Low electric field induced large electromechanical properties of BiFeO3-BaTiO3-based ceramics via phase composition modulation

The development of high-temperature lead-free piezoelectric ceramics with excellent electromechanical properties under low field remains a key challenge. A series of 0.995(xBiFeO₃-(1-x)BaTiO₃)-0.005Bi(Zn_0.5Hf_0.5)O₃ ceramics were designed via modulating phase composition. The excellent electromechanical properties of d₃₃* = 511 pm/V (45 kV/cm) at room temperature and S = 0.476 % (d₃₃* = 1190 pm/V, 40 kV/cm) at 120 ℃ were achieved in the x = 0.67 ceramic owing to the synergistic contribution of phase composition and domain evolution. The XRD results verify that the x = 0.67 ceramic is dominated by the pseudocubic phase. The PFM results in the x = 0.67 and 0.71 ceramics confirm that the domain structures consist of nanodomains with strong and weak piezoelectric responses. More importantly, the temperature and voltage-dependent domain evolution testify the nanodomains are easier to switch in the x = 0.67 ceramic. This work provides a strategy to optimize the electromechanical performance at the low field and a deeper understanding of BF-BT-based piezoceramics.     

Multifunctional Properties of Multistage Spark Plasma Sintered HA–BaTiO3‐Based Piezobiocomposites for Bone Replacement Applications

This work reports the processing–microstructure–property correlation of novel HA–BaTiO₃‐based piezobiocomposites, which demonstrated the bone‐mimicking functional properties. A series of composites of hydroxyapatite (HA) with varying amounts of piezoelectric BaTiO₃ (BT) were optimally processed using uniquely designed multistage spark plasma sintering (SPS) route. Transmission electron microscopy imaging during in situ heating provides complementary information on the real‐time observation of sintering behavior. Ultrafine grains (≤0.50 μm) of HA and BT phases were predominantly retained in the SPSed samples. The experimental results revealed that dielectric constant, AC conductivity, piezoelectric strain coefficient, compressive strength, and modulus values of HA‐40 wt% BT closely resembles with that of the natural bone. The addition of 40 wt% BT enhances the long‐crack fracture toughness, compressive strength, and modulus by 132%, 200%, and 165%, respectively, with respect to HA. The above‐mentioned exceptional combination of functional properties potentially establishes HA‐40 wt% BT piezocomposite as a new‐generation composite for orthopedic implant applications.     

Enhanced piezoelectric properties in BF-BT based lead-free ferroelectric ceramics for high-temperature devices

Due to the high Curie temperature (T_C), BiFeO₃–BaTiO₃ (BF-BT) ceramics have been broadly investigated in high-temperature piezoelectric devices. The piezoelectric constant is one of the most significant factors in determining the sensitivity and reliability of piezoelectric functional components. However, the poor piezoelectric constant (d₃₃) of BF-BT ceramic has prevented the practical application of the material. In this work, we innovatively introduce the 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ (0.93NBT-0.07BT) component to 0.7BF-0.3BT ceramic, to build a morphotropic phase boundary (MPB) for enhancing d₃₃. The XRD analysis shows that the (0.7BF-0.3BT)-x(0.93NBT-0.07BT) ceramics are still in the MPB region with R–PC phases coexistence, and exhibits a homogeneous solid solution. Moreover, the introduction of 0.93NBT-0.07BT ceramic suppresses the generation of defects and facilitates grain growth, thus enhancing piezoelectric property. In consequence, an optimum piezoelectricity d₃₃ = 213 pC/N along with T_c～450 °C was obtained in (0.7BF-0.3BT)-0.01(0.93NBT-0.07BT). This research provides a new idea for the application of BF-BT ceramics in high-temperature piezoelectric devices.     

