Phase transition,microstructure and properties of (Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>)<Subscript>1-x</Subscript>Ba<Subscript>x</Subscript>TiO<Subscript>3</Subscript> lead-free piezoelectric ceramics

In this article, (Na_0.5Bi_0.5)_1-xBa_xTiO₃ lead-free piezoelectric ceramics were prepared by solid-state reaction. The influence of Ba contents on phase structures, compositional distribution and electrical properties of (Na_0.5Bi_0.5)_1-xBa_xTiO₃ ceramics were systematically investigated to further understand the nature of phase transition. It was found that the phase structure of (Na_0.5Bi_0.5)_1-xBa_xTiO₃ transforms from rhombohedral to tetragonal symmetry at x = 0.06 ~ 0.07 and Ba²⁺ segregation forms the coexistence of Ba-rich tetragonal and Ba-deficient rhombohedral phases close to MPB. The electrical properties of prepared samples regularly changed with Ba content, which is closely related to the distribution of rhombohedral and tetragonal phases. The prepared sample near MPB exhibited the largest dielectric constant and the excellent piezoelectric properties (the maximal measuring field reached 78 kV/cm and the piezoelectric constant d ₃₃ = 151pC/N).     

Lead-free (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)<Subscript>0.95</Subscript>(LiSb)<Subscript>0.05</Subscript>Nb<Subscript>0.95</Subscript>O<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> piezoceramics

Lead-free (1-x)(K_0.5Na_0.5)_0.95(LiSb)_0.05Nb_0.95O₃-xBaTiO₃ (abbreviated as (1-x)KNNLS-xBT) piezoceramics were synthesized by conventional solid state sintering and the effect of BaTiO₃ on the microstructure, dielectric and piezoelectric properties was investigated. It was found that both orthorhombic-tetragonal (T _O-T) and tetragonal-cubic (T _C) phase transition temperatures decreased obviously with increasing BaTiO₃ content. Although proper amount of BaTiO₃ facilitated the sintering of (1-x)KNNLS-xBT ceramics, the addition of BaTiO₃ affected the relaxor behavior slightly and it was not beneficial to improve piezoelectric strain coefficient d ₃₃, remnant polarization P _r and piezoelectric coupling constant k _p.     

Growth,domain dynamics and piezoelectric properties of some lead-free ferroelectric crystals

Lead-free solid solution crystals (Na, Bi)TiO₃–BaTiO₃ [NBBT] and (K,Na)NbO₃–LiNbO₃[KNN–LN] have been grown by the Bridgman method. Their piezoelectric constant d₃₃ reach 160 and 405 pC/N, respectively. Domain dynamics shown through in-situ observation using a polarizing microscopy in 0.94NBT-0.06BT crystals demonstrate that both of ferroelectric–antiferroelectric phase transition and antiferroelectric–paraelectric one take place in broad temperature ranges. 0.94NBT-0.06BT is more relaxor ferroelectric whereas 0.95KNN-0.05LN crystal is more normal ferroelectric. Moreover, it is found that the ferroelectric phase coexists with the paraelectric phase at the temperature much higher than their Curie temperature in both crystals. The low value of d ₃₃ may originate from the existence of an antiferroelectric tetragonal phase in a ferroelectric rhombohedral phase in NBBT crystals.     

Dielectric and Piezoelectric Properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-K<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-NaNbO<Subscript>3</Subscript>Lead-Free Ceramics

The ternary lead-free piezoelectric ceramics system of (1 – x) [0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃] – xNaNbO₃(x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) were synthesized by conventional solid state reaction method. The crystal structure, dielectric, piezoelectric properties and P-E hysteresis loops were investigated. The crystalline structure of all compositions is mono-perovskite phase ascertained by XRD, and the lattice constant was calculated from the XRD data. Temperature dependence of dielectric constant _r and dissipation factor tan measurement revealed that all compositions experienced two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric, and these two phase transitions have relaxor characteristics. Both transition temperatures T_d and T_m are lowered due to introduction of NaNbO₃. P-E hysteresis loops show that 0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃ ceramics has the maximum P_r and E_c corresponding to the maximum values of electromechanical coupling factor K_p and piezoelectric constant d_33. The piezoelectric constant d₃₃ and electromechanical coupling factor K_p decrease a little, while the dielectric constant ₃₃^T/₀ improves much more when the concentration of NaNbO₃ is 8 mol%.     

