Complex impedance studies of low temperature synthesized fine grain PZT/CeO2 nanocomposites

Fine grain nanocomposites of (100 ? x) PbZr_0.52Ti_0.48O₃ ? (x) CeO₂ with x = 0.5, 1 and 2 wt%, were prepared and characterized for structural and microstructural changes. Addition of ceria nanoparticles resulted into a fine grain microstructure with average grain size ranging from 600 nm to 440 nm and a significant decrease in sintering temperature (～200 °C). Size distribution profile, as analyzed by lognormal distribution function suggests a very narrow size distribution. X-ray diffraction analyses of sintered samples reveal that fine grain PZT/CeO₂ nanocomposite could retain distorted tetragonal structure even with grain size as low as 440 nm. Further, complex impedance spectroscopy studies were performed to illustrate the electrical properties of bulk and grain boundary phases in fine grain ceramics. Two electrical processes in the impedance spectra at temperatures above 350 °C were attributed to bulk and grain boundary phase. Magnitude of grain boundary capacitance and corresponding transition was found to be strongly dependent on grain size of the system. Both bulk and grain boundary relaxation processes follows Arrhenius law.     

Transport properties of BaCe0.85Y0.15O3−δ at closed-cycle refrigerator temperature

The electrical conducting properties of both hydrated and dehydrated BaCe_0.85Y_0.15O_3?δ (barium cerate, BCY) were investigated at low temperature (473–203 K) by an AC impedance analyzer combined with a dielectric interface. For the BCY, the bulk and grain boundary conductivities were separated with the equivalent circuit model, and the bulk conductivity was approximately two orders of magnitude higher than the grain boundary conductivity. At very low temperature (203 K), a single semicircle was obtained in the impedance plot, whereas three distinct semicircles were plotted in modulus plot due to the three different resistance components in the system. The activation energy of bulk conductivity was 0.55 eV and 0.57 eV for the hydrated and dehydrated BCY samples, respectively.     

Electrical conductivity of Ca-substituted lanthanum manganites

The physico-chemical properties of substituted perovskites materials have been analyzed with the aim of studying the relationships between structure and properties in this class of materials. Investigations were carried out into the effect of substitution in lanthanum manganites La_1–xCa_xMnO₃ (x = 0; 0.05; 0.1; 0.15) materials obtained through sol-gel method followed by heat treatment at low temperatures and X-ray diffraction, into the surface area thereof, as well as into transmission electron microscopy for purposes of morpho-structural characterization. The results indicated a well-crystallized Pm-3m perovskite-type structure, and 20 nm average crystallite sizes for all samples. By means of complex impedance measurements in the 20 Hz–2 MHz frequency range, the electrical conductivity was determined at temperatures between 30 °C and 120 °C; the results showed that the conductivity obeys a Jonscher's universal law. It was found that below 10 kHz, the dc component of the conductivity increases with temperature for all samples, indicating that electrical conduction processes are activated thermally, in agreement with Mott's variable-range hopping (VRH) model; the model parameters (hopping distance and hopping energy) were also determined. In the high frequency range (f > 200 kHz) the ac conductivity is attributed to charge carriers hopping between the nearest neighboring states, in agreement with the correlated barrier hopping (CBH) model. Using this model, the energy band gap values: 0.364 eV, 0.372 eV and 0.424 eV of the substituted samples were found.     

Dielectric behavior and impedance spectroscopy in lead-free BNT–BT–NBN perovskite ceramics for energy storage

The dielectric behavior, impedance spectroscopy and energy-storage properties of 0.85[(1−x)Bi_0.5Na_0.5TiO₃–xBaTiO₃]–0.15Na_0.73Bi_0.09NbO₃ [(BNT–xBT)–NBN] ternary ceramics were investigated. Temperature dependent permittivity curves displayed two depressed anomalies, resulting in significantly improved dielectric temperature stability. (BNT–9BT)–NBN showed a permittivity of 1680 at 150 °C with Δε/ε_150 °C varying no more than ±10% up to 340 °C. From the complex impedance analysis, grain and grain boundary shared the same time constant. The high temperature resistivity followed the Arrhenius law with E_a=1.7–2.0 eV, suggesting intrinsic band-type electronic conduction. The maximum energy-storage density of all the samples reached 1.1–1.4 J/cm³, accompanied with good temperature stability in the range of 25–140 °C. These results indicate that (BNT–xBT)–NBN system should be a promising lead-free material for energy-storage capacitor applications.     

