Dielectric responses in Mg<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>-replaced Pb[(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>),Ti]O<Subscript>3</Subscript> ceramics

Octahedral lattice sites of Pb[(Zn_1/3Nb_2/3),Ti]O₃ were replaced by 20 at.% Mg_1/3Ta_2/3 complex to enhance perovskite development, especially at Pb(Zn_1/3Nb_2/3)O₃-rich compositions. Resultant changes in the perovskite formation and associated dielectric responses were investigated. A perovskite structure was identified at Pb(Zn_1/3Nb_2/3)O₃-rich compositions by X-ray diffraction, although the development was rather incomplete. Phase transition modes in the dielectric constant spectra changed from diffuse to sharp ones, regardless of the introduction of Mg_1/3Ta_2/3. Dielectric maximum temperatures of the ceramics shifted linearly with the compositional change.     

Dielectric properties of Pb(Zn<Subscript>1/3</Subscript>Ta<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-introduced (Ba,Pb)TiO<Subscript>3</Subscript> ceramic system

Ceramic powders of the Pb(Zn_1/3Ta_2/3)O₃-introduced BaTiO₃–PbTiO₃ system were prepared using a B-site precursor method. Perovskite formation tendencies of the system compositions were determined by X-ray diffraction. Weak-field low-frequency dielectric properties of the sintered ceramics were investigated. Dielectric constant spectra were further analyzed in terms of diffuseness. Internal microstructures of the ceramics were also examined.     

Preparation and phase formation of perovskite Pb(Ni<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> by a reaction-sintering process

Pyrochlore-free Pb(Ni_1/3Nb_2/3)O₃ perovskite ceramics produced by a simple and effective reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂ and Nb₂O₅ was pressed and sintered directly into PNN ceramics. Density of 98.5% of theoretical value was obtained after sintered at 1230 °C for 2 h in air. 99.3% of theoretical density was obtained after sintered at 1,200 °C for 2 h in PbO compensated atmosphere. PNN ceramic with dielectric constant 1,680 at 25 °C and 1 kHz has been obtained.     

Phase developments in Pb(Mg<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> and Pb(Zn<Subscript>1/2</Subscript>W<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> via B-site precursor route

Phase formation stages of MgWO₄ and ZnWO₄ (precursor compositions for following steps) were investigated by monitoring the reactions of oxide chemicals at various temperatures. Developed phases were examined by using X-ray diffraction (XRD). Successive attempts were also conducted for Pb(Mg_1/2W_1/2)O₃ (PMW) and Pb(Zn_1/2W_1/2)O₃ (PZW) by reacting PbO with the precursor compounds. Stages of phase development in the two compositions were also analyzed. The results are compared with those of another tungsten-containing perovskite Pb(Fe_2/3W_1/3)O₃ (PFW) and its B-site precursor Fe₂WO₆. After PbO addition to the precursor powders, a perovskite phase formed directly (i.e., without any intermediate phases) in the case of PMW. For PbO + ½ZnWO₄, in contrast, the decomposition of ZnWO₄ and preferential reaction with PbO resulted in Pb₂WO₅ and ZnO, instead of the perovskite PZW.     

Dielectric properties of iron doped calcium copper titanate,CaCu<Subscript>3</Subscript>Ti<Subscript>3.9</Subscript>Fe<Subscript>0.1</Subscript>O<Subscript>12</Subscript> ceramic

Dielectric properties of iron doped CaCu₃Ti₄O₁₂ (CCTO), viz. CaCu₃Ti_3.9Fe_0.1O₁₂ (CCTFO) prepared by a novel semi-wet route have been investigated. X-ray diffraction of powder sintered at 900 °C show formation of single phase solid solution. Energy dispersive X-ray spectroscopy (EDX) confirmed the presence of CuO rich phase at grain boundaries of CCTFO. Nature of dielectric relaxation observed above room temperature is studied using complex plane impedance analysis and modulus spectroscopy. It has been found that out of the two relaxations reported earlier above room temperature, one occurring at lower temperature is due to grainboundaries interfacial polarization.     

Structural,dielectric and electrical properties of Ca modified BaSn<Subscript>0.15</Subscript>Ti<Subscript>0.85</Subscript>O<Subscript>3</Subscript> Ceramics

Polycrystalline samples of (Ba_1-xCa_x)(Sn_0.15Ti_0.85)O₃ (x = 0, 0.03, 0.06 and 0.09) of perovskite structural family have been prepared by a high-temperature solid-state reaction technique. Preliminary room temperature X-ray study confirmed the formation of single-phase compound with tetragonal structure. The Scanning electron microscope shows the uniform distribution of the grains throughout the surface of the samples. Dielectric studies as a function of frequency at different temperature suggests that the compounds undergo diffuse phase transition (DPT). The d.c. and a.c. conductivities have been investigated over a wide range of temperature and the activation energy was calculated.     

