Artículos SCI
2023
2023
Nanotecnología en Superficies y Plasma
Paper-based ZnO self-powered sensors and nanogenerators by plasma technology
Garcia-Casas, X; Aparicio, FJ; Budagosky, J; Ghaffarinejad, A; Orozco-Corrales, N; Ostrikov, K; Sánchez-Valencia, JR; Barranco, A; Borras, ANano Energy, 114 (2023) 108686 DOI: 10.1016/j.nanoen.2023.108686
Abstract
Nanogenerators and self-powered nanosensors have shown the potential to power low-consumption electronics and human-machine interfaces, but their practical implementation requires reliable, environmentally friendly and scalable processes for manufacturing and processing. Furthermore, the emerging flexible and wearable electronics technology demands direct fabrication onto innovative substrates such as paper and plastics typically incompatible with high process temperatures. This article presents a plasma synthesis approach for the fabri-cation of piezoelectric nanogenerators (PENGs) and self-powered sensors on paper substrates. Polycrystalline ZnO nanocolumnar thin films are deposited by plasma-enhanced chemical vapour deposition on common paper supports using a microwave electron cyclotron resonance reactor working at room temperature yielding high growth rates and low structural and interfacial stresses. Applying Kinetic Monte Carlo simulation, we elucidate the basic shadowing mechanism behind the characteristic microstructure and porosity of the ZnO thin films, relating them to an enhanced piezoelectric response to periodic and random inputs. The piezoelectric devices are assembled by embedding the ZnO films in polymethylmethacrylate (PMMA) and using Au thin layers as elec-trodes in two different configurations, namely laterally and vertically contacted devices. We present the response of the laterally connected devices as a force sensor for low-frequency events with different answers to the applied force depending on the impedance circuit, i.e. load values range, a behaviour that is theoretically analyzed. The characterization of the vertical devices in cantilever-like mode reaches instantaneous power densities of 80 nW/ cm2 with a mean power output of 20 nW/cm2. Besides, we analyze their actual-scenario performance by acti-vation with a fan and handwriting. Overall, this work demonstrates the advantages of implementing plasma deposition for piezoelectric films to develop robust, flexible, stretchable, and enhanced-performance nano-generators and self-powered piezoelectric sensors compatible with inexpensive and recyclable supports.
Septiembre, 2023 | DOI: 10.1016/j.nanoen.2023.108686
Nanotecnología en Superficies y Plasma
Exalted dual-scale surface roughening in laser ablated aluminum capped with a transparent thin film: Wetting and anti-icing behavior
Ghemras, I; Montes, L; Lopez-Santos, C; Gonzalez-Elipe, AR; Rico, VApplied Surface Science, 630 (2023) 157357 DOI: 10.1016/j.apsusc.2023.157357
Abstract
Near infrared laser ablation of metals, specifically aluminum, has been systematically applied to generate surface roughness. Very high laser fluences may even lead to a so called "explosive" ablation regime where roughness becomes dramatically enhanced. In the present work we have developed an alternative methodology that, uti-lizing milder laser irradiation conditions (i.e. laser fluences from 0.37 to 0.72 J/cm2), renders aluminum surfaces with a dual-scale roughness character and Sp parameter values twice or even trice the value found in reference samples. This has been possible for aluminum substrates coated with a highly transparent aluminum oxynitride capping layer. The resulting surfaces, consisting of very rough partially oxidized aluminum with negligible amounts of nitrogen species, resulted highly hydrophobic and depicted long icing delay times as required for anti-icing applications. A correlation has been found between the wetting and anti-icing behaviors, the use of a capping layer and the laser irradiation conditions. To account for this exalted roughening phenomenon, we propose that the transparent capping layer confines the laser energy within the aluminum shallow zones, delays the formation of the plasma plume and produces an enhancement in the aluminum ablation, even at relatively low laser fluences.
Septiembre, 2023 | DOI: 10.1016/j.apsusc.2023.157357
Nanotecnología en Superficies y Plasma - Materiales Ópticos Multifuncionales
Effect of the effective refractive index on the radiative decay rate in nanoparticle thin films
Romero, M; Sánchez-Valencia, JR; Lozano, G; Míguez, HNanoscale, 15 (2023) 15279-15287 DOI: 10.1039/d3nr03348a
Abstract
In this work, we theoretically and experimentally study the influence of the optical environment on the radiative decay rate of rare-earth transitions in luminescent nanoparticles forming a thin film. We use electric dipole sources in finite-difference time-domain simulations to analyze the effect of modifying the effective refractive index of transparent layers made of phosphor nanocrystals doped with rare earth cations, and propose a correction to previously reported analytical models for calculating the radiative decay rate. Our predictions are tested against an experimental realization of such luminescent films, in which we manage to vary the effective refractive index in a gradual and controllable manner. Our model accurately accounts for the measurements attained, allows us to discriminate the radiative and non-radiative contributions to the time-resolved photoluminescence, and provides a way to rationally tune the spontaneous decay rate and hence the photoluminescence quantum yield in an ensemble of luminescent nanoparticles.
Septiembre, 2023 | DOI: 10.1039/d3nr03348a
Ruthenium nanoparticles stabilized by 1,2,3-triazolylidene ligands in the hydrogen isotope exchange of E-H bonds (E = B, Si, Ge, Sn) using deuterium gas
Molinillo, P; Puyo, M; Vattier, F; Lacroix, B; Rendon, N; Lara, P; Suarez, ANanoscale DOI: 10.1039/d3nr02637j
Abstract
A series of ruthenium nanoparticles (Ru & BULL;MIC) stabilized with different mesoionic 1,2,3-triazolylidene (MIC) ligands were prepared by decomposition of the Ru(COD)(COT) (COD = 1,5-cyclooctadiene; COT = 1,3,5-cyclooctatriene) precursor with H-2 (3 bar) in the presence of substoichiometric amounts of the stabilizer (0.1-0.2 equiv.). Small and monodisperse nanoparticles exhibiting mean sizes between 1.1 and 1.2 nm were obtained, whose characterization was carried out by means of transmission electron microscopy (TEM), including high resolution TEM (HRTEM), inductively coupled plasma (ICP) analysis and X-ray photoelectron spectroscopy (XPS). In particular, XPS measurements confirmed the presence of MIC ligands on the surfaces of the nanoparticles. The Ru & BULL;MIC nanoparticles were used in the isotopic H/D exchange of different hydrosilanes, hydroboranes, hydrogermananes and hydrostannanes using deuterium gas under mild conditions (1.0 mol% Ru, 1 bar D-2, 55 & DEG;C). Selective labelling of the E-H (E = B, Si, Ge, Sn) bond in these derivatives, with high levels of deuterium incorporation, was observed.
Agosto, 2023 | DOI: 10.1039/d3nr02637j
Nanotecnología en Superficies y Plasma - Materiales Nanoestructurados y Microestructura
Plasmas and acoustic waves to pattern the nanostructure and chemistry of thin films
Rico, V; Regodon, GF; Garcia-Valenzuela, A; Alcaide, AM; Oliva-Ramirez, M; Rojas, TC; Alvarez, R; Palomares, FJ; Palmero, A; Gonzalez-Elipe, ARActa Materialia, 255 (2023) 119058 DOI: 10.1016/j.actamat.2023.119058
Abstract
In this work, piezoelectric AWs and plasmas have been brought together during the growth of a thin film as a novel methodology of plasma-assisted thin film structuration. The ensuing effects have been investigated on a model system where SiO2 and SiOx (x<2) thin films have been deposited by magnetron sputtering at oblique angles (MS-OAD) on an electro-acoustically excited LiNbO3 piezoelectric substrate under resonant conditions. The microstructure of the resulting films was 2D patterned and depicted submillimeter size intermingled zones with different optical characteristics, compositions (SiO2 and SiOx) and porosity, from highly porous to dense and compact regions. The 2D nanostructural pattern mimics the AW distribution and has been accounted for by means of a specific simulation model. It is concluded that the morphological and chemical film pattern replicates the distribution of polarization potential on the surface of the AW activated substrate immersed in the plasma. Moreover, we show that the main mechanism responsible for the appearance of domains with different morphology and chemical composition is the focused impingement of Ar+plasma ions on certain regions of the substrate. The general character of this patterning process, the underlying physics and its possibilities to tailor the composition and microstructure of dielectric thin film materials are discussed.