Synthesis and characterization of Bi1.5Zn0.92Nb1.5−xSnxO6.92−x/2 pyrochlore ceramics

The morphological, compositional, structural, dielectric and electrical properties of Bi_1.5Zn_0.92Nb_1.5?xSn_xO_6.92?x/2 ceramics have been investigated by means of scanning electron microscopy (SEM), X-ray energy dispersion spectroscopy (EDS), X-ray diffraction (XRD), temperature and frequency dependent dielectric constant and temperature dependent conductivity measurements for Sn-contents in the range of 0.00 ≤ x ≤ 0.60. It was shown that single phase of the pyrochlore ceramics can only be obtained for x ≤ 0.25. Above this value a ZnO phase appeared in the XRD patterns and SEM micrographs as well. An increase in the lattice constant and in the temperature coefficient of dielectric constant and a decrease in the dielectric constant values with increasing Sn content was observed for the ceramics which exhibited a single phase formation. A temperature dependent but frequency invariant dielectric constant was observed for this type of ceramics. The lowest electrical conductivity and highest dielectric constant was observed for the sample which contains 0.06 Sn. The Bi_1.5Zn_0.92Nb_1.5?xSn_xO_6.92?x/2 pyrochlore ceramic conductivities are thermally active above 395 K. For temperatures greater than 395 K, the conductivity activation energy which was found to be 0.415 eV for the pure sample increased to 1.371 eV when sample was doped with 0.06 Sn.     

Electrical relaxation and conduction mechanisms in iron doped barium strontium titanate

Polycrystalline Ba_0.7Sr_0.3Ti_(1?x)Fe_xO₃ (x = 0.1) (BSTF) ceramics, synthesized via solid-state reaction route were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and complex impedance spectroscopy (CIS). The Rietveld refinement of the XRD data confirmed the presence of tetragonal and cubic phases in the prepared sample. The SEM image revealed that the sample has well distributed grains along with some degree of agglomerations. The electrical behaviour of the BSTF ceramic has been studied by complex impedance spectroscopy (CIS) as a function of frequency (1 Hz to 1 MHz) at different temperatures (RT to 700 K). Two semicircular arcs observed in the Cole-Cole plot confirm the contribution from the grain and grain boundary in overall impedance. Both the electrical as well as ac conduction phenomena take place via correlated barrier hopping (CBH) authenticated by detailed complex modulus analysis and ac fitted conductivity respectively. The values of activation energies calculated from electrical impedance, modulus, and conductivity data clearly reveal that the relaxation and conduction processes in BSTF ceramic are induced by doubly ionized oxygen vacancies.     

Structural and electrical properties of Dy3+ substituted NiFe2O4 ceramics prepared from powders derived by combustion method

Dysprosium (Dy) substituted nickel ferrite (NiDy_xFe_2-xO₄) powders with varying Dy content (x=0.0, 0.025, 0.05, 0.075, 0.1, 0.2) have been prepared by combustion method using DL-alanine fuel. Sintering characteristics of the powders and electrical properties of ceramics have been studied. Effective substitution of Dy³⁺ for Fe³⁺ is seen up to x=0.075 yielding improved properties, and a higher Dy content (x≥0.1) leads to partial substitution, disturbed stoichiometry, and diffusion of Dy to the grain boundaries and segregation as a secondary phase. Increasing Dy content reduces the crystallite size, powder particle size, and grain size in sintered ceramics, and the changing microstructural evolution is better resolved with back scattered electron imaging and compositional analysis. Raman spectroscopy confirms inverse spinel structure formation and substantiates the presence of secondary phase evidenced through X-ray diffraction and electron microscopy. A marginal increase in the electrical resistivity (ρ_dc) and magnetization are observed due to effectual substitution of Dy³⁺ for Fe³⁺ at the octahedral sites up to x=0.075. For x≥0.1, the increasing influence of highly resistive DyFeO₃ secondary phase at the inter-granular boundaries leads to a rapid increase in resistivity and reduction in dielectric losses, and the magnetization is reduced due to the anti-ferromagnetic nature of the secondary phase (DyFeO₃). Dense ceramics with high resistivity (~10⁹ Ω cm), low dielectric loss (tan δ ~0.002) at 1 MHz, and high magnetization (50.07 emu/g) are obtained for an optimum Dy content of x=0.075. Dielectric response, complex impedance, and electrical modulus spectroscopy in the frequency range (10⁻²–10⁶ Hz) reflect the changes in the microstructure, and suggests a non-Debye type relaxation.     

