Na2M2(SO4)(3) (M = Fe, Mn, Co and Ni): towards high-voltage sodium battery applications

Sodium-ion-based batteries have evolved as excellent alternatives to their lithium-ion-based counterparts due to the abundance, uniform geographical distribution and low price of Na resources. In the pursuit of sodium chemistry, recently the alluaudite framework Na2M2(SO4)(3) has been unveiled as a high-voltage sodium insertion system. In this context, the framework of density functional theory has been applied to systematically investigate the crystal structure evolution, density of states and charge transfer with sodium ions insertion, and the corresponding average redox potential, for Na2M2(SO4)(3) (M = Fe, Mn, Co and Ni). It is shown that full removal of sodium atoms from the Fe-based device is not a favorable process due to the 8% volume shrinkage. The imaginary frequencies obtained in the phonon dispersion also reflect this instability and the possible phase transition. This high volume change has not been observed in the cases of the Co- and Ni-based compounds. This is because the redox reaction assumes a different mechanism for each of the compounds investigated. For the polyanion with Fe, the removal of sodium ions induces a charge reorganization at the Fe centers. For the Mn case, the redox process induces a charge reorganization of the Mn centers with a small participation of the oxygen atoms. The Co and Ni compounds present a distinct trend with the redox reaction occurring with a strong participation of the oxygen sublattice, resulting in a very small volume change upon desodiation. Moreover, the average deintercalation potential for each of the compounds has been computed. The implications of our findings have been discussed both from the scientific perspective and in terms of technological aspects.

Anomalous Thermal Stability of Nd-Fe-Co-Al Bulk Metallic Glass

The thermal stability of Nd60Fe20Co10Al10 bulk metallic glass (BMG) has been studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), isochronal dilatation and compression tests. The results show that the glass transition of the BMG takes place quite gradually between about 460 and 650 K at a heating rate of 0.17 K/s. Several transformation processes are observed during continuous heating with the first crystallization process beginning at about 460 K, while massive crystallization takes place near the solidus temperature of the alloy. The positive heat of mixing between the two major constituents, Nd and Fe, and, consequently, a highly inhomogeneous composition of the attained amorphous phase are responsible for the anomalous thermal stability in this system. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Nonequilibrium microstructures and their evolution in a Fe-Cr-W-Ni-C laser clad coating

The laser-solidified microstructural and compositional characterization and phase evolution during tempering at 963 K were investigated using an analytical transmission electron microscope with energy dispersive X-ray analysis. The cladded alloy, a powder mixture of Fe, Cr, W, Ni, and C with a weight ratio of 10:5:1:1:1, was processed with a 3 kW continuous wave CO2 laser. The processing parameters were 16 mm/s beam scanning speed, 3 mm beam diameter. 2 kW laser power, and 0.3 g/s feed rate. The coating was metallurgically bonded to the substrate, with a maximum thickness of 730 mu m, a microhardness of about 860 Hv and a volumetric dilution ratio of about 6%. Microanalyses revealed that the cladded coating possessed the hypoeutectic microstructure comprising the primary dendritic gamma-austenite and interdendritic eutectic consisted of gamma-austenite and M7C3 carbide. The gamma-austenite was a non-equilibrium phase with extended solid solution of alloying elements and a great deal of defect structures, i.e. a high density of dislocations, twins, and stacking faults existed in gamma phase. During high temperature aging, in situ carbide transformation occurred of M7C3 to M23C6 and M6C. The precipitation of M23C6, MC and M2C carbides from austenite was also observed.

铁基抗高温磨损激光熔覆涂层强韧设计和研究II:Fe-Cr-C-W-Ni激光熔覆层的微观组织及性能

本文以对热工模具进行失效分析的基础上，利用激光熔覆技术，在５ＣｒＭｎＭｏ基础上设计并制备强韧兼备的抗高温磨损涂层。

Modeling Nonlinear Peeling of Ductile Thin Films-Critical Assessment of Analytical Bending Models Using FE Simulations

Three analytical double-parameter criteria based on a bending model and a two-dimensional finite element analysis model are presented for the modeling of ductile thin film undergoing a nonlinear peeling process. The bending model is based on different governing parameters: (1) the interfacial fracture toughness and the separation strength, (2) the interfacial fracture toughness and the crack tip slope angle, and (3) the interfacial fracture toughness and the critical Mises effective strain of the delaminated thin film at the crack tip. Thin film nonlinear peeling under steady-state condition is solved with the different governing parameters. In addition, the peeling test problem is simulated by using the elastic-plastic finite element analysis model. A critical assessment of the three analytical bending models is made by comparison of the bending model solutions with the finite element analysis model solutions. Furthermore, through analyses and comparisons for solutions based on both the bending model and the finite element analysis model, some connections between the bending model and the finite element analysis model are developed. Moreover, in the present research, the effect of different selections for cohesive zone shape on the ductile film peeling solutions is discussed.

