Research of Lead-free Na_(0.5)Bi_(0.5)TiO_(3)-BaTiO_(3)System Piezoelectric Ceramics

To reduce the coercive field of Na_(0.5)Bi_(0.5)TiO_(3),Ba TiO_(3)were added as dopant materials.Then the(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xBaTiO_(3)ceramic samples were produced in solid synthetic way.The optimum preparation condition and piezoelectric properties of the samples were investigated.The XRD results show that the fabric transites from rhombohedral to tetragonal gradually with the substitution of the Ba^(2+).The morphotropic phase boundaries(MPB)exists in the composition range of 0.06.

Effect of Li content on the microstructure and properties of lead-free piezoelectric(K_(0.5)Na_(0.5))_(1-x)Li_xNbO_3 ceramics prepared by SPS

Lead-free piezoelectric （K0.5sNa0.5）1-xLixNbO3 （x = 0at%-20at%） ceramics were synthesized by spark plasma sintering （SPS） at low temperature and the effects of LiNbO3 addition on its crystal structure and properties were also studied. When the Li content was less than 6at%, a single proveskite phase with the similar structure of （K0.5Na0.5）NbO3 was formed; and a secondary phase with K3Li2Nb5O15 structure was observed in the 6at% 〈 x 〈 20at% compositional range. Furthermore, LiNbO3 existed as the third phase when the Li content was higher than 8at%. The grain sizes increased from 200-500 nm to 5-8 μm when the K3Li2Nb5O15 and LiNbO3 like phases were formed. With increasing Li content, the relative density of the ceramics first decreased from 97% to 93% and then kept constant. The piezoelectric coefficient d33, dielectric constant, and planner electromechanical coupling factor exhibited a decreasing tendency with increasing Li content because of the decrease in density and the formation of the secondary phase such as K3Li2Nb5O15 and LiNbO3. The formation of dense microstructure with a single phase is necessary in improving the properties of the （K0.5Na0.5）1-xLixNbO3 ceramics.

Preparation and Piezoelectric Properties of CuO-added(Ag_(0.75)Li_(0.1)Na_(0.1)K_(0.05_)NbO_3 Lead-free Ceramics

CuO-doped（Ag0.75Li0.1Na0.1K0.05）NbO3（ALNKN-xCuO, x = 0.2mol%） lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2NbrO16- type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with＇the grain size of about 1 ~tm was formed for the ceramics with 0.5mo1% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = lm01% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.

Microstructure and electrical properties of Ti-modified (Na_(0.5)K_(0.5))(Ti_xNb_(1-x))O_3 lead-free piezoelectric ceramics

Ti-Modified (Na0.5K0.5)(TixNb1-x)O3 (NKNT) piezoelectric ceramics were fabricated by double-layer buried powder process at 1020°C for 2 h. The microstructures,and piezoelectric and dielectric properties of the lead-free NKNT ceramics were investigated. X-ray diffraction re-sults indicated that Ti4+ had diffused into the (Na0.5K0.5)NbO3 lattices to form a solid solution with a perovskite structure. The introducing of Ti into the (Na0.5K0.5)NbO3 solid solution effectively reduced the sintering temperature and...

Effect of doped Mn on piezoelectric properties of (Na_(0.5)Bi_(0.5))_ (0.92)Ba_(0.08)TiO_3 lead-free ceramics

Piezoelectric ceramics (Na0.5Bi0.5) （0.92）Ba0.08TiO3 +x%MnCO3（BNBT-Mn, x=0CD*21.6, mass fraction） were synthesized by conventional solid state reaction. The results show that when the addition of MnCO3 is 0CD*2 1.4%, BNBT-Mn ceramics exhibit a single-phase perovskite structure. With the increase of content of MnCO3, piezoelectric constant and electromechanical coupling factor increase rapidly when x is lower than 0.3. Then they both decrease when x is in the range of 0.3 and 1.6. When x=0.3, piezoelectric constant and electromechanical coupling factor reach the maximum value of 160pC/N and 58.5% respectively, which can improve the temperature stability of BNBT-Mn.

