Estudo da relação de ordem-desordem estrutural em nanopartículas de TiO2

Pós-graduação em Química - IQ

Efeito na osseointegração de um novo método de nanotexturização de superfície de implantes através de anodização

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Aplicação de carbono vítreo monolítico para produção de eletrodos a partir da resina furfurílica com diferentes variações de pH

Nowadays, we live in a time of rapid research for technological advances, in a way that this pursuit of new technologies is deeply connected to the diversity of new materials that have been developed by mankind. It deals with issues such as materials with enhanced properties which offer better quality, less cost and high performance, while they are accessible both in their production and moment of operation. In this context, it was required to develop electrodes that were easy to prepare as well as which present high electric conductivity and good mechanic proprieties by using carbonaceous material as basis. For this reason, the best parameters of the furfuryl resin cures were established with different pH variations through viscosimetric measurements and differential scanning calorimetry. By scanning electron microscopy (SEM) was possible to identify an increased porosity in the samples with pH 7 and pH 8, as compared to samples with lower pH content. After carbonization of the material, the characterization of monolithic glassy carbon was held by means of FT-IR techniques, Raman spectroscopy, X-ray diffraction and cyclic voltammetry. The spectra showed that the change in pH does not have significant influence on the crystallographic ordering of the material and its structural characteristics. As for the electrochemical character, the CVM electrodes showed excellent response, with good reversibility and wide potential window. Some voltammetric curve deviations were only observed for the sample with pH 4, which may be related to processing parameters adopted

Growth and Characterization of Silicon Carbide Thin Films Using a Nontraditional Hollow Cathode Sputtering Technique

Silicon carbide (SiC) is considered a suitable candidate for high-power, high-frequency devices due to its wide bandgap, high breakdown field, and high electron mobility. It also has the unique ability to synthesize graphene on its surface by subliming Si during an annealing stage. The deposition of SiC is most often carried out using chemical vapor deposition (CVD) techniques, but little research has been explored with respect to the sputtering of SiC. Investigations of the thin film depositions of SiC from pulse sputtering a hollow cathode SiC target are presented. Although there are many different polytypes of SiC, techniques are discussed that were used to identify the film polytype on both 4H-SiC substrates and Si substrates. Results are presented about the ability to incorporate Ge into the growing SiC films for the purpose of creating a possible heterojunction device with pure SiC. Efforts to synthesize graphene on these films are introduced and reasons for the inability to create it are discussed. Analysis mainly includes crystallographic and morphological studies about the deposited films and their quality using x-ray diffraction (XRD), reflection high energy electron diffraction (RHEED), transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Auger electron spectroscopy (AES) and Raman spectroscopy. Optical and electrical properties are also discussed via ellipsometric modeling and resistivity measurements. The general interpretation of these analytical experiments indicates that the films are not single crystal. However, the majority of the films, which proved to be the 3C-SiC polytype, were grown in a highly ordered and highly textured manner on both (111) and (110) Si substrates.

Aplicação de carbono vítreo monolítico para produção de eletrodos a partir da resina furfurílica com diferentes variações de pH

Nowadays, we live in a time of rapid research for technological advances, in a way that this pursuit of new technologies is deeply connected to the diversity of new materials that have been developed by mankind. It deals with issues such as materials with enhanced properties which offer better quality, less cost and high performance, while they are accessible both in their production and moment of operation. In this context, it was required to develop electrodes that were easy to prepare as well as which present high electric conductivity and good mechanic proprieties by using carbonaceous material as basis. For this reason, the best parameters of the furfuryl resin cures were established with different pH variations through viscosimetric measurements and differential scanning calorimetry. By scanning electron microscopy (SEM) was possible to identify an increased porosity in the samples with pH 7 and pH 8, as compared to samples with lower pH content. After carbonization of the material, the characterization of monolithic glassy carbon was held by means of FT-IR techniques, Raman spectroscopy, X-ray diffraction and cyclic voltammetry. The spectra showed that the change in pH does not have significant influence on the crystallographic ordering of the material and its structural characteristics. As for the electrochemical character, the CVM electrodes showed excellent response, with good reversibility and wide potential window. Some voltammetric curve deviations were only observed for the sample with pH 4, which may be related to processing parameters adopted

