Microstructural, dielectric and spectroscopic properties of Li2O-Nb2O5-ZrO2-SiO2 glass system crystallized with V2O5

Li₂O-Nb₂O₅-ZrO₂-SiO₂ glasses mixed with different concentrations of V₂O₅ were crystallized. The samples were characterized by XRD, SEM and DTA techniques. The SEM pictures indicated that the samples contain well defined and randomly distributed crystal grains. The X-ray diffraction studies have revealed the presence of several crystalline phases in these samples. Optical absorption, ESR and photoluminescence spectral studies on these samples have indicated that a considerable proportion of vanadium ions do exist in V⁴⁺ state in addition to V⁵⁺ state and the redox ratio seems to be increasing with increase in the concentration of crystallizing agent V₂O₅. The infrared spectral studies have pointed out the existence of conventional SiO₄, ZrO₄, NbO₆, VO structural units in the glass ceramic network. The study of dielectric properties suggested a decrease in the insulating character of the glass ceramics with increase in the crystallizing agent. A.C. conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from V⁴⁺↔V⁵⁺ ions.     

Nickel ion—A structural probe in BaO-Al2O3-P2O5 glass system by means of dielectric, spectroscopic and magnetic studies

BaO-Al₂O₃-P₂O₅ glasses containing different concentrations of NiO (ranging from 0 to 1.0 mol%) were prepared. A number of studies viz., chemical durability, differential thermal analysis, spectroscopic (infrared, optical absorption spectra), magnetic susceptibility and dielectric properties (constant ε′, loss tan δ, AC conductivity σ_AC over a range of frequency and temperature) of these glasses have been carried out. The studies on chemical durability indicate that there is a significant increase in the corrosion resistance of the glasses; where as the results of differential thermal analysis suggests that there is a substantial improvement in the glass forming ability, with increase in the concentration of NiO up to 0.6 mol% in the glass matrix. The optical absorption, magnetic susceptibility and IR spectral studies point out nickel ions occupy both tetrahedral and octahedral positions in the glass network; the later positions seems to be dominant when the concentration of NiO is beyond 0.6 mol% in the glass matrix. The studies of dielectric properties reveal that the presence of nickel oxide in the glass network causes a considerable improvement in the insulating strength of the se glasses when the concentration of NiO?0.6 mol%.     

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 properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

Effect of ZnO/CdO on the structure and electrical conductivity in Li2O·MO·Bi2O3·B2O3 glasses (M=Zn, Cd)

Studies of structural and electrical properties have been carried out on a number of glasses with wide ranging compositions in the glass systems Li₂O·MO·Bi₂O₃·B₂O₃ (where M=Zn or Cd), in order to understand the effect of transition metal (TM) ions on the structure of these glasses. The density and molar volume measurements have also been made to understand the structural changes occurring in these glasses. The dc conductivity measured in the temperature range 423-623 K obeys Arrhenius law. It increases with increase in Li₂O/MO ratio. The results of infrared spectra indicate that TM ions (Zn²⁺ or Cd²⁺) behave as network former in the present system. Boron exists in both tri- and tetra-hedral units in these glasses and no boroxol ring formation takes place in the glass structure. Values of theoretical optical basicity have also been reported.     

Complex impedance spectroscopic analysis of Mn-modified Pb(Zr0.65Ti0.35)O3 electroceramics

The polycrystalline samples of Pb(Zr_0.65−xMn_xTi_0.35)O₃ (PZMT) (x=0, 0.05, 0.10, 0.15) were prepared by a high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of manganese (Mn) on the electrical behavior (complex impedance Z*, complex modulus M*, electrical conductivity and relaxation mechanisms) of the PZMT systems have been carried out by a nondestructive complex impedance spectroscopy (CIS) technique at 400 °C. The Nyquist plots suggest that the grains only are responsible in the conduction mechanism of the materials. The occurrence of single arc in the complex modulus spectrum of all the compositions of Mn confirms the single-phase characteristics of the PZMT compounds, and also confirms the presence of non-Debye type of multiple relaxation in the material.     

Relaxation and conductivity behaviour in the compounds: FeRGe2O7 (R=Pr,Tb)

AC measurements were performed on the thortveitite-like layered compounds, FeRGe₂O (R=Pr,Tb) in order to study their dielectric features, e.g. as a function of temperature. The main electrical response lies on impedance plots composed of two successive arcs with depressed centers. Bulk conductivity behavior is mostly Arrhenius for the measured temperatures. The associated bulk activation energies are close to 1 eV. Raw data were used to follow the temperature dependence of the dynamic parameters, ε′(ω) and σ′(ω). From logarithmic σ′(ω) vs. ω curves the dc component was obtained. ε′(ω) vs. log ω curves exhibit a dispersive behavior at low frequencies, reflecting blocking effects. E_dc and E_ac activation energies were also calculated, the last one obtained from σ′(ω) vs. 1000/T plots. Conductivity results suggest the occurrence of an extrinsic conducting mechanism. A structural instability was detected via the temperature dependence of permittivity, which has been ascribed to the presence of Ga-O-Ga bonds having associated angles different of 180°. Analyses of the results show that the interchange of Tb and Pr in the general formula FeRGe₂O₇ (R=Pr, Tb) involves only small differences in their global ac and dc behavior.     

