Artículos SCI

Abstract

In the present work we determined the chromatic coordinates (L*, a*, b*) and ultrasound propagation speeds on the three spatial planes (Vx, Vy, Vz) of three ornamental granites (Aqueduct of Segovia, Spain) before, during, and after being subjected to 70 cycles of two types of accelerated ageing (typical of cold regions): a) freezing/thawing and cooling/heating (T1), and b) freezing/thawing and cooling/heating + salt crystallization (T2). A multivariate technique (Canonical Biplot) was applied to the data obtained, with the observation of significant variations between the two types of accelerated artificial ageing as compared with those obtained in quarry rock in the three chromatic coordinates (L*, a*, b*). With regard to the ultrasound propagation speed, we only detected differences in the results of the T2 artificial ageing treatment with respect to those of quarry rock. This fact is confirmed by the estimated data of resistance to compression.

Abstract

The formation of ZnSe via a mechanically-induced self-sustaining reaction (MSR) from a Zn/Se mixture showed that only size reduction and mixing of the reactants without product formation occurred during the induction period prior to ignition. Therefore, all mechanical energy supplied by the planetary mill during this time, called the ignition time (tig), was used exclusively in the activation of the reactants. This system was chosen to study the dependence of tig on the main parameters characterising the milling intensity of planetary mills. The variation of the ignition time with the process conditions reflected changes in the mechanical dose rate of the planetary mill. A direct relationship between the inverse of the ignition time and the power of the planetary mill was established, which allows the validation of theoretical models proposed in the literature for the energy transfer in milling devices and the comparison of milling equipment efficiencies.

Abstract

A simple and fast (7 min) procedure for synthesis of gadolinium phosphate nanocubes (edge = 75 nm) based on the microwave-assisted heating at 120 °C of gadolinium acetylacetonate and phosphoric acid solutions in buthylene glycol is reported. These nanocubes were highly crystalline and crystallized into a tetragonal structure, which has not been ever reported for pure gadolinium phosphate. Determination of such crystal structure has been carried out here for the first time in the literature by means of powder X-ray diffraction. The developed synthesis procedure was also successful for preparation of multifunctional europium(III)-doped the gadolinium phosphate nanocubes, which were nontoxic for cells and exhibited strong red luminescence under UV illumination and high transverse relaxivity (r2) values. These properties confer them potential applications as biolabels for in vitro optical imaging and as negative contrast agent for magnetic resonance imaging.

Abstract

The heterogeneous photocatalytic partial oxidation of cyclohexane in gas-phase as an alternative green process for fine chemicals synthesis was successfully achieved on Au/TiO2 photocatalysts prepared by photodeposition technique. Different gold loadings ranging between 0.5 and 2 wt.% of photodeposited Au on TiO2 synthesized by sol-gel method were obtained by changing the concentration of gold precursor at fixed illumination intensity and time. The cyclohexane partial photoxidation was conducted in a gas-solid photocatalytic fluidized bed reactor at high illumination efficiency. Main observed reaction products were cyclohexanol, cyclohexanone and CO2. The resulting selectivity was dramatically influenced by the gold content. The reaction temperature was a critical parameter to reach the photocatalysts stability, avoiding deactivation phenomena while the tuning of Au content of the photocatalysts, resulted in the promotion of the formation of cyclohexanol or cyclohexanone with high selectivity. In particular, by increasing Au content, the process selectivity is completely reversed, passing from high cyclohexanol selectivity (75%) to high selectivity to cyclohexanone (80%). These promising results evidenced that Au/TiO2 catalysts in the selected operating conditions, are effective materials for the synthesis of cyclohexanone and cyclohexanol in gas-phase by photocatalysis, at very low reaction temperatures and without the additional step of catalyst recovering needed in the liquid partial oxidation of cyclohexane.

Abstract

This paper describes the deep analysis of cerium conversion coatings developed with thermal activation on AA5083 under optimum processing conditions. Scanning electron microscopy (SEM), electron dispersive spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were employed to study these layers. Ar+ sputtering was also employed to analyse the coatings' core. Although conversion coatings based on Ce salts have been widely characterised in the literature for different aluminium alloys, the coatings developed with thermal activation on Al–Mg alloys have not been previously investigated with these techniques. SEM/EDX studies have demonstrated the existence of a heterogeneous layer formed by a film of aluminium oxide/hydroxide on the matrix as well as a series of dispersed islands of cerium deposited on the cathodic intermetallics. These results have been further confirmed by means of XPS. The XPS and AES results revealed that the outer layer comprises a mixture coating of Ce3 + (70%) and Ce4 + (30%) compounds. Although only Ce3 + compounds were detected at the inner part of the coating, possible reduction of Ce(IV) to Ce(III) due to the Ar+ beam could not be discarded. Obtained results allowed authors to confirm that the cerium conversion coatings developed have a similar structure to those previously reported for other aluminium alloys.

