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Scientific Papers in SCI



2020


Química de Superficies y Catálisis

Monolithic stirrer reactor: The selective lactose oxidation in liquid phase over Au/Al2O3 nanostructured catalysts

Regenhardt, SA; Meyer, CI; Sanz, O; Sebastian, V; Ivanova, S; Centeno, MA; Odriozola, JA; Montes, M; Marchi, AJ; Garetto, TF
Molecular Catalysis, 481 (2020) 110219

The performance of rotating metallic monolith stirrer reactor was studied for selective lactose oxidation in liquid phase at 65 degrees C, atmospheric pressure and with air as oxidant agent. The Au/Al(2)O(3)deposition on metallic substrates was performed by wash-coating, producing catalyst coating thicknesses between 5 and 20 mu m. Monoliths with different configuration (channel size between 0.36 and 1.06 mm) were used as stirrer blades in a batch reactor. Internal and external mass transfer limitations were observed during liquid phase lactose oxidation. For stirring rates equal or higher than 600 rpm there were no important external diffusional restrictions and this was also independent of the monolith configuration. Coating with thickness higher than 15 mu m presents loss of catalyst effectiveness due to internal diffusional restrictions. Excellent stability in the catalytic tests was obtained after three regeneration-reaction cycles. Regeneration was carried out at 400 degrees C in air flow. Gold particle size distribution in the monolith washcoat, determined by TEM before and after reaction, was homogeneous with a medium size of around 5 nm. This is in agreement with the very good reproducibility and stability obtained in the catalytic tests. After calcination at 500 degrees C, some sintering and a heterogeneous distribution of metal particle size was observed, accompanied by a slight loss in catalyst activity. It is concluded that metallic monolith stirrer reactors are a promising application for selective lactose oxidation in liquid phase.


February, 2020 | DOI: 10.1016/j.mcat.2018.10.014

Reactividad de Sólidos

Development of Ti(C,N)-based cermets with (Co,Fe,Ni)-based high entropy alloys as binder phase

de la Obra, AG; Sayagues, MJ; Chicardi, E; Gotor, FJ
Journal of Alloys and Compounds, 814 (2020) 152218

High entropy alloys have been proposed as novel binder phases in cemented carbides and cermets. Many aspects related to the stability of these alloys during the liquid phase sintering process are still unclear and were addressed in this work. Consolidated Ti(C,N)-based cermets using four different (Co,Fe,Ni)based high entropy alloys as the binder phase were obtained. The chosen alloys - CoCrCuFeNi, CoCrFeNiV, CoCrFeMnNi and CoFeMnNiV - were previously synthesized through mechanical alloying and a single alloyed solid solution phase with fcc structure and nanometric character was always obtained. The powdered alloys and the consolidated cermets were analyzed by X-ray diffraction, scanning electron microscopy, X-ray energy dispersive spectrometry and transmission electron microscopy. Differential thermal analysis was employed to determine the melting point of the four high entropy alloys that ranged between 1310 degrees C and 1375 degrees C. Although a high temperature of 1575 degrees C was required to obtain the highest cermet densification by pressureless sintering, porosity still remained in most of the cermets. Best densification was achieved when CoCrFeNiV was used as the binder phase. During liquid phase sintering, different compositional changes were observed in the ceramic and binder phases. A core-rim microstructure was observed in cermets containing V in the alloys (CoCrFeNiV and CoFeMnNiV), since this element was incorporated to the carbonitride structure during sintering. A slight Cr segregation was detected in cermets containing Cr, leading to CrTi-rich alloys in small binder regions. However, a great Cu segregation was produced when CoCrCuFeNi was used, and the formation of two different fcc alloys -a Cu-rich and a Cu-depleted- was observed. Finally, a loss of Mn was also evidenced in CoCrFeMnNi and CoFeMnNiV, probably due to its sublimation at the sintering temperature. 


