Effects of Li Substitution and Sintering Temperature on Properties of Bi0.5（Na,K）0.5TiO3 Lead-Free Piezoelectric Ceramics

Bi0.5 （Na0.72K0.28- x Lix ）0.5 TiO3 （BNKLT- 100x） lead-free piezoelectric ceramics are synthesized by conventional solid state sintering techniques. The dielectric and piezoelectric properties of the BNKLT-100x ceramics as a function of Li content are systematically investigated. It is found that not only Li content but also the sintering temperature has a strong effect on the piezoelectric properties of BNKLT. The piezoelectric constant d33 Of BNKLT varies from 120 to 252pC/N in the Li content range from 0.03 to 0.16. In the sintering temperature range from 1080 to 1130℃, the d33 value of BNKLT-6 changes from 200pC/N to 252pC/N. The BNKLT-6 sample sintered at 1100℃ has the highest piezoelectric constant d33 of 252pC/N, with the electromechanical coupling factors kp of 0.32 and kt of 0.44.     

KNN Based Lead-Free Piezoceramics with Improved Thermal Stability

Lead-free piezoelectric ceramics （1 - x） （Na0.53K0.404 Li0.066）Nb0.92 Sb0.08 03 ＋xZrTiO3 are fabricated by conventional solid-state sintering method, and their dielectric and piezoelectric characteristics are investigated. With the addition of SrTiO3, the growth of the grain size is restrained, meanwhile the phase transition temperature of orthorhombic-tetragonal is shifted below room temperature. It is found that the ceramics with x = 0.010 exhibit excellent piezoelectric properties （d33 = 220 pC/N, kp = 41%, kt = 39%） and improved thermal stability around room temperature. The results indicate that these materials are promising lead-free piezoceramics for practical operations.     

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5Na0.5NbO3- 0.04LiSbO3 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 K0.5Na0.5NbO3-based lead-free ceramics with enhanced electrical properties.     

Piezoelectricity in K_(1-x)Na_xNbO_3: First-principles calculation

The piezoelectric properties of K1-xNaxNbO3 are studied by using first-principles calculations within virtual crystal approximation. To understand the critical factors for the high piezoelectric response in K1-x Na x Nb O3, the total energy,piezoelectric coefficient, elastic property, density of state, Born effective charge, and energy barrier on polarization rotation paths are systematically investigated. The morphotropic phase boundary in K1-x Na x Nb O3 is predicted to occur at x = 0.521, which is in good agreement with the available experimental data. At the morphotropic phase boundary, the longitudinal piezoelectric coefficient d33 of orthorhombic K0.5Na0.5NbO3 reaches a maximum value. The rotated maximum of d*33is found to be along the 50° direction away from the spontaneous polarization(close to the [001] direction). The moderate bulk and shear modulus are conducive to improving the piezoelectric response. By analyzing the energy barrier on polarization rotation paths, it is found that the polarization rotation of orthorhombic K0.5Na0.5NbO3 becomes easier compared with orthorhombic KNbO3, which proves that the high piezoelectric response is attributed to the flattening of the free energy at compositions close to the morphotropic phase boundary.     

Phase Transition and High Piezoactivity of Sb Doped （Na0.53K0.435Li0.035）Nb0.94Ta0.06 O3 Lead-Free Ceramics

Lead-free piezoelectric ceramics with the composition of （Na0.53K0.435Li0.035）Nb0.94Ta0.06 O3 （NKLNST） axe synthesized by a conventional solid-state sintering process. An MPB-like region between orthorhombic and pseudocubic phases is found in this system. The density, piezoelectric and dielectric properties axe enhanced greatly in this region. A composition （Na0.53K0.435Li0.035）（Nb0.94Ta0.06）O3 is found to have excellent electrical properties： d33 = 320pC/N, kp= 49% and kt =43%, as well as relatively low loss, tan δ=4.2%, and high relative density higher than 96%, which indicate that this ceramics is a promising lead-free piezoceramics replacing for lead zirconate titanate.     

