric and microwave properties against sintering temperature has been carried out on CaO-SiO₂-B₂O₃ ceramic matrix composites with ZrO₂ addition. The results indicated that ZrO₂ addition was advantageous to improve the dielectric and microwave properties. X-ray diffraction (XRD) patterns show that the major crystalline β-CaSiO₃ and a little SiO₂ phase existed at the temperature ranging from 950 °C to 1050 °C. At 0.5 wt% ZrO₂, CaO-SiO₂-B₂O₃ ceramic matrix composites sintered at 1000 °C possess good dielectric properties: ?_r = 5.85, tan δ = 1.59 × 10⁻⁴ (1 MHz) and excellent microwave properties: ?_r = 5.52, Q · f = 28,487 GHz (11.11 GHz). The permittivity of Zr-doped CaO-SiO₂-B₂O₃ ceramic matrix composites exhibited very little temperature dependence, which was less than ±2% over the temperature range of −50 to 150 °C. Moreover, the ZrO₂-doped CaO-SiO₂-B₂O₃ ceramic matrix composites have low permittivity below 5.5 over a wide frequency range from 20 Hz to 1 MHz.     

Mg-substituted ZnNb2O6-TiO2 composite ceramics for RF/microwaves ceramic capacitors

Microstructure and microwave dielectric properties of Mg-substituted ZnNb₂O₆-TiO₂ microwave ceramics were investigated. Mg acted as a grain refining reagent and columbite phase stabilization reagent. With an increasing Mg content, the amount of ixiolite (Zn, Mg) TiNb₂O₈ decreased, and the amount of (Zn_0.9Mg_0.1)_0.17Nb_0.33Ti_0.5O₂ and columbite increased. ZnO-Nb₂O₅-1.75TiO₂-5 mol.%MgO exhibited excellent dielectric properties (at 950 °C): ?_r = 35.6, Q × f = 16,000 GHz (at 5.6 GHz) and τ_f = −10 ppm/°C. The material was applied successfully to make RF/microwaves ceramic capacitor, whose self-resonance frequency was 19 GHz at low capacitance of 0.13 pF.     

Piezoelectric and dielectric properties of Dy2O3-doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ + x wt% Dy₂O₃ with x = 0-0.3 ceramics were synthesized by conventional solid-state processes. The effects of Dy₂O₃ on the microstructure, the piezoelectric and dielectric properties were investigated. X-ray diffraction pattern confirmed that the coexistence of tetragonal and rhombohedral phases in the (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ composition was not changed by adding 0.05-0.3 wt% Dy₂O₃. SEM images indicate that all the ceramics have pore-free microstructures with high density, and that doping of Dy₂O₃ inhibits the grain growth of the ceramics. The addition of Dy₂O₃ shows the double effects on decreasing the piezoelectric and dielectric properties for 0 < x < 0.15 when Dy³⁺ ions substitute B-site Ti⁴⁺ ions, and increasing the properties for 0.15 < x < 0.3 when Dy³⁺ ions enters into A-site of the perovskite structure. The optimum electric properties of piezoelectric constant d₃₃ = 170 pC/N and the dielectric constant ?_r = 1900 (at a frequency of 1 kHz) are obtained at x = 0.3.