January, 2020 | DOI: 10.1016/j.jallcom.2019.152218

Materiales de Diseño para la Energía y Medioambiente

Preparation and Characterization of Bio-Based PLA/PBAT and Cinnamon Essential Oil Polymer Fibers and Life-Cycle Assessment from Hydrolytic Degradation

Correa-Pacheco, ZN; Black-Solis, JD; Ortega-Gudino, P; Sabino-Gutierrez, MA; Benitez-Jimenez, JJ; Barajas-Cervantes, A; Bautista-Banos, S; Hurtado-Colmenares, LB
Polymers, 12 (2020) 38

Nowadays, the need to reduce the dependence on fuel products and to achieve a sustainable development is of special importance due to environmental concerns. Therefore, new alternatives must be sought. In this work, extruded fibers from poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) added with cinnamon essential oil (CEO) were prepared and characterized, and the hydrolytic degradation was assessed. A two-phase system was observed with spherical particles of PBAT embedded in the PLA matrix. The thermal analysis showed partial miscibility between PLA and PBAT. Mechanically, Young's modulus decreased and the elongation at break increased with the incorporation of PBAT and CEO into the blends. The variation in weight loss for the fibers was below 5% during the period of hydrolytic degradation studied with the most important changes at 37 degrees C and pH 8.50. From microscopy, the formation of cracks in the fiber surface was evidenced, especially for PLA fibers in alkaline medium at 37 degrees C. This study shows the importance of the variables that influence the performance of polyester-cinnamon essential oil-based fibers in agro-industrial applications for horticultural product preservation.


January, 2020 | DOI: 10.3390/polym12010038

Reactividad de Sólidos

Processing and properties of Bi0.98R0.02FeO3 (R = La, Sm, Y) ceramics flash sintered at similar to 650 degrees C in <5 s

Gil-Gonzalez, E; Perejon, A; Sanchez-Jimenez, PE; Raj, R; Perez-Maqueda, LA
Journal of the American Ceramic Society, 103 (2020) 136-144

We show that flash sintering produces single‐phase, nanograin‐sized polycrystals of isovalent‐substituted multiferroic ceramics of complex compositions. Single‐phase polycrystals of Bi0.98R0.02FeO3 (R = La, Sm, Y) were produced at a furnace temperature of ~650°C in a few seconds by the application of an electric field of 50 V cm−1, with the current limit set to 40 mA mm−2. The dielectric and insulating properties compared favorably with expected values. Impedance spectroscopy suggests electrically homogenous microstructure, except for the sample Bi0.98La0.02FeO3 that shows a small grain boundary contribution to the impedance. These results reinforce the enabling nature of flash sintering for ceramics which pose difficulties in conventional sintering because they contain low melting constituents or develop secondary phases during the sintering protocol.


January, 2020 | DOI: 10.1111/jace.16718

Materiales Ópticos Multifuncionales

Finite Size Effects on Light Propagation throughout Random Media: Relation between Optical Properties and Scattering Event Statistics

Miranda-Munoz, JM; Esteso, V; Jimenez-Solano, A; Lozano, G; Miguez, H
Advanced Optical Materials, 8 (2020) 1901196

This work introduces a thorough analysis of light transport in thin optically disordered media. The diffusive properties of a turbid material are generally dictated by the transport mean free path, lt. For depths larger than this characteristic length, light propagation can be considered fully randomized. There is however a range of thicknesses for which light becomes only partly randomized, as it only undergoes a single or very few scattering events. The effects of such finitude are experimentally and theoretically studied on the optical properties of the material, such as the angular distribution of scattered light. Simulations provide insight into the phenomena that occur within the optically disordered slab, like the number of scattering events that photons undergo during propagation throughout the material, as a function of the built‐in wavelength dependent scattering mean free path, lsc. This approach provides fundamental information about photon transport in finite optically random media, which can be put into practice to design diffusers with specific requirements in terms of the spectral and angular properties of the scattered light.


January, 2020 | DOI: 10.1002/adom.201901196

Materiales Avanzados

New waste-based clinkers for the preparation of low-energy cements. A step forward toward circular economy

Martinez-Martinez, S; Perez-Villarejo, L; Eliche-Quesada, D; Sanchez-Soto, PJ; Christogerou, A; Kanellopoulou, DG; Angelopoulos, GN
International Journal of Applied Ceramic Technology, 17 (2020) 12-21

This paper describes the use of industrial wastes arising from different production processes of the ceramic and marble industries as raw materials for the design and formulation of new cement clinkers with a high content of dicalcium silicate (Belite). The aim was to reintroduce these wastes in the industrial sector and take advantage of them for a greater environmental benefit, as indicated by the principles of the circular economy. Formulations containing 2.5, 5 and 10 wt% of chamotte and marble sludge, respectively, and a waste-free formulation have been designed to obtain clinkers with a content of dicalcium silicate higher than 60 wt%. The different blends have been studied up to a maximum temperature of 1390 degrees C by Thermal Analysis. Other techniques such as XRD, XRF, Modified Bogue Equation, Quality Indexes (LSF, AM, SM) and Optical Microscopy have been used for the study and characterization of industrial wastes, the raw materials and the high belite-type cement dosages. The results indicate that this type of cements can be designed using different types of wastes and in this way reduce the environmental impacts caused by the extraction of raw materials and the deposition of the wastes in landfills, improving the circular economy of the construction industry.


