Scientific Papers in SCI

Abstract

Si-doped multifunctional bioactive nanostructured films (MuBiNaFs) were deposited by DC magnetron sputtering of composite TiC0.5 + CaO + Si (A) and TiC0.5 + CaO + Si3N4 (B) targets produced by self-propagating high-temperature synthesis method. The films were characterized in terms of their structure, elemental and phase composition using X-ray diffraction, scanning and transmission electron microscopy, electron energy loss spectroscopy, glow discharge optical emission spectroscopy. Raman, and IR spectroscopy. The Ti-Si-Ca-P-C-O-(N) films consisted of TiC(N) as a main phase with a minor amount of TiOx, SiNx, SiOx, SiC, and CaO phases probably mainly in amorphous state at the grain boundaries and COO- groups on the film surface. The excess of carbon atoms in the Ti-Si-Ca-P-C-O-N film (target A) precipitated in a DLC form. The films showed hardness in the range of 26-31 GPa, reduced Young's modulus of 200-270 GPa, and high percentage of elastic recovery of 60-71%. The best Ti-Si-Ca-C-O-N films exhibited low friction coefficient both in physiological solution and Dulbecko modified Eagle medium with fetal calf serum, hydrophilic properties, improved electrochemical characteristics, and excellent impact resistance. Nevertheless, the wear resistance of the Ti-Si-Ca-C-O-N films against Al2O3 ball was lower compared with the best Si-free MuBiNaFs. In vitro studies showed that the Si-doped Ti-Ca-C-O-N films possess improved osteoconductive characteristics during early stage of cell/material interaction. The film surface was highly adhesive for IAR-2 epithelial and MC3T3-E1 osteoblastic cells. The films revealed a high level of biocompatibility and biostability in experiments in vivo. The Ti-Si-Ca-C-O-N film (target A) did not show any bactericidal activity during cultivation of bacterial strains both on solid and in liquid Luria Bertani mediums. The film did not reveal any bactericidal and toxic activity against macrophages and therefore did not change bacterial status and defence system of macro-organisms.

Abstract

Superplasticity in ceramics has been the subject of intense research activity for the last two decades. Quite recently, the fabrication of fully dense nanocrystalline oxides with grain size below 100 nm enabled examination of their superplastic behaviour. This work presents a critical analysis of the plasticity of two important nanostructured oxide systems: MgO and yttria tetragonal zirconia polycrystals. A thorough comparison of their plastic deformation reveals that nano-structuring may be a necessary, but not a sufficient condition for superplasticity in ceramics as commonly assumed. Instead, the changes in the chemical composition and the transport properties, through the bulk and at grain boundaries, versus temperature and grain size can induce a rich variety of mechanical responses.

Abstract

New TiO2 catalysts have been synthesised by means of a sol-gel method in which aggregates have been selected before thermal treatment. Sieving and calcination temperature have been proved to be key factors in obtaining catalysts with greater photoactivity than that of Degussa P-25. These new catalysts have been characterized by means of transmission electron microscopy (TEM), BET surface area, diffuse reflectance spectroscopy (DRS). UV-vis spectroscopy, Fourier transformed infrared (FTIR) and X-ray diffraction (XRD). The different parameters studied were compared to those obtained from two commercial catalysts (Degussa P-25 and Hombikat-UV100). The photocatalytic efficiency of the new catalysts was evaluated by the degradation of various phenolic compounds using UV light (maximum around 365 nm, 9 mW). The catalyst sieved and calcinated at 1023 K, ECT-1023t, showed phenol degradation rates 2.7 times higher than those of Degussa P-25. Also in the degradation of different phenolic compounds, this catalyst showed a higher activity than that of the commercial one. The high photoactivity of this new catalyst has been attributed to the different distribution of surface defects (determined from FTIR studies) and its increased capacity to yield H2O2.

