Magnetic and dielectric properties of low vanadium doped nickel-zinc-copper ferrites

The new spinel-type of general formula Ni_0.6+xZn_0.2Cu_0.2V_xFe_2−2xO₄ with 0.0≤x≤0.25 was synthesized by the usual ceramic method. Structure of the prepared ferrites was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Room temperature magnetic hysteresis loops were measured using magnetic field strength up to 6 kOe. Saturation magnetization (M_s) increased with vanadium content up to x=0.05 and then decreased. Variation of (M_s) as a function of x is explained in terms of cation redistribution between A and B sublattices. Coercive force (H_c), remanent induction (B_r) and squareness of the hysteresis loop (B_r/M_s) as functions of x are presented. Dielectric permittivity (ε′, ε″) and dielectric loss tangent (tan δ) were measured as functions of frequency and temperature. These parameters were found to be strongly dependent on V₂O₅ concentration. The variation of dielectric loss tangent with frequency at different temperatures shows abnormal behavior, where more than one relaxation peaks were observed at low and high temperatures. This behavior could be attributed to the collective contribution of two types of carriers (p and n) to polarization.     

Physical studies on composites Ag7I4VO4-Al2O3

The electrical properties of the solid electrolytes Ag₇I₄VO₄-Al₂O₃ (0-40 mol% Al₂O₃) are investigated. The electrical conductivity, dielectric constant and dielectric loss are increased by increasing the concentration of Al₂O₃; showing a maximum at 30 mol% Al₂O₃. The conductivity is found to be increased by decreasing the particle size of Al₂O₃. The results are explained using the random resistor network model (RRN). This is due to the formation of a highly conducting interface layer along the matrix-particle interface. This layer is destroyed at concentrations higher than 30 mol% Al₂O₃.     

Remarkable influence on the dielectric and magnetic properties of lithium ferrite by Ti and Zn substitution

The effect of Zn and Ti substitution on the magnetic and electrical properties of Li_0.5Zn_xTi_xMn_0.05Fe_2.45−2xO₄ ferrites (x=0.0 to 0.30 in steps of 0.05) +0.5wt% Bi₂O₃ prepared by a standard ceramic technique has been investigated. Electrical conductivity and dielectric measurements at different temperatures from 300 K to 700 K in the frequency range from 100 Hz to 2 MHz have been analysed. The variation of the real part of dielectric constant (ε^′) and loss tangent (tanδ) with frequency and temperature has been studied; it follows the Maxwell–Wagner model based on the interfacial polarization in consonance with the Koops phenomenological theory. It is found that the permittivity of zinc and titanium substituted lithium ferrite improves and shows a maximum value ( 1.5×10⁵) at 100 Hz for the x=0.25 sample. The dielectric transition temperature (T_d) depends on the concentration of Ti and Zn in Li_0.5Zn_xTi_xMn_0.05Fe_2.45−2xO₄. The saturation magnetization and Curie temperature both decrease with increase in the concentration of Ti and Zn in the ferrite.     

The non-isotropic character of electric and dielectric properties of ammonium zinc chloride crystal

The dielectric constant, ε, and the d.c. conductivity, σ, were measured along the a-, b- and c-axes of (NH₄)₂ZnCl₄ (AZC) crystal in the 300-450 K temperature range. Crystals of AZC grown from aqueous solutions containing excess of ZnCl₂ were used. The value of the dielectric permittivity of AZC is extremely small compared to other ferroelectric crystals. Pronounced broad or step-like peaks at the phase transition temperatures were detected along the a- and b-axes, while ε along the c-axis is temperature independent up to the end of the measuring range. Reciprocal of the dielectric permittivity in the range of the commensurate to incommensurate phase transition obeys a relation similar to the Curie-Weiss law that is valid for second order ferroelectric/paraelectric phase transitions. The constants of the proposed relationship applied to the cooling run are given. The J-E characteristics along the three crystallographic axes were measured in the normal, incommensurate, commensurate and antiferroelectric phases. Hence, the type of conduction mechanism has been estimated. Parameters of Poole-Frenkel and Richardson-Schottky types of conduction mechanism have been determined. The effect of applied electric field on the conductivity measurement was also tested. Conductivity anomalies with different character were observed at the phase transition temperatures. The lnσ−1000/T dependence revealed thermal activation energy of conduction along the a-, b- and c-axes with different values in different phases of AZC.     

