Artículos SCI

Abstract

This paper discusses the numerical exponential instability of the transfer matrix method (TMM) in the framework of the symmetry formalism. This numerical weakness is attributed to a series of increasingly extreme exponentials that appear in the TMM when it is applied to geometries involving total internal reflection (TIR) or very high absorption. We design a TMM formalism that identifies the internal symmetries of the multilayer geometry. These symmetries suggest particular transformations of a reference system in the TMM that improve its ill-conditioned exponentials. To illustrate the numerical improvements, we present examples with calculations of electric fields.

Abstract

A multi-element, time-dependent model is used to examine additive-assisted copper electroplating in macro-channels. This model is an adaptation of the work of Akolkar and Landau [J. Electrochem. Soc., 156, D351 (2009)], used to describe plating in micro-vias for integrated circuits. Using their method for describing species movement in the channel, the model has been expanded to include transport and adsorption limitations of the inhibitor and accelerator, as well as the copper ions in solution. The model is used to investigate copper plating as an infiltration method across many size scales and aspect ratios. Biomorphic graphite scaffolds produced from wood are used as a representative system and the results of a two-additive bath are used to characterize the behavior of the additives and determine the effectiveness of the plating. The results indicate that at macro-scales, channel dimensions play an increasingly important role in dictating the behavior of additive-assisted plating. Because additive systems are designed to establish differential surface coverage within the channel, the success of which is determined by the additive's rates of diffusion and adsorption, certain size scale/aspect ratio combinations preclude such coverage. A guide for sample geometries that may be successfully infiltrated with a two-additive bath is provided.

Abstract

A family of 1D organic/inorganic core/shell materials formed by an inner organic nanowire (ONW) conformally covered with an inorganic wide band gap semiconductor (ZnO or TiO2) layer is presented. The developed procedure is a two-steps vacuum methodology involving the formation of supported single crystal small-molecule nanowires by physical vapor deposition and plasma enhance chemical vapor deposition (PECVD) of the inorganic shell. Critical characteristics of the last technique are the possibilities of low temperature and remote configuration deposition. Additionally, an initial step has to be included in order to create nucleation centers for the growth of the ONWs. The procedure and its general character in terms of the variability in organic core and inorganic shells composition and the applicability of the technique to different substrates are presented. The formation of the inorganic shell with no damage of the organic core single-crystalline structure is demonstrated by high resolution transmission electron microscopy. The vertical alignment of the hybrid nanostructure is achieved thanks to the interaction of the 1D organic nanostructured surfaces and the glow discharge during the deposition of the inorganic shell by PECVD. The optical properties of these core/shell NWs are studied by fluorescence spectroscopy and microscopy, and their application as nanoscale waveguides in the 550–750 nm range addressed.

Abstract

Silver-based nanostructures were prepared through reduction/oxidation reactions of aqueous silver nitrate solutions mediated by extracts of red fruits of the piquin pepper (Capsicum annuum var. aviculare) at room temperature. Detailed morphological and microstructural studies using X-ray diffraction, conventional and high-resolution transmission electron microscopy and selected area electron diffraction revealed that the product was constituted by three kinds of nanoparticles. One of them was composed of twinned metallic silver nanoparticles with a size of few nanometers. Other kind of particles was ultrafine disk-like single crystals of silver 4,4′-dimethyldiazoaminobenzene, being in our best knowledge the first time that this compound is reported in the form of nanoparticles. Both kinds of nanoparticles experienced processes of self-assembly and subsequent grain growth to form the third kind of nanoparticles. Such resulting nanostructures are monocrystalline and flattened metallic silver nanoparticles that have diameters around tens of nanometers, the [112] direction perpendicular to the particle plane, and are coated by a surface organometallic layer and residues of biomolecules. The ultraviolet-visible spectrum of the biosynthesized product showed a surface plasmon resonance (SPR) extinction band with an absorbance maximum at around 400 nm, thereby confirming the presence of fine Ag particles. Studies carried out by Fourier transform infrared spectroscopy indicated that the principal active compounds responsible of the reduction of the Ag ions are proteins and capsaicin (through the amino groups) and phenolic compounds (through hydroxyl groups).