Effects of Na/K ratio on the phase structure and electrical properties of Na_xK_(1-x)NbO_3 lead-free piezoelectric ceramics

Lead-free piezoelectric NaxK1-xNbO3（x = 0.3-0.8）（NKN） ceramics were fabricated by normal sintering at 1060°C for 2 h.Microstructures and electrical properties of the ceramics were investigated with a special emphasis on the influence of Na content.The grain size of the produced dense ceramic was decreased by increasing Na content.A discontinuous change in the space distance was found at the composition close to Na0.7K0.3NbO3 ceramic, which indicates the presence of a transitional composition between two different orthorhombic phases, which is similar to the behavior of morphotropic phase boundary（MPB） in NaxK1-xNbO3 ceramics.Such MPB-like behavior contributes to the enhanced piezoelectric coefficient d33 of 122 pC/N, planar-mode electromechanical coupling coefficient kP of 28.6%, and dielectric constant εr of 703, respectively for the Na0.7K0.3NbO3 ceramic.Cubic temperature TC and the transitional temperature TO-T from orthorhombic to tetragonal phase are observed at around 420°C and 200°C, respectively.

Microstructures and Electrical Properties of Bi_(0.5)-(Na_(1-x-y)K_xLi_y)_(0.5)TiO_3 Lead-free Piezoelectric Ceramics

The microstructures and electrical properties of Bi0.5（Na1-x-yKxLiy）0.5TiO3 lead-free piezoelectric ceramics were studied.These ceramics were prepared by conventional ceramic technique.XRD analysis reveals that the ceramics possess almost pure perovskite phase when y≤0.2.The SEM results show that,with more amounts of Li＋,the crystalline grain growing speed is accelerated,and the sintering temperature can effectively be decreased.The measurements of piezoelectric properties indicate that the ceramics with relatively low amount of Li＋ and high amount of K＋ have comparatively large piezoelectricity.The dielectric measurements show that the ceramics have properties like relaxor ferroelectrics and diffuse phase transition（DPT） at Td and Tc,respectively.The results of ferroelectric measurements reveal the system has relatively higher remanent polarization Pr（27.6 μC/cm2） and lower coercive field Ec（37.5 kV/cm）.

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K_(0.5)Na_(0.5)NbO_3-0.04LiSbO_3 lead-free piezoelectric ceramics

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5＋xNa0.5＋xNbO3- 0.04LiSbO3 lead-free piezoelectric ceramics were examined for 0 ≤ x ≤0.02. The piezoelectric coefficients exhibited a maximum, d33 = 187 pC/N at x = 0.0075, coinciding with the maximum of the grain size and the apparent density at x = 0.0075. The apparent density and the piezoelectric coefficients decreased with increasing x at higher x which was likely due to the crystal geometrical distortion of 0.96K0.5＋xNa0.5＋xNbO3-0.04LiSbO3. In addition, super-large grains were found and this may be due to liquid phase sintering. Excess （K＋＋Na＋） attracted a sum of space charges to keep the charge neutral, resulting in charge leakage during the course of ceramic polarization, influencing the piezoelectric and ferroelectric properties. These findings are of importance for guiding the design of Ko.sNao.sNbO3-based lead-free ceramics with enhanced electrical properties.

Manufacture and Cytotoxicity of a Lead-free Piezoelectric Ceramic as a Bone Substitute—Consolidation of Porous Lithium Sodium Potassium Niobate by Cold Isostatic Pressing

Aim The piezoelectric properties and cytotoxicity of a porous lead-free piezoelectric ceramic for use as a direct bone substitute were investigated. Methodology Cold isostatic pressing （CIP） was applied to fabricate porous lithium sodium potassium niobate （Li0.06Na0.5K0.44） NbO3 specimens using a pore-forming method. The morphologies of the CIP-processed specimens were characterized and compared to those of specimens made by from conventional pressing procedures. The effects of the ceramic on the attachment and proliferation of osteoblasts isolated from the cranium of 1-day-old Sprague- Dawley rats were examined by a scanning electron microscopy （SEM） and metbylthiazol tetrazolium （MTT） assay. Results The results showed that CIP enhanced piezoelectricity and biological performance of the niobate specimen, and also promoted an extracellular matrix-like topography of it. In vitro studies showed that the CIP-enhanced material had positive effects on the attachment and proliferation of osteoblasts. Conclusion Niobate ceramic generated by CIP shows a promise for being a piezoelectric composite bone substitute.

