Effect of nano-Al2O3 addition on the densification of YSZ electrolytes

This work investigates the effect of nanosized Al2O3 addition on the sinterability of YSZ electrolyte. (1-x)YSZ + Al2O3 ceramics with compositions x = 0 to 0.01 were prepared by the conventional mixed oxide route from a commercial powder suspension (particle size <50 nm), and sintered at 1200 to 1500 degrees C for 2 hours in air. Densification, phase evolution, and microstructure were characterized by SEM/EDS and XRD. An improvement in sintered density was observed for the samples with 0.2 to 0.5 mol% Al2O3, though depending on the sintering temperature. Only cubic zirconia was detected as crystalline phase, although XRD features suggested chemical interactions depending upon the amount of Al2O3. The grain size of YSZ was homogeneous and no second phase segregation was detected in the tested range of incorporated nano-Al2O3 and sintering temperatures.

Structure effect on the oxygen permeation properties of barium bismuth iron oxide membranes

In this work, we investigated the oxygen permeation properties of barium bismuth iron oxide within the family of [Ba_2−3xBi_3x−1][Fe_2xBi_1−2x]O_2+3x/2 for x = 0.17–0.60. The structure changed progressively from cubic to tetragonal and then to hexagonal as function of x in accordance with the different relative amounts of bismuth on A-site and B-site of ABO_3−δ perovskite lattices. We found that the oxygen flux and electrical conductivity correlated strongly, and it was prevalent for the cubic structure (x = 0.33–0.40) which conferred the highest oxygen flux of 0.59 ml min⁻¹ cm⁻² at 950 °C for a disk membrane x = 0.33 with a thickness of 1.2 mm. By reducing the thickness of the disk membrane to 0.8 mm, the oxygen flux increased to 0.77 ml min⁻¹ cm⁻², suggesting both surface kinetics and ion diffusion controlled oxygen flux, though the former was more prominent at higher temperatures. For disk membranes x = 0.45–0.60, the perovskite structure changed to tetragonal and hexagonal, and the oxygen flux was insignificant below 900 °C, clearly indicating electron conduction properties only. However, for two compositions with relatively high bismuth content, e.g. x = 0.55 and 0.60, there was a sudden and significant rise of oxygen permeability above 900 °C, by more than one order of magnitude. These materials changed conduction behavior from metallic to semiconductor at around 900 °C. These results suggest the advent of mixed ionic electronic conducting properties caused by the structure transition as bismuth ions changed their valence states to compensate for the oxygen vacancies formed within the perovskite lattices.

Novel B-site ordered double perovskite Ba2Bi0.1Sc0.2Co1.7O6-x for highly efficient oxygen reduction reaction

Double perovskite Ba₂Bi_0.1Sc_0.2Co_1.7O_6-x (BBSC) demonstrates low polarization resistance between 600 and 750 °C due to the high oxygen reduction rate of BBSC as reflected by its large D_V and k values, which are derived from the face centered cubic structure and high cobalt content.

Microphase separation in double crystalline poly (ethylene oxide)-block-poly (caprolactone)/poly (4-vinyl phenol) blends

We report microphase separation induced by competitive hydrogen bonding interactions in double crystalline diblock copolymer/homopolymer blends of poly(ethylene oxide)-block-poly(ɛ-caprolactone) (PEO-b-PCL) and poly(4-vinyl phenol) (PVPh). The diblock copolymer PEO-b-PCL consists of two immiscible crystallizable blocks wherein both PEO and PCL blocks can form hydrogen bonds with PVPh. In these A-b-B/C diblock copolymer/homopolymer blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically PVPh and PEO block interact strongly whereas PVPh and PCL block interact weakly. The TEM and SAXS results show that the cubic PEO-b-PCL diblock copolymer changes into ordered hexagonal cylindrical morphology upon addition of 20 wt % PVPh followed by disordered bicontinuous phase in the blend with 40 wt % PVPh and then to homogenous phase at 60 wt% PVPh and above. Up to 40 wt % PVPh there is only weak interaction between PVPh and PCL due to the selective hydrogen bonding between PVPh and PEO. However, with higher PVPh concentration, the blends become homogeneous since a sufficient amount of PVPh is available to form hydrogen bonds with both PEO and PCL. A structural model was proposed to explain the self-assembly and morphology of these blends based on the experimental results obtained. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen bonding interaction between each block of the block copolymer and the homopolymer (1-3).

