Temperature Sensitive Properties of the La(Ti<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>)O<Subscript>3</Subscript> System

The electric mechanisms of perovskite-type LaMnO₃ was investigated with B-site substitution in this paper. Samples of La(Ti_xMn_{1 − x})O₃ (0.1 ≰ x ≰ 0.7) were sintered at different temperature. The voltage-temperature (V-T) curves of the samples were tested from room temperature (25^∘C) to 300^∘C, then the electric properties were measured and analyzed. The experimental results showed that the resistivity-temperature (ρ-T) curves of the samples matched NTC characteristic. The resistivity increased slightly with the increase of Ti amount as x was less than 0.5, however, it rose greatly after x exceeded 0.5; The sintering temperatures have a little influence on the resistivity, except for the sample with x = 0.7.     

Microstructural and High-Temperature Electrical Characterization of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3 − δ</Subscript>

Strontium-doped lanthanum ferrites (LSF) were studied using scanning electron microscopy (SEM), X-ray diffraction (XRD), 4-point D.C. electrical conductivity and bulk property measurements. The results were compared to those of previous studies as well as selected processing conditions. The investigation focused on effects of sintering temperature, time, atmosphere (air, O₂ and N₂) and composition of La_1–xSr_xFeO_3– (x = 0.2–0.9), on the sintering behavior, microstructural development and electrical conductivity. An oxalate precipitation method was used to prepare lanthanum ferrite powders. Simultaneous thermogravimetric and differential thermal analysis (TGA/DTA) studies found calcination temperatures of 800 and 850^C were necessary to form single-phase crystalline powders, as determined by XRD. Specimens were sintered from 1300 to 1400^C with dwell times from to 2 hrs. Results from SEM/EDS analysis showed the presence of a second phase in the samples fired in air or oxygen. The second phase was not detected by x-ray diffraction due to the small amount of material present. Samples fired in nitrogen had the lowest conductivity while those fired in oxygen had the highest. A composition of x = 0.5 resulted in the highest conductivity, 352 S/cm, at an operating temperature of 550C in air. High strontium additions (x = 0.9) lowered the linear shrinkage of LSF.     

Effect of mechanical loading on the tuning of acoustic resonances in Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> thin films

The effect of mechanical loading on the tuning performance of a tunable Thin Film Bulk Acoustic Wave Resonator (TFBAR) based on a Ba_0.3Sr_0.7TiO₃ (BST) thin film has been investigated experimentally and theoretically. A membrane-type TFBAR was fabricated by means of micromachining. The mechanical load on the device was increased stepwise by evaporating SiO₂ on the backside of the membrane. The device was electrically characterized after each evaporation step and the results were compared to those obtained from modeling. The device with the smallest mechanical load exhibited a tuning of − 2.4% and − 0.6% for the resonance and antiresonance frequencies at a dc electric field of 615 kV/cm, respectively. With increasing mechanical load a decrease in the tuning performance was observed. This decrease was rather weak if the thickness of the mechanical load was smaller or comparable to the thickness of the active BST film. If the thickness of the mechanical load was larger than the thickness of the active BST layer, a significant reduction in the tuning performance was observed. The weaker tuning of the antiresonance frequency was due to a reduced tuning of the sound velocity of the BST layer with increasing dc bias. The resonance frequency showed a reduced tuning due to a decrease in the effective electromechanical coupling factor of the device with increasing mechanical load. With the help of the modeling we could de-embed the intrinsic tuning performance of a single, non-loaded BST thin film. We show that the tuning performance of the device with the smallest mechanical load we fabricated is close to the intrinsic tuning characteristics of the BST layer.     

Partial Electronic Conductivity and Chemical Diffusivity of Li<Subscript>3<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript>2/3−<Emphasis Type="Italic">x</Emphasis></Subscript>TiO<Subscript>3</Subscript> Solid Solution

Partial electronic conductivity and chemical diffusivity of Li have been measured on the system of Li_3xLa_2/3–xTiO₃ (LLT) with x = 0.13, a prospective Li⁺ electrolyte, against oxygen activity in the range of 10^–22 < a_O2 < 0.21 at 557, 610 and 663C, respectively by an ion-blocking polarization technique. It is found that the electronic conductivity of LLT, which in air is essentially an ionic conductor, varies as a_O2^–1/4 to render it mixed-conductive in reducing atmospheres, say, in a_O2 < 10^–12. The chemical diffusivity of component Li also increases from a value of the order of 10^–8 cm²/s in air atmosphere up to a maximum on the order of 10^–3 cm²/s as the electronic conductivity increases with decreasing oxygen activity. This is attributed to the variation of the electronic transference number and the thermodynamic factor with oxygen activity. The latter has been evaluated to be on the order of 10–10³.     

