Control of the properties of Pb(TixZr1-x )O3 solid solutions by external disturbances

The influence of x-ray irradiation to absorbed radiation doses D = (0.5?12) × 10⁸ rad on the properties of ferroelectric ceramic Pb(Ti_xZr_1?x )O₃ solid solutions with compositions close to the morphotropic phase boundary was studied. The effects of x-ray radiation on the electrical conductivity of ferroelectric ceramics are shown to differ with x ranging from 0.42 to 0.60. Using empirical equations and numerical techniques, quantitative relations are established between the composition, absorbed radiation dose, and electrical conductivity for Pb(Ti_xZr_1?x )O₃.     

Improved properties & fatigue resistant behaviour OF Ba(Zr0.15Ti0.85)O3 ferroelectric ceramics

The microstructure, dielectric and piezoelectric properties of Zr doped BaTiO₃ ceramics sintered at optimum temperature, are investigated. High energy ball milling technique is adopted to realize nano-sized powders of Ba(Zr_0.15Ti_0.85)O₃ ceramics. Increased boundary mobility of fine powders aided to obtain a relative density of >98.8% of theoretical density corresponding to ceramics under study. Internal stresses in these ceramics are found to be relieved by grain-boundary sliding. The Ba(Zr_0.15Ti_0.85)O₃ ceramics synthesized at relatively low sintering temperatures exhibit remarkable, enhanced dielectric properties viz. improved polarization, high unipolar strain values comparable to Zr doped BaTiO₃ single crystals of same composition, at relatively lower electric fields and also exhibit better fatigue tolerant properties. The underlying mechanisms responsible for superior dielectric, ferroelectric and piezoelectric properties are discussed.     

Dielectric and pyroelectric activities in Pb(Zr1−xTix)O3 ceramics: The role of the phase transition effects

Pure and Nb-doped Pb(Zr_1−xTi_x)O₃ (x = 0.47, 0.48, 0.50) ceramics were prepared by conventional solid-state reaction technique. Dielectric anomalies are observed in both kinds of samples near room temperature. The anomalies could be depressed by donor doping and prefer to be significant in ceramics with tetragonal crystallographic phase. Phase transition mechanism and domain wall pinning effect are proposed to explain this anomaly, and the former is considered as the dominated reason. Further results of the pyroelectric measurements confirm the existence of the ferroelectric–ferroelectric phase transition.     

Development of perovskite and phase transition in lead cobalt niobate modified lead zirconate titanate system

Ferroelectric lead zirconate titanate–lead cobalt niobate ceramics with the formula (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃ where x = 0.0–0.5 were fabricated using a high temperature solid-state reaction method. The formation process, the structure and homogeneity of the obtained powders have been investigated by X-ray diffraction method as well as the simultaneous thermal analysis of both differential thermal analysis (DTA) and thermogravimetry analysis (TGA). It was observed that for the binary system (1 − x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Co_1/3Nb_2/3)O₃, the change in the calcination temperature is approximately linear with respect to the PCoN content in the range x = 0.0–0.5. In addition, X-ray diffraction indicated a phase transformation from a tetragonal to a pseudo-cubic phase when the fraction of PCoN was increased. The dielectric permittivity is remarkably increased by increasing PCoN concentration. The maximum value of remnant polarization P_r (25.3 μC/cm²) was obtained for the 0.5PZT–0.5PCoN ceramic.     

Rietveld analysis and multiferroic properties of Fe doped Ba0.95Bi0.05TiO3 ceramics

We report on the structural, magnetic and ferroelectric properties of Fe doped Ba_0.95Bi_0.05TiO₃ (Ba_0.95Bi_0.05Ti_1−yFe_yO₃ (0 ≤ y ≤ 0.1)) ceramics prepared by solid state reaction. Rietveld analysis shows that compounds with y ≤ 0.07 have a single phase-tetragonal structure (space group P4mm), and the tetragonality (c/a) decreases as x increases. Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ ceramic shows ferromagnetic order with a Curie temperature of about 700 K and ferroelectric order at room temperature. These results indicate that the Ba_0.95Bi_0.05Ti_0.93Fe_0.07O₃ can be useful as a multiferroic material.     

