Influence of Alkali Ions in Enhancing the Nonlinearity of ZnO-Bi2O3-Co3O4 Varistor Ceramics

Zinc oxide ceramic varistors with simplified compositions of ZnO+Bi2O3+Co3O4+M(2)O (M=K or Na) show nonlinearity coefficients (alpha) of 40-75. The electron paramagnetic resonance spectra and optical reflectance spectra show that there is a direct interdependence between the oxidation state of transition metals and the alkali ions. The X-ray photoelectron spectra indicate that the alkali ions preserve a higher oxidation state of cobalt, Co(III), in the grain boundary regions than in the grain interiors having more Co(II). Admittance spectroscopy shows that, while the nature of traps remains unaltered, the trap density increases with the concentration of alkali ions near the interface. The observed defect states are associated with the grain bulk than with the grain boundary interfaces, as indicated by the isothermal capacitance transient signals

Multifunctional cryogenic sensors from n-BaTiO3 ceramics having strong negative temperature coefficient of resistance

Donor-doped n-BaTiO3 polycrystalline ceramics show a strong negative temperature coefficient of resistivity below the orthorhombic-rhombohedral phase transition point, from 10(2-3) Omega cm af 190 K to 10(10-13) Omega cm at less than or similar to 50 K, with thermal coefficient of resistance alpha = 20-23% K-1. Stable thermal sensors for low-temperature applications are realized therefrom. The negative temperature coefficient of resistivity region can be modified by substituting isovalent ions in the lattice. Highly nonlinear current-voltage (I-V) curves are observed at low temperatures, with a voltage maximum followed by the negative differential resistance. The I-V curves are sensitive to dissipation so that cryogenic sensors can be fabricated for liquid level control, flow rate monitoring, radiation detection or in-rush voltage limitation.

Microstructural and dielectric properties of KCl-added bismuth vanadate ceramics

The effect of KCI addition on the microstructural, structural and dielectric properties of bismuth vanadate, Bi2VO5.5 (BiV) has been examined. The average grain size of BN ceramics increases with increase in KCl content (from an average grain size of TO to 80 mu m) as a result of the increased liquid-phase formation of KCI, at the grain boundaries. Differential scanning calorimetry (DSC) carried out on the KCl-added samples indicates an upward shift in the transition temperature (T-c), from 723 K (for BN) to 734 K (for 5 mol% KCl-added BiV). On further increase in the KCI content, T-c shifts down to about 722 K for 10 mol%. This trend is consistent with that of the lattice strain data. The relative permittivity as well as the dielectric loss decrease by more than half of the original values upon the addition of KCI. The relative permittivities of the KCl-added ceramics are comparable with the values predicted by the logarithmic mixture rule. Impedance analyses suggest that the grain boundary resistance of the KCl-added BiV ceramics is higher by two orders of magnitude than that of BN ceramics. The KCl-added BN ceramics exhibit ferroelectric domains and the domain density decreases as the grain boundary region is approached.

Sensors based on the dissipation characteristics of n-BaTiO3 ceramics and its solid solutions

The humidity, heat flux and mass flow sensing capability of n-BaTiO3 and its solid solutions were evaluated based on their dissipation characteristics. The cubic/tetragonal phase content of the ceramics seem to play an important role in their sensitivity towards the measurand. The humidity-sensitive characteristics of these perovskites were studied with respect to different moisture sensitive coating materials. The sensor was also used to determine the heat of hydration during the curing process of cements and the mass flow rate of the gases. For all these applications, suitable operating points have been fixed from the highly non-linear I-V characteristics with the retention of good stability and high sensitivity. (C) 1997 Elsevier Science S.A.