Relaxor Ferroelectric BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for Energy Storage Application

Perovskite solid solution ceramics of (1 ? x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (BT–BMN) (x = 0.05–0.2) were synthesized by solid‐state reaction technique. The results show that the BMN addition could lower the sintering temperature of BT‐based ceramics. X‐ray diffraction results reveal a pure perovskite structure for all studied samples. Dielectric measurements exhibit a relaxor‐like characteristic for the BT–BMN ceramics, where broadened phase transition peaks change to a temperature‐stable permittivity plateau (from ?50°C to 300°C) with increasing the BMN content (x = 0.2), and slim polarization–electric field hysteresis loops were observed in samples with x ≥ 0.1. The dielectric breakdown strength and electrical resistivity of BT–BMN ceramics show their maxima of 287.7 kV/cm and 1.53 × 10¹³ Ω cm at x = 0.15, and an energy density of about 1.13 J/cm³ is achieved in the sample of x = 0.1.     

Remarkably High‐Temperature Stability of Bi(Fe1−xAlx)O3–BaTiO3 Solid Solution with Near‐Zero Temperature Coefficient of Piezoelectric Properties

The 0.72Bi(Fe_1?xAl_x)O₃–0.28BaTiO₃ (x = 0, 0.01, 0.03, 0.05, and 0.07, abbreviated as BFAx–BT) lead‐free high‐temperature ceramics were prepared by the conventional ceramic processing. Systematic investigation on the microstructures, crystalline structures, dielectric and piezoelectric properties, and high‐temperature stability of piezoelectric properties was carried out. The crystalline structures of BFAx–BT ceramics evolve from rhombohedral structure with x < 0.01 to the coexistence of rhombohedral structure and pseudocubic phases with x ≈ 0.01, finally to pseudocubic phases when x > 0.03. Remarkably high‐temperature stability with near‐zero temperature coefficient of piezoelectric properties (TCk_p), together with improved piezoelectric properties has been achieved for x = 0.01 BFAx–BT ceramics. The BFAx–BT(x = 0.01) ceramics simultaneously show the excellent piezoelectric properties of d₃₃ = 151 pC/N, k_p = 0.31 and super‐high‐temperature stability of T_d = 420°C, TCk_p = 1 × 10^?4. It is considered that the observed strong piezoelectricity and remarkably high‐temperature stability should be ascribed to the phase coexistence of rhombohedral and pseudocubic phases. The rhombohedral phases have a positive TCk_p value and the pseudocubic phases possess a negative TCk_p value. Thus, the TCk_p value of BFAx–BT ceramics can be tuned by composition of x.     

The Relationship Between Phase Structure and Electrical Properties in (1 − x)(Bi0.5Na0.5TiO3–Ba0.5K0.5TiO3–BaTiO3)‐ xK0.5Na0.5NbO3 Quaternary Lead‐Free Piezoelectric Ceramics

(1 ? x)(0.85Bi_0.5Na_0.5TiO₃–0.11Ba_0.5K_0.5TiO₃–0.04BaTiO₃)‐ xK_0.5Na_0.5NbO₃ lead‐free piezoelectric ceramics with x = 0.00, 0.02, 0.03, 0.04, 0.05, and 0.10 were prepared by a conventional solid state method. A coexistence of rhombohedral (R) and tetragonal (T) phases was found in the system, which tended to evolve into pseudocubic symmetry when x increases. The x = 0.04 sample exhibited improved electrical properties: the dielectric constant ε_r = 1900 with the low loss tangents 0.06, the S_max/E_max of ~400 and ~460 pm/V under unipolar and bipolar electric field, respectively. Meanwhile, piezoelectric constant d₃₃ still maintained ~160 pC/N. These could be owed to the formation of polar nanoregions for relaxor phase.     