Abstract

Nanoporous silica microparticles (NSiO2-MP) are considered to be potential drug delivery systems and scaffolding platforms in tissue engineering. However, few biocompatibility studies regarding NSiO2-MP interaction with the immune system have been reported. Toll-like receptors (TLR) are involved in host defence as well as autoimmune and inflammatory diseases. The results show that NSiO2-MP up to 100 μg ml−1 do not affect macrophage cell viability after 24 h cell culture. Moreover, NSiO2-MP do not compromise the cell viability of TLR-activated Raw 264.7 cells, for either cell surface TLR (TLR1/TLR2/TLR4/TLR6) or endocytic compartment TLR (TLR3/TLR7/TLR9). Furthermore, Raw 264.7 cells do not respond to NSiO2-MP exposure in terms of IL-6 or IL-10 secretion. NSiO2-MP co-treatment in the presence of TLR ligands does not impair or enhance the secretion of the pro-inflammatory cytokine IL-6 or the regulatory cytokine IL-10. Thus, NSiO2-MP do not affect macrophage polarization towards a pro-inflammatory or immunosuppressive status, representing added value in terms of biocompatibility compared with other SiO2-based micro- and nanoparticles.

Abstract

A systematic study of [M(H2O)n(OH)m]q+ complexes of Te(IV) and Bi(III) in solution has been undertaken by means of quantum mechanical calculations. The results have been compared with previous information obtained for the same type of Po(IV) complexes ( J. Phys. Chem. B 2009, 113, 487) to get insight into the similarities and differences among them from a theoretical view. The evolution of the coordination number (n + m) with the degree of hydrolysis (m) for the stable species shows a systematic decrease regardless the ion. A general behavior on the M–O distances when passing from the gas phase to solution, represented by the polarizable continuum model (PCM), is also observed: RM–O values corresponding to water molecules decrease, while those of the hydroxyl groups slightly increase. The hydration numbers of aquaions are between 8 and 9 for the three cations, whereas hydrolyzed species behave differently for Te(IV) and Po(IV) than for Bi(III), which shows a stronger trend to dehydrate with the hydrolysis. On the basis of the semicontinuum solvation model, the hydration Gibbs energies are −800 (exptl −834 kcal/mol), −1580 and −1490 kcal/mol for Bi(III), Te(IV), and Po(IV), respectively. Wave function analysis of M–O and O–H bonds along the complexes has been carried out by means of quantum theory of atoms in molecule (QTAIM). Values of electron density and its Laplacian at bond critical points show different behaviors among the cations in aquaions. An interesting conclusion of the QTAIM analysis is that the prospection of the water O–H bond is more sensitive than the M–O bond to the ion interaction. A global comparison of cation properties in solution supplies a picture where the Po(IV) behavior is between those of Te(IV) and Bi(III), but closer to the first one.

Abstract

Heterogeneous photocatalytic partial oxidation of ethanol was studied over different Pt/TiO2 as an alternative green process for acetaldehyde production.

The catalysts were synthesized through the photodeposition of Pt over sol–gel TiO2 with platinum loads of 0.5 and 1 wt.%. The effect of some experimental conditions during photodeposition, such as deposition time and Pt loading, was investigated. A short deposition time at 0.5 wt.% Pt nominal loading led to small average particle size of platinum (2–3 nm) homogeneously distributed all over the TiO2 surface.

Ethanol partial oxidation was tested in a gas–solid photocatalytic fluidized bed reactor at high illumination efficiency, using different reaction temperatures. Activity results have been correlated with characterization results of the different samples. Platinized samples prepared with short deposition times showed high conversion levels and high selectivity to acetaldehyde. Materials prepared at longer times, 120 min, showed selectivities >98%, although with lower ethanol conversion.

Sample with 1 wt.% Pt loading prepared with 15 min deposition time combined a good compromise between a relevant ethanol conversion and a very high selectivity to acetaldehyde at a selected reaction temperature of 80 °C, with an acetaldehyde yield higher than 80%, which make of this catalyst a good candidate for acetaldehyde production by photocatalysis.