Structural and electrical properties of Ba(Sb<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript> ceramic

Lead-free perovskite Ba(Sb_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1200 °C/5 h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were determined from the experimental results using FullProf software whereas crystallite size and lattice strain were estimated from Williamson–Hall approach. XRD analysis of the compound indicated the formation of a single-phase monoclinic structure with the space group P2/m. EDAX and SEM studies were carried out to evaluate the quality and purity of the compound. Dielectric study revealed the frequency-dependent dielectric anomaly. To find a correlation between the response of the real system and idealized model circuit composed of discrete electrical components, the model fittings were presented using the impedance data. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(Sb_1/2Nb_1/2)O₃. The ac conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy of the compound.     

Synthesis and Characterization of CoFe<Subscript>2</Subscript><Emphasis Type="Italic">O</Emphasis><Subscript>4</Subscript>/BaTiO<Subscript>3</Subscript> Multiferroic Composites

Three composite modes of CoFe₂ O ₄/BaTiO₃ (CFO/BTO) were created with appropriate stoichiometric proportion. They are nitrate solution of CFO mixed with BTO (SCB), self-propagating precursor of CFO mixed with BTO (PCB), and the made-up CFO mixed with BTO (MCB) separately. The microstructural, ferroelectric, and ferromagnetic properties of SCB, PCB, and MCB bulk composites were investigated. SCB, PCB, and MCB bulk composites with a molar ratio of 2:8 were calcined at 1020, 1120, and 1160 ^°C, respectively. And X-ray diffraction (XRD) analysis showed that they all correspond to the CFO with cubic spinel structure and the BTO with tetragonal perovskite structure. The formation temperature of BTO with hexagonal structure is related to the distance of inter-diffusion and Co ²⁺ concentration in the CFO/BTO bulk composite. The wet chemical routing is of benefit to inhibit the agglomeration of the BTO in the CFO/BTO bulk composite. The maximum polarization of 5.24 μC/cm ² was received in the MCB bulk composite sintered at 1160 ^°C with a molar ratio of 1:9. The maximum saturation magnetization of 31.609 emu/g and the remnant magnetization of 10.336 emu/g were obtained in the MCB bulk composite sintered at 1160 ^°C with a molar ratio of 4:6. The threshold ferromagnetic phase content of percolation which has an effect on the MCB bulk composite is less than 40 mol %.     

Synthesis and characterization of pseudo-ternary Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> ferroelectric ceramics via a B-site oxide mixing route

Perovskite phase formation and dielectric/ferroelectric properties of the pseudo-ternary Pb(Fe_1/2Nb_1/2)O₃-PbZrO₃-PbTiO₃ (PFN-PZ-PT) ferroelectric ceramics have been investigated as promising materials for multi-layer ceramic capacitors. Complete solid solution with pure perovskite phase can be formed in this system in the whole composition range studied using conventional solid-state reaction method via a B-site oxide mixing route. Crystal lattice of the ceramics obtained shrinkages with the increase of the concentration of Pb(Fe_1/2Nb_1/2)O₃ (PFN) and expands with the increase of the content of PbZrO₃ (PZ). With the increase of the concentration of PbTiO₃ (PT), crystal structure of PFN-PZ-PT changes from pseudo-cubic ferroelectric phase to tetragonal one while retains the fraction of PFN as constant. A morphotropic phase boundary (MPB) forms at the composition of 42 mol% PT regardless of whatever concentration of PFN, and the content of PFN affects little on the composition of MPB. The preliminary phase diagram of the PFN-PZ-PT system is determined by X-ray diffraction (XRD) measurements combining with dielectric/ferroelectric characterization. Dielectric measurements indicate that the value of dielectric maximum (ɛ_m) and the temperature where ɛ_m appears (T_m) increase with the increase of the concentration of PT. However, PFN exhibits opposite effects, i.e., ɛ_m increases with the increase of the concentration of PFN accompanied by the decrease of T_m.     