The effect of aluminosilicate on the delayed onset of upturn voltages of zinc oxide varistor ceramics

The effect of aluminosilicate (Al2SiO5) on the upturn characteristics of ZnO varistor ceramics has been investigated. Addition of Al2SiO5 shifts the point of upturn above 10(4) A cm(-2). The extended nonlinearity in the high current density region is better correlatable to the presence of higher density of trap stales and changing pattern of trap depths at the grain boundary interface as much as the grain interior conductivity. Microstructure studies show the formation and involvement of a liquid phase during sintering. The secondary phases, predominantly are antimony spinel, Zn7Sb2O12, zinc silicate, Zn2SiO4 and magnesium aluminium silicate. MgAl2Si3O10. Energy dispersive X-ray analyses (EDAX) show that Al and Si are distributed more in the grain boundaries and within the secondary phases than in the grain interiors. Capacitance-voltage analyses and dielectric dispersion studies indicate the presence of negative capacitance and associated resonance, indicative of the oscillatory charge redistribution involving increased trapping at the interface states. The admittance spectroscopy data show that the type of trap slates remains unaltered whereas the addition of Al2SiO5 increases the density of low energy traps. (C) 1997 Published by Elsevier Science S.A.

The two-step positive temperature coefficient in resistance characteristics of n-(Ba,Pb)TiO3 ceramics created through inclusion of grain boundary modifier additives

Donor-doped n-(Ba,Pb)TiO3 polycrystalline ceramics exhibit distinctly two-step positive temperature coefficient of resistance (PTCR) characteristics when formulated with suitable combinations of B2O3 and Al2O3 as grain boundary modifiers by heterogeneous addition. B2O3 or Al2O3 when added singularly resulted in either steep or broad PTCR jumps respectively across the phase transition. The two-step PTCR is attributed to the activation of the acceptor states, created through B2O3 and Al2O3, for various temperature regimes above the Curie point (T-c). The changing pattern of trap states is evident from the presence of Ti4+-O--Al3+ type hole centres in the grain boundary layer regions, identified in the electron paramagnetic resonance (EPR) spectra. That charge redistribution occurs among the inter-band gap defect states on crossing the Curie temperature is substantiated by the temperature coefficient in the EPR results. Capacitance-voltage results clearly show that there is an increase in the density of trap states with the addition of B2O3 and Al2O3. The spread in energy values of these trap states is evident from the large change in barrier height (phi similar or equal to 0.25-0.6 eV) between 500 and 650 K.

Low temperature fabrication and impedance spectroscopy of PMN-PT ceramics

Single phase perovskite 0.9Pb(Mg1/3Nb2/3)O-3-0.1(PbTiO3) ceramics were prepared using the columbite precursor method after optimizing the synthesis conditions. X-ray diffraction (XRD) studies were carried out to verify the phase formation at each processing step. Scanning electron microscopy (SEM) was employed to observe the microstructure of the sintered ceramics. Impedance and modulus spectroscopic data were used to gain an insight into the electrical properties of the samples and with a view to observing the relaxations in them. (C) 1999 Elsevier Science Ltd.

Microstructural, dielectric, pyroelectric and ferroelectric studies on partially grain-oriented SrBi2Ta2O9 ceramics

Partially grain-oriented (48%) ceramics of strontium bismuth tantalate (SrBi2Ta2O9) have been fabricated via conventional sintering. The grain-orientation factor of the ceramics was determined, as a function of both the sintering temperature and duration of sintering using X-ray powder diffraction (XRD) techniques. Variations in microstructural features (from acircular to plate like morphology) as a function of sintering temperature of the pellets were monitored by Scanning Electron Microscopy (SEM). The dielectric constant and loss measurements as functions of both frequency and temperature have been carried out along the directions parallel and perpendicular to the pressing axis. The anisotropy (epsilon(rn)/epsilon(rp)) associated was found to be 2.21. The effective dielectric constant of the samples with varying porosity was predicted using different dielectric mixture formulae. The grain boundary and grain interior contributions to the dielectric properties were rationalized using the impedance spectroscopy. The pyroelectric coefficient for strontium bismuth tantalate ceramic was determined along the parallel and perpendicular directions to the pressing axis and found to be -23 muC/m(2)K and -71 muC/m(2)K, respectively at 300 K. The ferroelectric properties of these partially grain-oriented ceramics are superior in the direction perpendicular to the pressing axis to that in the parallel direction.