Effect of heating rate on the structure evolution of (K0.5Na0.5)NbO3–LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃–xLiNbO₃ (abbreviated an KNLN) have been synthesized by traditional ceramics process. Effects of heating rate on the phase structure, microstructure evolution and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃–xLiNbO₃ were investigated. Results show that the heating rate has no effects on the phase structures. However, the fracture surface of the 0.94(K_0.5Na_0.5)NbO₃ −0.06 LiNbO₃ ceramics transforms from intergranular fracture mode to a typical transgranular fracture mode with the increasing of the heating rate. This result is ascribed to the presence of agglomerates of grains which exhibit different sintering behavior at diverse heating rates. The 0.94(K_0.5Na_0.5)NbO₃–0.06LiNbO₃ ceramic sintered at 1080°C with heating rate of 5°C/min shows the optimum piezoelectric properties(d ₃₃ = 210 pC/N, k _p = 0.403 and k _t = 0.498).     

Improved piezoelectric properties of Ag doped 0.94(K0.5–βNa0.5–δ)NbO3–0.06Li1–γNbO3 ceramics by templated grain growth method

In this work, Ag doped 0.94(K_0.5–βNa_0.5–δ)NbO₃–0.06Li_1–γNbO₃ lead-free piezoelectric ceramics have been prepared by templated grain growth (TGG) using cubic (K,Na)NbO₃ single crystal seeds as templates. Specimens were prepared by the conventional mixed method and sintered in controlled atmosphere. TGG method was well known, because that this method can improve piezoelectric properties by increasing the grain size during the sintering process. Sintering caused densification and grain growth of ceramics by the expense of matrix particles. Densification prior to grain growth was found to be necessary to obtain highly textured ceramics. Crystalline properties were analyzed by the XRD method. The effects of TGG on phase structure, microstructure, piezoelectric and dielectric properties of Ag doped 0.94(K_0.5–βNa_0.5–δ)NbO₃–0.06Li_1–γNbO₃ ceramics were investigated.     

High piezoelectricity associated with crossover from nonergodicity to ergodicity in modified Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectrics

The structural origin of high piezoelectricity in perovskite-type relaxor ferroelectrics is a fundamental issue that remains elusive for decades. In this study, high and unstable piezoelectricity for the poled ceramics, accompanied with a crossover from a nonergodic relaxor to an ergodic relaxor state at room temperature, has been observed for 0.95(Bi_0.5Na_0.5)_1-x (Li_0.5Sm_0.5) _x TiO₃–0.05BaTiO₃ ceramics with x = 0.06. The result suggests that the high piezoelectric activity origins from the electric field-induced-ordered nanodomains. The rapid loss of piezoelectricity stems from the reversibility of the ordered nanodomains after removing applied electric field.     

Effects of MnO<Subscript>2</Subscript> addition on microstructure and electrical properties of (Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>) <Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>TiO<Subscript>3</Subscript> ceramics

In this letter, MnO₂-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT-6) lead-free piezoelectric ceramics were synthesized by solid state reaction, and the microstructure and electrical properties of the ceramics were investigated. X-ray diffraction (XRD) reveals that all specimens take on single perovskite type structure, and the diffraction peaks shift to a large angle as the MnO₂ addition increases. Scanning electron microscopy shows that the grain sizes increases, and then decreases with increasing the MnO₂ content. The experiment results indicate that the electrical properties of ceramics are significantly influenced by the MnO₂ content, and the ceramics with homogeneous microstructure and excellent electrical properties are obtained with addition of 0.3 wt% MnO₂ and sintered at 1160°C. The piezoelectric constant (d₃₃), the electromechanical coupling factor (k _p ), the dissipation factor (tan δ) and the dielectric constant (ɛ _r ) reach 160 pC/N, 0.29, 0.026 and 879, respectively. These excellent properties indicate that the MnO₂-doped BNBT-6 ceramics can be used for actuators.     

Lead-free Na0.5K0.5NbO3 piezoelectric ceramics fabricated by spark plasma sintering: Annealing effect on electrical properties

Niobate ceramics such as NaNbO₃ and KNbO₃ have been studied as promising Pb-free piezoelectric ceramics, but their sintering densification is fairly difficult. In the present study, highly dense Na_0.5K_0.5NbO₃ ceramics with submicron grains were prepared using SPS, whose density was raised to 4.47 g/cm³ (>99% of the theoretical density) at 920 °C. Reasonably good ferroelectric and piezoelectric properties were obtained in the SPSed Na_0.5K_0.5NbO₃ ceramics after annealing in air. The effect of annealing time on the electrical properties was investigated to determine optimal processing condition. The piezoelectric parameter (d ₃₃) of the Na_0.5K_0.5NbO₃ ceramics annealed properly reached 148 pC/N.     

