High dielectric tunability of ferroelectric (Ba1−x,Srx)(Zr0.1,Ti0.9)O3 ceramics

(Ba_1?x,Sr_x)(Zr_0.1,Ti_0.9)O₃ (BSZT) ceramics with x = 0, 0.05, 0.15, 0.25, 0.35 and 0.45 were prepared by conventional solid state reaction method. The structural characterization with X-ray diffraction and scanning electron microscopy indicate a monotonical drop in lattice constants and grain size with the increase of Sr concentration. Consequently, the Curie temperature and remnant polarization of the ceramics exhibit a strong compositional dependence. A linear relationship between the Curie temperature and Sr concentration is revealed. At x = 0.45, the BSZT ceramics show substantially high tunability of over 55 % under 20 kV/cm dc electric field with very low dielectric loss value of 0.0025 at room temperature, suggesting the BSZT ceramics could be a promising alternative to traditional (Ba,Sr) TiO₃ ferroelectrics for developing high frequency tunable dielectric devices.     

Microstructure and dielectric properties of BaZr x Ti1−x O3 ceramics

The crystalline structure and dielectric properties of BaZr _x Ti_1−x O₃ ceramics with x = 0.05, 0.10, 0.15, and 0.20 were investigated. As zirconium increased, the a-axis lattice constant gradually increased, however, the c-axis lattice constant and c/a ratio gradually decreased. When x = 0.20, the crystal structures of the BZT ceramics are very close to cubic, different from the tetragonal structure when x < 0.20. The temperature dependence of the dielectric constant was studied and an enhanced diffuse phase transition behavior is found to be caused by the increased Zr content. The decreases of coercive electric field and remanent polarization were the result of increase of Zr/Ti ratio in BaZr _x Ti_1−x O₃.     

Structural and dielectric relaxor properties of A-site deficient samarium-doped (Ba1−x Sm2x/3)(Zr0.3Ti0.7O3) ceramics

Rare earth samarium (Sm)-doped barium zirconate titanate (Ba_1?x Sm_2x/3)(Zr_0.3Ti_0.7)O₃ (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were prepared using solid state reaction (SSR) route. The structural and microstructural characterizations of the materials were done by using X-ray diffraction and SEM analysis, respectively. Rietveld refinement technique employed to investigate the details of crystal structure revealed single-phase cubic perovskite structure belonging to space group Pm-3m. Microstructure of the doped ceramics were found to be porous and of irregular shape and size along with aggregative characteristic. FTIR technique was employed to study the influence of additives in ceramics compositions and to investigate the displacement of M–O bonds. Raman spectroscopic study revealed that the substitution of Ba²⁺ ions by Sm³⁺ ions shifted the Raman-active modes toward higher energy, which indicated that these materials undergo an increase in average cubicity with increase in Sm³⁺ ion concentration. The temperature dependence of dielectric properties was investigated in the frequency range from 1 kHz to 1 MHz. The dielectric measurement indicated a diffuse type of phase transition (DPT). The broadening in the dielectric permittivity and frequency dependence behavior with increase in frequency indicated a relaxor behavior of these materials. The relaxation strength of these materials was well adjusted by using the Vogel–Fulcher relation.     

Fabrication and characterization of high permittivity ceramics in the Ba(Ti1−x−ySnxZry)O3 system

Ceramics of solid solution compositions in the system BaTi_1–x–ySn_xZr_yO₃ have been fabricated using conventional mixed oxide processing routes. Samples with y = 0 or 0.01 exhibited maximum relative permittivities, _r ^max of ~ 65000 and ~ 62000 respectively. The Curie peaks became broader and _r ^max decreased with increasing zirconium substitutions. The Curie temperature decreased linearly from 35°C for y = 0 to –40°C for y = 0.11: for the latter, _r ^max was equal to ~ 20000. The results are interpreted on the basis of microstructural features and on the degree of compositional inhomogeneity in the system.     