Abstract

We show that the tilt angle of nanostructures obtained by glancing angle sputtering is finely tuned by selecting the adequate argon pressure. At low pressures, a ballistic deposition regime dominates, yielding high directional atoms that form tilted nanocolumns. High pressures lead to a diffusive regime which gives rise to vertical columnar growth. Monte Carlo simulations reproduce the experimental results indicating that the loss of directionality of the sputtered particles in the gas phase, together with the self-shadowing mechanism at the surface, are the main processes responsible for the development of the columns.

Abstract

Aleuritic (9,10,16-trihydroxypalmitic) acid self-assembly on mica from solution has been studied using AFM, ATR-FTIR and MD simulations. The goal of this study is to define the role of hydroxyl groups in the interaction between molecules as reference data to understand the mechanism of formation of synthetic and natural biopolyesters from polyhydroxylated long chain carboxylic acids. In a confined structure, such as the one imposed by a vertically self-assembled layer on mica, aleuritic acid has a tendency to adopt a monolayer configuration ruled by the lateral interactions between molecules via the two secondary hydroxyl groups. This (2D) growth competes with the multilayer formation (3D), which is conditioned by the terminal primary hydroxyl group. As the self-assembly spatial constraint is relaxed, MD has shown that the structure tends to become an amorphous and crosslinked phase that can be characterized by topographic and friction force AFM data.

Abstract

The effects of a high ion dose irradiation on TiO2 thin films under different conditions of temperature and ion nature are discussed. We have shown that anatase TiO2 thin films irradiated with N+ ions at room temperature develop a typical microstructure with mounds and voids open to the surface whereas irradiations at 700 K generate a surface pattern of well-ordered nanorods aligned with the ion beam. The formation of these patterns is caused by the simultaneous effect of ion irradiation near the film surface and a film temperature favoring the structural mobilization of the defective network of the material. To explain these phenomena, a qualitative model has been proposed and further tested by irradiating the TiO2 thin films with F+ and S+ ions under different conditions. The obtained results demonstrate that ion irradiation techniques enable the formation of tilted nanorod surface patterns with lengths of about 100 nm on anatase TiO2 thin films.

Abstract

Monolithic CeO2 and Au/CeO2 catalysts were prepared using austenitic stainless steel (AISI 304) as metallic substrate. Both monolithic and powdered catalysts were characterized before and after CO oxidation reaction by N-2 adsorption desorption, XRD, SEM, TEM and GD-OES. Catalyst deposition on the stainless steel surface results in modifications of the catalyst, the oxide scale and the oxide scale/alloy interface through the interaction between the coating and the steel oxidation layer. Besides this, oxidation of the alloy is also detected. The extension and nature of these modifications depends on the catalyst nature, and on the reaction conditions. As a result of these modifications CO oxidation on Au/CeO2 catalysts is enhanced and gold surface dynamics is modified.

Abstract

This work reports an easy-to-handle method for growing two-dimensional assemblies of Ag nanostructures presenting a tunable in-plane optical anisotropy. Ag is deposited by DC sputtering in an Ar plasma at room temperature onto bundled nanocolumnar SiO2 thin films grown by glancing angle physical vapor deposition. In contrast with previously reported processes involving the grazing angle deposition of the metal, DC sputtering is performed at normal incidence. By varying the deposition angle of SiO2 and the Ar pressure, it was possible to tune the deposited amount of Ag and thus the topology of the Ag deposit from isolated spherical Ag nanoparticles with isotropic optical properties to strongly dichroic Ag nanostripes oriented along the bundling direction of the SiO2 nanocolumns. Based on simple calculations taking into account the shadowing effects during metal deposition, it is proposed that the width and shape of the tip of the bundled SiO2 nanocolumns influence significantly the metal local atom flux arriving to them and thus the final structure of the deposit.

Abstract

Vanadium nitride (VN) has been prepared by mechanosynthesis from vanadium metal under a pressurized nitrogen atmosphere in a short milling time. The characterization of the final product by X-ray diffraction, scanning electron microscopy, electron energy loss (EELS), and X-ray absorption spectroscopy (XAS) is presented. The final product, VN with 96% of purity, is obtained at room temperature with nanometric particle size and a very high microhardness after sintering. A relationship between microstructure and microhardness as well as a comparison between the VN obtained mechanical and thermal method is also presented.