Buffered template strategy for improving texture quality and piezoelectric properties of heterogeneous templated grain growth (K,Na)NbO3-based ceramics through interface engineering

Notwithstanding the advances in improving piezoelectric properties through templated grain growth, insights into the mechanical stress and microstructure of such materials are necessary. This is because the properties can be significantly varied depending on these parameters. Constructing heterostructure templates (²D–⁰D), in which the 0D nanoparticles have compositions similar to that of matrix powders, has significant potential in improving the above aspects. Here, BaTiO₃ (BT) templates and elements-doped (K,Na)NbO₃ (KNN) matrix powders were selected. Heterostructure BT (h-BT) templates were prepared by nucleation and growth of dopant-free KNN nanoparticles on bare BT. h-BT enabled a reduction in the mechanical stress at the interfaces within textured ceramics (h-BT-KNN), leading to larger grain growth and a higher texturing degree than those of textured ceramics (BT-KNN) fabricated using bare BT. The h-BT-KNN exhibited the enhanced piezoelectric constant (d₃₃) by ～170% and ～600% compared to those of the BT-KNN and nontextured ceramics, respectively.     

Electrocaloric behavior and piezoelectric effect in relaxor NaNbO3-based ceramics

We firstly reported the electrocaloric properties in relaxor (1−x−y)NaNbO₃–yBaTiO₃–xCaZrO₃ ceramics, and high electrocaloric effect (∆T ~0.451 K and∣∆T/∆E∣~0.282 Km/MV) can be realized in the ceramics (x = 0.04 and y = 0.10) under low temperature and low electric field. Relaxor behavior of NaNbO₃ ceramics can be found by doping both BaTiO₃ and CaZrO₃. In addition, optimized piezoelectric effects (d₃₃ ~235 pC/N and d₃₃* ~230 pm/V) can be observed in the ceramics (x = 0.04 and y = 0.10) due to the involved morphotropic phase boundary (MPB). Excellent piezoelectric effect (ie, d₃₃~330 pm/V at 41°C, and d₃₃*~332 pm/V at 60°C) can be found because of the characteristics of MPB. Good temperature reliability of piezoelectric effect can be shown because of both MPB and relaxor behavior. We believe that the ceramics with high electrocaloric effect and good piezoelectric effect can be considered as one of the most promising lead-free materials for piezoelectric devices.     

Microstructure and electrical properties of BaTiO3/Cu ceramic composite sintered in nitrogen atmosphere

BaTiO₃/xCu composite ceramics with x = 0–30 wt.% were fabricated by the traditional mixing oxide method and their microstructure, relative density, electric conductivity, permittivity and dielectric loss were measured as a function of the Cu mass fraction. The X-ray diffraction (XRD) patterns indicated that the dense composite has no chemical reaction between BaTiO₃ and Cu during sintering, and the relative diffraction intensity of Cu increased with the increase of Cu. The electric properties showed that the percolation threshold of BaTiO₃/Cu composites was x = 0.25 and its conductivity increased as the Cu content increased after that. With increasing Cu content up to 30 wt.%, the permittivity (?_r) markedly increased from ～3000 for monolithic BaTiO₃ to ～8000 at 1 kHz. Additionally, the temperature coefficient of this system was less than 5% in the temperature range of 25–115°C.     

Dielectric and mechanical properties of CaCu3Ti3.925(Nb0.5Al0.5)0.075O12 & Al reinforced epoxy-composites (0–3) for embedded capacitor applications

CaCu₃Ti_3.925(Nb_0.5Al_0.5)_0.075O₁₂ [CCTNAO] ceramics were synthesized by microwave assisted solid state reaction technique. CCTNAO ceramics possessed room temperature (RT) dielectric constant (ε_r) ～ 24,173 with tanδ ～0.149 at 1 kHz frequency. Commercially available epoxy-resin, hardener, Al-powder along with CCTNAO powder were used to prepare epoxy based 0–3 composites. Maximum ε_r ～33.37 with tanδ ～0.107 at RT were obtained for 40 vol% CCTNAO loading in epoxy. For x = 0.2 in (1-x)[0.8 Epoxy-0.2 CCTNAO]-x Al Epoxy composites, highest ε_r ～77.6 with tanδ ～ 0.15 at 1 kHz frequency were observed. Increase in ε_r with the increase of Al filler content in composites is attributed to interfacial polarization and cluster formations. Different theoretical models were discussed to explain the dielectric properties of synthesized composites. Experimentally measured values of ε_eff were in close agreement with EMT model (n = 0.13) and Yamada Model (η = 7). An empirical proposed power law ε_eff = ε_m(1+x)ⁿ, with n ～ 10 had a considerable agreement with the experimental results. Vickers hardness test study was carried out to ascertain the mechanical properties of the synthesized composites.     

