Scientific Papers in SCI

Abstract

The measured Yb 4d(3/2) intensity is larger than the Yb 4d(5/2) in X-ray photoelectron (XPS) emission of metallic Yb, which is unexpected. The shape and intensity of photoelectron peaks are strongly affected by extrinsic excitations due to electron transport out of the surface (including bulk and surface effects) and to intrinsic excitations due to the sudden creation of the static core hole. To quantitatively extract from experimental XPS the primary excitation spectrum (ie, the initial excitation process) of the considered transition, these effects must be included within the theoretical description. The combined effect of both extrinsic and intrinsic excitations can be described by an effective energy-differential inelastic electron scattering cross section for XPS evaluated by a dielectric response model with the dielectric function as only input. Then, using this cross section, a direct evaluation of the primary excitation spectrum is performed by standard peak shape analysis for thick homogeneous samples. We use this approach in the present paper to determine the Yb 4d photoemission spectrum for metallic Yb. We show that the unexpected larger intensity of Yb 4d(3/2) compared to 4d(5/2) can be fully accounted for by our model and that the total spectrum consists of a sum of symmetric primary excitation peaks.

Abstract

Grain growth is a ubiquitous phenomenon in all materials, and it affects both structural and functional properties. Despite its intrinsic importance, a full comprehension of grain growth from a fundamental point of view-i.e., from the nanoscale to the macroscale-is still a pending issue. In practical terms, our knowledge relies on the classical kinetic laws reported sixty years ago. 

This paper reports the violation of such classical laws in boron carbide ceramics consolidated by spark plasma sintering. The conjunction of high temperature gradients with large compressive stress when a pulse electric current passes through the ceramic powders gives rise to an intense twinning-detwinning formation. These forming steps at the grain boundaries change the grain mobility drastically. Therefore, a new 'exotic' law for grain-growth kinetics is found and validated at different temperatures and dwell times.

Abstract

In this work, we demonstrate a synthetic route to attain methylammonium lead bromide (CH3NH3PbBr3) perovskite nanocrystals (nc-MAPbBr(3), 1.5 nm < size < 3 nm) and provide them with functionality as highly efficient flexible, transparent, environmentally stable, and adaptable color converting films. We use nanoparticle metal oxide (MOx) thin films as porous scaffolds of controlled nanopores size distribution to synthesize nc-MAPbBr(3) through the infiltration of perovskite liquid precursors. We find that the control over the reaction volume imposed by the nanoporous scaffold gives rise to a strict control of the nanocrystal size, which allows us to observe well-defined quantum confinement effects on the photo-emission, being the luminescence maximum tunable with precision between lambda = 530 nm (green) and lambda = 490 nm (blue). This hybrid nc-MAPbBr(3)/MOx structure presents high mechanical stability and permits subsequent infiltration with an elastomer to achieve a self-standing flexible film, which not only maintains the photo-emission efficiency of the nc-MAPbBr(3) unaltered but also prevents their environmental degradation. Applications as adaptable color-converting layers for light-emitting devices are envisaged and demonstrated.

Abstract

Herein, the preparation of 1D TiO2 nanocolumnar films grown by plasma-enhanced chemical vapor deposition is reported as the electron selective layer (ESL) for perovskite solar devices. The impact of the ESL architecture (1D and 3D morphologies) and the nanocrystalline phase (anatase and amorphous) is analyzed. For anatase structures, similar power conversion efficiencies are achieved using an ESL either the 1D nanocolumns or the classical 3D nanoparticle film. However, lower power conversion efficiencies and different optoelectronic properties are found for perovskite devices based on amorphous 1D films. The use of amorphous TiO2 as electron selective contact produces a bump in the reverse scan of the current-voltage curve as well as an additional electronic signal, detected by impedance spectroscopy measurements. The dependence of this additional signal on the optical excitation wavelength used in the IS experiments suggests that it stems from an interfacial process. Calculations using a drift-diffusion model which explicitly considers the selective contacts reproduces qualitatively the main features observed experimentally. These results demonstrate that for a solar cell in which the contact is working properly the open-circuit photovoltage is mainly determined by bulk recombination, whereas the introduction of a "bad contact" shifts the balance to surface recombination.