A first-principles study of the structural,elastic, electronic,vibrational, and optical properties of BaSe<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

The structural, elastic, electronic, vibrational, and optical properties of BaSe_1?xTe_x alloys are investigated by means of the full-potential linearized augmented plane wave method. The exchange–correlation effects are treated with the local density approximation, as well as the GGA-PBE, GGA-PBEsol, and GGA?+?mBJ schemes of the generalized gradient approximation. Ternary BaSe_1?xTe_x compounds have not yet been synthesized. Improved predictions of the structural parameters are obtained using the GGA-PBEsol approach. Calculations of the electronic and optical properties with the GGA?+?mBJ approach yield accurate results. Ternary BaSe_1?xTe_x alloys are wide-band-gap semiconductors with a direct gap Γ–Γ. The upper valence band is mainly due to Se p and Te p states, while the bottom of the conduction band results essentially from Ba d states. The dielectric function, refractive index, reflectivity, absorption coefficient, and energy-loss function are calculated in the range 0–35 eV. The increase in x gives rise to a redshift of the optical spectra. BaSe_1?xTe_x alloys exhibit reflective properties of metals in some energy ranges. The static dielectric constant ?₁(0) and the static refractive index n₀ are calculated. The investigation of the elastic and vibrational properties shows that ternary BaSe_1?xTe_x should be mechanically and dynamically stable, elastically anisotropic, brittle, and relatively soft.     

Microwave dielectric properties of (1-<Emphasis Type="Italic">x</Emphasis>) BiVO<Subscript>4</Subscript>–<Emphasis Type="Italic">x</Emphasis>Ln<Subscript>2/3</Subscript>MoO<Subscript>4</Subscript> (Ln=Er,Sm, Nd,la) ceramics with low sintering temperatures

A series of microwave dielectric ceramics of (1-x) BiVO₄ -xLn_2/3MoO₄ (Ln = Er, Sm, Nd and La; x = 0.06, 0.08, 0.10) sintered below 900 °C were prepared via solid-state reaction. As the x values increase, the monoclinic scheelite continuously changes to a tetragonal structure at x = 0.10. The incorporation of Ln_2/3MoO₄ into the BiVO₄ matrix increases the product (Q × f) of quality factor (Q) and resonance frequency (f), and temperature coefficient (τ _f ), but lowers the dielectric constant (ε _r). Microwave dielectric ceramics with low sintering temperatures (<900 °C) are obtained: ε _r of ~71.1, 81.6, 75.6 and ~75.3; Q × f values of ~8292, 5508, 8695 and 9043 GHz; τ _f of ~ ?51, 134, 149 and 158 ppm/°C, for 0.94BiVO₄–0.06Er_2/3MoO₄, 0.92BiVO₄–0.08Sm_2/3MoO₄, 0.9BiVO₄–0.1Nd_2/3MoO₄ and 0.9BiVO₄–0.1La_2/3MoO₄ ceramics, respectively. Moreover, (1-x) BiVO₄ -xLn_2/3MoO₄ (Ln = Er, Sm, Nd and La; x = 0.06, 0.08 and 0.10) ceramics are chemically compatible with both Ag and Cu powders at their sintering temperatures. The series of microwave dielectric ceramics might be potential candidates for low temperature co-fired ceramics (LTCC) technology applications.     

<Emphasis Type="Italic">T</Emphasis><Subscript>2</Subscript> mapping of cerebrospinal fluid: 3 T versus 7 T

Object

Cerebrospinal fluid (CSF) T ₂ mapping can potentially be used to investigate CSF composition. A previously proposed CSF T ₂–mapping method reported a T ₂ difference between peripheral and ventricular CSF, and suggested that this reflected different CSF compositions. We studied the performance of this method at 7 T and evaluated the influence of partial volume and B ₁ and B ₀ inhomogeneity.

Materials and methods

T ₂-preparation-based CSF T ₂-mapping was performed in seven healthy volunteers at 7 and 3 T, and was compared with a single echo spin-echo sequence with various echo times. The influence of partial volume was assessed by our analyzing the longest echo times only. B ₁ and B ₀ maps were acquired. B ₁ and B ₀ dependency of the sequences was tested with a phantom.