Polarization behavior of sol‐gel‐derived relaxor Ba(Zr,Ti)O3 films

Films of the relaxor ferroelectric BaZr_0.25Ti_0.75O₃ (0.25‐BZT) were synthesized via a sol‐gel route to investigate the effect of film thickness on the dielectric properties and for comparison with normal ferroelectric BaTiO₃ (BT). The as‐prepared films on Nb‐doped SrTiO₃ (Nb–ST) displayed a (100) orientation; thinner films had stronger (100) orientations. Microwave dielectric measurements up to a few GHz quantified the polarizations, that is, the dipole contribution, ε_dipole, the combination of the ionic and electronic polarizations, ε_ionic+el., and the total contribution, ε_total. The ε_dipole in the relaxors at a film thickness of t=630 nm was 360, which was double that for the normal ferroelectric BT (ε_dipole=180) at t=735 nm. The larger apparent permittivity of the BZT therefore originated from the larger ε_dipole of the polar nanoregions (PNRs), while the nanograins of BT with few domain walls led to a comparably smaller ε_dipole. The volume ratio of the surface and film‐substrate interface lacking the dipole interactions increased with the reduction in the film thickness, leading to the significant depression in the permittivity for both specimens. The difference in the thickness dependence of the dielectric properties of the sol‐gel derived relaxor BZT and the normal ferroelectric BT films was attributed to the different origins of their dipole contribution, that is, the PNRs and ferroelectric domains, respectively.     

Large electric‐field‐induced strain and enhanced piezoelectric constant in CuO‐modified BiFeO3‐BaTiO3 ceramics

In this work, we fabricated the (1‐x)BiFeO₃‐xBaTiO₃+y‰ mol CuO ceramics by the modified thermal quenching technique. The pure perovskite phase was formed and a morphotropic phase boundary (MPB) was observed in the ceramics with x = 0.30‐0.33. The addition of CuO can significantly enhance the density of the BiFeO₃‐BaTiO₃ material. Importantly, an enhanced piezoelectric constant (d₃₃=165 pC/N), a large electric‐field‐induced strain (?S = 0.54%: peak to peak strain) and a large piezoelectric actuator constant (d₃₃*=449 pm/V) together with a high Curie temperature (T_C) of 503°C were observed in the ceramics with x = 0.30 and y = 5. As a result, the enhanced piezoelectricity and large electric‐field‐induced strain could significantly stimulate further researches in BFO‐based ceramics.     

Enhanced piezoresponse and electric field induced relaxor-ferroelectric phase transition in NBT-0.06BT ceramic prepared from hydrothermally synthesized nanoparticles

0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃ (NBT-0.06BT) nanoparticles were synthesized by hydrothermal method and subsequently used to prepare NBT-0.06BT ceramics. After poling at the electric field of 3.5 kV/mm, the piezoelectric coefficient (d₃₃) and electromechanical coupling factor (κ_p) reached 171 pC/N and 0.31, respectively. The NBT-0.06BT ceramics also exhibited a large remanent polarization of 46.10 μC/cm² and electric field induced strain of 0.243% at 8 kV/mm corresponding to normalized strain d₃₃^*=303 pm/V (S_max/E_max). The effects of polarization on crystalline phase, microstructures, dielectric properties and domain structures were investigated to reveal the origin of enhanced piezoresponse and electric field induced strain in as-prepared NBT-0.06BT ceramics. It can be observed that the tetragonal phase in NBT-0.06BT ceramics was enhanced and polar nanoregions were transformed into tweed-like structures and some lamellar domains after E-field poling. The dielectric response of NBT-0.06BT ceramics also exhibited an electric-field-induced relaxor-to-ferroelectric phase transition.     

