Artículos SCI

Abstract

A series of synthesised TiO2-based and commercial photocatalysts were modified by Pt photodeposition and a study made of their photocatalytic activity in hydrogen production. The modified commercial photocatalysts were Evonik P25, Kronos vlp7000 and Hombikat UV-100, and the other modified photocatalysts were synthesised by our group using sol–gel and sol–gel hydrothermal processes (SG400, SG750 and HT). Pt weight percentages used in the study were 0.5, 1.0 and 2.1 wt.% (Pt/TiO2). The photocatalysts were extensively characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance, Brunauer–Emmett–Teller (BET) surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM–EDX), Fourier transform infrared spectroscopy (FTIR) and laser light dispersion. Methanol (25% vol.) was used as sacrificial agent over the 8 h of the hydrogen production tests and measurements were taken of the final concentrations of formaldehyde and formic acid as well as initial and final TOC. Photoactivity of all photocatalysts increased in the presence of Pt. The most efficient of the synthesised photocatalysts was SG750 and of the commercial photocatalysts P25. Maximum production of SG750 was 1846 μmol h−1 at 1.0 wt.% Pt and its production per surface unit was notably higher than that of P25.

Abstract

A computerized database was created, based on a Geographic Information System (GIS), with hyperlinks to the website for a Rural Development Association (Almería province, Andalusia, Spain). Thus, a catalogue of traditional rural buildings in this particular area was compiled, identifying and characterizing each one, establishing criteria for a dynamic and rational selection. The purpose to select this example was to facilitate their management by public organizations or private individuals, for their reuse, restoration or both. The cataloguing and promotion of rural architecture will contribute to creating jobs by stimulating new economic activity, such as the promotion of cultural tourism, while preserving a valuable source of information on rural culture, recovering local construction techniques, encouraging a sense of community, and making villages and rural areas more attractive to visitors. The assessment of the rehabilitation potential of rural buildings in this region has helped to establish a priority order for their reuse, and so an intervention map has been devised in terms of a “Decision Index” corresponding to each considered building.

Abstract

Which mechanisms mediate cell attachment to biomaterials? What role does the surface charge or wettability play on cell–material anchorage? What are the currently investigated strategies to modify cell–matrix adherence spatiotemporally? Considering the development of scaffolds made of biocompatible materials to temporarily replace the structure and/or function of the extracellular matrix, focus is given to the analysis of the specific (i.e., cell adhesive peptide sequences) and unspecific (i.e., surface charge, wettability) mechanisms mediating cell-matrix interactions. Furthermore, because natural tissue regeneration is characterized by the dynamic attachment/detachment of different cell populations, the design of advanced scaffolds for tissue engineering, based in the spatiotemporal tuning of cell–matrix anchorage is discussed.

Abstract

Erbium doped TiO2–Bi2WO6 have been synthesized by means of a surfactant free hydrothermal method having good photoactivities under sun-like excitation for the degradation of Rhodamine B. From the structural and morphological characterization it has been stated that the presence of Er3+ induces a progressive russelite cell contraction due to its incorporation in the Bi2WO6 lattice in substitutional sites. The best photocatalytic performance was attained for the samples with 1 at% of Er. From the study of the photocatalytic activity under different irradiation conditions it can be inferred that Er3+ presence induces a significant improvement of the photoactivity in the UV range. The evolution of band-gap values seems to be similarly related with the reaction rate progression. Thus, the higher band-gap values in lower Er doped systems would be the cause of a better electron hole separation under UV irradiation.

Abstract

Nanometric powdered TixTa1−xC0.5N0.5-based cermets were fabricated using a mechanically induced self-sustaining reaction and consolidated by spark plasma sintering. Highly dense cermets were obtained, and their chemistry, microstructure and mechanical properties were characterised by X-ray diffraction, scanning electron microscopy, image analysis, microindentation and nanoindentation. The microhardness was found to depend directly on the contiguity and size of the ceramic hard particles. The samples synthesised at the lowest temperature (1150 °C) exhibited more homogeneous microstructures and smaller ceramic particles and the best combination of microhardness and fracture toughness.