Agosto, 2023 | DOI: 10.1016/j.actamat.2023.119058
Química de Superficies y Catálisis
Charting a path to catalytic upcycling of plastic micro/nano fiber pollution from textiles to produce carbon nanomaterials and turquoise hydrogen
Silvia Parrilla-Lahoz; Marielis C. Zambrano; Vlad Stolojan; Rachida Bance-Soualhi; Joel J. Pawlak; Richard A. Venditti; Tomas Ramirez Reina; Melis S. DuyarRSC Sustainability, 1 (2023) 1177-1183 DOI: 10.1039/D3SU00095H
Abstract
Washing synthetic textile fibers releases micro/nano plastics, endangering the environment. As new filters and associated regulations are developed to prevent fiber release from washing machines, there emerges a need to manage the collected waste, for which the only current options are combustion or landfill. Herein we show for the first time the application of a catalytic pyrolysis approach to upcycle textile derived fibrous micro/nano plastics waste, with the aim of keeping carbon in the solid phase and preventing its release as a greenhouse gas. Herein, we demonstrate the co-production of hydrogen and carbon nanomaterials from the two most prevalent global textile microfiber wastes: cotton and polyester. Our results pave a way forward to a realistic process design for upcycling mixed micro/nano fiber waste collected from laundering, drying, vacuuming, and environmental cleanup.
Agosto, 2023 | DOI: 10.1039/D3SU00095H
Tribología y Protección de Superficies
Ti6Al4V coatings on titanium samples by sputtering techniques: Microstructural and mechanical characterization
Sanchez-Lopez, JC; Rodriguez-Albelo, M; Sanchez-Perez, M; Godinho, V; Lopez-Santos, C; Torres, YJournal of Alloys and Compounds, 952 (2023) 170018 DOI: 10.1016/j.jallcom.2023.170018
Abstract
Although titanium is widely used as biomaterial, the control of the interface properties between its surface and the surrounding physiological environment (like bone, other tissues or biofluids) results crucial to achieve a successful osseointegration and good biomechanical and functional performance. In this work, commercially pure titanium (Grade IV) discs obtained by conventional powder metallurgy were coated with 1-3 mu m of Ti6Al4V (Grade V) alloy using DC-pulsed or high-power impulse magnetron sputtering (HiPIMS) technique with the aim of improving their biomedical performance. SEM, confocal microscopy, X-ray dif-fraction, nanoindentation and wetting measurements are used to evaluate the bio-interface role of the titanium-coated implants. Conformal Ti6Al4V coatings with controlled nano-roughness can be deposited with enhanced mechanical (H = 5-8 GPa; E = 140-160 GPa) and hydrophobic properties thanks to a dense columnar structure. The increased Ti-O bonding at the interface helps to prevent the corrosion due to the formation of a surface passivation layer. Particularly in the case of the HiPIMS process, the surface mod-ification of titanium implants (chemistry, morphology and structure) appears as an effective strategy for satisfying the biomedical requirements and functionality, with enhanced mechanical properties and na-nostructuration for prevention of bacteria colonization.
Agosto, 2023 | DOI: 10.1016/j.jallcom.2023.170018
Química de Superficies y Catálisis
Hydrogen production by catalytic aqueous-phase reforming of waste biomass: a review
González-Arias, J; Zhang, Z; Reina, TR; Odriozola, JAEnvironmental Chemistry Letters, 21 (2023) 3089-3104 DOI: 10.1007/s10311-023-01643-w
Abstract
The rising adverse effects of climate change call for a rapid shift to low-carbon energy and reducing our dependence on fossil fuels. For that, biorefineries appear as promising alternatives to produce energy, chemicals, and fuels using biomass and waste as raw materials. Here, we review catalytic aqueous-phase reforming to convert biomass and organic waste carbohydrates into renewable hydrogen, with focus on reforming basics; catalyst design; reforming of model compounds, wastewater and biomass; economics and life cycle assessment. We found that platinum and palladium are technically highly effective, yet their high price may limit upscaling. Alternatively, addition of tin to nickel gives acceptable results and improves hydrogen selectivity from 35 to 90%. We observed that hydrogen production decreases from 14% for crude glycerol to 2% for pure glycerol, thus highlighting the need to do experiments with real wastewater. The rare experiments on real wastewater from brewery, juice, tuna, and cheese industries have given hydrogen production rates of up to 149.7 mg/L. Aqueous-phase reforming could be shortly competitive with prices around 3-6 USD per kg of hydrogen, which are nearing the current market prices of 2-3 USD per kg.
Agosto, 2023 | DOI: 10.1007/s10311-023-01643-w
Threads of memory: Reviving the ornament of a dead child at the Neolithic village of Ba`ja (Jordan)
Alarashi, H et al. [Aviles, MA]Plos One, 18 (2023) DOI: 10.1371/journal.pone.0288075
Abstract
In 2018, a well-constructed cist-type grave was discovered at Ba`ja, a Neolithic village (7,400-6,800 BCE) in Southern Jordan. Underneath multiple grave layers, an 8-year-old child was buried in a fetal position. Over 2,500 beads were found on the chest and neck, along with a double perforated stone pendant and a delicately engraved mother-of-pearl ring discovered among the concentration of beads. The first was found behind the neck, and the second on the chest. The meticulous documentation of the bead distribution indicated that the assemblage was a composite ornament that had gradually collapsed, partly due to the burying position. Our aim was to challenge time degradation and to reimagine the initial composition in order to best explore the significance of this symbolic category of material culture, not as mere group of beads, but as an ornamental creation with further aesthetic, artisanal and socioeconomic implications. The reconstruction results exceeded our expectations as it revealed an imposing multi-row necklace of complex structure and attractive design. Through multiple lines of evidence, we suggest that the necklace was created at Ba`ja, although significant parts of beads were made from exotic shells and stones, including fossil amber, an unprecedented material never attested before for this period. The retrieval of such an ornament from life and its attribution to a young dead child highlights the significant social status of this individual. Beyond the symbolic functions related to identity, the necklace is believed to have played a key role in performing the inhumation rituals, understood as a public event gathering families, relatives, and people from other villages. In this sense, the necklace is not seen as belonging completely to the realm of death but rather to the world of the living, materializing a collective memory and shared moments of emotions and social cohesion.
Agosto, 2023 | DOI: 10.1371/journal.pone.0288075
Materiales Ópticos Multifuncionales
Inkjet-Printed and Nanopatterned Photonic Phosphor Motifs with Strongly Polarized and Directional Light-Emission
Cabello-Olmo, E; Romero, M; Kainz, M; Bernroitner, A; Kopp, S; Muhlberger, M; Lozano, G; Miguez, HAdvanced Functional Materials, (2023) 2305907 DOI: 10.1002/adfm.202305907
Abstract
Herein a versatile and scalable method to prepare periodically corrugated nanophosphor surface patterns displaying strongly polarized and directional visible light emission is demonstrated. A combination of inkjet printing and soft lithography techniques is employed to obtain arbitrarily shaped light emitting motifs. Such predesigned luminescent drawings, in which the polarization and angular properties of the emitted light are determined and finely tuned through the surface relief, can be used as anti-counterfeiting labels, as these two specific optical features provide additional means to identify any unauthorized or forged copy of the protected item. The potential of this approach is exemplified by processing a self-standing photoluminescent quick response code whose emission is both polarized and directionally beamed. Physical insight of the mechanism behind the directional out-coupled photoluminescence observed is provided by finite-difference time-domain calculations.