Temperature dependent electrical properties of 0.95[(K0.5Na0.5)(1-x)Ag x NbO3]-0.05LiSbO3 ceramics

Lead free 0.95[(K_0.5Na_0.5)_1-x Ag _x NbO₃]-0.05LiSbO₃ (KNAN-LS) ceramics with x?=?0.02, 0.04, 0.06 and 0.08 have been synthesized by conventional solid state reaction route (CSSR). XRD analysis confirmed the presence of a mixed structure for x?=?0.06. The orthorhombic?Ctetragonal polymorphic phase transition (PPT) temperature and the Curie temperature (T_c) decreased with the increase in Ag⁺ ion content in KNAN-LS ceramics. The relationship between the PPT of the ceramics and the temperature dependence of electrical properties of KNAN-LS ceramics were discussed in detail. The KNAN-LS ceramics with x?=?0.06 showed better piezoelectric and electromechanical properties (d₃₃?=?227pC/N and k_p?=?42.5?%).     

Effects of co-doped CaO/MnO on the piezoelectric/dielectric properties and phase transition of lead-Free (Bi0.5Na0.5)0.94Ba0.06TiO3 piezoelectric ceramics

The piezoelectric properties of (1?x)(Bi_0.5Na_0.5)TiO₃-xBaTiO₃ ceramics were reported and their piezoelectric properties reach extreme values near the MPB (about x?=?0.06). The X-ray analysis of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramics for all compositions exhibited a pure perovskite structure without any secondary phase. Within a certain ratio of contents, the co-doped ceramics enhanced piezoelectric coefficient (d ₃₃ ), lowered the dielectric loss, and increased the sintered density. The temperature dependence of relative dielectric permittivity (K ₃₃ ^T ) reveals that the solid solutions experience two phase transitions, ferroelectric to anti-ferroelectric and anti-ferroelectric to relaxor ferroelectric, which can be proven by P-E hysteresis loops at different temperatures. In addition, the specimen containing 0.04/0.01 wt.% CaO/MnO showed that the coercive field E _c was a minimum value of 26.7 kV/cm, while the remnant polarization P _r was a maximum value of 38.7 μC/cm², corresponding to the enhancement of piezoelectric constant d₃₃ of 179 pC/N, electromechanical coupling factor k _p of 37.3%, and relative dielectric permittivity K ₃₃ ^T of 1137. (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramics co-doped with CaO/MnO were considered to be a new and promising candidate for lead-free piezoelectric ceramics owing to their excellent piezoelectric/dielectric properties, which are superior to an un-doped BNBT system.     

Nonstoichiometric (K,Na)NbO3 ceramics: Densification and electrical properties

In order to clarify the influence of excess ions in A or B sites on perovskite (K,Na)NbO₃ ceramics, various compositions of (K_0.48Na_0.52)Nb_1+x%O₃ (ABO₃) ceramics where x is in the range of ±1 % were prepared by conventional solid state method and their densification, structure, dielectric and piezoelectric properties were investigated. Results showed that a small amount of excess A-site ions could compensate for the deficiency of K and Na ions in A-sites caused by volatilization resulting in good piezoelectric properties. The ceramics with x?=??0.1 exhibited optimum piezoelectric properties with d ₃₃?=?127pC/N and k _p?=?0.41. However, presence of too much alkali elements (x?<??0.5) led to deterioration of density, dielectric and piezoelectric properties, although the crystal structure was not changed. The electrical properties, on the other hand, were not sensitive to the B-site excess ions. These results are expected to be very useful for further designing of (K,Na)NbO₃-based ceramics as lead-free alternatives to piezoelectric materials.     

