Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Density functional theory calculation of the electronic structure of Ba0.5Sr0.5TiO3: Photoluminescent properties and structural disorder

First-principles quantum-mechanical techniques, based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and deformed asymmetric models for Ba0.5Sr 0.5TiO3. Electronic properties are analyzed and the relevance of the present theoretical and experimental results on the photoluminescence behavior is discussed. The presence of localized electronic levels in the band gap, due to the symmetry break, would be responsible for the visible photoluminescence of the amorphous state at room temperature. Thin films were synthesized following a soft chemical processing. Their structure was confirmed by x-ray data and the corresponding photoluminescence properties measured.

Functional nanostructured catalysts based on the niobates to the dry methane reforming and ethylene homologation reactions

Catalytic activity and selectivity of niobate-based nanostructured materials were investigated. Dry methane reforming (DMR) and ethylene homologation reaction (EHR) were selected as test reactions. KSr 2Nb5O15, Sr2NaNb5O 15 and NaSr2(NiNb4)O15 δ niobate powders were prepared by the high energy ball milling method and calcined in a reductor atmosphere. N2 adsorption isotherms, X-ray diffraction and infrared spectroscopy characterization was performed. Hydrogen pretreated niobates showed from low to moderate catalytic initial activity in DMR's test, nevertheless the materials were deactivated rapidly and the kinetic parameters associated to deactivation were estimated. Otherwise, non-treated catalysts showed a high initial activity in EHR's test and KSr2Nb 5O15 catalyst requires 24 h to the total deactivation with a high selectivity to form propylene. A reaction mechanism to the propylene formation is discussed. © 2012 Elsevier Ltd. All rights reserved.

Mechanical properties of vulcanized natural rubber nanocomposites containing functional ceramic nanoparticles

Rubber nanocomposites containing different concentrations of ferroelectric and paramagnetic nanoparticles were fabricated. Nanostructures of ferroelectric potassium strontium niobate and paramagnetic nickel-zinc ferrite were synthesized using a modified polyol method. The nanoparticle characterization was carried out by transmission electron microscopy and X-ray diffraction, showing that the materials were produced with nanometer dimensions, specific crystallinity and microstrain. Mechanical tests such as hardness type Shore A, stress-strain and compression resistance were performed. They showed that increasing the concentration of nanoparticles enhance the rigidity of vulcanized films of natural rubber and this change is more pronounce for the nanocomposites formed with ferrite nanoparticles, likely due to the effect of its morphological and surface properties. © 2013 by American Scientific Publishers.

Influence of ethanol and glycerol concentration over functional and structural properties of zein-oleic acid films

This study was performed in order to determine the effect of the addition of different concentrations of glycerol and ethanol over functional and structural properties of zein-oleic acid films. Films were prepared from zein and oleic acid formulations, containing: 0, 10, 20 and 30% (w/w) of glycerol as plasticizer and 75, 80, 85, 90 and 95% (v/v) of ethanol as zein solvent. Water vapor permeability (WVP) at 4 and 24 C, opacity, water solubility and structural behavior of the film were assessed. The film water barrier properties, WVP and water solubility, were increased when higher ethanol concentration and lower glycerol concentration were used. Furthermore, WVP at 4 C was lower than WVP at 24 C due to the crystalline solid state of oleic acid at lower temperatures. Likewise, opacity, homogeneity and structure of the composite film were improved as ethanol increased and glycerol lowered. © 2013 Elsevier B.V. All rights reserved.

Long-term skeletal and dental effects and treatment timing for functional appliances in Class II malocclusion

Objective: To analyze the long-term skeletal and dentoalveolar effects and to evaluate treatment timing of Class II treatment with functional appliances followed by fixed appliances.Materials and Methods: A group of 40 patients (22 females and 18 males) with Class II malocclusion consecutively treated either with a Bionator or an Activator followed by fixed appliances was compared with a control group of 20 subjects (9 females and 11 males) with untreated Class II malocclusion. Lateral cephalograms were available at the start of treatment (mean age 10 years), end of treatment with functional appliances (mean age 12 years), and long-term observation (mean age 18.6 years). The treated sample also was divided into two groups according to skeletal maturity. The early-treatment group was composed of 20 subjects (12 females and 8 males) treated before puberty, while the late-treatment group included 20 subjects (10 females and 10 males) treated at puberty. Statistical comparisons were performed with analysis of variance followed by Tukey's post hoc tests.Results: Significant long-term mandibular changes (Co-Gn) in the treated group (3.6 mm over the controls) were associated with improvements in the skeletal sagittal intermaxillary relationship, overjet, and molar relationship (similar to 3.0-3.5 mm). Treatment during the pubertal peak was able to produce significantly greater increases in total mandibular length (4.3 mm) and mandibular ramus height (3.1 mm) associated with a significant advancement of the bony chin (3.9 mm) when compared with treatment before puberty.Conclusion: Treatment of Class II malocclusion with functional appliances appears to be more effective at puberty. (Angle Orthod. 2013;83:334-340.)

Cartilage Reconstruction Using Self-anchoring Implant with Functional Gradient

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Nanostructured Composites Based on Carbon Nanotubes and Epoxy Resin for Use as Radar Absorbing Materials

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Surface modification of polymeric materials by cold atmospheric plasma jet

In this work we report the surface modification of different engineering polymers, such as, polyethylene terephthalate (PET), polyethylene (PE) and polypropylene (PP) by an atmospheric pressure plasma jet (APPJ). It was operated with Ar gas using 10 kV, 37 kHz, sine wave as an excitation source. The aim of this study is to determine the optimal treatment conditions and also to compare the polymer surface modification induced by plasma jet with the one obtained by another atmospheric pressure plasma source the dielectric barrier discharge (DBD). The samples were exposed to the plasma jet effluent using a scanning procedure, which allowed achieving a uniform surface modification. The wettability assessments of all polymers reveal that the treatment leads to reduction of more than 40 degrees in the water contact angle (WCA). Changes in surface composition and chemical bonding were analyzed by x-ray photoelectron spectroscopy (XPS) and Fourier-Transformed Infrared spectroscopy (FTIR) that both detected incorporation of oxygen-related functional groups. Surface morphology of polymer samples was investigated by Atomic Force Microscopy (AFM) and an increase of polymer roughness after the APPJ treatment was found. The plasma-treated polymers exhibited hydrophobic recovery expressed in reduction of the O-content of the surface upon rinsing with water. This process was caused by the dissolution of low molecular weight oxidized materials (LMWOMs) formed on the surface as a result of the plasma exposure. (C) 2014 Elsevier B.V. All rights reserved.

Structural and functional characterization of barium zirconium titanate/epoxy composites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Elucidating the optical properties of novel heterolayered materials based on MoTe2-InN for photovoltaic applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Non-centrosymmetric crystals of new N-benzylideneaniline derivatives as potential materials for non-linear optics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.