Results

T _2,CSF was shorter at 7 T compared with 3 T. At 3 T, but not at 7 T, peripheral T _2,CSF was significantly shorter than ventricular T _2,CSF. Partial volume contributed to this T ₂ difference, but could not fully explain it. B ₁ and B ₀ inhomogeneity had only a very limited effect. T _2,CSF did not depend on the voxel size, probably because of the used method to select of the regions of interest.

Conclusion

CSF T ₂ mapping is feasible at 7 T. The shorter peripheral T _2,CSF is likely a combined effect of partial volume and CSF composition.

     

Effect of the air–fuel mixing on the NO<Subscript> <Emphasis Type="Italic">х</Emphasis> </Subscript> yield in a low-emission gas-turbine plant combustor

The article deals with construction of a simplified model of inhibition of nitric oxides formed in the combustors of the gas-turbine plants (GTPs) operating on natural gas. A combustor in which premixed, lean air–fuel mixtures are burnt is studied theoretically and experimentally. The research was carried out using a full-scale combustor that had parameters characteristic of modern GTPs. The article presents the results computed by the FlowVision software and the results of the experiments carried out on the test bench of the All-Russia Thermal Engineering Institute. The calculations and the tests were conducted under the following conditions: a flow rate of approximately 4.6 kg/s, a pressure to 450 kPa, an air temperature at the combustor inlet of approximately 400°C, the outlet temperature t₃ ≤ 1200°C, and natural gas as the fuel. The comparison of the simulated parameters with the experimental results underlies the constructed correlation dependence of the experimental NO_x emission on the calculated parameter of nonuniform fuel concentration at the premixing zone outlet. The postulate about a weak dependence of the emission of NO_x formed upon combustion of a perfectly mixed air–fuel mixture—when the methane concentration in air is constant at any point of the air–fuel mixture, i.e., constant in the mixture bulk—on the pressure in the combustor has been experimentally proven. The correctness and the practicability of the stationary mathematical model of the mixing process used to assess the NO_x emission by the calculated amount of the air–fuel mixture generated in the premixing zone has been validated. This eliminates some difficulties that arise in the course of calculation of combustion and formation of NO_x.     

Study of bulk and grain-boundary conductivity of Ln<Subscript>2+x</Subscript>Hf<Subscript>2−x</Subscript>O<Subscript>7−δ</Subscript> (Ln = Sm-Gd; x = 0, 0.096) pyrochlores

The electrical conductivity of new solid electrolytes Eu_2.096Hf_1.904O_6.952 and Gd₂Hf₂O₇ have been compared with those for different pyrochlores including titanates and zirconates Ln_2+xМ_2−xO_7−δ (Ln = Sm-Lu; M = Ti, Zr; x = 0−0.81). Impedance spectroscopy data demonstrate that Eu_2.096Hf_1.904O_6.952 and Gd₂Hf₂O₇ synthesized from mechanically activated oxides have high ionic conductivity, comparable to that of their zirconate analogues. The bulk and grain-boundary components of conductivity in Sm_2.096Hf_1.904O_6.952 (Т_synth = 1600oС), Eu_2.096Hf_1.904O_6.952 and Gd₂Hf₂O₇ (Т_synth = 1670oС) have been determined. The highest bulk conductivity is offered by the disordered pyrochlores prepared at 1600oC and 1670oC: ~1.5 × 10⁻⁴ S/cm for Sm_2.096Hf_1.904O_6.952, 5 × 10⁻³ S/cm for Eu_2.096Hf_1.904O_6.952 and 3 × 10⁻³ S/cm for Gd₂Hf₂O₇ at 780oС, respectively. The conductivity of the fluorite-like phases at the phase boundaries of the Ln_2+xМ_2−xO_7−δ (Ln = Eu, Gd; M = Zr, Hf; x ~ 0.286) solid solutions, as well as that of the high-temperature fluorite-like phases Ln_2+xМ_2−xO_7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.286), is lower than the conductivity of the disordered pyrochlores Ln_2+xМ_2−xO_7−δ (Ln = Eu, Gd; M = Zr, Hf; x = 0−0.096).     

Synthesis,and measurement of structural and magnetic properties,of La<Subscript>1−x</Subscript>Cd<Subscript>x</Subscript>CoO<Subscript>3</Subscript> perovskite ceramic oxides

Perovskite-type Cd-doped LaCoO₃ materials were synthesized by a simple solution-based combustion process. The synthesized materials were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance (DR) in the UV-VIS, and magnetic property measurements. The parent LaCoO₃ compound showed spin-glass transition at low temperatures, and with progressive Cd doping, showed transition to paramagnetic ordering. The changes in magnetic properties of the materials are correlated to the changes in structural features resulting from the Rietveld structural refinement of the materials.     