Microwave sintering effect on structural and dielectrical properties of Ba1−x(Sr/Pb)xTiO3 (x = 0.2 for Sr and Pb) ceramics

Microwave sintering has emerged in recent years as a new method for sintering a variety of materials that has shown significant advantages against conventional sintering procedures. Sr and Pb doped BaTiO₃ ceramics has been prepared by the high energy ball milling followed by conventional and microwave sintering. The phase formation was confirmed by X-ray diffractometer followed by Scanning electron microscopy, atomic force microscopy and Transmission electron microscopy. Dielectric constant was measured on both the samples and it is observed that, in Ba_0.8Pb_0.2TiO₃ (abbreviated as BPT), it increased more than one order of magnitude and in Ba_0.8Sr_0.2TiO₃ (abbreviated as BST), it increased two orders of magnitudes at room temperature and Curie transition temperature by microwave sintering. Interestingly the Curie transition temperature of BPT value decreased from 224 to 210 °C, where as in BST ferroelectric ceramics, no variation of transition temperature by conventional sintering and microwave sintering respectively. This promising technique has distinguished characteristics of energy saving, rapid processing and uniform temperature distribution throughout the samples.     

Microstructure and dielectric properties of Ba[Ti1 − x (Ln1/2Nb1/2) x ]O3 ceramics

We have studied the microstructure and dielectric properties of barium titanate-based ceramics containing niobium oxide and rare-earth (Nd, Sm, Gd, Dy, and Tm) oxide additions in a ratio needed for the formation of mixed perovskite solid solutions with the general formula Ba[Ti_{1 ? x} (Ln_1/2Nb_1/2) _x ]O₃. It was found that, after sintering at 1100–1120°C with the use of a zinc oxide-based sintering aid and manganese carbonate additions, the ceramics had a core-shell structure in which the core of the grains consisted of barium titanate and the shell consisted of a barium titanate-based solid solution. The average grain size of the major phase in the ceramics was within 0.7 μm. The ceramics contained additional phases in the form of inclusions which occasionally exceeded 5 μm in size. Their composition was determined. The Nd-, Sm-, and Gd-containing materials were shown to have the greatest potential as a base for the development of new engineering materials of stable groups with high dielectric permittivity for multilayer capacitors with electrodes containing 70% Ag and 30% Pd.     

Crystalline structure and dielectric properties of (Sr1−1.5x Bi x ) TiO3 ceramics

The crystalline structure, microstructure and dielectric properties of the (Sr_1–1.5x Bi _x )TiO₃ (0 x 0.267) ceramics were studied. Cubic solid solutions were determined for x 0.2 at room temperature. However, lattice distortion was detected by Raman spectra. A dense microstructure with the grain sizes of 2–4 m was obtained for (Sr_1–1.5x Bi _x )TiO₃ (0 x 0.2) ceramics. The Bi concentration was examined and found to be in agreement with the nominal composition and overall uniformly distributed in the sample. Different from the observations in the earlier literature for other doped quantum paraelectrics, where only an induced dielectric anomaly was reported, there are three Bi induced dielectric modes A, B, and C in the Bi doped SrTiO₃ samples. The occurrence of the impurity modes and the ferroelectric relaxor mode and their evolution are demonstrated as a function of Bi concentration.     

Crystal structure and dielectric properties of (Pb1−x Ca x )(Zr1−y Sn y )O3 ceramics

There has been an increasing demand for dielectric resonator materials that operate in the microwave frequency range for applications in microwave communications. (Pb,Ca)ZrO₃ ceramics have a dielectric constant (_r), high quality factor (Q) and a small temperature coefficient of resonant frequency (_f). However, basic properties such as its crystal structure, temperature characteristics and the nature of its phase transformation are not yet fully understood. The temperature coefficient of resonant frequency can be controlled fairly well with the temperature coefficient of the dielectric constant. In this paper, we report the results of investigated crystal structure and the dielectric properties of (Pb_1–x Ca _x )(Zn₁– _y Sn _y )O₃ ceramics with the objective of elucidating the relationship between the crystal structure and the dielectric properties. The crystal structure refinement was performed by the Rietveld method. The dielectric properties were measured from-150–350 °C. The phase transformation was analysed from high and low temperature XRD data.     

Physical and electrical properties of MnO2-doped Pb(Zr x Ti1−x )O3 ceramics

The effects of composition on the physical property change in the phase coexistence region between the tetragonal and rhombohedral phases have been investigated as a function of zirconium concentration, x, for the MnO₂-doped Pb(Zr _x Ti_1–x )O₃ (0.40x0.60) ceramics. The relative amount of phase coexisting between the tetragonal and rhombohedral phases affects greatly both dielectric and piezoelectric properties as a function of zirconium concentration. However, there are no detectable changes between the apparent density and microstructure. Also, in the coexistence region, the relative amount of coexistence of the rhombohedral phase increases with MnO₂ addition. The inflection points of the dielectric constant shift to lower zirconium concentration in proportion to the MnO₂ addition, owing to the substitution effect on the PZT lattice site.     