Structural and impedance spectroscopy study of Samarium modified Barium Zirconium Titanate ceramic prepared by mechanochemical route

Samarium modified Barium Zirconium Titanate (BZT) ceramics with general formula [Ba_1−xSm_2x/3](Zr_0.05Ti_0.95O₃) [x = 0, 0.01, 0.02, 0.03 and 0.04] have been prepared by high energy ball milling. The Rietveld refinement of BaZr_0.05Ti_0.95O₃ (BZT) shows a single phase tetragonal symmetry with space group P4mmm and TEM micrograph shows that the crystalline size is in the submicron range. X-ray diffraction (XRD) patterns confirm that no phase change occurs with the addition of Samarium in BZT upto x ≤ 0.03 and a small pyrochlore phase exists at x = 0.04. The complex impedance (Nyquist) plots display a single semicircle highlighting the influence of grain resistance on the electrical behavior. Negative temperature coefficient of resistance behavior is observed in all compositions. The activation energy calculated from Z″ and DC conductivity confirms that the oxygen vacancies play an important role in the conduction mechanism.     

Ferroelectric properties of Pb(Zr1/2Ti1/2)O3–Pb(Zn1/3Nb2/3)O3 ceramics under compressive stress

Effects of compressive stress on the ferroelectric properties of ceramics in PZT–PZN system were investigated. The ceramics with a formula (1−x)Pb(Zr_1/2Ti_1/2)O₃–xPb(Zn_1/3Nb_2/3)O₃ or (1−x)PZT–(x)PZN (x = 0.1–0.5) were prepared by a conventional mixed-oxide method. The ferroelectric properties under the compressive stress of the PZT–PZN ceramics were observed at the stress levels up to 170 MPa using a compressometer in conjunction with a modified Sawyer–Tower circuit. It was found that with increasing compressive stress the area of the ferroelectric hysteresis (P–E) loops, the saturation polarization (P_sat), the remnant polarization (P_r), and the coercive field (E_c) decreased. These results were interpreted through the non-180° ferroelastic domain switching processes.     

Influence of doping concentration on room-temperature ferromagnetism for Fe-doped BaTiO3 ceramics

Ba(Ti_1−xFe_x)O₃ ceramics (x=7, 30 and 70 at%) were prepared by solid-state reaction. All samples are single-phase with 6H-BaTiO₃-type hexagonal perovskite structure. Mössbauer spectra show all Fe atoms to be present as Fe³⁺ in BaTiO₃ lattice, occupying M1 octahedral and pentahedral sites. Room-temperature ferromagnetism is exhibited and saturation magnetization gradually decreases with increasing Fe content. The observed ferromagnetism is considered to be an intrinsic property of Ba(Ti_1−xFe_x)O₃, originating from super-exchange interactions between Fe³⁺ in different occupational sites associated with oxygen vacancies. The variation in magnetization with Fe content is related to the ratio of pentahedral to octahedral sites and oxygen vacancies.     

Structural and dielectric properties in the (Ba1−xCax)(Ti0.95Zr0.05)O3 ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.95Zr_0.05)O₃ (x = 0.05-0.40) (BCZT) ceramics were prepared by solid-state reaction technique. XRD results show that the samples in the composition range of 0.05 ≤ x ≤ 0.25 exhibit pure perovskite structures and undergo a polymorphic phase transitions from orthorhombic to tetragonal phase around room temperature. The biphasic structures are detected at x ≥ 0.30 and the dielectric peaks become broad and dielectric constants decrease with increasing Ca content. Ca replacement at Ba site leads to diffuseness, whereas Ca occupancy at Ti site leads to decrease of the T_c.     

Piezoelectric properties of [Li0.03(K0.48Na0.52)0.97](Nb0.97Sb0.03)O3-(Ba0.85Ca0.15)(Ti0.90Zr0.10)O3 lead-free piezoelectric ceramics

[Li_0.03(K_0.48Na_0.52)_0.97](Nb_0.97Sb_0.03)O₃-(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃ [(1−x)LKNNS-xBCTZ] lead-free piezoelectric ceramics were prepared by the conventional solid state method, and effects of BCTZ content on the piezoelectric properties of LKNNS ceramics were mainly investigated. A stable solid solution has been formed between LKNNS and BCTZ, and a morphotropic phase boundary of (1−x)LKNNS-xBCTZ ceramics is identified in the range of 0 < x ≤ 0.02. The Curie temperature of (1−x)LKNNS-xBCTZ ceramics decreases with increasing BCTZ content. A higher ?_r value and a lower tan δ value are demonstrated for the (1−x)LKNNS-xBCTZ ceramic with x = 0.02. The (1−x)LKNNS-xBCTZ ceramic with x = 0.02 has an enhanced electrical behavior of d₃₃ ∼ 237 pC/N, k_p ∼ 48.6%, ?_r ∼ 1451, tan δ ∼ 0.037, and T_c ∼ 335 °C. As a result, (1−x)LKNNS-xBCTZ ceramics are promising candidate materials for the field of lead-free piezoelectric materials.     

