CO-PrOx over nano-Au/TiO2: Monolithic catalyst performance and empirical kinetic model fitting

In this work, the performance of ceramic monoliths washcoated with Au/TiO2 is studied on CO preferential oxidation (CO-PrOx) reaction in H2-rich environments under a wide range of operating conditions of practical interest. The parameter estimation of a nonlinear kinetic empirical model representing this system is made via genetic algorithms by fitting the model predictions against our laboratory observations. Parameter uncertainty leading to inaccurate predictions is often present when kinetic models with nonlinear rate equations are considered. Here, after the fitting was concluded, a statistical study was conducted to determine the accuracy of the parameter estimation. Activation energies of ca. 30 kJ/mol and 55 kJ/mol were adjusted for CO and H2 oxidations, respectively. The catalyst showed appropriate activity and selectivity values on the CO oxidation on a H2-rich environment. After ca. 45 h on stream the catalyst showed no deactivation. Results show that the model is suitable for reproducing the behavior of the CO-PrOx reactions and it can be used in the design of reactors for hydrogen purification.Peer ReviewedPostprint (author's final draft

Direct-methane anode-supported solid oxide fuel cells fabricated by aqueous gel-casting

Direct methane Solid Oxide Fuel Cells (SOFCs) operated under catalytic partial oxidation (CPOX) conditions are investigated, focusing on the processing of the anode support and the anode deactivation caused by carbon deposition. Anode-supported SOFCs based on gadolinium-doped ceria (GDC) electrolyte, and NiO-GDC anode support were fabricated by the gel-casting method. Suitable aqueous slurries formulations of NiO–GDC were prepared, starting NiO-GDC nanocomposite powders, agarose as gelling agent and rice starch as pore former. Electrochemical and mechanical tests evidenced that the support of 550 ± 50 µm thickness and 10 wt% pore former is a good candidate for direct-methane SOFCs. The cells operating under stoichiometric conditions of CPOX reached a performance of 0.64 W·cm−2 at 650 ºC, a very close value to that measured under humidified hydrogen (0.71 W·cm−2). The best electrochemical stability of the cell is achieved at a CH4/O2 ratio of 2.5, showing no evidence of carbon deposition and reducing nickel re-oxidation significantly

Fracture micromechanisms and mechanical behavior of YBCO bulk superconductors at 77 and 300 K

In this study two YBa2Cu3O7−δ bulk superconductors were evaluated, with the aim of analyzing the influence of the processing method (TSMG and Bridgman) and the test temperature on their mechanical behavior. The relationship between their mechanical properties and fracture micromechanisms has also been studied. Both materials were tested at room and at service temperature. TPB tests were carried out to determine their mechanical behavior, strength and toughness. Moreover, one of the two materials, characterized by transversal microstructural anisotropy, was tested in two directions. Hardness of both materials at nano and micro scale was studied. The results show that the mechanical behavior of the materials is controlled by the defects and cracks that have been introduced during the processing of the materials. A good degree of agreement was found between the experimental crack defects detected by means of SEM and those gathered from the fracture mechanical analysis of the experimental dat

Focused ion beam tomography of WC-Co cemented carbides

The microstructure of three different grades of WC-Co cemented carbides (hardmetals) has been reconstructed in three dimensions after sequential images obtained by focused ion beam. The three dimensional microstructual parameters are compared against the well-known two dimensional parameters of grain size, phase percentages and mean free path. Results show good agreement with the exception of individual grain recognition, which could not be univocally segmented. In the case of mean free path, the three-dimensional image depicts a more realistic description of the metal interconnections in the composite. Aiming for a simple example of direct application of these FIB tomography outcomes, reconstructed real microstructure for the coarser hardmetal grade studied was translated in a finite element modelling mesh, and elastic residual stresses were estimated from sintering to room temperature. Calculated thermal stresses agree with experimental results and show significant local variations in their value due to the complex microstructure of cemented carbides.Postprint (author's final draft

Nanoindentation of Bridgman YBCO samples

In this study, the mechanical properties of YBa2Cu3O7−x, obtained by the Bridgman technique, were examined using a Berkovich tip indenter on the basal plane (0 0 1). Intrinsic hardness was measured by nanoindentation tests and corrected using the Nix and Gao model for this material. Furthermore, Vickers hardness tests were performed, in order to determine the possible size effect on these measurements. The results showed an underestimation of the hardness value when the tests were performed with large loads. Moreover, the elastic modulus of the Bridgman samples was 128 ± 5 GPa. Different residual imprints were visualised by atomic force microscopy and a focused ion beam, in order to observe superficial and internal fracturing. Mechanical properties presented a considerable reduction at the interface. This effect could be attributed to internal stress generated during the texturing process. In order to corroborate this hypothesis, an observation using transmission electron microscopy was performed

Identification of highly selective surface pathways for methane dry reforming using mechanochemical synthesis of Pd-CeO2

The methane dry reforming (DRM) reaction mechanism was explored via mechanochemically prepared Pd/CeO2 catalysts (PdAcCeO2M), which yield unique Pd–Ce interfaces, where PdAcCeO2M has a distinct reaction mechanism and higher reactivity for DRM relative to traditionally synthesized impregnated Pd/CeO2 (PdCeO2IW). In situ characterization and density functional theory calculations revealed that the enhanced chemistry of PdAcCeO2M can be attributed to the presence of a carbon-modified Pd0 and Ce4+/3+ surface arrangement, where distinct Pd–CO intermediate species and strong Pd–CeO2 interactions are activated and sustained exclusively under reaction conditions. This unique arrangement leads to highly selective and distinct surface reaction pathways that prefer the direct oxidation of CHx to CO, identified on PdAcCeO2M using isotope labeled diffuse reflectance infrared Fourier transform spectroscopy and highlighting linear Pd–CO species bound on metallic and C-modified Pd, leading to adsorbed HCOO [1595 cm–1] species as key DRM intermediates, stemming from associative CO2 reduction. The milled materials contrast strikingly with surface processes observed on IW samples (PdCeO2IW) where the competing reverse water gas shift reaction predominates.Peer ReviewedPostprint (published version

Dynamic deformation of metastable austenitic stainless steels at the nanometric length scale

Cyclic indentation was used to evaluate the dynamic deformation on metastable steels, particularly in an austenitic stainless steel, AISI 301LN. In this work, cyclic nanoindentation experiments were carried out and the obtained loading-unloading (or P-h) curves were analyzed in order to get a deeper knowledge on the time-dependent behavior, as well as the main deformation mechanisms. It was found that the cyclic P-h curves present a softening effect due to several repeatable features (pop-in events, ratcheting effect, etc.) mainly related to dynamic deformation. Also, observation by transmission electron microscopy highlighted that dislocation pile-up is the main responsible of the secondary pop-ins produced after certain cycles.Peer ReviewedPostprint (author's final draft