Ferroelectric‐quasiferroelectric‐ergodic relaxor transition and multifunctional electrical properties in Bi0.5Na0.5TiO3‐based ceramics

A‐site substituted 0.88(Bi_0.5Na_0.5)_1?x(Li_0.5Nd_0.5)_xTiO₃–0.12BaTiO₃ (BNTLNx–BT12) ceramics were synthesized using a conventional solid‐state reaction route. The structural transformation and miscellaneous electrical properties were systematically investigated. The A‐site modification induced two sequence transitions from ferroelectric tetragonal (T) to quasi‐ferroelectric pseudocubic (PC) phase, followed closely by the second transition from non‐ergodic to ergodic relaxor (NR‐ER), and finally to dynamic polar nanoregions (PNRs). The significant enhancement in piezoelectric activity, strain response, broad plateau‐like maximum dielectric permittivity over a large temperature range and energy‐storage level at different compositions may be attributed to the compositionally‐induced T‐PC to NR‐ER transition and the alignment of dynamically‐fluctuating PNRs, respectively. The evolution of multifunctional electrical properties, associated with the variations in structure/microstructure, might provide a new insight to investigate the underlying mechanism of structure‐electrical properties relationship in ferroelectric solid solutions.     

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.     

Structure and Dielectric Properties of Re0.02Sr0.97TiO3 (Re = La,Sm, Gd,Er) Ceramics for High‐Voltage Capacitor Applications

Rare–earth‐doped strontium titanate ceramics yielding the formula Re_0.02Sr_0.97TiO₃ (Re–ST, Re = La, Sm, Gd, Er) were prepared by solid‐state reaction route. All Re–ST ceramics had single cubic perovskite structure similar to pure SrTiO₃ (ST). The grain size of Re–ST ceramics dramatically decreased to 1–10 μm, depending on different rare‐earth elements, as compared to ~30 μm of pure ST. The relative dielectric constant of Re–ST ceramics (ε_r = 2750–4530 at 1 kHz) showed about 10–15 times higher than that of pure ST (ε_r = 300 at 1 kHz), whereas the dielectric loss of Re–ST ceramics still remained lower than 0.03 (at 1 kHz) at room temperature. Under 0–1.63 × 10⁶ V/m bias electric field testing conditions, the ε_r of Re–ST ceramics at room temperature changed within 14%. The P–E results indicated that the Re–ST ceramics were linear dielectrics. Together with their relatively high breakdown strength (E_b > 1.4 × 10⁷ V/m), the Re–ST ceramics could be very promising for high‐voltage capacitor applications. Meanwhile, the temperature stability of the ε_r of Re–ST ceramics was evaluated in a temperature range of ?60°C–200°C.     

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.     

Low‐Temperature Sintering and Electric Properties of Pb0.99(Zr0.95Ti0.05)0.98Nb0.02O3 Ferroelectric Ceramics with CuO Additive

The low‐temperature sintering and electric properties of Pb_0.99(Zr_0.95Ti_0.05)_0.98Nb_0.02O₃ (PZTN 95/5) ferroelectric ceramics with CuO addition was investigated. The CuO addition significantly promoted the densification and reduced the sintering temperature of PZTN 95/5 ceramics by more than 200°C. The 0.2 wt% CuO‐added sample sintered at 1150°C exhibited the optimum relative density of 96.7% and excellent electric properties with values of P_r = 37.80 μC/cm², T_C = 223°C, ε_r = 329, and tan δ = 0.016, which were superior to that of PZTN 95/5 ceramics sintered at 1350°C.     

Grain size effects and structure origin in high-performance BaTiO3-based piezoceramics with large grains

Grain size shows significant influence on electrical properties of piezoceramics. However, there are few works to investigate the grain size effects in high-performance and large-grain piezoceramics and uncover the structure origin. In this work, large grain size from ~53 to ~92 µm was achieved in a high-performance BaTiO₃ (BT)-based ceramic via tuning sintering conditions. With grain size increasing, the ceramics exhibit same multiphase coexistence state, similar phase transition temperature, upward T_C dielectric peaks and reduced diffuseness degree. Because of the larger and more complex non-180° domains within bigger grains, the improvement in remnant polarization (P_r), coercive field and negative strain were observed in bigger-grain ceramics. The elevated P_r finally leads to the piezoelectric coefficient d₃₃ increasing from 500 to 650 pC/N. However, too large grains may cause the reduced strain due to the high remnant strain in first cycle. Therefore, big grain size is conducive to achieve high piezoelectricity while moderate grain size can facilitate strain response in high-performance ceramics with large grains, which is quite different with pure BT ceramic. This work presents insights into the grain size effects and affords guides to further optimize electrical properties in high-performance piezoceramics with large grains.     

