Structural, dielectric, magnetic, magnetodielectric and impedance spectroscopic studies of multiferroic BiFeO3-BaTiO3 ceramics

Polycrystalline (1−x)BiFeO₃-xBaTiO₃ (x = 0.00, 0.10, 0.20 and 0.30) ceramics have been prepared via mixed oxide route. The effect of BaTiO₃ substitution on the dielectric, ferroelectric and magnetic properties of the BiFeO₃ multiferroic perovskite was studied. From XRD analysis it revealed that BaTiO₃ substitution does not affect the crystal structure of the (1−x)BiFeO₃-xBaTiO₃ system up to x = 0.30. Improved dielectric properties were observed in the prepared system. An anomaly in the dielectric constant (?) was observed in the vicinity of the antiferromagnetic transition temperature. Experimental results suggest that in the (1−x)BiFeO₃-xBaTiO₃ system, the increase of BaTiO₃ concentration leads to the effective suppression of the spiral spin structure of BiFeO₃, resulting in the appearance of net magnetization. The dependence of dielectric constant and loss tangent on the magnetic field is a evidence of magnetoelectric coupling in (1−x)BiFeO₃-xBaTiO₃ system. The impedance analysis suggests the presence of a temperature dependent electrical relaxation process in the material, which is almost similar for all the concentrations in the present studies. The electrical conductivity has been observed to increase with rise in temperature showing a typical negative temperature coefficient of the resistance (NTCR) behaviors analogous to a semiconductor and suggests a non-Debye type of electrical relaxation.     

Ba3ZnTa2−xNbxO9 and Ba3MgTa2−xNbxO9 (0≤x≤1): synthesis, structure and dielectric properties

Oxides belonging to the families Ba₃ZnTa_2−xNb_xO₉ and Ba₃MgTa_2−xNb_xO₉ were synthesized by the solid state reaction route. Sintering temperatures of 1300°C led to oxides with disordered (cubic) perovskite structure. However, on sintering at 1425°C hexagonally ordered structures were obtained for Ba₃MgTa_2−xNb_xO₉ over the entire range (0≤x≤1) of composition, while for Ba₃ZnTa_2−xNb_xO₉ the ordered structure exists in a limited range (0≤x≤0.5). The dielectric constant is close to 30 for the Ba₃ZnTa_2−xNb_xO₉ family of oxides while the Mg analogues have lower dielectric constant of ∼18 in the range 50 Hz to 500 kHz. At microwave frequencies (5-7 GHz) dielectric constant increases with increase in niobium concentration (22-26) for Ba₃ZnTa_2−xNb_xO₉; for Ba₃MgTa_2−xNb_xO₉ it varies between 12 and 14. The “Zn” compounds have much higher quality factors and lower temperature coefficient of resonant frequency compared to the “Mg” analogues.     

Structural, magnetic and dielectric properties of Bi1−ySryFe(1−y)(1−x)Sc(1−y)xTiyO3 (x = 0-0.2, y = 0.1-0.3) ceramics

In this study, bulk ceramics with general formula Bi_1−ySr_yFe_{(1−y)(1−x)}Sc_(1−y)xTi_yO₃ (x = 0-0.2, y = 0.1-0.3 mol%) were prepared by traditional solid-state reaction method. As a comparison, bulk BiFeO₃ (BF) was also sintered by rapid sintering method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that apart from a small amount of secondary phase detected in BF, all other samples crystallized in pure perovskite structure and maintained original R3c space group. The room temperature M-H curves were obtained. While BF had a coercive magnetic field (H_c) of 150 Oe, Bi_1−ySr_yFe_1−yTi_yO₃ solid solutions had a much larger value (for y = 0.1, 0.2, 0.3, H_c were 4537, 5230 and 3578 Oe, respectively). Sc³⁺ substitution decreased the H_c values of these solid solutions remarkably, and resulted in soft magnetic properties, as well as a decrease of the dielectric loss. At 1 MHz, the tan δ of Bi_0.7Sr_0.3Fe_0.7(1−x)Sc_0.7xTi_0.3O₃ with x = 0.05, 0.1, 0.15, 0.2 were 0.1545, 0.1078, 0.1046 and 0.1701, respectively.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