Abstract

Development of porous alumina has been the objective of numerous studies in recent decades, due to the intrinsic properties of aluminium oxide, such as high melting point, low thermal conductivity, chemical inertness and corrosion resistance which, in addition to a high surface area and permeability, make aluminas being used for many different industrial and technical applications. The crystallographic and textural stability of alumina acquires significant importance in those processes involving high temperatures; however, most of the synthesis methods yield metastable oxides of little interest in high-temperature processes due to the transformation to alpha phase, with the consequent reduction in surface area. The present article reviews diverse procedures for obtaining porous alumina with high specific surface area, including methods and strategies for preparing high surface alpha-alumina. Within this framework, the paper analyzes the results obtained through bioreplica of lignocellulosic materials. This technology allows preparing aluminas with the complex structural hierarchy of the lignocellulosic templates.

Abstract

Monomeric Ni and Pd hydroxides stabilized by the iPrPCP pincer ligand react with CO2 to give labile terminal bicarbonate complexes that readily lose CO2 and water to give binuclear carbonate complexes. Differential scanning calorimetry (DSC) has been used to monitor the decomposition of both bicarcabonates in the solid state. When the carbonate complexes are heated under reflux in thf in the presence of water, full decarboxylation takes place, restoring the starting hydroxides and demonstrating that CO2 insertion is a fully reversible process. The decarboxylation of the nickel carbonate complex is completed more readily, suggesting that the reaction of the Pd hydroxide with CO2 is more favourable than that of its nickel counterpart. This is supported by DFT calculations, which also shows that CO2 insertion takes place through a concerted Lipscomb-type mechanism. Monomeric Ni and Pd hydroxides stabilized by the iPrPCP pincer ligand react with CO2 to give labile terminal hydrogen carbonate complexes that readily lose CO2 and water to give binuclear carbonate complexes.

Abstract

A computational fluid dynamics (CFD) simulation study of the preferential oxidation of CO (CO-PROX) in microstructured reactors consisting in square and semicircular microchannels coated with an Au/CuOx–CeO2 catalyst is presented. The CO content of the feed stream was set at 1 vol.%. A parametric sensitivity analysis has been performed under isothermal conditions revealing that an optimal reaction temperature exists that leads to a minimum CO content at the microreactor exit. The influence of the space velocity, CO2 concentration and oxygen-to-CO molar ratio in the feed stream (λ), catalyst loading, and microchannel characteristic dimension (d) on the microreactor performance has been investigated. Under suitable conditions, the CO concentration can be reduced below 10 ppm at relatively low temperatures within the 155–175 °C range. A negative effect of the increase of d from 0.35 mm to 2.8 mm on the CO removal efficiency has been found and attributed to a more detrimental effect of the mass transport limitations on the oxidation of CO than that of H2. Non-isothermal CFD simulations have been performed to investigate the cooling of the CO-PROX reactor with air or a fuel cell anode off gas surrogate in parallel microchannels. Due to the very rapid heat transfer allowed by the microreactor and the strong influence of the reaction temperature on the exit CO concentration, a careful control of the coolant flow rate and inlet temperature is required for proper reactor operation. The microreactor behavior is virtually isothermal.

Abstract

TiO2 Degussa P25, TiO2 prepared by sol–gel submitted to sulfation pre-treatment and some metallized catalysts obtained by photodeposition of Au or Pt over the sulfated TiO2, were evaluated in the reaction of ethanol photo-oxidation. FT-IR spectroscopy was used to investigate the surface features of the photocatalysts, identifying adsorbed species and following the evolution of intermediate products in the ethanol photo-oxidation reaction. Nature of surface acidity in terms of Brönsted and Lewis centers was also studied.

Results showed that sulfation pre-treatment and metallization were important factors influencing the selectivity. Acetaldehyde was the main oxidation product on sulfated TiO2; in the case of P25 also acetates production was observed. The photodeposition of metals had a detrimental effect on the selectivity to acetaldehyde; on metallized catalysts the formation of stable secondary intermediates was detected.

Based on these findings, a reaction pathway for the ethanol photo-oxidation over the different photocatalysts, via acetaldehyde or via acetate formation is proposed.