Abstract

Experimental results are reported on the (Ca-looping) multicyclic CO2 capture of CaO and nanosilica/CaO composites derived from Ca(OH)2 and nanosilica/Ca(OH)2 dry mixtures subjected in situ to linear and constant rate thermal analysis (CRTA) preheating programs in either air or air/CO2 atmospheres. By means of CRTA preheating the rates of the reactions taking place during pretreatment are kept at a constant and small value along the entire process. In agreement with a pore skeleton model, previously proposed in the literature for explaining the behavior of natural limestones thermally pretreated, our results suggest that air/CO2-CRTA pretreatment yields a thermally stable hard skeleton of poorly reactive CaO on which a soft skeleton of reactive CaO would be supported. The sorbent subjected to this preheating program exhibits a reactivation in the very first carbonation/calcination cycles, after which CaO conversion decays slowly with the cycle number. In contrast, linearly or air-CRTA preheated sorbents show a significant decrease of CaO conversion within the first cycles. In the latter case, CaO multicyclic conversion fits well to a model where it is assumed that the progressive reduction of surface area as the number of carbonation/calcination cycles is increased obeys to sintering of the preheated sorbent skeleton as it is subjected to repeated calcinations during cycling. In the former case, CaO conversion data conforms to the prediction by a model in which the loss of surface area is mainly due to sintering of a nascent CaO soft skeleton regenerated in the diffusive carbonation phase, which is enhanced by the air/CO2-CRTA pretreatment. As regards the effect of nanosilica, the results indicate that it slows down CaO sintering during pretreatment, which hinders the development of a stable CaO skeleton thus hampering reactivation and stabilization of conversion. On the other hand, as CaO sintering is also lessened during looping calcination, nanosilica is useful to increase the absolute values of CaO conversion.

Abstract

A new approach is presented to produce amorphous porous silicon coatings (a-pSi) with closed porosity by magnetron sputtering of a silicon target. It is shown how the use of He as the process gas at moderated power (50–150 W RF) promotes the formation of closed nanometric pores during the growth of the silicon films. The use of oblique-angle deposition demonstrates the possibility of aligning and orientating the pores in one direction. The control of the deposition power allows the control of the pore size distribution. The films have been characterized by a variety of techniques, including scanning and transmission electron microscopy, electron energy loss spectroscopy, Rutherford back scattering and x-ray photoelectron spectroscopy, showing the incorporation of He into the films (most probably inside the closed pores) and limited surface oxidation of the silicon coating. The ellipsometry measurements show a significant decrease in the refractive index of porous coatings (n500 nm = 3.75) in comparison to dense coatings (n500 nm = 4.75). The capability of the method to prepare coatings with a tailored refractive index is therefore demonstrated. The versatility of the methodology is shown in this paper by preparing intrinsic or doped silicon and also depositing (under DC or RF discharge) a-pSi films on a variety of substrates, including flexible materials, with good chemical and mechanical stability. The fabrication of multilayers of silicon films of controlled refractive index in a simple (one-target chamber) deposition methodology is also presented.

Abstract

The use of RE2Si2O7 materials as environmental barrier coatings (EBCs) and in the sintering process of advanced ceramics demands a precise knowledge of the coefficient of thermal expansion of the RE2Si2O7. High-temperature X-ray diffraction (HTXRD) patterns were collected on different RE2Si2O7 polymorphs, namely A, G, α, β, γ, and δ, to determine the changes in unit cell dimensions. RE2Si2O7 compounds belonging to the same polymorph showed, qualitatively, very similar unit cell parameters behavior with temperature, whereas the different polymorphs of a given RE2Si2O7 compound exhibited markedly different thermal expansion evolution. The isotropy of thermal expansion was demonstrated for the A-RE2Si2O7 polymorph while the rest of polymorphs exhibited an anisotropic unit cell expansion with the biggest expansion directed along the REOx polyhedral chains. The apparent bulk thermal expansion coeficcients (ABCTE) were calculated from the unit cell volume expansion for each RE2Si2O7 compound. All compounds belonging to the same polymorph exhibited similar ABCTE values. However, the ABCTE values differ significantly from one polymorph to the other. The highest ABCTE values correspond to A-RE2Si2O7 compounds, with an average of 12.1 × 10−6 K−1, whereas the lowest values are those of β- and γ-RE2Si2O7, which showed average ABCTE values of ~4.0 × 10−6 K−1.