(5 − x)BaO-xMgO-2Nb2O5 ceramics prepared using a reaction-sintering process

(5 − x)BaO-xMgO-2Nb₂O₅ (x = 0.5 and 1; 5MBN and 10MBN) microwave ceramics prepared using a reaction-sintering process were investigated. Without any calcinations involved, the mixture of BaCO₃, MgO, and Nb₂O₅ was pressed and sintered directly. MBN ceramics were produced after 2-6 h of sintering at 1350-1500 °C. The formation of (BaMg)₅Nb₄O₁₅ was a major phase in producing 5MBN ceramics, and the formation of Ba(Mg_1/3Nb_2/3)O₃ was a major phase in producing 10MBN ceramics. As CuO (1 wt%) was added, the sintering temperature dropped by more than 150 °C. We produced 5MBN ceramics with these dielectric properties: ?_r = 36.69, Qf = 20,097 GHz, and τ_f = 61.1 ppm/°C, and 10MBN ceramics with these dielectric properties: ?_r = 39.2, Qf = 43,878 GHz, and τ_f = 37.6 ppm/°C. The reaction-sintering process is a simple and effective method for producing (5 − x)BaO-xMgO-2Nb₂O₅ ceramics for applications in microwave dielectric resonators.     

Role of structural changes in dielectric,ferroelectric properties of Sr2KxNa1−xNb5O15 lead-free ceramics

Lead-free Sr₂K_xNa_1−xNb₅O₁₅ (0.00 ≤ x ≤ 0.20) piezoelectric ceramics were prepared by two-step solid state reaction method. Pure tungsten bronze structure could be obtained in all ceramics and K substitution could accelerate the phase formation at lower temperatures. The lattice constant calculation indicated expansion of the unit cell and reduced distortion of the crystal structure with K substitution due to the bigger ionic size of K⁺ (1.64 Å) compared to that of Na⁺ (1.39 Å). Electrical properties of Sr₂K_xNa_1−xNb₅O₁₅ ceramics greatly depended on the K content. Curie temperature T_c shifted downward, whereas the maximum dielectric constant ?_m and the degree of diffusion phase transition all increased initially and then decreased as K content increased, indicating that proper amount of K substitution with x between 0.05 and 0.10 could enhance the dielectric properties. All the ceramics showed an intermediate relaxor-like behavior between normal and ideal relaxor ferroelectrics according to the modified Curie–Weiss law. With increasing K content, the remnant polarization (P_r) decreased gradually and the coercive field (E_c) decreased initially and then increased. But normal ferroelectric hysteresis loops could be observed in all compositions. Besides, the underlying mechanism for variations of the electrical properties due to K substitution was explained in this work.     

Novel transparent conducting oxide: Anatase Ti1−xNbxO2

Single-crystalline Ti_1−xNb_xO₂ (x = 0.2) films of 40 nm thickness were deposited on SrTiO₃ (100) substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction measurement confirmed epitaxial growth of anatase (001) film. The resistivity of Ti_1−xNb_xO₂ films with x ≥ 0.03 is 2-3 × 10^− 4 Ω cm at room temperature. The carrier density of Ti_1−xNb_xO₂, which is almost proportional to the Nb concentration, can be controlled in a range of 1 × 10¹⁹ to 2 × 10²¹ cm^− 3. Optical measurements revealed that internal transmittance in the visible and near-infrared region for films with x = 0.03 was more than 97%. These results demonstrate that the presently developed anatase Ti_1−xNb_xO₂ is one of the promising candidates for the practical TCOs.     