Structure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of BiFeO3‐BaTiO3‐Bi0.5Na0.5TiO3 Lead‐Free Multiferroic Ceramics

Lead‐free multiferroic ceramics of BiFeO₃‐BaTiO₃‐Bi_0.5Na_0.5TiO₃ have been prepared by a conventional ceramic technique. The microstructure, multiferroic, and piezoelectric properties of the ceramics have been studied. The ceramics sintered at 1000°C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and tetragonal phases is formed at x = 0.02. After the addition of Bi_0.5Na_0.5TiO₃, two dielectric anomalies are observed at high temperatures (T_m ~ 510°C–570°C and T₂ ~ 720°C). The phase transition around T_m becomes wider gradually with increasing x. The ferroelectricity, piezoelectricity, and ferromagnetism of the ceramics are significantly improved after the addition of Bi_0.5Na_0.5TiO₃. High resistivity (~1.3 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 27.4 μC/cm²), good piezoelectricity (d₃₃ =140 pC/N, k_p = 31.4%), and weak magnetic properties (M_r =0.19 emu/g) are observed.     

Low‐Temperature‐Fired ReVO4 (Re = La,Ce) Microwave Dielectric Ceramics

We report a series of ReVO₄ (Re = La, Ce) microwave dielectric ceramics fabricated by a standard solid‐state reaction method. X‐ray diffraction and scanning electron microscopy measurements were performed to explore the phase purity, sintering behavior, and microstructure. The analysis revealed that pure and dense monoclinic LaVO₄ ceramics with a monazite structure and tetragonal CeVO₄ ceramics with a zircon structure could be obtained in their respective sintering temperature range. Furthermore, LaVO₄ and CeVO₄ ceramics sintered at 850°C and 950°C for 4 h possessed out‐bound microwave dielectric properties: ε_r = 14.2, Q × f = 48197 GHz, τ_f = ?37.9 ppm/°C, and ε_r = 12.3, Q × f = 41 460 GHz, τ_f = ?34.4 ppm/°C, respectively. The overall results suggest that the ReVO₄ ceramics could be promising materials for low‐temperature‐cofired ceramic technology.     

Effects of Postdensification Annealing upon Microstructures and Microwave Dielectric Characteristics in Ba((Co0.6−x/2Zn0.4−x/2Mgx)1/3Nb2/3)O3 Ceramics

Effects of postdensification annealing upon microstructures and microwave dielectric characteristics in Ba((Co_0.6?x/2Zn_0.4?x/2Mg_x)_1/3Nb_2/3)O₃ (x = 0, 0.1, 0.2, and 0.3) complex perovskite ceramics have been investigated. Long‐time annealing at temperatures below the order–disorder transition temperature enhances the cation ordering degree and promotes the ordering domain growth. The most significant improvement of Qf value is obtained together with the suppressed temperature coefficient of resonant frequency in the samples annealed at 1400°C for 12 h, while the dielectric constant decreases slightly. The Qf value of ceramics annealed at 1400°C mainly attributes to the enhanced cation ordering degree, because their low‐energy domain boundaries are not detrimental to the Qf value. As the annealing temperature increases close to the transition temperature, coarse ordering domains with high‐energy boundaries are formed, and then the Qf value steadily decreases because of the inferior domain structure, even the cation ordering degree increases. The microwave dielectric characteristics of Ba((Co_0.6?x/2Zn_0.4?x/2Mg_x)_1/3Nb_2/3)O₃ ceramics are affected by the common function of ordering degree and domain structure. The best combination of microwave dielectric characteristics is obtained in the composition of x = 0.3 after annealing at 1400°C for 12 h: ε_r = 33.2, Qf = 117 200 GHz, and τ_f = 8.6 ppm/°C.     