Modified phase transition and electrical properties of [Li_(0.05)(Na_(0.535)K_(0.48))_(0.95)]- (Nb_(0.94)Sb_(0.06))O_3 lead-free piezoelectric ceramic by sintering temperature

Li/Sb-doped (Na,K)NbO3 with a nominal composition of [Li0.05(Na0.535K0.48)0.95](Nb0.94Sb0.06)O3 ceramic was synthesized by normal sintering. The phase structure, microstructure, and electrical properties were investigated with a special emphasis on the influence of the sintering temperature. A polymorphic phase transition (PPT) from orthorhombic to tetragonal symmetry was observed when the sintering temperature was raised from 1040 to 1050 ℃, whereby the piezoelectric coefficient d33 and the electromechanical coupling coefficient kp reached the peak values of 245 pC·N-1 and 41.2%, respectively. The PPT induced by varying the sintering temperature is due to the different volatilization extents of alkali metals and appears to a lower sintering temperature with increasing Li content. The trace modifying of alkali metal content is more effective than doping B site element to enhance the d33 value.

Influence of Composition on Properties of BNT-BT Lead-Free Piezoceramics

Lead-free piezoelectric ceramics of (Bi1/2Na1/2)TiO3-BaTiO3(BNT-BT) were prepared by the conventional piezoelectric ceramic preparation technique (free air atmosphere sintering). The influence of BaTiO3 additive amount and La2O3 additive amount on the properties of BNT-BT lead-free piezoceramics were investigated. The results show that the dielectric constant(ε) and piezoelectric strain constant(d33) of materials start increasing and then decreasing while BaTiO3 additive amount increasing, the e and d33 of materials have maximum value (ε= 1650, d33 = 120 PC·N -1 ) while x (BaTiO3) =0.06 mol. Theεand d33 of materials start increasing and then decreasing while La2O3 additive amount increasing, the e and d33 of materials have maximum value (ε= 1684, d33 = 153 PC·N-1) while w(La2O3) =0.3% . The influence of La2O3 additive amount on the microstructure of BNT-BT piezoelectric ceramics was analysed by SEM( scanning electron microscope). The influence mechanism of La2O3 additive amount on the properties of BNT-BT piezoelectric ceramics was discussed. The BNT-BT ceramics with optimum comprehensive properties were obtained.

Phase Structure, Microstructure and Electrical Properties of K_xNa_((1-x))NbO_3 Piezoelectric Ceramics with Different K/Na Ratio

The K_xNa_((1-x))NbO_3(x=0.45, 0.46, 0.47, 0.48, 0.49, 0.50) lead-free piezoelectric ceramics was fabricated by conventional solid-state sintering method. It was found that the ratio of alkaline metal would affect the microstructure, bulk density, and optimum sintering temperatures of ceramics. Meanwhile, the electrical properties were also influenced by modulating the K/Na ratio, exhibiting corresponding composition-dependent properties. The optimum electrical properties of K_xNa_((1-x))NbO_3 such as piezoelectric constant d_(33) = 115 pC/N, mechanical quality factor Q_m = 20, Curie temperature Tc = 365 ~oC, ε_(33)~T/ε_0= 588.1, dielectric loss tan δ = 0.024, bulk density(ρ) = 3.08 g/cm^3, remnant polarization(P_r) = 8.87 μC/cm^2 and coercive field(Ec) = 13.79 kV/cm were obtained at x = 0.46.

Effects of Excess Barium on the Structure and Electrical Properties of(Ba,Ca)TiO_3 Piezoelectric Ceramics with High Mechanical Quality Factors

Manganese-doped Ba（0.925）Ca（0.075）TiO3 lead-free piezoelectric ceramics（abbreviated as BCT）with high mechanical quality factor were synthesized by conventional solid-state reaction method.The effects of excess Ba on the crystal structure,microstructure,and electrical properties of the ceramics were systematically investigated.X-ray diffraction and Raman spectra revealed that Ca^2＋ions were pushed from Ba sites to Ti sites of BCT when 1.5 mol%extra Ba^2＋ions were added after sintering.The grain size of the ceramics was decreased by adding extra Ba^2＋ions.The mechanical quality factor and resistivity of the ceramics decreased dramatically when the excess Ba was more than 1.5 mol%.High piezoelectric coefficients（d（33）=150-190 pC/N）and high mechanical quality factors（Qm=1 000-1 200）were obtained in the ceramics when the excess of Ba was between 0.5 mol%and 1 mol%.These results indicated that the properties of BCT ceramics could be tailored by adjusting the content of Ba.

