Ferroelectric and piezoelectric properties of (1 − x) (Bi0.5Na0.5)TiO3–xBaTiO3 ceramics

Lead-free ceramics based on bismuth sodium titanate (Bi_0.5Na_0.5TiO₃, BNT)–barium titanate (BaTiO₃,BT) have been prepared by solid state reaction process. The (1?x)BNT–(x)BT (x = 0.01,0.03,0.05,0.07) ceramics were sintered at 1,150 °C for 4 h in air, show a pure perovskite structure. X-ray diffraction analysis indicates that a solid solution is formed in (1?x)BNT–(x)BT ceramics with presence of a morphotropic phase boundary (MPB) between rhombohedral and tetragonal at x = 0.07. Raman spectroscopy shows the splitting of (TO₃) mode at x = 0.07 confirming the presence of MPB region. The temperature dependence dielectric study shows a diffuse phase transition with gradual decrease in phase transition temperature (T_m). The dielectric constant and diffusivity increases with increase in BT content and is maximum at the MPB region. With the increase in BT content the maximum breakdown field increases, accordingly the coercive field (E_c) and remnant polarization (P_r) increases. The piezoelectric constant of (1 ? x)BNT–(x)BT ceramics increases with increase in BT content and maximum at x = 0.07, which is the MPB region. The BNT–BT system is expected to be a new and promising candidate for lead-free dielectric and piezoelectric material.     

Structural, optical, and electric properties of BNT–BT0.08 thin films processed by sol–gel technique

Thin films with the composition [(Bi_0.5Na_0.5)TiO₃]_0.92–[BaTiO₃]_0.08 (hereafter BNT–BT_0.08) were deposited on Pt–Si by spin-coating from a stable sol precursor. The BNT–BT_0.08 film, crystallized on the Bi_0.5Na_0.5TiO₃ rhombohedral lattice, was obtained after annealing the film-gel at 700 °C. The films have a smooth surface (Rms = 2.76 nm) and grains with ferroelectric domains. The film showed a bandgap of 3.25 eV and a refractive index of 2.20 at a wavelength of 630 nm. The dielectric characteristics of BNT–BT_0.08 thin films were measured at room temperature and 10 kHz the dielectric constant (ε _r) was 243 and the loss tangent (tanδ) was 0.38. The remnant polarization (P _r) was 0.87 μC/cm² and the coercive field (E _c) was 220 kV/cm at 10 kHz and room temperature. The current density was approximately 2.7 × 10⁻⁵ A/cm² at low electric fields (100 kV/cm). BNT–BT_0.08 thin films shown piezoelectric properties (d _33eff = 100 pm/V) comparable to those of PZT thin films.     

Significant effects of powder preparation processes on the physical properties of Bi0.5Na0.5TiO3–0.06BaTiO3 ceramic

(1?x)Bi_0.5Na_0.5TiO₃s (solid-state method)–xBi_0.5Na_0.5TiO₃g (sol–gel method)–0.06BaTiO₃ (0 ≤ x ≤ 1) ceramics were prepared and the effect of powder synthesis conditions on the physical properties of ceramics was investigated. A morphotropic phase boundary was observed in the Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ system. With increasing Bi_0.5Na_0.5TiO_3g content, the maximum value of dielectric constant reduces sharply. The Bi_0.5Na_0.5TiO₃g significantly disrupts the long-range ferroelectric order dominant of the ceramics, which leads to a degradation of the remanent polarization and coercive field. These results may be helpful to further understand and design new Bi_0.5Na_0.5TiO₃-based lead-free piezoelectric ceramics.     

Enhanced dielectric and piezoelectric properties of (100) oriented Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–SrTiO<Subscript>3</Subscript> thin films

The (100) oriented and random oriented 0.755Bi_0.5Na_0.5TiO₃–0.065BaTiO₃–0.18SrTiO₃ (BNT–BT–ST) thin films were deposited on LaNiO₃ (LNO) buffered Pt(111)/Ti/SiO₂/Si substrates by the sol–gel processing technique. The orientation is controlled by the concentration of solution. The structure, dielectric and piezoelectric properties of the thin films are significantly affected by the crystallographic orientation. The (100) oriented BNT–BT–ST thin film has improved dielectric and piezoelectric properties. For the (100) oriented and random oriented BNT–BT–ST thin films, the dielectric constants are 660 and 550, the dielectric losses are 0.045 and 0.076 and the effective piezoelectric coefficients are 140 and 110 pm/V, respectively. The large piezoelectric response is attributed to the uniform microstructure and increased lattice distortion along (100) direction.     

