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.

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.

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...

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）.

Influence of Sb_2O_3 doping on the properties of KBT-NBT-BT lead-free piezoelectric ceramics

0.144（K0.5Bi0.5）TiO3-0.85（Na0.5Bi0.5）TiO3-0.006BaTiO3（KBT-NBT-BT） lead-free piezoelectric ceramics were prepared using a conventional solid state method.The influence of Sb2O3 doping on the crystal phase,surface microstructure and properties of the KBT-NBT-BT lead-free piezoelectric ceramics were investigated using X-ray diffraction（XRD）,scanning electron microscope（SEM） and other analytical methods.The results show that all compositions are of pure perovskite structure solid states.Sb2O3 doping does not influence the microstructure of KBT-NBT-BT lead-free piezoelectric ceramics obviously in the Sb2O3 doping range of 0.1-0.5 wt.%.Sb2O3 functions as a donor when doped small amount,while functions as a acceptor when doped large amount.The piezoelectric strain constant（d33） increases first and then decreases;the dielectric constant（ε33^T/ε0） and the dielectric loss（tanδ） decrease continuously when the amount of Sb2O3 dopant increases.When the doping amount of Sb2O3 is 0.1 wt.%,the KBT-NBT-BT piezoelectric ceramics with good comprehensive properties are obtained,whose d33,ε33^T/ε0 and tanδ are 147 pC/N,1510 and 4.2%,respectively.

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.

Microstructure,crystalline phase and electrical properties of Li_(0.06)(Na_(0.5)K_(0.5))_(0.94)Nb_(1-2x/5)Mg_xO_3 lead-free piezoelectric ceramics

MgO-modified Li0.06（Na0.5K0.5）0.94NbO3O3 （L6NKN） lead-free piezoelectric ceramics were synthesized by normal sintering at a rela- tively low temperature of 1000℃. The crystalline phase, microstructure, and electrical properties of the ceramics were investigated with a special emphasis on the influence of MgO content. The addition of MgO effectively improves the sintembility of the L6NKN ceramics. X-my diffr cfion analysis indicates that the morphotropic phase boundary （MPB） separating orthorhombic and tetragonal phases for the ceramics lies in the range of Mg doping content （x） from 0.3at% to 0.7at%. High electrical properties of the piezoelectric constant （d33=238 pC/N）, planar electromechanical coupling coefficient （kp=41.5%）, relative dielectric constant （εr=905）, and remanent polarization （Pr=38.3 μC/cm2） are obtained from the specimen with x=0.5at%, which suggests that the Li0.06（Na0.5K0.5）0.94Nb（1-2x/5）MgxO3 （x=0.5at%） ceramic is a promising lead-free piezoelectric material.

Superflexible and Lead-Free Piezoelectric Nanogenerator as a Highly Sensitive Self-Powered Sensor for Human Motion Monitoring

For traditional piezoelectric sensors based on poled ceramics,a low curie tem-perature(T_(c))is a fatal flaw due to the depolarization phenomenon.However,in this study,we find the low T_(c) would be a benefit for flex-ible piezoelectric sensors because small alterations of force trig-ger large changes in polarization.BaTi_(0.88)Sn_(0.12)O_(3)(BTS)with high piezoelectric coefficient and low T_(c) close to human body temperature is taken as an example for materials of this kind.Continuous piezo-electric BTS films were deposited on the flexible glass fiber fabrics(GFF),self-powered sensors based on the ultra-thin,superflexible,and polarization-free BTS-GFF/PVDF composite piezoelectric films are used for human motion sensing.In the low force region(1-9 N),the sensors have the outstanding performance with voltage sensitivity of 1.23 V N^(−1) and current sensitivity of 41.0 nA N^(−1).The BTS-GFF/PVDF sensors can be used to detect the tiny forces of falling water drops,finger joint motion,tiny surface deformation,and fatigue driving with high sensitivity.This work provides a new paradigm for the preparation of superflexible,highly sensitive and wearable self-powered piezoelectric sensors,and this kind of sensors will have a broad application prospect in the fields of medical rehabilitation,human motion monitoring,and intelligent robot.

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.

Molten Salt Synthesis of (K_(0.47)Na_(0.47)Li_(0.06))NbO_3 Lead-Free Piezoelectric Ceramics

(K0.47Na0.47Li0.06)NbO3 (KNLN) lead-free ceramics were prepared by molten salt synthesis (MSS) method using k2CO3-Na2CO3 eutectic mixtures as the flux. The microstructure and piezoelectric properties when sintered at 980-1 030 ℃ were investigated. The calcined powders were examined by X-ray diffraction. The microstructure of the calcined powders and sintered bodies was observed using a scanning electron microscope (SEM).The piezoelectric constant d33 was measured using a quasi-static piezoelectric d33 meter. The planar coupling coefficient Kp was calculated by resonance-antiresonance method. The experimental data for each sample's performance indicators were the average values of 8 specimens. The relative densities of sintered specimens are above 97%, and the dielectric loss is below 0.03. It was found that (K0.47Na0.47Li0.06)NbO3 prepared by MSS is compact and lead-free. The piezoelectric constant d33 is 216 pC·N-1 and the planar electromechanical coupling factor Kp is 0.352.