Interface tailoring for adhesion enhancement of diamond-like carbon thin films

We have explored the suitability and characteristics of interface tailoring as a tool for enhancing the adhesion of hydrogen-free diamond-like carbon (DLC) thin films to silicon substrates. DLC films were deposited on silicon with and without application of an initial high energy carbon ion bombardment phase that formed a broad Si-C interface of gradually changing Si:C composition. The interface depth profile was calculated using the TRIDYN simulation program, revealing a gradient of carbon concentration including a region with the stoichiometry of silicon carbide. DLC films on silicon, with and without interface tailoring, were characterized using Raman spectroscopy, scanning electron microscopy, atomic force microscopy and scratch tests. The Raman spectroscopy results indicated sp3-type carbon bonding content of up to 80%. Formation of a broadened Si:C interface as formed here significantly enhances the adhesion of DLC films to the underlying silicon substrate. (C) 2012 Elsevier B.V. All rights reserved.

Graphene modification with gold nanoparticles using the gas aggregation technique

Gold nanoparticles (Au-NPs) were deposited on single layer graphene (SLG) and few layers graphene (FLG) by applying the gas aggregation technique, previously adapted to a 4-gun commercial magnetron sputtering system. The samples were supported on SiO2 (280 nm)/Si substrates, and the influence of the applied DC power and deposition times on the nanoparticle-graphene system was investigated by Confocal Raman Microscopy. Analysis of the G and 2D bands of the Raman spectra shows that the integrated intensity ratio (I-2D/I-G) was higher for SLG than for FLG. For the samples produced using a sputtering power of 30W, the intensity (peak height) of the G and 2D bands increased with the deposition time, whereas for those produced applying 60W the peak heights of the G and 2D bands decreased with the deposition time. This behaviour was ascribed to the formation of larger Au-NPs aggregates in the last case. A significant increase of the Full Width Half Maximum (FWHM) of the G band for SLG and FLG was also observed as a function of the DC power and deposition time. Surprisingly, the fine details of the Raman spectra revealed an unintentional doping of SLG and FLG accompanying the increase of size and aggregation of the Au-NPs. (C) 2011 Elsevier B.V. All rights reserved.

Interionic Interactions in Imidazolic Ionic Liquids Probed by Soft X-ray Absorption Spectroscopy

This work investigates pure ionic liquids (ILs) derived from an imidazolium ring with different carbonic chains and halides or bis(trifluoromethanesulfonilimide) (TFSI-) as anions, using X-ray absorption near edge spectroscopy (XANES) at different energies (N, S, O, F, and Cl edges) to probe the interionic interactions. XANES data show that the interaction with the anion is weaker when the cation is an imidazolium than when the salt is formed by smaller cations, as lithium, independently of the length of the carbonic chain attached to the imidazolium cation. The results also show that, for all studied as, it is not observed any influence of the anion on the XANES spectra of the cation, nor the opposite. 1-Methylimidazolium with Cl-, a small and strongly coordinating anion, presents in the N K XANES spectrum a splitting of the band corresponding to nitrogen in the imidazolic ring, indicating two different chemical environments. For this cation with TFSI-, on the contrary, this splitting was not observed, showing that the anion has a weaker interaction with the imidazolic ring, even without a lateral carbonic chain.