Abstract

WSex films with variable Se/W ratio were deposited by non-reactive r.f. magnetron sputtering from WSe2 target changing the applied d.c. pulsed bias conditions and substrate temperature. The structural and chemical properties were measured by cross-sectional scanning electron microscopy (X-SEM), energy dispersive analysis (EDX), X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The tribological properties were measured in ambient air (RH = 30–40%) and dry nitrogen by means of a reciprocating ball-on-disk tribometer. A clear correlation was found between the Se/W ratio and the measured friction coefficient displaying values below 0.1 (in ambient air) and 0.03 (in dry N2) for ratios Se/W ≥ 0.6 as determined by electron probe microanalysis (EPMA). The results demonstrated that notable tribological results could be obtained even in ambient air (friction ≤ 0.07 and wear rate ≈10−7 mm3 Nm−1) by controlling the film microstructure and chemical composition. By incorporating carbon, wear and chemical resistance can be gained by formation of non-stoichiometric carbides and/or alloying into the defective WSex hexagonal structure. The existence of a WSe2 rich interfacial layer (either on the ball scar or embedded in the film track) was evidenced by Raman in low friction conditions. The improvement in tribological performance is therefore obtained by means of layered WSex, the formation of gradient composition from metallic W (hard) to WSe2 (lubricant) and carbon incorporation.

Abstract

The highly visible and infrared (up to 6 mu m) transparent Sr3Al2O6 polycrystalline ceramic was obtained by full crystallization of the corresponding glass composition. The glass synthesis and the direct congruent crystallization processes are described, and the material transparency is discussed in light of its microstructure. This new transparent ceramic exhibits a high density (i.e., complete absence of porosity) and micrometer-scale crystallites with very thin grain boundaries. These microstructural characteristics, inherent to the preparation method, minimize light scattering and demonstrate the advantages of this synthesis route compared to the high-pressure process used for the few reported transparent polycrystalline materials. This Sr3Al2O6 ceramic shows a H = 10.5 GPa hardness, a E-r = 150 GPa reduced elasticity modulus, and a 9.6 x 10(-6) K-1 thermal expansion coefficient. Such a transparent strontium aluminate ceramic opens the way to a wide range of applications, especially photonics when doped by various doping agents. As examples, the luminescence of Sr3Al2O6:Eu3+ and Sr3Al2O6:Er3+, which show strong emissions in the visible and infrared ranges, respectively, is presented. Moreover, the Sr3Al2O6:Ce3+ material was found to exhibit scintillation properties under X-ray excitation. Interestingly, the analogous Sr3Ga2O6 transparent polycrystalline ceramic material could equally be prepared using the same elaboration method, although its hygroscopicity prevents the preservation of its high transparency under normal conditions. The establishment of the key factors for the transparency of this economical and innovative synthesis method should enable the prediction of new classes of technologically relevant transparent ceramics.

Abstract

Two alkoxysilyl-modified ionic liquids (ILs) have been synthesized and further grafted onto mesoporous silica, MCM-41; these ionic liquids were used for dispersing AuCl3 catalysts that activate C–H bonds as required for the synthesis of propargylamines by coupling alkyne, aldehyde and amine (A3 coupling) species. 29Si NMR experiments demonstrate the formation of covalent bonds between alkoxysilyl-modified Bmim IL and the MCM-41 surface through silanol groups. The catalytic activities of Au(III)-supported MCM-41 and Au(III) homogeneous catalysts are lower than those obtained for the IL functionalized Au–MCM-41 solids when the same gold loading is considered. An interaction between Au(III) species and the IL is proposed for explaining the stabilization of gold(III) species. However, successive reaction cycles result in a decrease in the catalytic activity that has been explained on the basis of gold leaching.

Abstract

The aim of this study is to elucidate the coarsening kinetics involved during densification of fine-grained pure α-alumina by spark plasma sintering. Low temperature and short dwell time sintering conditions were used to preserve the nanocrystalline structure of the starting commercial powder (about 50 nm). Notwithstanding the above, submicron grain coarsened microstructures have been developed. The microstructure evolution of alumina under different sintering conditions points to a nanograin rotation densification mechanism as being responsible for the fast grain growth observed.

Abstract

Micro-monoliths and foams made of aluminium, Fecralloy® and brass were studied as substrates for structured systems for methanol steam reforming (MSR). All the alloys exhibited very adherent oxide layer produced by pre-treatment to improve the adhesion between substrate and catalyst. 2.5% Pd/ZnO catalyst was prepared and deposited on structured substrates. Both, good catalyst adhesion and stable catalytic performance were achieved in the case of brass micro-monoliths. The Fecralloy® and aluminium substrates reacted with the catalytic active components resulting in catalyst modification. The aluminium based substrates promoted dimethyl ether (DME) formation. Aluminium foam produced better performance than aluminium micro-monoliths that could be related to improved mass and heat transfer properties in foams.