Role of spin-glass phase for magnetoresistance enhancement in nickel substituted lanthanum calcium manganite

Effect of Ni substitution in lanthanum calcium manganite (LCMO) has been investigated for change in magnetoresistance (MR). Scanning electron microscopy images revealed decrease in grain size from 3.72 µm to 0.55 µm by Ni substitution. Maximum increase in MR has been found 28% at low temperature (100 K) for x=0.10, Ni substitution at Mn site. Metal insulator transition temperature has been decreased from 253.2 K for x=0.0–90 K for x=0.10. Above x=0.10, Ni substitution no metal-insulator transition temperature appeared due to the presence of porosity in the samples. Ni substitution lowered the magnetic transition temperature from 255 K for x=0.0–125 K for x=0.25. Lowering of irreversible temperature (T_irr) from 250 K for x=0.0–135.4 K for x=0.20 has been obtained by zero field cooled (ZFC) and field cooled (FC) measurements confirm reduction of ferromagnetic clusters and spin-glass phase like behavior due to Ni presence. The spin-glass phase presence allows spin-polarized tunneling even at low magnetic field, which ultimately results in enhancement of MR at low temperature. Core level X-ray photoelectron spectroscopy measurements confirm Ni²⁺ charge state of Ni ions and increase in Mn⁴⁺/Mn³⁺ ratio with increasing Ni content. Increase in resistivity and weakening of ferromagnetism with Ni substitution at Mn site has been observed due to the reduction in grain size and dilution of double exchange interaction.     

Synthesis and thermoelectric performance of Li-doped NiO ceramics

Ni_1?xLi_xO (x = 0, 0.03, 0.06, 0.09) powders were prepared by sol–gel method combined with sintering procedure using Ni(CH₃COO)₂·4H₂O and citric acid as the raw materials and alcohol as solvent. The crystal structures of the samples were investigated by X-ray diffraction and Raman spectroscopy. The thermoelectric properties, such as the electrical conductivity, the Seebeck coefficient and the thermal conductivity were measured. The results showed that all the samples are p-type semiconductors. The electrical conductivity increases with the increase of the temperature, which indicates that the substitution of Li⁺ for Ni²⁺ can increase the concentrations and mobility of the carriers. The thermal conductivity decreases remarkably with the increase of the Li doping content, which indicates that Li doping can enhance the scattering of phonon. However, the Seebeck coefficient will decline with the increase of the Li doping content. As results of the increase of electrical conductivity and reduction of thermal conductivity, Li doping can increase the figure of merit (ZT) of NiO, the ZT value reach 0.049 at 770 K for Ni_1?xLi_xO with x = 0.06.     

Preparation and tunability properties of Ba(ZrxTi1−x)O3 thin films grown by a sol–gel process

Ba(Zr_xTi_1−x)O₃ (BZT) thin films were deposited via sol–gel process on LaNiO₃, as buffer layer, and Pt-coated silicon substrates. The BZT films were perovskite phase and showed a (1 0 0) preferred orientation dependent upon zirconium content. The grain size decreased and the microstructure became dense with increasing zirconium content. The addition of Zr to the BaTiO₃ lattice decreased the grain size of the crystallized films. The temperature dependent dielectric constant revealed that the thin films have relaxor behavior and diffuse phase transition characteristics that depend on the substitution of Zr for Ti in BaTiO₃. The dependence of electrical properties on film thickness has been studied, with the emphasis placed on dielectric nonlinear characteristics. Ba(Zr_0.35Ti₆₅)O₃ thin films with weak temperature dependence of tunability in the temperature range from 0 to 130 °C could be attractive materials for situations in which precise control of temperature would be either impossible or too expensive.     