Agosto, 2023 | DOI: 10.1002/adfm.202305907
Materiales Semiconductores para la Sostenibilidad
Surfactant-Dependent Bulk Scale Mechanochemical Synthesis of CsPbBr3 Nanocrystals for Plastic Scintillator-Based X-ray Imaging
Ghosh, J; O'Neill, J; Masteghin, MG; Braddock, I; Crean, C; Dorey, R; Salway, H; Anaya, M; Reiss, J; Wolfe, D; Sellin, PACS Applied Nano Materials, DOI: 10.1021/acsanm.3c02531
Abstract
We report a facile, solvent-free surfactant-dependentmechanochemicalsynthesis of highly luminescent CsPbBr3 nanocrystals (NCs)and study their scintillation properties. A small amount of surfactantoleylamine (OAM) plays an important role in the two-step ball millingmethod to control the size and emission properties of the NCs. Thesolid-state synthesized perovskite NCs exhibit a high photoluminescencequantum yield (PLQY) of up to 88% with excellent stability. CsPbBr3 NCs capped with different amounts of surfactant were dispersedin toluene and mixed with polymethyl methacrylate (PMMA) polymer andcast into scintillator discs. With increasing concentration of OAMduring synthesis, the PL yield of CsPbBr3/PMMA nanocompositewas increased, which is attributed to reduced NC aggregation and PLquenching. We also varied the perovskite loading concentration inthe nanocomposite and studied the resulting emission properties. Themost intense PL emission was observed from the 2% perovskite-loadeddisc, while the 10% loaded disc exhibited the highest radioluminescence(RL) emission from 50 kV X-rays. The strong RL yield may be attributedto the deep penetration of X-rays into the composite, combined withthe large interaction cross-section of the X-rays with the high-Zatoms within the NCs. The nanocomposite disc shows an intense RL emissionpeak centered at 536 nm and a fast RL decay time of 29.4 ns. Further,we have demonstrated the X-ray imaging performance of a 10% CsPbBr3 NC-loaded nanocomposite disc.
Agosto, 2023 | DOI: 10.1021/acsanm.3c02531
Química de Superficies y Catálisis
H2-rich syngas production from biogas reforming: Overcoming coking and sintering using bimetallic Ni-based catalysts
Carrasco-Ruiz, S; Zhang, Q; Gándara-Loe, J; Pastor-Pérez, L; Odriozola, JA; Reina, TR; Bobadilla, LFInternational Journal of Hydrogen Energy, 48 (2023) 72 DOI: 10.1016/j.ijhydene.2023.03.301
Abstract
Dry reforming of methane is a very appealing catalytic route biogas (mainly composed by greenhouse gases: carbon dioxide and methane) conversion into added value syngas, which could be further upgraded to produce liquid fuels and added value chemicals. However, the major culprits of this reaction are coking and active phase sintering that result in catalysts deactivation. Herein we have developed a highly stable bimetallic Ni–Rh catalyst supported on mixed CeO2–Al2O3 oxide using low-noble metal loadings. The addition of small amounts of rhodium to nickel catalysts prevents coke formation and improves sintering resistance, achieving high conversions over extended reaction times hence resulting in promising catalysts for biogas upgrading.
Agosto, 2023 | DOI: 10.1016/j.ijhydene.2023.03.301
Materiales Ópticos Multifuncionales
Measurement principles for quantum spectroscopy of molecular materials with entangled photons
Moretti, L; Rojas-Gatjens, E; Uboldi, L; Tiede, DO; Kumar, EJ; Trovatello, C; Preda, F; Perri, A; Manzoni, C; Cerullo, G; Kandada, ARSJournal of Chemical Physics, 159 (2023) 084201 DOI: 10.1063/5.0156598
Abstract
Nonlinear spectroscopy with quantum entangled photons is an emerging field of research that holds the promise to achieve superior signal-to-noise ratio and effectively isolate many-body interactions. Photon sources used for this purpose, however, lack the frequency tunability and spectral bandwidth demanded by contemporary molecular materials. Here, we present design strategies for efficient spontaneous parametric downconversion to generate biphoton states with adequate spectral bandwidth and at visible wavelengths. Importantly, we demonstrate, by suitable design of the nonlinear optical interaction, the scope to engineer the degree of spectral correlations between the photons of the pair. We also present an experimental methodology to effectively characterize such spectral correlations. Importantly, we believe that such a characterization tool can be effectively adapted as a spectroscopy platform to optically probe system-bath interactions in materials.
Agosto, 2023 | DOI: 10.1063/5.0156598
Reactividad de Sólidos
Touch-free reactive flash sintering of dense strontium hexaferrite permanent magnet
Jalali, SIA; Manchon-Gordon, AF; Chacartegui, R; Sanchez-Jimenez, PE; Blazquez, JS; Perejon, A; Raj, R; Pérez-Maqueda, LAJournal of the American Ceramic Society (2023) DOI: 10.1111/jace.19389
Abstract
This work presents an extension of the touch-free flash sintering technique. In the proposed technique, chemical reaction and sintering occur in a single step, without the use of electrodes, in the presence of electric and magnetic fields. We show that a dense, single-phase strontium hexaferrite magnet can be produced from a mixture of commercial carbonate and oxide powders in a single step in a little more than a minute. This new technique implies significant reduction in energy and time consumption (primarily because of ultrafast processing) relative to conventional sintering.
Agosto, 2023 | DOI: 10.1111/jace.19389
Reactividad de Sólidos
Seville history insight through their construction mortars
Perez-Rodriguez, JL; Perez-Maqueda, LA; Franquelo, ML; Duran, AJournal of Thermal Analysis and Calorimetry, (2023) DOI: 10.1007/s10973-023-12313-y
Abstract
Seville is intimately linked to its historic role and extensive cultural heritage. The city has been occupied by Romans, Arabs and Christians, who built important historical buildings. Roman (first-second centuries) and Arabic (eleventh century) buildings, medieval Shipyard (thirteenth century), San Isidoro and Santa Maria de las Cuevas monasteries (fifteenth century), Santa Maria de las Cuevas (fifteenth century modified in eighteenth century), El Salvador Church (eighteenth century), the Royal Ordnance building (eighteenth century) and Santa Angela de la Cruz convent (twentieth century) performed with lining mortars, and mortars used in building stones (City Hall and Marchena Gate), all of them located in Seville (Spain), have been studied. Ninety-four mortar samples (employed as structural, plaster, coating) originally used or applied in restoration processes have been collected to perform an archaeometry study. The ratio of CO2 mass loss to hydraulic water (H2O) mass loss, and the mineralogical characterization by X-ray diffraction has been used to compare the mortars used in the different historical periods. Mainly hydraulic mortars were widely used in all these studied monuments as most mortars showed CO2/H2O ratios within the 4-10 range. Moreover, the thermal analysis curves also showed a broad temperature range for the thermal decomposition of the carbonate fraction of the mortars.