Abstract

Previous studies have indicated that long-chain linear carboxylic acids form commensurate packed crystalline monolayers on graphite even at temperatures above their melting point. This study examines the effect on the monolayer formation and structure of adding one or more secondary hydroxyl, functional groups to the stearic acid skeleton (namely, 12-hydroxystearic and 9,10-dihydroxystearic acid). Moreover, a comparative study of the monolayer formation on recompressed and monocrystalline graphite has been performed through X-ray diffraction (XRD) and Scanning Tunneling Microscopy (STM), respectively. The Differential Scanning Calorimetry (DSC) and XRD data were used to confirm the formation of solid monolayers and XRD data have provided a detailed structural analysis of the monolayers in good correspondence with obtained STM images. DSC and XRD have demonstrated that, in stearic acid and 12-hydroxystearic acid adsorbed onto graphite, the monolayer melted at a higher temperature than the bulk form of the carboxylic acid. However, no difference was observed between the melting point of the monolayer and the bulk form for 9,10-dihydroxystearic acid adsorbed onto graphite. STM results indicated that all acids on the surface have a rectangular p2 monolayer structure, whose lattice parameters were uniaxially commensurate on the a-axis. This structure does not correlate with the initial structure of the pure compounds after dissolving, but it is conditioned to favor a) hydrogen bond formation between the carboxylic groups and b) formation of hydrogen bonds between secondary hydroxyl groups, if spatially permissible. Therefore, the presence of hydroxyl functional groups affects the secondary structure and behavior of stearic acid in the monolayer.

Abstract

We study in this paper the conversion of CaO-based CO2 sorbents when subjected to repeated carbonation–calcination cycles with a focus on thermally pretreated/doped sorbents. Analytical equations are derived to describe the evolution of conversion with the cycle number from a unifying model based on the balance between surface area loss due to sintering in the looping-calcination stage and surface area regeneration as a consequence of solid-state diffusion during the looping-carbonation stage. Multicyclic CaO conversion is governed by the evolution of surface area loss/regeneration that strongly depends on the initial state of the pore skeleton. In the case of thermally pretreated sorbents, the initial pore skeleton is highly sintered and regeneration is relevant, whereas for nonpretreated sorbents the initial pore skeleton is soft and regeneration is negligible. Experimental results are obtained for sorbents subjected to a preheating controlled rate thermal analysis (CRTA) program. By applying this preheating program in a CO2 enriched atmosphere, CaO can be subjected to a rapid carbonation followed by a slow rate controlled decarbonation, which yields a highly sintered skeleton displaying a small conversion in the first cycle and self-reactivation in the next ones. Conversely, carbonation of the sorbent at a slow controlled rate enhances CO2 solid-state diffusion, which gives rise, after a quick decarbonation, to a highly porous skeleton. In this case, CaO conversion in the first cycle is very large but it decays abruptly in subsequent cycles. Data for CaO conversion retrieved from the literature and from further experimental measurements performed in our work are analyzed as influenced by a variety of experimental variables such as preheating temperature program, preheating exposition time, atmosphere composition, presence of additives, and carbonation–calcination conditions. Conversion data are well fitted by the proposed model equations, which are of help for a quantitative interpretation of the effect of experimental conditions on the multicyclic sorbent performance as a function of sintering/regeneration parameters inferred from the fittings and allow foreseeing the critical conditions to promote reactivation. The peculiar behavior of some pretreated sorbents, showing a maximum conversion in a small number of cycles, is explained in light of the model.

Abstract

A new type of nanostructured selective ultraviolet (UV) reflecting mirror is presented. Periodic porous multilayers with photonic crystal properties are built by spin-coating-assisted layer-by-layer deposition of colloidal suspensions of nanoparticles of ZrO2 and SiO2 (electronic band gap at λ < 220 nm). These optical filters are designed to block well-defined wavelength ranges of the UVA, UVB, and UVC regions of the electromagnetic spectrum while preserving transparency in the visible. The shielding against those spectral regions arises exclusively from optical interference phenomena and depends only on the number of stacked layers and the refractive index contrast between them. In addition, it is shown that the accessible pore network of the as-deposited multilayer allows preparing thin, flexible, self-standing, transferable, and adaptable selective UV filters by polymer infiltration, without significantly losing reflectance intensity, i.e., preserving the dielectric contrast. These films offer a degree of protection comparable to that of traditional ones, without any foreseeable unwanted secondary effects, such as photodegradation, increase of local temperature or, as is the case for organic absorbers, generation of free radicals, all of which are caused by light absorption.

Abstract

Gas-solid heterogeneous photocatalytic oxidation (PCO) of cyclohexane in humidified air over TiO2 and Pt/TiO2 catalyst was studied.

