Project description:The separation of oxygen from air by means of inorganic ceramic membranes requires gas-tight ceramic-metal joints that enable reliable permeation operation in the oxygen partial pressure gradient at 850 °C. Reactive air brazing is a promising method to solve this challenge. However, reactive air brazed BSCF membranes suffer from a significant strength degradation that is caused by unhindered diffusion from the metal component during aging. In this study, we investigated how diffusion layers applied on the austenitic steel AISI 314 influence the bending strength of BSCF-Ag3CuO-AISI314 joints after aging. Three different approaches were compared as diffusion barriers: (1) aluminizing via pack cementation, (2) spray coating with NiCoCrAlReY, and (3) spray coating with NiCoCrAlReY and an additional 7YSZ top layer. Coated steel components were brazed to bending bars and aged for 1000 h at 850 °C in air prior to four-point bending and subsequent macroscopic as well microscopic analyses. In particular, coating with NiCoCrAlReY showed low-defect microstructures. The characteristic joint strength was raised from 17 MPa to 35 MPa after 1000 h aging at 850 °C. In addition, the dominant delamination fracture between the steel and the mixed oxide layer, observed in the reference series with uncoated steel, could be replaced by mixed and ceramic fractures of higher strength. The effect of residual joint stresses on the crack formation and path is analyzed and discussed. Chromium poisoning could no longer be detected in the BSCF, and interdiffusion through the braze was effectively reduced. Since the strength degradation of reactive air brazed joints is mainly caused by the metallic joining partner, the findings on the effect of the diffusion barriers in BSCF joints might be transferred to numerous other joining systems.
Project description:Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal-based catalysts. We report the enhanced performance of Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering. The surface nickel oxide layer of the Ni substrate and the thickness of the BSCF film were further used to tune the intrinsic OER activity and stability of the BSCF catalyst by optimizing the electronic configuration of the transition metal cations in BSCF via the interaction between the nanofilm and the surface nickel oxide, which enables up to 315-fold enhanced mass-specific activity compared to the crystalline BSCF bulk phase. Moreover, the amorphous BSCF-Ni foam anode coupled with the Pt-Ni foam cathode demonstrated an attractive small overpotential of 0.34 V at 10 mA cm-2 for water electrolysis, with a BSCF loading as low as 154.8 μg cm-2.
Project description:The development of highly active and cost-effective catalysts based on noble metal free oxygen electro-catalysis is critical to energy storage and conversion devices. Herein, we highlight a plasma-treated Bi0.1(Ba0.5Sr0.5)0.9Co0.8Fe0.2O3-δ perovskite (denoted as P-Bi0.1BSCF) as a promising catalyst for oxygen evolution reaction (OER) in alkaline media. H2/Ar plasma engraving could significantly increase electrochemically active O22-/O- concentration and tune the electronic structure of Co ions efficiently, and consequently tailor the intrinsic electrocatalytic ability for OER. Of note, P-Bi0.1BSCF, with unique crystalline core/amorphous shell structure, exhibits an enhanced intrinsic OER activity and higher stability than the noble metal IrO2 catalyst, which outperforms most of the reported perovskite catalysts. The present work provides new insights into exploring efficient catalysts for OER, and it suggests that, in addition to the extensively applied for surface treatment of various catalysts such as carbons and metal oxides, the plasma engraved perovskite materials also exhibits great potential as precious metal-free catalysts.
