Structural,dielectric, vibrational and magnetic properties of Sm doped BiFeO3 multiferroic ceramics prepared by a rapid liquid phase sintering method

Rare earth Sm substituted Bi_1−xSm_xFeO₃ with x=0, 0.025, 0.05, 0.075 and 0.10 polycrystalline ceramics were synthesized by a rapid liquid phase sintering method. The effect of varying composition of Sm substitution on the structural, dielectric, vibrational, optical and magnetic properties of doped BiFeO₃ (BFO) ceramics have been investigated. X-ray diffraction patterns of the synthesized rare earth substituted multiferroic ceramics showed the pure phase formation with distorted rhombohedral structure with space group R3c. Good agreement between the observed and calculated diffraction patterns of Sm doped BFO ceramics in Rietveld refinement analysis of the X-ray diffraction patterns and Raman spectroscopy also confirmed the distorted rhombohedral perovskite structure with R3c symmetry. Dielectric measurements showed improved dielectric properties and magnetoelectric coupling around Néel temperature in all the doped samples. FTIR analysis establishes O–Fe–O and Fe–O stretching vibrations in BiFeO₃ and Sm-doped BiFeO₃. Photoluminescence (PL) spectra showed visible range emissions in modified BiFeO₃ ceramics. The magnetic hysteresis measurements at room temperature and 5 K showed the increase in the magnetization with the increase in doping concentration of Sm which is due to the structural distortion and partial destruction of spin cycloid caused by Sm doping in BFO ceramics.     

Structural,vibrational, optical,magnetic and dielectric properties of Bi1−xBaxFeO3 nanoparticles

Bi_1−xBa_xFeO₃ (x=0.05, 0.10 and 0.15) nanoparticles were synthesized by the sol–gel method. X-ray diffraction and Raman spectroscopy results showed the presence of distorted rhombohedral structure of Bi_1−xBa_xFeO₃ nanoparticles. Rietveld refinement and Williamson–Hall plot of the x-ray diffraction patterns showed the increase in lattice parameters, unit cell volume and the particle size. Infrared spectroscopy and Raman analysis revealed the shifting of phonon modes towards the higher wavenumber side with increasing Ba concentration. These samples exhibited the optical band gap in the visible region (2.47–2.02 eV) indicating their ability to absorb visible light. Magnetic measurement showed room temperature ferromagnetic behavior, which may be attributed to the antiferromagnetic core and the ferromagnetic surface of the nanoparticles, together with the structural distortion caused by Ba substitution. The magnetoelectric coupling was evidenced by the observation of the dielectric anomaly in the dielectric constant and the dielectric loss near antiferromagnetic Neel temperature in all the samples.     

Phase development and dielectric responses in PMN–BNT ceramics

(1 − x)Pb(Mg_1/3Nb_2/3)O₃–x(Bi_0.5Na_0.5)TiO₃ ceramics were prepared by the conventional mixed-oxide method. All compositions show complete perovskite solid solutions and the structure to change from cubic to rhombohedral at x = 0.5. The dielectric constant and dielectric loss tangent were measured as a function of both temperature and frequency. The results indicated a relaxor ferroelectric behavior for all ceramics. The temperature at maximum of the dielectric constant of PMN–BNT ceramics were seen to increase with increasing BNT content. Moreover, the broadest dielectric peak occurs at x = 0.9, which leads to a morphotropic phase boundary in this system.     

Piezoelectric and dielectric properties of (Bi0.5Na0.5)0.94Ba0.06TiO3–Ba(Zr0.04Ti0.96)O3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of (1 − x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃–xBa(Zr_0.04Ti_0.96)O₃ (abbreviated as BNBT–BZT100x, wherein x from 0 to 10 mol%) were fabricated. We have studied effects of amount of BZT content on the electrical properties and microstructures. X-ray diffraction analysis indicates that a solid solution is formed when BZT diffuses into the BNBT lattice, and further the crystal structure of sintered hybrid changes from rhombohedral to tetragonal symmetry along with increasing BZT content. Piezoelectric property measurements reveal that the BNBT–BZT4 ceramics has the highest piezoelectric performance, for example, the piezoelectric constant d₃₃ reaches to 167 pC/N and planar electromechanical coupling factor k_p is up to 0.27. In addition, the effect of Bi₂O₃ on the electrical properties and microstructure of the BNBT–BZT4 ceramics have also been studied, and found that the doping of Bi enhances the piezoelectric properties of ceramics.     

