Crystallographic study of BaTiO3-BaM1/3N2/3O3 solid solutions (M=Co or Mg and N=Nb or Ta)

In order to understand the effect of niobium, tantalum, cobalt and magnesium cations on the ferroelectric properties of barium titanate we study solid solutions between BaTiO₃ and BaM_1/3N_2/3O₃ perovskite compounds where M=Co²⁺ or Mg²⁺ and N=Nb⁵⁺ or Ta⁵⁺. These solid solutions become cubic at room temperature for very weak additions. This result cannot be explained by geometrical consideration and suggests that an intermediate solid solution is made for weak additions.     

Dielectric properties of Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Dielectric properties of lead zinc niobate (PZN) ceramics modified by barium zinc niobate (BZN) and BaTiO₃ (BT) were investigated. By adding the modifier of BT and BZN, the stabilization of perovskite phase of PZN increased, but its Curie temperature decreased linearly with the amount of added modifier. Room temperature dielectric constant of PZN increased by addition of stabilizers up to 12 and 15 mol% of BZN and BT, respectively. The maximum room temperature dielectric constant was observed to be 7800 at 12 mol% of BZN, and 9800 at 15 mol% of BT, respectively.     

Structural order in Ba(Zn1/3Ta2/3)O3, Ba(Zn1/3Nb2/3)O3 and Ba(Mg1/3Ta2/3)O3 microwave dielectric ceramics

The process and nature of structural ordering and the factors that influence them have been investigated in the microwave dielectric perovskites, barium zinc tantalate (BZT), barium zinc niobate (BZN), and barium magnesium tantalate (BMT), sintered at various temperatures. The samples were characterized mainly by X-ray powder diffraction and transmission electron microscopy. The results show that short-range 1 : 1 B-site order features strongly in the early stages of ordering in BZT and BZN, but it is extremely rare in BMT, for which most grains commence with 1 : 2 order. As sintering progresses, 1 : 1 order is replaced by 1 : 2 long-range order in BZT and by disorder in BZN. Orientational variants of the ordered domains within grains occur in similar numbers when order is fine-scale, but their distribution is less homogeneous in well-ordered samples. Local inhomogeneities in the degree of order within grains, which will affect dielectric properties, correlate with both residual non-stoichiometry and the presence of dislocations. Incompletely reacted starting materials which may persist to late stages of sintering can also strongly influence order. Anomalously large ordered domains at grain boundaries are attributed to grain-boundary migration accompanied by enhanced diffusion. The results indicate that with starting materials that are well-mixed and homogeneous at the nanoscale, tailoring of physical properties should be possible by controlling the type and degree of order through chemical composition. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of the level of addition of Nb2O5/Co2O3 and Ba(Nb2/3Co1/3)O3 on the structure, microstructure, and dielectric properties of BaTiO3

In this work attempt is made to study the effects of the level of the addition of two dopant systems, that is, Nb₂O₅/Co₂O₃ and Ba(Nb_2/3Co_1/3)O₃ on the structure, microstructure, and dielectric properties of BaTiO₃(BT) prepared by ceramic route. For the BT samples doped with 2 and 3 at % Nb₂O₅/Co₂O₃ a broad maxima for _r–T variations was observed. Higher levels of addition, that is, 6, 8, and 10 at % Nb₂O₅/Co₂O₃, however, caused a drastic reduction in the magnitude of _r and vanishing of maxima peaks observed. The reduction in the magnitudes of the _r for these samples is related to the observed reduction of the tetragonality of doped BT samples as well as the existence of some non-ferroelectric extra phase, evidenced by our XRD analysis. The existence of this extra phase is also believed to be mainly responsible for the observed increase of the dielectric loss. For the BT samples doped with Ba(Nb_2/3Co_1/3)O₃ perovskite solid solution, the _r maxima peak could only be detected for the samples doped with 2 at %. In the case of the samples doped with 4, 6, 8, and 10 at % perovskite solid solution, however, a very uniform distribution of _r–T was observed. The increase of the level of dopant for these series of samples was also seen to give rise in the reduction of the magnitude of _r. However, this reduction was not as strong as the cases observed for the samples doped with 8 and 10 at % Nb₂O₅/Co₂O₃. XRD patterns obtained for these series of samples also revealed the reduction of tetragonality of the BT samples when doped with Ba(Nb_2/3Co_1/3)O₃. Further, microstructural studies carried out by scanning electron microscopy (SEM) on both series of samples revealed a contrasting picture. While a uniform grain size distribution was observed for the whole series of the samples doped with Ba(Nb_2/3Co_1/3)O₃, a non-uniform size distribution of grain sizes was observed in the case of samples doped with Nb₂O₅/Co₂O₃. This is thought to be due to the possible formation and non-uniform distribution of a liquid phase due to the formation of Ti-rich region in the shell region of Nb₂O₅/Co₂O₃-doped samples. The existence of such liquid phase, in case of Nb₂O₅/Co₂O₃-doped samples, would have the consequence of an increased rate of diffusion of Nb/Co into the BT cores leaving narrow compositional fluctuations for the shell regions.     

Dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low temperatures

Dielectric characteristics of Ba(Mg_1/3Ta_2/3)O₃ ceramics (BMT ceramics) sintered at low temperatures with 2–3 wt% NaF additives were determined. A dielectric constant of 25 and extremely low dielectric loss (< 0.0001) were measured at 100 kHz and 1 MHz in BMT ceramics sintered under these conditions, and no frequency dependence of the dielectric constant was observed. This suggested that NaF as sintering additive had no harmful influence on the dielectric properties of the ceramics.     

Dielectric properties of low-fitting Pb(Mg1/3Nb2/3)1−xTixO3-Bi2O3/Li2O ceramics

Dielectric properties of low-firing Pb(Mg_1/3Nb_2/3)_1–x Ti _x O₃-Bi₂O₃/Li₂O ceramics are studied in this work. With the addition of Bi₂O₃/Li₂O eutectic composition, the sintering temperature of PMN_1–x PT _x could be lowered to 900° C. Relaxor behaviour of PMN_1–x PT _x is enhanced by the incorporation of Bi₂O₃/Li₂O due to the substitution of Bi⁺³/Li⁺ into the PMN_1–x PT _x framework. Bi₂O₃/Li₂O eutectic composition is used as a fluxing agent, Curie shifter and depressor. Evaporation of Bi₂O₃/Li₂O and PbO during firing is checked and examined via energy dispersive spectrometry (EDS) and X-ray diffraction (XRD) is used to clarify the Curie shifting and depressing effect of Bi₂O₃/Li₂O.     

Electrical properties of BaTi1−x M x O3 (M = Nb, Ta, Mo, W) ceramics

The electrical properties of BaTi_1?x M _x O₃ (M = Nb, Ta, Mo, W) ceramics (partial substitution of Group V (Nb, Ta) or VI (Mo, W) metals on the titanium site) have been studied by impedance spectroscopy. The results indicate that the Group VI metals (Mo and W) are less effective as donor dopants of barium titanate than are Nb and Ta because most of the Mo and W ions reside in the outer layer of the grains, raising its resistance.     

Phase Transitions and Physical Properties of K3Nb3B2O12 and K3Nb3 – x M x B2O12 (M = Ta, Sb) Crystals

This work continues our studies into the nature and mechanisms of phase transitions in K₃Nb₃B₂O₁₂ (KNB) crystals, which have a framework structure with spacious continuous channels and combine ferroelectric, ferroelastic, and superionic properties. Single crystals of KNB-based solid solutions in which Nb⁵⁺ is partially substituted with Ta⁵⁺ (KNBT) or Sb⁵⁺ (KNBS) are grown from off-stoichiometric melts. The KNBT solid solutions containing more than 15 at. % Ta are found to decompose at room temperature. The introduction of Ta leads to marked broadening of phase transitions but has little effect on the transition temperatures. KNBS solid solutions exist in a limited composition range. Increasing the Sb content shifts the high-temperature phase transitions to much lower temperatures and raises the electric conductivity of the crystals by 1–1.5 orders of magnitude.     

Dielectric and ferroelectric properties of Ba3M3Ti5Nb5O30 (M=Sm or Y) ceramics

(M=Sm or Y) compounds were synthesized by the conventional powder compaction and high temperature solid state reaction technique. The calcined compounds were pelletized and sintered in the range 1275–1325 °C for 4 h. The dielectric and ferroelectric properties of the sintered pellets were measured and further characterised by X-ray diffraction and scanning electron microscopy (SEM). Sm and Y substituted compounds were found to have tetragonal structure and shown dielectric constants of 145 and 49 respectively at 1 MHz. The dielectric loss increases with frequency. Samarium compound had undergone a diffuse phase transition in the temperature range 195–210 °C whereas the same with Yttrium had shown the transition at around 25 °C.     