Correlation of crystal structure and microwave dielectric properties for Zn(Ti1−xSnx)Nb2O8 ceramics

The correlation of crystal structure and microwave dielectric properties for Zn(Ti_1−xSn_x)Nb₂O₈ ceramics were investigated. The Zn(Ti_1−xSn_x)Nb₂O₈ ceramics contained ZnTiNb₂O₈ and an unknown Columbite-type phase. The columbite structure phase with increasing degree of ordering led to decrease of dielectric constant, increase of Qf and τ_f. The ZnTiNb₂O₈ with decreasing cation valence led to increase of τ_f. The typical values were: ? = 30.88, Qf = 43,500 GHz, τ_f = −54.32 × 10⁻⁶/ °C.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Structural and microwave dielectric behavior of (Li1/4Nb3/4) substituted ZrxSnyTizO4 (x + y + z = 2) system

The phase structure, microwave dielectric properties, and their stability with different annealing conditions have been investigated in (Li_1/4Nb_3/4) substituted Zr_xSn_yTi_zO₄ system. The sintering temperature of Zr_xSn_yTi_zO₄ ceramic was lowered from 1500 to 1140 °C by (Li_1/4Nb_3/4) substitution. Both X-ray diffraction (XRD) analysis and electron diffraction (ED) analysis revealed that the (Li_1/4Nb_3/4) substituted Zr_xSn_yTi_zO₄ ceramic crystallized as the high-temperature disordered ZrTiO₄ phase. As the content of Sn increased from 0.10 to 0.30, the permittivity of the (Zr_1−xSn_x)(Li_1/4Nb_3/4)_0.4Ti_0.6O₄ ceramic decreased gradually from 35.5 to 31.5, the Q_f value increased from 37,800 to 58,300 GHz, and TCF value shifted slightly from −4.5 to −33.0 ppm °C⁻¹. Both the phase structure and microwave dielectric properties of (Zr_1−xSn_x)(Li_1/4Nb_3/4)_0.4Ti_0.6O₄ ceramics were stable with annealing conditions.     

Microwave dielectric properties of Ba2 − xSrxLa3Ti3NbO15 ceramics

High dielectric constant and low loss ceramics in the system Ba_2 − xSr_xLa₃Ti₃NbO₁₅ (x = 0-1) have been prepared by conventional solid-state ceramic route. Ba_2 − xSr_xLa₃Ti₃NbO₁₅ solid solutions adopted A₅B₄O₁₅ cation-deficient hexagonal perovskite structure for all compositions. The materials were characterized at microwave frequencies. They show a linear variation of dielectric properties with the value of x. Their dielectric constant varies from 48.34 to 43.03, quality factor Q_u × f from 20,291 to 39,088 GHz and temperature variation of resonant frequency from 8 to 1.39 ppm/°C as the value of x increases. These low loss ceramics might be used for dielectric resonator (DR) applications.     

Dielectric and pyroelectric anisotropy in melt-quenched BaBi2(Nb1 − xVx)2O9 ceramics

The (0 0 l) textured BaBi₂(Nb_1 − xV_x)₂O₉ (where x = 0, 0.03, 0.07, 0.1 and 0.13) ceramics were fabricated via the conventional melt-quenching technique followed by high temperature heat-treatment (800-1000 °C range). The influence of vanadium content and sintering temperature on the texture development and relative density were investigated. The samples corresponding to the composition x = 0.1 sintered at 1000 °C for 10 h exhibited the maximum orientation of about 67%. The Scanning electron microscopic studies revealed the presence of platy grains having the a-b planes perpendicular the pressing axis. The dielectric constant and the pyroelectric co-efficient values in the direction perpendicular to the pressing axis were higher. The anisotropy in the dielectric constant is about 100 (at 100 kHz) at the dielectric maximum temperature and anisotropy in the pyroelectric co-efficient is about 50 μC cm⁻² °C⁻¹ in the vicinity of pyroelectric anomaly for the sample corresponding to the composition x = 0.1 sintered at 1000 °C. Higher values of the dielectric loss and electrical conductivity were observed in the direction perpendicular to the pressing axis which is attributed to the high oxygen ion conduction in the a-b planes.     

