High strain (0.4%) Bi(Mg2/3Nb1/3)O3-BaTiO3-BiFeO3 lead-free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg2/3Nb1/3)O3-(0.95-x)BaTiO3-xBiFeO3 (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core-shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X-ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63<x<0.70, characterised by the coexistence of phases. The temperature dependence of relative permittivity, polarisation-electric field hysteresis loops, bipolar strain-electric field curves revealed that BBFT transformed from relaxor-like to ferroelectric behaviour with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41 % for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d33*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d33 (148 pC/N) was obtained for x = 0.70. We propose that d33* is optimised at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d33 is optimised in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175oC, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 m displacement at 150 oC

Atomic structure study of the pyrochlore Yb₂Ti₂O₇ and its relationship with low-temperature magnetic order

There has been great interest in the magnetic behavior of pyrochlore oxides with the general formula A2B2O7, in which rare-earth (A) and transition metal (B) cations are ordered on separate interpenetrating lattices of corner-sharing tetrahedra. Such materials exhibit behaviors including quantum spin-ice, (quantum) spin-liquid, and ordered magnetic ground states. Yb2Ti2O7 lies on the boundary between a number of competing magnetic ground states. Features in the low-temperature specific heat capacity that vary in sharpness and temperature from sample to sample suggest that, in some cases, the magnetic moments order, while in others, the moments remain dynamic down to temperatures as low as ∼16 mK. In this paper, three different Yb2Ti2O7 samples, all grown by the optical floating zone technique but exhibiting quite different heat capacity behavior, are studied by aberration-corrected scanning transmission microscopy (STEM). Atomic-scale energy-dispersive x-ray analysis shows that a crystal with no specific heat anomaly has substitution of Yb atoms on Ti sites (stuffing). We show that the detailed intensity distribution around the visible atomic columns in annular dark field STEM images is sensitive to the presence of nearby atoms of low atomic number (in this case oxygen) and find significant differences between the samples that correlate both with their magnetic behavior and measurements of Ti oxidation state using electron energy loss spectroscopy. These measurements support the view that the magnetic ground state of Yb2Ti2O7 is extremely sensitive to disorder

High quality factor cold sintered Li2MoO4BaFe12O19 composites for microwave applications

Ceramics-ceramic composites in series (1-x)Li2MoO4-xBaFe12O19 (LMO-BF12, 0.00 ≤ x ≤ 0.15) have been cold sintered at 120 °C and their structure and properties characterized. X-ray diffraction, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) confirmed that compositions were dual phase and had a dense microstructure. Composites in the xBF12-(1-x)LMO (0.0 ≤ x ≤ 0.15) series resonated at MW frequencies (∼6 GHz) with 5.6≤εr ≤ 5.8 and Qf = 16,000–22,000 GHz, despite the black colour of compositions with x > 0. The permeability of the composites was measured in the X band (∼8 GHz) and showed an increase from 0.94 (x = 0.05) to 1.02 (x = 0.15). Finite element modelling revealed that the volume fraction of BF12 dictates the conductivity of the material, with a percolation threshold at 10 vol% BF12 but changes in εr as a function of x were readily explained using a series mixing model. In summary, these composites are considered suitable for the fabrication of dual mode or enhanced bandwidth microstrip patch antennas

Fatigue resistant lead-free multilayer ceramic capacitors with ultrahigh energy density

The critical role of electrical homogeneity in optimising electric-field breakdown strength (BDS) and energy storage in high energy density (0.7 − x)BiFeO3–0.3BaTiO3–xBi(Li0.5Nb0.5)O3 (BF–BT–xBLN) lead-free capacitors is demonstrated. The high BDS for bulk ceramics and multilayers (dielectric layer thickness ∼ 8 μm) of ∼260 and ∼950 kV cm−1, respectively, gives rise to record-performance of recoverable energy density, Wrec = 13.8 J cm−3 and efficiency, η = 81%. Under an electric field of 400 kV cm−1, multilayers are temperature stable up to 100 °C, frequency independent in the range 10−2 to 102 Hz, have low strain (<0.03%) and are fatigue-resistant up to 104 cycles (Wrec variation < 10%). These properties show promise for practical use in pulsed power systems

Superior energy density through tailored dopant strategies in multilayer ceramic capacitors