Julio, 2023 | DOI: 10.1007/s10973-023-12313-y
Química de Superficies y Catálisis
New 3D Printing Strategy for Structured Carbon Devices Fabrication
Delgado-Martin, G; Rodriguez, N; Dominguez, MI; Agamez-Pertuz, YY; Tejada, MM; Ruiz-Lopez, E; Ivanova, S; Centeno, MACatalysts, 13 (2023) 1039 DOI: 10.3390/catal13071039
Abstract
This work shows a new method for the preparation of 100% carbon-structured devices. The method is based on resorcinol-formaldehyde polymerization, using starch as a binder with the addition of a certain amount of external carbon source before polymerization. Molds obtained by 3D printing are used to shape the structured devices in the desired shape, and the ultimate pyrolysis step consolidates and produces the carbonaceous devices. The proposed method allows obtaining supports with different textural and surface properties varying the carbonaceous source, the solvent, or the pyrolysis conditions, among other factors. The as-obtained devices have demonstrated their usefulness as palladium supports for the gas-phase formic acid dehydrogenation reaction. The monolith shows a high conversion of formic acid (81% according to H-2 production) and a high selectivity towards hydrogen production at mild temperatures (80% at 423 K).
Julio, 2023 | DOI: 10.3390/catal13071039
Reactividad de Sólidos
Thermochemical energy storage using calcium magnesium acetates under low CO2 pressure conditions
Amghar, N; Jimenez, PES; Maqueda, LAP; Perejon, AJournal of Energy Storage, 63 (2023) 106958 DOI: 10.1016/j.est.2023.106958
Abstract
The calcium looping multicycle performance of CaO-based materials, derived from calcium magnesium acetates with different Mg content were tested under experimental conditions compatible with thermochemical energy storage. In order to reduce the sintering-induced decay in performance, calcination at an absolute CO2 pressure of 0.1 bar and 0.01 bar is implemented. CaO carbonation is performed at standard 1 bar CO2 conditions. The samples can be fully calcined in short residence times. Samples with MgO present high cycling stability, even when the MgO content is as low as 5 mol%. The effective conversion values lie within the range 0.88-0.84 over ten calcination/carbonation cycles, which provides an accumulated energy storage density of 90.9 GJ/m3. This outstanding reactivity is related with the microstructure of the sample after calcination composed of CaO nanoparticles that are highly reactive for carbonation.
Julio, 2023 | DOI: 10.1016/j.est.2023.106958
Nanotecnología en Superficies y Plasma
Setting a comprehensive strategy to face the runback icing phenomena
Mora, J et al.Surface & Coatings Technology, 465 (2023) 129585 DOI: 10.1016/j.surfcoat.2023.129585
Abstract
The development of anti-icing robust surfaces is a hot topic nowadays and particularly crucial in the aeronautics or wind energy sectors as ice accretion can compromise safety and power generation efficiency. However, the current performance of most anti-icing strategies has been proven insufficient for such demanding applications, particularly in large unprotected zones, which located downstream from thermally protected areas, may undergo secondary icing. Herein, a new testing methodology is proposed to evaluate accretion mechanisms and secondary icing phenomena through, respectively, direct impact and running-wet processes and systematically applied to anti-icing materials including commercial solutions and the latest trends in the state-of-the-art. Five categories of materials (hard, elastomeric, polymeric matrix, SLIPS and superhydrophobic) with up to fifteen formulations have been tested. This Round-Robin approach provides a deeper understanding of anti-icing mechanisms revealing the strengths and weaknesses of each material. The conclusion is that there is no single passive solution for anti-ice protection. Thus, to effectively protect a given real component, different tailored materials fitted for each particular zone of the system are required. For this selection, shape analysis of such a component and the impact characteristics of water droplets under real conditions are needed as schematically illustrated for aeronautic turbines.
Julio, 2023 | DOI: 10.1016/j.surfcoat.2023.129585
Materiales Ópticos Multifuncionales
Ultrapure Green High Photoluminescence Quantum Yield from FAPbBr3 Nanocrystals Embedded in Transparent Porous Films
Romero-Pérez, C; Delgado, NF; Herrera-Collado, M; Calvo, ME; Míguez, H (MigChemistry of Materials, 35 (2023) 5541-5549 DOI: 10.1021/acs.chemmater.3c00934
Abstract
Achieving highly transparent and emissive films based on perovskite quantum dots (PQDs) is a challenging task since their photoluminescence quantum yield (PLQY) typically drops abruptly when they are used as building blocks to make a solid. In this work, we obtain highly transparent films containing FAPbBr(3) quantum dots that display a narrow green emission (lambda = 530 nm, full width at half-maximum (FWHM) = 23 nm) with a PLQY as high as 86%. The method employed makes use of porous matrices that act as arrays of nanoreactors to synthesize the targeted quantum dots within their void space, providing both a means to keep them dispersed and a protective environment. Further infiltration with poly(methyl methacrylate) (PMMA) increases the mechanical and chemical stability of the ensemble and serves to passivate surface defects, boosting the emission of the embedded PQD and significantly reducing the width of the emission peak, which fulfills the requirements established by the Commission Internationale de l'E ' clairage (CIE) to be considered an ultrapure green emitter. The versatility of this approach is demonstrated by fabricating a color-converting layer that can be easily transferred onto a light-emitting device surface to modify the spectral properties of the outgoing radiation.
Julio, 2023 | DOI: 10.1021/acs.chemmater.3c00934
Química de Superficies y Catálisis
Effect of noble metal addition over active Ru/TiO2 catalyst for CO selective methanation from H2 rich- streams
Bobadilla, LF; Muñoz-Murillo, A; Gandara-Loe, J; Perez, A; Laguna, OH; Martinez, TLM; Penkova, A; Centeno, MA; Odriozola, JAInternational Journal of Hydrogen Energy, 48 (2023) 25065-25074 DOI: 10.1016/j.ijhydene.2022.07.072
Abstract
Selective CO methanation from H2-rich stream has been regarded as a promising route for deep removal of low CO concentration and catalytic hydrogen purification processes. This work is focused on the development of more efficient catalysts applied in practical conditions. For this purpose, we prepared a series of catalysts based on Ru supported over titania and promoted with small amounts of Rh and Pt. Characterization details revealed that Rh and Pt modify the electronic properties of Ru. The results of catalytic activity showed that Pt has a negative effect since it promotes the reverse water gas shift reaction decreasing the selectivity of methanation but Rh increases remarkably the activity and selectivity of CO methanation. The obtained results suggest that RuRh-based catalyst could become important for the treatment of industrial-volume streams.
Julio, 2023 | DOI: 10.1016/j.ijhydene.2022.07.072
Reactividad de Sólidos
R-curve evaluation of 3YTZP/graphene composites by indirect compliance method
Lopez-Pernia, C; Munoz-Ferreiro, C; Prada-Rodrigo, J; Moreno, P; Reveron, H; Chevalier, J; Morales-Rodriguez, A; Poyato, R; Gallardo-Lopez, AJournal of the European Ceramic Society, 43 (2022) 3486-3497 DOI: 10.1016/j.jeurceramsoc.2023.02.002
Abstract
This work addresses the crack growth resistance of 3 mol% Yttria-doped Tetragonal Zirconia Polycrystalline (3YTZP) spark-plasma sintered (SPS) composites containing two types of graphene-based nanomaterials (GBN): exfoliated graphene nanoplatelets (e-GNP) and reduced graphene oxide (rGO). The crack growth resistance of the composites is assessed by means of their R-Curve behavior determined by three-point bending tests on single edge "V" notched beams (SEVNB), in two different orientations of the samples: with the crack path perpendicular or parallel to the pressure axis during the SPS sintering. The sharp edge notches were machined by ultrashort laser pulsed ablation (UPLA). The compliance and optical-based methods for evaluating the crack length are compared on the basis of the experimental R-Curve results in composites with 2.5 vol% rGO tested in the perpendicular orientation. Moreover, the activation of reinforcement mechanisms is evaluated by both the fracture surface inspection by Scanning Electron Microscopy and a compliance analysis. It is shown that the indirect compliance method is relevant and reliable for calculating the R-Curve of 3YTZP/GBN composites. The effect of the type and content of GBN on the crack growth resistance of the composites is also discussed.
