Characterization of high-fracture toughness K-fluorrichterite-fluorapatite glass ceramics

Stoichiometric K-fluorrichterite (Glass A) and the same composition with 2 mol% P2O5 added (Glass B) were prepared and then heat-treated isothermally from 550°1000°C with 50°C intervals. Samples were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The biaxial flexural strength and indentation fracture toughness of heat-treated glass specimens were also determined for both materials. XRD traces and TEM images showed similar phase evolution and fine microstructures for both systems at ≤950°C, with mica and diopside reacting with residual glass to form K-fluorrichterite as the temperature was increased from 650°C. However, in Glass B, fluorapatite was also present at >800°C. In contrast, coarser microstructures were observed at 1000°C, with larger K-fluorrichterite (20 μm) and enstatite (10 μm) crystals in Glasses A and B, respectively. The highest fracture toughness (2.69 ± 0.01 MPa·m(1/2)) and biaxial strength (242.6 ± 3.6 MPa) were recorded for Glass B heat-treated at 1000°C. This was attributed to the presence of enstatite coupled with an interlocked lath-like crystalline microstructure

Synthesis of magnetocaloric LaFe11.6Si1.4 alloy by spark plasma sintering

LaFe11.6Si1.4 alloys have been successfully fabricated by spark plasma sintering (SPS). An annealing study of the SPS LaFe11.6Si1.4 alloys at different temperatures ranging from 1373 to 1523 K for annealing times from 30 minutes to 72 hours was carried out. This annealing study showed that LaFe11.6Si1.4 samples annealed at 1473K (for annealing times between 30 minutes and 6 hours) have a significantly higher amount of the NaZn13-type phase compared to samples annealed at other temperatures. Thus the critical annealing temperature which enhances the formation of the NaZn13-type phase in SPS LaFe11.6Si1.4 compounds is 1473K. A second study investigated the effect of different particle sizes of the starting powders on the formation of the NaZn13-type phase. This study found that the samples synthesized using larger sized powder particles exhibited a significantly higher amount of the NaZn13-type phase compared to samples synthesized using smaller sized powder particles, for the same heat treatment

Controlling mixed conductivity in Na 1/2 Bi 1/2 TiO 3 using A-site non-stoichiometry and Nb-donor doping

Precise control of electronic and/or ionic conductivity in electroceramics is crucial to achieve the desired functional properties as well as to improve manufacturing practices. We recently reported the conventional piezoelectric material Na1/2Bi1/2TiO3 (NBT) can be tuned into a novel oxide-ion conductor with an oxide-ion transport number (tion) > 0.9 by creating bismuth and oxygen vacancies. A small Bi-excess in the nominal starting composition (Na0.50Bi0.50+xTiO3+3x/2, x = 0.01) or Nb-donor doping (Na0.50Bi0.50Ti1−yNbyO3+y/2, 0.005 ≤ y ≤ 0.030) can reduce significantly the electrical conductivity to create dielectric behaviour by filling oxygen vacancies and suppressing oxide ion conduction (tion ≤ 0.10). Here we show a further increase in the starting Bi-excess content (0.02 ≤ x ≤ 0.10) reintroduces significant levels of oxide-ion conductivity and increases tion ∼ 0.4–0.6 to create mixed ionic/electronic behaviour. The switch from insulating to mixed conducting behaviour for x > 0.01 is linked to the presence of Bi-rich secondary phases and we discuss possible explanations for this effect. Mixed conducting behaviour with tion ∼ 0.5–0.6 can also be achieved with lower levels of Nb-doping (y ∼ 0.003) due to incomplete filling of oxygen vacancies without the presence of secondary phases. NBT can now be compositionally tailored to exhibit three types of electrical behaviour; Type I (oxide-ion conductor); Type II (mixed ionic-electronic conductor); Type III (insulator) and these results reveal an approach to fine-tune tion in NBT from near unity to zero. In addition to developing new oxide-ion and now mixed ionic/electronic NBT-based conductors, this flexibility in control of oxygen vacancies allows fine-tuning of both the dielectric/piezoelectric properties and design manufacturing practices for NBT-based multilayer piezoelectric devices

Optimization of magnetocaloric properties of arc-melted and spark plasma-sintered LaFe11.6Si1.4

