Na0.5K0.5NbO3-BiFeO3 lead-free piezoelectric ceramics

Lead-free (Na_0.5K_0.5)NbO₃-based piezoelectric ceramics were successfully fabricated by substituting with a small amount of BiFeO₃ (BF). Difficulty in sintering of pure NKN ceramics can be eased by adding a few molar percent of BF, and the crystalline structure is also changed, leading to a morphotropic phase boundary (MPB) between ferroelectric orthorhombic and rhombohedral phases. The MPB exists near the 1-2 mol% BF-substituted NKN compositions, exhibiting enhanced ferroelectric, piezoelectric, and electromechanical properties of P_r=23.3 μC/cm², d₃₃=185 pC/N, and k_p=46%, compared to an ordinarily sintered pure NKN ceramics. The MPB composition has a Curie temperature of ∼370 °C, comparable to that of some commercial PZT materials.     

Crystalline structural phase boundaries in (K,Na,Li)NbO 3 ceramics

Lead-free (K_xNa_1−x)_1−yLi_yNbO₃ ceramics (with x=0.50, y=0–0.08 and x=0.30–0.70, y=0.06, respectively) were synthesized using the conventional solid-state reaction technique. Compositional influences of K, Na and Li constituents on microstructures, crystalline structures, dielectric and piezoelectric properties were investigated. It has been known that microstructures change largely with the alkali constituents and that there exist three orthorhombic-tetragonal phase boundaries at room temperature. One occurs in (K_0.50Na_0.50)_1−yLi_yNbO₃ ceramics at y=0.05–0.06, which corresponds to the previously reported morphotropic phase boundary (MPB). The other two appear in (K_xNa_1−x)_0.94Li_0.06NbO₃ ceramics near x=0.40 and x=0.60, respectively. (K_0.50Na_0.50)_0.935Li_0.065NbO₃ and (K_0.45Na_0.55)_0.94Li_0.06NbO₃ ceramics show high piezoelectric properties with the d₃₃ values over 200 pC/N and the k_p values around 45% at room temperature. It is thought that the observed high piezoelectric properties are largely affected by the temperature-driven orthorhombic-tetragonal phase transition.     

Relationship between phase structure and electrical properties of (K0.5Na0.5)NbO3-LiTaO3 lead-free ceramics

Lead-free piezoelectric ceramics of (1−x)K_0.5Na_0.5NbO₃-xLiTaO₃ (KNN-LT) system have been investigated in this work. X-ray diffraction, Raman spectra measurements, DSC (Differential Scanning Calorimetric), and dielectric constant versus temperature provide direct evidence that the phase transition temperature between tetragonal and orthorhombic shift to lower temperature with the increasing of LT content. The KNN-0.05LT ceramics exhibit the highest high-field d₃₃ up to 220 pm/V. At the same time, we also investigated the relationship between phase structure and electric properties, showing that the orthorhombic phase presents better piezoelectric temperature stabilities than the tetragonal phase. The result may provide a new way for KNN-based lead-free ceramics.     

Microstructure and piezoelectric properties of Bi0.5(Na0.82K0.18)0.5TiO3−NaSbO3 ceramics

Lead-free piezoelectric ceramics (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ have been prepared by a conventional ceramics technique, and their microstructure and electrical properties have been investigated. The addition of NaSbO₃ has no remarkable effect on the crystal structure within the studied doping content; however, an obvious change in microstructure took place. With increase in NaSbO₃ content, the temperature from a ferroelectric to antiferroelectric phase transition increases, and the temperature for a transition from antiferroelectric phases to paraelectric phases changes insignificantly. Simultaneously, the temperature range between the rhombohedral phase transition point and the Curie temperature point becomes smaller. The piezoelectric properties significantly increase with increase in NaSbO₃ content and the piezoelectric constant and electromechanical coupling factor attain maximum values of d₃₃=160 pC/N and k_p=0.333 at x=0.01. The results indicate that (1−x)Bi_0.5(Na_0.82K_0.18)_0.5TiO₃−xNaSbO₃ ceramic is a promising lead-free piezoelectric candidate material.     

Phase transformation behavior and dielectric characteristics of BaTi1−x(Al1/2Nb1/2)xO3 (0.01≤x≤0.40) ceramics

Microstructure, phase transformation behavior and dielectric properties of BaTi_1−x(Al_1/2Nb_1/2)_xO₃ (0.01≤x≤0.40) ceramics were investigated. A high level of (Al_1/2Nb_1/2)⁴⁺ substitution for Ti⁴⁺ ions was not conducive to the stability of the perovskite structure and resulted in the formation of BaAl₂O₄. As x was increased, lattice constants and unit cell volume decreased, reached a minimum at x=0.10 and then increased. The BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics at room temperature experienced a transformation from ferroelectric to paraelectric phase with increasing (Al_1/2Nb_1/2)⁴⁺ concentration. Meanwhile, permittivity of the BaTi_1−x(Al_1/2Nb_1/2)_xO₃ ceramics was markedly reduced, while Q value was slightly increased. Frequency dispersion of dielectric peak was obviously increased as x was increased from 0.01 to 0.10. It is of great interest that a dielectric abnormity represented by a broad dielectric peak at 200-400 K was observed for the composition with x=0.40.     