Abstract

Herein we present a synthetic route to attain porous one-dimensional photonic crystals of high optical quality. The method employed, based on the alternate deposition of TiO2 and SiO2 porous layers by glancing angle physical vapour deposition, yields a highly accessible interconnected pore network throughout the entire multilayer structure. Furthermore, it allows a strict control over the average size and density of the interstitial sites, which results in the precise tuning of the refractive index of the individual layers and thus of the optical response of the ensemble. The controlled environmental response of the multilayer is confirmed by the optical monitoring of the infiltration of liquids of different refractive index.

Abstract

Pyrophyllite is a raw material of significant interest due to its large number of applications. Most of these applications require a thermal transformation of pyrophyllite; this thermal transformation implies the release of structural OH groups and the formation of new phases. In this paper, we report on the dehydroxylation of pyrophyllite and the reversibility of the process. A value of 224 +/- 16 kJ/mol for the dehydroxylation of pyrophyllite was obtained. In addition, it was observed that the partially or totally dehydroxylated pyrophyllite suffered a partial reversible rehydroxylation when cooled to room temperature. This rehydroxylation was substantiated by thermogravimetric measurements, while infrared spectroscopic studies showed that, during the rehydroxylation, the intensity of the OH band at 3675 cm-1 increased as two new bands at 3690 and 3702 cm-1 appeared. This rehydroxylation process was heavily influenced by the particle size of the pyrophyllite. Thus, smaller particles (< 1 mu m) showed a larger rehydroxylation percentage (about 12%), while the larger ones (20-40 mu m) showed a smaller percentage (about 1.6%). The extent of rehydroxylation also depended on the dehydroxylation temperature and reached a maximum value at 750 degrees C.

Abstract

In this paper, a novel method for calculating degradation kinetics is presented. The method has been applied to the thermal dehydrochlorination of two different samples of PVC. It has been observed that this dehydrochlorination is complex and involves two different processes. A model that accounts for the entire dehydrochlorination is proposed. This model involves nucleation and growth and diffusion controlled mechanisms. The kinetic parameters are obtained from linear heating rate, isothermal and sample controlled thermal analysis experiments. Kinetic results obtained from the macroscopic thermal analysis measurements demonstrate the correlation between the kinetics of the thermal dehydrochlorination of PVC and the structure of this macromolecule.

Abstract

A mechanochemical procedure is proposed for an easy preparation of a BaTiO3-Ni composite in a single step. BaTiO3 and Ni powders available in the market are mixed by dry ball milling producing a decrease of particle size and an evenly distribution of both phases. In the sintered pellets the nickel particles are homogeneously distributed into the BaTiO3 matrix and isolated from others Ni particles. The dielectric constant of the composite is considerably higher than that of the barium titanate. Moreover, the temperature of the ferroelectric <-> paraelectric transition of the BaTiO3-Ni composite here prepared is much lower than the one of the pure BaTiO3 single phase.

Abstract

The aims of the present study is to describe for the first time the Sc-45 MAS NMR spectra of X-2-Sc2SiO5 and C-Sc2Si2O7, to combine the spectroscopic information with the structures published from diffraction data, and to propose a rational interpretation of the chemical shifts and quadrupolar parameters. For that purposed, we have correlated the experimental quadrupole coupling parameters of Sc-45 determined for a number of scandium compounds to those found by a simple electrostatic calculation and we have found that the isotropic chemical shift of the Sc-45 is linearly correlated to the shift parameter, calculated by bond-valence theory. We also show that a simple point charge calculation can approximate the electric field gradient to a sufficiently good approximation that it provides a valuable mean to assign the NMR spectra.

