Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane

The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates.

Síntese de membranas cerâmicas via método sol-gel utilizando TEOS e N,N-dimetilformamida

In this work we obtained microporous and mesoporous silica membranes by sol-gel processing. Tetraethylortosilicate (TEOS) was used as precursor. Nitric acid was used as catalyst. In order to study the affect of N,N-dimethylformamide (NDF) as drying additive, we used a molar ratio TEOS/NDF of 1/3. The performance of N,N-dimethylformamide was evaluated through monolithicity measurements. The structural evolutions occurring during the sol-gel transition and in the interconnected network of the membranes during thermal treatment were monitored by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses and nitrogen sorption. We noted that in the presence of N,N-dimethylformamide, polymerization goes through a temporary stabilization of oligomers. The Si-O(H) bonds are stronger and belong to a more cross-linked structure for the N,N-dimethylformamide containing sol. The membranes obtained in the presence of N,N-dimethylformamide have larger surface area and its pore structure is in the range of mesoporous. The membranes obtained without additive have pore structure in the range of microporous.

Obtenção e caracterização de blendas colágeno-quitosana

Biodegradable polymer blends were obtained using collagen and chitosan. Membranes of collagen and chitosan in different proportions (3:1, 1:1 and 1:3) were prepared by mixing their acetate solutions (pH 3.5) at room temperature. The blends were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier Transform infrared (FTIR) spectroscopy, specific viscosity, water absorption and stress-strain assays. The results showed that chitosan did not interfere in the structural arrangement of the collagen triple helix and the properties of the blends can be controlled by varing the proportion of the collagen and the chitosan.

New Distance Transforms for Gray Level Image Compression

This thesis deals with distance transforms which are a fundamental issue in image processing and computer vision. In this thesis, two new distance transforms for gray level images are presented. As a new application for distance transforms, they are applied to gray level image compression. The new distance transforms are both new extensions of the well known distance transform algorithm developed by Rosenfeld, Pfaltz and Lay. With some modification their algorithm which calculates a distance transform on binary images with a chosen kernel has been made to calculate a chessboard like distance transform with integer numbers (DTOCS) and a real value distance transform (EDTOCS) on gray level images. Both distance transforms, the DTOCS and EDTOCS, require only two passes over the graylevel image and are extremely simple to implement. Only two image buffers are needed: The original gray level image and the binary image which defines the region(s) of calculation. No other image buffers are needed even if more than one iteration round is performed. For large neighborhoods and complicated images the two pass distance algorithm has to be applied to the image more than once, typically 3 10 times. Different types of kernels can be adopted. It is important to notice that no other existing transform calculates the same kind of distance map as the DTOCS. All the other gray weighted distance function, GRAYMAT etc. algorithms find the minimum path joining two points by the smallest sum of gray levels or weighting the distance values directly by the gray levels in some manner. The DTOCS does not weight them that way. The DTOCS gives a weighted version of the chessboard distance map. The weights are not constant, but gray value differences of the original image. The difference between the DTOCS map and other distance transforms for gray level images is shown. The difference between the DTOCS and EDTOCS is that the EDTOCS calculates these gray level differences in a different way. It propagates local Euclidean distances inside a kernel. Analytical derivations of some results concerning the DTOCS and the EDTOCS are presented. Commonly distance transforms are used for feature extraction in pattern recognition and learning. Their use in image compression is very rare. This thesis introduces a new application area for distance transforms. Three new image compression algorithms based on the DTOCS and one based on the EDTOCS are presented. Control points, i.e. points that are considered fundamental for the reconstruction of the image, are selected from the gray level image using the DTOCS and the EDTOCS. The first group of methods select the maximas of the distance image to new control points and the second group of methods compare the DTOCS distance to binary image chessboard distance. The effect of applying threshold masks of different sizes along the threshold boundaries is studied. The time complexity of the compression algorithms is analyzed both analytically and experimentally. It is shown that the time complexity of the algorithms is independent of the number of control points, i.e. the compression ratio. Also a new morphological image decompression scheme is presented, the 8 kernels' method. Several decompressed images are presented. The best results are obtained using the Delaunay triangulation. The obtained image quality equals that of the DCT images with a 4 x 4