Structure evolution and microwave dielectric response of (Ca0.5+xSr0.5−x)[(Al0.5Nb0.5)0.5Ti0.5]O3 solid solutions

The phase assemblage, crystal structure evolution and microwave dielectric response of (Ca_0.5+xSr_0.5−x)[(Al_0.5Nb_0.5)_0.5Ti_0.5]O₃ ceramics (abbreviated as CSANT hereafter) are investigated. Single perovskite solid solution is formed in the CSANT ceramics in Sr-rich composition range of x < −0.05, however, Ca₄Ti₃O₁₀-type layered perovskite phase begins to segregate after x = −0.05. The CSANT perovskites crystallized in Fm3m cubic symmetry in the composition range of x ≤ −0.2, however, as the Ca²⁺ content in A-site increased, the oxygen octahedral began to be anti-phase tilted at x = −0.1 and the crystal structure transited to P2₁/n pseudo-orthorhombic space group thereafter. The microwave dielectric response of the CSANT ceramics is elaborately discussed in terms of their crystallographic structure and chemical composition. When sintered at 1500 °C for 4 h, a dielectric constant ɛ_r of 52.5, a Qf product of 28000 GHz and a τ_f of +25.4 ppm/°C microwave dielectric ceramic can be obtained in the CSANT ceramics at x = 0.3.     

In situ hot-stage transmission electron microscopy of Pb(Zr0.52Ti0.48)O3

The domain structure of Pb(Zr_0.52Ti_0.48)O₃ before and after hot-stage experiment has been studied. The influence of maximum temperature, heating and cooling rate on the domain configuration of Pb(Zr_{1? x} , Ti _x )O₃ with x = 0.40, 0.45, 0.48 and 0.55 was analysed. A reliable basis for further hot-stage experiments of Pb(Zr_1?x, Ti_x)O₃ has been established. The investigations revealed a temperature dependent appearance and disappearance of nano- and microdomains. The appearance of microdomains in the nano scale range during cooling, denoted as domain miniaturisation, and the time dependent recovering of the former domain structure, revealed that under specific experimental conditions the domain configuration is reversible.     

Enhanced piezoelectric properties and lowered sintering temperature of Ba(Zr0.07Ti0.93)O3 by B2O3 addition

The effects of B₂O₃ doping on densification, ferroelectric, and piezoelectric properties of Ba(Zr_0.07Ti_0.93)O₃(BZT) ceramics were investigated. The addition of B₂O₃ to the ceramics lowered the sintering temperature by ∼200 °C as well as changed their microstructures. Higher B₂O₃ concentration caused a decrease in remanent polarization and coercive field, while the piezoelectric coefficient d₃₃ remained at a high value of 291 pC/N for the ceramic sample with 2 wt.% B₂O₃. The relationship between piezoelectric properties and ferroelectric constant was examined.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

Microstructure,dielectric and piezoelectric properties of (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript>-Ba(Ti<Subscript>0.95</Subscript>Zr<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> lead-free ceramics with CuO sintering aid

Using an ordinary ceramic fabrication technique, we fabricated lead-free (1-x)(K_0.5Na_0.5)NbO₃-xBa(Ti_0.95Zr_0.05)O₃ ceramics with CuO sintering aid . Ba(Ti_0.95Zr_0.05)O₃ diffuses into (K_0.5Na_0.5)NbO₃ to form a new solid solution. The ceramics with perovskite structure possess orthorhombic phase at x≤0.04 and become tetragonal phase at x≥0.06. Both the paraelectric cubic–ferroelectric tetragonal and the ferroelectric tetragonal–ferroelectric orthorhombic phase transition temperatures decrease with increasing the concentration of Ba(Ti_0.95Zr_0.05)O₃. The doping of CuO effectively promotes the densification of the ceramics. The coexistence of the orthorhombic and tetragonal phases at 0.04<x<0.06 and the improvement in sintering performances of the ceramics significantly enhance the piezoelectric and dielectric properties at room temperature. The ceramics with x=0.04–0.06 and y=0.75–1.50 possess excellent properties: d₃₃=119–185 pC/N, k_P=37–44%, k_t=35–49%, ε=341–1129, cosδ=0.7–4.4% and T_c=312–346 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s     