Abstract

Herein, we present an overview of recent progress on the development of different types of porous 1-D photonic crystal coatings which are optically responsive to gas pressure changes in the environment. Modification of the surrounding vapor pressure gives rise to adsorption and condensation phenomena within the porous networks of the photonic crystal building blocks, varying their refractive index and hence their optical features. This effect can be put into practice to precisely detect and monitor changes in the ambient through the spectral shift of either the photonic bandgap of the structure or of some other optical features. Our results demonstrate the potential of these optical coatings as new materials for gas sensing devices.

Abstract

The tribological performance of nanocomposite coatings containing Ti-B-C phases and amorphous carbon (a-C) are studied. The coatings are deposited by a sputtering process from a sintered TiB2:TiC target and graphite, using pulsed direct current and radio frequency sources. By varying the sputtering power ratio, the amorphous carbon content of the coatings can be tuned, as observed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The crystalline component consists of very disordered crystals with a mixture of TiB2/TiC or TiBxCy phases. A slight increase in crystalline order is detected with the incorporation of carbon in the coatings that is attributed to the formation of a ternary TiBxCy phase. An estimation of the carbon present in the form of carbide (TiBxCy or TiC) and amorphous (a-C) is performed using fitting analysis of the C 1s XPS peak. The film hardness (22 to 31 GPa) correlates with the fraction of the TiBxCy phase that exists in the coatings. The tribological properties were measured by a pin-on-disk tribometer in ambient conditions, using 6 mm tungsten carbide balls at 1 N. The friction coefficients and the wear rates show similar behavior, exhibiting an optimum when the fraction of C atoms in the amorphous phase is near 50%. This composition enables significant improvement of the friction coefficients and wear rates (mu similar to 0.1; k < 1 x 10(-6) mm(3)/Nm), while maintaining a good value of hardness (24.6 GPa). Establishing the correlation between the lubricant properties and the fraction of a-C is very useful for purposes of tailoring the protective character of these nanocomposite coatings to engineering applications.

Abstract

We report on a study of electromagnetic waves propagation in thin periodically ordered photonic nanostructures in the spectral range where the light wavelength is on the order of the lattice parameter. The vector KKR method we use allows us to determine the group index from finite photonic structures including extinction providing confirmation of recently emerged results. We show that for certain frequencies the group velocity of opal slabs can either be superluminal or approach zero depending on the crystal thickness and the unavoidable presence of losses. In some cases, group velocity can be negative. Such behavior can be clearly attributed to the finite character of the three-dimensional structure and reproduces previously reported experimental observations. Calculations show that contrary to the predictions of extraordinary group velocity reductions for infinite periodic structures, the group velocity of real opals may exhibit strong fluctuations at the high energy range. Hence, a direct identification between the calculated anomalous group velocities, for an actual opal film, and the predicted propagating low dispersion modes for an ideal infinite ordered structure seems difficult to establish.

Abstract

Epitaxial YBCO thin films have been grown on hexagonal GaN/c-sapphire substrates using DC magnetron sputtering and pulsed laser deposition. An MgO buffer layer has been inserted between the substrate and the YBCO film as a diffusion barrier. X-ray diffraction analysis indicates a c-axis oriented growth of the YBCO films. &#934;-scan shows surprisingly twelve maxima. Transmission electron microscopy analyses confirm an epitaxial growth of the YBCO blocks with a superposition of three a&#8211;b YBCO planes rotated by 120° to each other. Auger electron spectroscopy and X-ray photoelectron spectroscopy reveal no surface contamination with Ga even if a maximum substrate temperature of 700 °C is applied.