Kalman Filtering in Online Paper Quality Assessment

Controlling the quality variables (such as basis weight, moisture etc.) is a vital part of making top quality paper or board. In this thesis, an advanced data assimilation tool is applied to the quality control system (QCS) of a paper or board machine. The functionality of the QCS is based on quality observations that are measured with a traversing scanner making a zigzag path. The basic idea is the following: The measured quality variable has to be separated into its machine direction (MD) and cross direction (CD) variations due to the fact that the QCS works separately in MD and CD. Traditionally this is done simply by assuming one scan of the zigzag path to be the CD profile and its mean value to be one point of the MD trend. In this thesis, a more advanced method is introduced. The fundamental idea is to use the signals’ frequency components to represent the variation in both CD and MD. To be able to get to the frequency domain, the Fourier transform is utilized. The frequency domain, that is, the Fourier components are then used as a state vector in a Kalman filter. The Kalman filter is a widely used data assimilation tool to combine noisy observations with a model. The observations here refer to the quality measurements and the model to the Fourier frequency components. By implementing the two dimensional Fourier transform into the Kalman filter, we get an advanced tool for the separation of CD and MD components in total variation or, to be more general, for data assimilation. A piece of a paper roll is analyzed and this tool is applied to model the dataset. As a result, it is clear that the Kalman filter algorithm is able to reconstruct the main features of the dataset from a zigzag path. Although the results are made with a very short sample of paper roll, it seems that this method has great potential to be used later on as a part of the quality control system.

Decomposição do NO sobre Cu suportado em zeólitas

Direct decomposition of NO on copper supported on zeolite catalysts such as MCM-22 and Beta was compared with that on the thoroughly studied Cu-ZSM-5. The catalysts were prepared by ion-exchange in basic media. They were characterized by atomic absorption, surface area, nitrogen adsorption at 77K, X-ray diffraction and temperature programmed reduction. The products of the reaction were analyzed by Fourier transform infrared spectroscopy using a gas cell. Catalytic activity tests indicated that zeolite catalysts, like Beta and MCM-22, lead to NO conversion values comparable to ZSM-5.

Determination of the HMX and RDX content in synthesized energetic material by HPLC, FT-MIR, and FT-NIR spectroscopies

A new method has been developed for determining the content of mixtures of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), the HMX/RDX ratio, in explosive compositions by Fourier transform infrared spectroscopy (FT-IR), in the regions MIR (mid infrared) and NIR (near infrared) with reference values obtained by chromatographic analysis (HPLC). Plots of relative MIR (A917 / A783) or NIR absorbance values (A4412 / A4317) versus HMX/RDX ratio determined by HPLC analysis revealed good linear relationships.

Técnicas de caracterização para investigar interações no nível molecular em filmes de Langmuir e Langmuir-Blodgett (LB)

This paper discusses fundamental concepts for the characterization of Langmuir monolayers and Langmuir-Blodgett (LB) films, with emphasis on investigations of material properties at the molecular level. By way of illustration, results for phospholipid monolayers interacting with the drug dipyridamole are highlighted. These results were obtained with several techniques, including in situ grazing incidence X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, fluorescence microscopy, in addition to surface pressure and surface potential isotherms. Also mentioned are the difficulties in producing Langmuir and LB films from macromolecules, and how molecular-level interactions in mixed polymer LB films can be exploited in sensors.

The Emerging Human Rights Revolution: The Beginning of the Fifth Historical Process in the Consolidation of Human Rights

Emerging human rights are destined to modify, improve and transform a number of already traditional concepts so as to achieve greater guarantees and protection for the rights of individuals and collectivities. One of the big changes that will be brought about by the concept and conception of emerging human rights is that, following on from the processes of positivization, generalization, internationalization and specification, they represent the beginning of the fifth historical process in the consolidation of human rights, namely the process of interaction. A number of breakthroughs have already been achieved, such as the recognition of emerging biocultural rights in the recently adopted Nagoya Protocol on access to genetic resources and shared benefits.