Characterization of lithium borate–bismuth tungstate glasses and glass-ceramics by impedance spectroscopy

Transparent glasses in the system (1−x)Li2B4O7–xBi2WO6 (0≤x≤0.35) were prepared via melt quenching technique. Differential thermal analysis was employed to characterize the as-quenched glasses. Glass-ceramics with high optical transparency were obtained by controlled heat-treatment of the glasses at 720 K for 6 h. The amorphous nature of the as-quenched glass and crystallinity of glass-ceramics were confirmed by X-ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) shows the presence of nearly spherical nanocrystallites of Bi2WO6 in Li2B4O7 glass matrix. Capacitance and dielectric loss measurements were carried out as a function of temperature (300–870 K) in the frequency range 100 Hz–40 MHz. Impedance spectroscopy employed to rationalize the electrical behavior of glasses and glass-ceramics suggest the coexistence of electronic and ionic conduction in these materials. The thermal activation energies for the electronic conduction and ionic conduction were also estimated based on the Arrhenius plots.

Structural and dielectric properties of Bi2NbxVi−xO5.5 ceramics

Bi2Nbx V1−xO5.5 ceramics with x ranging from 0.01 to 0.5 have been prepared. The crystal system transforms from an orthorhombic to tetragonal at x 3= 0.1 and it persists until x = 0.5. Scanning electron microscopic (SEM) investigations carried out on thermally etched Bi2NbxV1−xO5.5 ceramics confirm that the grain size decreases markedly (18 μm to 4 μm) with increasing x. The shift in the Curie temperature (725 K) toward lower temperatures, with increasing x, is established by Differential Scanning Calorimetry (DSC). The dielectric constants as well as the loss tangent (tan δ) decrease with increasing x at room temperature.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Role of interface states associated with transitional nanophase precipitates in the photoluminescence enhancement of SrTiO3 : Pr3+,Al3+

SrTiO3:Pr3+,Al3+ phosphor samples with varying ratios of Sr/Ti/Al were prepared by the gel-carbonate method and the mechanism of enhancement of the red photoluminescence intensity therein was investigated. The photoluminescence (PL) spectra of SrTiO3:Pr3+ show both D-1(2) --> H-3(4) and P-3(0) --> H-3(4) emission in the red and blue spectral regions, respectively, with comparable intensity. The emission intensity of D-1(2) --> H-3(4) is drastically enhanced by the incorporation of Al3+ and excess Ti4+ in the compositional range Sr(Ti,Al-y)(O3+3y/2):Pr3+ (0.2 less than or equal to y less than or equal to 0.4) and SrTi1+xAlyO3+z:Pr3+ (0.2 less than or equal to x less than or equal to 0.5; 0.05 less than or equal to y less than or equal to 0.1; z = 2x + 3y/2) with the complete disappearance of the blue band. This cannot be explained by the simple point defect model as the EPR studies do not show any evidence for the presence of electron or hole centers. TEM investigations show the presence of exsolved nanophases of SrAl12O19 and/or TiO2 in the grain boundary region as well as grain interiors as lamellae which, in turn, form the solid-state defects, namely, dislocation networks, stacking faults and crystallographic shear planes whereby the framework of corner shared TiO6 octehedra changes over to edge-sharing TiO5-AlO5 strands as indicated from the Al-27 MAS NMR studies. The presence of transitional nanophases and the associated defects modify the excitation-emission processes by way of formation of electronic sub-levels at 3.40 and 4.43 eV, leading to magnetic-dipole related red emission with enhanced intensity. This is evidenced by the fact that SrAl12O19:Pr3+,Ti4+ shows bright red emission whereas SrAl12O19:Pr3+ does not show red photoluminescence.