Abstract

The enhanced high-temperature creep resistance in alumina/single-wall carbon nanotubes (SWNTs) composites has been attributed to the unprecedented grain-boundary structure of these composites, where the SWNTs bundles segregated at the alumina grain boundaries partially impede grain-boundary sliding. In this study, the effect of SWNTs distributions at alumina grain boundaries on the creep behavior of alumina/SWNTs composites has been investigated. Microstructures of two different alumina/10 vol% SWNTs composites, one with heterogeneous and the other with homogenous distributions of SWNTs at grain boundaries, have been characterized quantitatively. The steady-state creep rate (uniaxial compression) in the heterogeneous composite has been found to be over three times higher than that in the homogeneous composite at 1300° and 1350°C (argon atmosphere). It is argued that the less uniform distribution of SWNTs at the alumina grain boundaries in the heterogeneous composite results in less effective obstruction of grain-boundary sliding, and attendant higher creep rate. This also results in more efficient recovery in that composite.

Abstract

In this work, we demonstrate that optical resonators built using all-nanoparticle-based porous building blocks provide a responsive multifunctional matrix, totally different emission spectra being attained from the same embedded luminescent nanophosphors under varying environmental conditions. We show a clear correlation between modifications in the ambient surroundings, the induced changes of the resonant modes, and the resulting variations in the emission response. The method is versatile and allows nanophosphors of arbitrary shape to be integrated in the cavity. By precise control of the spectral features of the optical resonances, luminescence is strongly modulated in selected and tuneable wavelength ranges. Applications in the fields of sensing and detection are foreseen for these materials.

Abstract

Gold-supported ceria and europium-doped ceria catalysts were prepared by the deposition-precipitation method. The influence of the pretreatment atmosphere and temperature on the concentration of oxygen vacancies and gold dispersion on the Au/CeEti(10) catalyst under actual reaction conditions was investigated by "in situ" X-ray diffraction and Raman analysis. By Raman spectroscopy, a preferential interaction of the gold with the support across the oxygen vacancies was established and correlated with the gold dispersion. The increase in the concentration of oxygen vacancies in the presence of hydrogen induces changes in the gold crystallite size by breaking-off and migration of gold nanoparticles toward the oxygen vacancies on the CeEu(10) support. The activity of the Au/CeEu(10) solid in the CO oxidation reaction was significantly improved when the catalyst was preactivated in a reducing atmosphere. This trend could be associated with the redispersion of gold together with the increase in the concentration of oxygen vacancies in the support.

Abstract

An experimental and theoretical analysis of the angular dependence of the diffracted light beams emerging from three-dimensional colloidal photonic crystals is herein presented. Diffracted beams are identified according to their associated reciprocal-lattice vectors, and their intensities are obtained as a function of the zenithal and azimuthal incidence angles. Significant changes in the beam intensities are observed for large zenithal incidence angles as the azimuthal angle is varied. This phenomenon is related to the excitation of new resonant modes inside the photonic crystal which cannot be observed under normal incidence conditions.

Abstract

Periodic multilayers of wide photonic bandgap and high reflectance in the visible and near infrared regions are fabricated. Optical properties show that reflectance intensities close to 90% are reached for stacks of only six layers, as well as gap-to-midgap ratios of 50%. The optical response of the hybrid ensemble can be accurately tuned through the number of infiltration cycles performed.

Abstract

TiCxVy/Ni and TiCxNy/Ti-Co composites formed by ceramic and intermetallic binder phases were produced by pressureless sintering at 1400 degrees C from powders synthesized by a mechanically induced self-sustaining reaction (MSR) process. Four different composites were characterized using high-resolution electron microscopic techniques, in both scanning (SEM, HRSEM) and transmission (TEM, HRTEM, ED, EDS and EELS) modes and using an energy filtered technique (EFTEM) associated with electron energy loss spectroscopy (EELS). The microcharacterization showed that the ceramic phase with an fcc-cubic structure displayed a short-range order in many crystals detected by diffuse scattering in the ED patterns. This was possibly due to a sequence of C, N, and vacancies of both atoms along certain directions in the structure. On the other hand, even though the binder phase was introduced as metal in the reaction process, it was formed by Ni-Ti or Co-Ti known intermetallic compounds (NiTi2, Ni3Ti, and Co3Ti). An unknown Ni-Ti intermetallic structure with a Ni:Ti ratio close to 2:1 was only found in one of the synthesized composites and displayed a cubic structure with a lattice parameter, a, of about 8.7 angstrom.