Preparation of Pb(Zr,Ti)O<Subscript>3</Subscript>–Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics by dry–dry method

Ternary perovskite ceramics of Pb[(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x]_0.98Nb_0.02O_3.01 (PZTMN, x = −0.075, −0.05, −0.025, 0, 0.025, 0.05, and 0.075 ), are synthesized via dry–dry method. B-site precursors of PZTMN ([(Zr_0.5Ti_0.5)_0.8−x (Mg_1/3Nb_2/3)_0.2+x ]_0.98Nb_0.02O_2.01, ZTMN) can be synthesized via a two-step solid state reaction method. The first calcination temperature is 1,300 °C, and the second is not higher than 1,360 °C. Incorporation of magnesium and niobium ions promotes the formation of the single phase solid solution with ZrTiO₄ structure. Single phase perovskite PZTMN is formed at 780 °C, much lower than that in conventional process. Dense ceramics can be sintered at about 1,260 °C with dielectric and piezoelectric properties comparable to that of wet–dry method and higher than that of conventional method. It seems that B-site precursor method is cost effective in preparation of ternary piezoelectric ceramics.     

Fabrication of thin films by sputtering deposition using (Ba<Subscript>0.3</Subscript>Sr<Subscript>0.7</Subscript>)(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramic as target

Dielectric ceramic thin films were fabricated on SiO₂ (110) substrates by the radio frequency (RF) magnetron sputtering method using (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ microwave dielectric ceramic as target. The microstructure, components, and morphology of the thin films were investigated thoroughly. The results reveal that the experimental conditions can affect the growth of the thin films significantly. The main phases of the thin films are Ba_0.5Sr_0.5Nb₂O₆ and Ba_0.27Sr_0.75Nb₂O_5.78, which are of different composition from that of the ceramic target due to Zn loss. The thin films are polycrystalline with high-quality crystalline and are made up of dense rod-like structures. The growth mechanism of the thin films is discussed in particular.     

Chemical solution deposition of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin film

CaCu₃Ti₄O₁₂ (CCTO) thin film was successfully deposited on boron doped silica substrate by chemical solution deposition and rapid thermal processing. The phase and microstructure of the deposited films were studied as a function of sintering temperature, employing X-ray diffractometry and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using impedance spectroscopy. Polycrystalline pure phase CCTO thin films with (220) preferential orientation was obtained at a sintering temperature of 750°C. There was a bimodal size distribution of grains. The dielectric constant and loss factor at 1 kHz obtained for a film sintered at 750°C was k ∼ 2000 and tan δ ∼ 0.05.     

Dielectric and impedance studies of (Pb<Subscript>1−x</Subscript>Ca<Subscript>x</Subscript>)(Fe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> dielectric ceramics

Ceramic samples of (Pb_1?xCa_x)(Fe_0.5Nb_0.5)O₃ with x = 0.20, 0.40, 0.45, 0.50, 0.55 and 0.60 were obtained by columbite precursor method. All the synthesized samples have perovskite structure with pseudo-cubic symmetry. Dielectric properties of all the samples were measured as a function of frequency from room temperature up to 573 K. Two dielectric anomalies were observed in ε_r–T plots at about 400 and 500 K. The impedance analysis depicts a single relaxation process. Activation energies obtained from temperature dependence of relaxation frequency, f₀ and grain resistance, R_g were found to be more or less comparable. The observed relaxation in all the samples seems to be due to electron relaxation associated with oxygen vacancies.     

Ca<Subscript>3</Subscript>WO<Subscript>6</Subscript>: a novel microwave dielectric ceramic with complex perovskite structure

Present work introduces a novel Ca₃WO₆ microwave dielectric ceramic with a complex perovskite structure. The Ca₃WO₆ ceramic was prepared by solid state reaction method and can be well densified at above 1,260 °C for 2 h in air. All the XRD patterns can be fully indexed as a single-phase monoclinic structure (space group P2₁/n). The sharp Raman vibration mode at 810 cm⁻¹ suggests the long range order in the Ca₃WO₆ structure. The best microwave dielectric properties can be obtained in ceramic sample sintered at 1,275 °C for 2 h with a permittivity ~15.3, a Qf value ~29,200 GHz and a TCF value about −30 ppm/°C. Applying the oxide additivity rule, the calculated permittivity agrees well with the measured value. This kind of ceramic might have some potential value for microwave application for its good microwave dielectric behavior. The (Ca_1/2W_1/2) complex cations holding the site of Ti⁴⁺ in perovskite structure would introduce many new systems in complex perovskite compounds in the future.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Effects of addition of BiFeO<Subscript>3</Subscript> on phase transition and dielectric properties of BaTiO<Subscript>3</Subscript> ceramics