Lead-Free Piezoelectric Ceramics as Candidates on the Development of Morphing Winglets in Aircrafts

In this paper we discussed the development of a morphing wingtip device or winglet for aircraft.The aim of this research is enhancing the aerodynamic of aircrafts,by optimizing the winglet shape,angle and torsion,to reduce wingtip vortices at each flight stage,reduce drag,fuel consumption and increase its endurance.The development of a working physical wingtip device with morphing functionality,is possible by using piezoelectric MFCs(Macro Fiber Composites)as actuators in wing structures.Due to their excellent properties like flexibility,light weight,tolerant to damage and long term stability MFC fit most of the requirements and specifications of morphing structures.Unfortunately,they are based on the toxic compound of PbZrxTi1-xO3(PZT).Lead-free materials can replace lead based compounds.Also,other aim of this inquiry is the development of piezoelectric lead-free compounds based on the solid solution Ba1-xCaxTi0.9Zr0.1O3(BCZT)with x=0.1,0.125,0.15.The reason for choosing these compositions is because BZCT compounds could reach a piezoelectricity coefficient d33~400 pC/N.This value is comparable with commercial PZT,therefore it is a great candidate to replace it.

STRUCTURE AND ELECTRICAL PROPERTIES OF CuO-DOPED (K_(0.5)Na_(0.5))Nb_(0.9)Ta_(0.1)O_3 LEAD-FREE PIEZOELECTRIC CERAMICS

CuO-doped(K0.5Na0.5)Nb0.9Ta0.1O3 lead-free piezoelectric ceramics have been prepared by conventional sintering technique and the effects of CuO on the phase structure and piezoelectric properties of the ceramics have been studied.The results show that a small amount of CuO can improve the densification of the ceramics,consequently,the electric properties are improved.Good piezoelectric and dielectric properties of d33=125 pC/N,Kp=0.38,εr=700,Qm= 248,and Tc=370°C were obtained for the K0.5Na0.5Nb0.9Ta 0.1O3 ceramics doped with 0.5mol% CuO sintered at 1000℃ for 2h.

Enhanced electric-field induced strain in Eu^(3+) doped 0.67BiFeO_(3)-0.33BaTiO_(3) lead-free piezoelectric ceramics

Lead-free ferroelectric ceramics,0.67Bi_(1-x)Eu_(x)FeO_(3)-0.33BaTiO_(3)(BF-BT-xEu,x=0-0.02),were prepared via a solid-state reaction,The effect of Eu^(3+) doping on the microstructure,dielectric properties,ferroelectric properties,and electric-field-induced strain was investigated.The X-ray diffraction(XRD) results indicate the presence of a mixed phase of tetragonal and rhombohedral at the morphotropic phase boundary(MPB).Doping with an appropriate amount of Eu^(3+) reduces the Fe^(3+) content and decreases the leakage current in the binary system.A converse piezoelectric coefficient(d_(33)*) of 392 pm/V is obtained at BF-BT-0.003Eu under an electric field of 60 kV/cm at room temperature,which has a Curie temperature(T_(C)) of 414℃,The unipolar strain and d_(33)* of BF-BT-0.003Eu ceramics increase to 0.438%and 730 pm/V at 125℃ The field-induced strain response of the BF-BT-0.003Eu ceramics is greater than that of 0.67BF-0.33BT,mainly due to its optimal grain size,reduction of leakage current,and coexistence of ferroelectric-relaxation phases,BF-BT-0.003Eu ceramic is a lead-free candidate for high-temperature actuator applications.

Flexible and self-powered blinking and eyeball movements sensing based on electrospun lead-free piezoelectric nanofibers

Potassium sodium niobate(KNN)-based nanofibers could combine piezoelectric properties with exceptional flexibility and biocompatibility,making them highly promising for flexible sensors in electronic skin and wearable applications.However,the suboptimal piezoelectric performance limits their sensitivity in detecting minute human body motions,such as blinking and eye movements.Herein,Li and Ta-doped KNN nanofibers were fabricated via an electro-spinning process.Co-doping with 6%Li at the A-site and 30%Ta at the B-site induces lattice distortion and an orthorhombic(O)to tetragonal(T)phase transition in the electrospun nanofibers,resulting in a significantly enhanced piezoelectric response,with an average d_(33)*value reaching 110.7 pm/V.The outstanding piezoelectric response gives rise to a remarkable sensitivity(0.3365 V/(N cm^(2)))in a self-powered flexible pressure sensor based on the doped KNN nanofibers,encapsulated in a polydimethylsiloxane matrix.The sensors,when attached to the temple regions,can detect tiny facial motions induced by blinking,enabling the distinction of abnormal blinking patterns associated with mental fatigue and excessive eye use.Additionally,they support real-time,continuous,and unobtrusive eyeball tracking,highlighting their potential as critical components in human-computer interaction and artificial intelligence applications.

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.

PROGRESSES AND FURTHER CONSIDERATIONS ON THE RESEARCH OF PEROVSKITE LEAD-FREE PIEZOELECTRIC CERAMICS

The research on lead-free piezoelectric ceramics has been one of the importantfields worldwide for years for the sustainable development of the world.In recent years,the author and his group concentrated their work on perovskite lead-free piezoelectric ceramics,especially on(Bi_(1/2)Na_(1/2))TiO_(3)(BNT)-and K_(1/2)Na_(1/2)NbO_(3)(KNN)-based ceramics.In this paper,the researches of the composition design on BNT-and KNN-based lead-free piezoelectric ceramics,the effects of doping on the properties of these ceramics,the study of the temperature stability of these ceramics,and the fabrication technique used in the author's group for these ceramics are reviewed,and the further considerations and some prospects to be resolved in coming years from the viewpoint of the device applications of these ceramics are suggested.

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.