Structure,dielectric and optical properties of Bi1.5+xZnNb1.5O7+1.5x pyrochlores

Non-stoichiometric pyrochlore ceramics with formula Bi_1.5+xZnNb_1.5O_7+1.5x were systematically investigated. Crystal structures of the compounds were studied by X-ray diffraction (XRD) technique. The structures were identified as pure cubic pyrochlores when |x| < 0.1. Dielectric and optical properties of the compositions when x = −0.1, 0 and 0.1 were studied. All samples have high resistivities and low dielectric loss. With increasing x in Bi_1.5+xZnNb_1.5O_7+1.5x, the lattice constant, permittivity, temperature coefficient of permittivity and thermal expansion coefficient increased, while dielectric loss decreased. Raman spectra indicated that the intensity of Bi–O stretching become stronger with increasing x. A vibration mode emerging at 861 cm⁻¹ when x = −0.1 means that the B–O coordination environment is significantly more disordered. Absorption spectra suggested that the bandgap energy become lower from 2.86 to 2.70 eV as lattice constants increased. Strong absorption occurs at wavelengths from 433 to 459 nm, shows that samples have the ability to respond to wavelengths in the visible light region.     

Effect of Eu doping on structure and electrical properties of lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Eu-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT6-xEu, x=0.00–2.00 at%) lead-free piezoelectric ceramics have been synthesized by the solution combustion method. The effect of Eu doping concentration on the phase structure, microstructure and electrical properties of BNBT6 ceramics has been investigated. The XRD analysis confirms that the europium additive incorporates into the BNBT6 lattice and results in a phase transition from the coexistence of rhombohedral and tetragonal phases to a more symmetric pseudocubic phase. The SEM images indicate that the europium additive has little effect on the ceramic microstructure and the average grain size is about 2.0 μm. The electrical properties of BNBT6 ceramics can be improved by appropriate Eu doping. The 0.25 at% Eu doped BNBT6 ceramic presents excellent electrical properties: piezoelectric constant d₃₃=149 pC/N, remnant polarization P_r=40.27 μC/cm², coercive field E_c=2.95 kV/mm, dielectric constant ε_r=1658 and dissipation factor tan δ=0.0557 (10 kHz).     

Phase transition and piezoelectric properties of lead-free (Bi1/2Na1/2)TiO3–BaTiO3 ceramics

(1−x)(Bi_0.5Na_0.5)TiO₃–xBaTiO₃ ceramics (x=0.03, 0.06, 0.08, 0.12, 0.15, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, and 0.90) were fabricated by a conventional solid-state reaction and their phase transitions and piezoelectric properties were investigated using XRD analyses, Curie temperature, the frequency dependance of dielectric constant, and P–E curves. A complete solid solution with a perovskite structure was formed in the whole composition range of BNT–BT and more than two phase transitions arising from a compositional change were found. With increasing BaTiO₃ content, the sequence of phase transitions from a rhombohedral structure to unknown tetragonal structures and finally a tetragonal structure with the space group P4mm has been established. While the rhombohedral–tetragonal phase transition led to superior piezoelectric properties in BNT–BT ceramics, other phase transitions between tetragonal structures had a little effect on piezoelectric properties. The d₃₃, ε_r, k_p, k_t, and Q_m and values lied in ranges of 40–130 pC/N, 400–900, 10–30%, 15–30%, and 50–250, respectively.     

Structural and electrical properties of BZT-added BNLT ceramics

Lead free piezoelectric ceramics (1−x)BNLT−xBZT with x=0.00, 0.06, 0.09 and 0.12 were prepared using a two-step mixed oxide method. Dielectric, ferroelectric and piezoelectric properties of the ceramics were improved by the addition of the BZT. XRD results show tetragonal symmetry structure of the BNLT–BZT ceramics. It was found that the tetragonality increases with increasing BZT content. The optimum composition is x=0.09, where the maximum values of the piezoelectric constant d₃₃ (~126 pC/N) and dielectric constant (~2400) were obtained at room temperature. This BNLT–BZT system can be a promising candidate for lead-free piezoelectric ceramics.     