Structural,electrical, and magnetic properties of Zn substituted magnesium ferrite

Zinc substituted magnesium (Mg–Zn) ferrites with the general formula Mg_1−xZn_xFe₂O₄ (x=0.00, 0.25, 0.50, 0.75, and 1.00) were prepared using the solution combustion route. The dried powder after calcination (700 °C for 2 h) was compacted and sintered at 1050 °C for 3 h. The structural, morphological, dielectric and magnetic properties of the sintered ferrites were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), impedance spectroscopy, and vibration sample magnetometry (VSM). The XRD analysis of sintered samples confirmed that the expected spinel cubic phase was formed for all samples. The crystallite sizes evaluated using Scherre's formula were found to be in the range of 47–80 nm. SEM analysis showed homogeneous grains with a polyhedral structure. The electrical conductivity increased with increasing frequency, which is normal dielectric behavior for such materials. The dielectric constant, dielectric loss tangent, and AC conductivity were found to be lowest for x=0.50. The VSM results showed that the zinc concentration had a significant influence on the saturation magnetization and coercivity.     

Study of electrical transport properties of Eu+3substituted MnZn-ferrites synthesized by co-precipitation technique

Eu substituted MnZn-ferrites with nominal composition Mn_0.78Zn_0.22Eu_x Fe_(2?x)O₄ (x=0.0, 0.02, 0.04, 0.06, 0.08 and 0.10) were prepared by co-precipitation technique. The effect of Europium substitution on electrical transport properties of Mn–Zn ferrites is reported. XRD analysis reveals fcc phase in all the samples along with few traces of second phase. The lattice constant shows decreasing trend with the substitution of Eu due to partial solubility of Eu-ions in the lattice. Room temperature resistivity both at 10 and 20 V shows on average an increasing trend. This increase in resistivity is attributed to the unavailability of Fe⁺³ ions in the lattice due to Eu-substitution. The dc resistivity decreases with temperature for all the samples at 10 V and 20 V indicating the semiconducting behavior of these samples. Room temperature dc resistivity and activation energies show similar trend both at 10 V and 20 V indicating that the samples with high resistivity have high activation energies and vice versa. The dielectric constant (ε′), complex dielectric constant (ε″) and loss tangent of these samples decreased with the increase of Eu-concentration, following the Maxwell–Weigner model.     

Processing and enhanced electrical properties of Sr1-x(K0.5Bi0.5)xBi2Nb2O9 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, Sr_1−x(K_0.5Bi_0.5)_xBi₂Nb₂O₉ (SKBN-x, x=0, 0.2, 0.5, 1.0), were synthesized by a conventional solid-state reaction. Structural and electrical properties of SKBN-x ceramics were investigated. X-ray diffraction analysis suggested that the substitution led to the formation of a layered perovskite structure. Plate-like morphologies for the grains were clearly observed in all the samples, which are characteristic for layer-structure Aurivillius compounds. The Curie temperature (T_c) is found to shift to higher temperature from 445 °C to 509 °C with increasing (K, Bi) content. Excellent remanent polarization (2P_r∼15 μC/cm²) were obtained for SKBN-0.2 ceramic. High piezoelectric coefficient of d₃₃∼21  pC/N were obtained for the samples at x=0.5. Additionally, thermal annealing studies indicated that the piezoelectric coefficient (d₃₃) of SKBN-0.5 was unchanged even if annealing temperature increased to be 450 °C, demonstrating the ceramics are the promising candidates for high-temperature applications.     