Abstract

Trivalent cation-doped barium cerate perovskites are attractive materials for clean-energy applications, in particular solid oxide fuel cells, due to their singular proton conductivity in wet environments. Furthermore, these devices operate at high temperatures, where creep and other deformation processes determine the lifetime and overall performance. In this work, the structural and microstructural characteristics of undoped and ytterbium-doped (1 to 10 at.%) BaCeO ₃ polycrystals produced by solid state reaction have been investigated. A single orthorhombic perovskite phase was found after sintering in air at 1500 °C for 10 h. The microstructure shows a complex evolution with doping: the average grain size firstly decreases with increasing Yb content up to 5 at.%, and then increases with further Yb additions. The high-temperature mechanical properties have been studied in compression between 1100 and 1250 °C in air at constant initial strain rate. The creep strength increases with increasing Yb content. Extended steady states of deformation were attained at lower strain rates and higher temperatures when increasing doping amount.

Abstract

A series of 1% m/m gold particles supported on Fe, Ce and Al pillared bentonite (from Valle del Cauca, Colombia) and clay “M64” (from Tolima, Colombia) using three different fractions of aggregate sizes (≤ 2 μm, ≤ 50 μm, and ≤ 150 μm) were characterized by particle size measurements, X-ray diffraction, transmission electronic microscopy (TEM), SBET and X-ray fluorescence spectrometry (XRF) techniques. The materials tested with CO oxidation. The separation yield for each fraction depended on the type of clay. Whatever the clay or the aggregate size, the pillaring process was successfully carried out, introducing Fe, Ce and Al pillars and increasing the microporosity and the specific surface area of the material. Gold particles presented a homogenous distribution of 2–3 nm on the pillared bentonite, and of about 10 nm on the pillared clay M64. The aggregate size slightly influenced the amount of deposited gold particles and their size. All gold catalysts were active in CO oxidation, the activity depending on the nature of the clay as well as the gold loading and average gold particle size but not on the aggregate size.

Abstract

NiO/8YSZ (8 mol% Y ₂O ₃-stabilized ZrO ₂) composites with different NiO contents (10, 20 and 40 mol%) have been fabricated by a conventional route of mechanical mixing of NiO and 8YSZ powders and sintering at 1500 °C for 10 h in air. The resulting microstructures have been characterized by electron microscopy. In 10 and 20 mol% NiO/8YSZ, the composite is formed by isolated NiO particles surrounded by zirconia matrix grains; this phase is interconnected in the 40 mol% NiO/8YSZ composite. Mechanical tests at constant strain rate and at constant load were conducted on these materials at temperatures of up to 1350 °C. Different behaviors were found depending on the percolation of the NiO phase. Microstructural observations after deformation are essential to understand the overall mechanical behavior of the composites.

Abstract

Magnetron sputtered chromium aluminium nitride films are excellent candidates for advanced machining and protection for high temperature applications. In this work CrAlN-based coatings including Y or Zr as dopants (≈ 2 at.%) are deposited by d.c. reactive magnetron sputtering on silicon substrates using metallic targets and Ar/N2 mixtures. The hardness properties are found in the range of 22–33 GPa with H/E ratios close to 0.1. The influence of the dopant element in terms of oxidation resistance after heating in air at 1000 °C is studied by means of X-ray diffraction (XRD), cross-sectional scanning electron microscopy (X-SEM) and energy dispersive X-ray analysis (EDX). The microstructure and chemical bonding are investigated using a transmission electron microscope (TEM) and electron energy-loss spectroscopy (EELS) respectively. The improvement in oxidation resistance as compared to pure CrN coating is manifested in the formation of a Al-rich outer layer that protects the underneath coating from oxygen diffusion. The best performance obtained with the CrAlYN film is investigated by in situ annealing of this sample inside the TEM in order to gain knowledge about the structural and chemical transformations induced during heating.

Abstract

The homemade bare TiO2 photocatalyst obtained in a previous work was modified with nanosized silver particles by liquid impregnation and photodeposition methods to obtain different noble metal loadings (0.3–1 at.%). Characterization of the synthesized photocatalysts was carried out by the BET method, XPS, TEM, SEM-EDX, XRD and diffuse reflectance measurements. Photocatalytic activity of these silver-deposited TiO2 nanoparticles was tested by photocatalytic degradation of phenol as a reference model representing phenolic pollutants. The noble metal content on the TiO2 surface affected the efficiency of the photocatalytic process, and the photocatalytic activity of noble metal-modified TiO2 was considerably better than that of bare TiO2. Phenol decomposition rate was higher with TiO2 modified by the liquid impregnation method than with TiO2 modified by the photodeposition method.

