Band gap narrowing in ferroelectric KNbO3-Bi(Yb,Me)O3 (Me=Fe or Mn) ceramics

The direct optical band gap in ferroelectric KNbO3-Bi(Yb,Me)O3 (Me=Fe or Mn) ceramics fabricated by the solid state reaction method varies from 3.2 eV for KNbO3 down to 2.2 eV for 0.95KNbO3-0.05BiYbO3, as revealed by optical spectroscopic ellipsometry. This narrowing of band gap is accompanied by an apparent increase of the room-temperature relative permittivity from 320 for KNbO3 to 900 for 0.95KNbO3-0.05BiYbO3. All compositions studied exhibit dielectric anomalies associated with structural phase transitions and their ferroelectric nature is corroborated by the presence of a sharp mixed mode (at ~190 cm-1) and by a Fano-type resonant dip in their Raman spectra

Temperature Dependent Piezoelectric Properties of Lead-Free (1-x)K0.6Na0.4NbO3–xBiFeO3 Ceramics

(1-x)K0.4Na0.6NbO3–xBiFeO3 lead-free piezoelectric ceramics were successfully prepared in a single perovskite phase using the conventional solid-state synthesis. Relative permittivity (εr) as a function of temperature indicated that small additions of BiFeO3 not only broadened and lowered the cubic to tetragonal phase transition (TC) but also shifted the tetragonal to orthorhombic phase transition (TO–T) toward room temperature (RT). Ceramics with x = 1 mol.% showed optimum properties with small and large signal piezoelectric coefficient, d33 = 182 pC/N and d∗33 = 250 pm/V, respectively, electromechanical coupling coefficient, kp = 50%, and TC = 355°C. kp varied by ∼5% from RT to 90°C, while d∗33 showed a variation of ∼15% from RT to 75°C, indicating that piezoelectric properties were stable with temperature in the orthorhombic phase field. However, above the onset of TO–T, the properties monotonically degraded in the tetragonal phase field as TC was approached

Structure–property relationships in (1 − x)BaTiO3–xBiGdO3 ceramics

(1 − x)BaTiO3–xBiGdO3 ceramics were prepared by the solid state reaction method. X-ray diffraction and Raman spectroscopy indicate a maximum co-solubility of Bi/Gd in BaTiO3 at x = 0.10 with a change of symmetry from tetragonal to pseudo-cubic at x = 0.08. Backscattered electron images, however, reveal the presence of a secondary phase in x ≥ 0.06. The dielectric behaviour evolves continuously with x from a classical ferroelectric to a typical relaxor and this transition is accompanied by a shift in the permittivity maxima towards lower temperatures. The presence of two dielectric anomalies for x ≥ 0.06 is associated with residual core–shell structures, as revealed by transmission electron microscopy. The dielectric anomaly associated with the core regions remains at ∼120 °C, whereas the other anomaly decreases continuously towards lower temperature with x. This study shows that chemical equilibrium is much more difficult to achieve than in other (1 − x)BaTiO3–xBi[Me]O3 systems, where Me is Yb or Sc

Site occupancy and electric-field induced strain response of Er-doped (Bi0.4Na0.4Sr0.2)TiO3 ceramics

© 2018 Elsevier B.V. Er-doped (Bi0.4Na0.4Sr0.2)TiO3 powders were prepared by solid state reactions according to A-site donor (Bi0.4-x/3Na0.4-x/3Sr0.2-x/3Erx)TiO3 (x = 0.0.015 and 0.02) and B-site acceptor (Bi0.4Na0.4Sr0.2)Ti1-yEryO3 (y = 0, 0.015 and 0.02) substitutional doping mechanisms. In both cases, room-temperature X-ray diffraction analyses revealed a decrease of the unit cell volume with increasing Er contents, suggesting A-site occupancy to be thermodynamically more favourable. Over the 25–175 °C temperature range, A-site doped ceramics, in particular x = 0.015, showed enhanced thermal stability of the maximum achievable electric-field induced strain. Importantly, this minor doping level also reduced dielectric loss at high temperature and led to a transition from non-ergodic to ergodic relaxor behaviour. These results may further motivate the study of the impact of other minor dopants in this family of Pb-free piezoceramics

Effects of quenching on phase transformations and ferroelectric properties of 0.35BCZT-0.65KBT ceramics

© 2019 Elsevier Ltd Solid solutions of 0.35(Ba,Ca)(Zr,Ti)O3-0.65(K0.5Bi0.5)TiO3 (BCZT-KBT) having various Ca and Zr contents were synthesized by solid state reaction. The sintered ceramics exhibited interesting features comprising core-shell type microstructures and relaxor ferroelectric behaviour. The influence of air-quenching on structure and electrical properties has been systematically investigated. The results indicate that the compositional heterogeneity in the shell regions, for the slow-cooled state, was reduced by air quenching. Improvements are evident in ferroelectric tetragonal phase content, accompanied by increased polarisation values and depolarisation temperatures. Comparing the results obtained for two BCZT compositions, it was demonstrated that the stability of the ferroelectric tetragonal phase in slow-cooled BCZT-KBT samples was improved for the ceramic with lower Ca and Zr concentrations, denoted x = 0.06, comparing with that for higher levels, denoted x = 0.15. Furthermore, the electric field-induced ferroelectric state in the quenched ceramic with x = 0.06 was found to be more stable during heating, yielding an enhanced depolarisation temperature

Optimising dopants and properties in BiMeO3 (Me = Al, Ga, Sc, Y, Mg2/3Nb1/3, Zn2/3Nb1/3, Zn1/2Ti1/2) lead-free BaTiO3-BiFeO3 based ceramics for actuator applications