Pt/TiO2 photocatalysts were synthesized by photodeposition method at different Pt loadings (0.5–2 wt.%). The addition of 0.5 wt.% Pt does not significantly modify the TiO2 properties. The increase in Pt loading induces to an aggregation of metallic particles on TiO2 surface.

The cyclohexane PCO was performed in a fluidized bed photoreactor at 60 and 100 °C. Pure TiO2 was more active than 1 and 2 wt.% Pt/TiO2 samples at 60 °C. Nevertheless, the conversion level increases with temperature on Pt/TiO2 photocatalysts. The cyclohexane was mineralized into CO2, water and low amount of CO. A beneficial effect of Pt addition was found, since total CO2 selectivity was obtained. The Pt/TiO2 photocatalysts prepared by photodeposition provide the total cyclohexane PCO without CO production. Photocatalysts deactivation was not observed in any performed test. Evidence of an opportune tuning of temperature is highlighted.

Abstract

The conversion of thermally pretreated CaO along successive carbonation/calcination cycles has been investigated, as affected by looping-calcination conditions, by means of Thermogravimetric Analysis (TGA). Sorbent samples have been subjected in situ to a thermal preheating program based on Constant Rate Thermal Analysis (CRTA) by virtue of which decarbonation is carried out at a low controlled rate, which is able to promote self-reactivation in the first carbonation/calcination cycles. Our observations support a pore-skeleton model according to which solid-state diffusion in the first carbonation stages, which is enhanced by thermal pretreatment, gives rise to a soft skeleton with increased surface area. Yet, the results show that self-reactivation is hindered as looping-calcination conditions are harshened. Increasing the looping-calcination temperature and/or the looping calcination time period favors sintering of the soft skeleton and eventually self-reactivation is precluded. A model is developed that retrieves the main features of multicyclic conversion of thermally pretreated sorbents in the first cycles based on the balance between surface area gain due to promoted solid-state diffusion carbonation and surface area loss due to sintering of the soft skeleton in the looping-calcination stage, which can be useful to investigate the critical looping-calcination conditions that nullify self-reactivation. The proposed model allows envisaging the behavior of the sorbent performance as a function of the pretreatment conditions.

Abstract

The preparation of hard coatings with low friction coefficient over a wide temperature range is still a challenge for the tribological community. The development of new nanocomposite materials consisting of different metal-ceramic phases, each of which exhibiting self-lubricating characteristics at different temperatures, may help to solve this problem. We report on the structure and tribological properties of MoCN-Ag coatings deposited by magnetron co-sputtering of Mo and C (graphite) targets and simultaneous sputtering of an Ag target either in pure nitrogen or in a gaseous mixture of Ar + N2. The structure and elemental composition of the coatings were studied by means of X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive spectroscopy, Raman spectroscopy, and glow discharge optical emission spectroscopy. The tribological properties of the coatings against an Al2O3 ball were investigated first at discrete temperatures of 25, 500, and 700 °C, and then during continuous heating in the temperature range of 25–700 °C. The coating structure and their respective wear tracks were also examined to elucidate their phase transformations during heat treatments. The lowest friction coefficients (<0.4) were observed in the temperature ranges of 25–100 °C and 400–700 °C and can be explained by the presence of a free amorphous carbon phase, which served as a lubricant at low temperatures, and by a positive role of silver and two phases forming at elevated temperatures, molybdenum oxide and silver molybdate, which provided lubrication above 400 °C. In the temperature range between 100 and 400 °C, the friction coefficient was relatively high. This problem is to be addressed in future works.

Abstract

In this work, we report on the determination of the infrared Yb3+ → Tm3+ energy transfer efficiency in YF3:Yb3+/Tm3+ nanocrystals through the study of Yb3+ dynamics. The obtained results are compared to those previously reported in macrocrystals to analyze possible changes related to size reduction. Luminescence lifetimes are much shorter in the nanoparticles than in bulk samples, a behavior that can be related to Yb3+ → Yb3+ migration and the enhanced surface/volume ratio of the nanoparticles. On the other hand, Yb3+ → Tm3+ energy transfer macroparameter remains unaltered, demonstrating that spectroscopic intrinsic parameters such as radiative and non-radiative probabilities are not affected by size reduction. Finally, a formula that describes Yb3+ lifetime dependence with Yb3+ and Tm3+ concentration is proposed, considering both the effects produced by migration between Yb3+ ions and energy transfer from Yb3+ to Tm3+ ions.