Investigations on the electrical and structural properties of polyaniline doped with camphor sulphonic acid

Polyaniline is chemically synthesised and doped with camphor sulphonic acid. FTIR studies carried out on these samples indicate that the aromatic rings are retained after polymerisation. The percentage of crystallinity for polyaniline doped with camphor sulphonic acid has been estimated from the X-ray diffraction studies and is around 56% with respect to polyaniline emeraldine base. The change in dielectric permittivity with respect to temperature and frequency is explained on the basis of interfacial polarisation. AC conductivity is evaluated from the observed dielectric permittivity. The values of AC and DC conductivity and activation energy are calculated. The activation energy values suggested that the hopping conduction is the prominent conduction mechanism in this system.     

Stretched exponential relaxation and dispersive conductivity behavior in lithium bismuth silicate glasses

Glasses having compositions xLi₂O∙(85 − x)Bi₂O₃∙15SiO₂ (x = 35, 40, and 45 mol%) were prepared by normal melt quenching technique. Electrical relaxation and conductivity in these glasses were studied using impedance spectroscopy in the frequency range from 20 Hz to 1 MHz and in the temperature range from 453 to 603 K. The ac and dc conductivities, activation energy of the dc conductivity and relaxation frequency were extracted from the impedance spectra. The dc conductivity increases with increase in Li₂O content providing modified glass structure and large number of mobile lithium ions. Similar values of activation energy for dc conduction and for conductivity relaxation time indicate that the ions overcome the same energy barrier while conducting and relaxing. The non-exponential character of relaxation processes increases with decrease in stretched exponential parameter ‘β’ as the composition parameter ‘x’ increases. The observed conductivity spectra follow a power law with exponent ‘s’ which increases regularly with frequency and approaches unity at higher frequencies. Nearly constant losses (NCL) characterize this linearly dependent region of the conductivity spectra. A deviation from the ‘master curve’ for various isotherms of conductivity spectra was also observed in the high-frequency region and at low temperatures, which supports the existence of different dynamic processes like NCL in addition to the ion hopping processes in the investigated glass system.     

Studies of dielectric and impedance properties of KCa2V5O15 ceramics

A polycrystalline sample, KCa₂V₅O₁₅, with tungsten bronze structure was prepared by a mixed-oxide method at low temperature (i.e., at 630 °C). A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound was studied by scanning electron microscopy (SEM). Two dielectric anomalies at 131 and 275 °C were observed in the temperature dependency of dielectric response at various frequencies, which may be attributed to the ferroelastic-ferroelectric and ferroelectric-paraelectric transitions, respectively. The nature of variation of the electrical conductivity, and value of activation energy of different temperature regions, suggest that the conduction process is of mixed-type (i.e., ionic-polaronic and space charge generated from the oxygen ion vacancies). The impedance plots showed only bulk contributions, and non-Debye type of relaxation process occurs in the material. A hopping mechanism of electrical transport processes in the system is evident from the modulus analysis. The activation energy of the compound (calculated both from loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers.     

Electrical and electromechanical properties of lead-potassium-yttrium-niobate ceramics—piezoelectric applications