Self-assembly and competitive hydrogen bonding interactions of double crystalline diblock copolymer/homopolymer blends

In the present work, nanostructured blends were prepared from double crystalline diblock copolymer poly(ɛ-caprolactone)-block-poly(ethylene oxide) and homopolymer poly(4-vinyl phenol) (PVPh). The diblock copolymer PEO-b-PCL consists of two immiscible crystallizable blocks wherein both PEO and PCL blocks can form hydrogen bonds with PVPh. In these A-b-B/C diblock copolymer/homopolymer blends, microphase separation takes place due to the disparity in intermolecular interactions; specifically, PVPh and PEO block interact strongly whereas PVPh and PCL block interact weakly. The TEM and SAXS results show that the cubic PEO-b-PCL diblock copolymer changes into ordered hexagonal cylindrical morphology upon addition of 20 wt % PVPh followed by disordered bicontinuous phase in the blend with 40 wt % PVPh and then to homogeneous phase at 60 wt % PVPh and above blends. Up to 40 wt % PVPh there is only weak interaction between PVPh and PCL due to the selective hydrogen bonding between PVPh and PEO. However, with higher PVPh concentration, the blends become homogeneous since a sufficient amount of PVPh is available to form hydrogen bonds with both PEO and PCL. A structural model was proposed to explain the self-assembly and microphase morphology of these blends based on the experimental results obtained. The formation of nanostructures and changes in morphologies depend on the relative strength of hydrogen bonding interaction between each block of the block copolymer and the homopolymer.

Deactivation and regeneration of oxygen reduction reactivity on double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x cathode for intermediate-temperature solid oxide fuel cells

in situ high-temperature X-ray diffraction and thermal gravimetric- differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba₂Bi_0.1Sc_0.2Co _1.7O_6-x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-dependent thermal expansion coefficient which relates well with its structure evolution. Furthermore, the oxygen reduction reaction (ORR) of BBSC was probed by symmetrical cell and three-electrode configurations. The presence of hexagonal phase at 700 °C rarely affects the ORR performance of BBSC as evidenced by a slight increase of its area-specific resistance (ASR) value following 48 h of testing in this three-electrode configuration. This observation is in contrast to the commonly held point of view that noncubic phase deteriorates performance of perovskite compounds (especially in oxygen transport applications). Moreover, cathodic polarization treatment, for example, current discharge from BBSC (tested in three-electrode configuration), can be utilized to recover the original ORR performance. The cubic structure seems to be retained on the cathodic polarization - the normal cathode operating mode in fuel cells. Stable 72-h performance of BBSC in cathodic polarization mode further confirms that despite the presence of phase impurities, BBSC still demonstrates good performance between 500 and 700 °C, the desired intermediate operating temperature in solid oxide fuel cells.

A single-step synthesized cobalt-free barium ferrites-based composite cathode for intermediate temperature solid oxide fuel cells

Cobalt-free perovskite cathode with excellent oxygen reduction reaction (ORR) properties below 800 °C is a key material toward wide implementation of intermediate-temperature solid oxide fuel cells. This work reports the phase structure, microstructure and performance of such cathode based on the composite phases of triclinic Ba0.9Bi0.1FeO3-δ, cubic BaFeO3 and orthorhombic BaFe2O4 prepared by sol–gel route. The resultant barium ferrites composite cathode exhibits uniform particles, pores and elements distribution. In particular, favorable ORR properties of this cathode is demonstrated by very low interfacial resistance of only 0.036 and 0.072 Ω cm2 at 750 and 700 °C and maximum power density of 1295 and 840 mW cm−2 at 750 and 700 °C.

Investigation of cell shape effect on the mechanical behaviour of open-cell metal foams

The mechanical behaviours of metal foams greatly depend on their cell topology, including cell shape, cell size etc. as well as relative density and material properties of the cell wall. However, the cell shape effect on the mechanical behaviours of such materials appears to be ignored in previous research. In this paper, both analytic and finite element models are developed and employed to investigate the effect of cell shape on the mechanical behaviour of open-cell magnesium alloy (AZ91) foams under compression, including deformation modes and failure modes. For numerical modelling, both two-dimensional (2-D) and three-dimensional (3-D) finite element models are developed to predict the compressive behaviours of typical open-cell metal foams and capture the deformation modes and failure mechanisms. Two typical cell shapes i.e. cubic and diamond are taken into consideration. To validate these models, the analytic and numerical results are compared to the experimental data. Both the numerical and experimental data indicate that the cell shape significantly affects the compression behaviour of open-cell metal foams. In general, numerical results from the three-dimensional solid-element model show better agreement with the experimental results than those from other finite element models.

Efficient subwindow search with submodular score functions

Subwindow search aims to find the optimal subimage which maximizes the score function of an object to be detected. After the development of the branch and bound (B&B) method called Efficient Subwindow Search (ESS), several algorithms (IESS [2], AESS [2], ARCS [3]) have been proposed to improve the performance of ESS. For nn images, IESS's time complexity is bounded by O(n³) which is better than ESS, but only applicable to linear score functions. Other work shows that Monge properties can hold in subwindow search and can be used to speed up the search to O(n³), but only applies to certain types of score functions. In this paper we explore the connection between submodular functions and the Monge property, and prove that sub-modular score functions can be used to achieve O(n³) time complexity for object detection. The time complexity can be further improved to be sub-cubic by applying B&B methods on row interval only, when the score function has a multivariate submodular bound function. Conditions for sub-modularity of common non-linear score functions and multivariate submodularity of their bound functions are also provided, and experiments are provided to compare the proposed approach against ESS and ARCS for object detection with some nonlinear score functions.

