BaTiO_3-(Bi_(1/2)Na_(1/2))TiO_3无铅正温度系数电阻陶瓷势垒高度的计算

采用还原再氧化的烧结工艺制备了0.2 mol%Y_2O_3施主掺杂的95 mol%BaTiO_3-5 mol%(Bi_(1/2)Na_(1/2))TiO_3无铅正温度系数电阻(Positive temperature coefficient of resistivity,PTCR)陶瓷。研究发现,还原气氛下烧结的样品没有明显的PTCR效应,需要进一步在空气中氧化处理。其中1200℃氧化2 h的样品PTCR性能最好,电阻突跳大于3个数量级。利用交流阻抗分析方法计算了材料的晶粒、晶界电阻,发现氧化后的陶瓷晶界电阻迅速增加,而晶粒电阻基本保持不变。最后根据Heywang-Jonker理论,计算了陶瓷晶界势垒高度、势垒宽度和受主浓度。

Enhanced energy storage properties and good stability of novel(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xCa(Mg_(1/3)Nb_(2/3))O_(3) relaxor ferroelectric ceramics prepared by chemical modification

The increase in energy consumption and its collateral damage on the environment has encouraged the development of environment-friendly ceramic materials with good energy storage properties.In this work,(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xCa(Mg_(1/3)Nb_(2/3))O_(3) ceramics were synthesized by the solid-state reaction method.The 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramic exhibited a high recoverable energy storage density of 8.1 J/cm3 and energy storage efficiency of 82.4% at 550 kV/cm.The introduction of Ca(Mg_(1/3)Nb_(2/3))O_(3) reduced the grain size and increased the band gap,thereby enhancing the breakdown field strength of the ceramic materials.The method also resulted in good temperature stability(20–140℃),frequency stability(1–200 Hz),and fatigue stability over 10^(6) cycles.In addition,an ultrahigh power density of 187 MW/cm^(3) and a fast charge-discharge rate(t_(0.9)=57.2 ns)can be obtained simultaneously.Finite element method analysis revealed that the decrease of grain size was beneficial to the increase of breakdown field strength.Therefore,the 0.88Na_(0.5)Bi_(0.5)TiO_(3)-0.12Ca(Mg_(1/3)Nb_(2/3))O_(3) ceramics resulted in high energy storage properties with good stability and were promising environment-friendly materials for advanced pulsed power systems applications.

Structural and microstructural description of relaxor-ferroelectric transition in quenched Na_(1/2)Bi_(1/2)TiO_(3)-BaTiO_(3)

Quenching lead-free Na_(1/2)Bi_(1/2)TiO_(3)-based ceramics from sintering temperature is established to increasethe depolarization temperature,Td and the lattice distortion.In situ synchrotron X-ray diffractionmeasurements were carried out on furnace cooled and quenched Na_(1/2)Bi_(1/2)TiO_(3)-BaTiO_(3)(NBT-BT)with 6and 9 mol.%BT to discern the field-induced ferroelectric order.Phase fractions were determined fromfull pattern Rietveld refinements and utilized together with the change in unit cell volume to calculatevolumetric strain resulting from phase transformations.NBT-6BT demonstrates a cubic symmetry in thefurnace cooled state but quenching stabilizes the rhombohedral R3c phase and delays the formation of afield-induced,long range-ordered tetragonal phase,thereby shifting the onset of macroscopic strain tohigher fields.A field-induced phase transition from a weakly distorted rhombohedral to tetragonal phasecan be observed in furnace cooled NBT-9BT.However,this phase transition cannot be detected inquenched NBT-9BT,since the ferroelectric tetragonal P4mm phase is stabilized in the initial state.Incontrast to the furnace cooled materials,both the quenched compositions exhibit overall negligiblevolumetric strain as a function of electric field.Furthermore,scanning electron micrographs of chemi-cally etched,poled and unpoled samples reveal an increased lamellar domain contrast in the quenchedmaterials.All these findings strengthen the hypothesis of a stabilized ferroelectric order resulting in theabsence of a field-induced phase transformation in quenched NBT-BT.

Super-stable permittivity and low dielectric loss of(1-x)Na_(0.5)Bi_(0.5+y)TiO_(3-x)NaTaO_(3)ceramics within an ultra-wide temperature range

This work designs a new system(1-x)Na_(0.5)Bi_(0.5+y)TiO_(3-x)NaTaO_(3)with a nonstoichiometric bismuth ratio,which is used as dielectrics of ceramics capacitors.Phase structure evolution of(1-x)Na_(0.5)Bi_(0.5+y)TiO_(3-x)NaTaO_(3)is characterized using XRD,Raman and TEM.Dielectric and resistant properties of(1-x)Na_(0.5)Bi_(0.5+y)TiO_(3-x)NaTaO_(3)are investigated with increasing concentration of NaTaO_(3).With these in-vestigations,the structure and defect chemistry of(1-x)Na_(0.5)Bi_(0.5+y)TiO_(3-x)NaTaO_(3)are rationalized and their respective impact on capacitor properties are elucidated.The optimized composition 0.8Na_(0.5)Bi_(0.51)TiO_(3)-0.2NaTaO_(3)possesses an ultra-wide operating temperature range(-92e398C),in which both stable permittivity and low dielectric loss is obtained.Furthermore,the fabrication of multilayer ceramics capacitors(MLCC)based on 0.8Na_(0.5)Bi_(0.51)TiO_(3)-0.2NaTaO_(3)dielectrics is investigated.With the addition of sintering aids,0.8Na_(0.5)Bi_(0.51)TiO_(3)-0.2NaTaO_(3)could be co-fired with Ag at 910℃in air,and the low temperature co-fired ceramic(LTCC)capacitors maintain good temperature stability of permittivity and low dielectric loss in-100-352℃.Therefore,our work provides a new route for pre-paring ultra-wide operating temperature capacitors at low manufacturing costs.