Effect of Nd substitution on the microstructure and electrical properties of Bi7Ti4NbO21 piezoceramics

Neodymium (Nd) doped intergrowth bismuth layer-structured ferroelectric compounds Bi_7?xNd_xTi₄NbO₂₁ (x = 0, 0.5, 0.75, 1.0, 1.25, 1.5, 1.75 and 2.0) were synthesized through a solid-state method. The influence of the Nd³⁺ substitution of Bi³⁺ on the lattice, microstructure and electrical properties of these compounds were investigated. The X-ray diffraction and Raman scattering analyses demonstrate that a phase transition from orthorhombic to pseudo-tetragonal occurs in these compounds, relying on substitution proportions and sites of Nd³⁺ for Bi³⁺. With the increasing Nd³⁺ dopants, the growth of plate-like grains along the a–b plane and a secondary intergranular metallic Bi phase were retarded which resulted in the increases of sintering temperature, density and electrical resistance of the doped ceramics. The resultant ceramic with x = 1.25 possesses a piezoelectric coefficient d₃₃ up to 16.3 pC/N with a Curie temperature T_C above 750 °C were obtained for the compound.     

Effect of zinc concentration on the magnetic properties of cobalt–zinc nanoferrite

Nano-cobalt–zinc ferrite (CZFO) Co_(1?x)Zn_xFe₂O₄ with varied quantities of zinc (x = 0.0, 0.1, 0.2, 0.3, 0.4) have been prepared by solution combustion method. X-ray diffraction and transmission electron microscopy confirmed the size, structure and morphology of the nanoferrites. The addition of zinc in cobalt ferrite has been shown to play a crucial role in enhancing the magnetic properties. Ferromagnetic ordering is observed in nano samples at room temperature. Zn substitution shows maximum saturation magnetization for x = 0.1, that is 56.74 emu/g and then decreases for further increase in Zn substitution. The dependence of Mössbauer parameters viz. isomer shift and hyperfine magnetic field with zinc concentration has been studied. Mössbauer results are also supported by magnetization data. The results obtained from this method make these samples suitable for preparing high quality nanocrystalline ferrite for high density data storage applications.     

Preparation and characterization of Co2+ substituted Li–Dy ferrite ceramics

Stoichiometric compositions of ferrites with the chemical formula Li_0.5?0.5xCo_xFe_2.4?0.5xDy_0.1O₄ with x=0, 0.25, 0.5, 0.75, 1.0 were prepared by the standard double sintering ceramic method. X-ray diffraction analysis confirmed the cubic spinel structure of the prepared samples. The structural, morphological and magnetic properties were studied by X-ray diffraction, infra-red spectroscopy (IR), scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and ac susceptibility measurements. Lattice constant, grain size and density increase whereas porosity decreases with the increase in Co²⁺ substitution. IR measurements show the characteristic ferrite bands. Spectral absorption bands were observed in IR spectroscopic analysis at ν₁=564?601 cm^?1, ν₂=486?519 cm^?1 and ν₃=551?578 cm^?1. The cation distribution estimated by the X-ray diffraction is supported by magnetization and susceptibility studies. The saturation magnetization decreases from 44.25 to 17.14 emu/g whereas coercivity remarkably increases from 240.69 to 812.14 emu/g with increasing Co²⁺ substitution. The mechanisms involved are discussed.     

Dielectric and Magnetic properties of (1 − x)BiFeO3–xBa0.8Sr0.2TiO3 ceramics

The polycrystalline samples of (1 ? x)BiFeO₃–xBa_0.8Sr_0.2TiO₃ (x = 0, 0.1, 0.2, 0.25, 0.3, 0.4 and x = 1) were prepared by the conventional solid state reaction method. The effect of substitution in BiFeO₃ by Ba_0.8Sr_0.2TiO₃ on the structural, dielectric and magnetic properties was investigated. X-ray diffraction study showed that these compounds crystallized at room temperature in the rhombohedral distorted perovskite structure for x ≤ 0.3 and in cubic one for x = 0.4. As Ba_0.8Sr_0.2TiO₃ content increases, the dielectric permittivity increases. This work suggests also that the Ba_0.8Sr_0.2TiO₃ substitution can enhance the magnetic response at room temperature. A remanent magnetization M_r and a coercive magnetic field H_C of about 0.971 emu/g and 2.616 kOe, respectively were obtained in specimen with composition x = 0.1 at room temperature.     