Tungsten bronze (TB)-type oxide ceramic Pb_0.74K_0.13Y_0.13Nb₂O₆ (PKYN) has been synthesized by the standard solid state reaction method. Single phase formation, orthorhombic crystal structure was confirmed by X-ray diffraction (XRD). The substitution of Y³⁺ in Pb_0.74K_0.52Nb₂O₆ (PKN) decreased the unit cell volume and T_C=260 °C. PKYN exhibited the remnant polarization, P_r=8.5 μC/cm², and coercive field, E_c=28.71 kV/cm. Electrical spectroscopy studies were carried out over the temperature (35-595 °C) and frequency (45 Hz-5 MHz) ranges, and the charge carrier phenomenon, grain-grain boundary contribution and non-Debye-type relaxation were analyzed. The relaxation species are immobile charges in low temperature and oxygen vacancies at higher temperature. The theoretical values computed using the relations, ε′=ε_∞+sin(n(T)π/2)(a(T)/ε₀)(ω^n(T)−1); σ(ω)=σ_dc+Aωⁿ are fitted with the experimental one. The n and A parameters suggested that the charge carrier's couple with the soft mode and become mobile at T_C. The activation enthalpy, H_m=0.38 eV, has been estimated from the hopping frequency relation ω_p=ω_e exp(−H_m/k_BT). The piezoelectric constants K_t=35.4%, d₃₃=69×10⁻¹² C/N, d₃₁=−32×10⁻³ mV/N, S₁₁^E=17.8 pm²/N, etc., achieved in PKYN indicate the material is interesting for transducer applications. The activation energies from different formalisms confirmed the ionic-type conduction.     

Electron paramagnetic resonance, optical and electrical properties of vanadyl doped alkali germanoborate glasses

Glasses with composition xGeO₂.(0.30−x)M₂O.0.70B₂O₃ (M=Li, K) containing 2.0 mol% of V₂O₅ have been prepared in the range 0.00≤x≤0.15 by normal melt quenching method. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHPs) of VO²⁺ ions, dipolar hyperfine coupling parameter, P, Fermi contact interaction parameter, K and molecular orbital coefficients (α² and γ²) have been calculated. In GeO₂·Li₂O·B₂O₃ glasses there is no change in the tetragonality of the V⁴⁺O₆ complex and the size of 3d_xy orbit also remains unchanged with increase in GeO₂ content. In GeO₂·K₂O·B₂O₃ glasses, there is an increase in the tetragonality of the V⁴⁺O₆ complex and the 3d_xy orbit expands with increase in GeO₂ content. Values of the theoretical optical basicity, Λ_th, have also been reported. Optical band gap decreases with increase in GeO₂ content. The dc conductivity of these glasses decreases and the activation energy increases with increase in GeO₂:M₂O ratio.     

Dielectric relaxation and a.c. conduction phenomena of PbO-PbF2-B2O3 glasses doped with FeO

PbO-PbF₂-B₂O₃ glasses containing different concentrations of FeO have been prepared. The glasses are characterized by X-ray diffraction and differential thermal analysis. The dielectric properties viz., dielectric constant, loss, conductivity, over a moderately wide range of frequency and temperature and dielectric breakdown strength have been investigated. The results of these studies have been analyzed in the light of different oxidation states of iron with the aid of the data on IR, ESR, optical absorption and magnetic susceptibility measurements. The analysis shows that iron ions exist mainly in Fe³⁺ state, occupy tetrahedral positions and increase the insulating strength of the glass if FeO is present in smaller concentrations. However, if FeO is present in higher concentrations in the glass matrix, (i) the dielectric relaxation intensity has been observed to increase, (ii) the intensity and the half width of the ESR signal has been observed to decrease and (iii) the value of magnetic moment (evaluated from magnetic susceptibility) has been observed to drop to a value of 4.6 μ_B from 5.7 μ_B. From these results it has been concluded that in this concentration range, iron ions exist mainly in divalent state.     

Charge conduction process and photoelectrical properties of bulk heterojunction device based on sulphonated nickel phthalocyanine and rose Bengal

The dependence of photovoltaic performance of the bulk heterojunction photovoltaic device based on the blend of sulphonated nickel phthalocyanine (NiPcS) and rose Bengal (RB) on their composition, thermal annealing and oxygen exposure has been investigated. It is found that both electron and hole mobility in RB phase and NiPcS phase, respectively has been increased on thermal annealing. The power conversion efficiency of the device increases upon thermal annealing, attributed the balance charge transport. The power conversion efficiency of the device experiences a drastic increase upon oxygen exposure, which attributed to the photo-induced doping, increase in exciton diffusion length in NiPcS phase and increased volume of exciton dissociation interfacial sites. From the impedance spectroscopy, we conclude that the change in bulk resistance and dielectric constant of the active material due to the illumination has a direct relevance to the photocurrent generated by the device.     