Properties of Co-Doped 0.92（Na0.5Bi0.5） TiO3-0.08BaTiO3 Lead-Free Ceramics

Lead-free piezoelectric ceramics 0.92（Bi0.5Na0.5）TiO3-0.08BaTiO3 ＋ xmol% Co3＋ （BNBT-Co, x = 0-8） are prepared by the solid state reaction method. Effects of the amount of Co^3＋ on the electrical properties and phase transition are studied. The results indicate that the addition of Co^3＋ enhances the mechanical quality factor Q^3＋ significantly, whereas the dissipation factor tanδ has a minimum value at x = 3.5. Meanwhile, addition of Co^3＋ leads to small decreases of piezoelectric constant d33, and planar electromechanical coupling kp. The present 0.92（Bio.aNao.5） TiO3-0.08BaTiO3＋3.5 moi% Co^3＋ ceramics exhibit good performance with mechanical quality factor Qm = 910, piezoelectric constant d33 = 106pC/N, planar electromechanical coupling kp =10% and dissipation factor tanδ = 1.1% at 1 kHz. Saturated polarization hysteresis loops have been obtained for BNBT-Co ceramics. Two dielectric peaks at depolarization temperature Td and Tm appear in the curves of ε33^T vs temperature for the pure BNBT ceramics. However, the first dielectric peak Td disappears after the addition of Co^3＋, which means that the transition from ferroelectric to antiferroelectric phase has been eliminated.     

Relaxor Behaviour and Ferroelectric Properties of （Li0.12Na0.88） （Nb0.9-xWa0.10Sbx）O3 Lead-Free Ceramics

New lead-free ceramics （Lio.12Na0.88） （Nbo.9-x Ta0.10 Sbx） 03 （0.01 × 0.06） are synthesized by solid-state reaction method. The dielectric, piezoelectric and ferroelectric properties of the ceramics are studied. The dielectric constant dependence with temperature and frequency of the ceramic specimen with x = 0.04 shows typical characteristics of relaxor ferroelectrics, and the Vogel-Fulcher relationship is fulfilled. The dielectric behaviour and its relation to the phase transition phenomena are discussed. The polarization hysteresis loops at room temperature are also measured.     

Effects of （LiCe） co-substitution on the structural and electrical properties of CaBi2Nb209 ceramics

The piezoelectric,dielectric,and ferroelectric properties of the(LiCe) co-substituted calcium bismuth niobate(CaBi2Nb2O9,CBNO) are investigated.The piezoelectric properties of CBNO ceramics are significantly enhanced and the dielectric loss tan δ decreased.This makes poling using(LiCe) co-substitution easier.The ceramics(where represents A-site Ca2+ vacancies,possess a pure layered structure phase and no other phases can be found.The Ca0.88(LiCe)0.04 0.04Bi2Nb2O9 ceramics possess optimal piezoelectric properties,with piezoelectric coefficient(d 33) and Curie temperature(TC) found to be 13.3 pC/N and 960 C,respectively.The dielectric and piezoelectric properties of the(LiCe) co-substituted CBNO ceramics exhibit very stable temperature behaviours.This demonstrates that the CBNO ceramics are a promising candidate for ultrahigh temperature applications.     

（Na0.52K0.44Li0.04）Nb0.9-xSbxTa0.1O3 Lead-Free Piezoelectric Ceramics with High Performance and High Curie Temperature

（Na0.52K0.44Li0.04）Nb0.9-x Sbx Ta0.1O3 lead-free piezoelectric ceramics are prepared by a solid-state reaction method. With increasing Sb content, the transition temperature from orthorhombic to tetragonal polymorphic phase decreased. A composition （Na0.52K0.44Li0.04）Nb0.863Sb0.037Ta0.1O3 is found to possess excellent piezo- electric and electromechanical performances （d33 = 306pC/N, kp =48%, and kt=50%）, and high Curie temperature （Tc = 320 ℃）. These results indicate that （Na0.52K0.44Li0.04）Nb0.863Sb0.037 Ta0.1O3 is a promising lead-free piezoceramics replacement for lead zirconate titanate.     

Temperature dependences of optical properties,chemical composition,structure,and laser damage in Ta2O5 films

Ta2O5 films are prepared by e-beam evaporation with varied deposition temperatures,annealing temperatures,and annealing times.The effects of temperature on the optical properties,chemical composition,structure,and laserinduced damage threshold(LIDT) are systematically investigated.The results show that the increase of deposition temperature decreases the film transmittance slightly,yet annealing below 923 K is beneficial for the transmittance.The XRD analysis reveals that the film is in the amorphous phase when annealed below 873 K and in thehexagonal phase when annealed at 1073 K.While an interesting near-crystalline phase is found when annealed at 923 K.The LIDT increases with the deposition temperature increasing,whereas it increases firstly and then decreases as the annealing temperature increases.In addition,the increase of the annealing time from 4 h to 12 h is favourable to improving the LIDT,which is mainly due to the improvement of the O/Ta ratio.The highest LIDT film is obtained when annealed at 923 K,owing to the lowest density of defect.     