Abstract

BiVO₄ hierarchical structures were synthesized by means of a surfactant free hydrothermal method having good photoactivities for the degradation of Methylene Blue and Rhodamine B under UV–vis irradiation. From the structural and morphological characterization it has been stated that BiVO₄ present the monoclinic crystalline phase with different morphologies depending on the pH value. For Methylene Blue the photodegradation rate is strongly affected by the crystallite size and higher (0 0 4) facet exposition. On the contrary, for Rhodamine B, the ζ-potential of the surface clearly determines the photocatalytic performance of BiVO₄ catalyst.

Abstract

Pairs of samples containing Ag nanoparticles (NPs) of different dimensions have been produced under the same conditions but on different substrates, namely standard glass slides and a thin layer of amorphous aluminum oxide (a-Al2O3) on-glass. Upon storage in ambient conditions (air and room temperature) the color of samples changed and a blue-shift and damping of the surface plasmon resonance was observed. The changes are weaker for the samples on-glass and tend to saturate after 12 months. In contrast, the changes for the samples on a-Al2O3 appear to be still progressing after 25 months. While x-ray photoelectron spectroscopy shows a slight sulfurization and negligible oxidation of the Ag for the on-glass samples upon 25 months aging, it shows that Ag is strongly oxidized for the on a-Al2O3 samples and sulfurization is negligible. Both optical and chemical results are consistent with the production of a shell at the expense of a reduction of the metal core dimensions, the latter being responsible for the blue-shift and related to the small (<10 nm initial diameter) of the NPs. The enhanced reactivity of the Ag NPs on the a-Al2O3 supports goes along with specific morphological changes of the Ag NPs and the observation of nitrogen.

Abstract

Se presenta un procedimiento para la planificación de recogida y flujo de los residuos sólidos (de construcción y demolición, hormigón, cerámica, vidrio y otros) basado en la utilización de una herramienta informatizada, para conseguir una optimización de su gestión. Dicho procedimiento parte de normativa establecida según un Plan Director Territorial de la Gestión de Residuos Sólidos Urbanos (RSU) aprobado en una Comunidad Autónoma, en este caso se particulariza a la de Andalucía, tomando como ejemplo el volumen de residuos que se producen en una colectividad de tamaño medio (provincia de Almería), siendo extensible a otras mayores en población y territorio, disponiendo de datos actualizados.
El procedimiento utiliza una herramienta informática de gran difusión en el mundo, como es Google Earth y, de este modo, genera un número de “Centros deTransferencia” con objeto de minimizar el gasto de transporte, partiendo de una premisa previa en cuanto a distancia entre núcleos poblacionales y centros de tratamiento. Los Centros generados con la aplicación del procedimiento se pueden visualizar en un mapa topográfico, con áreas de influencia y vías de acceso a los mismos y se le pueden asociar una serie de datos tabulados con información adicional de utilidad. El procedimiento propuesto se va retroalimentando de manera constante con datos reales e información de campo, permitiendo a las empresas que producen residuos de distinta tipología como son los residuos de construcción y demolición principalmente, pero también hormigón, cerámica, vidrio, mezclas de todos ellos, residuos clasificados como peligrosos e incluso de otros materiales, a la propia administración y a la sociedad, en general, conocer las tasas de cada planta de tratamiento y qué se hace con los residuos entregados para contribuir a la reducción del impacto medioambiental de los mismos y a su gestión sostenible.
 

Abstract

The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

Abstract

The concept of generalized time θ=∫exp(−Ea/RT)dt θ = ∫ exp ( − E a / RT ) d t in non-isothermal kinetics was introduced by Ozawa in 1965, together with the well-known isoconversional plot, i.e., Ozawa plot. The generalized time is the key concept to tie the kinetic data under varying temperature to the kinetic relationship at a constant temperature. It is well known that many processes studied by thermal analysis and calorimetry reveal a complex nature. Therefore, the generalized time concept seems to be very useful for the description of the change in the rate behavior depending on the fractional conversion. Using the concept of θ, three kinds of experimental master plots can be formalized in differential, integral, and multiplied forms. Among others, combination of the differential and multiplied master plots, y(α) = (dα/dθ) and z(α) = (dα/dθ)θ, show a high performance to discriminate the kinetic model based on the maxima condition of y(α y*) and z(α z*). The α y* − α y* kinetic plot is a useful tool to visualize the complexity of the kinetic process and to determine the most suitable kinetic model. The usefulness of α y* − α y* kinetic plot and the YZ-master plots is illustrated as exemplified by the kinetic analyses of complex crystallization processes of the as-prepared, thermally and mechanically treated amorphous zirconia.