Low-temperature sintered(Na_(1/2)Bi_(1/2))TiO_(3)-based incipient piezoceramics for co-fired multilayer actuator application

Low-temperature sintered(Na_(1/2)Bi_(1/2))_(0.935)Ba_(0.065)Ti_(0.975)(Fe_(1/2)Nb_(1/2))_(0.025)O_(3)(NBT-BT-0.025FN)lead-free incipient piezoceramics were investigated using high-purity Li_(2)CO_(3) as sintering aids.With the ≤0.5 wt%Li_(2)CO_(3) addition,the introduced Li^(+) cations precede to enter the A-sites of the perovskite lattice to compensate for the A-site deficiencies.Once the addition exceeds 0.5 wt%,the excess Lit cations will occupy B-sites and give rise to the generation of oxygen vacancies,which accelerate the mass transport and thus lower the sintering temperature effectively from 1100℃ down to 925℃.It was also found that a small amount of Lit addition has little effect on the phase structure and electromechanical properties of the system,but overweight seriously disturbs these characteristics because of the large lattice distortion.The sintered NBT-BT-0.025FN incipient piezoceramics with 1.25 wt%Li_(2)CO_(3) addition at 925℃ provides a large strain of 0.33% and a corresponding large signal piezoelectric coefficient d_(33)^(*) of 550 pm/V at 60 kV/cm,indicating this system is a very promising candidate for lead-free co-fired multilayer actuator application.

Growth of single crystals in the (Na_(1/2)Bi_(1/2))TiO_(3)-(Sr_(1-x)Ca_(x))TiO_(3) system by solid state crystal growth

Ceramics based on(Na_(1/2)B_(1/2))TiO_(3) are promising candidates for actuator applications because of large strains generated by an electric field-induced phase transition.For example,the(1-x)(Na_(1/2)Bi_(1/2))TiO_(3)-xSrTiO_(3) system exhibits a morphotropic phase boundary at x=0.2-0.3,leading to high values of inverse piezoelectric constant d_(33),which can be further improved by the use of single crystals.In our previous work,single crystals of (Na_(1/2)B_(1/2))TiO_(3)-SrTiO_(3) and (Na_(1/2)Bi_(1/2))TiO_(3)-TiO_(3) were grown by the solid state crystal growth technique.Growth in the(Nai/2Bi/2)TiO3-SrTiO3 system was sluggish whereas the (Na_(1/2)B_(1/2))TiO_(3)-CaTiO_(3) single crystals grew well.In the present work,0.8(Na_(1/2)Bi_(1/2))Ti0_(3)-0.2(Sr_(1-x)Ca_(x))Ti0_(3) single crystals(with x=0.0,0.1,0.2,0.3,0.4)were produced by the solid state crystal growth technique in an attempt to improve crystal growth rate.The dependence of mean matrix grain size,single crystal growth distance,and electrical properties on the Ca concentration was investigated in detail.These investigations indicated that at x=0.3 the matrix grain growth was suppressed and the driving force for single crystal growth was enhanced.Replacing Sr with Ca increased the shoulder temperature T_(s) and temperature of maximum relative permittivity T_(max),causing a decrease in inverse piezoelectric properties and a change from normal to incipient ferroelectric behavior.

Role of matrix phase and electric field gradient in Na_(1/2)Bi_(1/2)TiO_(3)eBaTiO_(3) :ZnO composites

Na_(1/2)Bi_(1/2)TiO_(3)-based materials exhibit potential for applications in high-power ultrasonics.The com-posites of Na_(1/2)Bi_(1/2) TiO_(3)-yBaTiO_(3)(NBTyBT;y denotes mole%)with ZnO inclusions were demonstrated to stabilize a ferroelectric equilibrium that led to enhanced thermal depolarization temperature(T_(d))and increased mechanical quality factor(Q_(m)).This work addresses the influence of the matrix NBTyBT phase by investigating two limiting choices based on symmetry(tetragonal/rhombohedral)and polar(relaxor/ferroelectric)nature.While the composites constituting the tetragonal NBT9BT(non-ergodic relaxor at room temperature)matrix phase exhibit improved T d,the critical temperatures in the composites with rhombohedral NBT3BT(displaying spontaneous ferroelectric order at room temperature)exhibit only marginal changes.Further,NBT3BT composites feature a 45%increase in Q m,while the corresponding increase is roughly three-fold for the NBT9BT composites.A 3-D Finite Element Method is used to simulate the electric field gradient at the matrix/inclusion interface,with the effective field distribution estimated to be higher than the applied field for highly conducting ZnO inclusions.The electrical properties indicate that,while the deviatoric stress at the matrix/inclusion interface stabilizes the ferroelectric equilibrium for the relaxor matrix phase,the stresses disrupt the long-range order for the ferroelectric matrix phase.These results establish the volume-limit of the second phase to stabilize a ferroelectric equilibrium,in addition to substantiating the role of residual stress evidenced by changes in the polar nature.Finally,a comparison of the composites with different NBTyBT phases is presented,with NBT6BT:ZnO composites demonstrating an optimal increase in both T_(d) and Q_(m).

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.