Microwave dielectric properties of Na<Superscript>+</Superscript> and M<Superscript>3+</Superscript>-doped Ba(Mg<Subscript>0.5</Subscript>W<Subscript>0.5</Subscript>)O<Subscript>3</Subscript> ceramics

In this study, phase evolution, microstructure, and microwave dielectric properties of (Ba_0.98Na_0.02)(Mg_0.48M³⁺_0.02W_0.5)O₃ (M³⁺?=?Al, Ga, Sc, In, Yb, Y, Dy, Gd, and Sm) ceramics sintered at 1700 °C for 1 h were investigated. All the compounds exhibited an ordered cubic perovskite structure. Regardless of the ionic radius of the doped M³⁺ ions, BaWO₄ was detected as the secondary phase in all the compounds. The field emission scanning electron microscopy (FE-SEM) images revealed a dense microstructure in all the compounds, except in the Al-doped compound, which exhibited an insufficient grain growth. The large and irregularly shaped grains indicated that the liquid phase sintering occurred. Splitting of the A_1g(O) mode was observed in the Raman spectra of large M³⁺ ion-doped compounds. Splitting of the F_2g modes did not occur and the bands were sharp, indicating that the cubic symmetry was retained. As the ionic radius of the doped M³⁺ ions increased, the dielectric constant (ε_r) increased slightly. The compounds doped with M³⁺?=?Sc, In, Yb, and Y exhibited a very high quality factor (Q?×?f₀) in the range of 250,000 ~ 280,000 GHz. In the case of the compounds doped with M³⁺?=?Al, Ga, Sc, In, Yb, Y, and Dy, the value of the temperature coefficient of resonant frequency (τ_f) was in the range of ?24 ~ ?19 ppm/°C, while the Gd and Sm-doped compounds exhibited positive values of 2.8 and 31.2 ppm/°C, respectively. The dielectric constant, quality factor, and temperature coefficient of resonant frequency of the In-doped compound, i.e., (Ba_0.98Na_0.02)(Mg_0.48In_0.02W_0.5)O₃, were 18.7, 286,557 GHz, and???24.4 ppm/°C, respectively.     

Preparation,characterisation, and electrical properties of (K0.5Na0.5)NbO3 lead-free piezoelectric ceramics

Na_0.5?K_0.5NbO₃ (KNN) ceramics were sintered at different temperatures (970 °C, 1000 °C, 1030 °C, 1060 °C, and 1090 °C) for 3 h by a pressureless sintering method. The powders had been synthesised by sol–gel method, using citric acid as a coordination agent and ethylene glycol as an esterifying agent. The effects of temperature on the phase, microstructure, dielectric, ferroelectric, and piezoelectric properties of the as-prepared ceramics were analysed. The results revealed that all of the ceramics had a pure perovskite phase with orthorhombic symmetry. The piezoelectric constant (d ₃₃), the relative dielectric constant (ε _r), the planar electromechanical coupling coefficient (K _p), and the remnant polarization (P _r) initially increased and then decreased with increasing of temperature in such KNN ceramics. The volatilization of sodium and potassium increased with increasing sintering temperature. Over the range of temperatures studied, those ceramics sintered at 1060 °C had the following optimal properties: (ρ?=?3.97 g/cm³, d ₃₃?=?119 pC/N, ε _r?=?362.46, tan δ?=?0.05, K _p?=?0.23, P _r?=?11.97 μC/cm², E _c?=?10.35 kV/cm, and T _c?=?408 °C).     

Enhanced piezoelectricity around the tetragonal/orthorhombic morphotropic phase boundary in (Na,K)NbO3–ATiO3 solid solutions

The high density perovskite titanates-modified potassium–sodium niobate solid solutions (1?x)(Na_0.5K_0.5)NbO₃?xBaTiO₃ and (1?x)(Na_0.5K_0.5)NbO₃?xSrTiO₃ have been prepared by the solid state reaction method. The phase diagram summarized from the dielectric property measurement reveals that there exists a tetragonal/orthorhombic morphotropic phase boundary for both the solid solutions. The piezoelectric properties show enhanced behavior at around the tetragonal/orthorhombic morphotropic phase boundary. It is believed that the origin for the high piezoelectric performance (Na,K)NbO₃-based lead-free piezoelectric ceramics is the same as that for the lead zinc niobate-lead titanate solid solution.     