Project description:The electrochemical reduction of molecular oxygen is a fundamental process in Solid Oxide Fuel Cells and requires high efficiency cathode materials. Two La0.25Ba0.25Sr0.5Co0.8Fe0.2O3-δ-based perovskite compounds were prepared by solution combustion synthesis, and characterized for their structural, microstructural, surface, redox and electrochemical properties as potential cathodes in comparison with Ba0.5Sr0.5Co0.8Fe0.2O3-δ and La0.5Sr0.5Co0.8Fe0.2O3-δ perovskites. Results highlighted that calcination at 900 °C led to a "bi-perovskite heterostructure", where two different perovskite structures coexist, whereas at higher calcination temperatures a single-phase perovskite was formed. The results showed the effectiveness of the preparation procedures in co-doping the A-site of perovskites with barium and lanthanum as a strategy to optimize the cathode's properties. The formation of nanometric heterostructure co-doped in the A-site evidenced an improvement in oxygen vacancies' availability and in the redox properties, which promoted both processes: oxygen adsorption and oxygen ions drift, through the cathode material, to the electrolyte. A reduction in the total resistance was observed in the case of heterostructured material.
Project description:Bulk Bi0.5Sr0.5Fe0.5Cr0.5O3 (BSFCO) is a new compound comprising the R3c structure. The structural, magnetic property and exchange bias (EB) details are investigated. The material was in the super-paramagnetic (SP) state at room temperature. Exchange bias usually occurs at the boundary between different magnetic states after field cooling (HFC) acts on the sample. Here the result shows that changing HFC from 1 to 6 T reduces the HEB value by 16% at 2 K at the same time. Meanwhile, HEB diminishes as the ferromagnetic layer thickness increases. The variation of (the thickness of ferromagnetic layer) tFM with the change of HFC leads to the tuning of HEB by HFC in BSFCO bulk. These effects are obviously different from the phenomenon seen in other oxide types.
Project description:A multiferroic composite consisting of single phases of 30 vol.% magnetostrictive ferrite and 70 vol.% relaxor ferroelectric has been synthesized. The ferrite exhibits a diffuse dielectric phase transition (DPT)with the transition temperature varying from 450 K to 600 K and an activation energy of 0.29 eV. Magnetically, it has a soft behavior with 70 emug-1 saturation magnetization and a Curie transition at ~620 K. The relaxor ferroelectric phase on the other hand exhibits two clear DPTs at 390 K-400 K and 150 K-300 K. The composite of these two shows a soft ferromagnetic behavior reminiscent of the ferrite along with 3 DPTs. There is strong coupling between the two orders - magnetostrictive and piezoelectric in the composite. The capacitance decreases by 45% in the presence of magnetic field corresponding to a sensitivity of 0.9% kOe-1, an extremely large value. The magnetoelectric coupling constant is found to be 20.6 mVcm-1Oe-1, a large value for a bulk composite. Microwave band stop filters of different thicknesses made from the composite have resonant frequencies which upshift in the presence of magnetic field indicating a multiferroic behavior with possibility for electric field tuning of resonant frequency.
Project description:Ferroelectric materials exhibiting switchable and spontaneous polarization have strong potential to be utilized in various novel electronic devices. Solid solutions of different perovskite structures induce the coexistence of various phases and enhance the physical functionalities around the phase coexistence region. The construction of phase diagrams is important as they describe the material properties, which are linked to the underpinning physics determining the system. Here we present the phase diagram of (K0.5Na0.5NbO3)-(Ba0.5Sr0.5TiO3) (KNN-BST) system as a function of composition and their associated physical properties. Lead-free (1 - x)KNN-xBST (0 ≤ x ≤ 0.3) solid solution ceramics were synthesized by conventional solid-state reaction technique. The X-ray diffraction and Raman spectroscopic studies indicate composition-dependent structural phase transitions from an orthorhombic phase for x = 0 to orthorhombic + tetragonal dual-phase (for 0.025 ≤ x ≤ 0.15), then a tetragonal + cubic dual-phase (x = 0.2) and finally a cubic single phase for x ≥ 0.25 at room temperature (RT). Among these, the orthorhombic + tetragonal dual-phase system shows an enhanced value of the dielectric constant at room temperature. The phase transition temperatures, orthorhombic to tetragonal (TO-T) and tetragonal to cubic (TC), decrease with the increase in BST concentrations. The ferroelectric studies show a decrease of both 2Pr and EC values with a rise in BST concentration and x = 0.025 showed a maximum piezoelectric coefficient.