Flexible BaTiO3/SiC@PbTiO3/epoxy composite films with enhanced dielectric performance at high frequency

Flexible polymer composites with high dielectric constants and low dielectric losses at high frequencies are highly desired in microwave and RF applications. However, a high dielectric constant is often obtained at the expense of flexibility because a high loading of filler is needed. In this work, we synthesize a core-shell structured 1D filler by coating high-dielectric-constant PbTiO₃ onto the surface of low-thermal-expansion-coefficient SiC nanofibers, which are then incorporated into the epoxy matrix together with BaTiO₃ nanoparticles to form the multi-phase BaTiO₃/SiC@PbTiO₃/epoxy composite film. A high dielectric constant (35 at 100 Hz and 20 at 5 GHz) and a low dielectric loss (0.023 at 100 Hz and 0.13 at 5 GHz) are achieved as the filling content of SiC@PbTiO₃ and BaTiO₃ is 5.24 wt% and 80 wt%, respectively. Prediction models of the effective dielectric constant of polymer-based composites reveal that a continuous polarization network is constructed in the composites owing to the physical contact between BaTiO₃ and PbTiO₃. The construction of the multi-phase filler provides a feasible way to effectively adjust and improve the dielectric properties of polymer-based composite films.     

Correlation of structure and dielectric response in Ce-doped double perovskite cobaltite

Double perovskite Bi₂Ca_2-xCe_xCoO₆; x = 0.00, 0.05, 0.10 and 0.15 (BCCCO) is synthesized by co-precipitation route. X-ray diffraction (XRD) confirms the monoclinic single-phase crystal structure with negligible variation in unit cell parameters, indicating that the Cerium (Ce) has been successfully incorporated. With Ce doping, the average crystallite size of Bi₂Ca₂CoO₆ (BCCO) nanoparticles decreases. Scherrer's formula was used to determine the crystallite sizes (33–37 nm) of BCCO nanoparticles. Jonscher's power law is used to investigate the conduction mechanism of all the prepared specimens. The power-law specifies the correlated barrier hopping for BCCCO x = 0.00 and 0.05, short polaron tunneling for x = 0.10, while BCCCO x = 0.15 follows overlapping large polaron tunneling. The dielectric permittivity has been calculated with a frequency range of 20 Hz - 3 MHz, and the Ce doped samples show a high value of dielectric permittivity ε_r = 1.79 × 10⁵ at 500 °C. The influence of crystallite size on the dielectric permittivity of BCCCO was examined in this work. The relaxation time and spreading factor of all samples are investigated using Non-linear Debye's function. All these features are studied as a function of frequency at temperatures ranging from 100 to 500 °C. Here, the DC electrical conductivity of BCCCO is investigated by the four-probe method at 50–400 °C. In Ce-doped specimen the lowest value of thermal conductivity (k = 0.797 W/m-K at 120 °C) has been observed.     

Tailoring and improving the strong-electric-field electrical properties of the BNT-BT ferroelectric ceramics by a functional-group-doping

Lead-free ferroelectric ceramics with high tailored strong-electric-field electrical properties (energy storage, electrocaloric cooling, and energy harvesting, etc.) are attractive to many fields, such as modern electronics, medical and military, etc. We demonstrated that the strong-electric-field electrical properties of the 0.89(Bi_0.5Na_0.5TiO₃)-0.11(BaTiO₃) (BNT-BT) relaxor ceramics not only could be tailored easily after doping the (BaTiO₃)_0.5-(BiMg_0.5Ti_0.5O₃)_0.5 (BT-BMT, the functional-group), but also could be improved largely. As a result, an optimized electrostrain (S ~ 0.4%) was acquired at x = 0.12, and an optimized energy storage density (W ~ 0.775 J/cm³) with a high efficiency (η ~ 50%) was achieved at x = 0.24, as well as a phase-induced negative electrocaloric (EC) effect (ΔT ~ 3.72 K) was harvested at x = 0.04. It is concluded that the functional-group-doping can be regarded as a new strategy to tailor and improve the strong-electric-field electrical properties of ferroelectric materials.     