Abstract

In this work, it is reported that thermal analysis techniques such as differential thermal analysis and thermogravimetric analysis are very useful for evaluating metals threads and fibres used in the manufacture of historical artifacts. Thermal analysis has been used to characterize the silk, cotton and linen employed as supports and the copper, silver and aluminium as the metallic components in the studied threads. Other organic compounds, mainly added for the conservation of the threads, have also been characterized.

Abstract

High energy planetary ball milling has been used to synthesize pseudo-cubic highly-pure LaGaO3 in one hour from its oxide components in an air atmosphere. Calcination at different temperatures led to the crystallization of lanthanum gallate in an orthorhombic structure with its local lanthanum coordination number environment changing from 12 to 7 when the temperature was increased. This change was attributed to the thermal expansion of the Ga-O bonds that varied non-monotonically inducing GaO6 tilting. Rietveld analysis, Raman spectroscopy, and transmission electron microscopy were used to elucidate the LaGaO3 structures at different temperatures.

Abstract

The effect of single walled carbon nanotubes (SWNT) at zirconia grain boundaries on the stability of a tetragonal zirconia polycrystalline matrix has been explored in as-sintered composites and after low temperature hydro thermal degradation (LTD) experiments. For this purpose, highly-dense 3 mol% Y2O3-doped tetragonal zirconia polycrystalline (3YTZP) ceramics and SWNT/3YTZP composites were prepared by spark plasma sintering (SPS). Quantitative X-ray diffraction analysis and microstructural observations point out that an increasing amount of well-dispersed SWNT bundles surrounding zirconia grains decreases the metastable tetragonal phase retention in the ceramic matrix after sintering. In contrast, the tetragonal ceramic grains in composites with SWNTs are less sensitive to the presence of water, i.e. to undergo a martensitic transformation under LTD conditions, than monolithic 3YTZP ceramics. The SWNT incorporation diminishes micro-cracking due to tetragonal to monoclinic ZrO2 phase transformation in the composites.

Abstract

Geopolymers are a new class of non-Portland cements produced using an alumino-silicate material and an activating solution, which is mainly composed of sodium or potassium and waterglass to be subsequently cured at relatively low temperatures. Those can be formulated by adding natural minerals, waste and/or industrial by-products. The study investigates the microstructural properties of geopolymers synthesized from metakaolin (MK) and the admixture of fly ash (FBA) and aluminium industry slags (AIS) at different ages of curing. Five different geopolymer compositions were prepared and characterized by XRD, ATR-FTIR and SEM/EDS. The study revealed that geopolymeric gels are identified, which show mainly glassy microstructures, in agreement with the X-ray amorphous diffraction patterns, broad FTIR features and confirmed by SEM/EDS, with promising results prior to an industrial scale.

Abstract

Fly ash is a biomass combustion by-product produced by dragging ash from the base of the furnace. Disposing of ash is a growing economic and environmental burden. Based on physical and chemical properties, fly ash could be used in the manufacture of construction materials. This paper investigates the influence of biomass fly ash from olive pomace as additive to manufacture of clay ceramic composite materials. Fired clay brick at 950 degrees C were prepared containing between 0 and 25 wt% fly ash. Final products are studied by water absorption, bulk density, loss of ignition, linear shrinkage, compressive strength and physisorption N-2. The results reveal that the porosity of the materials increases with the level of fly ash replacement (10% up to 25 wt%) resulting in to increased water absorption and decreased compressive strength. Fired clay brick developed in this study can be used for construction materials based on criteria of the current regulations. 

Abstract

Poor adhesion is a recurrent problem for the wider use of diamond-like carbon (DLC) coatings in industrial applications. In this work, we investigate the effectiveness of high-power impulse magnetron sputtering (HiPIMS) metal ion etching to improve the adhesion of DLC coatings on high speed steel substrates. The influence of HiPIMS pretreatment parameters, the metal ion selection for the process and the addition of bonding layers on the adhesion properties were studied. Daimler-Benz and nanoscratch test methods were used to evaluate the adhesion. The elemental composition, morphology and microstructure of the samples were evaluated by EELS, SEM, AFM and HRTEM. In general, samples pretreated with HiPIMS metal ion etching withstand larger critical loads than those pretreated by conventional Ar + glow discharge and bonding layers. The pretreatment is proven to be very effective at removing surface contaminants and providing a gradual interface. The selection of Cr over Ti contributes to a significant improvement on the adhesion due to the reduction of the oxygen level at the interface thus ensuring an optimal coating-substrate contact and a more compliant structure, which prevents the delamination failure.