Structural and multiferroic properties of Pr and Ti co-doped BiFeO3 ceramics

Bi_0.9Pr_0.1FeO₃ (BPF), BiFe_0.9Ti_0.1O₃ (BFT), Bi_0.9Pr_0.1Fe_0.9Ti_0.1O₃ (BPFT-10), and Bi_0.9Pr_0.1Fe_0.95Ti_0.05O₃ (BPFT-5) ceramics are prepared for a comparison study. X-ray diffraction indicates that all of the samples crystallize in rhombohedral structures with R3c symmetry. The Pr and Ti co-doped samples show an especially low dielectric loss of 0.02–0.04 throughout the entire investigated frequency range. A markedly improved polarization hysteresis loop is successfully achieved for samples BPFT-10 and BPFT-5, and their remnant polarization P_r values are 0.11 and 0.29 μC/cm², respectively. Magnetic measurements indicate that the substitution of Ti⁴⁺ for Fe³⁺ improves the ferromagnetic properties due to the suppression of the spiral spin structure. A remnant magnetization M_r of 0.176 emu/g was observed for BPFT-10 at 5 K.     

Structural,magnetic and dielectric behavior of Mg1−xCaxNiyFe2−yO4 nano-ferrites synthesized by the micro-emulsion method

Ca–Ni co-substituted samples of nanocrystalline spinel ferrites with chemical formula Mg_1−xCa_xNi_yFe_2−y O₄ (x=0.0–0.6, y=0.0–1.2) were synthesized by the micro-emulsion method and were annealed at 700 °C for 7 h. The synthesized samples were characterized by x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometry (VSM) and dielectric measurements. The XRD and FTIR analysis reveals that single phase samples can be achieved by substituting Ca and Ni ions at Mg and Fe sites respectively in cubic spinel nano-ferrites. The crystallite size of the synthesized samples was found in the range 29–45 nm. The saturation magnetization (M_s) increases from 9.84 to 24.99 emu/g up to x=0.2, y=0.4 and then decreases, while the coercivity (H_c) increases continuously from 94 to 153 Oe with the increase in dopants concentration. The dielectric properties of these nano materials were also studied at room temperature in the frequency range 100 MHz to 3 GHz. The dielectric parameters were found to decrease with the increased Ca–Ni concentration. Further the peaking behavior was observed beyond 1.5 GHz. The frequency dependent dielectric properties of all the samples have been explained qualitatively on the basis of the Maxwell–Wagner two-layer model according to Koop's phenomenological theory. The enhanced magnetic parameters and reduced dielectric properties make the synthesized materials suitable for switching and high frequency applications, respectively.     

Effects of compressive stress on the dielectric properties of PIN–PT ceramics

Lead indium niobate, Pb(In_1/2Nb_1/2)O₃ (PIN), is an interesting ferroelectric due to a transition from a disordered to an ordered state by long-time thermal annealing. However, the temperature related to the maximum dielectric constant (T_max) of PIN in relaxor phase is low (at 1 kHz, T_max = 66 °C). In this study, lead titanate PbTiO₃ (PT) was added to PIN with compositions (1 − x)PIN–xPT (for x = 0.1–0.5) to increase their T_max. The influence of stress on dielectric properties of (1 − x)PIN–PT ceramics was then investigated. The dielectric properties were measured under various uniaxial compressive stresses up to 400 MPa. The results showed the reduction of dielectric constant in 0.9PIN–0.1PT with superimposed compression load. For other compositions, dielectric constants first increased with compressive stress, then decreased when the stress was further increased up to 400 MPa. The loss tangent of all composition was found to decrease with increasing compressive stress.     

Bi(Zn1/2Ti1/2)O3 modified BiFeO3–BaTiO3 lead-free piezoelectric ceramics with high temperature stability

Lead-free high-temperature ceramics with compositions of 0.71BiFe_1−x(Zn_1/2Ti_1/2)_xO₃–0.29BaTiO₃ (BFZTx–BT, x=0–0.05 mol fraction) were fabricated by a conventional solid state reaction method. The effect of Bi(Zn_1/2Ti_1/2)O₃ (BZT) addition on the microstructure, electrical properties, relaxor behavior, and temperature stability has been studied. XRD patterns revealed that all compositions formed a single perovskite phase of pseudo-cubic crystal structure. The grain size was slightly affected by BZT addition. The diffuse phase transition and strong frequency dispersion of dielectric permittivity are observed for BZT modified ceramics. The addition of BZT into BFZTx–BT was also found to affect the piezoelectric properties and temperature stability of the ceramics with maximum values observed for x=0.5% and 1% BFZTx–BT compositions, respectively. The optimum piezoelectric properties with d₃₃=163 pC/N, together with high-temperature stability with a depolarization temperature T_d∼380 °C, reveal the BFZTx–BT ceramics to be promising high-temperature Pb-free piezoelectric materials.     