Impedance and modulus spectroscopy characterization of lead free barium titanate ferroelectric ceramics

In this work, dense BaTiO₃ ceramics were successfully prepared by the solid state reaction process. X-ray diffraction technique showed single-phase polycrystalline sample with perovskite structure. Dielectric behavior and the impedance relaxation were investigated in a wide range of temperature (room temperature (RT) – 40 °C) and frequency (1 kHz–1 MHz). A broad dielectric constant peak was observed over a wide temperature range around the phase transition temperature. The complex impedance plot exhibited two impedance semicircles identified over the frequency range of 1 kHz–1 MHz, which is explained by the grain and grain boundary effects. The presence of non-Debye type of relaxation has been confirmed by the complex impedance analysis. The centers of the impedance semicircles lie below the real axis, which indicates that the impedance response is a Cole–Cole type relaxation.     

Effect of Nd-doping on structural,thermal and electrochemical properties of LaFe0.5Cr0.5O3 perovskites

The structural, thermal and electrochemical properties of the perovskite-type compound La_1−xNd_xFe_0.5Cr_0.5O₃ (x=0.10, 0.15, 0.20) are investigated by X-ray diffraction, thermal expansion, thermal diffusion, thermal conductivity and impedance spectroscopy measurements. Rietveld refinement shows that the compounds crystallize with orthorhombic symmetry in the space group Pbnm. The average thermal expansion coefficient decreases as the content of Nd increases. The average coefficient of thermal expansion in the temperature range of 30–850 °C is 10.12×10⁻⁶, 9.48×10⁻⁶ and 7.51×10⁻⁶ °C⁻¹ for samples with x=0.1, 0.15 and 0.2, respectively. Thermogravimetric analyses show small weight gain at high temperatures which correspond to filling up of oxygen vacancies as well as the valence change of the transition metals. The electrical conductivity measured by four-probe method shows that the conductivity increases with the content of Nd; the electrical conductivity at 520 °C is about 4.71×10⁻³, 6.59×10⁻³ and 9.62×10⁻³ S cm⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. The thermal diffusivity of the samples decreases monotonically as temperature increases. At 600 °C, the thermal diffusivity is 0.00425, 0.00455 and 0.00485 cm² s⁻¹ for samples with x=0.10, 0.15 and 0.20, respectively. Impedance measurements in symmetrical cell arrangement in air reveal that the polarization resistance decreases from 55 Ω cm⁻² to 22.5 Ω cm⁻² for increasing temperature from 800 °C to 900 °C, respectively.     

Improved dielectric properties and grain boundary response of SrTiO3 doped Y2/3Cu3Ti4O12 ceramics fabricated by Sol-gel process for high-energy-density storage applications

A chemical solution processing method based on sol-gel chemistry (SG) was used to synthesize (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.25) ceramics successfully. The 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics sintered at 1050 °C for 20 h showed fine-grained microstructure and high dielectric constant (ε′ ≈ 1.7 × 10⁵) at 1 kHz. Furthermore, the 0.85Y_2/3Cu₃Ti₄O₁₂-0.15SrTiO₃ ceramics appeared distinct pseudo-relaxor behavior. Two electrical responses were observed in the combined modulus and impedance plots, indicating the presence of Maxwell-Wagner relaxation. Sr vacancies and additional oxygen vacancies had substantial contribution to the sintering behavior, an increase in grain growth, and relaxation behaviors in grain boundaries. The contributions of semiconducting grains with the nanodomain and insulating grain boundaries (corresponding to high-frequency and low-frequency electrical response, respectively) played important roles in the dielectric properties of (1-x)Y_2/3Cu₃Ti₄O₁₂-xSrTiO₃ ceramics. The occurrence of the polarization mechanism transition from the grain boundary response to the electrode one with temperature change was clearly evidenced in the low frequency range.