January, 2020 | DOI: 10.1111/ijac.13390

Reactividad de Sólidos

Obituary: Prof. José Manuel Criado

Perez-Maqueda, LA; Real, C; Gotor, FJ; Alcala, MD; Malek, J; Koga, N
Journal of Thermal Analysis and Calorimetry, (2020)

Reactividad de Sólidos

Influence of DSC thermal lag on evaluation of crystallization kinetics

Svoboda, R; Maqueda, LP; Podzemna, V; Perejon, A; Svoboda, O
Journal of Non-Crystalline Solids, 528 (2020) 119738

Influence of added thermal resistance on crystallization kinetics, as measured by differential scanning calorimetry (DSC), of the Se70Te30 glass was studied. The increase of thermal resistance was achieved by adding polytetrafluorethylene discs of different thicknesses (up to 0.5 mm) in-between the DSC platform and the pan with sample. Increase of the thermal resistance led to an apparent decrease (by more than 30%) in the crystallization enthalpy. Significant change of model-free kinetics occurred: apparent activation energy E of the crystallization process decreased (by more than 20%) due to the DSC data being progressively shifted to higher temperatures with increasing heating rate. The model-based kinetics was changed only slightly; the DSC peaks retained their asymmetry and the choice of the appropriate model was not influenced by the added thermal resistance. The temperature shift caused by added thermal lag was modeled for the low-to-moderate heating rates.


January, 2020 | DOI: 10.1016/j.jnoncrysol.2019.119738

Materiales Nanoestructurados y Microestructura

Low gas consumption fabrication of He-3 solid targets for nuclear reactions

Fernandez, A; Hufschmidt, D; Colaux, JL; Valiente-Dobon, JJ; Godinho, V; de Haro, MCJ; Feria, D; Gadea, A; Lucas, S
Materials & Design, 186 (2020) 108337

Nanoporous solids that stabilize trapped gas nanobubbles open new possibilities to fabricate solid targets for nuclear reactions. A methodology is described based on the magnetron sputtering (MS) technique operated under quasistatic flux conditions to produce such nanocomposites films with He-3 contents of up to 16 at.% in an amorphous-silicon matrix. In addition to the characteristic low pressure (3-6 Pa) needed for the gas discharge, the method ensures almost complete reduction of the process gas flow during film fabrication. The method could produce similar materials to those obtained under classical dynamic flux conditions for MS. The drastic reduction (>99.5%) of the gas consumption is fundamental for the fabrication of targets with scarce and expensive gases. Si:He-3 and W:He-3 targets are presented together with their microstructural (scanning and transmission electron microscopy, SEM and TEM respectively) and compositional (Ion Beam Analysis, IBA) characterization. The He-3 content achieved was over 1 x 10(18) at/cm(2) for film thicknesses between 1.5 and 3 mu m for both Si and W matrices. First experiments to probe the stability of the targets for nuclear reaction studies in inverse kinematics configurations are presented. 


January, 2020 | DOI: 10.1016/j.matdes.2019.108337

Nanotecnología en Superficies y Plasma

Enhanced Stability of Perovskite Solar Cells Incorporating Dopant-Free Crystalline Spiro-OMeTAD Layers by Vacuum Sublimation

Barranco, A; Lopez-Santos, MC; Idigoras, J; Aparicio, FJ; Obrero-Perez, J; Lopez-Flores, V; Contreras-Bernal, L; Rico, V; Ferrer, J; Espinos, JP; Borras, A; Anta, JA; Sanchez-Valencia, JR
Advanced Energy Materials, (2020) 1901524

The main handicap still hindering the eventual exploitation of organometal halide perovskite-based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid-state hole conductor (SSHC), i.e., the Spiro-OMeTAD [2,2 ',7,7 '-tetrakis (N,N-di-p-methoxyphenyl-amine) 9,9 '-spirobifluorene], and how its dopant-free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution-processed reference and after annealing in air up to 200 degrees C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the pi-pi stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light-emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro-OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X-ray diffraction, grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.


January, 2020 | DOI: 10.1002/aenm.201901524

 

 

 

 

 

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