Abstract

Kanemite belongs to the group of naturally occurring sodium silicate minerals that was first found in Kanem, at the edge of the Lake Chad, and has been synthesized in different ways from NaOH-SiO2 mixtures and used as precursor for the design of microporous and mesoporous materials. The fluoride route to the synthesis of microporous materials is based on the substitution of OH− anions by fluoride anions, which may subsequently also play a mineralizing role, and gives rise to materials with higher hydrophobicity and thermal and hydrothermal stability. Moreover, F− plays an important role in the incorporation of framework heteroatoms, thereby affecting the activity of the final material. The aim of this study was to synthesize fluorokanemite using different synthetic routes and different F− source. The final product was characterized by a combination of methods that provided information regarding the incorporation of fluorine into the framework and the short- and long-range structural order of the fluorosilicate. Kanemite with water content close to ideal was obtained in all cases. The washing process was found to have no effect in the long- or short-range structural order of the layer framework, although it did affect the structure of the cation in the interlayer space of kanemite. The mineralizing agent therefore appears to be the key to the synthesis. Furthermore, it governs the resulting kanemite structure by controlling the formation of hydrogen bonds in the framework, and therefore the degree of lamellar structure condensation.

Abstract

Different commercial TiC–TiN/Co/Ni mixtures were used as raw materials for Ti(C,N) cermets, and the effects of the sintering parameters (binder content, binder nature, sintering time and additives) on the final hard ceramic phase were studied at the sintering temperature of 1400 °C. When Co is used as the binder medium, it is possible to completely convert the starting commercial TiC–TiN mixture into TiCxN1−x. When Ni is used, which exhibits lower solubilising capacity than Co, the total conversion can never be reached and the metallurgical reactions between TiC and TiN during the liquid-phase sintering are more dependent on the sintering time than on the binder content. However, the use of Co–Ni mixtures, showing a synergic effect between the wettability capacity of Ni and the solubilising capacity of Co, enhances the metallurgical reactions at short sintering times.

Abstract

Complete solid-solution cermets based on titanium–tantalum carbonitride using a starting nominal composition with 80 wt.% of (Ti0.8Ta0.2)(C0.5N0.5) and 20 wt.% of Co were performed by pressure-less sintering at 1550 °C for different times (from 0 to 180 min) in an inert atmosphere. Chemical and phase analyses were conducted using X-ray diffraction (XRD), elemental analysis and energy dispersive X-ray spectrometry (EDX). The binder mean free path and the contiguity of the carbonitride particles were used to rationalise the microstructural effects of the mechanical behaviour. Mechanical characterisation included determining the Vickers hardness, the fracture toughness (conventional indentation microfractures, IM), the dynamic Young's modulus (ultrasonic technique), the biaxial strength (ball on three ball) and a detailed fractographic examination. Finally, the experimental findings were combined with a theoretical fracture mechanics analysis to estimate the critical processing flaw sizes. Binder-less carbonitride clusters, pores and coarse carbonitride grains were the main defects observed and were responsible for the fractures.

Abstract

Smectite is a family of clay minerals that have important applications. In the majority of these clay minerals, the hydrated interlayer cations play a crucial role on the properties of the clay. Moreover, many studies have revealed that both thermal and grinding treatments affect the MMT structure and that interlayer cations play an important role in the degradation of the structure, primarily after mechanical treatment. In this study, the effects of these treatments on MMTs homoionized with mono (Na+, Li+ or K+) or polyvalent (Ca2+ or Al3+) cations were analyzed by the combination of a set of techniques that can reveal the difference of bulk phenomena from those produced on the surface of the particles. The thermal and mechanical (in an oscillating mill) treatments affected the framework composition and structure of the MMT, and the thermal treatment caused less drastic changes that the mechanical one. The effect of the interlayer cations is primarily due to the oxidation state and, to the size of the cations, which also influenced the disappearance of aluminum in the MMT tetrahedral sheet. These treatments caused a decrease in the surface area and an increase in the particle agglomeration and the isoelectric point. Both treatments caused the leaching of the framework aluminum. Furthermore, the mechanical treatment induced structural defects, such as the breakup of the particles, which favored the dehydroxylation and the increase of the isoelectric points of the montmorillonites.