Abstract

In this work, the carboxylic acid derivatives of a free-base porphyrin, 5,10,15,20-tetrakis(4-carboxyphenyl)-21H,23H-porphyrin, and 10 of its metal derivatives (TCPPs) have been used for optical gas sensing. For this purpose, microstructured columnar TiO2 thin films prepared by GAPVD (glancing angle physical vapor deposition) have been used as host materials for the porphyrins as they are non–dispersive and porous, allowing their use for UV–visible spectroscopy and gas sensing. The chemical binding between the dye molecules and the TiO2 has been studied through infrared spectroscopy, and the obtained spectral changes have been found to be compatible with chelating and/or bidentate binding modes of the carboxylate groups on the TiO2 surface. When hosted in the film, the UV–visible spectra of the porphyrins featured a blue shift and broadening of the Soret band with respect to the solution, which has been attributed to the formation of π–π aggregates between porphyrin molecules. The composite porphyrin/TiO2 films obtained from each of the 11 porphyrins have been exposed to 12 different volatile organic compounds (VOCs), and their respective gas–sensitive properties have been analyzed as a function of the spectral changes in their Soret band region in the presence of the analytes. The set of composite films has shown high selectivity to the analyzed volatile compounds. For each analyte, an innovative way of showing the different responses has been developed. By means of this procedure, an imagelike recognition pattern has been obtained, which allows an easy identification of every compound. The kinetics of the exposure to several analytes showed a fast, reversible and reproducible response, with response times of a few seconds, which has been attributed to both the sensitivity of the porphyrins and the high porosity of the TiO2 films. Also, increasing concentrations of the analytes resulted in an increase in the magnitude of the response, indicating that the sensor behavior is also concentration-dependent.

Abstract

Samples of β-SiC/Si ecoceramics with a silicon concentration of ∼21 vol % have been prepared using a series of consecutive procedures (carbonization of sapele wood biocarbon, synthesis of high-porosity biocarbon with channel-type pores, infiltration of molten silicon into empty channels of the biocarbon, formation of β-SiC, and retention of residual silicon in channels of β-SiC). The electrical resistivity ρ and thermal conductivity κ of the β-SiC/Si ecoceramic samples have been measured in the temperature range 5–300 K. The values of ρ Si chan(T) and κ Si chan(T) have been determined for silicon Sichan located in β-SiC channels of the synthesized β-SiC/Si ecoceramics. Based on the performed analysis of the obtained results, the concentration of charge carriers (holes) in Sichan has been estimated as p ∼ 1019 cm−3. The factors that can be responsible for such a high value of p have been discussed. The prospects for practical application of β-SiC/Si ecoceramics have been considered.

Abstract

High resolution synchrotron powder XRD, 89Y CPMG NMR, and 139La MAS NMR spectroscopy have been applied to eventually draw the phase diagram of the La2Si2O7–Y2Si2O7 system. The diagram presents a solid solubility region of G-(La,Y)2Si2O7, which extends to the La0.9Y1.1Si2O7 composition at any temperature of this study. Compositions richer in Y show two-phase domains, with G + α at T < 1450 °C and G + δ at T > 1450 °C. The Y-rich extreme is more complex, showing two solid solution regions of δ- and γ-(La,Y)2Si2O7 polymorphs which appear with increasing Y content, respectively. It is interesting to note that the La for Y substitution mechanism in the G-(La,Y)2Si2O7 polymorph is not homogeneous, but a preferential occupation of Y for the RE2 site is observed. Finally, the 89Y and 139La isotropic chemical shift values in G-(La,Y)2Si2O7 have been described here for the first time and assigned to the different RE crystallographic sites of the unit cell.

Abstract

A system with a continuous reactor to produce hydrogen by sodium borohydride hydrolysis was designed and built. The purpose was to test a supported Co–B catalyst durability upon cycling and long life experiments in high conversion conditions. A Stainless Steel monolith was built and calcined to improve adherence. For comparison a Ru–B catalyst was tested upon cycling. Both Co–B and Ru–B catalysts are durable during 6 cycles and then deactivate. A known reactivation procedure has proven to be more effective for the Co–B than for the Ru–B catalyst. This is related to stronger adsorption of B–O based compounds on the Co–B catalyst which is reversible upon acid washing. For the Ru–B catalyst deactivation may be more related to particle agglomeration than to the adsorption of B–O based species. The continuous system enlarges the catalysts durability because of the continuous borate elimination at elevated temperatures.

Abstract

Colour analysis appears to be a robust technique for characterizing vitamin E doping and gamma irradiation of medical grade polyethylene samples. The analysis procedure described in this paper is of great interest because it can easily distinguish between polyethylene samples with differences in vitamin E (α-tocopherol) doping of about 0.1 wt% and gamma irradiation doses of 30 kGy. It is found that the colour differences (with respect to untreated samples) induced by gamma irradiation and/or vitamin E doping add-up linearly. This method for detecting the presence of vitamin E is fast, simple and non-destructive.