Electrical and optical properties of Jäger-nickel (II)-based molecular-material thin films prepared by the vacuum thermal evaporation technique

Semiconductor molecular-material thin films of [6,13-Ac₂-5,14-Me₂-[14]-4,6,11,13-tetraenato-1,4,8,11-N₄] and the bidentate amines 1,4-diaminebutane, 1,12-diaminedodecane and 2,6-diamineanthraquinone have been prepared by vacuum thermal evaporation on corning glass substrates and crystalline silicon wafers. The films thus obtained were characterized by infrared (FTIR), ultraviolet-visible (UV-VIS) and photoluminescence (PL) spectroscopies. The surface morphology, thickness and structure of these films were analyzed by atomic force microscopy (AFM), ellipsometry and X-ray diffraction (XRD), respectively. IR spectroscopy showed that the molecular-material thin films exhibit the same intra-molecular bonds as the original compounds, which suggests that the thermal evaporation process does not significantly alter their bonds. The effect of temperature on conductivity was also measured in these samples; it was found that the temperature-dependent electric current is always higher for the voluminous amines with large molecular weights and suggests a semiconductor behavior with conductivities in the order of 10⁻⁶-10⁻¹ Ω⁻¹ cm⁻¹. Finally, the optical band gap (E_g) and cubic χ⁽³⁾ non-linear optical (NLO) properties of these amorphous molecular complexes were also evaluated from optical absorption and optical third harmonic generation (THG) measurements, respectively.     

Electrical behaviour of Li2O-ZnO-SiO2 glass and glass-ceramics system

Sealing quality lithium zinc silicate (LZS) glasses of compositions (wt.%) (a) LZSL- Li₂O: 12.65, ZnO: 1.85, SiO₂: 74.4, Al₂O₃: 3.8, K₂O: 2.95, P₂O₅: 3.15, B₂O₃: 1.2 (low ZnO), and (b) LZSH- Li₂O: 8.9, ZnO: 24.03, SiO₂: 53.7, Na₂O: 5.42, P₂O₅: 2.95, B₂O₃: 5 (high ZnO) were prepared by conventional melt-quench technique and converted to glass-ceramics by controlled crystallization process. The electrical properties of these samples were measured using ac impedance spectroscopy technique over a frequency range of 10 Hz-15 MHz at several temperatures in the range of 323-673 K. The ac conductivity, dc conductivity, dielectric constant and loss factor were obtained from these measurements. The dc conductivity (σ_dc) follows the Arrhenius behaviour with temperature. It is observed that σ_dc in LZSL glass is significantly higher than in the LSZH glass and the activation energies for σ_dc for LZSL and LZSH glasses are 0.59 and 1.08 eV, respectively. It further observed that the conductivity value decreases nearly one order of magnitude on conversion to glass-ceramics. The behaviour is explained on the basis of distributions and nature of alkali ions and network structures in these samples.     

A systematic study on magnetic, dielectric and magnetocapacitance properties of Ni doped bismuth ferrite

In this paper we report the structural, magnetic, magnetocapacitance and dielectric properties of BiFe_1−xNi_xO₃ nanoceramics (with x=0, 0.1) prepared by the sol-gel method. XRD analysis showed formation of single phase nanoceramics (particle size ∼50 nm by TEM). Samples of BiFe_1−xNi_xO₃ were divided into two parts—one of them quenched in liquid nitrogen and another sintered in the normal way. We observed the enhancement in magnetic and dielectric properties of quenched sample. The splitting of zero field cool (ZFC) and field cool (FC) magnetization curves at low temperature reveals spin- glass behavior. Quenched sample showed the enhancement of blocking temperature.     