Exceptional electrostrain with minimal hysteresis and superior temperature stability under low electric field in KNN-based lead-free piezoceramics

Over the past two decades,(K_(0.5)Na_(0.5))NbO_(3)(KNN)-based lead-free piezoelectric ceramics have made significant progress.However,attaining a high electrostrain with remarkable temperature stability and minimal hysteresis under low electric fields has remained a significant challenge.To address this long-standing issue,we have employed a collaborative approach that combines defect engineering,phase engineering,and relaxation engineering.The LKNNS-6BZH ceramic,when sintered at T_(sint)=1170℃,demonstrates an impressive electrostrain with a d_(33) value of 0.276%and 1379 pm·V^(-1)under 20 kV·cm^(-1),which is comparable to or even surpasses that of other lead-free and Pb(Zr,Ti)O_(3)ceramics.Importantly,the electrostrain performance of this ceramic remains stable up to a temperature of 125℃,with the lowest hysteresis observed at 9.73%under 40 kV·cm^(-1).These excellent overall performances are attributed to the presence of defect dipoles involving V′_(A)-V∙∙_(O) and B′_(Nb)-V∙∙O,the coexistence of R-O-T multiphase,and the tuning of the trade-off between long-range ordering and local heterogeneity.This work provides a lead-free alternative for piezoelectric actuators and a paradigm for designing piezoelectric materials with outstanding comprehensive performance under low electric fields.

Influence of CeO_2 doping amount on property of BCTZ lead-free piezoelectric ceramics sintered at low temperature

Ba0.85Ca0.15Ti0.9Zr0.1O3 （BCTZ） lead-free piezoelectric ceramics co-doped with CeO2 （x=0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%） and Li2CO3 （0.6 wt.%） were prepared by conventional solid-state reaction method. Influence of CeO2 doping amount on the piezoelectric properties, dielectric properties, phase composition and microstructure of prepared BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were investigated by X-ray diffraction （XRD） and scanning electron microscopy （SEM） and other analytical methods. The results showed that the sintered temperature of BCTZ lead-free piezoelectric ceramics doped with CeO2 decreased greatly when Li2CO3 doping amount was 0.6 wt.%;a pure perovskite structure of BCTZ lead-free piezoelectric ceramics co-doped with Li2CO3 and CeO2 and sintered at 1050 ℃ could also be obtained. The piezoelectric constant （d33）, the relative permit-tivity （εr） and the planar electromechanical coupling factor （kp） of BCTZ ceramics doped with Li2CO3 increased firstly and then de-creased, the dielectric loss （tanδ） decreased firstly and then increased and decreased at last when CeO2 doping amount increased. The influence of CeO2 doping on the properties of BCTZ lead-free piezoelectric ceramics doped with Li2CO3 were caused by“soft effect”and “hard effect”piezoelectric additive and causing lattice distortion. When CeO2 doping amount （x） was 0.2 wt.%, the BCTZ ceramics doped with Li2CO3 （0.6 wt.%） and sintered at 1050 ℃ possessed the best piezoelectric property and dielectric property with d33 of 436 pC/N, kp of 48.3%,εr of 3650, tanδof 1.5%.

Multi-phase structure and electrical properties of Bi_(0.5)Li_(0.5)ZrO_3 doping K_(0.48)Na_(0.56)NbO_3 lead-free piezoelectric ceramics

(1–x)K_(0.48)Na_(0.56)NbO_3–xBi_(0.5)Li_(0.5)ZrO_3(KNN–x BLZ, x = 0–0.06) lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method, and their phase structures and electric properties as well as T_C were systematically investigated. The orthorhombic–tetragonal(O–T) two phases were detected in all(1–x)K_(0.48)Na_(0.56)NbO_3–xBi_(0.5)Li_(0.5)ZrO_3 ceramics at 0.01 ≤ x ≤ 0.05. Due to the appropriate ratio between O phase and T phase(CO/C T= 45/55), high piezoelectric properties of d 33= 239 pC/N, k_p= 34%, and P_r = 25.23 μC/cm^2 were obtained at x = 0.04. Moreover, a high T_C = 348 ℃ was also achieved in KNN–x BLZ ceramic at x = 0.04. These results indicate that (1–x)K_(0.48)Na_(0.56)NbO_3–xBi_(0.5)Li_(0.5)ZrO_3 system is a promising candidate for high-temperature piezoelectric devices.