Effects of uniaxial stress on dielectric properties of lithium modified potassium sodium niobate ceramics

In this work, the solid solution of ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics with x=0.03, 0.04, 0.05, 0.06 and 0.07 was prepared by a conventional mixed-oxide and solid-state sintering method. The structural phase formation and microstructure were characterized by X-ray diffraction technique and scanning electron microscopy. The ceramics were identified by XRD as a single-phase perovskite structure with symmetry gradually changing from orthorhombic to tetragonal. The grain size and the optimum density of the sintered ceramics were noticeably compositional-dependent. The dielectric properties of the ((K_0.5Na_0.5)_1−xLi_x)NbO₃ ceramics under the uniaxial compressive stress were observed at stress up to 180 MPa. The results showed that the dielectric constant and the dielectric loss tangent increased with applied stress. The change in the dielectric properties with stress was seen to depend on the composition and grain size. The observations were interpreted in terms of the intrinsic and extrinsic contributions to the changes in dielectric properties upon the applied compressive stress.     

Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Evolution from relaxor-like dielectric to ferroelectric in Ba[(Fe0.5Nb0.5)1−xTix]O3 solid solutions

Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ (x=0.2,0.4,0.6,0.8,0.85,0.9 and 0.95) solid solutions were synthesized by a standard solid-state reaction technique. X-ray diffraction at room temperature and dielectric characteristics over a broad temperature and frequency range were evaluated systematically. The structure of Ba[(Fe_0.5Nb_0.5)_1−xTi_x]O₃ solid solutions changed from cubic to tetragonal with increasing x. A Debye-like dielectric relaxation following the Arrhenius law similar to that in Ba(Fe_0.5Nb_0.5)O₃ was observed at lower temperature in the composition range 0.2≤x≤0.8, while the relaxor ferroelectric, diffused ferroelectric and normal ferroelectric behavior were observed for x=0.85,0.9 and 0.95, respectively. The process of the evolution of relaxor-like dielectric to ferroelectric suggested the changing from dilute polar micro-domains to polar micro-domains, polar micro/macro-domains and then polar macro-domains in the present ceramics.     

In situ neutron diffraction study (300-1273 K) of non-stoichiometric strontium ferrite SrFeOx

The high-temperature cubic phase of non-stoichiometric strontium ferrite SrFeO_x (2.5≤x≤3.0) has been studied by in situ neutron powder diffraction in air over the temperature range 300-1273 K. The composition of SrFeO_x changes within the range 2.56≤x≤2.81 from 1273 to 673 K, respectively.Rietveld refinements of the diffraction patterns show that the high-temperature cubic phase of SrFeO_x is consistent with a face-centred Fm3c structure. This structure leads to agreement with previous density measurements. This cell allows the high-temperature structure of SrFeO_x to be described in terms of a solid solution of the composition end members. Cubic SrFeO_x at high temperature is found to closely obey Vegard's law. The density of cubic SrFeO_x is also found to exhibit a linear relationship with composition.     

Ferroelectric-relaxor behavior of (Na0.5K0.5)NbO3-based ceramics

We report that ferroelectric-relaxor behavior is induced by doping of SrO and TiO₂, or BaO and TiO₂ into classic ferroelectric (Na_0.5K_0.5)NbO₃. It is found that [(Na_0.5K_0.5)_0.9Sr_0.1](Nb_0.9Ti_0.1)O₃ ceramics exhibit a pronounced ferroelectric-relaxor behavior, comparable to that of [(Na_0.5K_0.5)_0.9Ba_0.1](Nb_0.9Ti_0.1)O₃ ceramics. Our results indicate that the relaxor behavior is closely related to the appearance of micropolar regions in these systems. The relaxor behavior should arise from the dynamic response of micropolar clusters. Raman spectra of [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics measured in the wavenumber range from 100 to 1200 cm⁻¹ confirm that the first order scattering is dominant in phonon bands should result from both short-range ordered region (micropolar regions) and disordered matrix. The frequency dependence of dielectric permittivity measurements show that the relaxor behavior of SrO and TiO₂, or BaO and TiO₂ doped (Na_0.5K_0.5)NbO₃ ceramics is not a Debye type in the radio frequency range.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Structural distortion and phase transition studies of Aurivillius type Sr1−xPbxBi2Nb2O9 ferroelectric ceramics

In this paper, effects of lead doping on the lattice response and phase transitions of Sr_1−xPb_xBi₂Nb₂O₉ (x=0.0-0.5 in steps of 0.1) ferroelectric ceramics are reported. It is observed that structure attains more tetragonality with doping of lead up to 40%. Increased orthorhombic distortion is observed for undoped SBN and 50 at.% lead substituted SBN. Phase transitions for all samples were studied using Curie temperature measurements and are explained in terms of lattice response of these ceramics. Sample with x=0.5 shows decreased tetragonal strain and Curie temperature. Relationship of polarization with lattice response is discussed.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