Abstract

This work reports about the sensing and biosensing applications of a novel screen printed electrode (SPE) modified by nanostructured nickel oxide thin films obtained by reactive magnetron sputtering under an oblique angle configuration. Using these films as electrodes we demonstrate their ability to detect hydrogen peroxide under neutral pH conditions. Furthermore, as a proof-of-concept, NiO-modified SPEs have been developed and their cholesterol biosensing properties determined by cyclic voltammetry and chronoamperometry.

Abstract

Eu-doped ZrO2 solid solutions have been synthesized in order to prepare proton conductors as water-enhancer additives for the WGS reaction. Elemental characterization has been carried out revealing homogeneous dopant distribution resulting in fluorite-type solid solutions for Eu2O3 contents up to similar to 9 mol.%. Representative samples of the Eu-doped ZrO2 series have been analysed by Impedance Spectroscopy (IS) in inert, oxygen and wet conditions. The solid solution with 5 mol.% of Eu2O3 has presented the highest conductivity values for all tested conditions indicating an optimal amount of dopant. Moreover, the presence of vapour pressure results in an increment of the conductivity at temperatures lower than 300 degrees C, meanwhile at higher temperatures the conductivity is the same than that in inert conditions. To elucidate these results, in situ DRIFTS studies were carried out. These experiments evidenced the existence of water dissociation at oxygen vacancies (band at 3724 cm(-1)) as well as the presence of physisorbed water at temperatures up to similar to 300 degrees C where the band at 5248 cm(-1) characteristic of these species disappeared. These results points to a layer model where the physisorbed water interacts with surface hydroxyls generated by dissociated water that improves the proton conductivity through Grotthuss' mechanism in the RT-300 degrees C temperature range. These samples were successfully tested in WGS reaction as additive to a typical Pt-based catalyst. The presence of the mixed oxide reveals an increase of the catalyst' activity assisted by the proton conductor, since improves the water activation step.

Abstract

Sr1-xLaxTiO3 (SLT; 0 <= x <= 0.5) powder samples were synthesised at room temperature by a mechanochemical method from SrO, La2O3 and TiO2 mixtures in 90 min. The obtained SLT samples as potential anode materials in solid oxide fuel cells (SOFCs) were investigated. The microstructure, electrical conductivity and chemical compatibility with yttria-stabilised zirconia (YSZ) were studied. The powder samples had a nanometric character after milling. After a subsequently heating at 900 degrees C, the particle size slightly increased, but still remained nanometric. At this high temperature, a good chemical compatibility with YSZ was found. The x = 0.2 sample gave the best electrical conductivity values, i.e. 0.23 W cm(-2). These features make such as-obtained samples good candidates to be used as anodes in SOFCs.

Abstract

The use of allotropic phases of carbon (i.e. nanotubes, graphene or carbon nanofibers) as second phases to design ceramic composites is a hot topic at present. Researchers try to provide a remarkable improvement of the parent ceramic assuming that some of the outstanding mechanical properties of these phases migrate to the resultant composite. This reasonable idea has been questioned severely in the case of nanotubes addition but there is not any analysis for the other two phases cited previously. To elucidate this question, zirconia was selected as a model ceramic. This paper reports the mechanical properties of zirconia composites reinforced either with graphene or carbon nanofibers, with special emphasis on the high-temperature plasticity.

Abstract

Na-Mica-4, a synthetic fluorophlogopite, is an attractive adsorbent. However, the synthesis at large scale demands an economically prized, feasible scalable and sustainable synthesis method, which requires a deep knowledge of the influence of each synthesis step. A set of Na-Mica-4 were synthesized by methods that had one synthesis parameter as variable. The purity, crystallinity and heteroatoms distribution were analysed thorough X-ray diffraction and nuclear magnetic resonance. The results shed a light on the main factors for the design of the final product and indicated that an environmental friendship synthesis could be possible. 