Abstract

A microstructural modelling of the microstructure in single wall carbon nanotubes reinforced alumina ceramics has been developed. The model accounts for the main microstructural features, being quite useful to describe the carbon nanotube distribution along the ceramic matrix. The microstructural analysis derived from this model is found to give a deeper insight into the high-temperature creep of these composites.

Abstract

The implantation of controlled drug release devices represents a new strategy in the treatment of neurodegenerative disorders Sol-gel titania implants filled with valproic acid, have been used for this purpose to treat induced epilepsy in rats The kinetics of the drug release depend on. (a) porosity, (b) chemical interactions between valproic acid and surface hydroxyl groups of titania, (c) particle size, and (d) particle size agglomerates The concentration of water used in the hydrolysis reaction is an important variable in the degree of porosity, hydroxylation, and structural defects of the nanostructured titanium oxide reservoir The titanium n-butoxide/water ratio was systematically varied during the sol-gel synthesis, while maintaining the amount of valproic acid constant. Characterization studies were performed using DTA-TGA, FTIR, Raman, TEM, SEM, BET, and in vitro release kinetic measurements The particle agglomerate size and porosity were found to depend on the amount of water used in the sol-gel reactio.

Abstract

An enhanced fluorescent emission of the dye Rhodamine 800 in the Near-IR is observed in the presence of other xanthene dye molecules (RhX) when they are hosted in different matrices due to the formation of a new type of fluorescent J-heteroaggregates.

This enhanced emission of the acceptor occurs despite the low spectral overlapping and the low quantum yield of Rh800.

Abstract

A series of nanosized W,N-codoped and single-doped N- and W-anatase-TiO2 catalysts have been prepared by a microemulsion method and calcined at different temperatures. The activity in the sunlight selective photo-oxidation of toluene and styrene has been correlated with structural, electronic, and surface examinations of the catalysts done with the help of XRD-Rietveld, N-2 physisorption, X-ray photoelectron, infrared, electron paramagnetic resonance (EPR) and UV-vis spectroscopies. Irrespective of the reaction, W,N-codoped nanocatalysts showed an enhanced photoactivity with respect to bare anatase and single-doped N-TiO2 and W-TiO2 materials. A strong W-N synergistic interaction appears to play a decisive role in driving the excellent photoactivity performance of W,N-codoped materials by affecting (i) electronic properties, particularly maximizing the anatase band gap decrease and enhancing the subsequent visible light photon absorption, and (ii) surface properties, in turn related to the formation of OH radicals upon light excitation. The maximum photoactivity is reached by calcination at 450 degrees C and is concomitantly observed with a near complete selectivity to partial oxidation products. Higher calcination temperatures yielded solids with significantly inferior photocatalytic performance. The properties of the W-N interaction are discussed as a function of the calcination temperature.

Abstract

Nanostructured cryptomelanes (KMn8O16) were synthesized from manganese sulphate and manganese acetate precursors by the reflux method. The respectively obtained samples, CRYSO4 and CRYAc, were functionalised with hydroxyl, ammonium, sulphate and phosphate groups in order to modify the biocompatibility and surface properties of cryptomelane. Characterization by FTIR and XRD confirmed bond formation of CRY-NH, CRY=S=O, CRY-NH, and CRY=PO4. In both functionalise samples (CRYSO4-F and CRYAc-F), IR bands occurred at 1399 cm(-1), corresponding to the sulphate species, and 1106 cm(-1), related to phosphate vibrations; along with the OH and NH characteristic vibration bands in the high energy region. Biocompatibility of functionalised samples was tested by implantation of cryptomelane reservoir in the basolateral amygdala and caudal nucleus of Wistar rats using stereotactic surgery. The brains of the rats were processed in order to evaluate any damage associated with the implant. The results showed that functionalised cryptomelanes did not cause tissue damage or inflammation while not functionalised cryptomelanes caused cell death.