Synthesis and Electrical Properties of Li-modified Bi_(0.5)Na_(0.5)TiO_3-BaTiO_3 Lead-free Piezoelectric Ceramics

Lead-free piezoelectric ceramics （1-y）Bi0.5（Na1-xLix）0.5TiO3-yBaTiO3 with x=0-0.125 and y=0.02-0.12 were fabricated by a solid-state reaction process, and their dielectric, piezoelectric and ferroelectric properties were investigated. The results show that the addition of Li^＋ significantly improves the sintering performance and piezoelectric properties of the ceramics. X-ray diffraction （XRD） patterns indicate that the ceramics possess pure perovskite structure. At room temperature, the ceramics provide high piezoelectric charge constant d33 （up to 210 pC/N）, high planar electromechanical coupling factor kp （34.5%）, large remanent polarization Pr （up to 40 μC/cm^2）, and low coercive field Ec （3.0 kV/mm）, which indicates that （1-y）Bi0.5（Na1-xLix）0.5TiO3-yBaTi03 is a good lead-free piezoelectric ceramic.

Oxygen octahedron tilting,electrical properties and mechanical behaviors in alkali niobate-based lead-free piezoelectric ceramics

In this work,we present a new piezoelectric solid solution consisting of two typical alkali niobate-based materials,K_(0.5)Na_(0.5)NbO_(3)(KNN)and Li_(0.15)Na_(0.85)NbO_(3)(LNN).Although KNN and LNN have the same perovskite structure,they exhibit extremely different electrical properties and mechanical behaviors.The phase structures,electrical and mechanical evolutions of the new lead-free piezoelectric materials with different ratios of KNN and LNN are comprehensively and theoretically investigated.According to the Xray diffraction patterns and curves of permittivity versus temperature,a series of complicated phase transitions can be found with varied LNN content.Rietveld refinement results based on XRD patterns reveal an oxygen octahedron tilting in the LNN-rich crystal structure,and simultaneously the reasons for octahedron tilting are discussed.The distorted crystal structure is accompanied by extremely decreased electric properties but increased mechanical properties,which reveals electrical and mechanical properties of alkali niobate-based piezoelectric ceramics strongly depend on their inner structures,and the enhancement of intrinsic hardness results in the deterioration of piezoelectric properties.Our work exhibits the detailed evolutions of structure,electrical and mechanical properties from KNN to LNN,which provides experimental and theoretical basis for development of new alkali niobate-based piezoelectric materials.

A REVIEW ON LEAD-FREE PIEZOELECTRIC CERAMICS STUDIES IN CHINA

There are a large number of research publications on the hot topic of environmental friendly leadfree piezoelectric materials worldwide in the last decade.The number of researchers and institutions involved from China is much larger than other countries or regions.The publications by Chinese researchers cover a broad spectrum on the preparations,structures,properties and applications of lead-free piezoelectric ceramics.This has motivated us to come out with a review on recent advances in development of lead-free piezoelectric ceramics in China.The emphases are especially on the preparation and electric properties of barium titanate-based materials,bismuth sodium titanate and related materials,alkaline niobate and related materials,bismuth layerstructured materials,as well as texture engineering of ceramics and some of their single crystals.Hopefully,this could give further impetus to the researchers to continue their e®orts in this promising area and also draw the attentions from legislature,research o±ce,industrial and publics.

Large electro-strain signal of the BNT-BT-KNN lead-free piezoelectric ceramics with CuO doping

This paper investigates a system of 0.93Bi_(0.5)Na_(0.5)TiO_(3)–0.06BaTiO_(3)–0.01K_(0.5)Na_(0.5)NbO_(3)–xCuO(BNT–BT–KNN–xCuO,x=0-0:04 mol.%)ceramics,which were fabricated by the conventional solid-state process through the granulation of vacuum freeze drier.The results show that the CuO doping made a significant enhancement on the piezoelectric properties of the BNT–BT–KNN ceramics.With the doping of CuO,the transition temperature between ferroelectric phase and ergodic relaxor state is reduced to near room temperature,resulting in pinched P–E loops and“sprout”shape S-E curves.For the composition with x=0.01,a high unipolar strain of 0.39%under 5 kV/mm contributes a large d^(*)33~780 pm/V at room temperature,which is competitive with the other BNT-based ceramics.