90‡ domain reversal in Pb(Zr x Ti1−x )O3 ceramics

A simple and direct method has been proposed, which may be used for quantitatively distinguishing the mechanisms of domain reorientation processes in polycrystalline materials. Using this method, the 90 domain reorientation in the Pb(Zr _x Ti_1–x )O₃ ceramic under an electric field was examined through the X-ray diffraction analysis. It was found that polarization switching in the PZT ceramic with a composition near the morphotropic phase boundary, is predominantly controlled by the two successive 90 domain processes rather than only the 180 domain reversal process. Experimental results also indicate that the coercive field of ferroelectric ceramics is related to the cooperative deformation associated with each grain. This cooperative deformation arises from the 90 domain-reversal process.     

Microstructure and electrical properties of (1 − x)K0.5Na0.5NbO3–x(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 lead-free piezoelectric ceramics

The (1 ? x)K_0.5Na_0.5NbO₃ ? x(Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (KNN–BCTZ) lead-free ceramics were fabricated by conventional solid-state sintering technique. The microstructure and electrical properties of the ceramics were investigated. The X-ray diffraction analysis revealed that the ceramics formed a single phase perovskite solid solutions with the symmetry of orthorhombic at x < 0.03. The crystal phase of the ceramics changed from orthorhombic phase to pseudocubic phase when x > 0.04. The coexistence of orthorhombic and pseudocubic (tetragonal) phases was observed near room temperature when 0.03 ≤ x ≤ 0.04. The grains grew up obviously when 2 mol% BCTZ was added, but the grain size was found to reduce gradually with further increasing BCTZ content. The T _C and T _O-T decreased with the increasing BCTZ content. The ferroelectric and piezoelectric properties were abruptly degraded as x ≥ 0.05. Optimum properties (d ₃₃ = 136 pC/N, k _p = 27 %, k _t = 26.5 %, Q _m = 25, P _r = 14.67 μC/cm², E _c = 11.23 kV/cm, T _C = 347 °C, $\varepsilon_{33}^{\text{T}} /\varepsilon_{0} = 8 6 1. 5$ ε 33 T / ε 0 = 8 6 1.5 , tan δ = 0.04) were obtained for the ceramica with x = 0.03.     

Crystalline structure and dielectric properties of Ba(Ti1−y Ce y )O3

Crystalline structure, microstructure and dielectric properties for Ba(Ti_1–y Ce _y )O₃ (0 y 0.5) ceramics have been studied. Dense ceramics with the relative density higher than 95% and grain size of 0.7–1.5 m have been obtained. The limit of the solid solubility is determined as y = 0.3 by the X-ray diffraction, SEM, and dielectric properties measurements. The crystalline symmetry is tetragonal for the sample with y = 0.02 and cubic for y 0.06 at room temperature, and the unit cell increases with increasing Ce content in the solid solution range. Correspondingly, the dielectric response exhibits three dielectric peaks for y = 0.02, and one pinched dielectric peak with ferroelectric relaxor behavior for y 0.06.     

Microwave dielectric properties of Ba(Sn x Zn(1−x)/3Nb(1−x)2/3)O3 (0 ⩽ x ⩽ 0.32) ceramics

The dielectric properties of the (1–x)Ba(Zn_1/3Nb_2/3)O₃–xBaSnO₃ (0 x 0.32) composition at microwave frequencies were investigated in this study. With the addition of BaSnO₃, the dielectric Q(Q _d) value of Ba(Zn_1/3Nb_2/3)O₃ (BZN) can be improved and a small temperature coefficient of resonant frequency (_f) can be achieved. When 22.6 mol % of Sn is added to BZN, the characteristics of the Ba(Sn_0.226Zn_0.258Nb_0.516)O₃ ceramics sintered at 1500°C are as follows: dielectric constant _r = 32, _f = + 12 p.p.m.°C¹ and high Q _d value of 9700 at 10 GHz. Based on the classical dispersion theory and the logarithmic mixing rule, the effects with additions of substitutional element of BaSnO₃ on the microwave dielectric properties of Ba(Zn_1/3Nb_2/3)O₃ can be mostly explained.     