The electronic structures,Born effective charge tensors,and phonon properties of cubic,tetragonal,orthorhombic,and rhombohedral K0.5Na0.5NbO3： A first-principles comparative study

The electronic structures, Born effective charges（BECs）, and full phonon dispersions of cubic, tetragonal, orthorhombic, and rhombohedral K0.5Na0.5Nb O3 are investigated by the first principles method based on density functional theory.The hybridized states of Nb 4d and O 2p states are observed in the valence band, showing the formation of a strong Nb–O covalent bond which should be responsible for the displacement of Nb and O atoms. The abnormally large BECs of Nb and O indicate the possibility of phase instability induced by the off-center displacement of Nb and O atoms. The phonon dispersions reveal that the ferroelectric instability of K0.5Na0.5Nb O3 is dominated by Nb and O displacements with significant Na characteristics. In addition to the ferroelectric instability, there is also rotational instability coming from the oxygen octahedra rotation around one axis. Moreover, the Γ phonon properties of orthorhombic KNb O3, Na Nb O3, and K0.5Na0.5Nb O3 are also studied in detail.     

Mechanical Reinforcement and Piezoelectric Properties of PZT Ceramics Embedded with Nano-Crystalline

The double-scale lead zirconate titanate （PZT） piezoelectric ceramics were prepared by the solid state processing with PZT nano-crystalline and micro-powder. The microstructures, electrical and mechanical properties of the double-scale PZT are investigated. All the sintered ceramics exhibit a single perovskite structure and the grain size of the dou ble-scale PZT reduces due to the incorporation of PZT nano-crystalline. Compared to normal PZT, the mechanical properties increase significantly and the piezoelectric properties decrease slightly. Mechanisms responsible for the reinforcement of the double-scale PZT are discussed.     

Preparation and piezoelectric properties of potassium sodium niobate glass ceramics

This paper describes the preparation of a piezoelectric glass ceramic material from potassium sodium niobate(K0.5Na0.5Nb O3;KNN) using a novel melting method.The effects of the subsequent heat-treatment on the optical,thermal,electrical,and mechanical properties of the material are carefully examined,and its crystal structure and surface morphology are characterized respectively by x-ray diffraction and scanning electron microscopy.This new material has a much higher piezoelectric coefficient(163 p C·N-1) than traditional piezoelectric ceramics(131 p C·N-1).On this basis therefore,a strategy for the future study and development of lead-free KNN-based piezoelectric glass ceramics is proposed.     

Phase Transition and High Piezoactivity of Sr Doped Lead-Free （Na0.53K0.422Li0.048） （Nb0.89Sb0.06Wa0.05）O3 Ceramics

Lead-free piezoelectric ceramics （Na0.53K0.422Li0.048 ） （Nb0.89Sb0.06 Ta0.05 ）03 （NKLNST） ＋ x tool SrCO3 are prepared by conventional solid state sintering method. The specimens with pure perovskite structure show tetragonal phase at x 〈 0.01, and become pseudo-cubic phase at x 〉 0.02. A lattice parameter discontinuity is found in the specimens with 0.004 〈 x 〈 0.0075, along with a great improvement in piezoactivity. The 0.004 mol SrCO3 added NKLNST ceramics possesses outstanding performances of kp = 0.53, kt = 0.26, and d33=309 pC/N. Moreover, the Sr^2＋ modification inhibits the gra/n growth, decreases the Curie temperature, and induces a diffuse phase transition.     

Influence of Rapid Thermal Annealing on the Structure and Electrical Properties of Ce-Doped HfO2 Gate Dielectric

Ce-doped Hf02 （HfCeO） films are prepared by radio-frequency magnetron sputtering. The influences of rapid thermal annealing on the structure and electrical properties of HfCeO films are investigated. The results show that the incorporation of Ce into Hf02 increases the crystallization temperature of Hf02, and the cubic phase of Hf02 can be stabilized by incorporating Ce into Hf02. After high temperature annealing, Hf 4f core level spectra shift to a higher energy, whereas O 1s core level spectra shift to a lower energy. With increasing annealing temperatures, the effective permittivity increases, whereas the flat-band voltage shift and effective oxide charge density decrease. Moreover, the leakage current density of the HfCeO films decreases initially, and then increases as the annealing temperature increases.     