Julio, 2023 | DOI: 10.1016/j.jeurceramsoc.2023.02.002
Nanotecnología en Superficies y Plasma
Dielectric multilayers for broadband optical rotation enhancement
Pellegrini, G; Mogni, E; Gil-Rostra, J; Yubero, F; Fossati, S; Dostálek, J; Vázquez, RM; Osellame, R; Celebrano, M; Finazzi, M; Biagioni, PNuovo Cimento C-Colloquia and Communications in Physics, 46 (2023) 111 DOI: 10.1393/ncc/i2023-23111-1
Abstract
We design a simple dielectric multilayer capable of sustaining broadband superchiral surface waves. We show that the platform can produce large optical chirality enhancements in a wavelength range of hundreds of nanometers. We finally demonstrate that these properties result in the enhancement of the optical rotation signal well above two orders of magnitude, thus extending surface-enhanced chiral spectroscopies beyond the traditionally addressed circular dichroism signals.
Julio, 2023 | DOI: 10.1393/ncc/i2023-23111-1
Fotocatálisis Heterogénea: Aplicaciones
ZnO/TiO2 and ZnO/Nb2O5 as effective systems for the treatment of enteric bacteria and commercial dyes
Hernandez, JS; Murcia, JJ; Rojas, H; Hidalgo, MC; Navio, JARevista Facultad de Ingeniería-Universidad de Antioquia, 108 (2023) 9-17 DOI: 10.17533/udea.redin.20220785
Abstract
In this study, ZnO/TiO2 and ZnO/Nb2O5 photocatalysts were evaluated in the river pollution remediation and wastewater treatment from textile factories, thus, the target pollutants selected for this study were enteropathogenic bacteria and commercial dyes. The mixed oxide systems were extensively analyzed in order to explore their physicochemical properties. From this analysis, it was found that the coupling of two oxides did not modify the crystallinity of the pristine semiconductors. As a result, XRD Wurtzite phase, hexagonal phase, and anatase phases were identified for ZnO, Nb2O5, and TiO2 photocatalyst, respectively. Using UV-Vis DRS, a higher absorption for mixed oxides in the visible region of the electromagnetic spectrum was observed, along with a decrease in the band gap value in these materials. The results of the photocatalytic activity evaluation showed that the coupling of ZnO with Nb2O5 and TiO2 increased the effectiveness of the total organic carbon (TOC) and E. Coli elimination. 83% of TOC and elimination of 64% of E. coli were achieved using ZnO/Nb2O5 photocatalyst for the treatment of water samples from the polluted river.
Julio, 2023 | DOI: 10.17533/udea.redin.20220785
Reactividad de Sólidos
An overview of polymeric composite scaffolds with piezoelectric properties for improved bone regeneration
Donate, R; Paz, R; Moriche, R; Sayagués, MJ; Alemán-Domínguez, ME; Monzón, MMaterials & Design, 231 (2023) 112085 DOI: 10.1016/j.matdes.2023.112085
Abstract
Despite the dramatic change that Tissue Engineering or stem cell therapies have brought to current therapeutic strategies, there is a lack of functionalities in the available biomaterials for manufacturing scaffolds to treat several highly prevalent osseous diseases (osteochondral defects, osteoporosis, etc.). One promising approach to fill this gap involves the development of innovative piezoelectric scaffolds for improved bone regeneration. Scaffolds with the appropriate piezoelectricity can positively influence the proliferation and differentiation of mesenchymal stem cells to regenerate bone tissue, since surface electrical charges play a key role in the mechanotransduction process. In this work, polymeric-based composite scaffolds with piezoelectric properties intended for bone tissue engineering are reviewed. Special attention is paid to biocompatible, piezoelectric polymers that show suitable properties to be pro-cessed by additive manufacturing techniques. Previous works on composite scaffolds based of these poly-meric matrices and containing piezoceramic additives are summarized. The use of piezoelectric nanostructured composite formulations containing lead-free ceramic oxide nanoparticles with per-ovskite structure is highlighted. Also, different commonly applied mechanical stimuli to activate the piezoelectric effect of the developed materials are presented. Finally, other applications of such scaffolds are mentioned, including their capabilities for real-time monitoring
Julio, 2023 | DOI: 10.1016/j.matdes.2023.112085 http://hdl.handle.net/10261/355426
Química de Superficies y Catálisis
Biochar production from cellulose under reductant atmosphere: influence of the total pyrolysis time
Santos, JL; Centeno, MA; Odriozola, JARSC Advances, 13 (2023) 21071-21079 DOI: 10.1039/d3ra03093h
Abstract
Today's rising energy costs, coupled with increasing energy demand, make it necessary to search for more efficient energy processes. In recent years, there have been increasing efforts to develop efficient catalysts based on waste-derived char, by a single step where the carbon precursor and the metallic active phase one undergo a single common thermal process under a reductant atmosphere at high temperature. The use of a reductant atmosphere drives the formation of carbonaceous materials with different characteristics than those obtained under the standard nitrogen-inert one. Our work evaluates the influence of the residence time and the heating rate on the physicochemical properties of the biochar obtained. Relatively long residence times and slow heating rates, improve the yield to the resulting biochar, without increasing production cost, making the subsequent char-based metallic catalyst synthesis more efficient. The heating rate was shown to be key in improving the properties of the char in a smoother and more controlled way, unlocking a new working pathway for the efficient design and production of char-based catalysts in a one-pot synthesis.
Julio, 2023 | DOI: 10.1039/d3ra03093h
Materiales Avanzados
Influence of firing temperature on the ceramic properties of illite-chlorite-calcitic clays
Martinez-Martinez, S; Perez-Vilarejo, L; Garzon, E; Sanchez-Soto, PJCeramics International, 49 (2023) 24541-24557 DOI: 10.1016/j.ceramint.2022.11.077
Abstract
The influence of firing temperature on the ceramic properties of illite-chlorite-calcitic clays has been investigated. Three samples of the same clay deposit have been selected. Weight loss, dimensional changes, water absorption, bulk density, open porosity, flexural and compressive strengths, initial capillary water absorption rate and thermal conductivity have been determined as a function of firing temperature in the range 900-1200 degrees C with 1 h of soaking time. The microstructures of the fired samples have been examined by SEM and the phase evolution studied by XRD. The water absorption capacity decreased from similar to 22% at 900 degrees C/1 h to a maximum of 12% at 1200 degrees C/1 h with a maximum linear shrinkage of similar to 2.7%. The open porosities decreased from similar to 22% at 900 degrees C/1 h up to similar to 20% at 1200 degrees C/1 h as an effect of progressive sintering with higher densification degree of the ceramic bodies. The flexural strength reached a maximum value of similar to 34 MPa at 1200 degrees C/1 h. In contrast, the compressive strengths increased by firing up to a maximum of similar to 114 MPa at 1200 degrees C/1 h. The thermal conductivity increased slightly as increasing firing temperature with a maximum value of 0.582 W/m.K in samples fired at 1200 degrees C/1 h. The Ryshkevitch-Duckworth equation was applied and the results indicated that compressive strength is related linearly with open porosity. A linear correlation was found between thermal conductivity and open porosity. The microstructural evolution by SEM indicated that there is a change of the fired samples at 1100 degrees C as compared to SEM observations at 900 and 1000 degrees C. There is an increase of contacts between particles and layered structures associated to dehydroxylated clay minerals (illite and chlorite), quartz particles and pores developed by firing. At 1200 degrees C/1 h, the microstructures have changed associated to the higher degree of vitrification in the fired sample, with consolidation of the material, interparticle and neck contacts with formation of vitrified bridges. The formation of closed and large open pores of several sizes has been achieved by firing. Small particles were observed as a fine precipitation of crystals in the vitrified structures associated to anorthite, hematite and quartz relicts. This change in microstructure allowed deduce that the compressive strength increased upon firing, with maximum values of this ceramic property at 1200 degrees C. The ceramic bodies were more sintered by firing and the open porosity decreased progressively. Brickmaking is the main application of these fired illite-chlorite calcitic clays. These clays fired at 900-1100 degrees C, with 1 h of soaking time, could be applied in the fabrication of clay roofing tiles, tiles and even porous ceramic supports with small variations on shrinkage and porosity, good flexural strengths and high compressive strengths. Samples fired at higher temperatures, 1100 degrees C/1 h, could be applied as ceramic bricks showing a medium porosity (similar to 20%). They show almost the same bulk density when they are fired at lower temperatures (900 degrees C). Samples fired at higher temperatures (1150-1200 degrees C/1 h) could be applied as dark ceramic products. This investigation was interesting because a better knowledge of illite-chlorite-calcitic clays applied as ceramic raw materials has been achieved.