SYNTHESIS AND CHARACTERIZATION OF SB-SUBSTITUTED (K0.5Na0.5)NbO3 PIEZOELECTRIC CERAMICS

ABSTRACT

Lead-free piezoelectric ceramics (K_0.5Na_0.5)(Nb_1-xSb_x)O₃+0.5 mol.%MnO₂, where x = 0 ÷ 0.10, with single phase structure and rhombohedral symmetry at room temperature were prepared by conventional ceramic technology. The optimal sintering temperatures of compositions were within 1100°–1140°C. MnO₂ functions as a sintering aid and effectively improves the densification. The samples reached density from 4.26 g/cm³ for undoped (K_0.5Na_0.5)NbO₃ to 4.40 g/cm³ for Mn/Sb⁵⁺ co-doped ceramics. The co-effects of MnO₂ doping and Sb⁵⁺ substitution lead to significant improvement in dielectric and piezoelectric properties: ε at the T_c increased from 6000 (KNN) to 12400 (x = 0.04), d₃₃ = 92 ÷ 192 pC/N, k_p = 0.32 ÷ 0.46, k_t = 0.34 ÷ 0.48.     

Raman and infrared spectroscopy of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> - BaTiO<Subscript>3</Subscript> ceramics

Lead-free Na_0.5Bi_0.5TiO₃ -BaTiO₃ ceramics have been prepared in the whole range of concentrations and studied at room-temperature by means of X-ray, Raman scattering and infrared techniques. X-ray measurements revealed rhombohedral, rhombohedral-tetragonal boundaries and tetragonal modifacations depending on the contents of BaTiO₃. The distinct changes of the Raman and infrared spectra with increasing of BaTiO₃ content, which were correlated with X-ray results, were observed. The broad phonon spectra indicated the disorder in the A site of Na_0.5Bi_0.5TiO₃ -BaTiO₃ system.     

Effect of BiAlO3 concentration on the dielectric and piezoelectric properties of lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 piezoelectric ceramics

In this paper, lead-free (1-x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-xBiAlO₃ (BNBT-BA, x?=?0, 0.010, 0.015, 0.020, 0.025, and 0.030) piezoelectric ceramics were synthesized using a conventional solid-state reaction method. The effect of BiAlO₃ concentration on dielectric, ferroelectric and piezoelectric properties were investigated. The ferroelectric and piezoelectric properties of BNBT ceramics are significantly influenced by the presence of BA. In the composition range studied, X-ray diffraction revealed a perovskite phase with the coexistence of rhombohedral and tetragonal phases. The temperature dependence of dielectric properties showed that the depolarization temperature (T _d) shifted towards lower temperatures and that the degree of diffuseness of the phase transition around T _d and T _m became more obvious with increasing BiAlO₃ content. The remanent polarization increased with increasing BA, and reached a maximum value of 30 μC/cm² at x?=?0.020. As a result, at x?=?0.020, the piezoelectric constant (d ₃₃) and the electromechanical coupling factor (k _p) of the ceramics attained maximum values of 188 pC/N and 34.4 %, respectively. These results indicate that BNBT-BA ceramics is a promising candidate for lead-free piezoelectric materials.     

Mechanical and electrical properties of Bi<Subscript>1.5-x</Subscript>La<Subscript>x</Subscript>Zn<Subscript>0.92</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>6.92</Subscript> pyrochlore ceramics

BiFeO₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (BF-PMN-PT) ternary ceramics with pure perovskite phase were prepared through a two-step solid reaction method. Based on structural analysis, the ternary phase diagram of BF-PMN-PT solid solution at room temperature has been established. The Curie temperature T_C, remnant polarization P_r and piezoelectric constant d₃₃ vary in the range of 138 to 225 °C, 15.12 to 23.65 μC/cm² and 129 to 276 pC/N, respectively. The coercive field Ec increases gradually from 5.77 to 29.56 kV/cm upon PT content increasing. The magnetic study suggests that the magnetism turns from diamagnetism for PMN-PT to paramagnetism for BF-PMN-PT by adding BiFeO₃ into PMN-PT and adding more content of BF does not change the paramagnetism further.     

Improvement of Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Co<Subscript>2</Subscript>O<Subscript>y</Subscript> thermoelectric performances by Na doping

Bi₂Sr_2-xNa_xCo₂O_y thermoelectric materials with x = 0, 0.025, 0.05, 0.075, 0.10, 0.125, and 0.15 have been prepared by the classical solid state reaction. Microstructure has shown an important grain growth when Na is added, leading to very high bulk densities confirmed through density measurements. These modifications have produced a drastic decrease of electrical resistivity without significant modification of Seebeck coefficient. As a consequence, Power Factor has been increased in all Na-doped samples, reaching the maximum value (0.21 mW/K².m at 650 °C) for 0.075 Na samples, which is fairly close to the reported for single crystals.