Electrocatalytic Activity of Pd, Pt, and Rh for the Electro-oxidation of Ethanol in Alkaline Electrolyte: An Online DEMS Study

The electro-oxidation of ethanol was investigated on electrodeposited layers of Pd, Pt, and Rh in alkaline electrolyte. The reaction products were monitored by experiments of online differential electrochemical mass spectrometry (DEMS). Potentiodynamic curves for the ethanol electro-oxidation catalyzed by these three different metal electrocatalysts showed similar onset potentials, but the highest Faradaic current peak was observed for the Pt electrocatalyst. Online DEMS experiments evidenced similar amounts of CO2 for the three different materials, but Pd presented the higher production of ethylacetate (acetic acid). This indicated that the electrochemical oxidation of ethanol on the Pd surface occurred to a higher extent. The formation of methane, which was observed for Pt and Rh, after potential excursions to lower potentials, was absent for Pd. On the basis of the obtained results, it was stated that, on Pt and Rh, the formation of CO2 occurs mainly via oxidation of CO and CH (x,ad) species formed after dissociative adsorption of ethanol or ethoxy species that takes place only at low potentials. This indicates that the dissociative adsorption of ethanol or ethoxy species is inhibited at higher potentials on Pt and Rh. On the other hand, on the Pd electrocatalyst, the reaction may occur via nondissociative adsorption of ethanol or ethoxy species at lower potentials, followed by oxidation to acetaldehyde and, after that, by a further oxidation step to acetic acid on the electrocatalyst surface. Additionally, in a parallel route, the acetaldehyde molecules adsorbed on the Pd surface can be deprotonated, yielding a reaction intermediate in which the carbon-carbon bond is less protected, and therefore, it can be dissociated on the Pd surface, producing CO2, after potential excursions to higher potentials.

Optical and thermal investigation of GeO2-PbO thin films doped with Au and Ag nanoparticles

The present work reports on the thermo-optical study of germanate thin films doped with Au and Ag nanoparticles. Transmission Electron Microscopy images, UV-visible absorption and Micro-Raman scattering evidenced the presence of nanoparticles and the formation of collective excitations, the so called surface plasmons. Moreover, the effects of the metallic nanoparticles in the thermal properties of the films were observed. The thermal lens technique was proposed to evaluate the Thermal Diffusivity (D) of the samples. It furnishes superficial spatial resolution of about 100 mu m, so it is appropriate to study inhomogeneous samples. It is shown that D may change up to a factor 3 over the surface of a film because of the differences in the nanoparticles concentration distribution. (C) 2011 Elsevier B.V. All rights reserved.

Structural, morphological, and magnetic characterization of In1-xMnxAs quantum dots grown by molecular beam epitaxy

In this paper, we present a method to order low temperature (LT) self-assembled ferromagnetic In1-xMnxAs quantum dots (QDs) grown by molecular beam epitaxy (MBE). The ordered In1-xMnxAs QDs were grown on top of a non-magnetic In0.4Ga0.6As/GaAs(100) QDs multi-layered structure. The modulation of the chemical potential, due to the stacking, provides a nucleation center for the LT In1-xMnxAs QDs. For particular conditions, such as surface morphology and growth conditions, the In1-xMnxAs QDs align along lines like chains. This work also reports the characterization of QDs grown on plain GaAs(100) substrates, as well as of the ordered structures, as function of Mn content and growth temperature. The substitutional Mn incorporation in the InAs lattice and the conditions for obtaining coherent and incoherent structures are discussed from comparison between Raman spectroscopy and x-ray analysis. Ferromagnetic behavior was observed for all structures at 2K. We found that the magnetic moment axis changes from [110] in In1-xMnxAs over GaAs to [1-10] for the ordered In1-xMnxAs grown over GaAs template. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4745904]

Gold nanoparticle formation in diamond-like carbon using two different methods: Gold ion implantation and co-deposition of gold and carbon

We describe work in which gold nanoparticles were formed in diamond-like carbon (DLC), thereby generating a Au-DLC nanocomposite. A high-quality, hydrogen-free DLC thin film was formed by filtered vacuum arc plasma deposition, into which gold nanoparticles were introduced using two different methods. The first method was gold ion implantation into the DLC film at a number of decreasing ion energies, distributing the gold over a controllable depth range within the DLC. The second method was co-deposition of gold and carbon, using two separate vacuum arc plasma guns with suitably interleaved repetitive pulsing. Transmission electron microscope images show that the size of the gold nanoparticles obtained by ion implantation is 3-5 nm. For the Au-DLC composite obtained by co-deposition, there were two different nanoparticle sizes, most about 2 nm with some 6-7 nm. Raman spectroscopy indicates that the implanted sample contains a smaller fraction of sp(3) bonding for the DLC, demonstrating that some sp(3) bonds are destroyed by the gold implantation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757029]