Abstract

This work reports a thorough characterization analysis of various porous thin film multilayers by means of grazing-incidence small-angle X-ray scattering (GISAXS). Alternated TiO2/SiO2 nanocolumnar layers deposited at oblique angles are fabricated in slanted, chiral, and zig-zag configurations by rotating azimuthally the substrate from one layer to the next. Multilayer systems formed by the stacking of 3 and 15 alternant thin films of these two oxides are morphologically characterized by scanning electron microscopy (SEM) and structurally by GISAXS. This technique has provided a means to determine various vertical and lateral correlation lengths and to assess the anisotropic electron density distribution along the structural elements existing in the multilayers. This information can be systematically used to account for the actual arrangement of nanostructural elements in multilayer systems.

Abstract

The waste vitrification of abandoned open sky vermiculite deposits has been considered by combining with a natural phosphate mineral residue. Several batches haven been designed from the composition system: Li2O-MgO-Al2O3-P2O5-SiO2 including some Fe2O3 and Fluoride. The resulting glasses are transparent and smooth green coloured, giving rise after TTT treatments to several opal, opaque glass-ceramics with iridescent surface. Full characterization has been carried out by XRD and electron microscopy with EDS, as well as by XPS spectroscopies, concluding that the main crystalline phases formed were alpha-cordierite and beta-spodumene. The surface of these glass-ceramics from vermiculiteamblygonite is enriched in Fe2O3. Compared to the parent glasses, the final glass-ceramics exhibited and improvement in fracture toughness.

Abstract

Medical grade of both titanium (Ti) and Ti6A14V alloy are recognized as the metallic biomaterials with the better outcomes for clinical repair of bone tissue thanks to their suitable mechanical properties and corrosion resistance. However, those Ti advantages are not enough to avoid failure risks of bone implants; between 5 and 10% of Ti implants fail due to a deficient osseointegration, within 5 years of post-implantation. Most of these failures indicate the necessity of getting a better biomechanical-biofunctional balance. Microstructural and tribo-mechanical characterizations were performed on Ti6A14V samples obtained by selective laser melting and subjected to different surface treatments (thermal stress relief, acid etching, chemical treatment and thermochemical treatment). Scanning electron microscopy and X-ray diffraction were used for detailed characterization of the elemental composition, phase analysis and surface morphology. Micro-hardness and scratch tests were employed to evaluate the tribo-mechanical properties, which were improved after consecutive surface treatments. Protuberances with spherical morphology, as a remainder of the original powder, were present on the surface. The resulting modified surfaces were constituted by rutile (major phase) and anatase (minor phase). Submicro-nano-topographies were obtained after the chemical and thermochemical treatments.

Abstract

SiC-Si3N4 composites have been obtained by carbothermal reduction of rice husk under a nitrogen-argon atmosphere at 1450 degrees C, which is a lower temperature than those used by other authors. On the other hand, tailoring the argon/nitrogen ratio led to the obtained of SiC-Si3N4 composites across the whole range of compositions. Phosphoric acid treatment permited the synthesis of the composite without a pyrolysis step. The final products were characterized by X-ray diffractometry, IR spectroscopy and scanning electron microscopy.

Abstract

This work analyzes the relevant influence of milling on the CO2 capture performance of CaO derived from natural limestone. Diverse types of milling mechanisms produce contrasting effects on the microstructure of the CaO formed after calcination of the milled limestone samples, which affects crucially the kinetics of carbonation at conditions for CO2 capture. The capture capacity of CaO derived from limestone samples milled using either shear or impact based mills is impaired compared to as-received limestone. After calcination of the milled samples, the resulting CaO porosity is increased while crystallinity is enhanced, which hinders carbonation. Conversely, if the material is simultaneously subjected to intense impact and shear stresses, CaO porosity is promoted whereas CaO cristanillity is reduced, which enhances carbonation in both the reaction and solid-state diffusion controlled regimes.