La participación política de los intelectuales durante la transición democrática : el Grupo Esmeralda y el prresidente Alfonsín

Resumen: El presente artículo tiene por objeto analizar las relaciones que se establecieron entre un grupo de intelectuales de izquierda y el presidente radical Raúl Alfonsín durante la transición democrática en la Argentina. Se describirán en primer lugar los desplazamientos teóricos de la izquierda intelectual marcados por el exilio mexicano; en segundo lugar, las características del campo cultural en la transición democrática en los ochenta, centrándose en la producción de los intelectuales vinculados con la revista Punto de Vista y el Club de Cultura Socialista y, por último, los vínculos que se establecieron entre el presidente Alfonsín y los intelectuales de la izquierda renovada, analizando los dilemas ético-políticos que debieron enfrentar. La construcción de sentido en torno a un personaje político, en el que los intelectuales veían la posibilidad de que se convirtiera en un moderno líder socialdemócrata, es la hipótesis a partir de la cual intenta explicarse la vinculación, siguiendo las teorías de Pierre Bourdieu.

Temperature Dependence of the Tribological Properties of Laser Re-Melted Al-Cu-Fe Quasicrystalline Plasma Sprayed Coatings

The aim of this study was to investigate the effect of temperature on tribological properties of plasma-sprayed Al-Cu-Fe quasicrystal (QC) coating after laser re-melting treatment. The laser treatment resulted in a more uniform, denser and harder microstructure than that of the as-sprayed coatings. Tribological experiments on the coatings were conducted under reciprocating motion at high frequency in the temperature range from 25 to 650 degreesC. Remarkable influence of temperature on the friction behavior of the coating was recorded and analyzed. Microstructural analysis indicated that the wear mechanisms of the re-melted QC coatings changed from abrasive wear at room temperature, to adhesive wear at 400 degreesC and severe adhesive wear at 650 degreesC owing to the material transfer of the counterpart ball. It was also observed that the ratio of the icosahedral (i)-phase to beta-Al-50(Fe,CU)(50) phase in the coating was higher after test at 400 'C than that at 650 'C. The variation of the ratio UP of coating and of the property of the counterpart ball and coating with the temperature are the two main factors influencing the wear mechanisms and value of the friction coefficient.

Santo Tomás y las razones de la fe

Pocos días antes del cierre del Concilio Vaticano II, el papa Pablo VI expresaba a los miembros de la Academia Santo Tomás de Aquino lo siguiente: …vuestros estudios pueden contribuir a disipar el menosprecio de un cierto número de creyentes que hoy son tentados por un renaciente fideísmo. Al no atribuir valor más que al pensamiento de tipo científico, y desconfiando de las certezas propias de la sabiduría filosófica, son llevados a fundar sobre una opción de la voluntad su adhesión al orden de las verdades metafísicas. Frente a esta abdicación de la inteligencia, que tiende a arruinar la doctrina tradicional de los preámbulos de la fe, vuestros trabajos deben evocar el valor indispensable de la razón natural, solemnemente afirmado por el Concilio Vaticano I (Dz-Sch. 3004, 3009, 3015 y 3026), en conformidad con la enseñanza constante de la Iglesia, de la que Santo Tomás de Aquino es uno de los testimonios más autorizados y eminentes...

La independencia política, de la segunda escolástica a “Maastricht” (y vuelta)

Resumen: El artículo trata la cuestión del poder político como superiorem non recognoscens en Vitoria y Suárez, y vincula los principios de la escolástica aristotélica del siglo de oro con un fallo contemporáneo clave, con el fin de destacar el sentido y valor del principio de independencia política, un eje de los fundamentos del derecho internacional público moderno afirmado por la escuela española.

La práctica política en la Roma antigua, especificidad y debates

En esta intervención, desarrollaré algunas consideraciones sobre la política en el mundo romano antiguo y el reciente debate acerca de ella. Me refiero a la política como práctica; entendiendo por esto lo que sea funcional a los mecanismos de la vida pública, a la formación del consenso, al ejercicio del poder, al cursus honorum en sus varios niveles, a los procesos decisorios y a la determinación de los rumbos del gobierno.

Una aproximación al concepto de “razón de estado” en Giovanni Botero desde la teoría política de Carl Schmitt

Resumen: El trabajo se propone analizar la conceptualización del término “razón de Estado” en el teólogo piamontés Giovanni Botero a la luz de las teorías políticas de Carl Schmitt. En especial se hará hincapié en la aparición dentro del pensamiento de Botero de conceptos que luego Schmitt caracterizará como esenciales en la conformación del Estado Moderno, entre los cuales están el de soberanía, la idea del enemigo político, y la conformación de un orden frente a la existencia de un estado de excepción. Principalmente se busca usar estos conceptos schmittianos como marco teórico para entender cómo Botero intentó definir el concepto de “razón de Estado” frente a las problemáticas políticas, sociales y religiosas que se producían a fines del siglo XVI.

Hermeneútica jurídica y comunión en la fe católica. (Apostillas al discurso de Benedicto XVI a la Rota romana, el 21 de enero de 2012)

La convocatoria a recorrer un “Año de la fe” permitió a Benedicto XVI centrar su alocución de 2012 a la Rota romana en ese próximo acontecimiento eclesial. La extrema importancia que el Pontífice atribuye a su llamada a renovar la fe católica se puso de manifiesto en las palabras que dirigiera unos días más tarde a la plenaria de la Congregación para la Doctrina de la Fe...

Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.