Control of Microwave Dielectric Properties in the System BaO ⋅ Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>—BaO ⋅ Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 4TiO<Subscript>2</Subscript>

BaO ⋅ Nd₂O₃ ⋅ 4TiO₂—based ceramics were prepared by the mixed oxide route. Specimens were sintered at temperatures in the range 1200–1450^∘C. Microstructures were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM); microwave dielectric properties were determined at 3 GHz by the Hakki and Coleman method. Product densities were at least 95% theoretical. The addition of up to 1 wt% Al₂O₃ to the starting mixtures reduced the sintering temperatures by at least 100^∘C. Incorporation of small levels of Al into the structure (initially Ti sites) led to an increase in Q × f values, from 6200 to 7000 GHz, a decrease in relative permittivity (ε_r) from 88 to 78, and moved the temperature coefficient of resonant frequency (τ_f) towards zero. The addition of 0.5 wt% Al₂O₃ with 8 wt% Bi₂O₃ improved densification, increased both ε_r (to 88) and Q× f (to 8000 GHz) and moved τ_f closer to zero. Ceramics in the system (1 − x)BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + xBaO ⋅ Al₂O₃ ⋅ 4TiO₂ exhibited very limited solid solubility. The end member BaO ⋅ Al₂O₃ ⋅ 4TiO₂ was tetragonal in structure with the following dielectric properties: ε_r = 35; Q× f = 5000 GHz; τ_f = −15ppm/^∘C. Microstructures of the mixed Nd-Al compositions contained two distinct phases, Nd-rich needle-like grains and large Al-rich, lath-shaped grains. Products with near zero τ_f were achieved at compositions of approximately 0.14BaO ⋅ Nd₂O₃ ⋅ 4TiO₂ + 0.86BaO ⋅ Al₂O₃ ⋅ 4TiO₂, where Q× f = 8200 GHz and ε_r = 71.     

Selective 3D ultrashort TE imaging: comparison of “dual-echo” acquisition and magnetization preparation for improving short-<Emphasis Type="Italic">T</Emphasis><Subscript>2</Subscript> contrast

Objective The objective of this study was to compare two different schemes for long-T ₂ component suppression in ultrashort echo-time (UTE) imaging. The aim was to increase conspicuity of short-T ₂ components accessible by the UTE technique. Materials and methods A “dual-echo” and a magnetization-preparation approach for long-T ₂ and fat suppression were implemented on clinical scanners. Both techniques were compared in 3D UTE exams on healthy volunteers regarding short-T ₂ Signal-to-noise ratio (SNR), long-T ₂ suppression quality, and scan efficiency. A quantitative SNR evaluation was performed using ankle scans of six volunteers. T ₂ suppression profiles were simulated for both approaches to facilitate interpretation of the observations. Results At 1.5 T, both techniques perform equally well in suppressing long-T ₂ components and fat. Magnetization preparation requires more shimming effort due to the use of narrow-band pulses, while the “dual-echo” technique requires a post-processing step to form a subtraction image. For scans with a short repetition time (TR), the “dual-echo” approach is much faster than the magnetization preparation, which depends on slow T ₁ recovery between preparation steps. The SNR comparison shows slightly higher short-T ₂ SNR for the “dual-echo” approach. At 3.0 T, magnetization preparation becomes more challenging due to stronger off-resonance effects. Conclusion Both techniques are well suited for long-T ₂ suppression and offer comparable short-T ₂ SNR. However, the “dual-echo” approach has strong advantages in terms of scan efficiency and off-resonance behavior.     

Preparation and characterization of negative temperature coefficient (Ni,Mn)<Subscript>3</Subscript>O<Subscript>4</Subscript>–La(Mn,Ni)O<Subscript>3</Subscript> composite

The composites made of spinel-structured (Ni,Mn)₃O₄ and perovskite-structured La(Mn,Ni)O₃ were investigated for potential application as negative temperature coefficient (NTC) thermistor. The composites were prepared using the standard ceramic route. The electrical resistivity of the composite at 25°C was found to decrease by one to two orders of magnitude depending the amount of the low-resistivity perovskite phase, while the thermal constant determining the temperature sensitivity of the NTC thermistor was still reasonably large in the range of 4,000 to 3,000 K, and the resistivity drift after annealing at 150°C for 1,000 h in air was relatively small (∼1.2%). The general effective media model was adopted to fit the electrical resistivity data of the composites, giving a value of 0.37 for the percolation volume fraction of the perovskite phase. This work demonstrates that it is possible to tune the electrical resistivity and thermal constant of the spinel-structured oxide through making composite with low-resistivity perovskite-structured oxide.     