Abstract

Yttria tetragonal zirconia polycrystalline (3YTZP) ceramic composites with 5, 10 and 20 vol% graphene nano-platelets (GNPs) were prepared by spark plasma sintering (SPS) and their electrical conductivity as a function of temperature was characterized. The composites exhibit anisotropic microstructures so the electrical conductivity studies were carried out in two directions: perpendicular (sigma(perpendicular to)) and parallel (sigma(parallel to)) to the SPS pressing axis. The composites with 5 and 10 GNP vol% showed high electrical anisotropy, whereas the composite with 20 GNP vol % exhibited nearly isotropic electrical behavior. sigma(perpendicular to) shows metallic-type behavior in the composites with 10 and 20 vol% GNP revealing that charge transport takes place through defect-free GNPs. For the composite with 5 vol % GNP the observed semiconductor-type behavior was explained by a two dimensional variable range hopping mechanism. sigma(parallel to)shows metallic-type conductivity in the composite with 20 GNP vol% and positive d sigma(parallel to)/dT slope in the composites with 5 and 10 GNP vol%.

Abstract

The reaction mechanism of the reverse water gas shift (RWGS) reaction was investigated using two commercial gold-based catalysts supported on Al2O3 and TiO2. The surface species formed during the reaction and reaction mechanisms were elucidated by transient and steady-state operando DRIFTS studies. It was revealed that RWGS reaction over Au/Al2O3 proceeds through the formation of formate intermediates that are reduced to CO. In the case of the Au/TiO2 catalyst, the reaction goes through a redox mechanism with the suggested formation of hydroxycarbonyl intermediates, which further decompose to CO and water. The Ti-3+ species, the surface hydroxyls, and oxygen vacancies jointly participate. The absence of carbonyl species adsorbed on gold particles during the reaction for both catalysts indicates that the reaction pathway involving dissociative adsorption of CO2 on Au particles can be discarded. To complete the study, operando ultraviolet visible spectroscopy was successfully applied to confirm the presence of Ti3+ and to understand the role of the oxygen vacancies of TiO2 support in activating CO2 and thus the subsequent RWGS reaction.

Abstract

The rapid mechanochemical synthesis of nanocrystalline CuFeS2 particles prepared by high-energy milling for 60 min in a planetary mill from copper, iron and sulphur elements is reported. The CuFeS2 nanoparticles crystallize in tetragonal structure with mean crystallite size of about 38 ± 1 nm determined by XRD analysis. HRTEM study also revealed the presence of nanocrystals with the size of 5–30 nm with the tendency to form agglomerates. The Raman spectrum confirms the chalcopyrite structure. Low temperature magnetic data for CuFeS2 support the coexistence of antiferromagnetic and paramagnetic spin structure. Moreover, the hysteresis loops taken at temperatures from 5 K to 300 K revealed a presence of very small amount of ferromagnetic phase, which seems to be associated with the non-consumed elemental Fe in as-prepared nanoparticles. The optical band gap of CuFeS2nanoparticles has been detected to be 1.05 eV, larger than band gap of the bulk material. The wider gap possibly resulted from the nano-size effect. Photoresponses of CuFeS2nanoparticles were confirmed by I-V measurements under dark and light illumination. It was demonstrated that mechanochemical synthesis can be successfully employed in the one step preparation of nanocrystalline CuFeS2 with good structural, magnetic, optical and electrooptical properties.

Abstract

Different carbon supported metal catalysts were synthesized, and characterized with various physico-chemical methods and tested in vanillin hydrodeoxygenation under 30 bar total pressure in water as a solvent at 100 degrees C. The catalysts exhibited high specific surface area and the metal dispersion decreased in following order: Pt/ C > Pd/C > Au/C > Rh/C > Ru/C. The most active catalyst was Pd/C followed by Ru/C. Vanillin hydrodeoxygenation proceeded via hydrogenation forming vanillyl alcohol further to its hydrogenolysis forming p-creosol. Both hydrogenation and hydrogenolysis were promoted by Pd/C, which exhibited rather high dispersion. The highest selectivity to p-creosol, 95% at complete vanillin conversion, was obtained with Pd/C. Kinetic modelling of vanillyl alcohol selectivity as a function of vanillin conversion was performed.

