High-temperature phase transitions in a quaternary lead based perovskite structured materials with negative temperature coefficient of resistance (NTCR) behavior

Impedance spectroscopy measurements were carried out on lead based, 0.25 (PbZr_0.52Ti_0.48O₃) + 0.25 (PbFe_0.50Ta_0.50O₃) + 0.25 (PbFe_0.67W_0.33O₃) + 0.25 (PbFe_0.50Nb_0.50O₃) (PZT–PFT–PFW–PFN) solid solution over a wide range of temperatures (400–650 K) and frequencies (100 Hz–1 MHz). Impedance data showed the presence of both grains and grain boundaries effects in the electrical transport properties of quaternary. The role of the grains and grain boundaries to the impedance become more prominent around the phase transition (~420 K). Two thermally activated processes were found from the temperature dependences of the relaxation time (τ). Activation energies calculated from relaxation times obtained from imaginary part of impedance were estimated ~1.21 and ~1.84 eV over 400–490 K and 490–650 K respectively. The sum of the activation energies for the grain and grain boundary resistances is basically of the same order of magnitude that is from the impedance at high temperatures. A constant phase element is used in the equivalent electrical circuits for fitting of experimental impedance data. The nature of variation of the grain and grain boundary resistance with temperature suggested negative temperature coefficient of resistance behavior.     

Effect of temperature on nonlinear electrical behavior and dielectric properties of (Ca, Ta)-doped TiO2 ceramics

TiO₂ ceramics doped with 0.75 mol% Ca and 2.5 mol% Ta were sintered at different temperatures ranging from 1300 to 1450°C. The effects of sintering temperature on the microstructure, nonlinear electrical behavior, and dielectric properties of the ceramics were studied. The sample sintered at 1300°C exhibits the highest nonlinear coefficient (5.5) and a comparatively lower relative dielectric constant.     

A new alternative representation of impedance data using the derivative of the tangent of the phase angle: Application to the YSZ system and composites

The aim of this work is to propose a new alternative representation of impedance data using the derivative of the tangent of the phase angle, which allows enhanced discrimination between processes with relaxation frequencies that are very close. The new representation allows discrimination between overlapped processes within a factor of 2 in their relaxation frequencies for process with similar strength. Equations for the simplified behaviour of the impedance data have been proposed to obtain all the parameters of the processes involved in the impedance spectrum. This new alternative representation has been applied to bulk and grain boundary responses of YSZ with very satisfactory results. It has also been applied to the qualitative study of impedance data of a CuO composite showing the usefulness of this representation to discriminate different electrode processes. This approach provides an ab initio method of identify the contributing components to an electrochemical impedance spectrum with quite remarkable resolution. It is suggested that if this method is applied to provide starting parameters for non-linear least squares fitting using constant phase elements, then problems due to correlation of parameters and identification of components can be minimised.     

Microstructure and DC electrical conductivity of spinel nickel ferrite sintered in air and nitrogen atmospheres

In recent years, the development of inert anode materials has gained considerable attention because such materials are capable of producing only environment-friendly O₂ and saving energy during aluminum electrolysis. Nickel ferrite was prepared by a solid-state reaction as the inert anode in this study and its microstructures and direct current conductivities were analyzed in detail regarding the effects of different sintering atmospheres. A single-phase spinel structure was confirmed for all samples by X-ray powder diffraction. The grain sizes and the relative densities of the samples sintered in nitrogen increased by over 7 μm and 10.8%, respectively, compared to those sintered in air. The direct current conductivities of the samples sintered in nitrogen showed a drastic increase compared to those sintered in air, believed to be due to the effects of increased Fe²⁺ ion concentration at octahedral sites and the increase of the relative density.     

Dielectric properties of barium strontium titanate thick films prepared by electrophoretic deposition

Ba_xSr_1−xTiO₃ (x = 0.5, 0.6, 0.7) thick films were prepared by electrophoretic deposition (EPD) technique on platinum metallic foils using BaTiO₃ and SrTiO₃ nanoparticles with different molar proportion of 1:1, 3:2 and 7:3, respectively. An isostatic pressure method was used to increase density of the thick films before high temperature sintering. Microstructures of the deposited films were examined with XRD and SEM techniques. Porosity of the thick films decreased after the isostatic pressure process. The Ba_0.5Sr_0.5TiO₃ thick films of 10 μm, 15 μm and 20 μm showed a tunability of 28.8%, 33.3% and 33.9%, respectively, at room temperature and at a biasing field of 2 kV/mm. The dielectric constant was from 2138 to 3446 and dielectric loss was from 0.016 to 0.011 at zero bias field at 10 kHz. The temperature dependence of dielectric constant was also measured and the effect of porosity and thickness on the electrical performance of the thick films was discussed.     