Julio, 2023 | DOI: 10.1016/j.ceramint.2022.11.077
Reactividad de Sólidos
Partial oxycombustion-calcium looping hybridisation for CO2 capture in waste-to-energy power plants
Ortiz, C; García-Luna, S; Chacartegui, R; Valverde, JM; Pérez-Maqueda, LJournal of Cleaner Production, 403 (2023) 136776 DOI: 10.1016/j.jclepro.2023.136776
Abstract
Integrating bioenergy and carbon capture and storage (BECCS) presents a great opportunity for power produc-tion with negative global CO2 emissions. This work explores a novel synergetic system that integrates mem-branes, partial biomass oxycombustion and the calcium looping (CaL) process. Polymeric membranes generate oxygen-enriched air (OEA) with an O2 concentration of 39%v/v, which is used for partial oxycombustion of biomass waste. The CO2-enriched flue gas evolves from the waste-to-energy plant to the CaL unit, where CO2 concentration is increased up to 90-95%v/v, ready for purification and sequestration. Compared to only oxy-combustion systems, the proposed concept presents fewer technological challenges in retrofitting boilers to waste-to-energy plants. Moreover, this new approach is highly efficient as integrating membranes to produce OEA instead of cryogenic distillation systems significantly reduces energy consumption. A novel integration concept is modelled to evaluate the whole process efficiency and the effect of key parameters on the system performance, such as the temperature of the reactors, the membrane surface area, and the partial oxy-combustion degree. The results show that the so-called mOxy-CaL system has an energy consumption associ-ated with CO2 capture below 4 MJ/kg CO2 (a 31% lower than that for a conventional CaL process), with a higher CO2 capture efficiency than oxycombustion and the CaL process separately. On the other hand, the economic analysis shows a higher CO2 capture cost for the novel configuration than for the typical CaL configuration due to the additional investment cost of the membrane system. Improvements in membrane performance by increasing its permeance and diminishing the required surface area would significantly reduce the economic cost of this novel integration. Using membranes with permeance over 400 GPU would boost the system's competitiveness.
Junio, 2023 | DOI: 10.1016/j.jclepro.2023.136776
Química de Superficies y Catálisis
Hydrothermal carbonization vs. anaerobic digestion to valorize fruit and vegetable waste: A comparative technical and energy assessment
Metyouy, K; Gonzalez, R; Gomez, X; Gonzalez-Arias, J; Martinez, EJ; Chafik, T; Sanchez, ME; Cara-Jiménez, JJournal of Environmental Chemical Engineering, 11 (2023) 109925 DOI: 10.1016/j.jece.2023.109925
Abstract
Herein, the valorization of vegetable and fruit waste was assessed via hydrothermal carbonization (HTC) and anaerobic digestion (AD) in terms of product characterization and energy requirements. HTC was conducted at reaction temperatures between 150 & DEG;C and 190 & DEG;C, and residence times between 20 min and 40 min. The increase in the process severity resulted in hydrochars with higher carbon contents and higher energy densification ratios. AD was performed in two different ways. i.e., batch and semi-continuous reactions. From the batch experiments a methane yield of 300 L CH4/kg VS was obtained, while for the semi-continuous, the average specific methane production estimated (for HRTs from 75 to 50 days) was 213 & PLUSMN; 32 L CH4/kg VS. To estimate the energy re-quirements, mass and energy balances were performed considering the basic stages of each process to obtain a suitable biofuel material. In this sense, it was concluded that for this specific waste, AD was a more suitable process with a positive energy net balance. On the contrary, HTC presented a negative energy net balance being required 1.29 MJ/kg of fresh food waste. A combined HTC-AD treatment may be an efficient method to take advantage of both technologies leading to higher energy efficiencies and other valuable products.
Junio, 2023 | DOI: 10.1016/j.jece.2023.109925
Química de Superficies y Catálisis
Are Ni/ and Ni5Fe1/biochar catalysts suitable for synthetic natural gas production? A comparison with g-Al2O3 supported catalysts
González-Castaño, M; Morales, C; de Miguel, JCN; Boelte, JH; Klepel, O; Flege, JI; Arellano-Garcia, HGreen Energy & Environment, 8 (2023) 744-756 DOI: 10.1016/j.gee.2021.05.007
Abstract
Among challenges implicit in the transition to the post-fossil fuel energetic model, the finite amount of resources available for the technological implementation of CO2 revalorizing processes arises as a central issue. The development of fully renewable catalytic systems with easier metal recovery strategies would promote the viability and sustainability of synthetic natural gas production circular routes. Taking Ni and NiFe catalysts supported over g-Al2O3 oxide as reference materials, this work evaluates the potentiality of Ni and NiFe supported biochar catalysts for CO2 methanation. The development of competitive biochar catalysts was found dependent on the creation of basic sites on the catalyst surface. Displaying lower Turn Over Frequencies than Ni/Al catalyst, the absence of basic sites achieved over Ni/C catalyst was related to the depleted catalyst performances. For NiFe catalysts, analogous Ni5Fe1 alloys were constituted over both alumina and biochar supports. The highest specific activity of the catalyst series, exhibited by the NiFe/C catalyst, was related to the development of surface basic sites along with weaker NiFe-C interactions, which resulted in increased Ni0:NiO surface populations under reaction conditions. In summary, the present work establishes biochar supports as a competitive material to consider within the future low-carbon energetic panorama.
Junio, 2023 | DOI: 10.1016/j.gee.2021.05.007 http://hdl.handle.net/10261/246312
Química de Superficies y Catálisis
Review and Perspectives of CO2 Absorption by Water- and Amine-Based Nanofluids
Yuan, CT; Wang, Y; Baena-Moreno, FM; Pan, Z; Zhang, R; Zhou, H; Zhang, ZEnergy & Fuels, 37 (2023) 8883-8901 DOI: 10.1021/acs.energyfuels.3c00874
Abstract
The emission of greenhouse gases, especially CO2, hasbecome a major cause of environmental degradation, and carbon capture,utilization, and storage (CCUS) is a proposed solution to mitigateits impact. Nanofluids, a relatively new method for CO2 absorption, have gained attention in recent years. This review focuseson conventional methods for preparing nanofluids along with techniquesto improve their stability and enhance the CO2 absorptionand desorption mechanisms. Additionally, the influences of factors,i.e., nanoparticle and base solution types as well as nanoparticleconcentration, on the CO2 absorption process are summarized.Furthermore, models that can predict the absorption of CO2 accurately are outlined. It is found that the types of both baseliquids and nanoparticles have an important impact on the absorptionby nanofluids. In-depth studies on the predictive capabilities ofartificial intelligence (AI) models hold immense potential in thisregard. This review also puts forth effective strategies to addressprevailing challenges. This will provide a solid theoretical basisfor this field and underscore the promising potential of nanofluidsas CO2 solvents. There are still many unexplored aspectsto be considered, such as the economic viability and energy consumptionof this technology.