First-Principle Calculations for Transition Phase and Elastic Properties of SrS

The transition phase and elastic properties of SrS from NaCl structure （B1） to CsCl structure （B2） are investigated by ab initio plane-wave pseudopotential density functional theory method and by the quasi-harmonic Debye model. The transition pressure varies non-linearly with temperature, and the pressure of the mechanical instability increases linearly with increasing temperature. It is shown that the B1 structure SrS is a most elastically anisotropic minerat any pressure. The Debye temperature, the heat capacity, thermal expansion and Gruneisen parameter over a wide range of pressures and temperatures are also obtained.     

Anomalous magnetic properties of an iron film system deposited on fracture surfaces of α-Al2O3 ceramics

An iron film percolation system is fabricated by vapour-phase deposition on fracture surfaces of α-Al2O3 ceramics. The zero-field-cooled （ZFC） and field-cooled （FC） magnetization measurement reveals that the magnetic phase of the film samples evolve from a high-temperature ferromagnetic state to a low-temperature spin-glass-like state, which is also demonstrated by the temperature-dependent ac susceptibility of the iron films. The temperature dependence of the exchange bias field He of the iron film exhibits a minimum peak around the temperature T=5 K, which is independent of the magnitude of the cooling field Hcf. However, for T 〉 10K, （1） He is always negative when Hcf=2kOe and （2） for Hcf= 20 kOe （1Oe≈80 A/m）, He changes from negative to positive values as T increases. Our experimental results show that the anomalous hysteresis properties mainly result from the oxide surfaces of the films with spin-glass-like phase.     

Grain-Size Effect on the Dielectric Properties of Bi0.5Na0.5TiO3

We prepared bismuth sodium titanate (Bi0.5Na0.5TiO3)ultrafine powders by the sol-gel method.The dielctric properties of the pressed pellets and fired ceramics with different grain sizes as a function of tempernature at various frequencies were studied.With decreasing grain size,the dielecric anomaly around 200℃ increases,while the dielectric thermal hysteresis decreases,All the samples with grain sizes larger than 100nm show dielectric peaks at temperature of about 350℃.The very little change in Tm observed down to the critical size indicates that Bi0.5Na0.5TiO3 is an order-disorder system above 200℃,In addition,the dielectric peak becomes lower with decreasing grain size and the ferroelectric critical size of Bi0.5Nan0.5TiO3 was eventually determined to be about 100nm according to the disappearance of dielectric peak.     

Influences of spark plasma sintering temperature on the microstructures and thermoelectric properties of(Sr_(0.95)Gd_(0.05))TiO_3 ceramics

(Sr0.95Gd0.05)Ti O3(SGTO) ceramics are successfully prepared via spark plasma sintering(SPS) respectively at 1548,1648,and 1748 K by using submicron-sized SGTO powders synthesized from a sol–gel method.The densities,microstructures,and thermoelectric properties of the SGTO ceramics are studied.Though the Seebeck coefficient shows no obvious difference in the case that SPS temperatures range from 1548 K to 1648 K,the electrical conductivity and the thermal conductivity increase remarkably due to the increase in grain size and density.The sample has a density higher than 98%theoretical density as the sintering temperature increases up to 1648 K and shows average grain sizes increasing from～ 0.7 μm to 7 μm until 1748 K.As a result,the maximum of the dimensionless figure of merit of ～ 0.24 is achieved at～ 1000 K for the samples sintered at 1648 K and 1748 K,which was ～ 71% larger than that(0.14 at ～ 1000 K) for the sample sintered at 1548 K due to the enhancement of the power factor.     

The low-temperature sintering and microwave dielectric properties of （Zno.7Mgo.3） TiO3 ceramics with H3BO3

The effects of the addition of H3BO3 on the microstructure, phase formation, and microwave dielectric properties of （Zn0.TMg0.3）TiO3 ceramics sintered at temperatures ranging from 890 ℃ to 950 ℃ are investigated. H3BO3 as a sintering agent can effectively lower the sintering temperature of ZMT ceramics below 950 ℃due to the liquid-phase effect. The microwave dielectric properties are found to strongly correlate with the amount of H3BO3. With the increase in H3BO3 content, the dielectric constant （er） monotonically increases, but the quality factor （Q x f） reaches a maximum at 1 wt% H3BO3, and the apparent density of ZMT ceramics with H3BO3〉 1 wt% gradually decreases. At 950 ℃, the ZMT ceramics with 1% H3BO3 exhibit excellent microwave dielectric properties： er = 19.8, and Q x f -- 43800 GHz （8.94 GHz）.