Abstract

Mullite precursors were prepared using kaolin waste, sericite clay containing kaolinite and industrial kaolin with addition of alumina in a wet medium to synthesize mullite (72 wt% Al2O3 and 28 wt% SiO2). Uniaxial pressed bars of the powdered mullite precursors were fired in the range 1400-1600 degrees C with soaking times 30-120 min. The resultant materials were studied by XRD and SEM-EDX. Bulk densities, apparent porosities and flexural strengths in four points were determined in the fired bars at 1500, 1550 and 1600 degrees C. It was concluded that the thermal behaviour of these mullite precursors was influenced by the presence of impurities in the raw materials. These impurities originate a liquid phase forming a glassy phase which produces a progressive and enhanced densification of the mullite materials by reaction sintering at 1500-1600 degrees C. The technical properties were also influenced by the relative proportion of vitreous phase. The microstructure of characteristic mullite crystals was revealed by SEM. It was emphasized the use of kaolin waste by-products of mining and sericite clays as valuable raw materials for mullite preparation.

Abstract

Herein we present a combined study of the evolution of both the photoluminescence (PL) and the surface chemical structure of organic metal halide perovskites as the environmental oxygen pressure rises from ultrahigh vacuum up to a few thousandths of an atmosphere. Analyzing the changes occurring at the semiconductor surface upon photoexcitation under a controlled oxygen atmosphere in an X-ray photoelectron spectroscopy (XPS) chamber, we can rationalize the rich variety of photophysical phenomena observed and provide a plausible explanation for light-induced ion migration, one of the most conspicuous and debated concomitant effects detected during photoexcitation. We find direct evidence of the formation of a superficial layer of negatively charged oxygen species capable of repelling the halide anions away from the surface and toward the bulk. The reported PL transient dynamics, the partial recovery of the initial state when photoexcitation stops, and the eventual degradation after intense exposure times can thus be rationalized.

Abstract

The development of Deep Geological Repositories (DGP) to the storage of high-level radioactive waste (HLRW) is mainly focused in systems of multiple barriers based on the use of clays, and particularly bentonites, as natural and engineered barriers in nuclear waste isolation due to their remarkable properties. 
Due to the fact that uranium is the major component of HLRW, it is required to go in depth in the analysis of the chemistry of the reaction of this element within bentonites. The determination of uranium under the conditions of HLRW, including the analysis of silicate matrices before and after the uranium-bentonite reaction, was investigated. The performances of a state-of-the-art and widespread radiochemical method based on chromatographic UTEVA resins, and a well-known and traditional method based on solvent extraction with tri-n-butyl phosphate (TBP), for the analysis of uranium and thorium isotopes in solid matrices with high concentrations of uranium were analysed in detail. 
In the development of this comparison, both radiochemical approaches have an overall excellent performance in order to analyse uranium concentration in HLRW samples. However, due to the high uranium concentration in the samples, the chromatographic resin is not able to avoid completely the uranium contamination in the thorium fraction.

Abstract

The design of hybrid mesoporous TiO2-SiO2(TS1) materials decorated with Ag and Pt nanoparticles was performed. The photocatalytic degradation of phenol under artificial solar irradiation was studied and the activity and selectivity of the intermediate products were verified. TiO2-SiO(2)was prepared by sol-gel method while Ag- and Pt-based photocatalysts (TS1-Ag and TS1-Pt) were prepared by photodeposition of the noble metals on TS1. Two series of photocatalysts were prepared varying Ag and Pt contents (0.5 and 1.0 wt%). An increase in the photocatalytic activity up to two and five times higher than TS1 was found on TS1-Ag-1.0 and TS1-Pt-1.0, respectively. Changes in the intermediate products were detected on Ag- and Pt-based photocatalysts with an increase in the catechol formation up to 3.3 and 6.6 times higher than that observed on TS1, respectively. A two-parallel reaction mechanism for the hydroquinone and catechol formation is proposed. A linear correlation between the photocatalytic activity and the surface concentration of noble metals was found indicating that the electron affinity of noble metals is the driven force for both the increase in the photoactivity and for the remarkable changes in the selectivity of products.