Electro-chemo-mechanical studies of perovskite-structured mixed ionic-electronic conducting SrSn<Subscript>1-x</Subscript>Fe<Subscript>x</Subscript>O<Subscript>3-x/2+δ</Subscript>part I: Defect chemistry

Oxygen nonstoichiometry and the defect chemistry of the SrSn_1-xFe_xO_3-x/2+δ (SSF) system were examined by means of thermogravimetry as a function of oxygen partial pressure in the temperature range of 700–1000 °C and compared against the corresponding mixed ionic-electronic conducting titanate, SrTi_1-xFe_xO_3-x/2+δ (STF) system. The alternate B site host cation, Sn, was selected to replicate and extend the STF studies, given its distinct band structure and higher electron mobility associated with its 5s derived conduction band as compared to the 3d nature of the conduction band in the titanate. Though shifted slightly by the larger size of Sn, the defect equilibria – including the oxygen vacancy concentration – were found to be largely dominated by Fe oxidation state, and thus differed only in a limited way from those in STF. Key thermodynamic parameters for SrSn_0.65Fe_0.35O_2.825+δ (SSF35) were derived including the reduction enthalpy (4.137 ± 0.175 eV), the high temperature electronic band gap (1.755 ± 0.015 eV) and the anion Frenkel enthalpy (0.350 ± 0.350 eV). The implications these observations have for cathode behavior in solid oxide fuel cells are briefly discussed.     

Large signal electrical property of CuO-doped of a Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–SrTiO<Subscript>3</Subscript>

This report describes the sintering and ferroelectric characteristic of 0.76 Bi_0.5Na_0.5TiO₃ (BNT)–0.26SrTiO₃ (ST) with CuO addition, synthesized by using a solid-state reaction. The XRD, microstructure, and density results reveal that Cu element reduces the sintering temperature from 1150 to 1000 °C. In dielectric study, CuO addition induces the increase of relaxation behavior for 26ST ceramic in the high temperature regime. In the low temperature regime (< 150 °C), the Cu doping to 26ST accelerates the degree in freezing of dipole, presumably due to the interaction between A site vacancy and nanodomain boundaries. The electromechanical properties of 26ST ceramics with CuO doping show a significant decay in frequency dependence of polarization and strain, which might be related to the formation of A-site cation vacancy.     

Impedance/Dielectric Spectroscopy of Electroceramics–Part 1: <Emphasis Type="Italic">Evaluation of Composite Models for Polycrystalline Ceramics</Emphasis>

In the microcrystalline regime, the electrical (impedance/dielectric) behavior of grain boundary-controlled electroceramics is well described by the brick-layer model (BLM). In the nanocrystalline regime, however, grain boundary layers can represent a significant volume fraction of the overall microstructure. Simple boundary-layer models no longer adequately describe the electrical properties of nanocrystalline ceramics. The present work describes the development of a pixel-based finite-difference approach to treat a nested-cube model (NCM), which is used to investigate the validity of existing models for describing the electrical properties of polycrystalline ceramics over the entire range of grain core vs. grain boundary volume fractions, from the nanocrystalline regime to the microcrystalline regime. The NCM is shown to agree closely with the Maxwell-Wagner effective medium theory.     

Structural,electrical, and multiferroic properties of Aurivillius Bi<Subscript>6</Subscript>Fe<Subscript>2</Subscript>(Ti<Subscript>3-x</Subscript>V<Subscript>x</Subscript>)O<Subscript>18+δ</Subscript> thin films prepared by chemical solution deposition

Aurivillius type five-layered V-doped Bi₆Fe₂(Ti_3-xV_x)O_18+δ (x = 0.00, 0.03, 0.06, and 0.09) thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by using a chemical solution deposition method. All the thin films were crystallized in Aurivillius structures, which have been confirmed by using X-ray diffraction and Raman spectroscopy studies. On comparing the thin films, the Bi₆Fe₂(Ti_2.94V_0.06)O_18+δ thin film showed the most enhanced electrical and multiferroic properties, with a leakage current density value about four orders of magnitude lower than that of the Bi₆Fe₂Ti₃O₁₈ thin film, for example. All of these thin films showed anti-ferromagnetic hysteresis loops at room temperature. The significant decrease in the concentration of oxygen vacancies and the formation of a stable structure caused by doping with the donor V⁵⁺-ion are related to the improved properties in the V-doped Bi₆Fe₂(Ti_3-xV_x)O_18+δ thin films.     