On the green density, sintering behavior and electrical property of tape cast Ce0.9Gd0.1O1.95 electrolyte films

Gadolinia doped ceria (Ce_0.9Gd_0.1O_1.95, GDC) electrolyte films were tape cast from oxalate coprecipitated GDC powders, gelcast GDC powders and their mixtures, respectively, to evaluate the effects of the original particle size and distribution on the properties of the green and sintered GDC cast tapes. The apparent density of different original powders, as well as the green density, sintered behavior, and electrical conductivity of tapes cast from the various starting powders were investigated. Mixing the coprecipitated and the gelcast GDC powders not only results in a higher packing efficiency of particles in the loose powders, but also results in higher green and sintered densities of cast tapes. Furthermore, tapes cast from the 50/50 powder mixtures can be sintered to 96.2% of theoretical density at relatively low sintering temperature of 1400°C, whereas those from the oxalate coprecipitated and from the gelcast powders were only 89.7 and 94.1% dense, respectively. The ac impedance measurement shows that GDC films cast from the 50/50 powder mixture exhibit good electrical conductivity (4.2 and 6.0 S m⁻¹ at 700 and 800°C in air, respectively). The test results have revealed that high-density GDC films can be fabricated by tape casting technique at relatively low sintering temperature by optimizing the particle size distribution of the starting powders.     

Synthesis, characterization and electrical properties of quaternary selenodiphosphates: AMP2SE6 with A = Cu, Ag and M = Bi, Sb

The new quaternary selenophosphate phases AMP₂Se₆ (A=Cu, Ag and M=Bi, Sb) were synthesized by ceramic methods at 1023 K. These phases were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray analysis (EDX) and a.c. and d.c. electrical conductivity measurements. The phases all show values of electrical conductivity, σ, of about 10⁻⁴ Ω⁻¹ cm⁻¹ at 303 K and photoconductive effect. The conductivity is nearly five orders of magnitude larger than that of related phases.     

From tin oxalate to (Fe, Co, Nb)-doped SnO2: Sintering behavior, microstructural and electrical features

Highly reactive SnO₂-doped nanocrystalline powders with average particle size of 20 nm and specific surface areas above 30 m²/g were obtained through the polymeric precursor method with tin oxalate (SnC₂O₄) as a chloride-free precursor for SnO₂. Powders and sintered discs were characterized by means of X-ray powder diffraction (XRD), SEM and TEM. The influence of Co and Fe on the microstructure development and on the electrical properties of dense SnO₂-based ceramics was studied. Co and Fe species were found to decrease in more than 70 °C the sintering temperature of SnO₂ with respect to mixed oxide procedures. Secondary phases enriched in Co and Fe were detected and identified in sintered samples with XRD. Current-voltage curves were registered for electrical characterization. Doping with iron increased the electrical breakdown field and a nonlinearity coefficient of 20 was achieved.     

Water based gelcasting of lead zirconate titanate

Gelcasting is a novel forming method for making high-quality ceramic parts by means of in situ polymerization where only a few percents of a polymerizable binder are needed. In this article the viscosities of lead zirconate titanate (PZT) suspensions with 15-52 vol.% solids loading were studied. After developing a concentrated PZT suspension with a low viscosity, gelcasting was successfully used to form PZT ceramic parts. Microstructures and piezoelectric properties of gelcast samples derived from suspensions with different solids loading were also investigated in comparison with those of die pressed ones. It was found that gelcast samples exhibited slightly stronger piezoelectric effect than the die pressed ones at the same sintering procedure. Based on the comparison of the density and pore structure results of the samples prepared by these two methods, their different piezoelectricity may be attributed to their microstructure difference.     

Effects of Ag particles on sintering and electrical properties of ZnO-based varistor

ZnO-based varistors containing Ag particles (abbreviated as Z-Ag) were prepared using the conventional solid-state reaction method. The sintering and electrical properties of Z-Ag composites show that the composites can be achieved at a lower sintering temperature (920 °C) relative to that of a commercial ZnO-based varistor. The composites possess non-ohmic behavior analogous to that of the ZnO-based varistor, and the nonlinear voltage can be easily controlled by the content of Ag particles in the ceramic matrix. Meanwhile, the dielectric constant and dissipation factor indicate that the composites have enhanced dielectric properties at room temperature with increasing content of Ag particles, especially at frequencies of 0.5-30 kHz. The mechanisms involved are discussed.     