Properties of non-stoichiometric 0.935(K0.5+xNa0.5+x)NbO3-0.065LiSbO3 lead-free piezoelectric ceramics

0.935(K_0.5+xNa_0.5+x)NbO₃-0.065LiSbO₃ lead-free piezoelectric ceramics were prepared by normal sintering, and their piezoelectric and dielectric properties were investigated by varying the compensating amount x of alkaline elements (Na and K) addition. It was found that the crystal structure changed from tetragonal to orthorhombic with increasing x from −0.010 to 0.010. An MPB was tailored by optimizing the alkaline elements contents. Enhanced electrical and electromechanical responses of d₃₃=253 pC/N, k_p=0.47, k_t=0.45 and tanδ=0.027 were obtained in the ceramics with x=0.005. These excellent piezoelectric and electromechanical properties indicate that this system may be an attractive lead-free material for a wide range of electro-mechanical transducer applications.     

Impedance spectroscopy and piezoresponse force microscopy analysis of lead-free (1 − x) K0.5Na0.5NbO3 − xLiNbO3 ceramics

(1 ? x) K_0.5Na_0.5NbO₃ ? xLiNbO₃ (where x = 0.0, 5.0, 5.5, 6.0, and 6.5 wt.%) (KNLN) perovskite structured ferroelectric ceramics were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that single phase was formed for pure KNN while a small amount of second phase (K₆Li₄Nb₁₀O₃₀, ～3%) was present in LN doped KNN ceramics. Phase analysis indicated the change in the crystal structure from orthorhombic to tetragonal with increase in LN content. The electrical behavior of the ceramics was studied by impedance spectroscopy technique in the high temperature range. Impedance analysis was performed using an equivalent circuit model. The impedance response in pure KNN and KNLN ceramics could be deconvoluted into two contributions, associated with the bulk (grains) and the grain boundaries. Activation energies for conductivity were found to be strongly frequency dependent. The activation energy obtained from dielectric relaxation data was attributed to oxygen vacancies. From PFM we found that the composition with 6.5 wt.% LN displays stronger piezocontrast as compared to pure KNN implying an evidence of a pronounced piezoelectric coefficient.     

Structural characterization of dense reduced BaTiO3 and Ba0.95La0.05TiO3 nanoceramics showing colossal dielectric values

BaTiO_3−x and Ba_0.95La_0.05TiO_3−x nanoceramics showing colossal permittivity values have been characterized. While starting powders are of cubic symmetry, X-ray and Neutron Diffraction techniques and Raman Spectroscopy measurements show that the one-step processed ceramics obtained by Spark Plasma Sintering (SPS) contain cubic and tetragonal phases. Rather large oxygen deficiency determined in such ceramics by Electron Micro Probe analysis and Electron Energy Loss Spectroscopy analyzes is explained by the presence of Ti³⁺, as evidenced by X-ray Photoelectron Spectroscopy measurements. Transmission Electron Microscopy and High Resolution Transmission Electron Microscopy show that these ceramics contain 50-300 nm grains, which have single-domains, while grain boundaries are of nanometer scale. Colossal permittivity values measured in our dense nanoceramics are explained by a charge hopping mechanism and an interfacial polarization of a large number of polarons generated after sample reduction in SPS apparatus.     

Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

Electrical and electrochemical properties of molten salt-synthesized Li4Ti5−xSnxO12 (x=0.0, 0.05 and 0.1) as anodes for Li-ion batteries

Submicron-sized polyhedral Li₄Ti_5−xSn_xO₁₂ (x=0.0, 0.05, and 0.1) materials were successfully prepared by a single-step molten salt method. The structural, morphological, transport and electrochemical properties of the Li₄Ti_5−xSn_xO₁₂ were studied. X-ray diffraction patterns showed the formation of a cubic structure with a lattice constant of 8.31 Å, and the addition of dopants follows Vegard's law. Furthermore, FT-IR spectra revealed symmetric stretching vibrations of octahedral groups of MO₆ lattice in Li₄Ti₅O₁₂. The formation of polyhedral submicron Li₄Ti_5−xSn_xO₁₂ particles was inferred from FE-SEM images, and a particle size reduction was observed for Sn-doped Li₄Ti₅O₁₂. The chemical composition of Ti, O and Sn was verified by EDAX. The DC electrical conductivity was found to increase with increasing temperature, and a maximum conductivity of 8.96×10⁻⁶ S cm⁻¹ was observed at 200 °C for Li₄Ti₅O₁₂. The galvanostatic charge–discharge behavior indicates that the Sn-doped Li₄Ti₅O₁₂ could be used as an anode for Li-ion batteries due to its enhanced electrochemical properties.