Role of Pr in Eu-123 high Tc nanometer-sized superconductors

Samples of Eu_1−xPr_xBa₂Cu₃O_7−δ with compositions x=0.0, 0.1 and 0.3 were prepared by the solid state reaction route. The structural, electrical and microstructural properties were investigated by X-ray diffraction, Physical Property Measurement System (PPMS) and scanning electron microscopy (SEM) techniques respectively. The lattice parameters, oxygen deficiency, hole concentration in the CuO₂ plane, average charge on Cu–O plane were evaluated from X-ray diffraction data. From XRD data, it is observed that the lattice parameters and oxygen deficiency increase with increasing Pr concentration. It was also observed that the hole concentration in CuO₂ plane and average charge on Cu–O plane decrease with increasing Pr concentration. The electrical resistivity of all samples was measured in the temperature range 300 K to 4 K. It was found that the normalized transition temperature decreases with increasing Pr concentration. This may be due to reduction in hole concentration or average charge on Cu–O plane. From scanning electron microscopy images, it was observed that grain size increases with increasing Pr concentration. This increase may be the possible cause for suppression of T_c.     

Preparation and characterization of ceramic nanocomposites in the PZT–BT system

Nanocomposites of the (1 − x)PZT-xBT system were fabricated by the bimodal particle concept. The effect of fabricating conditions on structural characteristics and dielectric properties of the ceramics was investigated using XRD, SEM, and a standard dielectric measurement. The ceramic–solid solutions and -nanocomposites in the PZT–BT system were comparatively explored. It was clearly seen that the microstructures and the dielectric properties of PZT–BT ceramic-nanocomposites are totally different from those of ceramic–solid solutions. The dielectric behavior of ceramic-nanocomposites displayed superimposition of two phase transitions with a lower maximum value of the dielectric constant than that of the solid solutions.     

Dielectric,ferroelectric, and piezoelectric properties in potassium sodium niobate ceramics with rhombohedral–orthorhombic and orthorhombic–tetragonal phase boundaries

A new phase boundary with rhombohedral–orthorhombic and orthorhombic–tetragonal phase boundaries is designed in (K_0.48Na_0.52)NbO₃ by adding Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5ZrO₃ (BNKLZ), where Zr⁴⁺ and (BNKL)²⁺ are respectively used to improve the temperature of a rhombohedral phase and to decrease the temperature of an orthorhombic–tetragonal phase coexistence. These ceramics endure several continuous phase transitions with increasing BNKLZ content, i.e., an orthorhombic phase (0≤x<0.03), orthorhombic–tetragonal phases (x=0.03), orthorhombic–tetragonal and rhombohedral–orthorhombic (O–T and R–O) phase existence (0.03<x≤0.05), a rhombohedral phase (0.05<x≤0.07). The ceramics with O–T and R–O have a better piezoelectric behavior as compared with other phases because of more polarization states, enhanced ε_r and P_r, and a dense microstructure. Moreover, piezoelectric properties could be further optimized by modifying their sintering and poling temperatures. As a result, the construction of O–T and R–O phase coexistence benefits the improvement of piezoelectric properties in KNN-based ceramics.     

Effect of Li addition on phase formation behavior and electrical properties of (K0.5Na0.5)NbO3 lead free ceramics

In this work, Li-modified KNN ceramic compositions ((K_0.5Na_0.5)_1−xLi_x)NbO₃ with x = 0.03, 0.04, 0.05, 0.06, 0.65 and 0.07 were prepared by a conventional solid-state mixed-oxide method. The structural phase formation and microstructure were characterized by X-ray diffraction technique (XRD) and scanning electron microscopy (SEM). It has been found that a morphotropic phase boundary (MPB) between orthorhombic phase and tetragonal phases should exist between compositions with Li contents of 6-6.5%. The Curie temperature (T_c) of the ceramics shifted to higher temperature with increasing Li content. The room temperature dielectric constant was also seen to be higher than the pure KNN ceramics. In addition, the ferroelectric properties were found to enhance at near MPB compositions. This study clearly showed that the addition of Li could improve the dielectric and ferroelectric properties in (K_0.5Na_0.5)NbO₃ ceramics.     