Study of the dielectric properties in the NaNbO3 -KNbO3-In2O3 system using AC impedance spectroscopy

We report a comparative study of the dielectric properties of solid-state (ceramic method) synthesized NaNbO₃ (NN), Na_0.75K_0.25NbO₃ (K25NN), K_0.5Na_0.5NbO₃ (KNN) and some composite materials containing In₂O₃ and NN or KNN using an AC impedance method. Powder X-ray diffraction (PXRD) was employed to investigate the phase purity. No significant amount of impurity phase was observed for NN, K25NN, and KNN. Substitutions of 10, 15 and 25 mol% In³⁺ for Nb⁵⁺ in KNN and NN using solid-state reactions at 1150 °C resulted in composite materials. AC impedance studies of NN, KNN and K25NN in the temperature range of 500-800 °C showed a single semicircle (attributed to the bulk property) in the high-frequency range of 10³ to 10⁶ Hz. The individual contributions from the bulk and grain boundary on the dielectric properties were resolved and quantified from the impedance data. The calculated dielectric values for NN were consistent with previously reported in the literature. 10% Indium based KNN composite materials had the lowest dielectric loss 0.585 and the dielectric constant of 233 at 100 kHz at the temperature of 650 °C.     

Dielectric characteristics of bismuth-modified lead magnesium niobate ceramics

Aliovalent Bi was substituted for Pb in Pb(Mg_1/3Nb_2/3)O₃ with required alteration in the Mg/Nb ratio. Resultant changes in the perovskite developments, lattice parameters as well as dielectric characteristics were investigated. Powders were prepared via a two-step B-site precursor route to enhance the perovskite formation. The perovskite structure persisted up to the range of 30 mol% Bi(Mg_2/3Nb_1/3)O₃ substitution. Values of the maximum dielectric constant decreased drastically, while the dielectric maximum temperatures changed only moderately. Meanwhile, the diffuseness exponent values decreased continuously with the Bi modification.     

Conductivity of reduced La2Mo2O9 based oxides: The effect of tungsten substitution

The electrical properties of reduced LAMOX-type oxides (La_1.9Y_0.1Mo_2−yW_yO_9−δ with y = 0, y = 0.5, y = 1.0) were investigated by complex impedance spectroscopy.When reduced at 605 °C in hydrogen, La_1.9Y_0.1Mo₂O_9−δ is 10 times and 3 × 10⁵ times more conductive at 605 and 180 °C, respectively, than in air at the same temperatures. The conductivity curve presents a low slope (0.37 eV versus 1.2 eV in air).Besides, the stabilising effect of tungsten against reduction is evidenced, in good agreement with previous reports.In low oxygen partial pressures however (PO₂ < 10⁻¹⁸ Pa), the decomposition of the materials is detected, whatever the tungsten content (0 ≤ y ≤ 1 in La_1.9Y_0.1Mo_2−yW_yO_9−δ). This observation points out the efficiency limit of Mo⁶⁺/W⁶⁺ substitution to stabilise the structure against reduction, and the limit for an application as IT-SOFC electrolyte.However, given the high electronic conductivity upon reduction, the application of these materials in IT-SOFC electrodes could be considered.     

Characterization of ZnO-degraded varistors used in high-tension devices

The effects of the degradation process on the structural, microstructural and electrical properties of ZnO-based varistors were analyzed. Rietveld refinement showed that the BiO_2−x phase is affected by the degradation process. Besides the changes in the spinel phase, the degradation process also affects the lattice microstrain in the ZnO phase. Scanning electron microscopy analysis showed electrode-melting failure, while wavelength dispersive X-ray spectroscopy qualitative analysis showed deficiency of oxygen species at the grain boundaries in the degraded samples. Atomic force microscopy using electrostatic mode force illustrated a decrease in the charge density at the grain boundaries of the degraded sample. Transmission electron microscopy showed submicrometric spinel grains embedded in a ZnO matrix, but their average grain size is smaller in the degraded sample than in the standard one. Long pulses appeared to be more harmful for the varistors’ properties than short ones, causing higher leakage current values. The electrical characteristics of the degraded sample are partially restored after heat treatment in an oxygen-rich atmosphere.     