Junio, 2023 | DOI: 10.1021/acs.energyfuels.3c00874
Química de Superficies y Catálisis
Toluene combustion on MnOx, CeO2, and Mn-Ce-O solids prepared via citrate complexation, and citrate and urea combustion methods
Rahou, S; Benadda-Kordjani, A; Ivanova, S; Odriozola, JA; Chebout, R; Mahzoul, H; Zouaoui, NJournal of Nanoparticle Research, 25 (2023) 114 DOI: 10.1007/s11051-023-05759-6
Abstract
MnOx, CeO2, and MnCe-O (Mn/Ce = 1) solids have been prepared via the citrate complexation and combustion method using citrate and urea precursors. The solids have been characterized by XRD, SEM-EDX, N-2-adsorption-desorption, UV-Vis spectroscopy, TPR, O-2-TPD, and XPS techniques. The catalytic reactivity of the manganese oxides was not affected by the preparation protocol. In the case of ceria and mixed oxides, the synthesis method greatly affected the structural and chemical properties, ultimately altering their reactivity. The citrate complexation method produced the most homogeneous and active mixed oxide, whereas the urea combustion method resulted in less active solids. The mixed oxide prepared via urea combustion was less active than the manganese single oxide; the decrease in activity was attributed to phase separation and the formation of Mn3O4 domains on the surface of ceria. In contrast, citrate complexation resulted in solids with the lowest particle size (similar to 3 nm), the highest oxidation state for manganese, and the highest proportion of oxygen vacancies, which promote the oxidation reaction.
Junio, 2023 | DOI: 10.1007/s11051-023-05759-6
Química de Superficies y Catálisis
Formic Acid Dehydrogenation over a Monometallic Pd and Bimetallic Pd:Co Catalyst Supported on Activated Carbon
Pelaez, MR; Ruiz-Lopez, E; Dominguez, MI; Ivanova, S; Centeno, MACatalysts, 13 (2023) 977 DOI: 10.3390/catal13060977
Abstract
In this study, palladium is proposed as an active site for formic acid dehydrogenation reaction. Pd activity was modulated with Co metal with the final aim of finding a synergistic effect that makes possible efficient hydrogen production for a low noble metal content. For the monometallic catalysts, the metal loadings were optimized, and the increase in the reaction temperature and presence of additives were carefully considered. The present study aimed, to a great extent, to enlighten the possible routes for decreasing noble metal loading in view of the better sustainability of hydrogen production from liquid organic carrier molecules, such as formic acid.
Junio, 2023 | DOI: 10.3390/catal13060977
Nanotecnología en Superficies y Plasma
Structure and Void Connectivity in Nanocolumnar Thin Films Grown by Magnetron Sputtering at Oblique Angles
Alvarez, R; Regodon, G; Acosta-Rivera, H; Rico, V; Alcala, G; Gonzalez-Elipe, AR; Palmero, ACoatings, 13 (2023) 991 DOI: 10.3390/coatings13060991
Abstract
The morphology and void connectivity of thin films grown by a magnetron sputtering deposition technique at oblique geometries were studied in this paper. A well-tested thin film growth model was employed to assess the features of these layers along with experimental data taken from the literature. A strong variation in the film morphology and pore topology was found as a function of the growth conditions, which have been linked to the different collisional transport of sputtered species in the plasma gas. Four different characteristic film morphologies were identified, such as (i) highly dense and compact, (ii) compact with large, tilted mesopores, (iii) nanocolumns separated by large mesopores, and (iv) vertically aligned sponge-like coalescent nanostructures. Attending to the topology and connectivity of the voids in the film, the nanocolumnar morphology was shown to present a high pore volume and area connected with the outside by means of mesopores, with a diameter above 2 nm, while the sponge-like nanostructure presented a high pore volume and area, as well as a dense network connectivity by means of micropores, with a diameter below 2 nm. The obtained results describe the different features of the porous network in these films and explain the different performances as gas or liquid sensors in electrochromic applications or for infiltration with nanoparticles or large molecules.
Junio, 2023 | DOI: 10.3390/coatings13060991
Reactividad de Sólidos
Effect of thermal treatments below devitrification temperature on the magnetic and magnetocaloric properties in mechanically alloyed Fe70Zr30 powders
Manchon-Gordon, AF; Blazquez, JS; Kowalczyk, M; Ipus, JJ; Kulik, T; Conde, CFJournal of Non-Crystalline Solids, 609 (2023) 122267 DOI: 10.1016/j.jnoncrysol.2023.122267
Abstract
In this work, the relaxation of the amorphous structure of mechanically alloyed Fe70Zr30 powders has been analyzed through interrupted heating ramps below the devitrification temperature. As a result of such thermal treatment, Curie temperature and temperature at maximum magnetic entropy change curves shift to higher temperatures as the temperature of heating treatment increases. This effect can be attributed to both the release of the stress accumulated in the amorphous powder during the milling process and to the initiation of nucleation of alpha-Fe crystallites, as it has been shown by Mo center dot ssbauer spectroscopy.
Junio, 2023 | DOI: 10.1016/j.jnoncrysol.2023.122267
Nanotecnología en Superficies y Plasma - Tribología y Protección de Superficies
Low temperature nucleation of thermochromic VO2 crystal domains in nanocolumnar porous thin films
Alcaide, AM; Regodon, G; Ferrer, FJ; Rico, V; Alvarez, R; Rojas, TC; Gonzalez-Elipe, AR; Palmero, ANanotechnology, 34 (2023) 255702 DOI: 10.1088/1361-6528/acc664
Abstract
The low temperature formation of monoclinic VO2 crystal domains in nanocolumnar vanadium/oxygen thin films prepared by magnetron sputtering at oblique angles is analyzed. The synthesis procedure involved the deposition of amorphous nanocolumnar VO1.9 thin films at room temperature and its subsequent annealing at temperatures between 250 °C and 330 °C in an oxygen atmosphere. The thermochromic transition of these films was found at a temperature of 47 °C when the annealing temperature was 270 °C and 58 °C when the annealing temperature was 280 °C and 290 °C, presenting a clear drop of the optical transmittance in the infrared region of the spectrum. The significant downshift in the temperature window to obtain VO2 in comparison with compact films and other strategies in literature is explained by the particular morphology of the nanocolumnar structures, which contains numerous defects along with open and embedded porosity.
Junio, 2023 | DOI: 10.1088/1361-6528/acc664
Materiales Nanoestructurados y Microestructura
Microstructural characterization and thermal stability of He charged amorphous silicon films prepared by magnetron sputtering in helium
Fernández, A; Sauvage, T; Diallo, B; Hufschmidt, D; de Haro, MCJ; Montes, O; Martínez-Blanes, JM; Caballero, J; Godinho, V; Ferrer, FJ; Ibrahim, S; Brault, P; Thomann, ALMaterials Chemistry and Physics, 301 (2023) 127674 DOI: 10.1016/j.matchemphys.2023.127674
Abstract
Sputtering of silicon in a Helium magnetron discharge has been reported as a bottom-up procedure to obtain amorphous Si films containing high amounts of gas-filled nanopores. Here we compare the microstructure and composition of Si-He nanocomposite films deposited by magnetron sputtering (MS) with 4He in DC or RF and 3He in RF operation modes. Electron microscopy (SEM and TEM), X-ray diffraction (XRD) and ion beam analysis (IBA) have been used to analyze the films and to investigate the in-situ and ex-situ thermal evolution. Depending on deposition conditions different in depth compositions, nanopore size and shape distributions, porosity and He content could be obtained. The presence of impurities (i.e. oxygen) has shown to promote He diffusivity reducing He accumulation. The start temperature of He-release varied in the range 473-723 K without films crystallization. Films grown in RF mode reached contents of 32 and 29 at% of 4He and 3He and were respectively stable up to 573 and 723 K both in vacuum and under inert gas flow. In-situ p-EBS (proton Elastic Back Scattering) allowed monitoring the He release accompanied by blistering/delamination effects visualized by SEM. These results show the potentiality of annealing to hold nano-porous structures after liberation of trapped gas.