Stabilization of the perovskite phase in Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Stabilization of the perovskite phase in PZN-BT-BZN ceramics prepared by solid-state sintering was investigated. With the addition of BT and/or BZN, the amounts of perovskite phase in PZN ceramics increased, but the amount of pyrochlore phase decreased. Optimum calcination conditions for this system, to obtain PZN ceramics with the minimum amount of the pyrochlore phase, are a temperature range between 950 and 1000°C and a sintering time of 2–4 h. The perovskite phase of these systems could be 100% stabilized by the addition of more than 7 mol% BT, 8 and 10 mol% BTZN and BZN, respectively. This revised version was published online in November 2006 with corrections to the Cover Date.     

Microwave dielectric properties of (A2+(1/3)B5+(2/3))0.5Ti0(0.5)O2 (A2+ = Zn, Mg, B5+ = Nb, Ta) ceramics

Dielectric properties of (A(2+)(1/3)B(5+)(2/3))(0.5)Ti0(0.5)O(2) (A(2+) = Zn, Mg, B(5+) = Nb, Ta) ceramics were investigated at microwave frequencies. A single phase with tetragonal rutile structure was obtained through the entire compositions. Dielectric properties were strongly dependent on the structural characteristics. The specimens with B(5+) = Nb showed a larger dielectric constant than those with B(5+) = Ta due to the decrease of bond valence. Quality factors (Qf) of the specimens with B(5+) = Ta were larger than those with B(5+) = Nb. Temperature coefficient of the resonant frequencies (TCF) of (Zn(1/3)Nb(2/3) )0(0.5)Ti0(0.5)O(2) was larger than that of (Mg(1/3)Ta(2/3))0(0.5)Ti0(0.5)O(2). These results could be attributed to the changes of the temperature coefficient of dielectric constant and the degree of oxygen octahedral distortion.     

Dielectric relaxation in complex perovskite Ba(Bi1/2Ta1/2)O3

A new lead-free perovskite Ba(Bi_1/2Ta_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1,200 °C/4 h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were determined from the experimental results using FullProf software. The crystallite size and lattice strain were estimated from Williamson-Hall approach. XRD analysis of the compound indicated the formation of a single-phase cubic structure with the space group Pm3m. EDAX and SEM studies were carried out in order to evaluate the quality and purity of the compound. Permittivity data showed a low temperature coefficient of capacitance (T _CC  < 4%) up to +125 °C. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. Electric modulus studies supported the hopping type of conduction in Ba(Bi_1/2Ta_1/2)O₃.     

Dielectric characteristics of Mg-replaced Pb[(Zn1/3Ta2/3)0.2(Zn1/3Nb2/3)0.6Ti0.2]O3 ceramics

Powders of a Pb[(Zn_1/3Ta_2/3)_0.2(Zn_1/3Nb_2/3)_0.6Ti_0.2]O₃ system with gradual replacement of Zn by Mg were prepared by employing a B-site precursor method and developed structures were studied by X-ray diffractometry. Dielectric properties of the sintered ceramics were characterized under weak-field low-frequency conditions. A high maximum dielectric constant value of 38,000 (@1 kHz) was realized when 3/4 of octahedral Zn was replaced by Mg. Field-dependent polarization responses were also monitored at various temperatures to investigate ferroelectricity. Microstructures of the fractured ceramics were examined using a scanning electron microscope.     

Sinterability improvement of Ba(Mg1/3Ta2/3)O3 dielectric ceramics

The sinterability of Ba(Mg_1/3Ta_2/3)O₃ ceramics synthesized by solid-state-reaction methods was investigated. The poor sinterability of the present ceramics was found to be primarily due to the presence of satellite secondary phases of Ba₅Ta₄O₁₅ and Ba₄Ta₂O₉, and the nearly complete densification of Ba(Mg_1/3Ta_2/3)O₃ ceramics was accomplished successfully by controlling the phase constitution of the calcined powders. For this purpose, enhanced ball-milling processes were found to be extremely effective. Moreover, excellent microwave dielectric characteristics (_r = 24.5–24.7, Q = 26 000 at 9.8 GHz, and _f = 1.7 p.p.m. C^–1) were attained in the dense Ba(Mg_1/3Ta_2/3)O₃ ceramics without additives.