LaFe11.6Si1.4 alloy has been synthesized in polycrystalline form using both arc melting and spark plasma sintering (SPS). The phase formation, hysteresis loss and magnetocaloric properties of the LaFe11.6Si1.4 alloys synthesized using the two different techniques are compared. The annealing time required to obtain the 1:13 phase is significantly reduced from 14 days (using the arc melting technique) to 30 min (using the SPS technique). The magnetic entropy change (ΔSM) for the arc-melted LaFe11.6Si1.4 compound, obtained for a field change of 5 − 0T (decreasing field), was estimated to be 19.6 J kg−1 K−1. The effective RCP at 5T of the arc-melted LaFe11.6Si1.4 compound was determined to be 360 J kg−1 which corresponds to about 88 % of that observed in Gd. A significant reduction in the hysteretic losses in the SPS LaFe11.6Si1.4 compound was observed. The ΔSM, obtained for a field change of 5 − 0T (decreasing field), for the SPS LaFe11.6Si1.4 compound decreases to 7.4 J kg−1 K−1. The TC also shifts from 186 (arc-melted) to 230 K (SPS) and shifts the order of phase transition from first to second order, respectively. The MCE of the SPS LaFe11.6Si1.4 compound spreads over a larger temperature range with the RCP value at 5T reaching 288 J kg−1 corresponding to about 70 % of that observed in Gd. At low fields, the effective RCP values of the arc-melted and spark plasma-sintered LaFe11.6Si1.4 compounds are comparable, thereby clearly demonstrating the potential of SPS LaFe11.6Si1.4 compounds in low-field magnetic refrigeration applications

Design of a bilayer ceramic capacitor with low temperature coefficient of capacitance.

We show how a simple bilayer system that combines a layer of undoped BaTiO3 (BT) with a second layer of Ba0.975Na0.025Ti0.975Nb0.025O3 (2.5NNBT) can be used to improve the temperature coefficient of capacitance (TCC) of BaTiO3-based materials for capacitor applications. The bilayer system emulates the volume ratio between a conventional core and shell phase microstructure allowing a simple resource efficient approach to optimise the system for low TCC. Optimisation was achieved with a volume ratio of 0.67 2.5NNBT with 0.33 BT and results in a TCC of ±6% over the temperature range ∼25 to 125 °C whilst maintaining a permittivity of εr ∼ 3000 and low dielectric loss

Microstructure Evolution of In Situ Pulsed-Laser Crystallized Pb(Zr0.52Ti0.48)O3 Thin Films

Integration of lead zirconate titanate (PZT) films with temperature-sensitive substrates (CMOS, polymers) would benefit from growth at substrate temperatures below 400°C. In this work, in situ pulsed-laser annealing [Rajashekhar et al. (2013) Appl. Phys. Lett., 103 [3] 032908] was used to grow crystalline lead zirconate titanate (PbZr0.52Ti0.48O3) thin films at a substrate temperature of ~370°C on PbZr0.30Ti0.70O3-buffered platinized silicon substrates. Transmission electron microscopy analysis indicated that the films were well crystallized into columnar grains, but with pores segregated at the grain boundaries. Lateral densification of the grain columns was significantly improved by reducing the partial pressure of oxygen from 120 to 50 mTorr, presumably due to enhanced adatom mobility at the surface accompanying increased bombardment. It was found that varying the fractional annealing duration with respect to the deposition duration produced little effect on lateral grain growth. However, increasing the fractional annealing duration led to shift of 111 PZT X-ray diffraction peaks to higher 2θ values, suggesting residual in-plane tensile stresses in the films. Thermal simulations were used to understand the annealing process. Evolution of the film microstructure is described in terms of transient heating from the pulsed laser determining the nucleation events, while the energy of the arriving species dictates grain growth/coarsening