Structure and Microwave Dielectric Properties of Low Firing Bi2Te2W3O16 Ceramics

Dense Bi₂Te₂W₃O₁₆ ceramics were prepared by the conventional solid‐state reaction route. X‐ray diffraction data show the room‐temperature (RT) crystal symmetry of Bi₂Te₂W₃O₁₆ to be well described by the centrosymmetric monoclinic C2/c space group [a = 21.280(5) Å, b = 5.5663(16) Å, c = 12.831(3) Å and β = 124.014(19)° and Z = 4]. Raman spectroscopy analyses are in broad agreement with space group assignment, but also revealed the presence of Bi₂W₂O₉ as a secondary phase. This phase is present as plate‐like grains embedded on a fine‐grained equiaxed matrix, as revealed by scanning electron microscopy. From the fitting of infrared reflectivity data the relative permittivity, ε_r, was estimated as 34.2, and the intrinsic quality factor, Q_u × f as 57 500 GHz. At RT and microwave frequencies, Bi₂Te₂W₃O₁₆ ceramics sintered at 720°C for 6 h exhibit ε_r ~ 34.5, Q_u × f = 3173 GHz (at 7.5 GHz), and temperature coefficient of resonant frequency, τ_f = ?92 ppm/°C. This shows a good agreement between the estimated and measured ε_r values, but also shows that, in principle, the dielectric losses of the ceramics are of extrinsic origin.     

Srn+1TinO3n+1 (n=1, 2) microwave dielectric ceramics with medium dielectric constant and ultra‐low dielectric loss

Sr_n+1Ti_nO_3n+1 (n=1, 2) ceramics with tetragonal Ruddlesden–Popper structure were prepared via a standard solid‐state reaction process, and their microstructures and microwave dielectric properties were investigated systematically. The phase composition, grain morphology, and densification behavior were explored using X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Outstanding microwave dielectric properties were achieved in the present ceramics: ε_r=42, Q × f=145 200 GHz, τ_f=130 ppm/°C for Sr₂TiO₄, and ε_r=63, Q × f=84 000 GHz, τ_f=293 ppm/°C for Sr₃Ti₂O₇, respectively. The present ceramics might be expected as excellent candidates for next‐generation medium‐permittivity microwave dielectric ceramics after the further optimization of τ_f value.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

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.     

Enhanced insulating and piezoelectric properties of BiFeO3-BaTiO3-Bi0.5Na0.5TiO3 ceramics with high Curie temperature

BiFeO₃-BaTiO₃ ceramics are promising lead-free piezoelectric ceramics due to their high piezoelectric properties and high Curie temperature, but their high leakage current density makes the poling difficult. In this study, a decreased leakage current density by three orders of magnitude was obtained in Bi_0.5Na_0.5TiO₃ (BNT) added 0.67BiFeO₃-0.33BaTiO₃ (BF-BT) ceramics. It was found that the largely improved insulating properties benefit from the reduced oxygen vacancies and weak reduction of Fe³⁺ to Fe²⁺ as confirmed by photoluminescence and X-ray photoelectron spectroscopy measurements, thereby contributing to high-temperature and high-field poling. In addition, the introduction of BNT leaded to increased grain size. Due to the grown grains as well as reduced oxygen vacancies and Fe²⁺, enhanced insulating and optimal piezoelectric properties with P_r = 24.2 µC/cm², d₃₃ = 183 pC/N, k_p = 0.28, and T_C = 467°C were achieved in BF-BT-0.05BNT ceramics.     

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.     

Synthesis and Electrical Properties of New Lead‐free (100−x)(Li0.12Na0.88)NbO3–xBaTiO3 (0 ≤ x ≤ 40) Piezoelectric Ceramics

New lead‐free (100?x)Li_0.12Na_0.88NbO₃‐xBaTiO₃ (0 ≤ x ≤ 40) piezoelectric ceramics have been synthesized using conventional ceramics processing route. Structural analysis revealed an existence of morphotropic phase boundary (MPB), separating orthorhombic and tetragonal phases, between the BaTiO₃ content, x = 10–12.5. A partial phase diagram has been established based on temperature‐dependent permittivity data for this new system and a almost vertical temperature‐independent MPB is observed. Improvement in electrical properties near MPB (e.g., for x = 12.5; ε_r = 8842 at T_m and 795 at room temperature, d₃₃ = 30 pC/N, k_p = 12.0%, Q_m = 162, P_r = 11.2 μC/cm², E_c = 19.2 kV/cm, = 174 pm/V) is observed, and is attributed to the ease of polarization rotation due to coexistence of orthorhombic and tetragonal phases. The results show that these materials could be suitable for piezoelectric vibrators and ultrasonic transducer applications. The sample with x = 25, also exhibited high dielectric permittivity, ε_r = 2400, and low dielectric loss, tanδ = 0.033 at room temperature which could be suitable for capacitor (X7R/Z5U) applications.     