The Gerson–Marshall (1959) relationship predicts an increase in dielectric breakdown strength (BDS) and therefore, recoverable energy density (Wrec) with decreasing dielectric layer thickness. This relationship only operates however, if the total resistivity of the dielectric is sufficiently high and the electrical microstructure is homogeneous (no short circuit diffusion paths). BiFeO3–SrTiO3 (BF–ST) is a promising base for developing high energy density capacitors but Bi-rich compositions which have the highest polarisability per unit volume are ferroelectric rather than relaxor and are electrically too conductive. Here, we present a systematic strategy to optimise BDS and maximum polarisation via: (i) Nb-doping to increase resistivity by eliminating hole conduction and promoting electrical homogeneity and (ii) alloying with a third perovskite end-member, BiMg2/3Nb1/3O3 (BMN), to reduce long range polar coupling without decreasing the average ionic polarisability. These strategies result in an increase in BDS to give Wrec = 8.2 J cm−3 at 460 kV cm−1 for BF–ST–0.03Nb–0.1BMN ceramics, which when incorporated in a multilayer capacitor with dielectric layers of 8 μm thickness gives BDS > 1000 kV cm−1 and Wrec = 15.8 J cm−3

Atomic structure study of pyrochlore ytterbium titanate

There has been great interest in the magnetic behaviour of pyrochlore oxides with the general formula A2B2O7, in which rare-earth (A), and transition metal (B) cations are ordered on separate interpenetrating lattices of corner-sharing tetrahedra. Such materials exhibit behaviours including quantum spin-ice, (quantum) spin-liquid, and ordered magnetic ground states. Yb2Ti2O7 lies on the boundary between a number of competing magnetic ground states. Features in the low-temperature specific heat capacity that vary in sharpness and temperature from sample to sample suggest that in some cases the magnetic moments order, while in others the moments remain dynamic down to temperatures as low as ~16 mK. In this work, three different Yb2Ti2O7 single crystal samples, all grown by the optical floating zone technique but exhibiting quite different heat capacity behaviour, are studied by aberration-corrected scanning transmission microscopy (STEM). Atomic-scale energy-dispersive X-ray (EDX) analysis shows that a crystal with no specific heat anomaly has substitution of Yb atoms on Ti sites (“stuffing"). In fact, EDX analysis shows for the first time that “stuffing” of Yb (A) cations onto Ti (B) sites in the lattice can be observed directly in the pyrochlore structure. Moreover, I show that the detailed intensity distribution around the visible atom columns in annular dark field STEM images is sensitive to the presence of nearby atoms of low atomic number (in this case oxygen) and find significant differences between the samples that correlates both with their magnetic behaviour and measurements of Ti oxidation state using electron energy loss spectroscopy. These measurements support the view that the magnetic ground state of Yb2Ti2O7 is extremely sensitive to disorder. On the other hand, structural modification of ytterbium titanate by deviation from stoichiometry as well as electron irradiation is studied in this work. I show that Ti excess is accommodated by Yb cation vacancies while Yb excess is compensated by Yb interstitials. Furthermore, two MATLAB programs, Detect Columns and BurgersVectors, to analyse STEM images and calculate the dislocation density tensor of STEM images as well as their Burgers vector(s) are respectively introduced in this work

Fabrication, mechanical properties and in vitro degradation behavior of newly developed ZnAg alloys for degradable implant applications

Zn and Zn-based alloys have been recognized as highly promising biodegradable materials for orthopedic implants and cardiovascular stents, due to their proved biocompatibility and, more importantly, lower corrosion rates compared to Mg alloys. However, pure Zn has poor mechanical properties. In this study, Ag is used as a promising alloying element to improve the mechanical properties of the Zn matrix as well as its biocompatibility and antibacterial properties. Accordingly, we design three ZnAg alloys with Ag content ranging from 2.5 to 7.0wt% and investigate the influence of the Ag content on mechanical and corrosion behavior of the alloys. The alloys are developed by casting process and homogenized at 410°C for 6h and 12h, followed by hot extrusion at 250°C with extrusion ratio of 14:1. Degradation behavior is assessed by electrochemical and static immersion tests in Hank's modified solution. Microstructural analysis reveals that hot extrusion significantly reduces the grain size of the alloys. Zn-7.0%Ag alloy shows a reasonably equiaxed and considerably refined microstructure with mean grain size of 1.5μm. Tensile tests at room temperature suggest that increasing the Ag content steadily enhances the tensile strength, while it does not affect the tensile ductility significantly. Zn-7.0%Ag shows high yield strength and ultimate tensile strength of 236MPa and 287MPa, respectively, which is due to the grain refinement and high volume fraction of fine AgZn3 particles precipitating along the grain boundaries during the extrusion process. Among all these alloys, Zn-7.0%Ag displayed superplasticity over a wide range of strain rates (from 5×10(-4)s(-1) to 1.0×10(-2)s(-1)) providing the possibility of exploiting forming processes at rapid rates and/or even at lower temperatures. In addition, extruded alloys exhibit slightly faster degradation rate than pure Zn. X-ray diffraction results show the presence of ZnO and Zn(OH)2 on the degraded surfaces. Moreover, scanning electron microscopy imaging reveals that micro-galvanic corrosion is more pronounced on the alloys with higher Ag content due to the higher volume fraction of AgZn3 particles. [Abstract copyright: Copyright © 2017 Elsevier B.V. All rights reserved.