Flow Cytometry Analysis of Cytotoxicity In Vitro and Long‐Term Toxicity of HA‐40 wt% BaTiO3 Nanoparticles In Vivo

The development of new implantable biomaterials requires bone‐mimicking physical properties together with desired biocompatible property. In continuation to our earlier published research to establish compositional dependent multifunctional bone‐like properties and cytocompatibility response of hydroxyapatite (HA)‐BaTiO₃ composites, the toxicological property evaluation, both in vitro and in vivo, were conducted on HA‐40 wt% BaTiO₃ and reported in this work. In particular, this work reports in vitro cytotoxicity of mouse myoblast cells as well as in vivo long‐term tissue and nanoparticles interaction of intra‐articularly injected HA‐40 wt% BaTiO₃ and BaTiO₃ up to the concentration of 25 mg/mL in physiological saline over 12 weeks in mouse model. The careful analysis of flow cytometry results could not reveal any statistically significant difference in terms of early/late apoptotic cells or necrotic cells over 8 d in culture. Extensive histological analysis could not record any signature of cellular level toxicity or pronounced inflammatory response in vital organs as well as at knee joints of Balb/c mice after 12 weeks. Taken together, this study establishes nontoxic nature of HA‐40 wt% BaTiO₃ and therefore, HA‐40 wt% BaTiO₃ can be used safely for various biomedical applications.     

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.     

Two phase Mg0.7Cd0.3Fe2O4–BaTiO3 composite ceramics with excellent magneto-dielectric properties for antennas in GHz band

Two phase-based composites comprising barium titanate (BaTiO₃) and spinel magnesium ferrite (1-x)Mg_0.7Cd_0.3Fe₂O₄ +xBaTiO₃ (x = 0.00, 0.03, 0.06, 0.09, and 0.12) were investigated. The phase structure revealed the coexistence of the perovskite BaTiO₃ and spinel MgFe₂O₄ phases. The microstructural analysis indicated that the average crystallite size initially increased and then decreased, as the increase in x weakened magnetisation, decreased saturation magnetisation (from 47.5 to 35.9 emu/g) and coercivity (150–0 Oe) were obtained, resulting in reduced permeability at low frequency. The permittivity gradually increased owing to tuning by barium titanate, which has strong dielectric properties, promising a relatively large miniaturisation factor. Further, low magnetic loss (tan δ_μ ∼10⁻²) and dielectric loss (tan δ_ε ∼ 10⁻² to 10⁻³) guarantee high quality factor. The low losses and enhanced dielectric properties of the as-synthesised composites could be conducive to improving the behaviour of such magneto-dielectric composite systems in microwave applications.     

High-temperature dielectrics in CaZrO3-modified Bi1/2Na1/2TiO3-based lead-free ceramics

Materials in two composition regimes, Bi_1/2Na_1/2TiO₃–BaTiO₃–CaZrO₃ (BNT–BT–CZ) and Bi_1/2Na_1/2TiO₃–BaTiO₃–K_0.5Na_0.5NbO₃–CaZrO₃ (BNT–BT–KNN–CZ), were synthesized via the mixed oxide route and their structural, dielectric and electrical properties were investigated. CZ was identified to render the two local maxima in permittivity more diffused. This resulted in temperature-insensitive relative permittivity spectra with average values from ～470 up to ～2300 and operational windows of at least ～400 °C with less than 15% of variation in the temperature range from ?100 up to above 500 °C. Moreover, loss factors are below ～10% and RC constants range from ～0.03 s up to ～4 s at 300 °C. The materials of current investigation are highly attractive for developing capacitors of wide temperature usage.