Junio, 2023 | DOI: 10.1016/j.matchemphys.2023.127674
Reactividad de Sólidos
A practical analysis for decelerated growth processes to get physically meaningful kinetic parameters from classical nucleation and growth theory despite of overgrowth
Blazquez, JS; Caballero-Flores, R; Manchon-Gordon, AF; Borrego, JM; Conde, CFJournal of Non-Crystalline Solids, 610 (2023) 122305 DOI: 10.1016/j.jnoncrysol.2023.122305
Abstract
We have analyzed the overgrowth problem arising in decelerated growth processes of spherical crystals in the frame of classical nucleation and growth theory developed by Kolmogorov, Johnson and Mehl, and Avrami (KJMA). To do that, simulations of decelerated growth transformations with a constant nucleation rate have been performed, changing the linear growth rate of spherically shaped nuclei from null (instantaneous growth rate) to constant (characteristic of interface controlled growth processes). We propose the determination of the actual kinetic parameters through the analysis of the inflection point of time evolution of transformed fraction. The correlations found between the effective kinetic parameters from direct KJMA analysis and the actual ones make it possible obtaining physically meaningful parameters. The proposed analysis has been applied to the nano-crystallization of amorphous FINEMET-type compositions.
Junio, 2023 | DOI: 10.1016/j.jnoncrysol.2023.122305 http://hdl.handle.net/10261/356185
Reactividad de Sólidos
Reversibility and thermal dependence of the martensitic transformation in a melt-spun Ni55Fe17Ga26Co2 Heusler alloy
Manchon-Gordon, AF; Vidal-Crespo, A; Blazquez, JS; Kowalczyk, M; Ipus, JJ; Kulik, T; Conde, CFJournal of Alloys and Compounds, 946 (2023) 169484 DOI: 10.1016/j.jallcom.2023.169484
Abstract
An almost single phase 14 M modulated martensite is obtained in melt spun ribbon of Ni55Fe17Ga26Co2 Heusler alloy. The effect of thermal treatments on the stability of the reverse martensitic transformation from 14 M modulated martensite to austenite phase in this system has been investigated by both non -isothermal and isothermal treatments. Heating above martensitic transformation promotes a continuous reduction of the martensitic transformation temperature, which stabilizes the austenite phase at room temperature and induces the precipitation of the gamma phase. However, thermal treatments at tem-peratures between the austenite start and finish temperatures induce the decoupling of the austenite formation in a subsequent heating. The two successive reverse martensitic transformations could be as-cribed to the untransformed martensite in the previous interrupted heating and to the new martensite formed during cooling.
Junio, 2023 | DOI: 10.1016/j.jallcom.2023.169484
Materiales y Procesos Catalíticos de Interés Ambiental y Energético
Catalytic performance of cobalt supported onto APTES functionalized TiO2 for Fischer-Tropsch reaction
Platero, F; Caballero, A; Colon, GFuel, 340 (2023) 127528 DOI: 10.1016/j.fuel.2023.127528
Abstract
Cobalt supported TiO2 catalysts have been prepared by wet-impregnation and by immobilization over APTES (3-aminopropyl triethoxysilane) grafted TiO2. Impregnated system showed better catalytic performance after reduction at 260 degrees C but significant deactivation is observed. On the contrary, functionalized catalyst showed better catalytic performance after reduction at 400 degrees C with notable stability. We have stated from CO-DRIFT operando analysis that impregnated system is strongly affected by negative SMSI (strong metal-support inter-action) upon reduction at higher temperature. While immobilization on APTES hinders the loss of metal active sites. The study of spent catalysts denotes that Co is redispersed in the impregnated catalyst while functionalized trends to form agglomerates.
Mayo, 2023 | DOI: 10.1016/j.fuel.2023.127528
Materiales Avanzados
Characterization, thermal and ceramic properties of clays from Alhabia (Almeria, Spain)
Rat, E; Martinez-Martinez, S; Sanchez-Garrido, JA; Perez-Vilargejo, L; Garzon, E; Sanchez-Soto, PJCeramics International, 49 (2023) 14814-14825 DOI: 10.1016/j.ceramint.2022.05.328
Abstract
Clays from Alhabia (Almeria, Spain) have been investigated in this work using several analytical techniques: X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF), thermal analysis (Thermogravimetry, TG, and its first deriv-ative, DTG), Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Texture characteristics (granulometry) and plasticity have been examined. The main ceramic properties (firing shrinkage, water absorption, bulk density, open porosity, flexural strength and thermal conductivity) have been determined using pressed and fired clay samples. Thus, the mineralogical, chemical, textural and ceramic features of these clays have been evidenced for the first time. The mineralogical analysis by XRD indicated that the clay samples are constituted by a mixture of chlorite and illite, as main clay minerals, being quartz and other minerals in lower relative proportion (calcite, gypsum and hematite). This finding is important because the investigations on chlorite-illite-calcitic clays are very scarce. The chemical analysis by XRF showed that silica and alumina are predominant, as expected by the mineralogy, with medium contents of calcium oxide, from calcite, and alkalis, from illite, being-8 and-5%, respectively, besides iron and titanium oxides (-8%). The particle size analysis showed 71.76% of "clay fraction" (<2 mu m) and 21.66% of silt fraction (2-50 mu m). The plasticity index (Atterberg) was 14.3%, with acceptable moulding and extrusion properties. Thermal analysis by TG/DTG indicated a weight loss associated to dehydroxylation of structural water of the clay minerals and decarbonation of calcite by progressive heating. After the characterization of raw clays, the next step was the determination of ceramic properties of mixed and ground clays after firing using pressed bodies. For this purpose, two firing temperatures were selected (900 and 1100 degrees C) for 1 h. The examination of the resultant fired bodies indicated that porous ceramic materials (-36% open porosity and-22% of water absorption capacity) can be obtained by firing at 900 degrees C, with small variations in dimensions (<0.8% at 1100 degrees C). The porosity changed at relatively lower values by firing at 1100 degrees C (-34-35%), being associated to the presence of decomposed calcite. Bulk density was found almost constant from 900 to 1100 degrees C, with a maximum value of-1.67 g/cm3 at 1100 degrees C. Flexural strength reached a maximum value of 34.47 MPa at 1100 degrees C for the ground sample. Finally, thermal conductivity after firing the clay bodies was found almost constant at 900 and 1100 degrees C (0.457 and 0.479 W/mK, respectively). Taking into account these results, the main applications of the Alhabia clays have been evaluated. These clays can be used for the fabrication of porous ceramic supports and tiles by firing at 900 degrees C. Firing the clays at higher temperature (1100 degrees C) is of great interest for the fabrication of ceramic tiles and ceramic bricks of higher flexural strength with variable porosity and practically constant in dimensions. It is economically important although at higher processing costs. Finally, it can be emphasized that this work is a contribution of a better scientific knowledge of chlorite-illite-calcitic clays as ceramic raw materials.
Mayo, 2023 | DOI: 10.1016/j.ceramint.2022.05.328
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