Fabrication of lead-free piezoelectric (Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript> ceramics using electrophoretic deposition

Electrophoretic deposition (EPD) process has certain advantages such as it can be applied for a mass production and also can be combined with magnetic crystal alignment technique. In this work, we prepared lead-free 85(Bi_0.5Na_0.5)TiO₃–15BaTiO₃ (85BNT–15BT) piezoelectric ceramics by conventional uniaxial pressing and EPD process. Various conditions were optimized such as suspension media, applied electrical field, and deposition time in order to yield dense green ceramics of 85BNT–15BT composition using EPD process. 85BNT–15BT ceramics prepared using EPD process revealed the Curie temperature of about 250 °C, coercive field of about 30 kV/cm, and piezoelectric constant (d ₃₃) of 75 pC/N. The EPD-processed samples exhibited structural and electrical properties similar to that of the conventionally processed one suggesting the successful fabrication of 85BNT–15BT piezoelectric ceramics by EPD method without composition deviation. This study lays a foundation on the fabrication of Bi-based lead-free piezoelectric ceramics by an alternative route other than the conventionally practiced solid-state reaction method maintaining the similar chemical composition, moreover, leaving a large space to explore more in the future.     

Crystallographic textured evolution in 0.85Na0.5Bi0.5TiO3–0.04BaTiO3–0.11K0.5Bi0.5TiO3 ceramics prepared by reactive-templated grain growth method

0.85Na_0.5Bi_0.5TiO₃–0.04BaTiO₃–0.11K_0.5Bi_0.5TiO₃ (BNBK) lead-free piezoelectric ceramics with extensive [001]_pc (pc: pseudo cubic) texture were fabricated by the reactive-templated grain growth method using anisotropic Bi₄Ti₃O₁₂ (BIT) particles as templates. The degree of grain orientation increased with increasing heat treatment temperature (600–1,200 °C). The obtained textured ceramics showed dense and brick-wall like microstructure, giving a Lotgering factor of 0.6. A physical understanding of interaction between BIT templates and matrix powders and the mechanism of texture evolution were proposed and confirmed by experimental evidences of X-ray diffraction patterns, scanning electron microscope images and density measurements. The piezoelectric response was enhanced by the grain orientation, and the piezoelectric constant (d₃₃) of the textured ceramics sintered at 1,170 °C attained a value of 254 pC/N, which was 41 % higher than random ceramics (180 pC/N).     

Structure,ferroelectric, piezoelectric and ferromagnetic properties of BiFeO3–Ba0.6(Bi0.5K0.5)0.4TiO3 lead-free multiferroic ceramics

(1?x)BiFeO₃–xBa_0.6(Bi_0.5K_0.5)_0.4TiO₃ + 1 mol% MnO₂ lead-free multiferroic ceramics were fabricated by a conventional ceramic technique and the effects of Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃ doping and sintering temperature on the microstructure, ferroelectric, piezoelectric and ferromagnetic properties of the ceramics were studied. All the ceramics show good electric insulation with the resistivity values of 1.97 × 10⁹–1.20 × 10¹⁰ Ω cm. After the addition of Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃, two dielectric anomalies are observed at high temperatures (T ₁ ~ 453–710 °C and T ₂ ~ 716–755 °C, respectively). The ceramic with x = 0.275 exhibits the optimum piezoelectricity (d ₃₃ = 48 pC/N and k _p = 13.6 %, respectively). The Ba_0.6(Bi_0.5K_0.5)_0.4TiO₃ doping and the increasing in sintering temperature improve significantly the ferromagnetic properties of the ceramics. The ceramic with x = 0.25 sintered at 1,040 °C gives the optimum remnant magnetization M _r of 0.13 emu/g.     

Synthesis of Na0.5Bi0.5TiO3 anisotropic particles with grain orientation by conversion of Na0.5Bi4.5Ti4O15 crystals

Abstract

A novel method for synthesizing Na_0.5Bi_0.5TiO₃ (BNT) anisotropic particles with grain orientation is reported. Anisotropically shaped particles of BNT were prepared by conversion of Na_0.5Bi_4.5Ti₄O₁₅ (NBT15) single crystals. Platelet NBT15 was produced by molten-salt synthesis. They were converted to BNT by second molten-salt synthesis at 800—1200 ?C. NBT15 single-crystal platelets were transformed into platelet particles of polycrystalline BNT. The reaction is topotaxial, those recrystallized BNT were oriented with (h 0 0) plane parallel to the platelet. The use of converted BNT particles as seed was confirmed by performing templated grain growth (TGG) of BNT with 5% grain-oriented, anisotropic particles of BNT.     