Crystal structures and textures in the hot-forged Ni-Mn-Ga shape memory alloys

Three ferromagnetic shape-memory alloys with the chemical compositions of Ni₅₃Mn₂₅Ga₂₂, Ni₄₈Mn₃₀Ga₂₂, and Ni₄₈Mn₂₅Ga₂₂Co₅ were prepared by the induction-melting and hot-forging process. The crystal structures were investigated by the neutron powder diffraction technique, showing that Ni₅₃Mn₂₅Ga₂₂ and Ni₄₈Mn₂₅Ga₂₂Co₅ have a tetragonal, 14/mmm martensitic structure at room temperature, while Ni₄₈Mn₃₀Ga₂₂ has a cubic, L2₁ austenitic structure at room temperature. The development of textures in the hot-forged samples shows the in-plane plastic flow anisotropy from the measured pole figures by means of the neutron diffraction technique. Significant texture changes were observed for the Ni₄₈Mn₂₅Ga₂₂Co₅ alloy after room temperature deformation, which is due to the deformation-induced rearrangements of martensitic variants. An excellent shape-memory effect (SME) with a recovery ratio of 74 pct was reported in this Ni₄₈Mn₂₅Ga₂₂Co₅ polycrystalline alloy after annealing above the martensitic transformation temperature, and the “shape-memory” influence also occurs in the distributions of grain orientations.

Influence of grain size and training temperature on strain of polycrystalline Ni50Mn29Ga21 samples

The alloy Ni-Mn-Ga aroused great interest for application as a magnetic shape memory (MSM) material. This effect is caused by reorientation of twin variants by an external magnetic field. So far, most of the experiments were concentrated on single crystals. But, the MSM effect can also be realised in polycrystals which can be prepared much more efficiently. Here, polycrystalline samples were prepared by directional solidification with a <100> fibre texture of the high temperature cubic austenitic phase parallel to the heat flow. Afterwards, a heat treatment was applied for chemical homogenisation and stress relaxation in the austenitic state. Then the samples were heated up to the austenitic state and cooled down under load. The microstructure was analysed by Electron Back Scatter Diffraction (EBSD) before and after that treatment. Mechanical training at room temperature and 40°C was tracked by recording stress-strain curves. By increasing the number of training cycles the strain also increases. The influence of different training temperatures was investigated on samples with different grain sizes.

Crystal structures and textures of hot forged Ni48Mn30Ga22 alloy investigated by neutron diffraction technique

A ferromagnetic shape memory alloy of Ni48Mn30Ga22 prepared by induction melting was successfully hot forged. Strong textures and a large anisotropy of in plane plastic flow were developed during the hot forging process. The crystal structures, both in austenitic and martensitic states, were investigated by means of neutron powder diffraction technique. The result suggests that Ni48Mn30Ga22 has a cubic L21 Heusler structure at room temperature, the same as that in the stoichiometric Ni2MnGa. When cooled to 243 K, the Ni48Mn30Ga22 alloy changes into a seven layered orthorhombic martensitic structure. No substantial change of the neutron diffraction pattern was observed upon further cooling to 19 K, indicating that there is no intermartensitic transformation in the investigated alloy, which is different from the transformation processes in the Ni–Mn–Ga alloys with higher martensitic transformation temperatures.

High-pressure structural transitions of Sc2O3 by X-ray diffraction, raman spectra, and ab initio calculations

The high-pressure behavior of scandium oxide (Sc₂O₃) has been investigated by angle-dispersive synchrotron powder X-ray diffraction and Raman spectroscopy techniques in a diamond anvil cell up to 46.2 and 42 GPa, respectively. An irreversible structural transformation of Sc₂O₃ from the cubic phase to a monoclinic high-pressure phase was observed at 36 GPa. Subsequent ab initio calculations for Sc₂O₃ predicted the phase transition from the cubic to monoclinic phase but at a much lower pressure. The same calculations predicted a second phase transition at 77 GPa from the monoclinic to hexagonal phase.

Structural phase transformations of Mg3N2 at high pressure : experimental and theoretical studies

The structural behavior of Mg₃N₂ has been investigated up to 40.7 GPa at room temperature by means of angle-dispersive X-ray diffraction. A reversible, first-order structural phase transition from the ambient cubic phase (Ia3̅) to a high-pressure monoclinic phase (C2/m) is found to start at ~ 20.6 GPa and complete at ~ 32.5 GPa for the first time. The equation of state determined from our experiments yields bulk moduli of 110.7(2) and 171.5(1) GPa for the cubic and monoclinic phases, respectively, indicating higher incompressibility of the high-pressure phase of Mg₃N₂. First-principles calculations reproduced the phase stability and transition pressure determined in our experiment. In addition, a second phase transition from the monoclinic phase to a hexagonal phase (P3̅m₁) was predicted around 67 GPa for Mg₃N₂. The electronic band structures of three phases of Mg₃N₂ are also calculated and discussed.