Optical properties of samarium doped zinc-phosphate glasses

Samarium doped zinc-phosphate glasses having composition Sm₂O_{3 (x)}ZnO_(60−x) P₂O_{5 (40)} (where x=0.1-0.5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been calculated. The values of density range from 3.34 to 3.87 gm/cm³ and those of molar volume range from 27.62 to 31.80 cm⁻³. The optical absorbance studies were carried out on these glasses to measure their energy band gaps. The absorption spectra of these glasses were recorded in UV-visible region. No sharp edges were found in the optical spectra, which verifies the amorphous nature of these glasses. The optical band gap energies for these glasses were found to be in the range of 2.89-4.20 eV. The refractive index and polarizability of oxide ion have been calculated by using Lorentz-Lorentz relations. The values of refractive index range from 2.13 to 2.42 and those of polarizability of oxide ion range from 6.51×10⁻²⁴ to 7.80×10⁻²⁴ cm³.     

Impedance spectroscopy and conduction mechanism of multiferroic (Bi0.6K0.4)(Fe0.6Nb0.4)O3

Polycrystalline (Bi_0.6K_0.4) (Fe_0.6Nb_0.4)O₃ material has been prepared using a mixed-oxide route at 950 °C. It was shown by XRD that at room temperature structure of the compound is of single-phase with hexagonal symmetry. Some electrical characteristics (impedance, modulus, conductivity etc.) were studied over a wide frequency (1 kHz–1 MHz) and temperature (25–500 °C) ranges. The Nyquist plot (i.e., imaginary vs real component of complex impedance) of the material exhibit the existence and magnitude of grain interior and grain boundary contributions in the complex electrical parameters of the material depending on frequency, input energy and temperature. The nature of frequency dependence of ac conductivity follows Joncher׳s power law, and dc conductivity follows the Arrhenius behavior. The appearance of P–E hysteresis loop confirms the ferroelectric properties of the material with remnant polarization (2P_r) of 1.027 µC/cm² and coercive field (2E_c) of 16.633 kV/cm. The material shows very weak ferromagnetism at room temperature with remnant magnetization (2M_r) of 0.035 emu/gm and coercive field (2H_c) of 0.211 kOe.     

Elastic properties of lead-phosphate glasses doped with samarium trioxide

A series of ternary lead-phosphate glasses doped with samarium trioxide, xSm₂O₃-(40−x)PbO-60 P₂O₅ (where x=0.1 to 0.5 mol%) have been prepared by using conventional melt quenching method and their elastic properties have been studied at room temperature. Results from the studies show that both longitudinal and transverse sound velocities decrease by increasing the Sm₂O₃ content. Elastic moduli, Poisson's ratios decrease with increase of Sm₂O₃ composition up to 0.3 mol% and then there is a slight increasing trend observed at 0.4 mol%. The densities of these glasses have been measured by using displacement method. The variations of these parameters have been discussed with respect to samarium trioxide concentration.     

Development of a system for measuring the complex impedance of borosilicate glasses at high pressures and temperatures: Application to the study of Li- and Na-doped borosilicate glasses

An apparatus for measuring the complex impedance of samples with high impedances is described. Complex impedance spectra were collected from a range of borosilicate glasses of composition (B₂O₃)₄(Li₂O)(LiBr)_x(NaBr)_1−x at pressures and temperatures ranging from 1 to 5 GPa and 350 to 450 °C, respectively. These data were used to determine AC conductivities and activation energies in order to test the Modified Random Network model of glass structure. Our results are in line with the predictions of this theory.     

Thermal,vibrational, and dielectric studies on PVP/LiBF4+ionic liquid [EMIM][BF4]-based polymer electrolyte films

Free-standing polymer electrolyte membranes based on poly(vinyl) pyrrolidone (PVP)/salt(LiBF₄) having different amounts of ionic liquid (IL) [EMIM][BF₄] were prepared and characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, and alternating current (AC) impedance spectroscopic techniques. The DSC results show a shift in T_m of PVP with salt/or IL content. TGA and DTGA (first derivative of TGA) results give evidence of the presence of uncomplexed PVP, PVP/salt, and PVP/IL complexes. Signatures of these entities are also present in the dielectric spectra. Complexation of PVP with salt and IL has been confirmed by FT-IR analysis. Electrical conductivity as a function of temperature has been studied for PVP/LiBF₄/IL [EMIM][BF₄]. Role of IL in changing phase transition, conductivity, and dielectric relaxation frequency has been discussed.