Synthesis of nanocrystalline xCuFe2O4-(1 − x)BiFeO3 magnetoelectric composite by chemical method

xCuFe₂O₄-(1 − x)BiFeO₃ spinel-perovskite nanocomposites with x = 0.1, 0.2, 0.3 and 0.4 were prepared using citrate precursor method. X-ray diffraction (XRD) analysis showed phase formation of xCuFe₂O₄-(1 − x)BiFeO₃ calcined at 500 °C. Transmission electron microscopy (TEM) shows formation of nanocrystallites of xCuFe₂O₄-(1 − x)BiFeO₃ with an average particle size of 40 nm. Variation of dielectric constant and dielectric loss with frequency showed dispersion in the low frequency range. Coercivity, saturation magnetization and squareness have been found to vary with concentration of ferrite phase and annealing temperature due to the increase in crystallite size. Squareness and coercivity increased with an increase in annealing temperature up to 500 °C and then decreased with a further increase in temperature to 600 °C. Magnetoelectric effect of the nanocomposites was found to be strongly depending on the magnetic bias and magnetic field frequency.     

Lattice vibrations and dielectric functions of ferroelectric SrBi2−xNdxNb2O9 bismuth layer-structured ceramics determined by infrared reflectance spectra

Infrared optical properties of SrBi_2−xNd_xNb₂O₉ (SBNN) ceramics with different Nd compositions (from 0 to 0.2) have been investigated by near-normal incident reflectance technique. The experimental spectra in the wavenumbers range of 350-1500 cm⁻¹ were analyzed using the Lorentz oscillator model for five infrared-active phonon mode observed. It is found that the frequencies of the NbO₆ tilting and symmetric stretching modes linearly decrease with the Nd composition due to the octahedra distortion. The high-frequency dielectric constant varies in the range from 4.55 ± 0.04 to 4.80 ± 0.04. Owing to the contribution from the stronger electronic transitions, the real part of dielectric function Re(?) is estimated to about 4.0 in the high-frequency transparent region.     

Effect of BiFeO3 additions on the dielectric and piezoelectric properties of (K0.44Na0.52Li0.04)(Nb0.84Ta0.1Sb0.06)O3 ceramics

(1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ (x = 0, 0.002, 0.004, 0.006, 0.008, 0.01) lead-free piezoelectric ceramics were prepared by the conventional ceramic processing. The compositional dependence of the phase structure and the electrical properties of the ceramics were studied. A morphotropic phase boundary between the orthorhombic and tetragonal phases was identified in the composition range of 0.004 < x < 0.006. The ceramics near the morphotropic phase boundary exhibit a strong compositional dependence and enhanced piezoelectric properties. The ceramics with 0.6 mol.% BiFeO₃ exhibit good electrical properties (d₃₃ ∼ 246 pC/N, k_p ∼ 43%, T_c ∼ 285 °C, ?_r ∼ 1871, and tan δ ∼ 1.96%). These results show that the (1 − x) (K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.1Sb_0.06)O₃ − x BiFeO₃ ceramic is a promising lead-free piezoelectric material for applications in different devices.     

Preparation of Ti1− zNbzN ceramics by spark plasma sintering Ti1− zNbzOxNy nanopowders

Ti_1−zNb_zN ceramics were fabricated by sintering nanocrystalline titanium-niobium oxynitride (Ti_1−zNb_zO_xN_y) powders using spark plasma sintering (SPS) technique at 1060 °C for 3 min in an N₂ atmosphere. The phase composition and microstructure were characterized by XRD, SEM, TEM and EDS. The results showed that Ti_1−zNb_zN ceramics remained the cubic structures of Ti_1−zNb_zO_xN_y powders. There were XRD peak shifts in the cubic phases between Ti_1−zNb_zN ceramics and corresponding Ti_1−zNb_zO_xN_y powders. During the sintering process, oxygen separated from Ti_1−zNb_zO_xN_y to form titanium-niobium oxides. Ti_1−zNb_zN (0 < z < 1) had a more compact structure than TiO_xN_y and NbO_xN_y. Ti_0.5Nb_0.5N ceramic had the biggest grain size in the series of Ti_1−zNb_zN.     