Maghemite-like regions at crossing of two antiphase boundaries in doped BiFeO3

We report the observation of a novel structure at the point where two antiphase boundaries cross in a doped bismuth ferrite of composition (Bi0.85Nd0.15)(Fe0.9Ti0.1)O0.3. The structure was investigated using a combination of high angle annular dark field imaging and electron energy loss spectroscopy spectrum imaging in the scanning transmission electron microscope. A three-dimensional model was constructed by combining the position and chemistry data with previous results and assuming octahedral coordination of all Fe and Ti atoms. The resulting structure shows some novel L shaped arrangements of iron columns, which are coordinated in a similar manner to FeO6 octahedra in maghemite. It is suggested that this may lead to local ferromagnetic orderings similar to those in maghemite

Cold-sintered temperature stable Na0.5Bi0.5MoO4–Li2MoO4 microwave composite ceramics

© 2017 American Chemical Society. A cold sintering process (150 °C, 30 min and 200 MPa) was employed to fabricate Na 0.5 Bi 0.5 MoO 4 -Li 2 MoO 4 (NBMO-LMO) composites with up to 96.4% relative density. X-ray diffraction traces, backscattered electron images and Raman spectra indicated the coexistence of NBMO and LMO phases in all composites with no detectable secondary phases. The pemittivity (ϵ r ) and temperature coefficient of resonant frequency (TCF) decreased, whereas microwave quality factor (Q × f) increased, with increasing weight % LMO. Near-zero TCF was obtained for NBMO-20 wt %LMO with ϵ r ∼ 17.4 and Q × f ∼ 7470 GHz. Functionally graded ceramics were also fabricated with 5 ≤ ϵ r ≤ 24. To illustrate the potential of these cold sintered composites to create new substrates and device architecture, a dielectric graded radial index lens was designed and simulated based on the range of ϵ r facilitated by the NBMO-LMO system, which suggested a 78% aperture efficiency at 34 GHz

Novel nanorod precipitate formation in neodymium and titanium codoped bismuth ferrite

The discovery of unusual nanorod precipitates in bismuth ferrite doped with Nd and Ti is reported. The atomic structure and chemistry of the nanorods are determined using a combination of high angle annular dark field imaging, electron energy loss spectroscopy, and density functional calculations. It is found that the structure of the BiFeO3 matrix is strongly modified adjacent to the precipitates; the readiness of BiFeO3 to adopt different structural allotropes in turn explains why such a large axial ratio, uncommon in precipitates, is stabilized. In addition, a correlation is found between the alignment of the rods and the orientation of ferroelastic domains in the matrix, which is consistent with the system's attempt to minimize its internal strain. Density functional calculations indicate a finite density of electronic states at the Fermi energy within the rods, suggesting enhanced electrical conductivity along the rod axes, and motivating future investigations of nanorod functionalities

Environmental life cycle assessment and techno-economic analysis of triboelectric nanogenerators

As the world economy grows and industrialization of the developing countries increases, the demand for energy continues to rise. Triboelectric nanogenerators (TENGs) have been touted as having great potential for low-carbon, non-fossil fuel energy generation. Mechanical energies from, amongst others, body motion, vibration, wind and waves are captured and converted by TENGs to harvest electricity, thereby minimizing global fossil fuel consumption. However, only by ascertaining performance efficiency along with low material and manufacturing costs as well as a favorable environmental profile in comparison with other energy harvesting technologies, can the true potential of TENGs be established. This paper presents a detailed techno-economic lifecycle assessment of two representative examples of TENG modules, one with a high performance efficiency (Module A) and the other with a lower efficiency (Module B) both fabricated using low-cost materials. The results are discussed across a number of sustainability metrics in the context of other energy harvesting technologies, notably photovoltaics. Module A possesses a better environmental profile, lower cost of production, lower CO2 emissions and shorter energy payback period (EPBP) compared to Module B. However, the environmental profile of Module B is slightly degraded due to the higher content of acrylic in its architecture and higher electrical energy consumption during fabrication. The end of life scenario of acrylic is environmentally viable given its recyclability and reuse potential and it does not generate toxic gases that are harmful to humans and the environment during combustion processes due to its stability during exposure to ultraviolet radiation. Despite the adoption of a less optimum laboratory manufacturing route, TENG modules generally have a better environmental profile than commercialized Si based and organic solar cells, but Module B has a slightly higher energy payback period than PV technology based on perovskite-structured methyl ammonium lead iodide. Overall, we recommend that future research into TENGs should focus on improving system performance, material optimization and more importantly improving their lifespan to realize their full potential