Relaxor behaviour and dielectric properties of BiFeO3 doped Ba(Zr0·1Ti0·9)O3 ceramics

Ba_1???x Bi _x (Ti_0·9Zr_0·1)_1???x Fe _x O₃ ( x = 0–0·075) ceramics are prepared using a conventional solid state reaction method. X-ray diffraction shows the presence of a single phase. Addition of Bi^3?+? and Fe^3?+? strongly influences the crystal structure and dielectric properties of the ceramics. The evolution from a normal ferroelectric to a relaxor ferroelectric is emphasized. Ba_0·99Bi_0·01(Ti_0·9Zr_0·1)_0·99Fe_0·01O₃ ceramic shows a relaxor behaviour at room temperature with Δ T _m =12 K. P– E hysteresis loop of the composition, x = 0·007, shows a remanent polarization ( P _r ) of 0·5 μC/cm² with a coercive field ( E _C ) of 2 kV/cm. Raman spectra of all compounds are performed and correlated well with the X-ray diffraction and dielectric measurement results.     

Fabrication of perovskite-type Ba(Sn1−x Ta x )O3 ceramics and their power factors

Perovskite-type Ba(Sn_1?x Ta _x )O₃ (0.01 ≤ x ≤ 0.06) ceramics with high relative densities (92.7–94.4 %) were fabricated using the hot isostatic pressing (HIP) method at 1273 K and 196 MPa for 4 h in an atmosphere of argon gas. The lattice parameter decreased slightly with increasing x. From the XPS measurement, the Ta⁵⁺ ion was stable in Ba(Sn_1?x Ta _x )O₃ ceramics and the broad peak of the Ta4f level was the overlap between the Ta⁵⁺4f_5/2 and Ta⁵⁺4f_7/2 levels. Ba(Sn_1?x Ta _x )O₃ ceramics were n-type semiconductors, and their electrical resistivities increased with increasing x. The increase in the electrical resistivity was explained by impurity scattering due to the presence of the Ta ions. The absolute value of the Seebeck coefficient (S) increased with increasing temperature and x. The power factor (S ² σ), which was calculated from electrical conductivity (σ) and the Seebeck coefficient, was ca. 1.0 × 10^?5 W m^?1 K^?2 at x = 0.01.     

Effect of Pr and Ca Substitution on the (La1−x−u Pr x Ca u )(Ba1.5Sr0.5)Cu3O y Superconductors

In the fully oxygenated single phase (La_1–x–u Pr _x Ca _u )(Ba_1.5Sr_0.5)Cu₃O _y (0x1.00, 0u0.20) system, if u=0, the z-coordinate of the Ba site, z(Ba), and d _Ba–bp (distance between the Ba site and the basal plane) are lowered by increasing the amount of Pr in the (La_1–x Pr _x )(Ba_1.5Sr_0.5)Cu₃O _y series. On the contrary, if u0, z(Ba) and d _Ba–bp are raised by increasing the amount of Ca ion in the (La_1–x–u Pr _x Ca _u )(Ba_1.5Sr_0.5)Cu₃O _y (0x0.30, 0u0.20) series. Linear relationships are found between z(Ba), d _Ba–bp and the oxygen stoichiometry (y). T _c and p _sh (the hole concentration in CuO₂ layers) increase with increasing the angle of Cu(2)-Ba-Cu(2). Relative positions of the Cu(2) and Ba sites are important in determining the T _c of these 123 compounds.     

Temperature dependence of elastic and dielectric properties of (Bi2O3)1 − x(CuO)x oxide glasses

Oxide glasses with the general formula (Bi₂O₃)_{1 - x}(CuO)_x have been prepared by quick quenching technique. Their longitudinal and shear elastic moduli have been determined by measuring the corresponding ultrasonic wave velocities between 300 and 470 K, which are well below the glass transition temperature of this system. Temperature variation of ultrasonic velocity and attenuation exhibit anomalies around 435 K in glasses with x 0.3. A nonlinear behaviour is also reflected in the CuO concentration dependent dielectric constant curve around x = 0.3. These anomalies are interpreted in terms of a structural softening (or transformation) taking place in samples having CuO concentration above the critical value. The high dielectric constant of these glasses show very little increase with increase of temperature. Anomalies are also found in the temperature dependence of dielectric constant around 435 K. This behaviour is again considered to be associated with the softening of the glass network.