Structure,ferroelectric and piezoelectric properties of Bi0.5(Na0.8K0.2)0.5TiO3 modified BiFeO3–BaTiO3 lead-free piezoelectric ceramics

A new lead-free solid solution of (0.75 ? x)BiFeO₃–0.25BaTiO₃–xBi_0.5(Na_0.8K_0.2)_0.5TiO₃ + 1 mol% MnO₂ has been prepared by a conventional ceramic technique and the effects of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ and sintering temperature on the structure, ferroelectric and piezoelectric properties of the material have been studied. The ceramics sintered at 960 °C for 2 h possess a pure perovskite structure and no second phases can be detected. After the addition of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃, a morphotropic phase boundary of rhombohedral and orthorhombic phases is formed at x = 0.01. The addition of a small amount of Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ can promote the grain growth, while excess Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ causes an inhibition of grain growth. Sintering temperature has an important influence on the structure and electrical properties of the ceramics. The sintering temperature of 960 °C is a critical temperature to obtain the ceramics with good piezoelectric properties. For the ceramic with x = 0.01 sintered at/above 960 °C located at the morphotropic phase boundary, large grains, good densification, high resistivity and enhanced electrical properties are obtained.     

Structural and electrical properties of Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–Sr<Subscript>3</Subscript>CuNb<Subscript>2</Subscript>O<Subscript>9</Subscript> lead-free piezoelectric ceramics

The structure, microstructure, field-induced strain, ferroelectric, piezoelectric and dielectric properties of (1 ? x) (Bi_0.5Na_0.5)_0.935Ba_0.065TiO₃–xSr₃CuNb₂O₉ (BNT-BT6.5–xSCN, with x = 0, 0.003, 0.006, 0.009) ceramics were investigated. X-ray diffraction patterns show that all samples are pure perovskite structure and Sr₃CuNb₂O₉ (SCN) effectively diffused into the 0.935Bi_0.5Na_0.5TiO₃–0.065BaTiO₃ (BNT–BT6.5) solid solution which also reflected in the Raman spectra and the energy disperse spectroscopy (EDS) analysis. With the increases of SCN content, the coercive field (E _c  = 18.41 kV/cm) decreases greatly, whereas the remnant polarization (P _r  = 29.11 μC/cm²) increases a little at x = 0.003 which is showed in the polarization hysteresis (P–E) loops, the result indicate that the ferroelectric order would be disrupted. Around critical composition (x = 0.003) at a driving field of 60 kV/cm, a large unipolar strain of 0.29 % with a normalized strain (d ₃₃ ^*  = 483 pm/V) is obtained at room temperature. The results indicate that BNT-BT6.5-xSCN ceramics with excellent properties are promising to replace lead-based piezoelectric ceramics and can be used in practical applications.     

The effects of sintering temperature and poling condition on the piezoelectric properties of 0.935(Bi0.5Na0.5)TiO3 - 0.065BaTiO3 ceramics

The 0.935(Bi_0.5Na_0.5) TiO₃ -0.065BaTiO₃ (abbreviated as BNT6.5BT) lead-free ceramics were prepared by conventional solid state sintering technique. The effects of sintering temperature (1150–1200 °C) and poling condition on its piezoelectric properties were examined. Piezoelectric properties like the piezoelectric constant (d₃₃) and electromechanical factors (k _p , k _t ) depend on the poling field and poling temperature, whereas different poling times, in the 5–30 min range, were not observed to have any significant effect on the piezoelectric properties. With respect to piezoelectric properties, the chosen sintering temperature range is suitable for BNT6.5BT ceramics.     

Dual relaxation behaviors and large electrostrictive properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–Sr<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> ceramics

Lead-free ceramics (1???x)Bi_0.5Na_0.5TiO₃–xSr_0.85Bi_0.1TiO₃ (BNT–xSBT, x?=?0.4, 0.5, 0.6 and 0.7) were prepared by a solid-state reaction process. Coexistence of ferroelectric relaxation at low temperature and Maxwell–Wagner dielectric relaxation at high temperature was revealed for the first time in this system. Meanwhile, hysteresis-free P–E loops combined with a very high piezoelectric strain coefficient (d₃₃) of 1658 pC/N concurrently with large electrostrictive coefficient Q?=?0.287 m⁴C^?2 were achieved. The ferroelectric relaxor behavior and large electrostrictive strain might be linked to easy reorientation and reversal of ergodic PNRs and the combined effect of Bi off-center position and lone pair electrons.     