Low sintering temperature for lead-free BiFeO3-BaTiO3 ceramics with high piezoelectric performance

Through modification of the heat-treatment process using a higher heating rate and a lower binder burnout temperature, the piezoelectric performance of water-quenched 0.67Bi_1.05FeO₃-0.33BaTiO₃ (BF33BT) lead-free piezoelectric ceramics was improved. The observed physical properties of BF33BT ceramics were very sensitive to the process temperatures. The sintering temperature (T_S) was changed within a narrow temperature range, and its effects were investigated. The largest rhombohedral distortion (90°-α_R = 0.14°) and tetragonality (c_T/a_T = 1.022) were observed for the ceramic sintered at 980°C, and its Curie temperature was 476°C. This ceramic showed good piezoelectric properties and large grains; the piezoelectric sensor charge coefficient (d₃₃) was 352 pC/N, and the piezoelectric actuator charge coefficient () was 270 pm/V. The high piezoelectric performance and low T_S of BF33BT ceramics indicate their potential as new low-cost eco-friendly lead-free piezoceramics.     

Exceptionally High Dielectric Constant in Ceramic Pr2CuO4

The pristine layered cuprate Pr₂CuO₄ samples of >95% density were fabricated as thin disks. The samples, analyzed by X‐ray diffraction and Scanning electron microscopy, showed clean T′‐type phase with Rietveld refined lattice parameters a = b = 3.95805(±5) Å and c = 12.2262(±5) Å. The measured dielectric properties of the Pr₂CuO₄ ceramics, in the temperature range ?100°C–150°C and frequencies (ν) 0.1 Hz–1 MHz, showed extremely high ε_r′ > 10⁴ (above ?30°C), and dissipation (tan δ = ε_r′′/ε_r′) between 0.1 and 5 (for 500 Hz ≤ ν ≤ 1 MHz, and ?100 ≤ T ≤ 150°C). The ac conductivity of Pr₂CuO₄ ceramics ranged between 10^?6 and 10^?3 Scm^?1 for the measured frequencies and temperatures, and showed frequency‐dependent double power law behavior akin to a modified Jonscher's power law.     

Microwave Dielectric Properties of Novel Glass‐Free Low‐Firing Li2CeO3 Ceramics

Novel glass–free low temperature firing microwave dielectric ceramics Li₂CeO₃ with high Q prepared through a conventional solid‐state reaction method had been investigated. All the specimens in this paper have sintering temperature lower than 750°C. XRD studies revealed single cubic phase. The microwave dielectric properties were correlated with the sintering conditions. At 720°C/4 h, Li₂CeO₃ ceramics possessed the excellent microwave dielectric properties of ε_r = 15.8, Q × f = 143 700 (GHz), and τ_f  = ?123 ppm/°C. Li₂CeO₃ ceramics could be excellent candidates for glass‐free low‐temperature co‐fired ceramics substrates.     

An effective optimization strategy and analysis for BaTiO3–Na0.5Bi0.5TiO3 system with colossal permittivity

Colossal permittivity (CP, ε＞10⁴) behavior in BaTiO₃–Na_0.5Bi_0.5TiO₃ (BT-NBT) ceramics has been studied, which showed extremely high permittivity up to ~10⁵. Dielectric properties of samples showed Debye-like relaxations in the frequency range 20 Hz–30 MHz. Two different polarizations located in grain boundaries and grains respectively are responsible for the CP behavior and the models of defect charge compensation achieved by niobium doping are proposed to explain the phenomenon of abnormal variation of dielectric constant.By using defect engineering, a Nb-doped BaTiO₃ ceramics with stable colossal permittivity (ε_r =1.3×10⁴ at 1 kHz and room temperature),high bulk resistivity (>10¹⁰ Ω·cm) as well as relative low dielectric loss (tanδ~0.06) has been obtained over a wide temperature range of −55–150 °C, satisfying IEA X8R specification, which has a potential application prospect in high capacity solid supercapacitor.