Multi-scale investigation of electronic transport and electromechanical behavior in carbon nanotube materials

Using home-built experimental setups, electrical properties and electromechanical characterization of two systems based on multiwalled carbon nanotubes (MWNTs) were investigated at room temperature. The first system is formed by carbon nanotubes (CNTs) either isolated or in small groups on a gold substrate, while the second one concerns a macroscale three-dimensional entanglement of CNTs in powder form. The local electrical resistance on systems of the first type was measured using an atomic force microscopy with a conductive tip and showed a narrow distribution of resistance values as well for isolated CNTs as for small groups of them. However, in this latter case the average resistance value has been found to be one order of magnitude higher than that of individual CNTs, which was attributed to the contact resistance between CNTs. This parameter was then studied from a statistical viewpoint through electromechanical tests performed at a macroscopic scale. They consisted in applying an external compression to CNTs powder samples and measuring the evolution of the electrical resistance across the pressed material. These tests demonstrated an outstanding decrease of the electrical resistance resulting from the increasing number of random connections between CNTs under compression, and the experimental curves were fitted with an analytical model. Furthermore, it was deduced from this model that the elementary contact resistance between CNTs decreases under compression. The stability of this electrical contact was verified over several durations and under different constant applied loads.     

Structural and impedance properties of KBa2V5O15 ceramics

The polycrystalline sample of KBa₂V₅O₁₅ ceramics was prepared by a mixed oxide method at low temperature (i.e., at 560 °C). The formation of the compound was confirmed using an X-ray diffraction technique at room temperature. Scanning electron micrograph of the material showed uniform grain distribution on the surface of the sample. Detailed studies of dielectric properties of the compound as a function of temperature at different frequencies suggest that the compound has a dielectric anomaly of ferroelectric to paraelectric type at 323 °C, and exhibits diffuse phase transition. Electrical properties of the material were analyzed using a complex impedance technique. The Nyquists plot showed the presence of both grain (>10³ Hz) and the grain boundary (<10³ Hz) effects in the material. Studies of electrical conductivity over a wide temperature range suggest that the compound exhibits the negative temperature coefficient of resistance behavior. The ac conductivity spectrum was found to obey Jonscher's universal power law.     

Lead-free ceramics based on alkaline niobate tantalate antimonate with excellent dielectric and piezoelectric properties

This paper reports lead-free (Na_0.52K_0.48−x)(Nb_0.94−xSb_0.06)O₃-xLiTaO₃ compositions with significantly enhanced piezoelectric properties. The 6% Sb substituted Na_0.52K_0.48NbO₃ was modified by a small amount of LiTaO₃, leading to the formation of a morphotropic phase boundary between orthorhombic and tetragonal phases in the range of x = 0.035-0.04 where the materials show a strong compositional dependence of various electrical properties. Excellent properties of d₃₃ = 335 pC/N, k_p = 53%, , Q_m = 41 and T_c = 291 °C were obtained in the composition with x = 0.04, indicating that the ceramics studied are promising as a lead-free piezoelectric candidate.     

Effect of sintering temperature on magneto-transport properties of La0.67Ba0.33MnO3/Ba0.7Sr0.3TiO3 composites

La_0.67Ba_0.33MnO₃-20 wt.%-Ba_0.7Sr_0.3TiO₃ composites were sintered at different temperatures in order to explore the possibility of improving the magneto-transport properties of the composites. Detail studies on the magnetic and electrical transport properties for the sintered composite samples have been performed. Results show that the sintered composites have identical ferromagnetic to paramagnetic transition temperature and filamentary feature of metallic phase. When sintering temperature higher than 1300 °C, the composites show Efros-Shklovskii-like variable-range hopping in the temperature range lower than Curie temperature. For samples sintered lower than 1100 °C, a dome-like resistance peak appears at a temperature well below the Curie temperature. Magnetoresistance behavior indicates the existence of spin polarized tunneling in the low temperature range. Considering the contributions from Efros-Shklovskii-like variable-range hopping and spin polarized tunneling, the resistance peak can be well fitted.     

Combustion synthesis of La0.7Sr0.3Co0.5Fe0.5O3 (LSCF) porous materials for application as cathode in IT-SOFC

La_0.7Sr_0.3Co_0.5Fe_0.5O₃ (LSCF) porous materials have attracted a substantial interest for application as cathode in solid oxide fuel cells of intermediate temperature (IT-SOFC). This work investigates the effect of different propellants (urea, glycine, citric acid and sucrose) in the preparation of LSCF powders by the combustion method and also the influence of the sintering temperature on the porosity and electrical conductivity. TGA profiles of the as-prepared samples showed a lower weight loss for the sample prepared with glycine, associated with the higher combustion temperature. XRD patterns presented characteristic reflections of LSFC perovskite and a small formation of secondary phases, with nanometric crystallite sizes (9-20 nm). SEM analysis revealed the loose and porous structure of the powder materials. Densification studies were carried within 950-1100 °C, showing that porosity decreased with increasing sintering temperature. Electrical conductivity was measured in the temperature range 300-800 °C and correlated with the sintering temperature.