Project description:Efficient conversion of methane to value-added products such as olefins and aromatics has been in pursuit for the past few decades. The demand has increased further due to the recent discoveries of shale gas reserves. Oxidative and non-oxidative coupling of methane (OCM and NOCM) have been actively researched, although catalysts with commercially viable conversion rates are not yet available. Recently, [Formula: see text] (SFMO-075Fe) has been reported to activate methane in an electrochemical OCM (EC-OCM) set up with a C2 selectivity of 82.2%1. However, alkaline earth metal-based materials are known to suffer chemical instability in carbon-rich environments. Hence, here we evaluated the chemical stability of SFMO in carbon-rich conditions with varying oxygen concentrations at temperatures relevant for EC-OCM. SFMO-075Fe showed good methane activation properties especially at low overpotentials but suffered poor chemical stability as observed via thermogravimetric, powder XRD, and XPS measurements where SrCO3 was observed to be a major decomposition product along with SrMoO3 and MoC. Nevertheless, our study demonstrates that electrochemical methods could be used to selectively activate methane towards partial oxidation products such as ethylene at low overpotentials while higher applied biases result in the complete oxidation of methane to carbon dioxide and water.
Project description:We report about an in situ study of crystalline structural changes during thermal treatment of a Ba0.5Sr0.5TiO3 (BSTO) film grown on MgO. The study covers the complete cycle of heating, annealing and cooling and reveals simultaneous phenomena of phase transitions and strain evolution, which have been characterized by in situ 2D reciprocal space mapping (2D-RSM) using high-resolution synchrotron x-ray diffraction in coplanar and grazing incidence geometries. In this way, temperature induced phase transformation from the BSTO2 to the BSTO1 phase has been monitored and the appearance of a further crystalline phase was detected. Moreover, for both BSTO phases, transitions between in-plane compressive and tensile states have been determined during thermal treatment. Furthermore, a contraction of the out-of-plane lattice components has been observed during the annealing phase while the in-plane lattice components remain leading to the change of the residual in-plane strain towards tensile state. The in situ 2D-RSM findings provide valuable and versatile insights into strain engineering and structure modification upon thermal treatment.
Project description:A facile two-step strategy has been reported for the preparation of a ternary 3D reduced graphene oxide/Ni0.5Zn0.5Fe2O4/polyindole nanocomposite (GNP) and this composite is applied as an electrode material for supercapacitor applications. Remarkably, Ni0.5Zn0.5Fe2O4 nanoparticles (NZF) decorated on reduced graphene oxide (GN2) are achieved by a facile hydrothermal method followed by coating with polyindole (PIN) through an in situ emulsion polymerization process. The structure, porosity, morphology, and thermal stability of the resulting ternary GNP hybrid material were characterized via X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) surface area measurements, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). This combination of hybrid material has a favorable mesoporous structure that enables high exposure of active sites for fast electron transport for supercapacitor applications. We demonstrate here that the ternary GNP hybrid electrode material is capable of delivering a favorable specific capacitance of ∼320 F g-1 at 0.3 A g-1 within the potential range from -0.1 to 1 V, with desirable rate stability and excellent cycling stability in the three-electrode system. Furthermore, an asymmetric supercapacitor (ASC) of a two-electrode configuration was fabricated using 3D RGO and GNP as the negative and positive electrodes, respectively. Such a device manifests a favourable C sp of 48.9 F g-1 at 0.5 A g-1 and retains stability of 84% even after 2000 cycles. This ASC device exhibits a significant energy density of 16.38 W h kg-1 at a power density of 1784 W kg-1. The synergistic effects of pseudo and double layer capacitive contributions from PIN and GN2 make this ternary GNP hybrid electrode material of great promise in supercapacitor applications.