Samples of xBiFeO₃–(1 − x)BaTiO₃ (x = 0, 0.02, 0.04, 0.06, 0.07 and 0.08) were synthesized by solid state reaction technique and sintered in air in the temperature range 1,220–1,280 °C for 4 h. X-ray diffraction data showed that 2–8 mol% BiFeO₃ can dissolve into the lattice of BaTiO₃ and form single perovskite phase. The crystal structure changes from tetragonal to cubic phase at room temperature when 8 mol% of BiFeO₃ was added into BaTiO₃. Scanning electron microscope images indicated that the ceramics have compact and uniform microstructures, and the grain size of the ceramics decreases with the increase of BiFeO₃ content. Dielectric constants were measured as functions of temperatures (25–200 °C). With rising addition of BiFeO₃, the Curie temperature decreases. For the sample with x = 0.08, the phase transition occurred below room temperature. The boundary between tetragonal and cubic phase of the BiFeO₃–BaTiO₃ system at room temperature locates at a composition between 7 and 8 mol% of BiFeO₃. The diffusivity parameter γ for compositions x = 0.02 and x = 0.07 is 1.21 and 1.29, respectively. The relaxor-like behaviour is enhanced by the BiFeO₃ addition.     

Microwave dielectric properties and its compatibility with silver electrode of LiNb<Subscript>0.6</Subscript>Ti<Subscript>0.5</Subscript>O<Subscript>3</Subscript> with B<Subscript>2</Subscript>O<Subscript>3</Subscript> and CuO additions

The influences of B₂O₃ and CuO (BCu, B₂O₃: CuO = 1:1) additions on the sintering behavior and microwave dielectric properties of LiNb_0.6Ti_0.5O₃ (LNT) ceramics were investigated. LNT ceramics were prepared with conventional solid-state method and sintered at temperatures about 1,100 °C. The sintering temperature of LNT ceramics with BCu addition could be effectively reduced to 900 °C due to the liquid phase effects resulting from the additives. The addition of BCu does not induce much degradation in the microwave dielectric properties. Typically, the excellent microwave dielectric properties of ε_r = 66, Q × f = 6,210 GHz, and τ _f  = 25 ppm/^oC were obtained for the 2 wt% BCu-doped sample sintered at 900 °C. Chemical compatibility of silver electrodes and low-fired samples has also been investigated.     

Dielectric properties of a ceramic oxide: Li(Ni<Subscript>7/10</Subscript>Fe<Subscript>3/10</Subscript>)VO<Subscript>4</Subscript>

The Li(Ni_7/10Fe_3/10)VO₄ compound has been synthesized by solution-based chemical route. Its dielectric response is investigated using complex impedance spectroscopy technique. Frequency dependence of dielectric constant (ε_r) at different temperatures shows low-frequency dispersion due to polarized structure of the material and mobile charge carriers. Temperature dependence of ε_r at different frequencies exhibits the dielectric anomalies in ε_r at different temperatures. Dielectric relaxation process in the material is signified by the variation of tangent loss with frequency at different temperatures. The variation of relaxation time with temperature obeys the Vogel–Fulcher law.     

Dielectric response of Ag/BaTiO<Subscript>3</Subscript>/epoxy nanocomposites

Dielectric properties and relaxation phenomena of hybrid material (functionalized nanosilver/BaTiO₃/epoxy) were studied as a function of ceramic content. Nanoparticles were obtained through chemical reduction in ethanol and triethylenetetramine. Epoxy resin, functionalized Ag and BaTiO₃ were mixed and composites were prepared onto glass substrates by dipping technique. Samples containing various amounts of ceramic filler were examined by thermal and SEM analysis. Dielectric measurements were performed at different frequencies and temperatures. It was found that hybrid materials had high permittivities and their relaxation processes were influenced by the epoxy resin near its T _g, while metallic and ceramic content modified the real permittivity values.     

The effects of CuO-doping on dielectric and piezoelectric properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Ba(Zr,Ti)O<Subscript>3</Subscript> lead-free ceramics

CuO-doped lead-free ceramics based on bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT) and barium zirconate titanate (Ba(Zr_0.07Ti_0.93)O₃, BZT) were prepared via a multi-step solid-state reaction process. The BNT–BZT with CuO dopant ceramics sintered at 1150–1180 °C for 2 h in air showed a pure perovskite structure. SEM images reveal that a small amount of CuO (<2 mol%) play a significant role on the microstructure to improve its sintering attributes, while it will degrade when the dopant is added beyond 2 mol%. The dielectric and piezoelectric properties of CuO-doped BNT–BZT ceramics were evaluated. At room temperature, the sample doped with 2 mol% CuO shows quite good properties such as a high piezoelectric constant (d ₃₃ ∼156.5 pC/N) and a high electromechanical coupling factor (k _t ∼52%). The depolarization temperature increased dramatically and the maximum permittivity temperature decreased slightly.