Effect of Dy-substitution on structural,electrical and magnetic properties of multiferroic BiFeO3 ceramics

The polycrystalline samples of dysprosium (Dy)-modified bismuth ferrite (i.e., Bi_1−xDy_xFeO₃; x=0–0.2 with the interval of 0.05) (BDFO) were synthesized using a high-temperature solid-state reaction method. Preliminary X-ray structural analysis showed that the reported crystal structure of BiFeO₃ (rhombohedral) is invariant even with Dy-substitution at the Bi-site upto x=0.2. The scanning electron micrograph of the compounds showed (i) the uniform distribution of grains on the sample surface with high density and (ii) reduction of grain size on increasing Dy content in BiFeO₃ (BFO). Studies of impedance, electrical modulus and electric conductivity of the materials in wide frequency (10–1000 kHz) and temperature (30–500 °C) ranges using a complex impedance spectroscopy technique have provided new and interesting information on the contribution of grains, grain boundary and interface in these parameters. Detailed studies of impedance spectroscopy clearly exhibit the dielectric relaxation of non-Debye type. The ac conductivity of the Dy-substituted BFO obeyed Jonscher's universal power law. An increase in Dy-content in BDFO results in the increase of spontaneous magnetization of BFO due to the collapse of spin cycloid structure.     

Enhancement of the dielectric,piezoelectric, and ferroelectric properties in BiYbO3-modified (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 lead-free ceramics

Lead-free (1−x)(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃−xBiYbO₃ [(1−x)BCTZ−xBYO] piezoelectric ceramics in the range of BYO concentrations were prepared by the conventional oxide-mixed method, and the effect of BYO content on their microstructure, crystalline structure, density and electrical properties was investigated. A dense microstructure with large grain was obtained for the ceramics with the addition of BYO. The ceramics with x=0.1% exhibit an optimum electrical behavior of d₃₃~580 pC/N, r~10.9 Ω, k_p~56.4%, and tan δ~1.12% when sintered at a low temperature of ~1350 °C. When the measuring electric field is 40 kV/cm, the well-saturated and square-like P–E loops for the ceramics were observed with P_r~12.2 μC/cm² and E_c~1.83 kV/cm.     

Synthesis and multiferroism in mechanically processed BiFeO3–PbTiO3 ceramics

In this study, (1 − x)BiFeO₃–(x)PbTiO₃ multiferroic ceramics, with x = 0, 0.1, 0.2, 0.25, 0.3 and 0.4, were processed through high-energy ball milling followed by reactive sintering in air atmosphere. The optimization of the procedure for the preparation of highly-dense (1 − x)BiFeO₃–(x)PbTiO₃ ceramics was carefully investigated and structural/microstructural effects on ferroic properties were carefully addressed. Shrinkage dilatometric measurements revealed an expansion related to a sintering reaction that has occurred before densification. This sintering behaviour was highly PbTiO₃ concentration-dependent. The sintering mechanism was found to be directly related with the aliovalent substitution of Pb and Ti ions on A and B sites of the perovskite structure. The obtained ceramics were confirmed as ferroelectric ordered in ferroelectric characterizations. Remnant polarizations and coercive fields greatly dependent on grain size distribution and aliovalent substitutions were revealed. The magnetic hysteresis displayed a weak-ferromagnetic behaviour in all studied samples.     

Dielectric properties of Sm, Nd and Fe doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

New pyrochlore ceramics have been produced by doping Sm and Nd into the Bi site and Fe into the Nb site in the Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore. Doped pyrochlore ceramics were produced by conventional solid state mixing of oxides at different doping levels using the compositions of Bi_1.5−xSm_xZn_0.92Nb_1.5O_6.92, Bi_1.5−xNd_xZn_0.92Nb_1.5O_6.92 and Bi_1.5Zn_0.92Nb_1.5−xFe_xO_6.92−x. The solubility limit of cations was determined as x = 0.13, 0.18 and 0.15 for Sm, Nd and Fe, respectively. While Sm and Nd increased the dielectric constant (?), Fe doping led a decrease in ?. Dielectric constant of Sm and Nd doped BZN increased to 199 at x = 0.13 (Sm) and to 219 at x = 0.18 (Nd). At low Fe dopings (x = 0.05), the dielectric constant of BZN increased to 242 but decreased to 211 at x = 0.15. The dielectric losses were lower for Sm and Nd dopings than Fe but in all cases it was lower than 0.006. The dielectric constant of Sm, Nd and Fe doped BZN ceramics was nearly independent of frequency within the frequency range between 1 kHz and 2 MHz, but decreased considerably with temperature between 20 and 200 °C. Temperature coefficient of Sm doped BZN (−354 ppm/°C) was lower than Nd and Fe doped BZN ceramics at solubility limits (−538 ppm/°C for Nd and −565 ppm/°C for Fe).