Synthesis of Zr-doped TiO2 templated from cloth and its photocatalytic activity

Biomorphic Zr-doped TiO₂ (Zr _x Ti_{1 ? x} O₂) with hierarchical micro- and nanostructures was successfully fabricated using cloth as the host template. We found that the resulting Zr _x Ti_{1 ? x} O₂ faithfully duplicated the morphologic microstructures of the initial cloth with grain size of about 10–50 nm. The photocatalytic activity of the as-prepared Zr _x Ti_{1 ? x} O₂ was examined by the degradation of rhodamine B in aqueous solution under simulated solar light, which showed that templates pretreated with NaOH solution followed by mixed acid and an appropriate amount of doped Zr (3 mol%) could significantly enhance the photocatalytic activities of Zr _x Ti_{1 ? x} O₂. This simple template method provides a cost-effective and ecofriendly route to synthesize other metal-doped semiconductor materials of predicted morphology.     

Effects of Zr/Ti ratio on dielectric and ferroelectric properties of 0.8Pb(ZrxTi1−x)O3–0.2Pb(Co1/3Nb2/3)O3 ceramics

The influences of Zr/Ti ratio on electrical properties of the 0.8Pb(Zr_xTi_1−x)O₃–0.2Pb(Co_1/3Nb_2/3)O₃ ceramics prepared by a mixed-oxide method (with x = 0.46, 0.48, 0.50, 0.52, and 0.54) have been investigated in order to identify the morphotropic phase boundary composition in this system. With XRD analysis, the crystal structure of dense specimens appeared to change gradually from tetragonal to rhombohedral with increasing Zr content. The dielectric properties measurements showed a maximum dielectric constant at x = 0.50, while the transition temperature decreased with increasing Zr content in the system. Moreover, all ceramics showed diffused phase transition behaviors with a minimum diffusivity at x = 0.50. In addition, the Polarization–Electric field (P–E) hysteresis loops of the ceramic systems also changed significantly with the Zr content. Interestingly, the loop squareness parameter reached maximum around x = 0.50. Other ferroelectric hysteresis parameters showed noticeable change at x = 0.50. These results clearly showed the significance of Zr/Ti ratio in controlling the electrical properties of the PZT–PCN ceramic systems.     

Rhombohedral–orthorhombic phase coexistence and electrical properties of Ta and BaZrO3 co-modified (K,Na)NbO3 lead-free ceramics

The BaZrO₃ and Ta have been used to improve piezoelectric properties of (K, Na)NbO₃ ceramics by the construction of the phase boundary, and (1 ? x)K_0.48Na_0.52(Nb_0.95Ta_0.05)O₃–xBaZrO₃ [(1 ? x)KNNT–xBZ] ceramics were prepared by the conventional solid-state method. The effect of BZ content on their phase structure, microstructure, and electrical properties has been investigated. A rhombohedral and orthorhombic phase coexistence has been observed in the compositional range of 0.05 ≤ x ≤ 0.07. With increasing BZ content, their T_c and T_o–t values decrease gradually, and the dielectric constant increases linearly. The ceramic with x = 0.06 exhibits an enhanced piezoelectric behavior (d₃₃ ～ 193 pC/N and k_p ～ 32.6%) because of the coexistence of two phases together with a dense microstructure. As a result, the construction of a rhombohedral and orthorhombic phase boundary is an effective way to improve the piezoelectric properties of KNN-based ceramics.     

Dielectric properties and temperature stability of BaTiO3 co-doped La2O3 and Tm2O3

The influence of La₂O₃ and Tm₂O₃ co-doping on the dielectric properties and the temperature stability of BaTiO₃ was investigated. BaTiO₃ ceramics were prepared with the compositional formula of (Ba_1−xLa_x)(Ti_1-x/4−yTm_y)O₃. La₂O₃ and Tm₂O₃ co-doping in BaTiO₃ mainly had effects on an increase in the dielectric constant and the temperature stability, respectively. The increase of La₂O₃ concentration and the decrease of Tm₂O₃ concentration in BaTiO₃ resulted in a decrease of lattice parameter and tetragonality because La³⁺ ion substituting for Ba site is smaller than Ba²⁺ ion and Tm³⁺ ion substituting for Ti site is larger than Ti⁴⁺ ion. With the increase of La₂O₃ and the decrease of Tm₂O₃, the dielectric constant of BaTiO₃ was enhanced in spite of the reduction of tetragonality. P-E hysteresis measurements revealed that this phenomenon was based on the improvement of remanent polarization with the increase of La₂O₃ concentration. The introduction of excess Tm₂O₃ in BaTiO₃ suppressed the grain growth and BaTiO₃ ceramics showed higher temperature stability due to the stable tetragonal structure and the small grain size with the increase of Tm₂O₃ concentration.