Toward the Optimization of an e-Tongue System Using Information Visualization: A Case Study with Perylene Tetracarboxylic Derivative Films in the Sensing Units

The wide variety of molecular architectures used in sensors and biosensors and the large amount of data generated with some principles of detection have motivated the use of computational methods, such as information visualization techniques, not only to handle the data but also to optimize sensing performance. In this study, we combine projection techniques with micro-Raman scattering and atomic force microscopy (AFM) to address critical issues related to practical applications of electronic tongues (e-tongues) based on impedance spectroscopy. Experimentally, we used sensing units made with thin films of a perylene derivative (AzoPTCD acronym), coating Pt interdigitated electrodes, to detect CuCl(2) (Cu(2+)), methylene blue (MB), and saccharose in aqueous solutions, which were selected due to their distinct molecular sizes and ionic character in solution. The AzoPTCD films were deposited from monolayers to 120 nm via Langmuir-Blodgett (LB) and physical vapor deposition (PVD) techniques. Because the main aspects investigated were how the interdigitated electrodes are coated by thin films (architecture on e-tongue) and the film thickness, we decided to employ the same material for all sensing units. The capacitance data were projected into a 2D plot using the force scheme method, from which we could infer that at low analyte concentrations the electrical response of the units was determined by the film thickness. Concentrations at 10 mu M or higher could be distinguished with thinner films tens of nanometers at most-which could withstand the impedance measurements, and without causing significant changes in the Raman signal for the AzoPTCD film-forming molecules. The sensitivity to the analytes appears to be related to adsorption on the film surface, as inferred from Raman spectroscopy data using MB as analyte and from the multidimensional projections. The analysis of the results presented may serve as a new route to select materials and molecular architectures for novel sensors and biosensors, in addition to suggesting ways to unravel the mechanisms behind the high sensitivity obtained in various sensors.

USE OF THE LINEAR LIGHT SENSOR ILX554 IN OPTICAL SPECTROSCOPY

USE OF THE LINEAR LIGHT SENSOR ILX554 IN OPTICAL SPECTROSCOPY. This technical note describes the construction of a low-cost optical detector. This device is composed by a high-sensitive linear light sensor (model ILX554) and a microcontroller. The performance or the detector was demonstrated by the detection of emission and Raman spectra of the several atomic systems and the results reproduce those found in the literature.

Dependence of brittle-to-ductile transition on crystallographic direction in diamond turning of single-crystal silicon

The objective of this paper is to show the dependence relationship between the crystallographic orientations upon brittle-to-ductile transition during diamond turning of monocrystalline silicon. Cutting tests were performed using a -5 degrees rake angle round nose diamond tool at different machining scales. At the micrometre level, the feedrate was kept constant at 2.5 micrometres per revolution (mu m/r), and the depth of cut was varied from 1 to 5 mu m. At the submicrometre level, the depth of cut was kept constant at 500 nm and the feedrate varied from 5 to 10 mu m/r. At the micrometre level, the uncut shoulder generated with an interrupted cutting test procedure provided a quantitative measurement of the ductile-to-brittle transition. Results show that the critical chip thickness in silicon for ductile material removal reaches a maximum of 285 nm in the [100] direction and a minimum of 115 nm in the [110] direction, when the depth of cut was 5 mu m. It was found that when a submicrometre depth of cut was applied, microcracks were revealed in the [110] direction, which is the softer direction in silicon. Micro Raman spectroscopy was used to estimate surface residual stress after machining. Compressive residual stress in the range 142 MPa and smooth damage free surface finish was probed in the [100] direction for a depth of cut of 5 mu m, whereas residual stresses in the range 350 MPa and brittle damage was probed in the [110] direction for a depth of cut of 500 nm.