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.     

On the power-law behavior of the AC conductivity of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

A power law used to describe the AC conductivity from 299 to 393 K of the mixed crystal (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 led to fractional exponent values ranging from 1.08 to 0.91, depending on structural changes induced on temperature variation [B. Louati, M. Gargouri, K. Guidara and T. Mhiri, J. Phys. Chem. Solids 66 (2005) 762]. In the present note, we suggest that the fractional law exhibits features of lattice relaxation. Despite the structural changes, the parameters of the power law are mutually interconnected to yield a temperature independent phenomenon. Such behavior is probably of general validity and characterizes the universal fractional dispersion of the AC conductivity, as it was also observed in glasses of different composition.     

Dielectric and AC conductivity behavior of BaBi2Nb2O9 ceramics

The complex dielectric and AC conductivity response of BaBi₂Nb₂O₉ relaxor ferroelectric ceramics were studied as a function of frequency (100 Hz-10 MHz) at various temperatures. The observed dielectric behavior was characterized by two types of relaxation processes which were described by the ‘universal relaxation law’. The frequency dependence of conductivity which showed a classical relaxor behavior followed the Jonscher's universal law σ(ω)=σ₀+Aωⁿ. The exponent n exhibited a minimum in the vicinity of temperatures of dielectric anomaly while the pre-factor A showed a maximum. The temperature dependence of n followed the Vogel-Fulcher relation with activation energy of about 0.14 eV.     

Structural and electrical properties of high-energy ball-milled NASICON type Li1.3Ti1.7Al0.3(PO4)2.9(VO4)0.1 ceramics

Nano-crystallites of Li_1.3Ti_1.7Al_0.3(PO₄)_2.9(VO₄)_0.1 NASICON type material are prepared by means of solid-state reaction of a stoichiometric mixture after milling it for 22 and 55 h. The milling reduces the average crystallite size of the ceramic to 80 and 60 nm, respectively. Mechanical milling changes structural parameters and the strain induced at the grain-boundaries plays a major role in improving electrical conductivity. An order of magnitude increase in electrical conductivity is observed in the material milled for 55 h compared to the unmilled material, which is also reflected in permittivity loss. Modulus and permittivity representations substantiate the constriction effect of grain-boundaries observed in the complex impedance representation.     

Spectroscopic characterization, conductivity and relaxation anomalies in the Li2O-MgO-B2O3 glass system: Effect of nickel ions

Glass samples of the system, Li₂O-MgO-B₂O₃ containing different concentrations of nickel oxide (ranging from 0 to 1.0 mol%) were prepared by using the melt quenching technique. The optical absorption studies indicate that the nickel ions occupy both tetrahedral and octahedral positions in the glass network. However, the octahedral positions seem to be dominant when the concentration of nickel oxide is ?0.4 mol% in the glass matrix. When in the octahedral positions, nickel ions occupy the network modifying positions. This has a tremendous effect on the thermoluminescence, electrical conductivity and magnetic susceptibility studies. Electrical measurements were carried out as a function of frequency and temperature over the frequency range of 10-10⁶ Hz and a temperature range of 303-523 K. The electric modulus formalism was applied to study the relaxation behavior by using the impedance data for all the samples at 403 K, and also for analyzing the relaxation behavior of the highest conducting sample (0.4 mol% of nickel oxide) at different temperatures. An attempt has been made to relate the measured properties to the structural modifications in the glass network due to the modifying effect of octahedral Ni²⁺ ions.     

Physical properties of BaMg1/3Nb2/3O3-BaCo1/3Nb2/3O3 solid solutions

Structural, electric and magnetic properties of Ba₃Mg_1−xCo_xNb₂O₉ based dielectric ceramic compounds have been studied. The samples, prepared by a solid state reaction method, were characterised by X-ray powder diffraction (XRPD), electron microscopy (SEM), dielectric (ε(T)) and magnetic measurements (χ⁻¹(T)). The XRPD analyses showed that the crystal structure of these compounds does change by the increase of substitution degree, passing from a superstructure hexagonal-type, (no. 164), space group (SG) to a simple structure cubic-type, (no. 221), SG. However, the evolution of the elementary unit cell lattice parameter can be followed and it exhibit a linear increasing tendency with increase in the substitution, indicating the existence of a solid solution through out the investigated range of substitution (0-1). The microstructure analysis shows a variation in the grain size and also the porosity of the samples with the degree of substitution. The results are in good agreement with that of dielectric measurements, which also showed that the dielectric constant (ε) increases with the increase of cobalt content. The magnetic characterization of cobalt substituted samples showed an antiferromagnetic type super-exchange interaction between these magnetic ions. At the same time, the values of effective magnetic momentum (μ_eff) are close to the value that corresponds to Co²⁺ free ions. The study highlights the possibility of modelling these materials by substitutions, in order to improve properties of negative-positive-zero (NPO) type dielectric applications.     