Taninos hidrolisáveis em Bixa orellana L.

The aqueous material found in the fruits of Bixa Orellana L. was collected, dried, and characterized using several experimental techniques, namely phytochemical analysis in order to identify the biologically active constituents, Fourier transform infrared (FT-IR) spectroscopy for vibrational analysis, and X-ray powder diffraction in order to identify the presence of crystalline phases in the sample. The results showed that the aqueous material possesses high concentrations of hydrolyzable tannin. This result justifies the anti-inflammatory activity of this substance reported in other studies.

Caracterização de 2,2',4,4',6,6'-hexanitroestilbeno via análises instrumentais

2,2',4,4',6,6'-hexanitrostilbene (HNS) is a very important high explosive that is used in a range of military, aerospace and industrial formulations owing to its suitable properties. It is an insensitive and thermaly stable explosive that can be produced from 2,4,6-trinitrotoluene (TNT). This paper shows the characterization of synthesized HNS by different techniques, such as elementary analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FT-IR) and through the determination of the heat of combustion in a calorimeter.

De More a Moore : de la utopia al cos, i a l’inrevés

Through the graphic novel V for Vendetta by Alan Moore and David Lloyd, I problematize here the act of classification of the subgenres within each genre. This is a literary study that aims to reflect on the utopian genre. It is a genre which requires in order to be understood a consideration of society and its organization. The concept of society cannot be properly discussed without mentioning the surface on which it is based: people with their selves and their bodies. Institutions and conventions act subtly and constantly on us, offering more or less free roles, usually related to a particular physical appearance, as may be the mode of dress, or gesture- and generating a negotiation between our desires and our duties. In other words, they act on us to transform us into people suitable for the smooth running of the community

Caracterização espectroscópica de peixe do período cretáceo (Bacia do Araripe)

The study of fossils has made considerable progress over the last years as a result of the use of new experimental techniques. This paper describes the chemical composition of a fossilized fish of the Cretaceous period, from a 100 million-year-old, material originated from the Araripe Basin (northeastern Brazil). The chemical composition of the fossilized fish was analyzed by means of X-ray powder diffraction and Fourier transform infrared spectroscopy (FT-IR). The spectroscopic study has proven that the main substances found in the fossilized fish are CaCO3 and Ca5(PO4)3(OH). A tentative mechanism to explain the fossilization process is also given.

Cohesive Elements for Shells

A cohesive element for shell analysis is presented. The element can be used to simulate the initiation and growth of delaminations between stacked, non-coincident layers of shell elements. The procedure to construct the element accounts for the thickness offset by applying the kinematic relations of shell deformation to transform the stiffness and internal force of a zero-thickness cohesive element such that interfacial continuity between the layers is enforced. The procedure is demonstrated by simulating the response and failure of the Mixed Mode Bending test and a skin-stiffener debond specimen. In addition, it is shown that stacks of shell elements can be used to create effective models to predict the inplane and delamination failure modes of thick components. The results indicate that simple shell models can retain many of the necessary predictive attributes of much more complex 3D models while providing the computational efficiency that is necessary for design

Socio-Cultural Transformation and the Promotion of Learning

The main premise of Vygotsky’s cultural-historical theory is that to promotelearning, and thus development, educators must intervene in, and change, the students’ socio-cultural context. Vygotsky’s theory, however, has been misinterpreted and the opposite approach has been accepted: the teaching is adapted, according to the context. The result is widespread failure in schools. This article reclaims the true transformative meaning of Vygotskian theory and shows how successful schools in several countries implement various actions to transform their social and cultural environment. Data is presented from six casestudies of successful schools conducted in five European countries. The analysis showsthat these actions improve instrumental learning and, consequently, cognitive development. All these efforts focus on teaching methods that aim to increase the amount that students learn