Morphotropic phase boundary and electric properties in (1 − x)Bi0.5Na0.5TiO3–xBaSnO3 lead-free piezoelectric ceramics

Lead-free piezoceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBaSnO₃ (BNT–BS, x = 0, 0.02, 0.03, 0.04, 0.06, 0.09 and 0.12) have been synthesized and investigated. A rhombohedral–tetragonal morphotropic phase boundary (MPB) exists near x = 0.03. The MPB composition shows improved electrical properties: the saturated polarization, remnant polarization, coercive field, piezoelectric coefficient, planar electromechanical coupling factor, and unipolar strain are 35.8, 28.5 μC/cm², and 4.5 kV/mm, 93 pC/N, 0.19, and 0.18 %, respectively. It is also found the introduction of BS can significantly enhance dielectric property. The structural and electrical properties are discussed by comparing with other BNT-based piezoceramics.     

Role of strain and lattice distortion on ferroelectric and piezoelectric properties of bismuth magnesium zirconate substituted sodium bismuth titanate ceramics

Effect of weak ferroelectric perovskite, bismuth magnesium zirconate [Bi(Mg_0.5Zr_0.5)O₃] substitution in lead-free sodium bismuth titanate [(Na_0.5Bi_0.5)TiO₃] ceramics is studied. Influence of substitution on intrinsic and extrinsic contribution and impact on ferroelectric and piezoelectric properties are investigated. Improved spontaneous polarization (P_s), increased remnant polarization (P_r), decreased coercive field (E_c) and high piezoelectric coefficient (d₃₃) are obtained for x = 0.01 mole fraction of Bi(Mg_0.5Zr_0.5)O₃ substitution due to decrease in rhombohedral lattice distortion and homogeneous strain. Small rhombohedral lattice distortion (δ_r) and minimum homogeneous strain (δ) are the primary intrinsic parameters which favours the extrinsic parameters such as mobility of non-180° domain reorientation, domain switching and domain wall motion. Enhanced mobility softens the coercive field and increases remnant polarization to maximum. Reduced rhombohedral lattice distortion, low strain and enhanced mobility are the key factors for enhanced piezoelectric constant, highest remnant polarization and decreased coercive field in non-MPB (1 ? x)(Na_0.5Bi_0.5)TiO₃–xBi(Mg_0.5Zr_0.5)O₃ solid solutions.     

Crystal structure and properties of BaTiO<Subscript>3</Subscript>–(Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)TiO<Subscript>3</Subscript> ceramic system

(1 − x)BaTiO₃–x(Bi_0.5Na_0.5)TiO₃ (x ranged from 0.01 to 0.96) ceramics were fabricated by the conventional ceramic technique. The crystal structure, as well as dielectric and piezoelectric properties of the ceramics were studied. All the ceramics formed single-phase solid solutions with perovskite structure after sintering in air at 1150–1250 °C for 2–4 h. The crystal structure and microstructure varied gradually with the increase of (Bi_0.5Na_0.5)TiO₃ (BNT) content. The Curie temperature, T _c, shifted monotonously to high temperature as BNT increased. The ceramics with 20–90 mol% BNT had relatively low and stable dielectric loss characteristics. The piezoelectric constant, d ₃₃, enhanced with the increase of BNT content through a maximum value in a composition of 93 mol% BNT and then tended to decrease. The maximum value, 148 pC/N, of piezoelectric constant d ₃₃ together with the electromechanical coupling factors, k _t, 19.8% and k _p, 15.8%, were obtained when BNT was 93 mol%.     

(Bi1/2Na1/2)TiO3 additive effect for improved piezoelectric and mechanical properties in PZT ceramics

Bismuth sodium titanate, (Bi_1/2Na_1/2)TiO₃(BNT) additive effect for the improvement of piezoelectric and mechanical properties in PZT ceramics were discussed from the viewpoint of high-power applications. The addition of 5 wt% BNT in Pb(Zr_0.52Ti_0.48)O₃ ceramics showed suppressive effect for electro-mechanical coupling factor (k _p) value. On the other hand, the addition of 0.5 and 1.0 wt% BNT contributed to improve the four point mechanical bending strength when it was sintered at 1150°C.     