A crystallochemical framework is proposed based on electronegativity difference (en) and tolerance factor (t) to optimise the BiMeO3 dopants and therefore the piezoelectric and electrostrictive response in BaTiO3-BiFeO3 based ceramics. Compositions in the series 0.05Bi(Me)O3-0.25BaTiO3-0.7BiFeO3 (BMe-BT-BF, Me: Y, Sc1/2Y1/2, Mg2/3Nb1/3, Sc, Zn2/3Nb1/3, Zn1/2Ti1/2, Ga, and Al) were fabricated using solid state synthesis and furnace cooled. Scanning electron microscopy and X-ray diffraction revealed that only Bi(Mg2/3Nb1/3)O3 and BiScO3 dopants, which lie in a narrow range of en vs. t, form homogeneous ceramics, free from secondary phases reflected in their superior piezoelectric coefficients (d33 ~145 pC/N). All other BiMeO3 additions exhibited either secondary phases (Y) and/or promoted a two-phase perovskite matrix (Zn, Ga and Al). The promising initial properties of BiScO3 doped compositions prompted further studies on 0.05BiScO3-(0.95-x)BaTiO3-(x)BiFeO3 (BS-BT-BF, x = 0.55, 0.60, 0.625, 0.65, and 0.70) ceramics. As x increased the structure changed from predominantly pseudocubic to rhombohedral, resulting in a transition from a relaxor-like to ferroelectric response. The largest d33 * (465 pm/V) was achieved for x = 0.625 under 5 kV/mm at the crossover from relaxor to ferroelectric behaviour. BS-BT-BF with x = 0.625 showed >0.3% strain under 6 kV/mm up to 175ºC, demonstrating its potential for actuator applications

Selective Laser Melting processed Ti6Al4V lattices with graded porosities for dental applications

Dental implants need to support good osseointegration into the surrounding bone for full functionality. Interconnected porous structures have a lower stiffness and larger surface area compared with bulk structures, and therefore are likely to enable better bone-implant fixation. In addition, grading of the porosity may enable large pores for ingrowth on the periphery of an implant and a denser core to maintain mechanical properties. However, given the small diameter of dental implants it is very challenging to achieve gradations in porosity. This paper investigates the use of Selective Laser Melting (SLM) to produce a range of titanium structures with regular and graded porosity using various CAD models. This includes a novel 'Spider Web' design and lattices built on a diamond unit cell. Well-formed interconnecting porous structures were successfully developed in a one-step process. Mechanical testing indicated that the compression stiffness of the samples was within the range for cancellous bone tissue. Characterization by scanning electron microscopy (SEM) and X-ray micro-computed tomography (μCT) indicated the designed porosities were well-replicated. The structures supported bone cell growth and deposition of bone extracellular matrix

Photoresponse of KNbO3–AFeO3 (A = Bi3+ or La3+) ceramics and its relationship with bandgap narrowing

The crystal structure of (1-x)KNbO3–xBiFeO3 (KNBF) and (1-x)KNbO3-LaFeO3 (KNLF) (where x=0.00; 0.01; 0.02; 0.04; 0.08; 0.16; 0.32) was evaluated by XRD and Raman spectroscopy. XRD data show the crystal symmetry to evolve from orthorhombic to tetragonal with increasing x. The optical bandgap was found to narrow systematically with increasing x. Raman spectroscopy analysis corroborated long-range polar order in all compositions. The photoresponse of x=0.32 shows a typical diode–like behaviour, with current and voltage of 0.115 µA and 0.075 V for KNBF and 0.19 µA and 0.035 V for KNLF, respectively. To our knowledge these represent the largest values among KNbO3–based ceramics, making them promising for photovoltaic applications

Selective Laser Melting processed Ti6Al4V lattices with graded porosities for dental applications

Dental implants need to support good osseointegration into the surrounding bone for full functionality. Interconnected porous structures have a lower stiffness and larger surface area compared with bulk structures, and therefore are likely to enable better bone-implant fixation. In addition, grading of the porosity may enable large pores for ingrowth on the periphery of an implant and a denser core to maintain mechanical properties. However, given the small diameter of dental implants it is very challenging to achieve gradations in porosity. This paper investigates the use of Selective Laser Melting (SLM) to produce a range of titanium structures with regular and graded porosity using various CAD models. This includes a novel 'Spider Web' design and lattices built on a diamond unit cell. Well-formed interconnecting porous structures were successfully developed in a one-step process. Mechanical testing indicated that the compression stiffness of the samples was within the range for cancellous bone tissue. Characterization by scanning electron microscopy (SEM) and X-ray micro-computed tomography (μCT) indicated the designed porosities were well-replicated. The structures supported bone cell growth and deposition of bone extracellular matrix

Band gap evolution and piezoelectric-to-electrostrictive crossover in (1-x)KNbO3-x(Ba0.5Bi0.5)(Nb0.5Zn0.5)O3 ceramics

The band gap of (1-x)KNbO3-x(Ba0.5Bi0.5)(Nb0.5Zn0.5)O3 (0≤x≤0.25) ceramics narrows slightly from 3.22 eV for x=0 to 2.89 eV for x=0.25, in broad agreement with first-principle calculations [Phys. Rev. B 89, 235105 (2014)]. In addition, an unreported piezoelectric-to-electrostrictive crossover is observed in this compositional range, which is accompanied by a continuous decrease of the maximum electric field-induced strain due to the presence of a non-ferroelectric phase. An electrostriction coefficient of 0.023 m4/C2 is measured for x=0.05, whilst no electromechanical response is observed for non-ferroelectric x=0.25, even under an applied electric field of 80 kV/cm