Low temperature sintering of lead–free (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript>-SrTiO<Subscript>3</Subscript>-BiFeO<Subscript>3</Subscript> piezoelectric ceramics by adding excess CuO

This study examined the microstructures, crystal structures, and electrical properties of 0.01 mol CuO–added (1–x)(Bi_1/2Na_1/2)TiO₃–xSrTiO₃–2BiFeO₃ (BNST100x–2BF, x?=?0.20 ~ 0.28) ceramics synthesized at two different sintering temperatures. The sintering temperature of the BNST100x–2BF ceramics could be decreased from 1175 °C to 1000 °C by adding a 0.01 mol CuO excess. Low–temperature sintering led to a decrease in average grain size. The dielectrics, polarization hysteresis (P–E), switching current, and electric–field induced strain (S–E) curves changed with increasing SrTiO₃ content and decreasing sintering temperature. Interestingly, the highest reduction ratio of d₃₃^* was calculated to be somewhere in between the high–temperature sintered and low–temperature sintered BNST26–2BF ceramics. These results were attributed to the difference in the stabilized relaxor state and closely related to the electric field–induced reversible phase transition from the relaxor and ferroelectrics.     

Electro-chemo-mechanical studies of perovskite-structured mixed ionic-electronic conducting SrSn<Subscript>1-x</Subscript>Fe<Subscript>x</Subscript>O<Subscript>3-x/2+δ</Subscript> Part III: Thermal and chemical expansion

The thermal and chemical expansion of a potential solid oxide fuel cell (SOFC) cathode material SrSn_0.65Fe_0.35O_{3–0.35/2+δ} (SSF35) were investigated to assess its thermo-chemo-mechanical stability at SOFC operating temperatures and to establish the correlation between defect concentrations (oxygen vacancies and electrons) and chemical expansion with the aid of the defect chemical model reported in part I of this study. Thermochemical expansion was measured as a function of temperature and oxygen partial pressure. The chemical expansion of SSF35 showed a strong correlation with changes in oxygen nonstoichiometry associated with changes in Fe valence state. Coefficients of both chemical (CCE) and thermal (CTE) expansion were calculated and found to be smaller than that of the closely related mixed conducting perovskite oxide SrTi_0.65Fe_0.35O_{3–0.35/2+δ} (STF35). The thermal expansion coefficient of SSF was found to be close to that of YSZ (most popular solid oxide electrolyte), which makes SSF35 more attractive in terms of overall thermo-chemical stability. The chemical expansion of SSF35 showed decreasing CCE with increasing temperature and decreasing CTE with increasing oxygen deficiency, both opposite to the trends observed for STF35. Distortion in symmetry from the cubic structure seems to be responsible for the smaller coefficients and increasing asymmetry with expansion seems accountable for opposite trends of CCE and CTE compared to the STF counterpart.     

Electromechanical properties of ternary BiFeO<Subscript>3</Subscript>−0.35BaTiO<Subscript>3</Subscript>–BiGaO<Subscript>3</Subscript> piezoelectric ceramics

In the present work, composition dependent crystal structure, ferroelectric, piezoelectric, and temperature dependent dielectric properties of the BiGaO₃-modified (1–x)(0.65Bi_1.05FeO₃–0.35BaTiO₃) (BFBT35–xBG, where x?=?0.00–0.03) lead-free ceramics were systematically investigated by solid-state reaction method, followed by water quenching process. The substitution of BG successfully diffuses into the lattice of the BFBT ceramics, without changing the pseudo-cubic structure of the samples. The scanning electron microscopy (SEM) results revealed that the average grain size was increased with BG-content in BFBT system. The BFBT–xBG ceramics showed a maximum in permittivity (?_max) at temperatures (T_max) above 500 °C in the compositional range of 0.00?≤?x?≤?0.03. The electro-strain is measured to be 0.125% (d^*₃₃ ~ 250 pm/V) under unipolar fields (5 kV/mm) for BFBT–0.01BG ceramics. The same composition (x?=?0.01), large static piezoelectric constant (d₃₃ ~ 165 pC/N) and electromechanical coupling factor (k_p ~ 25%) were obtained. The above investigated characterizations suggests that BFBT–BG material is favorable for piezoelectric and high temperature applications.