SmAlO3-modified (K0.5Na0.5)0.95Li0.05Sb0.05Nb0.95O3 lead-free ceramics with a wide sintering temperature range

Lead-free ceramics (1 − x)(K_0.5Na_0.5)_0.95Li_0.05Sb_0.05Nb_0.95O₃-xSmAlO₃ (KNLNS-xSA) were prepared by conventional sintering technique. The phase structure, dielectric and piezoelectric properties of the ceramics were investigated. All compositions show a main perovskite structure, exhibiting room-temperature symmetries of tetragonal at x ≤ 0.0075, of pseudo-cubic at x = 0.0100. The Curie temperature of KNLNS-xSA ceramics decreases with increasing SmAlO₃ content. Moreover, the addition of SmAlO₃ can effectively broaden the sintering temperature range of the ceramics. The KNLNS-xSA ceramic with x = 0.0050 has an excellent electrical behavior of piezoelectric coefficient d₃₃ = 226 pC/N, planar mode electromechanical coupling coefficient k_p = 38%, dielectric loss tan δ = 3.0%, mechanical quality factor Q_m = 60, and Curie temperature T_C = 327 °C, suggesting that this material could be a promising lead-free piezoelectric candidate for piezoelectric applications.     

Structural, spectroscopic and dielectric investigations on Ba8Zn(Nb6−xSbx)O24 microwave ceramics

Ba₈Zn(Nb_6−xSb_x)O₂₄ (x = 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8 and 2.4) ceramics were prepared through the conventional solid-state route. The materials were calcined at 1250 °C and sintered in the range 1400-1425 °C. The structure of the system was analyzed by X-ray diffraction, Fourier transform infrared and Raman spectroscopic methods. The theoretical and experimental densities were calculated. The microstructure of the sintered pellets was analyzed using scanning electron microscopy. The low frequency dielectric properties were studied in the frequency range 50 Hz-2 MHz. The dielectric constant (?_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) are measured in the microwave frequency region using cavity resonator method. The τ_f values of the samples reduced considerably with the increase in Sb concentration. The materials have intense emission lines in the visible region. The compositions have good microwave dielectric properties and photoluminescence and hence are suitable for dielectric resonator and ceramic laser applications.     

Microwave dielectric properties of La1−xBix(Mg0.5Sn0.5)O3 ceramics

The La_1−xBi_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. An apparent density of 6.50 g cm⁻³, a dielectric constant (?_r) of 20.2, a quality factor (Q × f) of 58,100 GHz and a temperature coefficient of resonant frequency (τ_f) of −84.2 ppm °C⁻¹ were obtained for La_0.97Bi_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Synthesis and characterizations of A-site deficient perovskite Sr0.9Ti0.8−xGaxNb0.2O3

The effects of reduction and Ga-doping on the physicochemical properties of A-site deficient perovskites Sr_0.9Ti_0.8−xGa_xNb_0.2O₃ (x = 0, 0.05, 0.1, 0.15 and 0.2) are reported. With 10% Ga doping, the sample sintered in air and treated at 1400 °C in H₂ atmosphere exhibits the highest electrical conductivity. It is found that the Ga-doping lowers the sinterability but promotes the reduction of Sr_0.9Ti_0.8−xGa_xNb_0.2O₃. The XRD analysis on the reduced samples suggests that some cations are reduced during the treatment. However, without high temperature pre-reduction, the improvement of Ga-doping is limited and the overall cell performance using Sr_0.9Ti_0.8−xGa_xNb_0.2O₃ as an anode without catalysts is still relatively low.