Structural and high temperature conduction studies of (Na<Subscript>0.46</Subscript>Bi<Subscript>0.46</Subscript>Ba<Subscript>0.08</Subscript>) (Mn<Subscript>x</Subscript>Ti<Subscript>1−x</Subscript>O<Subscript>3</Subscript>)–CuO lead-free piezoelectric ceramics

Polycrystalline lead-free (Na_0.46Bi_0.46Ba_0.08)(Mn_xTi_1?xO₃)?+?0.2CuO ceramics (x?=?0.0, 0.5, 2.0, 3.0 wt%) were prepared via solid-state reaction method. X-ray diffraction (XRD) analysis confirmed the formation of single-phase perovskite structure and indicated the presence of morphotropic phase boundary, where the tetragonal and rhombohedral phases co-existed for all the synthesized compositions. Scanning electron microscopy (SEM) analysis revealed that the average grain size decreased with the increase in Mn content. Impedance spectroscopy (IS) indicated that Mn doping was found to decrease the grain boundary resistance. Two semi-circles were observed for higher Mn content which indicates the contribution of both bulk grains and grain boundaries. Non-Debye type and temperature dependent relaxation phenomenon was also revealed by IS studies. The activation energies at different frequencies were found to be 0.05–0.9 eV, indicating hopping charge conduction mechanism. These results have comprehensive implications for the expanded use of BNT based lead free piezoelectric ceramics for practical applications.     

Compositional effects on the properties of (1-x)BaTiO3-xBi0.5Na0.5TiO3 ceramics

The compositional effects on the crystal structure, phase transition, dielectric, ferroelectric and piezoelectric properties of the (1-x)BaTiO₃-x(Bi_0.5Na_0.5)TiO₃ solid solution ceramics were investigated. After sintering at 1200 °C for 2 h, the ceramics with different content of (Bi_0.5Na_0.5)TiO₃ (BNT) formed single-phase solid solutions with perovskite structure. The lattice constant c/a ratio of the solid solutions decreased as BNT content increased except that with 20 mol% BNT, which had the largest value of c/a ratio for all samples. The second phase transition corresponding to BaTiO₃ (BT) at about 5 °C shifted to low temperature and gradually disappeared as BNT increased. A new secondary phase transition appeared at 32 °C and 64 °C, respectively, when BNT content was 5 and 14 mol%. The Curie temperature, T _c, shifted in the temperature range between 112 °C and 166 °C, and the remanent polarization, P _r, decreased whereas the coercive field, E _c, increased as the BNT content increased. The relatively high value of piezoelectric coefficient d₃₃ together with a relatively high Curie temperature and low loss tangent and stable dielectric properties were obtained when the addition of BNT was 20 mol%.     

Structure and electrical properties of Bi0.5Na0.5TiO3-Y0.5Na0.5TiO3-BaTiO3 lead-free piezoelectric ceramics

New (1 – x ? y)Bi_0.5Na_0.5TiO₃-xY_0.5Na_0.5TiO₃-yBaTiO₃ lead-free ceramics have been prepared by a conventional ceramic fabrication technique, and their structure and electrical properties have been studied. A morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the partial substitutions of Y³⁺ for Bi³⁺ and Ba²⁺ for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ lower effectively the coercive field E _c and increase the remanent polarization P _r of the ceramics. Because of low E _c, large P _r and the MPB, the ceramics with x = 0–0.02 and y = 0.06 exhibit the optimum piezoelectric properties: d ₃₃ = 155–159 pC/N and k _p = 28.8–36.7%. The temperature dependences of dielectric properties of the ceramics show relaxor-like behaviors. The ferroelectric properties at different temperature suggest that the ceramics may contain both the polar and non-polar regions near/above T _d.     

Enhanced electric field tunable magnetic properties of lead-free Na0.5Bi0.5TiO3–MnFe2O4 multiferroic composites

Strong magnetoelectric (ME) interaction was exhibited at both dc and microwave frequencies in a lead-free multiferroic particulate composites of Na_0.5Bi_0.5TiO₃ (NBT) and MnFe₂O₄ (MFO) multiferroic, which were prepared by sol–gel route. The room temperature permeability measurements were carried out in the frequency range of 1 MHz–1 GHz. A systematic study of structural, magnetic and ME properties were undertaken. The room temperature ferromagnetic resonance (FMR) was studied. Strong ME coupling is demonstrated in 70NBT–30MFO composite by an electrostatically tunable FMR field shift up to 428 Oe (at E = 4 kV/cm), which increases to a large value of 640 Oe at E = 8 kV/cm. Furthermore, these lead-free multiferroic composites exhibiting electrostatically induced magnetic resonance field at microwave frequencies provide great opportunities for electric field tunable microwave devices.