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Scientific Papers in SCI



2020


Reactividad de Sólidos

Synthesis of all equiatomic five-transition metals High Entropy Carbides of the IVB (Ti, Zr, Hf) and VB (V, Nb, Ta) groups by a low temperature route

Chicardi, E; Garcia-Garrido, C; Hernandez-Saz, J; Gotor, FJ
Ceramics International, 46 (2020) 21421-21430

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The six possible equiatomic five-transition metal High Entropy Carbides (HECs) of the IVB (Ti, Zr, Hf) and VB (V, Nb, Ta) groups of the periodic table, i.e., TiZrHfVNbC5, TiZrHfVTaC5, TiZrHfNbTaC5, TiZrVNbTaC5, TiHfVNbTaC5 and ZrHfVNbTaC5, were successfully obtained via a powder metallurgy route at room temperature, specifically, by one-step diffusion mechanosynthesis starting from the elemental constituents (using graphite as the carbon source). Three of those HECs, TiZrHfVTaC5, TiZrVNbTaC5 and ZrHfVNbTaC5, were developed for the first time. Their development was possible without any subsequent thermal treatment, in contrast to the usual way (reactive sintering at 1800-2200 degrees C), and in a powder form, make them potential advanced raw ceramics for hard, refractory and oxidation resistance coatings or matrix phase composites.


September, 2020 | DOI: 10.1016/j.ceramint.2020.05.240

Química de Superficies y Catálisis

Experimental evidence of HCO species as intermediate in the fischer tropsch reaction using operando techniques

Diaz-Sanchez, RM; de-Paz-Carrion, A; Serrera-Figallo, MA; Torres-Lagares, D; Barranco, A; Leon-Ramos, JR; Gutierrez-Perez, JL
Applied Catalysis B-Environmental, 272 (2020) 119032

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Fischer Tropsch's reaction, known from 1925, receives special attention nowadays due to its key role in the CO2 or biomass valorization to liquid fuels and chemicals. Several aspects on the exact mechanism or the role of water in this reaction are not yet completely clear. Formyl species, HCO, have been proposed as the most probable reaction intermediate, but they have never been observed under operation conditions closed to the real ones. In this work, using DRIFTS-MS operando techniques, HCO intermediates are detected under a H2/CO flow and 200 °C. IR bands at 2900 cm−1 and 1440 cm−1 attributed to ν(C–H) and δ(HCO) vibrations modes characterize these species. Evolution of these bands with the reaction time evidences its high reactivity with OH groups, which explains the positive effect of water on the CO conversion previously observed.


September, 2020 | DOI: 10.1016/j.apcatb.2020.119032

Materiales de Diseño para la Energía y Medioambiente

Novel procedure for laboratory scale production of composite functional filaments for additive manufacturing

Diaz-Garcia, A; Law, JY; Cota, A; Bellido-Correa, A; Ramirez-Rico, J; Schafer, R; Franco, V
Materials Today Communications, 24 (2020) 101049

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Successful 3D printing by material extrusion of functional parts for new devices requires high quality filaments. Uniform homogeneity and good dispersion of particles embedded in filaments typically takes several cycles of extrusion or well-prepared feedstock by injection molding, industrial kneaders or twin-screw compounding. These methods need specific production devices that are not available in many laboratories non-specialized in polymer research, such as those working on different material science and technology topics that try to connect with additive manufacturing. Therefore, laboratory studies are usually limited to compositions and filler concentrations provided by commercial companies. Here, we present an original laboratory scale methodology to custom-prepare the feedstock for extruding magnetic composite filaments for fused filament fabrication (FFF), which is attainable by a desktop single-screw extruder. It consists in encapsulating the fillers in custom made capsules that are used as feedstock and reach the melting area of the extruder maintaining the same concentration of fillers. Results have shown that our approach can create smooth and continuous composite filaments with good homogeneity and printability with fine level of dimensional control. We further show the good dispersion of the particles in the composite filament using X-Ray Tomography, which enabled a 3D reconstruction of the spacial distribution of the embedded magnetic particles. The major advantage of this new way of preparing the composite feedstock is that it avoids the hassle of multiple extrusion runs and industrial machinery, yet providing uniform filaments of well controlled filler concentration, which is predictable and reproducible. The proposed methodology is suitable for different polymer matrices and applicable to other functional particle types, not just limited to magnetic ones. This opens an avenue for further laboratory scale development of novel functional composite filaments, useful for any community. This democratization of complex filament preparation, including consumers preparing their own desired uniform novel filaments, will facilitate to unify efforts nearing 3D printing of new functional devices.


September, 2020 | DOI: 10.1016/j.mtcomm.2020.101049

Materiales Nanoestructurados y Microestructura

Tailoring materials by high-energy ball milling: TiO2 mixtures for catalyst support application

Rinaudo, MG; Beltran, AM; Fernandez, MA; Cadus, LE; Morales, MR
Materials Today Chemistry, 17 (2020) 100340

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We carried out a rational design of catalyst supports by high-energy ball milling. Tailored mixtures of TiO2 crystalline phases were obtained using rotational speed and milling time as variable parameters. Polymorphic transformation from anatase to rutile through high-pressure TiO2 (II) as intermediate was confirmed by X-ray Diffraction (XRD), Raman Spectroscopy and Transmission Electron Microscopy (TEM). Also, starting material doubled its specific surface area due to particle fragmentation, as confirmed by surface area of Brunauer-Emmet-Teller (S-BET) and Scanning Electron Microscopy (SEM). Defects introduced during milling process generated oxygen vacancies in the surface and bulk of supports, as evidenced by X-ray Photoelectron Spectroscopy (XPS) and Electron Paramagnetic Resonance (EPR). Furthermore, longer milling time increased reducibility and oxygen mobility of supports, as observed by H-2 Temperature Programmed Reduction (H-2-TPR) and O-2 Temperature Programmed Desorption (O-2-TPD). Phase composition remained unchanged even under extreme conditions, highlighting the stability of unusual TiO2 (II) phase. Properties achieved in present materials could benefit metal-support interactions and play a major role in supported catalysts. 


September, 2020 | DOI: 10.1016/j.mtchem.2020.100340

Materiales de Diseño para la Energía y Medioambiente

Elucidating esterification reaction during deposition of cutin monomers from classical molecular dynamics simulations

Bueno, OVM; Benitez, JJ; San-Miguel, MA
Journal of Molecular Modeling, 26 (2020) 280

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The structural behavior of some cutin monomers, when deposited on mica support, was extensively investigated by our research group. However, other events, such as esterification reaction (ER), are still a way to explore. In this paper, we explore possible ER that could occur when these monomers adsorb on support. Although classical molecular dynamics simulations are not able to capture reactive effects, here, we show that they become valuable strategies to analyze the initial structural configurations to predict the most favorable reaction routes. Thus, when depositing aleuritic acid (ALE), it is observed that the loss of capacity to form self-assembled (SA) systems favors different routes to occur ER. In pure ALE bilayers systems, an ER is given exclusively through the -COOH and primary -OH groups. In pure ALE monolayers systems, the ER does not happen when the system is self-assembled. However, for disorganized systems, it is able to occur by two possible routes: -COOH and primary -OH (route 1) and -COOH and secondary -OH (route 2). When palmitic acid (PAL) is added in small quantities, ALE SAMs can now form an ER. In this case, ER occurs mostly through the -COOH and secondary -OH groups. However, when the presence of PAL is dominant, ER can occur with either of both possibilities, that is, routes 1 and 2.


September, 2020 | DOI: 10.1007/s00894-020-04544-9

 

 

 

 

 

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