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.     

The role of As2O3 on the stability and some physical properties of PbO-Sb2O3 glasses

PbO-Sb₂O₃ glasses added with different concentrations of As₂O₃ (10-55 mol%) were prepared to understand their IR spectra, elastic properties (Young's modulus E, Shear modulus G, microhardness H), optical absorption and dielectric properties (constant ε, loss tan δ, ac conductivity σ_ac over a moderately wide range of frequency and temperature and breakdown strength in air medium at room temperature). Results have indicated that the structure of the PbO-Sb₂O₃-As₂O₃ glass is more rigid when the concentration of As₂O₃ is around 40 mol%.     

Electrical and magnetic features in the perovskite-type system Y(Co, Mn)O3

Electrical and magnetic properties of the perovskite-type solid solution YCo_xMn_1−xO₃ (x=0.20-0.60) have been studied at different temperatures and magnetic fields. Electrical conductivity measurements show a semi-conducting behaviour throughout the solid solution. The room-temperature conductivity increases with the Co content up to 33 at.%, and then decreases. The effective moment in the paramagnetic state shows a non-monotonic decrease, when the Co content increases. In the ordered state, the behaviour at low or null magnetic fields corresponds to a spin-glass or antiferromagnetic system, with a transition temperature, which raises with the Co content (up to 50 at.% Co), and then decreases. At high fields, all the solid solutions show a ferromagnetic behaviour, although there is a marked difference in their ferromagnetic cycles, at a threshold value of 33 at.% Co.     

Frequency dependence of ionic conductivity and dielectric relaxation studies in Na3H(SO4)2 single crystal

Electrical impedance measurements of Na₃H(SO₄)₂ were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO₄ tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ω^s. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition.     

Dielectric spectroscopy on Bi3Zn2Sb3O14 ceramic: an approach based on the complex impedance

The dielectric properties and loss of Bi_1.5ZnSb_1.5O₇ a poor-semiconducting ceramic were investigated by impedance spectroscopy, in the frequency range from 5 Hz to 13 MHz. Electric measurements were performed from 100 to 700 °C. Pyrochlore type phase was synthesized by the polymeric precursor method. Dense ceramic with 97% of the theoretical density was prepared by sintering via constant heating rate. The dielectric permittivity dependence as a function of frequency and temperature showed a strong dispersion at frequency lower than 10 kHz. The losses exhibit slight dependence with the frequency at low temperatures presenting a strong increase at temperatures higher than 400 °C. A decrease of the loss magnitude occurs with increasing frequency. Relaxation times were extracted using the dielectric functions Z″(ω) and M″(ω). The plots of the relaxation times τ_Z′ and τ_M″ as a function of temperature follow the Arrhenius law, where a single slope is observed with activation energy values equal to 1.38 and 1.37 eV, respectively.     

Dielectric and modulus behavior of LiFe1/2Ni1/2VO4 ceramics

The polycrystalline sample of LiFe_1/2Ni_1/2VO₄ was prepared by a standard solid-state reaction technique and confirmed by X-ray diffractometry. LiFe_1/2Ni_1/2VO₄ has orthorhombic crystal structure whose dielectric and electric modulus properties were studied over a wide frequency range (100 Hz–1 MHz) at different temperatures (296–623 K) using a complex impedance spectroscopy (CIS) technique. The frequency and temperature dependence of dielectric constant (ε_r) and tangent loss (tan δ) of LiFe_1/2Ni_1/2VO₄ are studied. The variation of ε_r as a function frequency at different temperatures exhibits a dispersive behavior at low frequencies. The variation of the ε_r as a function of temperature at different frequencies shows the dielectric anomaly in ε_r at 498 K with maximum value of dielectric constant 274.49 and 96.86 at 100 kHz and 1 MHz, respectively. Modulus analysis was carried out to understand the mechanism of the electrical transport process, which indicates the non-exponential type of conductivity relaxation in the material. The activation energy calculated from electric modulus spectra is 0.38 eV.     

Influence of lithium phosphate concentration and temperature on the electrical conduction of (76V2O5-24P2O5)1−X (Li3PO4)X glasses

Characterization of the (76V₂O₅-24P₂O₅)_1−X (Li₃PO₅)_X, where X=0.0,0.01,0.02,0.10 and 0.15, glass has been done using X-ray diffraction and differential thermal analysis (DTA). The dc conductivity of the glass samples was studied over a temperature range from 300 to 593 K. The temperature dependence of dc conductivity shows two regions. One at relatively high temperature range, above θ_D/2, and the other at relatively low temperature range, below θ_D/2. The I-V characteristics of the glasses have been studied as a function of both temperature and Li₃PO₄ content. The I-V characteristics exhibits threshold switching with differential negative resistance. It's found that both the threshold voltage (V_th) and threshold current (I_th) are dependent on the temperature and lithium phosphate concentration.